ATC-13 Conference Proceedings Volume 3 by ATC-13

Volume 3

Table of Contents - Bold Content is in this Volume

Online link to: International Scientific Committee Volume 1: Invited Speakers Volume 1: Fashion and Clothing Science Volume 1: High Performance Fibres and Composites Volume 2: Nanofibres Volume 2: Natural Fibres Volume 2: Technical Textiles and Non-Wovens Volume 3: Textile Performance / Testing / Evaluation Volume 3: Textile Processing and Treatments

Page 3

Page 18 Page 22

Title: Asian Textile Conference (ATC-13) Conference Proceedings Editor: Christine Rimmer Abstracts and manuscripts have been submitted in accordance with the Terms and Conditions stated on the ATC-13 webpage https://atc-13.org/about/terms-and-conditions/. â&#x20AC;&#x153;ATC-13 organisers reserve the right to publish the title and abstract of your presentation / poster in various conference marketing materials and other products. Provided abstracts and manuscripts were peer reviewed. It was the responsibility of the Author(s) to amend the Abstract and Manuscript in response to the Review feedback provided by the International Scientific Committee. Occassionally the abstract and manuscript titles do not match. Copyright 2015 Asian Textile Conference Published by Deakin University. 2015 ISBN: 978-0-7300-0039-6

International Scientific Committee Name Chair: Prof Xungai Wang Mr. Sean Bassett Dr. Jeff Church Dr. Floreana Coman Professor Raul Fangueiro Professor Bronwyn Fox Mr Michael Gerakios Dr. Stuart Gordon Prof. Jinlian HU

Affiliation

Institute for Frontier Materials, Deakin University, Australia AWTA Product Testing, Melbourne, Australia Advanced Fibre Innovation Manufacturing Flagship, CSIRO Fabrics & Composites Science & Technologies, Melbourne, Australia School of Engineering, University of Minho, Portugal Institue of Frontier Materials, Deakin University, Australia Metis Technologies, NSW, Australia Advanced Fibre Innovation Manufacturing Flagship, CSIRO Institute of Textiles and Clothing, The Hong Kong Polytechnic University, Hong Kong Advanced Fibre Innovation Manufacturing Flagship, CSIRO Dr. Mickey Huson Dept. of Organic and Polymeric Materials, Graduate School of Science and Professor Takeshi Kikutani Engineering,Tokyo Institute of Technology, Japan Clothing and Textile Sciences, Head of Department Applied Sciences, University Professor Raechel M Laing of Otago, New Zealand Institue for Frontier Materials, Deakin University, Australia Professor Tong Lin Advanced Fibre Innovation Manufacturing Flagship, CSIRO Dr. Rob Long Division of Materials Science and Engineering, CSIRO Dr. Menghe Miao Professor Textile Engineering, Chemistry and Science, College of Textiles, North Carolina Stephen Michielsen State University, USA Dr. Keith Millington Advanced Fibre Innovation Manufacturing Flagship, CSIRO A/Prof Rajiv Padhye School of Fashion & Textiles, RMIT University, Australia A/Prof Joselite Razal Institute for Frontier Materials, Deakin University, Australia Department of Textile Technology, KSR College of Technology, Nadu, India Professor O.L. Shanmugasundaram Professor Sachiko Sukigara Department of Advanced Fibro Science, Graduate School of Science and Technology, Kyoto Institute of Technology, Japan Mr Brendan Swifte Geofabrics Australasia Pty Ltd Prof. Mangesh D. Teli Professor of Textile Chemistry, Institute of Chemical Technology, India Professor Dong Wang Wuhan Textile University, China Professor Qufu Wei Professor of Textile Sciences & Engineering, The Graduate School of Jiangnan University, China Lee Family Professor in Fashion and Textiles Prof John H Xin Institute of Textiles and Clothing, The Hong Kong Polytechnic University, Hong Kong President of the Asian Society of Protective Clothing Professor Kee Jong Yoon Chair Dept. of Fiber System Engineering, Dankook University Director of Personal Protective Equipment Center, Dankook University, Korea National Engineering Laboratory for Modern Silk Professor Ke-Qin Zhang College of Textile and Clothing Engineering, Soochow University, China

Volume 1: Invited Speakers Page

Abstract Title

Acoustic Fibre Board Screens for Office Speech Privacy

Fibrous Materials and Wearable Technologies in a Nonlinear Interactive World

Volume 1: Fashion and Clothing Science Page 34 38 46 51 56 61 65 70

89 93

Abstract Title A Novel Nonlocal Self-similarity Technique for Fabric Defect Detection

WONG Wai Keung Calvin | JIANG Jielin Institute of Textiles and Clothing | The Hong Kong Polytechnic University

Brief Introduction On Uyghur Traditional Headwear--Doppa

Gulistan IGEMBERDI | Xiaoming YANG Textile College of Donghua University, Shanghai China | Textile College of Donghua University, Shanghai China

Characteristic on Colour Expression of Luxury Brand’s Garments

Conditions for Laccase Immobilization onto Modified Polyamide Fabric

Design of Leg Compression Stockings Adaptable to Leg Size for Prophylaxis Against Deep-vein Thrombosis

Dynamic Manipulation of Repeat Formation for Engineered Printing of Graded Garments

Olga Gavrilenko School of Fashion & Textiles, RMIT University, Melbourne

Effect of Compression Deformation of Body Surface on Back Silhouette When Wearing a Brassiere

Yuhi Murasaki | Miyuki Nakahashi | Harumi Morooka Kyoto Women's University | Kyoto | Japan

Effect of Different Pigment Colorants on Inkjet Printing Performance

Effects of Acculturation on Acceptance of Cultural Apparel in the Global Fashion Consumption: A Case 2014 APEC Costume Le Xing | Hui-e Liang | Chuanlan Liu Han Nationality Costume Culture and Non-material Culture Heritage Base | Jiangnan University | Wuxi

Evaluation and Simulation of Clothing Assembly Line

Finite Element Modeling of Women’s Breasts for Bra Design

Handle Durability of Reusable Cloth Diapers after Use

Hiroko Yokura | Sachiko Sukigara Shiga University | Kyoto Institute of Technology

Optimization of Producing Bacterial Cellulose used for Fashion Fabrics

Su Min Yim | So Hee Lee | Hye Rim Kim Department of Clothing and Textiles | Sookmyung Womenâ€™s University | Research Institute of women's health

Relation among Three-dimensional Shapes of Women's Trunk, Breast, and Abdomen

110

Research on Suitability of Women's Jacket for Various Body Types

114

Scenario in BRICS Region and Textile Potential

118

Seam Pucker Evaluation of Fused Fabric Composites Based on Subjective Method

Volume 1: Fashion and Clothing Science Page

Abstract Title

122i

Study on the Model of Feature Points of Bust Curve

123

Sustainability Challenges in Fashion Business

127

The Application of Nvshu Pattern in the Modern Women's Apparel Design

132

Virtual Draping by Mapping and Manipulation

Gao Peipei | Xing Xiaoyu | Shang Xiaomei Soochow University | Hong Kong

Philip KW Yeung and Kit KY Li Clothing Industry Training Authority | Hong Kong

Volume 1: High Performance Fibres and Composites Page 136 139 143 147 152

Abstract Title A Study on the Thermal Properties of Polyhydroxyamide Derivatives

Analyzing the Tensile Behavior of Woven-Fabric Reinforced Composites using Fiber Orientation Theorem F Hasanalizadeh | H.Dabiryan | A.A. Jeddi Amirkabir University of Technology | Amirkabir University of Technology | Amirkabir University of Technology

Biodegradable Composites from Natural Bamboo Fibres

Erwan Castanet Institute for Frontier Material and Carbon Nexus

Biosynthesis of Bacterial Cellulose/Carboxylic Multi-Walled Carbon Nanotubes for Enzymatic Biofuel Cells Application

Characterization of Polyimide/Poly(VDF-co-HFP) Composite Membrane prepared by Electrospinning Il Jae Lee | Chan Sol Kang | Doo Hyun Baik Chungnam National University | Korea | Chungnam National University

155

Chemical Resistance of Polyphenylene Sulfide Needle Non-Woven Fabric

163

Cost-Efficient and Flexible Production of High Quality Fabrics for Composite Applications

168

Crystallization Kinetics and Structural Features of Polyarylate/Nylon6 Island-In-The-Sea Fibers used for Thermoplastic Composites

WENJUN DOU Wuhan Textile University

Dr. Josef Klingele Lindauer DORNIER GmbH

172

176 180

Development of Composite Technical Filament for Smart Applications

Development of Hydrophilic Polyamide and its Applications on Functional Textiles

Wei Hung Chen | Wei Peng Lin | Ta Chung An Taiwan Textile Research Institute | Taiwan Textile Research Institute | Taiwan Textile Research Institute

Effect of Cross-sectional Configuration on Fiber Formation Behavior in the Vicinity of Spinning Nozzle in Bicomponent Melt Spinning Process Yiwen Chen | Wataru Takarada | Takeshi Kikutani Tokyo Institute of Technology | Tokyo Institute of Technology | Tokyo Institute of Technology

184 189 193 197

201

Effects of Bonding System on the Interfacial Adhesion Between Polyketone Fiber and EPDM Rubber

Evaluating Acoustic and Climatic Ageing Properties of Natural Fiber Based Nonwovens for Automotive Applications

Dr. Asis Patnaik CSIR Materials Science and Manufacturing

Fabrication and Characterization of Flexible Polyaniline-Decorated Fiber Nanocomposite Mats for Supercapacitors

Danyun Lei | Tae Hoon Ko | Ji-young Park | Yong Sik Chung | Byoung-Suhk Kim Department of BIN Convergence Technology, Chonbuk National University | Department of Organic Materials and Fiber Engineering, Chonbuk National University | Department of Organic Materials and Fiber Engineering, Chonbuk National University | Department of Organic Materials and Fiber Engineering, Chonbuk National University | Department of Organic Materials and Fiber Engineering, Chonbuk National University

Fabrication of Core-Shell Conducting Fibers and their Characteristics

Volume 1: High Performance Fibres and Composites Page

Abstract Title

205

Fabrication of Superionic Conductive Nanofiber

209

Fiber-Reinforced Rigid Polyurethane Foam Composite Boards: Manufacturing and Property Evaluations

Young Ah Kang | Yang Hun Lee | Kyoung Hou Kim Dong-A University | Dong-A University | Shinshu University

213

217

Growth of Zinc Oxide Nanorodes with Respect to Surface Condition of Carbon Fiber and Post Annealing

Seung A Song | Seong Su Kim Chonbuk National University | Chonbuk National University

Heat and Moisture Transfer Properties of Natural Silkworm Cocoons

221

High Spatial Resolution Confocal Raman Mapping: New Frontiers in Carbon Fibre Research

225

High-speed Melt Spinning Behaviors of Flame-retardant PET Fibers Containing Antibacterial Deodorant Function

229

Hybridization of Preforms for Textile Composites

233

Improvement of Flexural Properties of FRP by Filament Cover Method

237

Mechanical and Open Hole Tensile Properties of Self-Reinforced Recycling PET Composites

242

Mechanical Properties of Poly(lactic acid)/Hemp Hurd Biocomposites using Glycidyl Methacrylate

246

Mechanical Properties of Woven Jute - Carbon Fiber Cloth Hybrid-Reinforced Epoxy Composite

Hireni Mankodi Department of Textile Engineering

Ryo Sakurada | Limin Bao Mechanical Robotics Course | Graduate School of Science and Technology

Zhili Zhong | Manyi Li | Zhendong Liao Tianjin Polytechnic University | Tianjin Polytechnic University| Tianjin Polytechnic University

250

Modeling of Tensile Mechanics of 3D Woven Orthogonal Composites

257

Modification of Chemically Stable Polymeric Materials 61. Improvement in the Adhesive Property of Polymeric and FRP Materials

262 266

270

Ashwini Kumar Dash | B.K.Behera Indian Institute of Technology Delhi, India | Indian Institute of Technology Delhi, India

Hitoshi Kanazawa | Aya Inada Dept. of Industrial Systems | Faculty of Symbiotic Systems Science

Morphology and Thermal Property of Neoprene Textiles Coated with CNF/polymer Composite Sunhee Lee Dept. Fashion Design

pH- / Temperature-responsive Materials Prepared from Amino Acid Ester Carrying Polymerizable Vinyl Group

Pitch-based Carbon Fiber Prepared by Melt Spinning Using Screw Type Extruder

Tae Hwan Lim | Sang Young Yeo | So Hee Lee Korea Institute of Industrial Technology | Korea Institute of Industrial Technology | Sookmyung Women`s University

Volume 1: High Performance Fibres and Composites Page 273

277

282 286 290

Abstract Title Preparation and Characteristics of Carbon Nanotube/Carbon Fiber Composite Paper

Wan Jin Kim | Yong Sik Chung | Han Jin Jang | Hyun Myung Kwon Department of Organic Materials & Fiber Engineering, Chonbuk National University, Jeonju 561-756, Korea | Department of Organic Materials & Fiber Engineering, Chonbuk National University, Jeonju 561-756, Korea | Department of Organic Materials & Fiber Engineering, Chonbuk National University, Jeonju 561-756, Korea | Department of Organic Materials & Fiber Engineering, Chonbuk National University, Jeonju 561-756, Korea

Preparation and Characteristics of Thermoplastic Composite Sheet using Recycle Carbon Fibers

Yong Sik Chung | Yun-Seon Lee | Wan Jin Kim | Jae Ho Shin | Chul Ho Lee Department of Organic Materials & Fiber Engineering, Chonbuk National University, Jeonju 561-756, Korea | Department of Organic Materials & Fiber Engineering, Chonbuk National University, Jeonju 561-756, Korea | Department of Organic Materials & Fiber Engineering, Chonbuk National University Jeonju 561-756, Korea | Department of Organic Materials & Fiber Engineering, Chonbuk National University, Jeonju 561-756, Korea | Department of Organic Materials & Fiber Engineering, Chonbuk National University, Jeonju 561-756, Korea

Preparation and Characterization of Aramid Copolymer Fibers Including Ester and Cyano Group

Preparation and Characterization of High Temperature Carbon/Silica Composite by Sol-gel Process

Preparation and Properties of Polyetherimide(PEI)-MWCNT Composite Nanofibers A-Rong Kim | Young-Ah Kang | Jong S. Park* Dong-A University | Dong-A University | Pusan National University

294

Preparation and Thermal Properties of Polybenzoxazole Precursors Containing Sulfone Group

298

Preparation of Helical Crystals of Poly(ester-imide) by Crystallization during Polymerization - Influence of Oligomer Structure on Helical Morphology -

302

Preparation of Rigid Polymer Nanofiber by using Crystallized from Dilute Solution and its Application Tetsuya Uchida | Masashi Furukawa | Haruka DoDo Okayama Univ. | JAPAN | Okayama Univ.

306

Preparation of Well-Defined Polyacrylonitrile Fiber-Forming Polymer via New Controlled Radical Polymerization Techniques Xiaohui Liu Tianjin Polytechnic University

310

Properties of Cellulose Regenerated Fibers Spun from Ionic Liquid Solutions

312

Property Evaluations of Composite Films made of Polyvinyl Alcohol and Graphene Nano-Sheets by Using the Solution Mixing Method

Jiaping Zhang | Keita Tominaga | Yasuo Gotoh Faculty of Textile Science and Technology | Shinshu University | Faculty of Textile Science and Technology

316 320

PVA-Gel with Colossal Dielectric Constant can Deflect Laser Beam Toshihiro Hirai | Hiromu Satou | Chizuru Sakaguchi Shinshu University | Shinshu University | Shinshu University

Rheological Investigation of PAN-based Polymer Solutions to Determine the Wet Spinning Parameters for Continuous Fibre Production

324

Stability of Red Rare Earth Luminous Fiber Emission Spectra Yanan Zhu | Mingqiao Ge School of Textile and Clothing | Jiangnan University

Volume 1: High Performance Fibres and Composites Page 329

332

Abstract Title Structure and Properties of Fibers Manufactured from Liquid Crystalline Poly(2-Cyano-1,4-Phenylene Terephthalamide)Based Copolymers Seong Jun Yu Chugnam University

Studies on Tensile and Flexural Properties of Hemp/PBTG Biocomposites

336

Study on Solid Erosion Properties of Fiber-Reinforced Thermoplastics with High Heat-Resistant Properties

339

Synthesis and Characterization of Poly (L-lactide) Poly (caprolactone) Segmented Block Copolymers

343 346

349

353 357

366

371 375 378

Liu Bing | Bao Limin Shinshu University | Shinshu University

Synthesis and Characterization of Polyacrylonitrile-based Terpolymers as Carbon Fiber Precursors Eunbin Lee | Won Ho Park | Young Gyu Jeong Chungnam National University | Daejeon 305-764 | Korea

The Chemical Modification of Oxy-PAN Nanofibrous Web by Sodium Hydroxide Solution

The Effect of Carbonization Temperature on Properties of PAN-Based Carbon Fiber

The Effects of Heat-Treatment Temperature on Carbonization Behavior of Heterocyclic Aromatic Polymer

The Functional Properties of PET/ Rayon Staple Fiber Made Woven Fabrics with ACC@Ag Powders

The Heating and Cooling Behaviours of Needle Punched Nonwoven Fabrics with Wool and Silver Coated Polyamide Fibres

Thermal Protective Performance of the Air Layer in Firefighterâ&#x20AC;&#x2122;s Protective Clothing

Three Dimensional Composite Prepared by Vacuum-Assisted Resin Transfer Molding

Transverse Modulus of Carbon Fibre by Compression and Nanoindentation

Volume 2: Nanofibres Page 383

Abstract Title A Comparison of the Influence of Superhydrophobic Surfaces and the Wetness on the Colours, Near-Infrared (IR) and Shortwave IR Properties of Uniform Jie Ding | Bin Lee Defence Science and Technology Group | Defence Science and Technology Group

387

Adhesion of Electrospun PVA/ES Composites using Spiral Disk Spinnerets

392

Application of the Synthesized Magnetic TiO2Nanofibres in Dye Removal from Effluent

396

Cellulose-Based Co-Axial Nanofiber Membrane for Separator of High Performance Lithium-Ion Battery from Waste Cigarette Filter Tips

407 412 416

Chuchu Zhao | Yao Lu | Zhijuan Pan Soochow University | Soochow University | Soochow University

Elmira Pajotan | M.Rahimdokht | N. Noormohammadi Amirkabir University of Technology | Amirkabir University of Technology | Amirkabir University of Technology

Fenglin Huang Jiangnan University

Characterisation of Nanofibres Fabricated by Meltblowing using various Fluids Rajkishore Nayak RMIT and CSIRO

CNTs and Graphene Oxide Coated Electrode for Anionic Dye Removal by Heterogeneous Electro-Fenton Process Z. Eshaghzadeh | h. Bahrami | A. Gholami Akerdi. Amirkabir University of Technology | Amirkabir University of Technology | Amirkabir University of Technology

Continuous Manufacturing Process of Carbon Nanotube-Grafted Carbon Fibers

420

Drug Loaded Porous Silica Nanoparticles Composites Nanofiber and Evaluation of Characteristics

423

Electrical Properties of Polypyrrole Coated Nanofibers on PET Fabric with Potential for Flexible Heating Element Applications

Ke Ma | Mayakrishnan Gopiraman | KimIck Soo Shinshu University,Japan | Shinshu University,Japan | Shinshu University, Japan

427

Electrospun Hybrid Poly(Lactic Acid)/Titania Fibrous Membranes with Antibacterial Activity for Fine Particulate Filtration

431

Electrospun PVA/PE Nanofiber Mask

436 440

443 447

451 456

Wang Zhe | Pan Zhijuan Soochow University | Soochow University YAMASHITA Yoshihiro The University of Shiga Prefecture

Examining Thermal Properties of Nano Surfaces Formed with Electro Spinning Method from Shape Memory Polymers Erkan Isgoren | Sinem Gulas | Metin Yuksek | Marmara University, Turkey

Fabrication and Evaluation of Bi-layered Matrix Composed of Human Hair Kratin Nanofiber and Gelatin Methacrylate Hydrogel Min Jin Kim | Su Jung Ryu | So Ra Lee | Chang Seok Ki | Young Hwan Park Seoul National University

Fabrication of Electrospun Juniperus Chinensis Extracts loaded PVA Nanofibers Jeong Hwa Kim | Jung Soon Lee | Ick Soo Kim Chungnam National University | Chungnam National University | Shinshu University

Fabrication of ZnO Nanowires on Fabrics Based on Biomimetic Adhesion of Seeds onto Fiber Surfaces and Hydrothermal Growth Chao-Hua Xue | Xue-Qing Ji | Shun-Tian Jia Shaanxi University, China

Hydrophobic Functionalization of Textiles using Atmospheric Pressure Pulse Plasma

Raghav Mehra | Manjeet Jassal | Ashwini K. Agrawal Indian Institute of Technology

Modification of Graphene Oxide and Halloysite Nanotubes by Poly(Propylene Imine) Dendrimer to Improve the Dye Removal Efficiency F. Shahamati Fard | , A. Ghasempour | H. Bahrami | S. Akbari Amirkabir University of Technology | Amirkabir University of Technology | Amirkabir University of Technology | Amirkabir University of Technology

Volume 2: Nanofibres Page 461

464 467 470

Abstract Title Morphologies of Colloid-Electrospun Sulfonated Polyetheretherketone Nanofiber

Morphologies of Electrospun Polyacrylonitrile/Polyvinylpyrrolidone Composite Nanofiber

Sheng-Yin Peng | Chien-Lin Huang | Chih-Kuang Chen Department of Fiber and Composite Materials | Feng Chia University | Department of Fiber and Composite Materials

Morphologies of HDPE/PA6/GNS Composites Chien-Lin Huang* Department of Fiber and Composite Materials

474

Polyvinyl Alchol/Water Soluble Chitosan Electrospun Fiber Membranes: Process and Property Assessment

478

Preparation and Characterization Nanofibres from Poly(Îľ-caprolactone) poly(vinyl alcohol) Gum Tragacanth Hybrid Scaffolds

Zare Khalili | M. Ranjbar Amirkabir University of Technology | Bonab University

486

Preparation and Characterization of Electrospun PCL/Gelatin Nanofibers containing Graphene Nanoparticles

489i

Preparation of Antibacterial Nano-silver Sol

490 493 497 505

M.Ranjbar | Mina Heydari Bonab University | Amirkabir University of Technology

Preparation of Beta-Chitin Nanofibers from Squid Pen by Water Jet Machine

Preparation of Nanoparticle Fluorescent Pigment Dispersions by Miniemulsion Polymerization and itâ&#x20AC;&#x2122;s Properties

Jie Liu | Shaohai Fu Jiangnan University | Jiangnan University | Jiangnan University

Preparation of Polyvinyl Butyral/Titanium Dioxide Composite used for UV Blocking

509

Proof-of-Concept Fabrication of Photoactive Tio2-PU Composite Nanofibers for Efficient Dye Degradation

513

Reexamination of the Polymerization of Amino Acid NCA 69. A New Type Topochemical Polymerization of Amino Acid N-Carboxy Anhydrides

Xiaowen Wang | Huawen Hu | Chenxi Liu | John H Xin Institute of Textile & Clothing at The Hong Kong Polytechnic University - Hong Kong | Institute of Textile & Clothing at The Hong Kong Polytechnic University - Hong Kong | Institute of Textile & Clothing at The Hong Kong Polytechnic University - Hong Ko |

Hitoshi Kanazawa | Aya Inada Dept. of Industrial System | Faculty of Symbiotic Systems Science

518

Sericin Separation from Silk Degumming Waste Water by Magnetic Nanoparticles: A Feasible Approach

523

Strain Sensitive Cotton Fabric with a Graphene Nanoribbon Layer

527

Synthesis of Ag3VO4 TiO2 CNT Hybrids with Enhanced Photocatalytic Activity under Visible Light Irradiation

Esfandiar Pakdel | Jinfeng Wang | Xungai Wang Australian Future Fibres Research and Innovation Centre | Institute for Frontier Materials | Deakin University

Lu Gan | Songmin Shang The Hong Kong Polytechnic University | The Hong Kong Polytechnic University

Chang-Mou Wu | Ching-Kai Wang Department of Materials Science and Engineering | National Taiwan University of Science and Technology

Volume 2: Nanofibres Page 531

Abstract Title Synthesis of Silver Nanoparticles Stabilized with DOPA and their Application to Colorimetric Sensor for Heavy Metal and Catalyst Reduction of Methylene Blue Ja Young Cheon | Hun Min Lee | So Yeon Jin | Won Ho Park Chungnam National University | Chungnam National University | Chungnam National University | Chungnam National University

535

The Effect of Chelidonium Majus var. Asiaticum Extract Concentration o PVA Nanofiber Web Diameter

539

The Thermal and Functional Properties of PU/CC@Ag Composite Films

544

Ultrathin Hierarchically Structured Poly(Vinyl Alcohol-Co-Ethylene) Nanofirous Separator for High Rate Lithium-Ion Battery

Heong Yeol Choi | Jung Soon Lee | Ick Soo Kim Chungnam National University | Chungnam National University | Shinshu University

Volume 2: Natural Fibres Page

Abstract Title

548

An Investigation on Cellulose-Based Carbon Composite Materials Fabricated by 3D Printing

553

Animal Fibre Diameter-Length Relationship and Its Effects on Yarn Properties

Saeed Dadvar Deakin University

557

Back to the Nature in Future

563

Brief Analysis of Uyghur Traditional Textile Technology

569 571 576

Effect of Licl/Dmac Solution Treatment on Solubility and Mechanism of Native Hemp Fibers Min Zhu | Zhili Zhong | Zhendong Liao | Qi Weng Tianjin Polytechnic University

Facile Manipulation of Silk Fibroin Hydrogel Property by Molecular Weight Control

579

Functional Modification of Coir Fibre for Enhanced Oil Absorbency

584

In-Situ Analysis of Fiber Structure Development in CO2 Laser-Heated Drawing of Syndiotactic Polystylene Fiber

588

Investigating Drug Delivery Properties of Silk Fibres and Particles Mehdi Kazemimostaghim | Rangam Rajkhowa | Xungai Wang Deakin University | Deakin University | Deakin and Wuhan Textile University

592

595

Modification of Chemically Stable Polymeric Materials 62. Improvement of the Hydrophilic Property of Wool Fibers and Preparation of Water-Wettable Polypropylene and Silicone Ruber

Hitoshi Kanazawa | Aya Inada Dept. of Industrial Systems | Faculty of Symbiotic Systems Science

Plasma Assisted Finishing of Cotton Fabric with Chitosan

Maryam Naebe | Aysu Onur | Xungai Wang Institute for Frontier Materials (IFM), Deakin University, Geelong, Australia | Institute for Frontier Materials (IFM), Deakin University, Geelong, Australia | Institute for Frontier Materials (IFM), Deakin University, Geelong, Australia |

599

Preparation and Characterization of TLCP/PA6 Island-Sea Type Bi-Component Fibers by Melt Spinning Process

602

Preparation and flame retardancy of 3-(hydroxyphenylphosphinyl)-propanoic acid esters of cellulose and their fibers

607

Preparation of Kapok/Tio2 UV-Blocking Fiber by in-Situ Deposition

612

Shrink Proofing of Wool Fibers: Effect of Pretreatments with Shellac and Keratinase

616

Silk Modification Through In-Situ Polymerization and Crosslink under Visible Light

620

The Effect of Copper and Iron on Wool Photostability

Volume 2: Natural Fibres Page

Abstract Title

624

The Glass Transition Temperature (Tg) of Cotton

628

The Role of Various Fabric Parameters on the FAST Results of Wool and Wool Blend Worsted Fabrics

633 637

Chantal Denham CSIRO/Deakin

Sweta Das Department of Textile Science

Use of Bamboo Fibre in Textile

Varinder Kaur | D P Charropadhyay Guru Nanak Dev University, India | The M. S. University of Baroda, India

641

Using Micro-Electron Spin Resonance to Study Free Radicals in Protein Fibres

645

Water-free Chemical Treatment and Enzymatic Treatment of Wool to Change the Fiber Surface Morphology and Mechanical Properties

Keith Millington CSIRO

Chendi Tu | Sachiko Sukigara | Satoko Okubayashi | Fusako Kawai | Kunihiko Watanabe Department of Advanced Fibro-Science, Kyoto Institute of Technology, Japan | Department of Advanced Fibro-Science, Kyoto Institute of Technology, Japan | Department of Advanced Fibro-Science, Kyoto Institute of Technology, Japan | Center for Fiber and Textile Science, Kyoto Institute of Technology, Japan | Division of Applied Life Sciences, Kyoto Prefectural University, Japan

Volume 3: Technical Textiles and Non-Wovens Page

Abstract Title

649

A Theoretical Model for Thermal Resistance of Single Layer Cotton/Nylon-Kermel Blended Fabrics

657

Application of Regenerated Animal Fibers for Scaffold Preparation

661 665

669

673

Ali Kakvan | Saeed Shaikhzadeh Najar Amirkabir University of Technology Kazuya Sawada Osaka Seikei College

Coated Fabric Geomembranes

Mike Sadlier | Steve Aggenbach | Geosynthetic Consultants Australia | Infrastructure Technologies Australia |

Development of 3-Dimensional Fibrous Scaffolds using draw Texturing and Tubular Knitting Process

Effect of Tensile Properties of Layers on the Performance of Geocells made from Woven Fabrics in Bearing Capacity of Reinforced Soil Hadi Dabiryan | Mohammad Maroufi | Ghazal Ghamkhar Amirkabir University of Technology | Amirkabir University of Technology | Amirkabir University of Technology

Effects of Different Extraction Conditions on the Efficacy of Shatterstone

677

Effects of Recycled Kevlar Fibers on Physical Properties of Nonwoven Geotextiles

681

Geotextiles Made by Different Nonwoven Fabric Manufacturing Conditions: Manufacturing Techniques and Property Evaluations

685

Highly Precise Nanofiber Web-based Dry Electrodes for Long-term Biopotential Monitoring

690

Preparation and Characterization of N-Octadecane Microcapsules used for Textile Coating

694

Preparation and Characterization of Super Absorbent Nonwoven Fabrics for Chronic Wound Care

698 702

Tae-Hee Kim | Jung-Nam Im KITECH | KITECH

Preparation of Chitosan/Polyvinyl Alcohol Fibers without the use of Acetic Acid

Preparation of PET Non-woven Mats using High Voltage Dosing of Thermoplastic Polymer Powders and Melt-Fixing Process and Characteristics thereof

Sun Young Moon | Young Ho Kim | Chang Woo Nam Soongsil University | Soongsil university | Korea Institute of Industrial Technology

706 710

Study on Mixed media composed of UHMWPE Filaments and Microfibers

Zhang Heng | Qian Xiaoming Tianjin Polytechnic University

Study on Production of Non-woven Fabric and Mesh Type Knit Fabric used for Medical Products using Biodegradable Polyester Yoon Cheol Park | Jae Yun Shim | Young Hwan Park Korea Institute of Industrial Technology | Korea Institute of Industrial Technology | Korea Institute of Industrial Technology

714

Superhydrophobic Nonwoven Prepared from Biopolymer Derivatives

717

Synthesis and Characterization of Bio-Polyurethanes using Vegetable Oil-Based Polyols for Breathable Textile Coatings

Hiroaki Yoshida Shinshu University

Volume 3: Technical Textiles and Non-Wovens Page

Abstract Title

721

Synthesis and Characterization of UV Curable Oligomer for Pressure-Sensitive Adhesives

725

Synthesis and Fluorescent Properties of Water-Soluble Chitosan Oligomer with Fluorophore

728

The Effect of Structure of Socks on Plantar Pressure Distribution

Volume 3: Textile Performance / Testing / Evaluation Page

Abstract Title

732

A Study on Tencel and Polylactic Acid Fibres Based Nonwoven Structure Properties

735

A Study on the Preparation and Characterization of Wet-laid Nonwoven Based on Poly ketone

739 743

748

Gyudong LEE | Song Jun DOH Technical Textile and Materials R&D Group | KITECH | Korea Institute of Industrial Technology

A study on the Reliability Evaluation of Industrial textile Hwan Kuk, Kim Korea Textile Machinery Research Institute

Analysis of 19 SVHCS in Textiles using Liquid Chromatography Coupled with LTQ/Orbitrap Mass Spectrometry

Anti-aging Properties of PP / PET Acupuncture Filter Material Cherry Wuhan Textlie Univercity

755

Application of Phase Change Materials in Motorcycle Helmets for Heat-Stress Reduction

759

Comparison General Turnout Gear to Various Special Turnout Gear for Firefighters using the Flash Fire Testing Methods

763

767

Sinnappoo Kanesalingam | Lachlan Thompson | Rajiv Padhye RMIT University | RMIT University | RMIT University

Composite Environmentally Protective Sandwich Insulation Material Design

Composite Nonwovens Composed of Viscose Rayon and Super Absorbent Fibers for Incontinence Pad Yoonjin Kim | Jung Nam Im | Ga Hee Kim Korea Institute of Industrial Technology | Korea Institute of Industrial Technology | Korea Institute of Industrial Technology

771

Compression and Recovery Behavior of 3-D Composite Nonwovens Fabricated by Different Web-laying Methods

775

Cotton Bale Laydown Management Using Fuzzy C-Means Algorithm

779

Degradable Chitosan/Polyvinyl Alcohol Coronary Stents: Effects of Genipin Cross-Linking on Structure and Mechanical Properties

784

789 793 797

Chang Whan Joo | Dong Su Park Chungnam National University | Daejeon

Subhasis Das | Anindya Ghosh | Abul Hasnat Government College of Engineering & Textile Technology | Berhampore | West Bengal

Determination of Nonylphenol Ethoxylate and Octylphenol Ethoxylate Surfactants in Textiles by Liquid Chromatography High-Resolution Mass Spectrometry Xiwen Ye | Xin Luo | Zengyuan Niu | Li Zhang Shandong Entry-Exit Inspection and Quarantine Bureau | Shandong Entry-Exit Inspection and Quarantine Bureau | Shandong Entry-Exit Inspection and Quarantine Bureau | College of Chemistry and Chemical Engineering, Ocean University of China

Developing a Meltstick Test Method Ahmed Bhoyro Defence Science and Technology Organisation

Development Of Conductive Wire Reinforced Cotton Yarns For Protective Textile Applications

Development of Rain Test Equipment(Rain Tower) and Waterproof Performance Evaluation Criteria

Volume 3: Textile Performance / Testing / Evaluation Page

Abstract Title

800

Effect of Adhesive Interlinings on Creep Behavior of Woven Fabrics under low Stress in Bias Direction

804

Effect of Needle-Punching Conditions on the Fiber Orientation in the Nonwoven Fabric Characterized by X-Ray Micro Computed Tomography

KyoungOk Kim | Ken Ishizawa | Masayuki Takatera Shinshu University | Shinshu University | Shinshu University

808

815

819

Effects of Fabric Structures and Yarn Constitutions on the Functional Properties of Knitted Fabric

Effects of Twisting Coefficients on Properties of Coolplus/Zinc Ion Yarns and Knitted Fabrics

Evaluation of Effective Permittivity of Nonwoven Fabrics Using Two-layer Microstrip Transmission Line Method

823

Exploring Phase Change Materials in Firefighter Hood for Cooling

826

Facile Synthesis of Core/Shell-like NiCo2O4-Decorated MWCNTs and its Electrocatalytic Activity for Methanol Oxidation

830

Far-Infrared Nonwoven Fabrics Made of Various Ratios of Bamboo Fiber to Far-Infrared Fiber: Far-Infrared Emissivity and Mechanical Property Evaluations

835

High Elastic-Recovery Metal/Polyester Knitting Fabric: Manufacturing Techniques and Property Evaluations

839

Investigating the Dimensional Properties of the Spectral Reflectance of the Woolen Yarns used in Persian Carpet

843

Sarvenaz Ghanean | Mansoureh Ghanbar Afjeh Textile Engineering Department | Amirkabir University of Technology

Investigation of Electromagnetic Shielding Effectiveness of the Nonwoven Carbon Mat Produced by Wet-Laid Technology

847

Knitted Strain Sensors for Monitoring Body Movements

851

Manufacture of PAN-Based Anode Fibers for Lithium Ion Battery through Wet Spinning

Volume 3: Textile Performance / Testing / Evaluation Page

Abstract Title

855

Manufacturing Techniques and Property Evaluations of PVA/LE Nano-fibrous Membranes

859

Moisture Management and Thermo-Physiological Properties of the Multi-Layered Clothing System Containing SuperAbsorbent Materials

864

868

872 877

881 885 890 894 898 903 910 914 920 924

A Prof Rajiv Padhye | Dr Shadi Houshyar | Dr Rajkishore Nayak RMIT University Australia | RMIT University Australia | RMIT University Australia

Organic/Inorganic PP-Coated Heating Wire and Composite Knitted Fabrics: Processing Technology and Property Evaluations

Performance Evaluation of Commercial and Test Textiles and Analysis of their Behavior against Washing Machine Parameters during Laundering Muhammed Heysem Arslan | Ikilem Gocek | Ilkan Erdem | Umut Kivanc Sahin | Hatice Acikgoz Tufan Istanbul Technical University | Istanbul Technical University | ARCELIK Incorporation Washing Machine Plant | Istanbul Technical University | Istanbul Technical University

Physical Properties and Manufacturing Process Evaluation of Complex Stainless Steel Wire/Bamboo Charcoal Nylon/ Spandex Piled Yarn and Knitted Fabric Chin-Mei Lin | Pei-Chen Hsiao Asia University | Asia University

Preparation and Characterization of Wet-Laid Nonwoven for Secondary Battery Separator

Seung Woo Han | Sung Won Byun | Chang Whan Joo Korea Institute of Industrial Technology | Korea Institute of Industrial Technology | Chungnam National University

Preparation and Property Evaluations of Electrically Conductive Composite Fabrics Ting An Lin | Ching-Wen Lou | Jia-Horng Lin Feng Chia University | Central Taiwan University of Science and Technology | Feng Chia University

Property Evaluations of Sodium Chloride/Polyvinyl Alcohol Hydrogels Prepared by Different Drying Methods

Strength Forecasting of Spun Yarns at Different Gauge Lengths Using Weibull Distribution Parameters Anindya Ghosh Government College of Engineering & Textile Technology | Berhampore | West Bengal | India-742101

Study on the Influence of Tight-Fitting Sports Socks on Human Legâ&#x20AC;&#x2122;s Pressure Distribution Chen Ling Soochow University

Study on Warm Moisture Heating UNIQLO Brand Thermal Underwear Jingjing Zheng | Xiaofen Ji | Chen Pang College of Fashion Zhejiang Sci-Tech University

The Characteristic Evaluation of Electric yarn coated with Electroconductive Material

Un-Hwan Park | In-Sung Lee | Kwang-nyun Cho Korea Textile Machinery Research Institute | Korea Textile Machinery Research Institute | Korea Research Institute For Fashion Industry

The Comparative Evaluation of Car Carpet Material Including Hollow Fiber for Sound Absorbing Performance

The Design of New Jacquard Fabric Based on Four-Needle Jacquard Technology Md Anwar Jahid | Deng Zhongmin Wuhan Textile University | Wuhan Textile University

The Effect of Elastic Strain on Tribological Characteristics of Fabrics Suitable for Therapeutic Gloves Siti Hana Nasir | Olga Troynikov School of Fashion and Textiles | RMIT University | School of Fashion and Textiles | RMIT University

Volume 3: Textile Performance / Testing / Evaluation Page 928

932

936 940 945 950

Abstract Title The Effect of Structural Parameters on Air Permeability of Bifacial Fabrics

Licheng Zhu | Maryam Naebe | Ian Blanchonette | Xungai Wang Australian Future Fibres Research & Innovation Centre, Institute for Frontier Materials, Deakin University | Australian Future Fibres Research & Innovation Centre, Institute for Frontier Materials, Deakin University | CSIRO Manufacturing, Geelong | Australian Future Fibres Research & Innovation Centre, Institute for Frontier Materials, Deakin University, School of Textile Science of Engineering, Wuhan Textile University

The Interaction between UV Light and Fibres with different Cross-Sectional Shapes within the Yarns

The Life Test and Analysis of the Fabric Switch

The Research on Feature Recognition of Raw Cotton Defects and Impurities based on Image Processing Technology

Yong Zhang | Md Anwar Jahid | Deng Zhongmin Wuhan Textile University | Wuhan Textile University | Wuhan Textile University

Unsupervised Fabric Defect Segmentation using Local Dictionary Approximation

Jian Zhou | Weidong Gao Jiangnan University | Jiangnan University

Visual Impression of Fabric Texture at Different Viewing Distance

Aya Goto | Aki Kondo | Sachiko Sukigara Department of Advanced Fibro-science | Kyoto Institute of Technology | Department of Advanced Fibro-science

Volume 3: Textile Processing and Treatments Page

Abstract Title

954

A Study of One-Direction-Moisture-Conducting Laminated Fabric

958

Antibacterial Cellulose Containing Triazine N-halamine

963

Application of Genetic Algorithm Optimisation in Bleaching Treatment of Cellulosic Fibers

968

Catechinone Hair Dyestuff Preparation by Chemical Oxidation Method in Water/Alcohol Mixed Solution -Solvent Effect and Reaction Mechanism-

972

Comparison of Dyeing Behaviors of Reactive Dyes according to different Sodium Sulfate Addition Method

976

Design of Safer Flame Retardant Textiles Through Inclusion Complex Formation with Beta-Cyclodextrin: A Combined Experimental and Modeling Study

Seokil Hong | Heecheol Cha Korea Institute of Industrial Technology | Korea Institute of Industrial Technology

981

Development of New AOX-free Processing Method Extended to Wool

986

Discoloration of Kapok Indigo Denim Fabric by Using Carbon Dioxide Laser with Different parameters

991

Durability of Antibacterial Efficacy for Atmospheric Plasma-Treated Knitted Fabrics with Metal Salts against Laundering

995

Dyeing and Fastness Properties of Wool Yarns Dyed with Sunflower Seed Hulls

999

Dyeing Properties and Energy Saving Ratios according to Dyeing Conditions of S Type Disperse Dyes

1003

Dyeing Properties of Poly(Ethylene Terephthalate)/Poly(Ethylene Glycol) Block Copolymer Fibers

1007

Masukuni Mori | Illya Kulyk Mori Consultant Engineering Office | Veneto Nanotech SCpA

zahra Ahmadi | fateme Gholami Art university of tehran faculty | master student

Seokil Hong | Beomsoo Lee Korea Institute of Industrial Technology | Korea Institute of Industrial Technology Shekh Md. Mamun Kabir | Joonseok Koh Konkuk University | Konkuk University

Dyeing Textiles by Using Extracts from Mulberry Branch/Trunk I. Dyestuff Fluorescence Property

1010

Effects of Roller Drafting and Twisting on the Structural and Mechanical Properties of Nano-fibrous Bundles

1014

Effects of Variety, Growth Location, Scouring Treatments, and Storage Conditions on Dye Uptake by Cotton Fabric

1018

Efficacy of Torque Adjustment to the Roller Draft Process

Volume 3: Textile Processing and Treatments Page 1022 1026 1031 1035

Abstract Title Elimination of Dyestuff using scCO2

Yao CHEN | Satoko OKUBAYASHI | Teruo HORI | Ryoma FUKUMOTO | Toya BANNO

Enhancing UV Protection of Green Bamboo Textiles during Bio-processing

Dr. Jayendra N Shah The M. S. University of Baroda

Evaluation on Dyeability and the Reproducibility of Natural Indigo Dyeing

Fabrication of Robust Superhydrophobic Fabrics through Roughening of Fibers by Chemical Etching and Hydrophobization via Thiol-Ene Click Chemistry

1039 1043 1047

1052

Glycerol 1,3-Diglycerolate Diacrylate - A Unique Surface Modifier for Keratin Fibres

Hemin-Fixed Non-Woven Fabrics for Removing a Trace of CO Gas Contained in H2 Gas

Teruo Hori | Koji Miyazaki University of Fukui | University of Fukui

Investigation on Structural and Physical Properties of N/CoPET and PET Nonwovens by Processing Steps

Manufacturing the Continuous Electro-spun Bundle and its Battery Application

JungHo, Lim | Tumen Ulzii Ganbat | You Huh Department of Textile Engineering,Graduate School, KyungHee University | Department of Textile Engineering, Graduate School, KyungHee University | KyungHee University

1057

Multi-Objective Self-Optimization of the Weaving Process

1061

Novel Oxidation Hair Dyeing by Using Bio-Catechol Materials

1065

Marco Saggiomo | Yves-Simon Gloy | Thomas Gries Institut fur Textiltechnik der RWTH Aachen University (ITA) | Institut fur Textiltechnik der RWTH Aachen University (ITA) | Institut fur Textiltechnik der RWTH Aachen University (ITA)

Production Technology Selection for the Development of Technical Fabrics

1069

Research of the Electroless Copper-Plating on Wool Fabrics through Supercritical CO2 Pretreatment

1073

Study on Water-Repellent Property of Multi-Layer Fabric by using Melt-Blown Nonwovens

1076

Superphobicity/philicity Fabrics with Switchable, Directional Transport Ability to Water and Oil Fluids

Hua Zhou | Hongxia Wang Deakin University | Deakin University

Volume 3: Textile Processing and Treatments Page 1080 1084

1088

Abstract Title Sustainable Fibre Production and Textile Wet Processing for Better Tomorrow

1092

Synthesis of Nanofibrillar Para-aramid Aerogel through Supercritical Drying

1097

Synthesis of Novel Cationic Gemini Surfactants having Benzene Dicarboxylic Ester Structures in the Spacer Group and the Solubilization of Non-Ionic Dyes in their Micellar Solutions

Yuichi Hirata | Misato Sakakibara | Kunihiro Hamada Shinshu University | Shiunshu University | Shinshu University

1100

Ultrasonic Dyeing of Cotton with Natural Dye Extracted from Marigold Flower

1106

Wool and Hair Dyeing by Using Saccharides and Amino Acids I. Dyeing Conditions and Dyeability

Page 732 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

A Study on Viscose and Polylactic Acid Fibers Based Nonwoven Structure Properties Muhammet Uzun, Erhan Sancak, İsmail Usta, Mehmet Akalın Marmara University, Department of Textile Engineering, Istanbul, Turkey

Abstract. Natural based hydrophilic fibres have strong potential to widen fibres application in technical textiles such as medical and hygiene sectors. This study was carried out to determine the effects of TENCEL® (TE) fibres reinforcement to Polylactic Acid (PLA) nonwoven structures’ absorbency, thermal, and physical properties. The nonwoven structures have been developed and produced by making use of needle punching method. Three different nonwoven combinations, 100% PLA, 50/50% PLA/TE and 80/20% PLA/TE, have been tested and analysed. The thermo physiological properties of the structures were determined by using an Alambeta instrument (Sensora Instruments, Czech Republic). The Alambeta instrument provides values for thermal conductivity, thermal resistance (insulation) and thermal absorbtivity (warmth-to-touch), fabric thickness and thermal diffusion. Water vapour permeability and the resistance to evaporative heat loss of the fabrics were tested using the Permetest instrument (Sensora Instruments, Czech Republic). This instrument is based on a skin model, which simulates dry and wet human skin in terms of its thermal feeling. The breaking force values of TE reinforced fabrics were considerably higher as compared to 100% PLA fabric’s value. A higher thermal resistance will cause the wearer to become uncomfortable and extremely warm. From the results, it has been seen that the TE reinforcement increases the thermal resistance of the structures. 50/50% PLA/TE was found to have 25.8 W-1 k m2×10-3; on the other hand, the thermal resistance value of 80/20% PLA/TE was 21.2 W-1 k m2×10-3. The increase in thermal resistance could be a desired property for some applications such as wound dressing. Overall, this study concluded that TE reinforcement enhances the tested properties of PLA structures noticeably. Keywords: polylactic acid, viscose, nonwoven, Alambeta, Permetest.

1. Introduction A number of bio-based textile fibres have been developed for the production of the traditional and technical textiles. These fibres include calcium alginate, chitosan, collagen, and carboxymethylcellulose for medical applications. Traditionally, natural fibres such as cotton, silk and later the regenerated cellulosic fibres (viscose rayon) and Polylactic Acid have been also extensively used in non-implantable materials and healthcare and hygiene products. The main properties of these fibres are non-toxic to humans and easy to degrade within the body. An increasing interest has been still noticed in the investigation, characterization and functionalization of textile fibres for medical applications [1]. Conventional viscose rayon is widely used for disposable cleaning and hygiene products due to its good temperature resistance, higher absorbency and sensitive moisture behaviour. The chemical structure of viscose is similar to that of cotton as both are cellulosic. The filaments of viscose rayon appear smooth, straight, and un-convoluted, this surface, however, has striations or longitudinal channels running along the length of the filaments. These channels or striations give a deeply serrated appearance to the cross section of viscose rayon [2, 3]. The hollow viscose fibre modification is achieved by extrusion of the viscose through a spinneret with a hollow-shaped orifice. Viscose hollow fibres are spun in different cross section shapes with special nozzles. PLA fibre is one of the fastest growing biodegradable fibre types in the current investigations where researchers are actively trying to introduce novel application areas as an alternative source to conventional synthetic fibres [4]. PLA has also some biomedical applications, such as sutures, scaffolds for tissue engineering and drug delivery systems [5, 6].

Page 733 of 1108

2. Methods 2.1.

Thermo physiological Comfort

All the fabrics were preconditioned before testing for 24 hours in 65 ±2 % relative humidity and 20±2 °C temperature. Fabric weight (gm-2) and thickness (mm) were determined in accordance with BS EN 12127:1998 [7] and ASTM D1777 – 96(2011)e1 [8], respectively. The thermo physiological properties of the knitted fabrics were determined by using the Alambeta and Permetest instruments (Sensora Instruments, Czech Republic). The Alambeta instrument provides values for thermal conductivity, thermal resistance (insulation), thermal absorptivity (warmth-to-touch), fabric thickness and thermal diffusivity. The test instrument was used to analyse the transient and steady state thermo physical properties of the fabrics. The specimens of 20 cm ×20 cm were prepared and placed in between two plates. With the two plates the heat flow through the fabric due to the different temperature of the bottom measuring plate (at ambient temperature) and the top measuring plate which is heated to 40º C. The thermal absorptivity of the textile structure is a measure of the amount of heat conducted away from structure’s surface per unit time [9-11]. The test was performed on the dry and wet states of the nonwoven fabrics which were wetted with 0.2 ml of distilled water in the centre of the fabrics and allowed 4 minutes before retesting, in order to allow for the thermal recovery of the fabric. All tests were carried out on both faces of each specimen and the mean values calculated. There are three fundamental ways by which heat energy can be transferred through the porous materials such as knitted fabrics conduction, convection, and radiation. Depending on the fibre’s specific thermal conductivities, the size and configuration of the space between the fibres in the woven specimen, heat transfer mechanisms - conductive, radiative, and convective – will provide very different contributions to the overall heat transfer throughout the specimens. Very complex interactions and contributions of various heat transfer mechanisms in the overall thermal properties of woven fabrics makes the direct instrumental measurement of the thermal conductivity [12]. The workings of Alambeta instrument is shown in Figure 1. The ultra-thin heat flow sensor 5 is attached to a metal block 2 with constant temperature which differs from the sample temperature. When the measurement begins, the measuring head 1 containing the mentioned heat flow sensor traverse down and touches the planar measuring sample placed on 4, which is located on the instrument base 3 under the measuring head. In this moment, the surface temperature of the sample suddenly changes and the instrument computer registers the heat flow course.

Figure 1. Schematics of Alambeta Instrument by Sensora, Czech Republic. Water vapour permeability and the resistance to evaporative heat loss of the fabrics were tested by using the Permetest Instrument. This instrument is based on the skin model, which simulates dry and wet human skin surface in terms of its moisture, water vapour and evaporative heat permeation [7]. The instrument uses the same principle as specified in ISO 11092 developed by Hohenstein Institute, whereby a heated porous membrane is used to simulate the sweating skin. The heat required for the water to evaporate from the membrane, with and without a fabric covering, is measured [4].

Page 734 of 1108

3. Results and Discussions The fabrics were determined in terms of thermal comfort properties including thermal conductivity, thermal resistance, thermal absorptivity, water vapour permeability, and heat loss. The thermal properties of the fabrics were determined using an Alambeta and Permetest devices. The thermo physiological comfort properties are given in Table 1. It has been clearly seen that the fibre blending has negligible effect on the fabrics on the tested properties. The thermal resistance of fabrics was obtained to be similar. The fabric that has 50/50% length had better thermal conductivity values as compared to the other fabrics. The water vapour permeability of fabrics was also found to be comparable. A higher thermal resistance will cause the wearer to become uncomfortable and extremely warm. Overall, the results indicate that the effect of fibre blending on the thermo physiological properties is negligible. Table 1. Thermo physiological comfort properties of fabrics Fabrics

100% PLA

50/50% PLA/V

80/20% PLA/V

Thermal conductivity (W/mK×10-3) Thermal resistance (W-1K m2×10-3) Thermal absorptivity (W m-2 s 0.5 K -1) Water vapor permeability (%) Resistance to evaporative heat loss (m2 Pa W-1)

47.5 39.4 132 40.8 7.4

46.5 40.0 139 39.0 8.1

45.3 39.4 112 42.9 6.8

4. References [1] Rigby, A.J., Anand S.C., Horrocks A.R., Textile Materials for Medical and Healthcare Applications. J. Text. Inst., 1997, 88(3), pp. 83-93 [2] Horrocks, A. R. and Anand, S., Handbook of Technical Textiles. Boca Raton, FL, USA: CRC Pub., 2007. –ISBN 0-849-31047-4 [3] Badawi S.S., Development of Weaving Procedures for the Hollow Filament Fibers for using in the Field of Medical Textiles (Medtech). Chinese-Egyptian Research Journal, 2013, pp.80-101 [4] Amass, A.J., et al. Polylactic acids produced from l- and dl-lactic acid anhydrosulfite: stereochemical aspects. Polymer. 1999, Vol. 40, pp. 5073-5078. [5] Lunt, J. Polylactic Acid Polymers for Fibers and Nonwovens. International Fiber Journal. 2000, Vol. 55, pp. 48-52. [6] Farrington, D.W., et al. Poly(lactic acid) fibers. [book auth.] R.S. Blackburn. Biodegradable and sustainable fibres. Cambridge : Woodhead Publishing, 2005. [7] BS EN 12127, (1998). Textiles. Fabrics. Determination of mass per unit area using small samples. [8] ASTM D1777 – 96. e1. (2011). Standard Test Method for Thickness of Textile Material. [9] Pereira, S., Anand, S. C., Rajendran, S., Wood, C. (2007). A study of the structure and properties of novel fabrics for knee braces. J. Ind. Text. 36, 279-300. [10] Alambeta Measuring Device: Users’ Guide Version 2.3. Sensora Instrument Liberec, Company Brochure. [11] Splendore, R., Dotti, F., Cravello, F. (2010) Thermo-Physiological Comfort of a PES fabric with Incorporated Activated Carbon-Part 1: Preliminary Physical Analysis. Inter. J. Clothing Sci. Technol. 22, 333-341. [12] Yachmenev, V., Negulescu, I., Yan, C. (2006). Thermal Insulation Properties of Cellulosic-based Nonwoven Composites. J. Ind. Text. 36-73.

Page 735 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

A Study on the Preparation and Characterization of Wet-laid Nonwoven Based on Poly ketone Gyu Dong Lee 1 and Song Jun Doh 1 + 1

Technical Textile and Materials R&D Group, KITECH, South Korea

Abstract. Technical textile materials having high strength and high elastic properties has been used in many fields such as engineering plastic and composite materials There have been many researches made to satisfy the properties of technical fibers and textiles such as chemical resistance, high strength, and abrasion resistance. Manufacturing of wetlaid nonwoven by modified paper production process has been tried for high performance filters, battery separators, Wet-laid nonwoven web manufactured by modified paper production process, has been tried for high performance filters, battery separators, protective clothes, and many other applications due to its high specific surface area and uniform porosity compared with dry nonwoven web. In this study, wet-laid nonwoven made of POK (poly ketone) fiber, and 2 types of binders- ES fiber (PE sheath/ PP core type, 5denier), and PE pulp - was prepared and their characteristics were analyzed. The effects of fiber/binder ratio and ES fiber/PE pulp binder ratio on tensile, morphological properties, and pore distribution were investigated in order to see the potential applications of this material.

Keywords: Wet-laid nonwoven, poly ketone, Binder ratio

1. Introduction Aliphatic poly ketones are family of polymers prepared by the polymerization of R-olefins and carbon monoxide in a perfectly 1:1 alternating sequence using palladium catalysts. [1] These polymers are semicrystalline thermoplastics and reported to have a useful combination of mechanical, high-temperature, chemical resistance, wear resistance, and barrier properties giving them significant commercial potential in a broad range of engineering, barrier packaging, fiber, and blend applications. [2] Poly ketone fiber is expected to be able to occupy a missing point between commercial high-strength PET (poly ethylene terephtalate) fiber and Aramid fiber. With these reasons, many attempts have been made to apply poly ketone fibers to woven, knitted, and nonwoven fabrics. Nonwoven has been applied to various industrial products including filtration, clothes, and so forth. There are several techniques to produce nonwoven materials. One of the technical methods is wet-laid nonwoven process. Wet-laid nonwoven web manufactured by modified paper production process, has been tried for high performance filters, battery separators, and many other applications due to its unique properties. These properties are derived from its process, obtaining a web by filtering a dispersion of fibers in a particular length on a medium like water through a sieve. Compared to the dry-laid process, wet-laid method has an advantage on uniform pore distribution. In this study, we performed the research on the manufacturing process of wet-laid nonwoven of poly ketone. By introducing binder fibers, we tried to improve the mechanical properties of the poly ketone wet-laid nonwoven. Wet-laid nonwoven made of POK (poly ketone) fiber and 2 types of binders - ES fiber (PE sheath/ PP core type, 5 denier), and PE pulp - was prepared and their characteristics were analyzed. Specifically, we investigated the effects of fiber/binder ratio and ES fiber/PE pulp binder ratio on tensile, morphological properties, and pore distribution in order to see the potential applications of this material.

Corresponding author. Tel.: + 82-31-8040 6087. E-mail address: wolfpack@kitech.re.kr

Page 736 of 1108

2. Experimentals 2.1.

Materials

POK filaments (1001 denier) were manufactured and provided by Hyosung Co.. Polyethylene / Polypropylene (PE/PE) sheath/core fibers (ES fiber, 2 den) and polyethylene (PE) pulp (FYBELESS5) were purchased from Woongjin Chemical Co. and Minifibers, Inc., respectively.

2.2.

Wet-laid nonwoven manufacturing process

Short-cut fibers were produced by cutting the above POK (poly ketone) filaments with the average staple length of 3 mm by using FiDoCut 0080 (Shchimdt heinzmann, Germany). Wet-laid nonwovens were prepared by a lab-scale wet-laid apparatus. POK fiber, PE/PP sheath/core fiber and PE pulp were dispersed in water. The detailed fiber compositions were shown in Table 1. Then, Dispersions of these fibers were filtered through a steel sieve. Basis weight and dimension of the nonwovens were 100 g/m² and 20×20 cm², respectively. The nonwovens were oven-dried at 80℃for 2 hours and calendered under line pressure 24 kgf/cm at 100℃ with roll speed of 2 m/min. Table 1: Sample code and composition of nonwovens Sample Code POK910 POK901 POK820 POK811 POK802 POK730 POK721 POK712 POK703

Composition (%) POK 90 90 80 80 80 70 70 70 70

ES fiber 10 0 20 10 0 30 20 10 0

PE pulp 0 10 0 10 20 0 10 20 30

2.3. Analyses 2.3.1 Morphology The morphologies of the fibers and wet-laid nonwovens were observed using a field emission scanning electron microscopy (FE-SEM S-4800, Hitachi).

2.3.2 Tensile Properties Tensile properties of nonwoven were measured with tensile testing machine (INSTRON 3343, Instron®, USA). The specimens of 20 mm width were tested with a gauge length 50 mm and constant extension rate of 20 mm/min.

2.3.3 Porosity The porosity (pore sizes and pressure) of samples were measured using porosimeter (CFP-1200-AEL, Porous material Inc., USA)

2.4.4 Filtration properties Using fractional efficiency filter tester (TSI 8130, TSI Inc.), filtration efficiency and resistance of nonwovens were measured. (at 0.26 ㎛, 5.0 L/min)

3. Result and Discussion Fig. 1 shows the surface and the structure of wet-laid nonwovens after calendering for POK721, POK712 samples. Compared to POK712 structure, The POK721 structure is less dense between the fibers and pulp, and it has larger pore size. This difference of surface structure is due to that only PE portion of PE/PP sheath/core fibers (ES fibers) were melted after calendering process. The melted PE portions of ES fibers acted as binders between fibers, but PP portions served to remain structure of POK web.

Page 737 of 1108

Fig. 1: Morphologies of nonwovens; (left) POK721, (right) POK712

Tensile properties were shown in Fig. 2 and Table 2. As the content of binder fibers increased, tenacity tended to increase. In same composition of poly ketone/ binder fibers ratio, PE pulp affected the tenacity mostly. The effect of binder on tenacity resulted from PE portion that melted and acted as binder with POK fibers. Elongation properties had tendency, but not significant to allow for standard deviation. This error was due to non-uniform length of short cut fibers.

Fig. 2: Tensile properties of nonwovens; (left) tenacity, (right) elongation Table 2: Tensile properties of nonwovens Tensile Properties Sample Code

POK910 POK901 POK820 POK811 POK802 POK730 POK721 POK712 POK703

Max Force (N)

Maximum Tenacity (kgf/cmÂ˛)

Elongation at Max (%)

0.62 6.42 0.41 6.50 16.22 1.62 9.49 25.28 35.41

1.2 16.2 0.7 22.7 52.3 3.2 25.2 79.1 123.7

0.5 1.4 0.7 0.7 0.9 0.4 0.7 1.1 1.7

Page 738 of 1108

Fig. 3 shows the average and max pore size of nonwovens. As the PE pulp increases, the maximum pore size decreased sharply. On the other hand, average pore size had no significant tendency. This error was also due to non-uniform length of short cut fibers and shortcoming of a dispersion step on wet-laid process. In general, nonwoven consisted of more than 30% binder fiber had an average pore size of less than 10 ㎛.

Fig. 3: Pore size and pressure of nonwovens; (left) average pore, (right) max pore

Fig. 4: Filtration properties (efficiency, resistance)

Fig. 4 shows the filtration efficiency and resistance for nonwovens at 0.26 ㎛, 5.0 L/min. As the PE pulp increases, the efficiency and resistance increased sharply. Generally, wet-laid nonwovens containing 20% of PE pulp had high filtration efficiency. But, resistance of those formulations is too high. It should be considered carefully for use as filter media.

4. Conclusion Wet-laid nonwoven production process and manufacturing techniques using POK fiber has been developed and evaluate the basic properties. In particular, the tensile properties and the porosity, depending on the manufacturing process, were analysed. Characterization of the type and ratio of binder fibers in a nonwoven was also analyzed. The possibility of filter media was confirmed.

Acknowledgement “ This research was supported by a grant from the Fundamental R&D Program for Technology of World Premier Materials funded by the Ministry of Trade, Industry and Energy, Republic of Korea”

5. References [1] Drent, E.; Budzelaar, P. H. M. Chem. Rev. 1996, 96, 633. Sommazzi, A.; Garbassi, F. Prog. Polym. Sci. 1997, 22, 1547. [2] Bonner, J. G.; Powell, A. K. Presented at the ACS Meeting, San Francisco, 1997.

Page 739 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

A study on the Reliability Evaluation of Industrial textile Hwan Kuk Kim1, Dae Kyu Park1 and Du Hwan Chun 2 1

Korea Textile Machinery Research Institute, Korea Department of Textile Engineering and Technology, Yeungnam University, Korea

Abstract. The following study was focused on developing the technology for the evaluation of industrial textile when reliability test among industrial textile is critical. As such, the intentions are to secure reliability of the products, to be used actively for inspecting the reliability of new innovative products, and to help increase quality. The research placed industrial textile in an even more strenuous condition that's different from the actual conditions they are normally used under in order to accelerate the potential for failure, and attempts to evaluate the performance and quality of the felt in order to establish a relationship between lifespan and performance. With this, the research deems possible that the process can be applied on the evaluation of the durability life of industrial textile products.

Keywords: Industrial textile, Reliability, tensile strength, fabrics, fatigue, accelerated testing, durability.

1. Introduction Reliability has a unique characteristic of maintaining the product's initial quality until the targeted duration in a satisfactory manner. As such, the definition comes down "basic quality over duration." With this in mind, in light of the real quality experienced by the consumer can be differentiated from the production quality set forth by the manufacturer.[1,2] With the recent changes in social environment, there's been an increased demand in reliability. Additionally, there's been an upward trend in focusing on the importance of the prediction and guaranty of the product's reliability.[3,4] Industrial felt, which is not only a technical textile product but also an important component of the finishing process in textile production, is a necessary component for increasing the value of the textile during the finishing process. Additionally, industrial felt is used in a very harsh environment where high operating temperature (100 ~ 200â&#x201E;&#x192;), high tensile, and high flexibility are common. As such, felt's quality and durability have a direct impact in the production goods' quality and yield. With these reasons in mind, industrial felt production technology requires an increased technical standard and a high operational reliability for the user. As such, major production companies in the developed countries utilize self-appraisal methods to specify the durability and life expectancy of the company's industrial felt. Finally, the reality is that the companies are designing and strengthening the appraisal standards on a continuous basis in order to increase the reliability of the products being sold.[5,6] However, such techniques for evaluation outlined in the developed foreign countries are thoroughly secretive. As a result, introducing the technological know-how to the domestic producers is impossible. Also, the evaluation methods and results for the reliability of industrial felt is entirely absent in Korea. Consequently, there's an ever increasing dissatisfaction from the textile finishing businesses in regards to the replacement cycle and reliability. As such, the following research is focused on creating the technology in evaluating the reliability standards when the management of industrial felt's reliability is pressing. The results can be actively applied to securing the reliability of the products and verification of newly developed products.

Page 740 of 1108

2. Experiment 2.1.

Reliability Measurement System Design and Production

As mentioned earlier, major factors that have an effect on the felt's performance are temperature, operating speed and operating load. And the following research attempts to evaluate the reliability under a strenuous condition that accelerates malfunction. As such, a performance evaluation device that can apply a more strenuous condition than the actual condition present is designed and created. The resulting device is depicted on Figure 1 and the specifications are listed on table 1. The structure of the device is the same as a real knit wrinkle-proof processing device, but for an accelerated test the testing device is manufactured at a smaller scale.

Fig. 1: Felt reliability evaluation device.. Table 1: Properties of Reliability Measurement System Classification Main Roller

Electricity heating (Temperature control: ∼250±1℃)

Load control

Load cell+servo motor load control ( ∼100±0.1kgf/cm2)

Speed control

Speed control by a Motor (∼200±1m/min)

Felt

2.2.

Specifications

Size : Width 2550mm × Perimeter 2750mm × Thickness 20mm Material : Nomex Fiber 6mm+ (Polyester+Wool 14mm), Screening : Kevlar+Polyester

Reliability Test and Evaluation

As the felt is exposed to the heating roller's temperature, pressure, speed and other factors, the coherence between textiles that compose the felt is reduced and malfunction occurs. In the following research, performance variation is examined by evaluating the properties between the old and the new malfunctioned product. Tensile test was carried out under 300×40×20mm specimen, 30kN load cell, and with a crosshead speed of 50mm/min. Finally, the results of examining the surface of the felt under a microscope and SEM analysis are illustrated in Figure 2. Additionally, there's no existing evaluation standard for testing the reliability of industrial felt used for shrink-proofing knitwear. As such, in order to develop the evaluative conditions and method for the accelerated reliability testing, the felt product's material properties and performance is cross evaluated between the new felt and one that has expired most of its life expectancy (old). In order to test the temperature, speed and load at the same time, a testing machine built using the results of the evaluation that's conducted between the old and the new is utilized. As such, an acceleration criteria outlined on table 2 is planned for the composite acceleration test. Three samples each from the processing criteria are collected to measure the tensile characteristics and elastic compression recovery rate. And finally, a comparative analysis conducted between the old and new products.

Page 741 of 1108

Fig. 2 SEM Analysis of Old vs New Table 2: Testing Conditions for Evaluating Reliability of Industrial Felt Test Temp. [oC]

Velocity [m/min]

Load [kgf]

Standard unit load[kgf/cm]

Sample Width[cm]

Test Time [day]

1st

180

3rd

180

4th 5th

180 190

110 88

60â&#x2020;&#x2019;40 60

20 20(14 day) +16(9 day) 20(14 day) +16(9 day) +12(13 day) 10 10

2nd

3 3(14day) +3.75(9day) 3(14day) +3.75(9day) +5(13day) 6â&#x2020;&#x2019;4 6

23 36 30 30

3. Results of the Acceleration Tests During the durability testing period, tensile strength was measured so that the research could find a temperature, pressure, speed and duration that closely exhibits the value found from the old product. And by utilizing an accelerated testing condition that's more strenuous than the real application, the results of the tensile strength were illustrated on table 3. The results show that as the testing period is increased, there's a remarkable decrease in strength and elongation values. When tested for 36 days, Samples have exhibited similar values to the characteristics of an old product. The acceleration factor was identified to be approximately 3.47(3,000/864). Next, in order to find a testing condition similar to a 30 day testing (acceleration value of approximately 4.17), many different tests were conducted. However, conditions that show similarities to the results of the 36 day samples were when temperature was 190â&#x201E;&#x192;, speed was 88m/min, and load was 60kgf/cm2, and under these criteria, strength was 5.67MPa, and elongation at max was 19.78%. Finally, in order to achieve the reliability of the testing standards, the same tests were conducted 3 times. The results show similar findings which the research deems to be indicative of the test's reliability. The results above confirms that the accelerated testing conditions applied in a 30 day period is a decent shortened proxy of the actual 1 year usage of the felt used for shrink-proofing knitwear. As such, by processing the new product under the accelerated testing equipment on 5 different accelerated conditions outlined on table 4, tensile strength and elastic compression rate tests were conducted. A typical load depth curve witnessed under the accelerated testing conditions is drawn on Figure 3.

Page 742 of 1108

Table 3: Industrial Felt Tensile Property after Acceleration Tests Classification

Max load [N]

Modulus [MPa]

Strength [MPa]

Elongation at max[%]

Elongation [%]

1st

14 day

6,597

30.45

8.70

61.27

85.67

2nd 3rd 4th 5th

23 day 36 day 30 day 30 day

6,195 4,616 4,968 4,516

31.27 35.98 36.62 42.67

7.74 5.77 6.21 5.67

57.30 19.77 34.28 19.78

77.33 50.93 49.98 69.70

5000 4500 4000

Load [N]

3500 3000 2500 2000 1500 1000 500 0 0

100

150

200

250

Displacement [mm]

Fig. 3: Tensile test results in the test conditions (time 30, temperature 190 â&#x201E;&#x192;, speed 88m / min, a load 60kgf / cm2).

4. Conclusions The purpose of the following study was to develop evaluative techniques to test the reliability of felt processed for shrink-proofing knitwear. As such, a reliable evaluation device was developed and created in order to have the same structure as the actual machine and to apply a more strenuous condition than what's usually realized. Additionally, by applying a more strenuous condition than usual, failure was accelerated, and the products' performance and quality were evaluated in order to establish a relationship between life expectancy and performance. The results have confirmed that an accelerated testing criteria conducted under a 30 day period was a good proxy for a year-long usage condition. Additionally, the results show that the old product's strength is only about 50% of the new product, which is a considerable difference. The reasons for such degradation are due to the reduction in coherence between fabrics which causes destruction in the fibrous tissue which in turn causes a reduction in strength values. Finally, it is determined that the process can be directly applied to future evaluations of the durability life of industrial felt products.

5. References [1] M. H. Attia and R. B. Waterhouse, ASTM STP 1159 (1992). [2] D. Kwon, S. J. Choi and Y. T. Bae, Key Eng. Mater., 261, 1221 (2004). [3] H. K. Kim and Y. H. Lee, Wear, 255, 1183 (2003). [4] J. D. Kwon, S. S. Sung and S. J. Choi, KSME, 25A, 1287 (2001). [5] K. H. Jung, T. J. Kang, B.H. Lee and Y. M. Kim, Fiber. Polym., 8, 438 (2007). [6] J. A. M. Ferreira, J. D. M. Costa, M. J. Santos and P.N.B. Reis, Fiber. Polym., 13, 1292 (2012).

Page 743 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Analysis of 19 SVHCs in textiles using liquid chromatography coupled with LTQ/Orbitrap mass spectrometry Xin Luo1, Li Zhang1,2, Zengyuan Niu1ď&#x20AC;Ť, Xiwen Ye1 1 2

Shandong Entry-Exit Inspection and Quarantine Technical Center of China, Qingdao 266000, China

College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266000, China

Abstract. A new analytical method was established and validated for the analysis of 19 substances of very high concern (SVHCs) in textiles, including phthalic acid esters (PAEs), organotins (OTs), perfluorochemicals (PFCs) and flame retardants (FRs). After a simple ultrasonic extraction in methanol, the textile samples were analyzed by high performance liquid chromatography-hybrid linear ion trap Orbitrap high-resolution mass spectrometry (HPLC-LTQ/Orbitrap). The extraction procedure, chromatographic separation and mass spectrometric parameters were optimized. MS2 product ions which were obtained in collision-induced dissociation (CID) and higher energy collision-induced dissociation (HCD) of Orbitrap were discussed. Using Trace Finder and Mass Frontier software, the assignments and theoretical m/z of the major MS2 fragments were predicted, which can make the identification more accurate without considering changes of the external environment. The values of method LOQ were in the range of 2-200 mg/kg. Recoveries at two levels (at the LOQ and at half the limit of regulation) ranged from 68% to 120%, and the repeatability was lower than 13%. It is the first time to develop a simultaneous method for analysis of multi-class SVHCs with different physicochemical properties in textiles. The high mass resolution and full-scan mode with narrow mass extraction windows (5 ppm) can dramatically simplify the progress of pretreatment and improve method selectivity. This method can be successfully applied to the screening of SVHCs in commercial textile samples.

Keywords: phthalic acid esters (PAEs), organotins (OTs), perfluorochemicals (PFCs), flame retardants (FRs), Orbitrap, textiles

1. Introduction Phthalic acid esters (PAEs), organotins (OTs), perfluorochemicals (PFCs) and flame retardants (FRs) are widely used in the manufacturing of textiles, and their serious and irreversible effects on human health and the environment have gained public attention. European Union regulation, REACH, has listed them as substances of very high concern (SVHCs). Additionally, other regulations such as OEKO-TEX Standard 100 and the Restricted Substances List (RSL) define criteria for the use and limitations of SVHCs. Various methods used for the determination of PAEs, OTs, PFCs and FRs included GC, GC-MS, LCMS and LC-MS/MS [1-4], whereas the latter two methods can avoid complex derivatization steps for analysis of certain compounds (ex. OTs) and have been used more widely in these years. Among various mass detectors, the Orbitrap with high resolution and high mass accuracy shows high sensitivity and selectivity, which can allow for the analysis of compounds in complex matrices with minimum or even no sample clean-up. The full-scan mode in the Orbitrap can provide data for all the compounds in a sample, which is useful for screening analysis. To date, the Orbitrap has been used extensively in proteomics and food safety research, but few studies have been reported on the detection of SVHCs in textiles [5, 6]. The aim of this study is to develop a rapid and reliable screening and confirmation method for the detection of 19 SVHCs, including PAEs, OTs, PFCs and FRs, in textiles using the HPLC-LTQ/Orbitrap.

ď&#x20AC;Ť

Corresponding author. Tel.: + 86-0532-88968060 E-mail address: zyniuqd@hotmail.com

Page 744 of 1108

2. Experimental 2.1.

Materials and chemicals

SVHC analytical standards, including dipentyl phthalate (DPP), diisopentyl phthalate (DIPP), n-pentylisopentyl phthalate (DniPP), bis(2-methoxyethyl) phthalate(DMEP), diisobutyl phthalate (DIBP), dibutyl phthalate (DBP), bis (2-ethylhexyl) phthalate (DEHP), benzyl butyl phthalate (BBP), 1,2-benzenedicarboxylic acid, di-C6-8-branched alkyl esters, C7-rich (DIHP), dihexyl phthalate (DHP), bis(tributyltin)oxide (TBTO), hexabromocyclododecane (HBCD) and tris(2-chloroethyl)phosphate (TCEP) were purchased from Dr. Ehrenstorfer (Augsburg, Germany). Ammonium pentadecafluorooctanoate (APFO), pentadecafluorooctanoic acid (PFOA), henicosafluoroundecanoic acid (PFuDA), tricosafluorododecanoic acid (PFDoA), pentacosafluorotridecanoic acid (PFTrA), heptacosafluorotetradecanoic acid (PFTeA), alphahexabromocyclododecane (α-HBCD), beta-hexabromocyclododecane (β-HBCD) and gammahexabromocyclododecane (γ-HBCD) were purchased from Sigma Aldrich (Steinheim, Germany).

2.2.

Sample preparation

A total of 0.5 g of textile samples (5 mm×5 mm) were weighed into 40 mL glass tubes. Then, 30 mL methanol was added, and the tubes were capped and extracted by an ultrasonic generator (40 KHz, KQ-500DE, Kun Shan, China) at a temperature of 50 °C for 20 min. After standing for 3 min, 50 μL supernatant was diluted with 950 μL methanol/water (3/1, v/v) to a volume of 1 mL, then filtered by a 0.22 μm nylon membrane.

2.3.

LC and MS conditions

The ACQUITY LC (Waters, Milford, MA, U.S.A.) equipped with an Accucore C18 column (100 mm×2.1 mm, 2.6 μm, Thermo Fisher, MA, U.S.A) was used for chromatographic separation of the 19 SVHCs. The mobile phase was 5 mmol/L ammonium acetate (containing 0.5% formic acid) (A)-methanol (B) in positive ionization mode, and 5 mmol/L ammonium acetate (A)-acetonitrile (B) in negative ionization mode. The LC gradient elution program in positive ionization mode was as follows: 0-14 min, 60-95% B, 14-17 min, 95% B, 17.1 min, 60% B, 17.1-24 min, 60% B. The LC elution gradient program in negative ionization mode was as follows: 0-7 min, 50-95% B, 7-10 min, 95% B, 10.1 min, 50% B, 10.10-17 min, 50% B. The total flow rate was 0.2 mL/min. The LTQ/Orbitrap XL (Thermo Fisher, MA, U.S.A), equipped with an electrospray ionization (ESI) source, was chosen for the screening and identification of 19 SVHCs. The parameters in positive ionization mode were as follows: Ispray voltage, 3 kV, capillary voltage, 30 V, tube lens, 60 V. The parameters in negative ionization mode were as follows: Ispray voltage, -2.5 kV, capillary voltage, -4 V, tube lens, -70 V. The parameters common to both of the two ionization modes were as follows: vaporizer temperature, 50 °C, capillary temperature, 350 °C, sheath gas flow rate, 30 arbitrary units, auxiliary gas flow rate, 10 arbitrary units. Rapid screening data acquisition occurred under the full-scan mode with a resolution of 30,000 and a scan range of m/z 100-1000. The MS2 confirmation was performed with a resolution of 7500. For compounds measured in positive ionization mode, collision-induced dissociation (CID) (at a normalized collision energy of 35%) was performed. For compounds measured in negative ionization mode, higher energy collision-induced dissociation (HCD) (at optimized collision energy of each SVHC) was performed. The width of the ion-extraction window of Xcalibur 2.2 software was 5×10-6 (5 ppm). The retention times and targeted MS parameters of the HPLC-LTQ/Orbitrap for the analysis of the 19 SVHCs are shown in Table 1. Table 1 The retention times and targeted MS parameters of HPLC-LTQ/Orbitrap for 19 SVHCs Compound

Molecular formula

RT (min)

1 2 3

DMEP TCEP TBTO

C14H18O6 C6H12Cl3O4P C24H54OSn2

DBP

C16H22O4

No.

BBP

C19H20O4

Parent ion

Collision mode

Collision energy

Product ion

Ionization mode

Theoretical m/z

Assignment and theoretical m/z

1.61 2.49 3.35

ESI+ ESI+ ESI+

283.11761 284.96115 291.11292

CID CID CID

35 35 35

C11H11O4+(207.06519) C3H8Cl2O4P+(222.96883) C8H19Sn+(235.05032)

7.22

ESI+

279.15909

CID

C8H5O3+ (149.02332)

7.32

ESI+

313.14344

CID

C8H5O3+(149.02332)

279.15909

CID

C8H5O3+ (149.02332)

DiBP

C16H22O4

7.50

ESI+

DniPP

C18H26O4

9.70

ESI+

307.19039

CID

C8H5O3+(149.02332)

DiPP

C18H26O4

9.89

ESI+

307.19039

CID

C13H15O3+ (149.02332)

Page 745 of 1108

DPP

C18H26O4

10.09

ESI+

307.19039

CID

C8H5O3+ (149.02332)

DHP

C20H30O4

12.21

ESI+

335.22169

CID

C8H5O3+(149.02332)

DIHP

C22H34O4

13.43

ESI+

363.25299

CID

C8H5O3+(149.02332)

DEHP

C24H38O4

14.71

ESI+

391.28429

CID

C8H5O3+(149.02332)

412.96643

HCD

C3F7- (168.98827)

APFO

C8H4F15NO2

1.30

ESI-

PFOA

C8HF15O2

1.30

ESI-

412.96643

HCD

C3F7- (168.98827)

562.95684

HCD

C3F7- (168.98827)

PFuDA

C11HF21O2

2.09

ESI-

PFDoA

C12HF23O2

2.53

ESI-

612.95365

HCD

C3F7- (168.98827)

662.95046

HCD

C3F7- (168.98827)

PFTrA

C13HF25O2

3.02

ESI-

PFTeA

C14HF27O2

3.55

ESI-

712.94726

HCD

C3F7- (168.98827)

α-HBCD

β-HBCD

ESI-

640.63746

HCD

γ-HBCD

Br- (78.91889); Br(80.91684)

6.54 C12H18Br6

6.74 7.42

3. Results and discussion 3.1.

Extraction procedure

Various methods aiming to extract a certain type of SVHCs from textiles, such as microwave-assisted extraction (MAE) , ultrasonic-assisted extraction (UAE) and accelerated solvent extraction (ASE) were reported previously, among which UAE was a common method for the extraction of PAEs, OTs, PFCs and FRs [6, 7]. The extraction solvents also vary with the different types of SVHCs. Generally, dichloromethane and toluene, etc. are used for extraction of PAEs and FRs, which have a relatively low polarity. As for OTs and PFCs, methanol is widely used as an extraction solvent [4, 8]. This research compared methanol and dichloromethane as extraction solvents and used UAE to extract four representative SVHCs (DHP, TBTO, PFOA and HBCD) from three spiked samples, and replicate (n=6) samples were run. All the results revealed that UAE was effective for the simultaneous extraction of four representatives and that methanol showed a higher efficiency than dichloromethane in this procedure. The results for three different kinds of textiles were similar and the extraction recoveries ranged from 75%-119%. Taking polyester as representative matrix, the extraction result was shown in Fig. 1.

Fig.1. Effect of different extraction solutions on the recoveries (n=6) of four representatives for polyester

3.2.

Optimization of chromatographic and mass spectrometric parameters

To achieve the best separation, especially for the three pairs of isomers in the 19 SVHCs, a series of trials were performed on the composition of the mobile phase and the gradient of elution. As for the compounds measured in positive ionization mode, methanol was used as the organic modifier as it gives a better intensity and separation than acetonitrile, especially for isomers of PAEs. A 5 mmol/L ammonium acetate solution with different amounts of formic acid (0%, 0.1% and 0.5%) was also tested. With the increase of acid concentration, the shape of the TBTO peak becomes sharper and the sensitivity becomes higher, while the chromatographic peaks of PAEs turned out to be similar for the latter two pHs. As for the compounds detected in negative ionization mode, acetonitrile was chosen as the organic modifier in the mobile phase because it achieved a better resolution and sensitivity than methanol. The increase of acid concentration does not improve the separation of these compounds. The extracted ion chromatography of 19 SVHCs was displayed in Fig. 2 and

Page 746 of 1108

numbers of peaks was in consistent with Table.1.

Fig.2. Extracted ion chromatograms of 19 SVHCs in positive ionization mode (a) and negative ionization mode (b)

Parent ions of most of the SVHCs, except for TBTO, APFO and HBCD, are simple in structure. For compounds in positive mode, the [M+H]+ ion was acquired, and the [M-H]- ion was acquired for compounds in negative mode. The parent ion of APFO was the same as PFOA, namely [C8HF15O2-H]-. Additionally, the parent ions for TBTO and HBCD are in clusters, which are caused by the existence of their natural isotopes. The most intense ion clusters of TBTO correspond to [C12H27120Sn]+, while the ions of HBCD correspond to [C12H1781Br379Br3]-. To choose an appropriate mode, the collision energy for both the collision-induced dissociation (CID) and the higher energy collision-induced dissociation (HCD) modes was optimized. Accordingly, the spectra of the 19 SVHCs’ product ions in CID (at normalized collision energy 35%) and HCD (at the optimized collision energy) were compared. For almost all compounds detected in positive ionization mode, the intensity and number of fragments in CID were better than HCD. However, for compounds detected in negative ionization mode, HCD was more effective than CID. Taking PFuDA as an example, the product ion spectrum produced with HCD not only provides the major product ion as in the CID spectra, but also provides additional MS2 ions of PFuDA (Fig. 3). For HBCD, all the references reported that 79Br and 81Br were the only product ions. This specific transition (m/z 640.6-m/z 78.9 and 80.9) cannot be monitored by CID because the m/z values of the product ions are lower than the “cut-off” value of the instrument (typically 25% of the parent ion), which is a main drawback of ion trap mass analyzers. However, HCD can effectively avoid this problem. With the assistance of Mass Frontier software, major fragments have been predicted and listed in Table 1. The relative mass deviations of all the product ions generated by LTQ/Orbitrap in this study were within 5 ppm of theoretical values.

Fig.3. Mass spectra of fragments of PFuDA acquired by CID (a) and HCD (b)

3.3.

Method validation

A validation was performed and several parameters such as linearity, matrix effect, LOQ, recovery and precision were studied. Most standards exhibited a good linearity in its own range, and the correlation coefficients exceeded 2 R >0.99. Matrix effects were expressed as the matrix-matched calibration slope to solvent calibration ratio in the whole calibration range. The results showed that the matrix effects of the 19 SVHCs in three different dilution factors ranging from 98% to 127% were not significant and can be neglected.

Page 747 of 1108

Since the noise level of ion chromatograms extracted by high resolution mass spectrometry (HRMS) with a mass extraction window of ± 5 ppm was almost absent. Therefore, the establishment of an LOQ based on traditional 10 S/N was not realistically feasible. Taking reports related with high-resolution mass spectrometry as references, LOQ was evaluated using the LCLs method (matrix-matched standard solutions were diluted successively to obtain the lowest concentration that can be, which can be repeatedly determined with a low RSD value during a longer time period) [9,10]. The LOQ values for most compounds, except for DBP, DIBP and DEHP, were between 2-20 mg/kg and RSD values calculated from six repeated injections at the LOQ level were as low as 2-12%. All these LOQ values are much lower than the SVHCs limitation of 0.1% (1000 mg/kg) as regulated in REACH. Recoveries were evaluated at two different concentration levels (at the LOQ and at half the limit of regulation). After cutting three representative textile samples (cotton, polyester and polyester/wool blend) into pieces, the mixed-standard solutions were added to the 0.5 g textiles mentioned above. When the standard solution was completely absorbed by the textile sample, the recovery percentage was determined by using the established method, and 6 parallel assays were also carried out. Recoveries at the two levels (at the LOQ and at half the limit of regulation) ranged from 68% to 120% and the relative standard deviation (RSD %) was below 13% .

4. References [1] X. J. Li, Z. R. Zeng, Y. Chen, Y. Xu. Determination of phthalate acid esters plasticizers in plastic by ultrasonic solvent extraction combined with solid-phase microextraction using calix 4 arene fiber. Talanta. 63 (2004) 10131019. [2] Q. R. Ou, C. W. Whang. Determination of butyltin and octyltin stabilizers in poly(vinyl chloride) products by headspace solid-phase microextraction and gas chromatography with flame-photometric detection. Anal. Bioanal. Chem. 386 (2006) 376-381. [3] Stapleton HM, Dodder NG, Kucklick JR, Reddy CM, Schantz MM, Becker PR, Gulland F, Porter BJ, Wise SA. Determination of HBCD, PBDEs and MeO-BDEs in California sea lions (Zalophus californianus) stranded between 1993 and 2003. Marine Pollution Bulletin 2006;52:522-531. [4] X. P. Wang, H. Y. Jin, L. Ding, H. R. Zhang, H. Q. Zhang, C. L. Qu, A. M. Yu. Organotin speciation in textile and plastics by microwave-assisted extraction HPLC-ESI-MS. Talanta. 75 (2008) 556-563.. [5] L. K. Sørensen. Determination of phthalates in milk and milk products by liquid chromatography/tandem mass spectrometry. Rapid. Commun. Mass. Sp. 20 (2006) 1135-1143. [6] Xiaolan H, Huiqin W, Fang H, Xiaoshan L, Zhixin Z. Determination of Perfluorooctane Sulphonate in Fabrics and Leathers using Liquid Chromatography-Mass Spectrometry. Chinese Journal of analytical chemistry 2007;35:1591-1595. [7] P. Guerra, E. Eljarrat, D. Barcelo. Determination of halogenated flame retardants by liquid chromatography coupled to mass spectrometry. Trac-Trend. Anal. Chem. 30 (2011) 842-855. [8] M. MB, S. AV, P. EF. Critical evaluation of fiber coatings for organotin determination by using solid phase microextraction in headspace mode. chromatography A 2000:9-14. [9] Domènech A, Francisco NC, Palacios O, Franco JM, Riobó P, Llerena JJ, Vichi S, Caixach J. Determination of lipophilic marine toxins in mussels. Quantificationand confirmation criteria using high resolution mass spectrometry. Journal of Chromatography A 2014: 16-25. [10] Choi JH, Lamshöft M, Zühlke S, Park JH, Rahman MM, Aty AMAE, Spitellera M, Shimb JH. Determination of anxiolytic veterinary drugs from biological fertilizer blood meal using liquid chromatography high-resolution mass spectrometry. Biomedical Chromatography 2014:751-759. [11] M. Zachariasova, T. Cajka, M. Godula, A. Malachova, Z. Veprikova, J. Hajslova. Analysis of multiple mycotoxins in beer employing (ultra)-high-resolution mass spectrometry. Rapid. Commun. Mass. Sp. 24 (2010) 3357-3367.

Page 748 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015, pp. xxx-xxx

Anti-aging Properties of PP / PET Filter Material Shuang Hu, Ruquan Zhang Wuhan Textile University

Abstract. The aging of the filter material has become a key issue to limit its further development and application. The aging of the filter material is not only made the premature failure of equipment, a huge loss of materials, and waste of resources, but also the aging decomposition of materials caused the environmental pollution. The PP / PET needle punched nonwovens were prepared in the needle machine with polypropylene fiber, and polyester as the raw material. The filter material samples prepared is accelerated aging test by using the oven method. The experiments were studied 3 influence factors of aging time, aging temperature and ratio of raw materials of the PP / PET needle punched nonwovens on barbed felting weight, thickness, breaking strength, elongation at break through the range and variance analysis by the application of orthogonal experimental design. The experimental results showed that under the condition of the significant level of 0.05, the process parameters such as the ratio of raw materials, aging temperature and aging time on the gram weight, thickness, strength and breaking elongation of PP/PET needled nonwovens had no significant effect.

Keywords. nonwovens; filter material; aging; aging temperature; orthogonal test

1. Introduction Filter material is an important industrial textile in the national economy. Aging filter material has become a very important issue. At present, the study about filter material of science has been a substantial progress and some result such as various of light stabilizers, antioxidants and other products. These reagents only can extend the life of filter material, but can not completely eliminate the problem of aging filter material. So the problem of aging filter material is still much concerned and valued so far. The polypropylene fiber not only has good mechanical properties, processing performance and electrical insulation properties, nontoxic, good water stability, but also has inexpensive feature which has led that polypropylene becomes one of the largest output, the most widely used species in the world. But the disadvantage of polypropylene is resistant to poor aging properties, and easily aging under the effect of UV light and oxygen. Polyester fiber has a high breaking strength and elastic modulus, resilience moderate, the outstanding performance of setting heat, the good performance of the heat and light fastness. The study of aging mechanism of filter material of the polypropylene fiber / polyester fiber is conducive to understand the aging process of the filter material and the critical factors caused by the aging of the filter material to improve the anti-aging properties of the filter material and reduce the economic losses caused by the aging of the filter material. The article used orthogonal experiment method and oven method for the aging test of the PP / PET needled filter material and tested the physical properties of the samples before and after, analysed the performance changes of the sample and understood the aging resistance of PP /

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PET filter material for the production of PP / PET filter material providing a reference.

2. Experiment 2.1 The Apparatus of the Experiment CP303 electronic scale,YG9（B）141D fabric thickness meter, YG065Helectronic fabric strength machine, Straightedge.

2.2 The Sample of the Experiment The PP fibers and PET fibers is mixed in proportion 80/20, 70 / 30,60 / 40 under the condition of keeping other process parameters consistent after opening, carding, pre-needling, main-spiking, main-spiking , lapping as volume process to prepare sample 1, sample 2, sample3. Experiment with each sample parameters are shown in Table 1. Table 1 The performance parameters of the sample Needling density

Breaking strength

Thickness Mass(g)

Sample (needling/cm2)

(mm)

sample 1

2.277

0.811

0.0049

sample 2

3.446

1.410

0.0193

sample 3

3.149

1.700

0.0077

(N/10cm)

2.3 Experimental Program Heat aging test is an artificial environment test. The instrument can simulate thermal environment during the process of storage, transport, using to Aging resistance explore the aging resistance of the products. The article adopted to experimental methods of artificial environment. Three main factors were considered in the process of exploring PP / PET needled filter material anti-aging properties: PP / PET fiber ratio, aging time and aging temperature. If the interaction was not considered each factor was selected three levels. The article was analyzed the impact of various factors on properties of PP / PET nonwovens anti-aging properties. And L9 (34) orthogonal test program was confirmed, Table 2. Since PET has excellent mechanical properties over a wide temperature range, long-term used temperature is up to 120 ℃. The melting temperature of The PP is up to 275 ℃.So when the aging test is carried out in a simulated atmosphere, the aging temperature can be set to 80 ℃, 100 ℃ and 120 ℃ three levels and the aging time is not more than 5 hours. If the interaction was not considered, the Specifically orthogonal experiment L9 (34) is shown in Table 3. Table2 Orthogonal factor level table Level

Factor A

material ratio

aging temperature

aging

(%)

(℃)

time (h)

80/20

70/30

100

2.5

60/40

120

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Table3 Orthogonal test program Experiment

Factor

No.

material ratio

aging temperature

aging time

(%)

(â&#x201E;&#x192;)

(h)

3. Experimental Results and Analysis According to the orthogonal schemeďź&#x152;the performance test results such as the weight, thickness, breaking strength and elongation at break and other aging performance of the PP / PET filter material are shown in Table 4. Table4 Orthogonal aging performance test results Experiment

mass(g)

thickness(mm)

Breaking strength

Elongation at break

(/N)

(mm)

2.189

77.55

134.00

No. 1

0.8096

0.7080

2.120

75.65

107.60

0.6259

1.988

67.49

102.29

0.9546

2.956

142.06

139.50

0.6280

2.809

136.18

118.90

1.1028

3.019

140.27

139.26

0.8580

0.008

142.06

129.20

1.1346

3.081

135.29

127.89

1.0020

3.023

127.83

114.23

3.1 Range Analysis of Anti-aging Properties of the Filter Material Range analysis is main to calculate the averaging of the test index for analysing the important order and influent trend in order to obtain the optimum parameters. The determinant R is determined the factors on the role of indicators. The greater the R-value is, the greater impact of the factors to the test indicators, which is a major factor of the test Indexes. On the contrary, the less the R-value is, the less impact of the factors to the test indicators, which is the secondary factors of the test indexes.

3.1.1 Range Analysis Gram PP / PET needled filter material grammage range analysis are shown in Table 5.

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Table5 Range Analysis Gram A

2.1435

2.8988

3.0470

2.6854

2.4706

2.6646

2.9946

2.7307

2.1119

0.7145

0.9663

1.0157

0.8951

0.8235

0.8882

0.9928

0.9102

0.7340

Range R

0.2783

0.1428

0.2817

The major factor

C>A>B

Optimal combination

C1A3B1

In table 5, K1，K2，K3 is respectively showed the sun of the level1,2,3 corresponding to the test index. The kl, k2, k3 are respectively showed the average of Kl, K2, K3. The table 5 is showed that the effect of weight for PP / PET filter material primary and secondary order is C> A> B, which is the aging time ˃ material ratio ˃ aging temperature. In terms of anti-aging properties of PP / PET needled filter material, the largest range is the aging time which shows that aging time on the anti-aging properties of the filter material plays a major factor. Because in a short time, temperature aging effects of the sample is not obvious, but as the temperature rises, the aggregate structure of fibers will happen to change, crystal fibers will be falled apart, the orientation will be dropped, the molecular mass will be declined.

3.1.2 Range Analysis Thickness PP / PET needled filter material thickness range analysis are shown in Table 6. Table6 Range Analysis Thickness A

6.297

8.153

8.2890

8.874

7.878

7.9670

9.112

8.03

7.8050

2.099

2.7177

2.7630

2.928

2.6260

2.6560

3.037

2.6767

2.6017

Range R

0.938

0.0917

0.1613

The major factor

A>C>B

Optimal combination

A3C1B1

The table 6 is showed that the effect of thickness for PP / PET filter material primary and secondary order is A> C> B, which is material ratio ˃ the aging time ˃ aging temperature. In terms of anti-aging properties of PP / PET needled filter material, the largest range is the material ratio which shows that aging time on the anti-aging properties of the filter material plays a major factor. In the heat treatment process, the molecular structure of the polymer changes, the macromolecular chains creep or slippage, which destroyed the original molecular structure and changed the relative position between the fibers. Besides the surface of the fabric structure occurs also changed by changing the local region of the polymer chain aggregation

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structure. The crystal lattice of the fiber of region deformes, the molecular orientation of the amorphous region increases, part of the macromolecule breakage readily occurs, and creep between the fibers occurs as well. But the PET has high elastic modulus, high heat resistance. Therefore during the filter material aging process, the percentage of PET, PP had a significant effect on the thickness variations.

3.1.3 Range Analysis Breaking strength PP / PET needled filter material Breaking strength range analysis are shown in Table7. Table7 Range Analysis Breaking strength

220.69

355.64

353.11

418.51

347.12

399.15

335.59

345.54

73.56

118.55

117.70

139.50

115.71

133.05

111.86

115.18

Range R

65.94

6.69

2.52

The major factor

A>B>C

Optimal combination

A2B1C1

The table7 is showed that the effect of breaking strength for PP / PET filter material primary and secondary order is A> B> C, which is material ratioË&#x192; aging temperature Ë&#x192; the aging time. In terms of anti-aging properties of PP / PET needled filter material, the largest range is the material ratio which shows that aging time on the anti-aging properties of the filter material plays a major factor. In the heat treatment process, the polypropylene gradually cleavages double, between fiber molecules thermal motion can be high, macromolecules flex improves, the bonding force between the intermolecular bonding force weakens, initial modulus decreases. So the percentage of PP, PET had a significant effect on the strength of filter material during the filter material aging process.

3.1.4 Range Analysis Elongation at break Table8 Range Analysis Elongation at break

343.9

399.7

401.2

397.7

354.4

361.3

371.3

355.8

350.4

114.6

133.2

133.7

132.6

118.1

120.4

123.8

118.6

116.8

Range R

18.0

15.1

16.9

The major factor Optimal combination

A>C>B A2C1B1

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The table 8 is showed that the effect of Elongation at break for PP / PET filter material primary and secondary order is A> C> B, which is material ratioË&#x192; the aging time Ë&#x192; aging temperature. In terms of anti-aging properties of PP / PET needled filter material, the largest range is the material ratio which shows that aging time on the anti-aging properties of the filter material plays a major factor. Whether the elongation at break is large or small depends on the flexibility of the molecular chain of materials. The process of stretching is essentially is a process of "consumption" polymer chain flexibility (conformational change capacity).

3.2 Variance Analysis of the Filter Material The Table 9, Table 10, Table 11 and Table 12 are showed the analysis of variance for the weight, thickness, breaking strength and elongation at break of PP / PET needled filter material. Table9 Variance Analysis gram Factor

The sum of

Freedom

F 0.05 (2,8)

Significance

Ratio

squared deviations A

0.124

1.670

4.460

0.011

0.148

4.460

0.147

1.980

4.460

Error

0.30

Table10 variance Analysis Thickness Factor

The sum of

Freedom

F 0.05 (2,8)

Significance

Ratio

squared deviations A

1.508

3.884

4.460

0.004

0.010

4.460

0.040

1.980

4.460

Error

1.63

0.098

Table11 variance Analysis Breaking strength Factor

The sum of

Freedom

F 0.05 (2,8)

Significance

Ratio

squared deviations A

7928.393

3.942

4.460

67.504

0.034

4.460

30.138

0.015

4.460

Error

8044.84

Table12 variance Analysis Elongation at break Factor

The sum of

Freedom

F 0.05 (2,8)

Ratio

squared deviations A

482.462

1.306

4.460

503.829

1.364

4.460

476.829

1.291

4.460

Error

1477.42

Significance

Page 754 of 1108

The table 9, Table 10, Table 11 and Table 12 are showed that if F ratio <F0.05 (2,8), under a significant level of 0.05 conditions, the raw material ratio, aging time and temperature for the gram, thickness, breaking strength and elongation on the PP / PET of the filter material has no significant effect. As for the PP / PET filter materials used for the project or others, the tensile strength and elongation at break is significantly better than the index weight and thickness targets. When selecting the optimal level, due to the A, B, C three factors in weight, thickness, breaking strength and elongation of the four indicators neither significant, therefore an important indicator should be followed the principle of giving priority to select the tensile breaking strength and elongation at break for the most important factor of the anti-aging properties exploration.

4. Conclusion The paper has studied the anti-aging properties of PP / PET filter material. By the comparison with the quality, thickness, breaking strength, elongation at break filter material before heat treatment and the test results of the analysis and research, it concluded as follows. (1)The longer thermal aging treatment time, the higher the temperature, the smaller the eight, thickness, breaking strength, elongation at break of the fabric. (2)The PET / PP ratio has a remarkable effect on the anti-aging properties of PP / PET filter material, and the greater the proportion of PET / PP, the better the anti-aging properties of PP / PET filter material.

6. References [1]Junqi He, Shaolin Xue. Technology and performance antistatic polypropylene needle punched filter materials [J]. Synthetic Fibers, 2013,12 (12): 1-2. [2]Zhongyu Fu, Shelley. Polypropylene fiber tensile strength and light aging properties [J]. Beijing Institute of Clothing Technology, 2004,4 (4): 22-26. [3]Chen Li. Performance changes of polyester fabric under outdoor environments [J]. Shanghai Textile Technology, 2011,9 (5): 9-31. [4]Yang Gao, Zhijiang Cai. Application Development of electrospinning nanofibers at filter material [J]. Polymer Bulletin .2013,6 (12): 6-17. [5] Zhangyin Jiang, Xu Xiaoping. Xenon-based climate under the sun PP and PET hot-rolled non-woven fabric aging comparative analysis [J] Technical Textiles, 2013,31 (7): 16-17. [6]WANG C,LIN H,CEN Y Y. Study on the preparation of steadystate chitosan nanoparticle as silkfabric finishing agent [J]. Advanced Material Research. 2011,(175): 745-749.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Application of phase change materials in motorcycle helmets for heatstress reduction Kanesalingam Sinnappoo1, Lachlan Thompson2, Rajiv Padhye1 1

School of Fashion and Textiles, 2School of Mechanical, Manufacturing and Aeronautical engineering RMIT University, Melbourne, Australia

Abstract. In tropical regions and hot climates, heat-stress due to wearing helmet while riding a motorcycle is a phenomenon that is commonly experienced. This research has investigated the novel application of innovative fabrics in the design of an interlayer between the scalp and the helmet lining of a motorcycle helmet to control the temperature inside the helmet. The innovative fabric used in the form of a liner consisting of a hood with replaceable inserts made from paraffinic Phase Change Materials (PCM). The textile liner covers the part of the head that is covered by the helmet. The materials used are non-toxic, low cost, lightweight and easy to use. It was found that the drop in temperature by the application of PCM materials ranged from 3.1 to 3.8 °C depending on the wind speed. The maximum drop in temperature for PCM materials was achieved at 75 kph wind speed because of the forced convection contributing to additional cooling. Finally it was concluded that for alleviating the motorcyclist’s heatstress in the helmet, textile liner with the hood and replaceable inserts of PCM materials can be manufactured and fitted to new helmets or retrofitted to old helmets without any alterations to the helmet. Keywords: Phase change material, helmet, heat-stress, wind tunnel, textile liner

1. Introduction In tropical regions and hot climates, heat-stress due to wearing helmet while riding a motorcycle is a phenomenon that is commonly experienced. Fonseca [1] studied the heat-transfer properties of military helmets and observed that the evaporation of sweat increased as the standoff distance of the helmet from the head was increased. Roszkowski [2] studied industrial helmets from different countries and concluded that the ability to allow sweat evaporation varied with the design of the helmets. Chinn et al. [3] suggested that wearing a motorcycle helmet can influence the cognitive performance of a motorcyclist. The concentration of the motorcyclist can be affected by the heat, moisture and carbon dioxide (CO 2 ) produced within a closed helmet. Many researchers have investigated the relationship between heat transfer and thermal comfort by evaluating the heat transfer characteristics of industrial helmets [4]. Very few of these studies were in the context of improving the comfort level of motorcyclist wearing a helmet. This research has investigated the novel application of innovative fabrics in the design of an interlayer between the scalp and the helmet lining of a motorcycle helmet to control the temperature inside the helmet. In addition, the research was carried out to investigate the practicality of using paraffinic Phase Change Materials (PCM) as a means of cooling the wearers of motorcycle helmets. The textile liner produced consists of a hood with replaceable inserts made from paraffinic PCM. The textile liner covers the part of the head that is covered by the helmet. The PCM inner fabric liner can be used without compromising the legal safety compliance of the helmet.

2. Materials Various fabric laminates and foams coated with paraffinic PCM were collected from Outlast Technologies (USA). The PCM used in the study fall under the paraffin classification, with the carbon chain containing 18 to 20 carbon atoms (i.e. octadecane to eikosane). The melting point of PCM ranges from 28–33 °C and the crystallisation point ranges from 22–30 °C. An additional composite material was prepared by stitching the PCM foam and PCM fabric laminates around the borders and gluing them together around the edges. This composite was then used in the experiments to observe any variations in performance in relation to the above range of single PCM materials. The materials used are non-toxic, low cost, lightweight and easy to use. It has

Page 756 of 1108

been established that there is a scope to reduce up to 3.8 °C temperature inside the helmet using PCM materials as a textile liner. The Specification of materials used in current study is shown in Table 1. Table 1: Specifications of materials used in current study Active Weight Name of material Style no. Functional layer constituent (g/m2) S7465 Paraffinic PCM in acrylic PCM nonwoven 169 PCM matrix coating Paraffinic PCM foam S6584 327 All-season coating PCM Paraffinic PCM fabric S5545 307 All-season coating PCM Paraffinic PCM composite N/A 634 All-season coating PCM

The scanning electron microscopic (SEM) images of the fabrics and foams used for the study are illustrated in Fig. 1 (a) to 1 (d).

(a)

(b)

(c)

(d)

Fig. 1: SEM images of the cross sections: (a) PCM nonwoven, (b) PCM foam, (c) PCM fabric and (d) PCM composite

3. Methods A wind tunnel was used to simulate the on-road conditions while riding a motorcycle with a helmet for investigating the reduction of heat-stress in the head of the motorcyclist. Fig. 2 gives a schematic diagram of the industrial wind tunnel at RMIT University. The wind tunnel contains an octagonal test chamber with dimensions of 1320 millimetres in width by 1070 millimetres in height and 2100 millimetres in length. The wind tunnel has a closed circuit design and is fitted with a 134 hp DC motor. A fan consisting of six blades is driven by the DC motor. It is a subsonic tunnel, where the air velocities can be varied from 1 ms–1 up to 45 ms–1 in the test chamber. The air entering the test chamber was conditioned by a honeycomb and an antiturbulence screen. A contraction ratio of 4:1 was used to condition the airflow entering the test section. The wind tunnel consists of various sections such as the expansion, working section, contraction, settling chamber and fan, as shown in the figure.

Fig. 2: Schematic diagram of wind tunnel at RMIT Aerospace Engineering The experiments were primarily based on visor-closed motorcycle helmet. The study was conducted using the PCM material inside the helmet as a textile liner and were investigated for their performance in the reduction of heat stress in the head of the motorcycle rider. PCM were tested at a temperature that was 10 °C above the ambient temperature (i.e. ambient +10 °C) which allowed the phase change temperature of the

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materials to be reached. For objective evaluation of the effectiveness of helmet ventilation, a heated aluminium head-form was used in the wind tunnel. T-type thermocouples were used to measure the temperatures on the surface of the aluminium head-form. The mean of all the thermocouple readings were considered to be the temperature of the aluminium head-form. The control curve (A) represents the difference between the mean and the ambient (i.e. mean â&#x20AC;&#x201C; ambient) for the helmet only and the PCM material curve (B) represents the difference between the mean and the ambient (i.e. mean â&#x20AC;&#x201C; ambient) for the PCM material used within the helmet and the helmet. The difference between the control curve and the PCM material curve represents the resultant cooling curve which corresponds to the drop in temperature achieved by using the PCM material as textile liner.

4. Results and Discussion 4.1 Drop in temperature (DIT) using PCM materials The resultant cooling curves for the PCM materials used at 555 and 75 kph are shown in Fig. 3 and Fig. 4. Ti me :h :mm:ss

0:00:00 0.0

0:07:12

0:14:24

0:21:36

0:28:48

0:36:00

0:43:12

0:50:24

0:57:36

1:04:48

Drop in temp. for PCM nonwoven material -1.0

Drop in temp. for PCM foam material Drop in temp. for PCM fabric material

Drop in temp. Deg.C

Drop in temp. for PCM composite material -2.0

-3.0

-4.0

-5.0

Fig. 3: Comparison of resultant cooling curves for PCM materials at 55 kph speed It can be observed from Fig. 3 that the drop in temperature is rapid for the initial duration of the experiment irrespective of the type of PCM material contained in the textile liner. This is because the amount of PCM microcapsules contained in each material begins to absorb a large quantity of heat initially by the process of melting, thus causing a rapid drop in temperature. After reaching the lowest point in the cooling curve, the drop in temperature then decreases gradually, as shown by the rising of the individual curves towards the Xaxis. The forced convection of air in the wind tunnel assists in further cooling of the helmet until the curves approach the steady state. After the PCM contained in the textile liner have melted (attaining the highest drop in temperature), there would not be further absorption of heat.

Fig. 4: Comparison of resultant cooling curves for PCM materials at 75 kph speed

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A similar phenomenon is observed in Fig. 4 similar to Fig. 3 but at a higher speed of 75 kph. It can be observed from the individual results of paraffinic PCM as shown in Table 2 that the differences in the readings of the maximum drop in temperature at the speed of 55 and 75 kph are not markedly different. This was due to the contribution of forced convection to achieve further cooling. In these experiments, the temperatures of the PCM were not near enough to the melting points of the PCM to obtain maximum heat absorption. To facilitate the maximum amount of heat absorption, the temperature should exceed the melting points of the PCM where all microcapsules present would have melted. It also depends upon the amount of microcapsules present in the PCM materials. All the PCM materials used in these experiments have the same surface area equivalent to the surface area of the head. But the density and thickness of the PCM materials are different and hence the amount of microcapsules also varies to a limited extent. In addition, the weights of the PCM materials are different even though they have the same surface area. The values of maximum drop in temperature and the corresponding time are also shown in Table 2. Table 2: Drop in temperature achieved by PCM materials at various speed Materials

Corresponding time of MDIT* (h:mm:ss)

Control ‘A’ (Mean – Ambient) (°C) 75 55 75 0:30:00 6.2 5.09 0:25:10 6.8 5.58 0:23:20 6.2 5.82 0:24:40 6.5 5.64 * Maximum drop in temperature

Wind speed (kph) PCM Nonwoven PCM Foam PCM Fabric PCM Composite

55 0:30:40 0:25:30 0:30:40 0:26:20

Material ‘B’ (Mean – Ambient) (°C) 55 75 3.1 2.0 3.1 1.87 2.5 2.07 2.9 1.94

MDIT* (B – A) (°C) 55 –3.1 –3.6 –3.7 –3.6

75 –3.1 –3.7 –3.8 –3.7

The drop in temperature varied from 3.1 °C to a maximum of 3.8 °C depending on the type of materials used and the duration of the experiments. However, there is a possibility of further cooling before it reaches the steady state. The values of maximum drop in temperature and the corresponding time are also shown in Table 2. Finally it was concluded that for alleviating the motorcyclist’s heat-stress in the helmet, textile liner with the hood and replaceable inserts of PCM materials can be manufactured and fitted to new helmets or retrofitted to old helmets without any alterations to the helmet.

5. Conclusions The textile liner consisted of different types of PCM materials and used as replaceable inserts within a hood. It was observed that the drop in temperature was up to 3.8 °C within the helmet. This provides adequate cooling till the steady state is reached. With improved PCM materials, additional drop in temperature and thus the cooling within the helmet could be substantially increased.

6. References [1] G. F. Fonseca, “Heat transfer properties of military protective headgear,” US Army Natick Labs, Accession Number: AD0783434, 1974. [2] W. Roszkowski, “Comparative tests of helmets of polish and foreign makes,” Health and Safety Executive, Britain, Translation Number-8526, 1977. [3] B. Chinn, B. Canaple, S. Derler, D. Doyle, D. Otte, E. Schuller, and R. Willinger, Belgium. Directorate General for Energy and Transport. Final Report of the Action Cost 327: Motorcycle Safety Helmets, Directorate General for Energy and Transport. [4] X. Liu, “Evaluation of thermal comfort of headgear,” PhD thesis, Lulea University of Technology, Lulca, Sweden.

Page 759 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Comparison general turnout gear to various special turnout gear for firefighters using the Flash fire testing methods Pyoung Kyu Park1 +, Young-Soo Kim2, Hae-Yong Kim3, Sang-IL Na3, Yi-Yeon Park3, Seung-Tae Hong3 , Lu Jin4 and Byoung-Sun Yoon1 1

Sancheong R&D center, 2University of HoSeo, 3Korea Fire Institute, 4University of Dankook

Abstract. Convective heat and Radiation heat may be a significant component of heat exposure in the case of firefighting. The temperature exceeds a certain value that firefighters can be confronted with a flashover situation. Base on reviews of turn out gear and evaluation from TPP testing in National Fire Protection Association (NFPA) 1971 and EN 468. The turnout gear in Korea is typically existing in general and special garment. The TPP value of general turnout gear (100% m-Aramid) was lower than special turnout gear (35% PBI). The PBI/m-Aramid padding turnout system had a TPP value of about 41 due to bulky. It’s padding layer was generated to air gap from the garment layer, improved TPP. We found that manikin must wear on PPE for flash fire testing. Finally, non-flame retardant Velcro hasn’t appropriate to protect burn injury.

Keywords: Firefighter suit, Turnout gear, TPP, RPP, Flash fire test

1. Introduction In general, firefighting suit with heat protect function if for protecting firefighter’s body. Their second skins are comprised of three separate components, the outer shell, the moisture barrier, and the thermal liner. At first skin provides resistance to flame and heat plus protects the remainder of the gear from rips, tears and abrasion. Second skin provides some thermal protection because it does have some insulating value, but its most important tasks are preventing fluids from entering the gear while still allowing perspiration out. Water must be kept out to prevent the saturation of the thermal layer. The moisture barrier must also allow body heat and perspiration to escape to reduce the firefighter’s rate of metabolic heat buildup. The thermal liner, is the inner most layer of turnout gear, provides the bulk of the thermal insulation in garment. The purpose of the face cloth is to provide a wicking agent which will move perspiration away from the body to keep the firefighter drier and more comfortable. The batt provides air gaps in order to maximize thermal insulation. Korea’s firefighter’s works with over 20kg of PPE (personal protective equipment), which are helmet, SCBA (Self-contained breathing apparatus), turnout gear, gloves and boots. But too many firefighters have injuries 2nd or 3rd degree burn. Also, excessive heat buildup can lead to stress related injuries for firefighters. It is composed of jacket and trouser type. Especially, garment performance requirements are TPP (Thermal protective performance), RPP(Radiation protective performance), which are certified by NFPA 1971(2013), EN 469 and KFIS018. Furthermore, firefighters are an intense, strenuous and hazardous occupation that exposes them to wide variety of challenging environmental conditions including extreme temperature like flash fire condition, high toxic chemicals and blood borne pathogens. In 2015, there are over 40,000 firefighters in Korea. They wear on general turnout gear (A) or specialized suit (B), were certified by KFI(Korea Fire Institute). They aren’t applied to flash fire testing. Flash fire is relative short durations, typically 8seconds or less. 2nd burn, blistering, epidermis. The body burn in a severe flash fire of 8 seconds with optional testing in EN 469 and exposure 3 seconds in ASTM F 1930 & NFPA 2112. The mannequin has 110 thermocouples evenly distributed over its surface to predict the extent, severity and location of body burn. As noted earlier, NFPA 2112 accordingly set the pass/fail performance test at 3 seconds to characterize performance in a worst case scenario. Protective +

Corresponding author. Tel.: + 86-31-321-4077 E-mail address: pkpark@sancheong.com

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clothing, also known as personal protective equipment (PPE), is a firefighter’s first line of defence to minimize the risk of second burn degree in flame and radiation environments. The aim of this study was to compare the second burn degree of different types of turnout gear in Korea. That is was done by the flash fire test for m-Aramid (100%), p-Aramid/m-Aramid (70/30), PBI (polybenzimidazole)/p-Aramid (35/65) and PBO (poly p-phenylene-2, 6-bezobisoxazole)/p-Aramid (35/65) as RPP and TPP. In addition the performance of thermal manikin and their equipment are influence by many other variables, which need to be investigated. Hence, the aim of this study is to determine the effect of the different type of ensemble.

2. Material and methods 2.1 Materials The four kinds of outershell materials were investigated. Each material was tested TPP and RPP. The materials chosen for this project are presented in table 1. The composite systems, composed of an outer-shell, moisture barrier and an insulator liner, were tested following three garments which are m-Aramid (100%), pAramid/m-Aramid(70/30), PBI/p-Aramid(35/65) and PBO/p-Aramid(35/65) as RPP(Radiation protective performance ), TPP(Thermal protective performance) and flash fire test. Table 1: The tested materials Layers Outershell(A) Outershell(B) Outershell(C) Outershell(D) Moisture barrier(B1) Moisture barrier(B2) Thermal barrier(C1) Thermal barrier(C2) Thermal barrier(C3)

2.1.

Materials m-Aramid (100%) p-Aramid/m-Aramid(70/30) PBI/p-Aramid(35/65) PBO/aramid(35/65) PTFE Membrane on Aramid woven PTFE/PU Membrane on Aramid woven Aramid felt/Aramid woven Aramid felt/Aramid woven m-Aramid padding

Weight(g/m2) 217 180 219 199 159

Thickness(mm) 0.47 0.32 0.51 0.43 0.32

160

0.33

314 275 80

1.76 1.66 4.48

Test Method

2.1.1 Heat transmission test The heat transmission of firefighter turnout composites was measured to ISO 9151(Protective clothing against heat and flame-Determination of heat transmission on exposure to flame) and ASTM D 4108(Standard test method for Thermal Protective Performance of materials for clothing by open-flame method). Test samples were exposed to a flashover conditions 84Kw/m2(0.2cal/cm2 s).

2.1.2 Radiation protective performance test A RPP test consisting mainly of four parts (source of radiation, specimen holder, calorimeter and temperature recorder, all of which conform to ISO 6942) was constructed. The calorimeter, the most important part of RPP tester, was calibrated using a Medtherm heat flux sensor (Model No. 64-5-16, Medtherm, USA). Radiant heat transfer index(RHTI) values of specimens which represent their RPP are determined, Various RHTI values are used including RHTI 12 , RHTI 24 which are defined as follows: RHTI 12 : Time to achieve a temperature rise of 12℃ in the calorimeter of the RPP tester, RHTI 24 : Time to achieve a temperature rise of 12℃ in the calorimeter of the RPP tester

2.1.3 Flash fire test ISO 13506:2008(Protective clothing against heat and flame - Test method for complete garments -

Page 761 of 1108

Prediction of burn injury using an instrumented manikin) was used to measure the flash fire method for evaluating the performance of turnout system. This test method characterizes the thermal protection provided by garments, based on the measurement of heat transfer to a full-size manikin exposed to a laboratory simulation of a fire with controlled heat flux density, duration and flame distribution. The heat transfer measurements can also be used to calculate the predicted skin burn injury resulting from the exposure. In addition, observations are recorded on the overall behavior of the test specimen during and after the exposure. The manikin is suspended from the center of the ceiling of a flame resistant burn chamber and surrounded by twelve industrial burners capable of producing a large volume, simulated flash fire that can fully engulf the manikin in flames. The manikin has 110 individual skin-simulant thermal sensors distributed over the manikin surface.

3. Results and Discussion 3.1 Effect of composition of layer on TPP and RPP In this study, four types of commercial turnout gear were examined. The comparison of TPP and RPP ratings achieved from the experimental measurements is presented in Table 2. The TPP value of general turnout gear (100% m-Aramid) was lower than special turnout gear (35% PBI). The PBI/m-Aramid padding turnout system had a TPP value of 40.7. Many researchers have studied TPP of various fabrics. The thick of fabric has a direct impact on TPP values, thicker fabrics leading to higher TPP values, consistent with the results of the other researcher. In this reason, air gap is generated in the middle of thick fabric. In other words, the thicker fabric exhibits better thermal insulation characteristic.

Table 2: The tested materials for TPP and RPP Composition of layers

Total weight(g m2)

TPP

RPP

A/B2

357

15.5

11.1

B/B2/C2

615

35.8

25.8

C/B2/C1

693

40.3

32.9

D/B1/C2

633

39.6

28.6

C/B2/C3

459

40.7

29.4

3.2 Effect of composition of layer on Flash fire behavior Whole garment samples were exposed to a thermal manikin at heat flux density 84kW/m2 (2.0cal/cm2sec). This flux corresponds to flashover conditions. The general turnout gear show a noticeable change in the level of damage as shirnks and crack. The value of second degree burn of the m-Aramid material is 16.7%. this value is lowest than the other garment. Nomex shrink away from a high heat source(575℃) or from a flash fire condition. Whereas, p-Aramid behaves elastically in tension and degradation at about 640℃. The PBI materials show that the coat exhibited second degree burn(6.4%). These results can explain that flame from the buner attack only coat at 8s expose. PBO garment also, show similar results. Therfore we supplied to wear on all personal protective equipment such as SCBA(Self-Contained Breathing Appartus), boots and heltmet. There was a hole of helmet for pull manikin. As can be seen from Fig. 2, the second degree burn of PBI garment decreases by 5.5%. The Velcro of turnout gear on full PPE was continuously burn long after initial flame exposure. In this study, the Velcro has to be changed aramid-based flame retardant. Most of Velcro’s are non-flame retardant materials as shown in NFPA 1971, EN 468 and KFI 032.

Page 762 of 1108

(a)

(b)

(c)

(d)

Fig. 1. Images of various turnout gear before and after flash fire manikin test (a) m-Aramid, (b) p-Aramid/m-Aramid, (c) PBI/p-Aramid, (d) PBO/p-Aramid

Fig. 2. Images of various turnout gear before and after flash fire manikin test on PPE wearing

4. Conclusions Different thermal barriers were studied in this work. Aramid padding as thermal barrier was generated to air gap from the garment layer, improved TPP. We found that manikin must wear on PPE for flash fire testing. Non-flame retardant Velcro hasn’t appropriate to protect burn injury.

5. Acknowledgement This research was supported by the Fire Fighting Safety & 119 Rescue Technology Research and Development Program funded by the Ministry of Public Safety and Security(“MPSS-소방안전-2012-60”). We are grateful to Sancheong Co. for continuous support in this study. We would like to express our deepest appreciations to Mr. Su-Young Kim of DanKook University, PPEC who help us in the testing.

6. References [1] Shalv I, Barker RL. Protective fabrics: a comparison of laboratory methods for evaluating thermal protective performance in convective/ radiant exposures. Textile Research Journal: 1984; 54(10): 648-654 [2] ISO 9151: 2007, Protective clothing against heat and flame-determination of heat transmission on exposure to flame. [3] ISO 13506: 2008, Protective clothing against heat and flame-Test method for completes garments-Prediction of burn injury using an instrumented manikin.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Composite Environmentally Protective Sandwich Insulation Material Design Ya-Lan Hsing 1, Wen-Hao Hsing 2, Chien-Teng Hsieh 3, Jia-Horng Lin 1, 4, 5 and Ching-Wen Lou 6 + 1

Laboratory of Fiber Application and Manufacturing, Department of Fiber and Composite Materials, Feng Chia University, Taichung City 40724, Taiwan, R.O.C. 2 The Department of Textile Engineering, Chinese Culture University, Taipei City 11114, Taiwan, R.O.C. 3 Department of Fashion Design and Merchandising, Shih Chien University Kaohsiung Campus, Kaohsiung City 84550, Taiwan, R.O.C. 4 Department of Fashion Design, Asia University, Taichung City 41354, Taiwan, R.O.C. 5 School of Chinese Medicine, China Medical University, Taichung City 40402, Taiwan, R.O.C. 6 Institute of Biomedical Engineering and Materials Science, Central Taiwan University of Science and Technology, Taichung City 40601, Taiwan, R.O.C.

Abstract. In order to effectively improve energy efficiency in industrial applications, and reduce energy consumption and the cost of production, to achieve energy efficiency through the design of thermal insulation materials is essential. To promote the widespread use of insulation materials and related research and development of high-performance products, will generate energy efficiency and environmental benefits of the economic side of the community. Development of thermal insulation materials have become more multifunctional, the study use three-dimensional crimp hollow polyester fiber, low melting polyester fiber and recycled far infrared polyester fiber composite adhesive coated aluminum foil film in order to forestall the loss of thermal radiation. Expectations the performance in insulation improved functional of composite material , and contribute to the development of energy efficiency in all areas. Keywords: environmentally protective, far infrared fiber, three-dimensional hollow fiber, composite material, foil.

1. Introduction One of the most important challenges of future in the world is the reduction of energy consumptions in all life phases. The introduction of the concept of â&#x20AC;&#x153;sustainabilityâ&#x20AC;? in building design process encouraged researches aimed at developing thermal and acoustic insulating materials using natural or recycled materials [1-5]. Because most thermal insulation materials exhibit heat flows by a combination of modes (i.e., conduction, radiation, and convection) resulting in property variation with material thickness, or surface emittance, the premise of a pure conduction mode is not valid, therefore, the term apparent is implicit in the term thermal conductivity of insulating materials [6], [7] and [8]. Therefore, this study intends to use recycled far-infrared fiber as well as the three-dimensional hollow fiber and low melting point fiber, to produce their thermal insulation composite materials for industrial use, not only save natural resources, but also to achieve the purpose of sustainable use of energy.

2. Experimental 2.1. +

Materials

Corresponding author. Tel.: + 886-4-2451-8672. E-mail address: cwlou@ctust.edu.tw

Page 764 of 1108

Low-melting-point PET (LPET) fiber (Far Eastern New Century, Taiwan, R.O.C.) has a fineness of 4 denier and a length of 51 mm. LMPET fibers have a sheath-core structure. The Tg of the sheath is 110℃. The three-dimensional crimp hollow polyester (TPET) fiber (Far Eastern New Century, Taiwan, R.O.C.) has a fineness of 7 denier and length of 51 mm. The glass transition temperature (Tg) of PET is 70 ℃ to 80℃, and the melting point (Tm) of PET is 260℃. Recycling far infrared PET (RFPET)fiber(True Young Co. , Taiwan, R.O.C.) has a fineness of 6 denier and a length of 64 mm length. Far infrared powder concentration 1.5 %.

2.2.

Nonwoven production process

In this study, by using three-dimensional crimp hollow polyester fiber, low melting point fiber and far infrared fiber. The fibers go through nonwoven molding technology, after opener, blending, webs forming, folding, needle punching consolidation and low melting point hot pressing process, maintain its fluffy and restoring elasticity, heat insulation in as the material can be staggered by the inside of the fiber and the fiber content of the amount of air space to resist heat transfer. In this study, by using three-dimensional crimp hollow polyester fiber, low melting point fiber and far infrared fiber. The fibers go through nonwoven molding technology, after opener, blending, webs forming, folding, needle punching consolidation and low melting point hot pressing process, maintain its fluffy and restoring elasticity, heat insulation in as the material can be staggered by the inside of the fiber and the fiber content of the amount of air space to resist heat transfer.

2.3.

Methods

Air permeability This test follows ASTM D737-04(2012) air permeability standard, air permeability testing by Textest FX3300, revision the machine to adjust the air volume stalls, in order to achieve the correct porosity, sample sized 25 x 25 cm2, number of samples tested N=10.

Tearing strength test HT2402 (Hung Ta Instrument Co., Ltd, Taiwan, R.O.C.) measures the tearing strength of the samples taken along the CD and the MD at a tensile speed of 300±10 mm/min, as specified in ASTM D5035-11, number of samples tested N=10.

Tensile strength test Tensile strength of the samples is tested by using HT2402 (Hung Ta Instrument Co., Ltd, Taiwan, R.O.C.), as specified in ASTM D5035-11, with a 300±10 mm/min pulling speed. Ten sample measurements are taken along the cross machine direction (CD) and machine direction (MD).

Far Infrared Emissivity Test A far infrared tester (TSS-5X, Desunnano Co., Ltd., Japan.) measures the far infrared emissivity of ten samples. The samples are placed on the platform and are randomly checked by the research head. The obtained far infrared emissivity level is then compared with that of the black body (0.94).

3. Results and Discussion 3.1.

Composite material in Air permeability

From Figure 1 can be learned, because the aluminum foil is not breathable, so this experiment using needle punching to composite, to make a basic compound in advance, the pin pierced aluminum foil by needle punching , that is where the air can go though, hot pressing compound temperature in this study was 160 degrees, the outer layer of the low melting point fibers formed melting bonding point, not only to fill the little holes, but also to block non-woven structure is more solid. And see in Figure 1 of 4 layer with foil, the air permeability of more than three layers reduced by 50%, which means that more nonwoven laminate, and the more air permeability is reduced.

Page 765 of 1108

Fig. 1: Air permeability of the composite material.

3.2.

Composite material in tearing strength

On account of the foil strength is not high, its role in this experiment also focused on the role of heat transfer, so the mechanical properties of the test, is to use a reference environment direction. From Figure 2, that the sandwich with foil of the tear strength is 160-220N, and 4 layers with foil of the tear strength is between 290-330N, thereâ&#x20AC;&#x2122;s a strong increase of about 100N after adding layer, when the foil in middle layer and the opposite direction by the force of time, the foil torn neatly from the middle of the gap at the presentation, therefore, we can see that the most important endurance comes from the fibers in non-woven, if there are breaks in the case, foil will not bring more tear strength in composite materials.

Fig. 2: Tearing strength of the composite material.

3.3.

Composite material in tensile strength

As seen in Figure three, four layers of tensile strength is far greater than the tensile strength of three layerâ&#x20AC;&#x2122;s, the main reason is that the four layer was repeated needle punching the web, makes composite structure more closely as well as hot pressing in same thickness, fiber structure staggered complex, so that the whole nonwoven becomes stronger.

Fig. 3: Tensile strength of the composite material.

Page 766 of 1108

3.4.

Composite material in far Infrared Emissivity

From Figure 4 can be seen, when the far-infrared radiation rate of foil in the middle of the sandwich get a really high Far-infrared emissivity, up to far infrared radiation rate of 0.94, which shows that there will be heat-reflecting, so far in order to achieve such a high infrared radiation rate, the 4 layers part, the upper foil sandwich caught the foil in the middle but the second layer, can be found that when the foil laminated closer the blackbody, it will show relatively high far infrared radiation rate, and 3 layer is allover high than 4 layerâ&#x20AC;&#x2122;s, because of the number of needle punching composite time has more than doubled, holes will have an impact on the amount of far-infrared radiation rate.

Fig. 4: Far Infrared Emissivity of the composite material.

4. Conclusions The study successfully composites environmentally protective sandwich composite materials. In air permeability found that the degree of difference from stacks, in tensile and tear test also found that the more number of laminated composite materials get more stronger force, CD direction also came stronger than MD direction, that the amount of holes on non-woven by needle punching, will affect the difference of far infrared radiation rate, but because the sandwich with foil, far infrared radiation rate remained at 0.8.

5. Acknowledgements The authors would like to thank Ministry of Science and Technology of Taiwan, for financially supporting this research under Contract MOST 103-2622-E-035-025-CC2.

6. References [1] E. H. Ahmad, in "The 6th Saudi Engineering Conference"Ed.^Eds.), 21, Year of Converence. [2] M. Alam, H. Singh, and M. C. Limbachiya, Applied Energy, 88, 3592 (2011). [3] F. Asdrubali, F. D'Alessandro, and S. Schiavoni, Sustainable Materials and Technologies, 4, 1 (2015). [4] S. Lechtenbohmer and A. Schuring, Energy Efficiency, 4, 257 (2011). [5] J. Nyers, L. Kajtar, S. Tomic, and A. Nyers, Energy and Buildings, 86, 268 (2015). [6] "ASTM Standard C 168-97" [7] A. M. Papadopoulos, Energy and Buildings, 37, 77 (2005). [8] B. A. Peavy, Journal of Thermal Insulation and Building Envelopes, 20, 76 (1996).

Page 767 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Composite nonwovens composed of Viscose rayon and Super absorbent fibers for Incontinence Pad Yoon Jin Kim 1, Ga Hee Kim 1, Jung Nam Im 1  1

Technical Textile & Materials R&D Group, Korea Institute of Industrial Technology, Korea

Abstract. In this study, the absorbent incontinence pads were prepared as follows: needle-punched composite nonwovens of hollow viscose rayon (HVR) and super absorbent fiber (SAF) were prepared with varying SAF percentages and mass per unit area. Blend ratios of HVR and SAF were 70/30, 80/20, 90/10, and 100/0. Mass per unit area of composite nonwovens ranged from 100 to 200 g/m2. Various liquid handling properties, such as free swell absorption capacity and fluid retention capacity, were evaluated based on blending ratios and mass per unit area. The results showed that the absorption properties of incontinence pads were significantly affected by the mass per unit area and content of SAF. This will be helpful to predict and optimize the liquid handling properties of incontinence pads.

Keywords: Incontinence pad, hollow viscose rayon, super absorbent fiber, liquid handling properties

1. Introduction Incontinence, any leakage of urine, refers to the phenomenon of urine flowing through the urethra regardless of intentions. Incontinence does not directly affect life support but it is a matter closely related to quality of life. As the elderly increases the average life, incontinence is emerging as a social issue. Typically, 10-12% of all women have regular incontinence symptoms. An incontinence pad is the most well-known product type to manage incontinence. High absorption capacity is the most important characteristics of incontinence pad. [1-4] In recent years, various approaches to improve the liquid handling properties have been suggested. For example, knitted fabrics with 80–20 % polyester staple fiber (PET)-SAF blend yarn were examined to improve absorption properties during repeated washing and drying treatment. [5] Antimicrobial viscose rayon/ O- carboxymethyl chitosan fibers were manufactured. The results showed that the blend fibers were characterized with good moisture absorption.[6] Hollow viscose rayon (HVR) is a hollow and segmented viscose fiber. The hollow segmented structure gives mechanical stability both in dry and in wet condition. Upon contact with an aqueous liquid, HVR, being collapsed when dry, fills completely with the fluid resulting in a significantly higher intrinsic absorbency. HVR can also be cyclically inflated and deflated. The use of HVR can improve high absorption capacity. [7] Super absorbent fiber (SAF), a fibrous superabsorbent material, is a new kind of fiber which can absorb a large amount of fluid quickly. It can be fabricated into nonwoven to improve the absorbency or retention of fluid such as water, urine, blood, and so on. [5, 8] In this study, composite absorbent cores for incontinence pads were prepared with HVR and SAF via needle-punching nonwoven process. The effects of blend ratios and mass per unit area on liquid handling properties, such as free swell absorption capacity and fluid retention capacity, were investigated. 

Corresponding author. Tel.: + 82-31-8040-6253. E-mail address: founder@kitech.re.kr.

Page 768 of 1108

2. Experimental 2.1. Materials

HVR (3.3 dtex, 40 mm) was purchased from Kelheim fibers. SAF (10 dtex, 52mm) was purchased from Technical Absorbents Ltd.

2.2. Preparation of the absorbent pads

Needle-punched composite nonwovens of HVR and SAF were prepared with varying SAF percentages and mass per unit area. Blend ratios of HVR and SAF were 70/30, 80/20, 90/10 and 100/0. Mass per unit area (basis weight) of composite nonwovens ranged from 100 to 200 g/m2.

2.3. Liquid handling properties 2.3.1. Free swell absorption capacity

Free swell absorption test was performed based on modified BS EN 13726-1. The dry nonwoven specimens were cut into 5 cm 5 cm and weighed. Then the cut specimens were immersed in 0.9% saline solution for 10 min at room temperature. After the hydration, the specimens were suspended by using forceps for 30 seconds at one corner in order to allow excess saline solution to drip off. The weights of wet specimens were measured. Free swell absorption capacity was calculated from Equation (1) and (2). Free swell absorption capacity (per unit area, g/cm2) = (W2 - W1) / (5 cm 5 cm) (1) Free swell absorption capacity (per unit mass, g/g) = (W2 - W1) / W1

(2)

where W1 is the weight (g) of dry specimen and W2 is the weight (g) of wet specimen.

2.3.2. Fluid retention capacity

After the wet specimens were weighed for measuring free swell absorption capacity, pre-determined pressure, equivalent to 40 mmHg, was applied to the specimens for 1 min and the saline solution out of the specimens were blotted carefully. Then the weights of specimens were measured again. Fluid retention capacity was calculated by the following Equation (3) and (4). Fluid retention capacity (per unit area, g/cm2) = (W3 - W1) / (5 cm 5 cm) (3) Fluid retention capacity (per unit mass, g/g) = (W3 - W1) / W1

(4)

where W1 is the weight (g) of dry specimen and W3 is the weight (g) of specimen after the application of pressure.

3. Results and discussion One of the most important requirements of an incontinence pad is the fluid handling property. The incontinence pad should not only absorb as much urine as possible, but also hold that urine without leakage until the pad is changed. In order to study these properties, free swell absorption capacity and liquid retention capacity of composite nonwovens were evaluated. Free swell absorption capacities of composite nonwovens were evaluated and the results are shown in Figure 1. As shown in Figure 1(a), free swell absorption per unit area (g/cm2) increased as the basis weight increased. It means that the amount of HVR and SAF affected the free swell absorption capacity of composite nonwovens. In addition, the free swell absorption capacity increased as the proportion of SAF in the composite nonwoven increased. It seems that SAF had more significant effect on the free swell absorption capacity of composite nonwovens than HVR. On the other hand, free swell absorption per unit mass (g/g) decreased as the basis weight increased as shown in Figure 1(b). It seems that the macro-structure of composite nonwovens, such as density, pore size, and porosity, was influenced by compression while the composite nonwovens are prepared in the needle punching process. The compression of nonwoven during needle-punching might be increased as the basis weight of nonwovens was increased. Higher compression might cause a dense structure of composite nonwovens and, in turn, result in the decrease of free swell absorption per unit mass. However, the free swell absorption per unit mass also increased as the content of SAF increased. It implies that the structural changes

Page 769 of 1108

during needle punching process were affected by the amount of fibers used, not influenced by the composition of nonwovens.

(a)

(b)

Fig. 1: Free swell absorption capacity of HVR/SAF composite nonwovens; free swell absorption (a) per unit area (g/cm2) and (b) per unit mass (g/g). The fluid retention capacity of the composite nonwovens, related to urine leakage of incontinence pad, was investigated, and the results are shown in Figure 2. As the basis weight increased, the fluid retention capacity per unit area (g/cm2) increased in Figure 2(a) and the fluid retention capacity per unit mass (g/g) decreased like Figure 2(b). With the increase in SAF content, the fluid retention capacity significantly increased. The differences between the composite nonwovens could be explained similarly to free swell absorption capacity. (a)

(b)

Page 770 of 1108

Fig. 2: Fluid retention capacity of HVR/SAF composite nonwovens; fluid retention capacity (a) per unit area (g/cm2) and (b) per unit mass (g/g).

4. Conclusion Needle-punched composite nonwovens of HVR and SAF were prepared with varying SAF percentages and mass per unit area. The effects of SAF percentages and mass per unit area were investigated. When investigating the free swell absorption and fluid retention capacity, the composite nonwovens showed excellent free swell absorption and fluid retention capacity. Both basis weight and content of SAF in composite nonwovens influenced liquid handling properties. The liquid absorption and retention per unit area was improved with the increase of basis weight, however, the liquid absorption and retention per unit mass decreased as the basis weight increased. The liquid handling properties was improved with the increase of SAF content from every point of liquid handling properties such as absorption per unit area, absorption per unit mass, retention per unit area, and retention per unit mass. When considering liquid handling properties, it is expected that needle-punched HVR/SAF composite nonwoven could be a good candidate material for absorbent products such as incontinence pad, sanitary napkin, moist wound dressing and so on.

5. References [1] Dolan L. M., Walsh, D., Hamilton, S., Marshall, K., Thompson, K., Ashe, R. G., Int. Urogynecol. J, 15 (3), 160â&#x2C6;&#x2019;164 (2004). [2] Tatyana A. Shamliyan, Robert L. Kane, Jean Wyman, Timothy J. Wilt, Ann Intern Med., 148 (6), 459â&#x2C6;&#x2019;473 (2008). [3] Kyung Min Park, Joo Young Son, Jong Hoon Choi, In Gul Kim, Yunki Lee, Ji Youl Lee, Ki Dong Park, Biomacromolecules, 15(6), 1979-1984 (2014). [4] A.M. Cottenden, J. Biomed. Eng., 10(6), 506-514 (1988). [5] Emre Beskisiz, Nuray Ucar, Ali Demir, Textile Research Journal, 79(16), 1459-1466 (2009). [6] Youbo Di, Guoqiang Long, Huiqin Zhang, Qingshan Li, Journal of Engineered Fibers and Fabrics, 6(3), 39-43 (2011). [7] Walter Roggenstein, Lenzinger Berichte, 89, 72-77 (2011). [8] Hongyi Liu, Yong Zhang, Juming Yao, Fibers and Polymers, 15(1), 145-152 (2014).

Page 771 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Compression and Recovery Behavior of 3-D Composite Nonwovens Fabricated by Different Web-laying Methods Dong Su Park and Chang Whan Joo + Department of Advanced Organic Materials and Textile System Engineering, Chungnam National University, Daejeon, 305-764, Korea

Abstract. The elastic nonwovens by the through-air bonded methods are widely used in various industrial fields such as filter, hygiene, cushion and mattress because of high porosity and low density. From these characteristics, the thermal-bonded nonwoven requires analysis of compression behavior. In this study, the nonwovens were bonded with the through-air technique with high elastic PET and low melting PET as binder fibers with two different web-laid methods, i.e., horizontal-laid and vertical-laid nonwovens. Two PET fibers have side-by-side biconponents and crimp structure. horizontal-laid and vertical-laid webs were made with 60wt% and 80wt% low melting PET fibers. The pressure-thickness curves of the prepared nonwovens were obtained by universal testing machine (Instron 4467, Instron, USA). Each nonwoven was compressed with three direction of thickness, machine direction(MD) and cross direction(CD). Also, the pressure-thickness curves were analyzed according to the Kawabata compression parameters including compression resistance, recovery, resilience, hysteresis and deformation of through-air bonded elastic nonwovens. As the results, vertical-laid nonwovens show higher hysteresis and compression recovery than horizontal-laid nonwovens. Both laid nonwovens show a wide gap between experimental and theoretical values at the initial stage of pressure-thickness curve due to low density and high bulkiness of thermal bonded elastic nonwovens. The differential values between experimental and theoretical results were narrowed with increase of compression level and the result of vertical-laid nonwovens shows more acceptable than horizontal-laid nonwovens. Keywords: compression, recovery, 3-D composite nonwoven, horizontal-laid, vertical-laid

1. Introduction Through-air bonded nonwovens have low density and high porosity, and used widely in filter, cushion or hygiene fields. Such through-air bonded nonwoven products are often exposed to a compressive load, and this nonwoven is highly susceptible to compressive deformation. Especially, compressive deformation and recovery of through-air bonded nonwovens which has three-dimensional web structure are regarded as important performance for the commercialization. Compression behavior of the nonwoven is divided in to compressive resistance, compressive work, recovery work and hysteresis, and the performance is evaluated by the analysis of compressive characteristic[1]. The compressive behavior of nonwovens is mainly determined by fiber properties, web structure, and bonding processing conditions. Fiber properties are modulus, fineness, cross-sectional shape, etc., and web structures are porosity, web orientation, binder contents, etc. Furthermore, the compressive behavior of nonwovens is determined by the combined effect on fiber parameters and structural parameters, and the prediction of compressive behavior is very hard[2,3]. Various methods such as coarse fiber and vertical lapper are used to improve the compressive resistance and recovery[4]. Classical theory is basically applied for predicting of compression behavior of fibrous assemblies, and theory of compression was improved by many researchers. Previous theories were developed by taking in to fiber volume fraction, fiber length, fiber number, and bonding number in nonwovens. But these theories were only limited about single fiber nonwovens, and the study of the composite nonwovens composed of two or more types of fibers did not considered. +

Corresponding author. Tel.: + 82-42-821-7696. E-mail address: changjoo@cnu.ac.kr

Page 772 of 1108

Compressive behavior of nonwovens can be predicted using Van wyk[5] or Rawal[6] two dimensional model, but application of this theory on the through-air bonded nonwoven is very hard because of low density, porosity and three dimensional structure of nonwoven. In addition, these theories do not take into account various factor such as crimp, friction, twist, Poisson ratio, etc. In this paper, we have investigated the compression behavior of horizontal-laid and vertical-laid through air bonded nonwovens according to the compress condition such as compression load and speed. And the experimental results were compared with Van wyk, Neckar[7] and Rawal’s theories to understand the compressive behavior of through-air bonded nonwovens.

2. Experimental 2.1.

Sample preparation

Nonwovens were prepared by through-air bond method using elastic PET and low melting PET as binder fiber. Both of two fibers were bicomponent fibers, and basic properties of fibers were listed in Table 1. Nonwoven samples were manufactured by horizontal-laying and vertical laying methods, and nonwovens were carded three times before the laying process. Four types of nonwovens were prepared according to the binder fiber contents and laying methods. Basic properties of nonwovens were listed in Table 2. Table 1: Basic properties of fibers. Fiber Binder fiber PET

Fineness (de) 5 7

Strength (kgf/mm2) 0.78 1.46

Elongation (%) 43.71 44.9

Crimp number (ea/inch) 9 5.4

Fiber length (mm) 51

Density (g/cm3) 0.01 0.03

Table 2: Basic properties of nonwovens. Sample

Binder content (%)

Web formation

Basic weight (gsm)

Density

515

0.26

515

0.26

515

0.26

515

0.26

(g/㎤)

Horizontal-laid C2

80 Vertical-laid

2.2.

Test methods

Compression behavior was analyzed base on the compression resistance, compression work, recovery and hysteresis by the compression factor of Kawabata system. Also, to compare the effect of compression direction, nonwovens were compressed toward thickness, MD and CD directions. Compression behavior was measured by universal testing machine (Instron 4467, Instron, USA), Load cell was 5kgf, compression speeds were 2 and 4mm/min, maximum loads were 500 and 1000gf/cm2. Sample size was 2×2cm2.

3. Results and discussion Figure 1 shows the compression curve of the nonwovens having different binder fibers with different maximum load. The samples (C1L5) and (C1L1) contained 80wt% binder fibers were presented in Figure 1. Samples (C1L5) and (C1L1) show same compression curve, and sample(C1L1) shows higher compressive recovery than sample(C1L5). Samples (C2L5) and (C2L1) which contain 60wt% binder fibers shows a same tendency with Samples (C1L5) and (C1L1) Figure 2 presents the compression-recovery curve of samples with difference binder fiber content. Sample (C2L5) which made by 60wt% binder fibers was more compressed than sample (C1L5) at the same compression load. When the Maximum load was 1000gf/㎠, also samples (C1L1) and (C2L1) show a same tendency with 500gf/㎠

Page 773 of 1108

C1L5 C1L1

1000

800

Pressure(gf/cm2)

1000

600 400 200

C2L5 C2L1

800 600 400 200

0.2

0.4

0.6

0.8

1.0

0.2

0.4

Strain

0.6

0.8

1.0

Strain

(a) C1 (b) C2 Fig. 1: Comparison with different maximum stress.

C1L5 C2L5

1000

400

Pressure(gf/cm2)

500

300 200 100

C1L1 C2L1

800 600 400 200

0.2

0.4

0.6

0.8

1.0

0.2

0.4

Strain

0.6

0.8

1.0

Strain

(a) 500gf/㎠

(b) 1000gf/㎠

Fig. 2: Comparison with different fiber content.

Figure 3 shows compression curve of the samples with laying methods. Sample(V1) shows higher compressive resistance than sample (V2), and hysteresis of sample(V1) was lower than sample(V2). Vertical laid nonwovens exhibit the higher compressive resistance than horizontal- laid nonwoven, and recovery of vertical laid nonwovens was lower than horizontal-laid nonwoven. Also, compressive strain of vertical-laid nonwoven was lower than horizontal- laid nonwovens.

Pressure(gf/cm2)

500

V1 V2 C1

400 300 200 100 0

0.2

0.4 Strain

0.6

0.8

Fig. 3: Compression curve with different laying methods.

Figure 4 shows difference between experimental and theoretical result. Van wyk’s theory present highest error with experimental data, Compression load of Van wyk’s theory was larger than experimental because Van wyk’s theory did not consider about change of fiber volume fraction during compression. Meanwhile, to interpret the sharp increase of compression load at high compression rate, Neckar and Rawal’s theories were

Page 774 of 1108

considered with fiber volume fraction of nonwovens. Rawal’s theory shows better match than other two theories. On the other hand, experimental result of vertical-laid nonwoven was coincide with Van wyk’s theory because the vertical-laid nonwoven exhibit high compression load at the initial compress stage. Van Wyk Neckar Rawal Experimental

450

300

450

300

150

Van Wyk Neckar Rawal Experimental

600

Pressure(gf/cm2)

600

0.2

0.4

0.6

0.8

1.0

Strain

0.2

0.4

0.6

0.8

Strain

(a) C1 (b) V1 Fig. 4: Comparison between theoretical and experimental results(C1 and V1).

4. Conclusion We have investigated the compression behavior of elastic nonwovens, and compared to experimental and theoretical results. As a result, the nonwoven contained 80wt% binder fiber shows high compressive resistance, and vertical-laid nonwovens present higher compressive resistance than horizontal-laid nonwoven. When the nonwoven was compressed on fiber axis direction, the compressive resistance of nonwoven was highest value. Compression speed shows little effect on the nonwoven contained 60wt% binder fibers, and the compressive recovery was decreased with increase of maximum compress rate. In case of horizontal-laid nonwoven, Rawal’s theory shows highest agreement among the three theories, and Van wyk’s theory shows higher error than other two theories. Thus, Rawal’s theory was suitable for prediction of compressive behavior of thermalbonded elastic nonwovens which have large porosity and low density. On the other hand, vertical-laid nonwoven was coincided with Van wyk’s theory.

5. References [1] Q. Liu, Z. Lu, M. Zhu, Z. Yang, Z. Hu and J. Li, “Experimental and FEM analysis of the compressive behavior of 3D random fibrous materials with bonded networks”, J Mater Sci, 2014, 49, 1386-1398.

[2] D. V. Parikh, T. A. Calamari, W. R. Goynes, Y. Chen and O. Jirsak, “Compressibility of Cotton Blend Perpendicular-Laid Nonwovens”, TRJ, 2004, 74(1), 7-15.

[3] D. V. Parikh, T. A. Calamari, A. P. S. Sawhney, K. Q. Robert, L. Kimmel, E. Glynn, O. Jirsak, I. Mackova and T. Saunders, “Compressional Behavior of Perpendicular-Laid Nonwovens Containing Cotton”, TRJ, 2002, 72(6), 550-554.

[4] F. Mokhtari, P. M. Vaghefi, M. Shamshirsaz and M. Latifi, “Analysis of Compressibility Behavior in Warp Knitted Spacer Fabrics: Experiments and Van Wyk Theory”, Journal of Engineered Fibers and Fabrics, 2013, 8(3), 125-130.

[5] A. Rawal, P. K. Mishra and H. Saraswat, “Modeling the compression induced morphological behavior of nonwoven materials”, J Mater Sci, 2012, 47, 2365-2374

[6] A. Rawal, “Application of Theory of Compression to Thermal Bonded Nonwoven Structures”, JT I, 2009, 100, 1, 28-34. [7] D. Das and B. Pourdeyhimi, “Compressional and Recovery Behavior of Highloft Nonwovens”, RJ, 2010, 35, 303-309. [8] A. Rawal, “Structure Analysis of PoreSize Distreibution of Nonwovens”, JTI, 2010, 101(4), 350-359. [9] F. Mokhtari, P. M. Vaghefi, M. Shamshirsaz and M. Latifi, “Analysis of Compressibility Behavior in Warp Knitted Spacer Fabrics: Experiments and Van Wyk Theory”, Journal of Engineered Fibers and Fabrics, 2013, 8(3), 125-130.

[10] S. Jaganathan, H. V. Tafreshi, E. Shim and B. Pourdeyhimi, “A study on compression-induced morphological changes of nonwoven fibrous materials”, Colloids and Surfaces A: Physicochem. Eng. Aspects, 2009, 173-179.

Page 775 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Cotton Bale Laydown Management Using Fuzzy C-Means Algorithm Subhasis Das1 +, Anindya Ghosh1 and Abul Hasnat2 1

Department of Textile Technology, Government College of Engineering & Textile Technology, Berhampore, West Bengal, India-742 101 2 Department of Computer Science & Engineering, Government College of Engineering & Textile Technology, Berhampore, West Bengal, India-742 101

Abstract. In this paper a new technique has been proposed for cotton bale management. Fuzzy c-means clustering algorithm has been applied for clustering cotton bales into 5 categories from 1200 randomly chosen bales of J-34 variety. In order to cluster bales of different categories, eight fibre properties, viz., strength, elongation, upper half mean length, length uniformity, short fibre content, micronaire, reflectance and yellowness of each bale have been considered. The fuzzy c-means algorithm can handle the imprecisions that present in cotton fibre properties compared to K-means clustering method. Once the bales are clustered into different categories, it is possible to prepare consistent bale mix for consecutive lay downs on the basis of frequency relative picking method. This method is suitable for consistent picking of different bale mixes from any number of bales in the warehouse. Keywords: Cotton bale, cluster analysis, fibre property, fuzzy logic, fuzzy c-means algorithm.

1. Introduction Cotton fibre is non-homogeneous and has very high variability in its characteristics. Conversion of cotton fibres into yarns with consistent quality throughout the year is an esteemed goal sought by every spinning industry. This goal can be fulfilled with the aid of a sound bale management system. If the cotton bales are grouped on the basis of individual fibre properties, the number of category combinations will be very high and practically uncontrollable. To overcome this situation, bales should be grouped on the basis of some overall quality index of cotton fibre. Bale management technique for consistent end product demands the grading of each and every bale in the population on the basis of fibre properties. In 1980, a computerized bale management technique, Engineered Fiber Selection (EFS) system was developed [1, 2]. The main drawback of the EFS is that as the number of fibre criteria and their levels increase, the number of category combination increases overwhelmingly. In an attempt to simplify the bale management system, some effective indices such as the fiber quality index (FQI), the spinning consistency index (SCI), and the premium discount index (PDI) have been developed based on the multivariate regression model [3]. These indices usually depend on the range of bales used to formulate the equations and seldom generalize to characterize the complex multivariate nature of cotton fiber properties. The SCI regression equation contemplates a linear relationship between HVI measured cotton fibre properties and some yarn properties such as strength, appearance and neppiness. However, a highly non-linear relationship actually exists between fibre and yarn properties. In addition SCI regression equation was derived based on the fibre properties of Pima and Upland cotton and it may not replicate a good fit with the other cotton. Authors in their earlier work [3] proposed K-means square clustering technique of cotton bale management in which a set of cotton bales were clustered into few groups by minimizing the within-group Euclidean distance of each member in a cluster and its cluster centre and maximizing the Euclidean distance between the cluster centres. Eight HVI fibre properties of each cotton bale were considered in the study. Basically the Kmeans square clustering method is used to classify the cotton bales in a crisp sense, i.e. each bale will be assigned to one, and only one, data cluster. The fibre properties for K-means square clustering algorithm must +

Corresponding author. Tel.: + 91-3482-252809. E-mail address: subhasis.tex@gmail.com

Page 776 of 1108

be precise and well defined. However, this is not always a realistic assumption. In practice, a spinner often uses the terms like low or high to assess the fibre properties like fineness, length, strength etc., which do not constitute well defined boundaries. Considering the abovementioned drawbacks of the K-means square clustering algorithm, Fuzzy c-means (FCM) algorithm has been proposed in this work to handle the imprecision in such situation.

2. Fuzzy Logic and Membership Functions The concept of Fuzzy Logic was fathered by Lotfi A. Zadeh (1965) at university of California at Berkeley, USA. A classical crisp set is a container that wholly includes or wholly excludes any given element. Suppose that we have a crisp set A which contains the individual elements x. Mathematically, if x â&#x2C6;&#x2C6; A ďŁą1, Âľ A ( x) = ďŁ˛ (2.1) if x â&#x2C6;&#x2030; A ďŁł0, where Âľ A ( x ) indicates the unambiguous membership of element x in set A. Obviously, Âľ A ( x) is either 0 or 1. On the contrary, the fuzzy set contains elements with only a partial degree of membership, i.e., membership of an element in the fuzzy set is not a matter of affirmation or rejection, but solely its degree of belongingness. Figure 1 depicts the crisp vs. fuzzy sets. A striking difference between crisp and fuzzy sets lies in the nature of their membership functions which are illustrated in Figure 2. For a fuzzy set, a membership function maps its elements onto a space in the interval between 0 and 1. Symbolically, Âľ Aď&#x20AC;Ľ ( x ) â&#x2C6;&#x2C6; [0,1] (2.2) ď&#x20AC;Ľ ď&#x20AC;Ľ is where Âľ Aď&#x20AC;Ľ ( x ) is the degree of membership of element x in fuzzy set A . Commonly, fuzzy set A expressed in terms of ordered pairs as: ď&#x20AC;Ľ = {x, Âľ ď&#x20AC;Ľ ( x)| x â&#x2C6;&#x2C6; X } A A

(2.3) All properties of crisp set are also applicable for fuzzy sets except for the excluded-middle laws. In fuzzy set theory, the union of fuzzy set with its complement does not yield the universe and the intersection of fuzzy set and its complement is not null. This difference is shown below. For crisp sets,

For fuzzy sets,

Fig.1: An illustration of crisp set (left) and fuzzy set (right)

đ??´đ??´ â&#x2C6;Ş đ??´đ??´đ??śđ??ś = đ?&#x2018;&#x2039;đ?&#x2018;&#x2039; đ??´đ??´ â&#x2C6;Š đ??´đ??´đ??śđ??ś = â&#x2C6;&#x2026;

đ??´đ??´Ě&#x192; â&#x2C6;Ş đ??´đ??´Ě&#x192;đ??śđ??ś â&#x2030; đ?&#x2018;&#x2039;đ?&#x2018;&#x2039; đ??´đ??´Ě&#x192; â&#x2C6;Š đ??´đ??´Ě&#x192;đ??śđ??ś â&#x2030; â&#x2C6;&#x2026;

(2.4)

(2.5)

Fig. 2: Representation of membership function for crisp and fuzzy sets

3. Theory of Cluster Analysis Cluster analysis involves categorization; dividing a large group of observations into smaller groups so that the observations within each group are relatively similar and they possess largely the same characteristics. The observations in different groups are relatively dissimilar. In other word, the cluster analysis aims at grouping data objects of similar kind into respective categories or clusters in such a way that the degree of association between two objects is maximum if they belong to the same group and minimum otherwise [4].

Page 777 of 1108

K-means square clustering algorithm is one of the simplest unsupervised learning algorithms that solve the well known clustering problem. The procedure follows a simple and easy way to classify a given set of n vectors, each of m dimension. V= {v 1 , v 2 , â&#x20AC;Ś.., v m } into a K number of clusters G={ g 1 , g 2 , â&#x20AC;Ś.., g k } (k clusters fixed a priori). The main idea is to define K centroids (C 1 , C 2 , â&#x20AC;Ś, C K ), one for each cluster and taking each of vectors belonging to the given set and associate it to the nearest centroid C i and include it in the cluster g i .

4. Fuzzy C-means Algorithm Bezdek [5] developed an extremely powerful classification method to accommodate fuzzy data. In this algorithm a single point can have partial membership in more than one class, which is not possible in Kmeans square algorithm. A family of fuzzy sets {Ai , i = 1, 2,....c} is a fuzzy c-partition on a universe of data points X. Then membership value of the kth data point in the ith fuzzy cluster is Âľ ik = Âľ Ai ( x k ) â&#x2C6;&#x2C6; [0, 1] with the constraint c

that sum of all membership value is unity i.e. â&#x2C6;&#x2018; Âľ ik = 1 for all đ?&#x2018;&#x2DC;đ?&#x2018;&#x2DC; = 1, 2, . . , đ?&#x2018;&#x203A;đ?&#x2018;&#x203A;. The steps of the algorithm are as i =1

follows [4]: Step 1: Fix c (2 â&#x2030;¤ c < n) and select a value for parameter m'. Initialize the partition matrix, U (0)' . Each step in this algorithm will be labeled r, where r = 0, 1 , 2 , â&#x20AC;Śâ&#x20AC;Ś.. Step 2: Calculate c centers vi(r ) for each step using n

â&#x2C6;&#x2018; Âľikm . xkj

vij =

k =1 n

;

â&#x2C6;&#x2018; Âľ ikm

where j = 1, 2, â&#x20AC;Ś m

(4.1)

k =1

Step 3: Update the partition matrix for the rth step, U ( r )' as follows :

or, where and and

đ?&#x153;&#x2021;đ?&#x153;&#x2021;đ?&#x2018;&#x2013;đ?&#x2018;&#x2013;đ?&#x2018;&#x2013;đ?&#x2018;&#x2013; (đ?&#x2018;&#x;đ?&#x2018;&#x;+1) = ďż˝â&#x2C6;&#x2018;đ?&#x2018;?đ?&#x2018;?đ?&#x2018;&#x2014;đ?&#x2018;&#x2014;=1 ďż˝

đ?&#x2018;&#x2018;đ?&#x2018;&#x2018;đ?&#x2018;&#x2013;đ?&#x2018;&#x2013;đ?&#x2018;&#x2013;đ?&#x2018;&#x2013; (đ?&#x2018;&#x;đ?&#x2018;&#x;) (mĘš â&#x2C6;&#x2019;1)

đ?&#x2018;&#x2018;đ?&#x2018;&#x2018;đ?&#x2018;&#x2014;đ?&#x2018;&#x2014;đ?&#x2018;&#x2014;đ?&#x2018;&#x2014; (đ?&#x2018;&#x;đ?&#x2018;&#x;)

ďż˝

â&#x2C6;&#x2019;1

Âľik ( r +1) = 0 for all classes i where i đ?&#x153;&#x2013;đ?&#x153;&#x2013;đ??źđ??źđ?&#x2018;&#x2DC;đ?&#x2018;&#x2DC;â&#x20AC;˛ I k = { i | 2 â&#x2030;¤ c < n; đ?&#x2018;&#x2018;đ?&#x2018;&#x2018;đ?&#x2018;&#x2013;đ?&#x2018;&#x2013;đ?&#x2018;&#x2013;đ?&#x2018;&#x2013;

(đ?&#x2018;&#x;đ?&#x2018;&#x;)

for đ??źđ??źđ?&#x2018;&#x2DC;đ?&#x2018;&#x2DC; = â&#x2C6;&#x2026;

=0}

đ??źđ??źđ?&#x2018;&#x2DC;đ?&#x2018;&#x2DC;â&#x20AC;˛ = { 1,2,â&#x20AC;Ś..,c } - đ??źđ??źđ?&#x2018;&#x2DC;đ?&#x2018;&#x2DC;

â&#x2C6;&#x2018;đ?&#x2018;&#x2013;đ?&#x2018;&#x2013;â&#x2C6;&#x2C6;đ??źđ??źđ?&#x2018;&#x2DC;đ?&#x2018;&#x2DC; đ?&#x153;&#x2021;đ?&#x153;&#x2021;đ?&#x2018;&#x2013;đ?&#x2018;&#x2013;đ?&#x2018;&#x2013;đ?&#x2018;&#x2013; (đ?&#x2018;&#x;đ?&#x2018;&#x;+1) = 1

(4.2) (4.3) (4.4) (4.5) (4.6)

Step 4: If ďż˝U (r+1)â&#x20AC;˛ â&#x2C6;&#x2019; U (r)â&#x20AC;˛ ďż˝â&#x2030;¤ Ďľ L , stop; otherwise set r = r +1 and return to step 2.

In step 4, a matrix norm || || of two successive fuzzy partitions is compared to a prescribed level of accuracy, Ďľ L , to determine whether the solution is good enough. The parameters I k and Iď&#x20AC;Ľk comprise a bookkeeping system to handle situations when some of the distance measures, d ij , are zero, or extremely small in a computational sense.

5. Application of FCM in Bale Management 1200 randomly chosen cotton bales of J-34 variety (suitable for 20â&#x20AC;&#x2122;s Ne mixing) were tested in a Indian spinning mill using Uster HVI-900 instrument to measure different fibre properties, viz., fibre strength (FS), fibre elongation (FE), upper half mean length (UHML), length uniformity index (UI), micronaire (Mic), reflectance (Rd), and yellowness (+b) for each and individual bale. The short fibre index (SFI) of each bale was tested by Uster AFIS instrument. If there are 5 groups each of which belongs to fibre strength and UHML, and 4 groups to fibre elongation, UI, SFI, micronaire, Rd and +b, the cotton bale population can be assumed to comprise of 52Ă&#x2014;46, i.e., 102400 varieties of bales. It is an unrealistic task to make a consistent selection of 40-bale mix from such a huge population of cotton bales. This apparently impossible task can be handled by employing FCM cluster algorithm for grouping the cotton bales into respective groups. The FCM can also

Page 778 of 1108

handle the the variability and imprecision that present in the cotton fibre properties. Hence a single cotton bale can have partial membership in more than one class. MATLAB 7.11 coding is used to execute the problem on a 2.6 GHz. PC. Figure 3 illustrates the belonging of the individual bales into 5 different clusters. The proportion of bales into 5 different clusters is given in Table 1. The number of bales belonging to cluster number 1 to 5 are 234, 254, 175, 245, and 292 respectively, which constitutes a ratio of 4: 4: 3: 4: 5 after rounding off. Now frequency relative picking method may well be employed for the consistent selection of cotton bales. Table 1: Proportion of bales into 5 different clusters Cluster No. 1 2 3 4 5

No. Of bales 234 254 175 245 292

Proportion of bales (%) 19.50 21.17 14.58 20.42 24.33

Cluster Number

4 3 2 1 0 0

200

400

600

800

1000

1200

Bale number Fig. 3: Clustering of 1200 bales in 5 group

6. Conclusion Fuzzy c-means based cotton bale management technique gives consistent selection of cotton bales. Present study has been conducted on 1200 randomly chosen cotton bales of J-34 variety to partition into 5 categories. Hence, it is possible to prepare a consistent 40-bale mix for 30 consecutive lay downs using the frequency relative picking method. This method is also suitable for consistent picking of different bale mixes from any number of bales in the warehouse. The proposed method is more realistic and capable of handling the imprecision that present in the cotton fibre properties.

7. References [1] Lewis H. L. (1989), Proceedings of Beltwide Cotton Conferences, Nashville, USA. [2] Chewning C., Zeplin J., and Vodicka S. (1994), Proceedings of Belt wide Cotton Conferences, San Diego, USA,. [3] Ghosh, A., Majumdar, A., and Das, S. (2012), A Technique of Bale Lay down Using Clustering Algorithm, Fibers and Polymers, 13(6), 809-813. [4] Ross, T. J. (2005), Fuzzy Logic with Engineering Applications, 2nd Edition, John Willey & Sons (Asia) Pte. Ltd., Singapore. [5] Bezdek J. (1981), Pattern recognition with fuzzy objective function algorithms, Plenum, New York.

Page 779 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Degradable Chitosan/Polyvinyl Alcohol Coronary Stents: Effects of Genipin Cross-Linking on Structure and Mechanical Properties Mei-Chen Lin 1, Jan-Yi Lin1, Ching-Wen Lou 2 and Jia-Horng Lin 1

1, 3, 4 +

Abstract. This study aims to examine the relationship between the Genipin cross-linking and the degradable polyvinyl alcohol (PVA) coronary stents that are coated with chitosan, in terms of their structure and mechanical properties. A braiding process is administered to produce degradable PVA coronary stents. The coronary stents are coated with chitosan films while being in a rotary status, and then cross-linked by using Genipin. Next, the coronary stents are observed by incorporating a stereoscopic microscope, and their pore area, coverage fraction, and cross-section reduction are then evaluated for their applications. The test results indicate that the coronary stents are network-constructed and are in a hollow and tubular form. This study proves that the administration of Genipin cross-linking is conducive to the PVA coronary stents that are successfully produced with more satisfactory requirements.

Keywords: polyvinyl alcohol (PVA), coronary stents, chitosan, Genipin, braid.

1. Introduction The heart is a crucial organ in the human body, and it pumps blood to all body parts and conduct the oxygen exchange in lungs. In order to retain the heartâ&#x20AC;&#x2122;s function, continuous oxygen and nutrition provision are indispensable, and the coronary arteries are in charge of these functions. When the coronary arteries suffer from Atherosclerosis, the blood vessels gradually become narrow and can be then possibly blocked that discontinues the provision of oxygen and nutrition, and then causes death of the patient.Coronary stents are thus developed for treatment of Atherossierosis. They are initially made by using metal [1], but metallic stents may cause wounds and infections when expanding the vessels. This may cause a proliferation of vascular smooth runscle cells (VSMC), and leads to Restenosis [2]. In order to prevent Restenosis, drug eluting stents (DES) are thus developed accordingly. DES takes advantage of the mobility of blood currents in order to attain drug release. However, medicine can refrain from the proliferation of VSMC and the growth of endothelial cells. Hematoblasts can then easily form gores over existing wounds, and gores may peel and lead to thrombus that has high fatal possibility [3]. Coronary stents are a biomedical material that requires a biodegradation. The trend in research materials for biodegradation includes the administration of chitosan, gelatin, and polyvinylalcohol (PVA) [4]. In addition, the cross-linking agent of Genipin is comparable to glutaraldehyde in terms of the mechanical strengths and degradation rate. Genipin also can decrease the biological toxicity that other synthesized cross-linking agents may cause [5]. Therefore, this study aims developing a model for degradable coronary stents. The dominant material is PVA, which is biodegradable. PVA plied yarns are braided into stents by incorporating a braiding technique, after which the stents are Genipin cross-linked in order to have a stabilized structure. The coronary stents are examined for their applications, including an observation by using a stereoscopic microscope along with evaluations of coverage fraction, mesh size, and shrinking rate of cutting sections. +

Corresponding author. Tel.: + 886-4-2451-8672. E-mail address: jhlin@fcu.edu.tw

Page 780 of 1108

2. Experimental 2.1.

Materials

Polyvinylalcohol (PVA) plied yarns (Asiatic Fiber Corporation, Taiwan, R.O.C.) have a 75D fineness and 80℃water solubility. Genpin is purchased from Challenge Bioproducts, Taiwan, R.O.C.

2.2.

PVA Coronary Stents

PVA plied yarns are wound surrounding sixteen carriers by using an automatic wefting bobbin winder (SY-01, Nan Hsing Machinery & Co., Ltd., Taiwan, ROC. The carriers are then mounted in a 16-spindle braid machine (Nan Hsing Machinery & Co., Ltd., Taiwan, R.O.C.) with a braiding speed being 18rpm. The braiding gear has a tooth number of 50 while the take-up gear has a tooth number of 80. The PVA plied yarns are braided surrounding a 3-mm soft tube, which is replaced by a 3-mm stainless steel mandrel. The braids are then thermally treated at 140℃ for thirty minutes, and thereby allows for the re-arrangement of molecules and a stabilized structure.

2.3.

Cross-linking Methods of Genipin Solution

The PVA coronary stents along with the stainless steel mandrel are affixed to an automatic stirrer, after which they are rotated in a 50ml of 0.5% chitosan solution with a speed of 500 rpm for 5 minutes. Chitosan is adhered to PVA coronary stents via a physical adhesion. The chitosan-coated PVA coronary stents are dried at 40 ℃, followed by Genipin cross-linking of various concentrations, and then washing with ethoxide three times, in order to form the degradable polymer-coated PVA coronary stents. The specification of samples is tabulated in Table 1. Table 1. Denotation and specification of samples Denotation N A B C D E F G H I

2.4.

Experimental Materials Chitosan-Coated (Control Group)

Chitosan-Coated PVA Coronary Stents

Genipin Concentration(%) 0.05 0.5 1 0.05 0.5 1 0.05 0.5 1

Cross-Linking Duration (hrs) 12 12 12 24 24 24 48 48 48

Tests

Surface Observation and Coverage Fraction A stereomicroscopic (SMZ-10A, Nikon Instruments Inc., Japan) is used to observe the morphology and photograph the samples, and the images are developed by using Motic Images Plus 2.0 software (Motic Group Co., Ltd., USA). Afterwards, the coverage fraction is measured by the Image Pro Plus (Media Cybernetics, Inc., USA) and is calculated by using the equation as follows. Coverage Fraction = (area of fibers/tubular area)×100% (1.1)

Mesh Area and Shrinkage Rate of Cutting Section The images developed by Motic Images Plus 2.0 software are then used for the analyses of mesh area and shrinkage rate of cutting section. The analyses demonstrate the influences of the coating parameters of PVA coronary stents on their mesh area and shrinkage rate of cutting section. The equation for shrinkage rate of cutting section is as follows. Shrinkage Rate of Cutting Section (%) = (L 0 -L t )/L0×100 % (1.2) where L 0 is the original diameter of PVA coronary stents and Lt is the diameter of the chitosan-coated coronary stents.

Page 781 of 1108

3. Results and Discussion 3.1.

Surface Observation

Fig. 1: Stereomicroscopic images (20Ă&#x2014;) of chitosan-coated PVA coronary stents as related to various Genipin cross-linking durations. The scale bar is 1mm. As indicated in Figure 1, in comparison of the control group (i.e., N) and experimental group (i.e., A-I), there are no significant differences in the structure whether or not the PVA coronary stents are Genipin crosslinked. All samples remain their braid structure with a hollow, tubular form. The darkening shades are as a result of the cross-linking between chitosan and Genipin for an increasing duration. This result is in conformity with the findings in study by Gao et al. in 2014, which is ascribed to a higher cross-linking level between chitosan and Genipin [6].

3.2.

Mesh Area and Section Shrinkage

According to the mesh area of A-I in Figure 2, the mesh area is found to be slightly enlarged as a result of incorporating a stainless steel mandrel. PVA fibers are water soluble, and they swell and then shrink in water. A temperature of 80â&#x201E;&#x192; is another factor that causes PVA fibers to dissolve. In addition, an immersion in a chitosan solution and cross-linking agent also possibly cause part of PVA plied yarn to dissolve, and the mesh size of the braids is thus increased.

Fig. 2: Mesh area of chitosan-coated PVA coronary stent as related to various Genipin cross-linking durations. It is also proven that the coronary stents supported with a stainless steel mandrel during the cross-linking process contribute to the stability of the formation of their hollow tubular formation, as indicated in Figure 3. The incorporation of the mandrel helps to retain the braiding structure, and improves the disadvantage of PVA coronary stents that water can permeate them. Therefore, the chitosan can be adsorbed by coronary stents, and then cross-linked with Genipin.

Page 782 of 1108

Fig. 3: Shrinking rate of cutting sections of chitosan-coated PVA coronary stent as related to various Genipin cross-linking durations.

3.3.

Coverage Fraction

Table 2 shows that the PVA coronary stents proposed by this study have a higher coverage fraction than the commercially available coronary stents (MULTI-LINK VISION Coronary Stent, Abbott) and this result is ascribed to metallic materials. Metallic materials are mechanically stronger than polymer materials, and thus can retain their formation when the resulted coronary stents have a high porosity [7]. This study also incorporates the polymer as the support material by using a braiding technique, and uses a higher coverage fraction to retain the tubular structure of the PVA coronary stents. Table 2. Comparison of strut cover rate of PVA coronary stents as related to chitoan coating

Strut Cover Rate (%)

Commercially Available Coronary Stent 22

4. Conclusions This study successfully incorporates a braiding technique to form degradable chitosan-coated PVA coronary stents that are constructed in a reticulate, tubular form. The test results indicate that the administration of chitosan coating and Genipin cross-linking can slightly decreases the mesh area by 42.3%. In addition, using a stainless steel mold can also provide the stents with a complete structure. In comparison to the commercially available metallic stents, the degradable PVA coronary stents have a 150% greater strut cover rate. This study has proven that stabilized manufacturing using a mold and a careful options of materials both contribute to production of coronary stents that meet the current manufacturing requirements and are able to decrease their damages to human body.

5. Acknowledgements The authors would like to thank Ministry of Science and Technology of Taiwan, for financially supporting this research under Contract MOST 103-2622-E-166-001-CC2.

6. References [1]T. Simard, B. Hibbert, F. D. Ramirez, M. Froeschl, Y. X. Chen, and E. R. O'Brien, Canadian Journal of Cardiology, 30, 35 (2014). [2]M. C. Chen, H. F. Liang, Y. L. Chiu, Y. Chang, H. J. Wei, and H. W. Sung, Journal of Controlled Release, 108, 178 (2005). [3]T. Higo, Y. Ueda, K. Matsuo, M. Nishio, A. Hirata, M. Asai, T. Nemoto, A. Murakami, K. Kashiwase, and K. Kodama, Thrombosis Research, 128, 431 (2011). [4]A. Tan, Y. Farhatnia, A. de Mel, J. Rajadas, M. S. Alavijeh, and A. M. Seifalian, Journal of Biotechnology, 164, 151 (2013). [5]R. A. A. Muzzarelli, Carbohydrate Polymers, 77, 1 (2009). [6]L. Gao, H. Gan, Z. Y. Meng, R. L. Gu, Z. N. Wu, L. Zhang, X. X. Zhu, W. Z. Sun, J. Li, Y. Zheng, and G. F. Dou, Colloids and Surfaces B-Biointerfaces, 117, 398 (2014).

Page 783 of 1108

[7]J. A. Ormiston and P. W. S. Serruys, Circulation-Cardiovascular Interventions, 2, 255 (2009).

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Determination of nonylphenol ethoxylate and octylphenol ethoxylate surfactants in textiles by liquid chromatography high-resolution mass spectrometry Xiwen Ye1, Xin Luo1, Zengyuan Niu1 +, Li Zhang1,2 1 2

Shandong Entry-Exit Inspection and Quarantine Technical Center of China, Qingdao 266000, China

College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266000, China

Abstract. Nonylphenol ethoxylates (NP(EO)n) and octylphenol ethoxylates (OP(EO)n) are highly toxic substances, which were widely used in textile industries. The present work is focused on developing a comprehensive method of liquid chromatography high-resolution mass spectrometry for the determination of NP(EO)n and OP(EO)n in textiles. Different extraction methods were evaluated. Ultimately, samples were extracted by ultrasonic assistant extraction in methanol and then analysed by LC coupled with highresolution mass spectrometry. The LOQ values of NP(EO)4-19 and OP(EO)3-17 oligomers were in the range of 0.1-2.2 mg/kg. With Commission Decision 2002/657/EC and OEKO-Tex Standard 100 as guidelines, recoveries were evaluated at three different concentration levels. The recovery ranged from 80% to 110% and the relative standard deviation (RSD %) was below 8%. 25 commercial textile samples were analysed. NP(EO)n was commonly detected in most samples with concentrations ranging from 2 mg/kg to 224 mg/kg, while OP(EO)n was not found. The method was proved to be rapid, precise and sensitive. Keywords: nonylphenol ethoxylate; octylphenol ethoxylate; liquid chromatography; high-resolution mass spectrometry; textile

1. Introduction Alkylphenol polyethoxylates (APEOs) are a group of non-ionic surfactants that are widespread applied in textile industries [1, 2]. Among APEOs, nonylphenol ethoxylates (NPEOs) and octylphenol ethoxylates (OPEOs) are the most commonly used compounds. Although APEOs are not classified as highly toxic substances, some of their metabolites, such as nonylphenol (NP), octylphenol (OP) and short chain APEOs, show estrogenic activity in vitro and cause a number of estrogenic responses in vivo in various aquatic organisms [3,4]. The International Association for Research and Testing in the Field of Textile Ecology has issued the OEKO-TEX Standard 100, in which NPEOs and OPEOs were listed as major hazardous compounds and their use was limited in textiles. Methods used to analyse APEOs included GC-MS [5,6], LC-MS and LC-MS/MS [7-9], while the physico-chemical properties of APEOs (moderate polarity, low volatility) make the latter two technics more suitable [10]. Among different MS detectors, the Orbitrap with high resolution and high mass accuracy shows high sensitivity and selectivity, which can allow for the analysis of targets in complex matrices with minimum or even no sample clean-up. To the best of our knowledge, no studies have been reported on the detection of APEOs in textiles using Orbitrap. In this work, a rapid and reliable determination method for the detection of NPEOs and OPEOs in textiles was established using the LC-LTQ/Orbitrap.

2. Experimental 2.1.

Materials and chemicals

Methanol and acetonitrile (HPLC-MS grade) were purchased from Merck (Darmstadt, Germany). Ammonium acetate (HPLC-grade) was purchased from Sigma Aldrich (Steinheim, Germany). Ultrapure Milli-Q water with 18.2 Mâ&#x201E;Śâ&#x20AC;˘cm-1 was obtained using a Milli-Q Advantage A10 system (Millipore, Milford,

Corresponding author. Tel.: + 86-0532-88968060. E-mail address: zyniuqd@hotmail.com.

Page 785 of 1108

MA, USA). 4-nonylphenyl-polyethylene glycol (NP(EO)n) and triton TM X-100-bioxtra (OP(EO)n)were purchased from Sigma Aldrich (Steinheim, Germany).

2.2.

Sample preparation

A total of 0.5 g of homogenized, spiked textiles (5 mm×5 mm) were weighed into 40 mL glass tubes. 40 mL methanol was added, and the tubes were capped and extracted by an ultrasonic generator at a temperature of 45 ℃ for 30 min. 200 μL supernatant was diluted with methanol/water (1/1, v/v) to a volume of 1 mL and filtered by a 0.22 μm PTFE membrane before analysis.

2.3.

LC and MS conditions

Analyses were performed on an Agilent 1100 Series LC systems (Waldbronn, Germany). The analytes were separated on an Accucore C18 column (100 mm×2.1 mm, 2.6 μm, Thermo Fisher, MA, U.S.A). A binary mobile phase with 5 mmol/L ammonium acetate in Milli-Q water (A)-acetonitrile (B) was used at a flow rate of 0.25 ml/min. The LC gradient elution program was as follows: 0-8 min, 60-90% B, 8-12 min, 90% B, 12-14 min, 60% B, 14-20 min, 60% B. The LTQ/Orbitrap XL (Thermo Fisher, MA, U.S.A) was equipped with an electrospray ionization (ESI) source. APEOs were detected in positive ionization mode and related parameters were as follows: Ispray voltage, 3 kV, capillary voltage, 30 V, tube lens, 70 V, vaporizer temperature, 50 °C, capillary temperature, 350 °C, sheath gas flow rate, 30 arbitrary units, auxiliary gas flow rate, 10 arbitrary units. Rapid screening data acquisition occurred under the full-scan mode with a resolution of 30,000 and a scan range of m/z 1001200. The MS2 confirmation was performed with a resolution of 7500. Collision-induced dissociation (CID) (at normalized collision energy of 35%) was performed. The retention times and targeted MS parameters of the LC-LTQ/Orbitrap for the analysis of APEOs oligomers are shown in Table 1. Table 1 The retention times and targeted MS parameters of HPLC-LTQ/Orbitrap for APEOs Oligomer NP(EO)4 NP(EO)5 NP(EO)6 NP(EO)7 NP(EO)8 NP(EO)9 NP(EO)10 NP(EO)11 NP(EO)12 NP(EO)13 NP(EO)14 NP(EO)15 NP(EO)16 NP(EO)17 NP(EO)18 NP(EO)19 OP(EO)3 OP(EO)4 OP(EO)5 OP(EO)6 OP(EO)7 OP(EO)8 OP(EO)9 OP(EO)10 OP(EO)11 OP(EO)12 OP(EO)13 OP(EO)14 OP(EO)15 OP(EO)16 OP(EO)17

RT/(min) 6.45 6.33 6.20 6.01 5.84 5.66 5.49 5.31 5.14 5.01 4.85 4.69 4.55 4.43 4.29 4.18 4.41 4.32 4.22 4.11 3.97 3.84 3.72 3.60 3.49 3.38 3.29 3.20 3.11 3.03 2.95

Formula [M+NH4]+ N+

C23H44O5 C25H48O6N+ C27H52O7N+ C29H56O8N+ C31H60O9N+ C33H64O10N+ C35H68O10N+ C37H72O12N+ C39H76O13N+ C41H80O14N+ C43H84O15N+ C45H88O16N+ C47H92O17N+ C49H96O18N+ C51H100O19N+ C53H104O20N+ C20H38O4N+ C22H42O5N+ C24H46O6N+ C26H50O7N+ C28H54O8N+ C30H58O9N+ C32H62O10N+ C34H66O11N+ C36H70O12N+ C38H74O13N+ C40H78O14N+ C42H82O15N+ C44H86O16N+ C46H90O17N+ C48H94O18N+

Theoretical/m/z

Measured/m/z

414.32140 458.34761 502.37382 546.40003 590.42624 634.45245 678.47866 722.50487 766.53108 810.55729 854.58350 898.60971 942.63592 986.66213 1030.68834 1074.71455 356.27954 400.30575 444.33196 488.35818 532.38439 576.41061 620.43682 664.46304 708.48925 752.51547 796.54168 840.5679 884.59402 928.62033 972.64654

414.32156 458.34790 502.37324 546.40027 590.42676 634.45306 678.47943 722.50549 766.53156 810.55768 854.58405 898.61035 942.63672 986.66284 1030.68909 1074.71545 356.27884 400.30582 444.33191 488.35788 532.38446 576.41083 620.43713 664.46344 708.48962 752.51563 796.54181 840.56812 884.59436 928.62061 972.64679

Accuracy/(∆ppm) 0.4 0.6 -1.2 0.4 0.9 1.0 1.1 0.9 0.6 0.5 0.6 0.7 0.8 0.7 0.7 0.8 -2.0 0.2 -0.1 -0.6 0.1 0.4 0.5 0.6 0.5 0.2 0.2 0.3 0.4 0.3 0.3

Page 786 of 1108

3. Results and discussion 3.1.

Comparison of extraction methods

To evaluate the possibility of substituting traditional Soxhlet extraction [11,12] by the more rapid and solvent-saving UAE [8,13], methanol was used as extraction solvent and both the traditional Soxhlet procedure and UAE were tested. Soxhlet extraction was carried out as following procedures: Triplicate samples (0.5 g, 5 mm × 5 mm) of homogenized, spiked textiles were placed in glass fiber thimbles and extracted for 3 h with 150 mL methanol in a Soxhlet apparatus, and the reflux rate was 1-2 drops/s. The extracts were then evaporated to dryness by rotary evaporation at 40 ℃ and 50 mL methanol was added to dissolve the residuals. 100 μL supernatant was diluted with methanol/water (1/1, v/v) to a volume of 1 mL and filtered by a 0.22 μm PTFE membrane before analysis. UAE was operated according to part 2.3 and three parallel assays were carried out for each matrix. Results revealed that the recovery results for three textile matrix were similar and the extraction efficiency of UAE was higher than Soxhlet extraction for all target compounds. Take the major NP(EO)n and OP(EO)n oligomers in polyesters as an example, the obtained recovery results were shown in Fig. 1.

120

UAE Extraction Soxhlet Extraction

Polyester

Recovery (%)

100

OP (E O) 7 OP (E O) 8 OP (E O) 9 OP (E O) 10 OP (E O) 11 NP (E O) 9 NP (E O) 10 NP (E O) 11 NP (E O) 12 NP (E O) 13

Fig. 1 Comparison of Soxhlet and ASE extraction efficiency of NP(EO)n and OP(EO)n in three different kinds of textile samples (n=3)

3.2.

Chromatography conditions

According to previous reports, the polyethylene oxide chain of the APEOs can trap metal ions, such as sodium, potassium and ammonium, to form a complex [14, 15]. And the ammonium adducts are well suited to perform MS/MS fragments, which allowed greater selectivity of the analytes of interest [1, 3, 9]. Therefore, this work chose 5 mmol/L ammonium acetate as mobile phase to ensure the ammonium adducts prevail in the spectrum and to improve selectivity of the analytes. Results revealed that the major adducts of NP(EO)n and OP(EO)n oligomers were [M+NH4]+.

3.3.

Method validation

Quantification for single NP(EO)n and OP(EO)n was performed by assuming that the response factors of individual oligomers are the same at unit concentrations [16,17]. A representative distribution of individual NP(EO)n and OP(EO)n oligomers was based on its abundance ratios of standard mass spectrums (NP(EO)n/NP(EO)n mixture). The distribution ratio for each oligomer was showed in Fig. 2. Linearity was evaluated in the range of 2-2000 μg/L as the sum of NP(EO)n or OP(EO)n. The calibration curve was based on the peak area versus concentration. Concentrations of each oligomer were normalized by the distribution ratio displayed in Fig. 2. All oligomers of NP(EO)4-19 or OP(EO)3-17 exhibited a good linearity in its own normalized range, and the correlation coefficients exceeded R2>0.99. Matrix effects were expressed as the matrix-matched calibration slope to solvent calibration ratio in the whole calibration range. The results showed that the matrix effects of the targets ranging from 94% to 116% were not significant and can be neglected.

Page 787 of 1108

13.5% 13.5%

12.2% 12

10.3%

Distribution ratio (%)

13.2%

11.6%

10.4% 8.3% 8

7.3%

5.2% 4.5%

14.6% 14.2%

3.3%

2.9% 2.7%

2.0% 1.1%

0.4%

6.4%

6.5%

6 4 2

0.6%

9.5%

3.7% 1.8% 0.6%

3.6% 1.8% 0.9% 0.5%

0 1 2 3 4 5 6 7 8 9 4 5 6 7 8 9 O) O) O) O) O) O) )1 )1 )1 )1 )1 )1 )1 )1 )1 )1 (E (E (E (E (E (E EO EO EO EO EO EO EO EO EO EO NP NP NP NP NP NP NP( NP( NP( NP( NP( NP( NP( NP( NP( NP(

1 0 3 2 5 4 7 6 4 3 6 5 8 7 9 O) EO) EO) EO) EO) EO) EO) O)1 O)1 O)1 O)1 O)1 O)1 O)1 O)1 ( (E ( ( ( ( ( E E E E E E E E OP OP OP OP OP OP OP OP( OP( OP( OP( OP( OP( OP( OP(

Fig. 2 Distribution of individual oligomers of NP(EO)n and OP(EO)n

Taking previous reports related with high-resolution mass spectrometry as references, LOQ was established using the LCLs method (matrix-matched standard solutions were diluted successively to obtain the lowest concentration that can be, which can be repeatedly determined with a low RSD value during a longer time period), to estimate the LOQ [18-20]. The LOQ values of NP(EO)4-19 and OP(EO)3-17 oligomers in this method ranged from 0.1-2.2 mg/kg. And RSD values calculated from six repeated injections at the LOQ level were <13%. Commission Decision 2002/657/EC and OEKO-Tex® Standard 100 were used as guidelines for the evaluation of recoveries. Recoveries were evaluated at three different concentration levels (25, 50 and 100 mg/kg) and six parallel assays were carried out at each level. At all three concentrations, the recoveries for most NP(EO)4-19 and OP(EO)3-17 oligomers ranged from 80% to 110% and the relative standard deviation (RSD %) was below 8%.

3.4.

Detection of real samples

Using the established method, this study realized the rapid screening of 25 real samples, including natural fiber, artificial fiber and blended fiber. NP(EO)n was commonly detected in most samples with concentrations ranging from 2 mg/kg to 224 mg/kg, while OP(EO)n was not found.

4. References [1] Loos R, Hanke G, Umlauf G, et al. LC–MS–MS analysis and occurrence of octyl- and nonylphenol, their ethoxylates and their carboxylates in Belgian and Italian textile industry, waste water treatment plant effluents and surface waters. Chemosphere 2007; 66:690-699. [2] Takasu T, Iles A, Hasebe K. Determination of alkylphenols and alkylphenol polyethoxylates by reversed-phase high-performance liquid chromatography and solid-phase extraction. Analytical and Bioanalytical Chemistry 2002; 372:554-561. [3] Jahnke A, Gandrass J, Ruck W. Simultaneous determination of alkylphenol ethoxylates and their biotransformation products by liquid chromatography/electrospray ionisation tandem mass spectrometry. Journal of Chromatography A 2004; 1035:115-122. [4] Boehme RM, Andries T, Dötz KH, et al. Synthesis of defined endocrine-disrupting nonylphenol isomers for biological and environmental studies. Chemosphere 2010; 80:813-821. [5] ISO 13907:2012 (E) [6] ISO 18857-2:2009 (E) [7] Loyo-Rosales JE, Rice CP, Torrents A. Octyl and nonylphenol ethoxylates and carboxylates in wastewater and sediments by liquid chromatography/tandem mass spectrometry. Chemosphere 2007;68:2118-2127. [8] Min; XZGJHLY. Determination of alkylphenols and alkylpheol polyethoxylates in textile by accelerated solvent extraction and rapid liquid chromatography. Chinese Journal of Analysis Laboratory 2012;31:112-115. [9] DeArmond PD, DiGoregorio AL. Rapid liquid chromatography-tandem mass spectrometry-based method for the analysis of alcohol ethoxylates and alkylphenol ethoxylates in environmental samples. Journal of Chromatography A 2013; 1305:154-163.

Page 788 of 1108

[10] Ferguson PL, Iden CR, Brownawell BJ. Analysis of alkylphenol ethoxylate metabolites in the aquatic environment using liquid chromatography-electrospray mass spectrometry. Analytical Chemistry 2000;72:4322-4330. [11] Weiya Z, Lixia L, Chengyun W, et al. Determination of alkylphenol (AP) and alkylphenol polyethoxylates (APEO) in textiles by HPLC. Journal of Textile Research 2007; 28:44-47. [12] GB/T 23322-2009. [13] Wen Y, Ou Y, Hong X, et al. Rapid Determination of Alkylphenol and Alkylphenol Ethoxylates in Leather and Textile by Ultrasonic-assisted Extraction and LC - MS. Journal of Instrumental Analysis 2010; 29:189-193. [14] Okada T. Complexation of poly(oxyethylene) in analytical chemistry. A review. Analyst 1993; 118:959-971. [15] Ma Q, Wang C, Bai H, et al. Determination of Alkylphenol Ethoxylates in Textiles by Gel Filtration Chromatography-Tandem Mass Spectrometry. Journal of Analytical Science 2012; 28:149-154. [16] Houde F, DeBlois C, Berryman D. Liquid chromatographic–tandem mass spectrometric determination of nonylphenol polyethoxylates and nonylphenol carboxylic acids in surface water. Journal of Chromatography A 2002; 961:245-256. [17] Einsle T, Paschke H, Bruns K, et al. Membrane-assisted liquid–liquid extraction coupled with gas chromatography–mass spectrometry for determination of selected polycyclic musk compounds and drugs in water samples. Journal of Chromatography A 2006;1124:196-204. [18] Zachariasova M, Cajka T, Godula M, et al. Analysis of multiple mycotoxins in beer employing (ultra)-highresolution mass spectrometry. Rapid Commun Mass Spectrom 2010; 24:3357-3367. [19] Choi JH, Lamshöft M, Zühlke S, et al. Determination of anxiolytic veterinary drugs from biological fertilizer blood meal using liquid chromatography high-resolution mass spectrometry. Biomedical Chromatography 2014:751-759. [20] Domènech A, Francisco NC, Palacios O, et al. Determination of lipophilic marine toxins in mussels. Quantificationand confirmation criteria using high resolution mass spectrometry. Journal of Chromatography A 2014: 16-25.

Page 789 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Developing a Meltstick Test Method Bhoyro, Ahmed Y. 1 Defence Science and Technology Group

Abstract. Although there is no clear definition, the term “meltstick’ is often used to describe a phenomenon whereby burning synthetic textile material melts and drips and then, upon cooling, the molten material solidifies and sticks to the skin that can lead to severe burns and complicate medical treatment due to the fusion of solidified material with the skin. To date, there are no adequate test methods to quantify or qualitatively evaluate meltstick. The aim of this work is to develop a laboratory based test method that assesses the meltstick properties of a burning textile material. There are two aspects to this assessment. Firstly, to identify and/or assess that the material melts/drips, and secondly, to measure the amount of, or propensity for, the molten material to stick. The findings suggest that it has not been possible to develop a quantitative method to measure and characterise the meltstick properties of a textile material. Instead, two qualitative methods have been devised that characterise the melting, and, the sticking nature of the material when ignited. A meltdrip scale 0 to 2 and meltstick categories (A, B and C) have been conceived to best describe and differentiate the degree of the meltstick of different fabrics. The methodologies were developed to be readily reproducible within a standard textile testing laboratory. Keywords: melting, dripping, sticking, textile

1. Background There have been few attempts to develop or evaluate a Meltstick test method. Hall [1] evaluated test methods based on heating fabric samples; in an oven, on a hot plate, exposed to radiant quartz lamps and with a hot-air gun. Hall developed a semi-quantitative method of determining the degree of meltstick of materials by ascribing a “points” system based on whether the materials experienced no stick, slight stick or stick for all test methods. Kandola et al. [2] measured the amount of molten polymer to fall on a weighing belt covered with aluminium foil to characterise the degree of melt drip for polymers as a function of time. The Australian and New Zealand standard [3] for children’s nightwear describes a melt drip test that allows the flaming molten polymer to drip onto a cellulose filter paper. A presentation by Powell [4] indicated a test method that allowed molten materials to adhere to aluminium foil during a vertical flame test which indicated melt stick behaviour of the textile sample. This was based on ASTM D6413, Flame Resistance of textiles (Vertical Test) [5]. While these test methods identified some aspects of meltstick and dripping behaviour, none of these methods adequately describe the degree or extent of meltstick for textile materials. This work investigates methodologies to characterise the melting, dripping and sticking nature of a range (natural, synthetic and blends thereof) of burning textile materials so as to provide a means of categorisation meltstick behaviour.

2. Experimental Method 2.1 Melting and Dripping Characteristics The lower end of a vertically oriented fabric sample of approximately 70 mm x 20 mm was exposed to a small flame until ignition. The flame was removed and the fabric allowed to burn (Figure 1). Table 1 provides descriptors of the burning samples and the basis for the Melt-Drip Scale (Table 2). This test procedure can be readily replicated using edge ignition test standard for a vertically oriented specimen, AS2755.1 [6]. 1

Correspondence: ahmed.bhoyro@defence.dsto.gov.au 506 Lorimer Street, Fishermans Bend, Victoria 3207, AUSTRALIA

Page 790 of 1108

Figure 1, Example of Burning Textile Material Table 1: Burning Features of Textile Material Sample Cotton (%)

Polyester (%)

100 75 50 35 0 16 % Elastane 24 % Spandex 9% Lycra速

0 25 50 65 100 84 % Polyester 76 % Nylon 91 % Nylon

Flame Propagation (yes/no) yes yes yes yes yes yes

Flame Sputtering (yes/no) no no no yes yes yes

Melting 2 (yes/no)

Dripping (yes/no)

no no no yes yes yes

yes

Residual Material 4 (Hard/Rigid) no no no yes yes yes

Melt/Drip Scale

no no no no yes yes

Combustion Product 3 (Debris) ash ash ash ash hard hard

yes

hard

yes

hard

yes

0 0 0 1 2 2

Table 2: Melt-Drip Scale Melt-Drip Scale

Description 5

No melting, no dripping

Some melting, no dripping

Melting and dripping

2.2 Melting and Sticking Characteristics An alternative method to Powell[4] was investigated that allowed the surface of the material to be exposed to a flame. This test method was based on AS2755.3 [7] and importantly allowed the fabric sample to be prepared and presented to the flame in a uniform and consistent manner. The sample holder consists of a front frame that engages onto a back plate that holds the prepared sample and is exposed to a small horizontal flame (Figure 2). The prepared sample consists of a 75x150x2 mm textile material (2) sandwiched between 70x170x0.024 mm Al foils (1 and 3) and backed by two pieces of 75x75x1 mm cardboard (4 and 5).

a. Sample Holder b. SDL ATLAS 233B Autoflam Figure 2, Sample Holder and Atlas Tester for Flammability Test Method AS2755.3 [7]

Subjectively assessed. The cooled debris that fell during combustion was compressed between thumb and finger and assessed 4 Residual Material = Fabric material remaining after the flame had been purposely extinguished so as to prevent further burning of the material. 5 Based on a subjective and visual assessment of melting and dripping 3

Page 791 of 1108

The assembly sequence of the sample is shown in Figure 3. 3. Al foil 1. Al foil

5. Cardboard

Front Frame Position

Heat

Back Plate Position

2. Sample

4. Cardboard

Figure 3, Diagrammatic Representation of the Sample Assembly. Note that Cardboard (4) provided the structural and uniform support for the sample assembly, whilst Cardboard (5) provided tension on the assembly to ensure that the fabric sample was in intimate contact with the Al foils (1) and (3).

The horizontal flame was applied at a fixed distance from the vertical surface of the sample assembly for 20 seconds. The sample was removed from the holder and allowed to cool. The degree of meltstick could be determined by the propensity of the molten material to stick to the Al foil (1) that was exposed directly to the flame. In practically all cases in which meltstick occurred, the material was strongly fused to the facing Al foil (1) but was relatively easy to detach from the backing Al foil (3) (Figure 4). Repeated testing on the fabric samples showed similar, consistent findings. Moreover, the melted and cooled (residual) fabric demonstrated a degree of flexibility and rigidity that was akin to a plastic sheet.

Figure 4, Typical Meltstick Feature for a Fabric Composed of Synthetic Material.

The meltstick characteristics of a range of textile materials assessed using this method is described in Table 3. Table 3, Meltstick Description of Textile Fabrics Using Modified AS2755.3 Test Method Composition (%) Cotton Polyester

Fabric Melting* (Yes/No)

100 75 50 35

0 25 50 65

No No No Yes

100

Yes

16 % Elastane

84 % Polyester

Yes

24 % 76 % Yes Spandex Nylon 9% 91 % Yes Lycra速 Nylon 100 % No Cotton 100 % No Wool 65 % 35 % Yes Nylon Lycra * Visual Assessment, ** Tactile Assessment

Sticks to Facing Al Foil** (Yes/No) Yes (Partially) No Yes (Some) Yes (Permanent) Yes (Permanent) Yes (Permanent)

Rigid/Plastic Feel** (Yes/No)

Meltstick Material (Yes/No)

Meltstick Category

No No Yes Yes

A A B B

Yes

Yes (Permanent) Yes (Permanent) Yes (Partially)

Yes

Yes (Partially)

Yes (Permanent)

Yes

Page 792 of 1108

Table 4, summaries and combines the features from Tables 2 and 3 to produce a meltstick categorisation for burning textile materials. Table 4, Meltstick Categorisation Category

Level

Melt (Visual)

Stick (Visual)

Rigid (Tactile)

Meltstick

Material Example

1 2

No No

No Partial

No No

3 4 5

Some Yes Yes

Some Some Permanent

Yes Yes Yes

Some Yes Yes

75/25 Cotton/Polyester 100 % Cotton or 100 % Wool 50/50 Cotton/Polyester 35/65 Cotton/Polyester 100 % Polyester

C Definitions: Melt: Stick:

Rigid: Meltstick:

Some = Some melting that is absorbed by other fibres Partial = Partial low adherence sticking due to combustion products Some = Some sticking but peels from facing aluminium foil Permanent = Permanent sticking to facing aluminium foil Residual fabric (after the flame has been extinguished) has rigid/plastic feel when handled. No = No evidence of meltstick Some = Some meltstick Yes = Clearly meltstick

3. Conclusions In the course of this investigation, it was not possible to devise a single quantitative method to measure and characterise the meltstick properties of a range of textile materials. Instead, two qualitative methods have been devised that characterise the melting, and, the sticking nature of the material when ignited. A melt-drip scale (0 to 2) and meltstick categories (A, B and C) have been formulated and combined to best describe and differentiate the degree of the meltstick. The test methods are readily reproducible within a standard textile testing laboratory using conventional equipment and test standards.

4. References 1. 2. 3. 4. 5. 6. 7.

Melt-Stick Characteristics of Flame-Retardant-Treated Polyester-Cotton Blend Fabrics, Hall, R. W., HighTech Fibrous Materials, 293-302, 1990 Characterization of Melt Dripping Behavior of Flame Retarded Polypropylene Nanocomposites, Kandola, B. K., et al., Fire and Polymers VI, ACS Symposium Series, American Chemical Society, 2012 AS/NZS 1249:2014, Childrenâ&#x20AC;&#x2122;s Nightwear and Limited Daywear Having Reduced Fire Hazard Military Requirements Relating to NFPA 1975, Presentation by Celia Sturatt Powell, US Army NSRDEC, 14 March 2012 Standard Test Method for Flame Resistance of Textiles (Vertical test), ASTM D6413-2012 Determination of Ease of Ignition of Vertically Oriented Specimens, AS2755.1 - 1985 Textile Fabrics â&#x20AC;&#x201C; Determination of Burning Behaviour - Determination of Surface Burning Time, AS2755.3-1988

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Development Of Conductive Wire Reinforced Cotton Yarns For Protective Textile Applications A. Ozbek1, E. Sancak2, İ. Usta2, M. Uzun2, M. Akalın2, M.S. Özen2, A. Pars3 1

Sinop University, Gerze Vocational School, Textile Technology and Clothing, Sinop, TURKEY. 2 Marmara University, Technology Faculty, Department of Textile Engineering, İstanbul, TURKEY. 3 Marmara University, Pure and Applied Science Institute, Textile Engineering, İstanbul, TURKEY.

Abstract. The aim of this study was to develop and evaluate conductive core wires reinforced cotton yarns for protective textile applications. The stainless steel (SS), copper (Cu) and silver treated copper (Cu/Ag) conductive wires at different diameters (40, 50 and 60 micron) were employed as the core of the cotton yarns. Two different yarn counts, which were Ne10 and Ne20 were produced with and without core wires. A conventional ring spinning system with an attachment was used to produce core yarns. The interaction between the yarn quality and the core wires were tested and analyzed. 20 copses of yarns were produced by using different yarn process combinations. The yarn properties were tested in terms of yarn count, yarn twist, yarn hairiness, breaking strength and elongation. As a result, the properties of cotton yarns were affected by the wire reinforcement. The tested parameters have changed in varied extents. The types of the conductive wires also had different effect on the core yarn properties. Keywords: Core Yarns, Conductive Textiles, Protective Textiles, Ring Spinning, Cotton.

1. Introduction Protective textiles stand in one of the fastest growing sectors among technical textiles. Chemical, Biological, Radiological and Nuclear (CBRN) are broadly used to define the threats to human. However, particularly in daily life technologies, perhaps the most important and prevalent hazard to people is the effects of electromagnetic waves and which are emitted by the increasing use of mobile communication systems and electronic devices. The electromagnetic waves and radiation pose a significant risk to the people health; against which the clothing may also need to provide protection against them [1-5]. Core and composite yarn constructions are commonly used in basic and technical textile applications and are known to add reasonable specific properties such as enhancing the resistance performance of the textile fabrics and making electrically conductive textile structures. Core yarn is mostly produced by two-component structure, which is core and sheath. The production of core yarn is a process that fibers are twisted around the core structures such as monofilament, staple-fiber yarn etc. It is important to mention that in general filament yarn is employed as core structure and they are covered by staple fibers [6-11]. The main aim of this study is to design and develop novel conductive core yarns by using Cu, SS, Cu/Ag wires. For this purpose, 18 different combinations of core yarns were produced and also two different counts 100% cotton yarns were produced as reference (control) yarn. The yarn characteristics were determined by using standard test methods. The tests aimed to establish the impact of the wires on the quality of cotton yarns. The results were conducted in an attempt to analyze the optimum production parameters.

2. Materials and Methods 2.1.

Materials

In this study, three different types of conductive wires which are copper (Cu), stainless steel (SS), silver treated copper (Cu/Ag) were employed to produce the conductive core yarns. The wires were obtained from ELEKTRISOLA, Izmir, Turkey. The technical properties of the wires are given in Table 1. The cotton roving was kindly provided by SANKO Iplik Co., Gaziantep, Turkey. The roving count was 630tex (Ne1) and irregularity values of 4.9 CV%. The cotton fiber specifications are shown in Table 2.

Page 794 of 1108

Table 1. Technical properties of conductive wires

Table 2. Cotton fiber specifications

2.2. Methods 2.2.1. Yarn Production The yarns were produced by making use of laboratory-type core-yarn ring spinning machine. The core yarns were developed at the R&D department of SANKO Co. Ltd., Gaziantep, Turkey. The ring spinning system is shown in Figure 1. Two different counts of yarns (Ne10 and Ne20) were produced with specific twist level and spindle speed, refer Table 3. The yarn production was carried out in a conditioned laboratory at 65% RH and 20oC atmosphere [12]. Table 3. Yarn production parameters

Figure 1. Core yarn production process by ring spinning system

2.2.2. Yarn Physical Properties The produced yarn samples were tested individually and analyzed to provide a comprehensive understanding of their yarn count, yarn twist, yarn hairiness, strength and elongation. a) Yarn counts and twists: The yarn counts were determined in accordance with TS 244 EN ISO 2060: 1999. The yarn samples were prepared in 100m lengths for each yarn types and their masses were weighed by using OHAUS balance and the results were calculated in Ne. The twists were assessed in accordance with TS 247 EN ISO 2061: 1999, by using James H. Heal twist counter equipment. b) Yarn tensile properties: The breaking strength (cN) and elongation (%) properties of yarns were determined using Instron 4411 with test parameters of 500 mm gauge length, 10 cN pre-tension, 5 kg load cell with a test speed of 500mm/min [13, 14]. c) Yarn hairiness: The yarn hairiness was determined by using Shirley Yarn Hairiness Tester. This equipment can detect over 3mm hairs in the yarn surface over a chosen period of 5 to 40 seconds.

3. Results And Discussion Yarn counts and yarn twist The Ne values of developed core yarns are presented in Figure 2. It can be observed that the yarn counts are affected by the diameter of the conductive wires. It was an expected outcome due to the English yarn numbering system (Ne). The present findings seem to be consistent with other research, which found that when core wire diameters increases, Ne count of yarns decreases. This suggests a weak link may exist between yarn mass and yarn thickness in the case of core spun yarns. Further research should be done to investigate the correlation between core diameter and yarn count. The Ne values of yarns decreased by the increase in Âľm values of core wires. The differences were found to be noteworthy. It is apparent from Figure 2 that both Ne10 and Ne20 yarns demonstrated similar decreasing range with the core wire reinforcement. It has been also found that the yarns which were reinforced with SS wire were slightly thinner than those produced by reinforced with Cu and Cu/Ag. Interestingly, for those

Page 795 of 1108

subjects with Ag coating had a varied Ne value as compared to 100% Cu wires. In general, therefore, it seems that Ag coating has an effect on the yarn physical properties such as yarn counts.

Figure 2. Yarn counts (Ne) Figure 3. Yarn twists (T/m) In almost all cases, the core yarns had higher twist values than control yarns. It seems possible that these results are due to the relationship between sheath fibers and core wires. The fibers need more twists to cover the core structures as compared to the control yarns. Further analysis needs to be done to highlight the twist angle of the yarns. The Ne20 yarns showed a higher yarn twist change than the Ne10 yarns. The effect of wire type of the core on yarn twist was analyzed and it was clearly observed that the 60 Âľm SS wire reinforced yarns had the highest twist values as compared to the all tested yarns. It is interesting to note that the type of wire has a great impact on the twist behavior of the yarns. Taken together, these results suggest that the production of core yarn need higher twist value than the 100% yarns.

Yarn breaking strength and elongation In general, yarn-breaking strength is directly dependent on number of twists per meter in yarn. Breaking strength will increase with increasing twist value; however, it will decrease after a certain point. Another important parameter for yarn breaking strength is fiber number at the cross-section of yarns. A higher fiber per cross-section of yarn will cause a higher breaking strength of yarn. Keeping these in mind, this study confirms that the breaking strength is associated with both yarn twist and fiber at cross-section of yarns. The highest breaking strength value was found at the control Ne10 due to its thicker yarn structure as compared to the control Ne20. The reinforcement of core wire reduces the breaking strength of the yarns. The yarn, which was reinforced with SS wires, had superior breaking strength in comparison with core wire combinations. It is important to mention that increased wire diameters cause a considerable increase at the yarn breaking strength.

Figure 4. Yarn breaking strength (cN/tex)

Figure 5. Yarn hairiness (H/m)

Yarn hairiness It can be seen from the data in figure 5 that in the case of yarn hairiness, the hairiness values increased when the wires were employed as the core reinforcement. It is also observed that in terms yarn hairiness, the Ne20 yarns were much more affected by the core wire as compared to the Ne10 yarns. The Ne20 had higher yarn hairiness values than the Ne10 yarns. It seems possible that these results are due to the yarn twist differences.

Page 796 of 1108

4. Conclusions The present study was designed to determine the effect of three conductive wires on the cotton yarn properties. These findings suggest that in general the cotton yarn properties have changed by the wire reinforcement. The observed changes were found to be considerable. The conductive core yarns that we have identified therefore assists in our understanding of the role of wire as core reinforcement in the cotton yarns. The current research was not specifically designed to evaluate factors related to twist angles and cross-section of yarns. Further investigation and experimentation into these two parameters is strongly recommended. The following conclusions can be drawn from the present study: - A part from 40 µm wires, the counts of the core yarns were observed to have thicker structures as compared to the control yarns. - From the results and discussion of this study it can be concluded that the twist values of the core yarns were found to be considerably greater than the control yarns. The diameters of the wires were also established as important parameter for the twist values of the yarns. - The conductive wires had a variable effect on the breaking strength of the core yarns. When the wires diameter increases, the breaking strength of the core yarns also increases; however, the core reinforcement reduces the strength of the yarns as compared to the control yarns. The most obvious finding to emerge from this study is that the decrease in strength is noticeably important. - It was also shown that the elongation results were found to be similar to those breaking strength results. - The yarn hairiness increases with the wire reinforcement. It is probably due to the yarn twist behavior of the yarns. The wire reinforced yarns need more twist than the 100% cotton yarns and it could increase the hairiness of the yarns.

References 1- Sparks, E., Advances in military textiles and personal equipment, Woodhead Publishing, 2012. ISBN: 978-1-84569-699-3 2- Perumalraj, R.; Dasaradan, B.S. Electromagnetic shielding effectiveness of copper core yarn knitted fabrics. Indian Journal of Fibre and Textile Research 2009, 34, 149–154. 3- Kayacan, O.; Bulgun, E.; Sahin, O. Implementation of steel-based fabric panels in a heated garment design. Textile Research Journal 2009, 79 (16), 1427–1437. 4- Vassiliadis, S.; Provatidis, C.; Prekas, C.; Rangussi, M. Novel fabrics with conductive fibres, intelligent textile structures. In Application, Production and Testing International Workshop, Thessaloniki, Greece, May 12–13, 2005. 5- Vigneswaran, C., Kandhavadivu, P., “Development of Electromagnetic Shielding Wearable Electronic Textiles using Core Conductive Fabrics” International Journal of Science and Engineering Applications, Special Issue NCRTAM ISSN-2319-7560. 6- Shawney, “Special purpose fabrics with Core spun yarns” Indian Journal of Fiber and Textile Research-Dec-1997 7- Johnson, T.F.N., (1996). World fiber demand 1890-2050 by main fiber type. Man Made Fiber Year Book (CFI). 31-37. 8- Mourad, K., Ethridge. D., (2004). A Qualitative Approach to Estimating Cotton Spinnability Limits. Textile Research Journal. 74(7), 611-616. 9- Krifa, M., Ethridge, M.D., (2006). Compact Spinning Effect on Cotton Yarn Quality: Interactions with Fiber Characteristics. Textile Research Journal. 76(5), 388-399. 10- Demir, A., Torun, A., (2003). Tekstilde Üretim Yöntemleri. İ.T.Ü., 75-92. 11- Huh, Y., Kim, Y.R., Oxenham W., (2002). Analyzing Structural and Physical Properties of Ring, Rotor, and Friction Spun Yarns. Textile Research Journal, 72(2), 156-163. 12- ASTM (D-1776-90), “Standard Practice for Conditioning Textiles for Testing. American Society for Testing and Materials, West Conshohocken, PA, 483-446. 13- Uzun, M., Patel, I., (2010). Mechanical properties of ultrasonic washed organic and traditional cotton yarns. Journal of Achievements in Materials and Manufacturing Engineering, 43/2, 608-612.

Page 797 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Development of Rainfall Test Equipment (Rain Tower) and Waterproof Performance Evaluation Criteria Jee Young Lim 1, Jun Ho Park 1, Kue Lak Choi 1 and Hee Cheol Cha 1 + 1

Korea Institute of Industrial Technology, ICT Textile and Apparel R&D Group, Korea

Abstract. The waterproof measurements widely used are KS K 0592, KS K 0593 or K ISO 811. However, those standards are difficult to evaluate the waterproof performance of the clothing. Therefore, we have developed rain test equipment (Rain Tower) to evaluate the performance of waterproof for clothing products.

Keywords: Artificial Rainfall, Rainfall Test Equipment, Waterproof.

1. Main Subject 1.1.

Rainfall Test Equipment

Rain test equipment has the size of height 5m, width 2m â&#x2026;š 1m(rain area). And the 2,000 droplets are simultaneously generated in the area of 2m â&#x2026;š 1m.

1.2.

Rain Test Method

For the rain test, the mannequin is installed in the chamber of the equipment real-time temperature and humidity changes can be observed with sensors attached on the mannequin surface. In addition, water permeability of the test subject can be observed with naked eyes. Ready-made clothing were the test subjects. Total test subjects were 23. Among the subjects, seven samples were selected in this study to evaluate waterproof properties of clothes after washing. In addition, the physical properties of clothing fabric were measured to compare the relationship between the physical properties and the waterproof. The seven samples washing test process are given in Table 1.

Table 1: Washing test process Step

Rainfall Rainfall time

100mm/h 30 min

Test list

Waterproof (naked eye)

Washing (10 times)

Waterproof (naked eye)

WVP* Waterproof**

* WVP : Water vapour permeability ** Waterproof : Determination of resistance to water penetration

Also, additional water permeability tests(Rain test) for the rest of 16 samples were conducted to evaluate the equipment performance. The test results can be observed with naked eyes.

Corresponding author. Tel.: + 82-010-2016-2691. E-mail address: heechul@kitech.re.kr.

Page 798 of 1108

Fig. 1. Rain test apparel(Left) and Test samples(Right)

1.3.

Results and Discussions

The rainfall in the initial experimental was too heavy. As a result, the experimental had no discrimination. In the end, we had concluded that 100mm/h and 30 min were the optimum conditions. Water vapour permeability was measured by using a WVP chamber as described in KS K 0594. Determination of resistance to water penetration was measured by using a test machine(FX3000, Textest Instuments) as described in KS K ISO 811. The WVP of before(step 1) and after(step 3) washing samples are presented in figure 2. The determination of resistance to water penetration of before(step 1) and after(step 3) washing samples are plotted in Figure 3.

Fig. 2: WVP (A : before wash, B : after wash)

Fig. 3: Determination of resistance to water penetration (A : before wash, B : after wash)

The WVP behaviors were increased after washing and the determination of resistance to water penetration were dropped in most of cases. However, Waterproof properties did not change. Table 2 shows the waterproof performance of after washing. Table 2: Waterproof performance(Pass/Fail) Waterproof (naked eye)

Step 1

Step 3(after wash)

PASS

C1, C2, E1, N2

FAIL

E2, N1, N3

Page 799 of 1108

The water permeability (Rain Test) on the test subject was observed with naked eyes. Table 3 showed that water permeability performance of 16 samples. And figure 4 showed weak point of clothing to the rainfall. We found observe that water permeation in the sewing section and seam-sealing section. Table 3: Waterproof performance(Pass/Fail) Waterproof (naked eye)

Sample name

Ratio(%)

PASS

B1, B2, B3, BT, E3, I1, K1, M1, MB1, ME1, R1

FAIL

A1, C3, N4, K2, J1

Fig. 4: Weak area of Rainfall

2. Conclusions As a result, we have learned that quality of the seam sealing and the sewing are the major contributors for the waterproof performance in clothing. We expect that rainfall test equipment(Rain Tower) will perform a variety of roles in the product development of the textile and clothing sector.

3. Acknowledgement This work was supported by Industrial Source Technology Development Programs (No. 10033501) funded by the Ministry of Trade, Industry and Energy (MOTIE, Korea)

4. References [1] H. S. Shim, The Korean Journal of Community Living Science v.25 no.4, 549 - 556, (2014)

Page 800 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Effect of Adhesive interlinings on creep behavior of woven fabrics under low stress in bias direction KyoungOk Kim1, Ken Ishizawa2, Masayuki Takatera1 1

Division of Kansei and Fashion Engineering, Institute for Fiber Engineering (IFES), Interdisciplinary Cluster for Cutting Edge Research (ICCER), Shinshu University, Ueda, Nagano, 386-8567, Japan 2 Faculty of Textile Science and Technology, Shinshu University, Ueda, Nagano, 386-8567, Japan

Abstract. Creep tests were carried out using face fabrics, adhesive interlinings, and those laminated fabrics without and with bonding adhesive interlining by hanging the samples in 45Âş bias direction under their own weight for seven days. As a result, creep strains of face fabrics bonded with adhesive interlining were smaller than ones of the face fabrics. The creep behavior for the face and interlining fabrics were able to be approximated using three elements viscoelastic model with appropriate parameters. The experimental creep behavior of laminated fabric without bonding was close to the experimental one. However, experimental creep strains of laminated fabrics with bonding interlining were smaller than the calculated ones due to the increase of stiffness by the adhesive. By revising the six element model with the strains at just after hanging and for 2 days, it was able to predict the creep strain during seven days.

Keywords: Adhesive interlining, creep behaviour, bias direction.

1. Introduction In manufacturing clothing, in order to keep their shape, interlining is used. Among interlining, adhesive interlining which adhesive was put on base cloth has been commonly used. It is known that mechanical properties such as bending rigidity and shear stiffness of face fabric changed by bonding interlining [1-6]. Bonding interlining could affect creep of garment. It is necessary to investigate effect of interlining on fabric creep and its prediction to select suitable interlining. So far, the effects and its prediction of creep of interlining in the bias direction are not carried out. Furthermore, study on creep of laminated fabric in bias direction is not investigated. Deformation of fabric in bias direction is large. In addition, bonding effect on rigidity of laminated fabric in shear is large and it cannot be ignored [5, 6].

2. Theoretical In this study, we employ three element viscoelastic models for single fabrics that can show creep behaviour. The models are represented by connecting Voigt model and a spring in series as shown in Fig. 1. In here, K 1 , K 2 , E 1 and E 2 are elastic moduli of each spring. Îˇ and y are viscosity coefficient of dash pot. F is applied load.

Îˇ

Fig. 1. Three element models

Îˇ E2

Fig. 2. Six element model

When we set t is time, strain of a fabric, Îľ f , can be obtained by equation (1). đ??žđ??ž đ??šđ??š đ??šđ??š â&#x2C6;&#x2019; 2 đ?&#x2018;Ąđ?&#x2018;Ą đ?&#x153;&#x20AC;đ?&#x153;&#x20AC;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C; = + ďż˝1 â&#x2C6;&#x2019; đ?&#x2018;&#x2019;đ?&#x2018;&#x2019; đ?&#x153;&#x201A;đ?&#x153;&#x201A; ďż˝ (1) đ??žđ??ž1 đ??žđ??ž2

Page 801 of 1108

Strain of another fabric, Îľ i , also can be obtained by equation (2). đ?&#x153;&#x20AC;đ?&#x153;&#x20AC;đ?&#x2018;&#x2013;đ?&#x2018;&#x2013; =

đ??šđ??š đ??¸đ??¸1

đ??šđ??š ďż˝1 đ??¸đ??¸2

â&#x2C6;&#x2019; đ?&#x2018;&#x2019;đ?&#x2018;&#x2019;

đ??¸đ??¸ â&#x2C6;&#x2019; 2đ?&#x2018;Ąđ?&#x2018;Ą đ?&#x2018;Śđ?&#x2018;Ś

ďż˝

(2)

When we ignored the effect of the adhesive, a model of those laminated fabric can be expressed by six element model connected the three element model in parallel as shown in Fig. 2. K 1 , K 2 , E 1 and E 2 are elastic moduli of each spring. Îˇ and y are viscosity coefficient of each dash pot. F is sum of tension of each fabric equal to applied load. When we set strain of six element model as Îľ, constitutive equation is represented by equation (3). Îľď&#x20AC;Śď&#x20AC;Ś + bÎľď&#x20AC;Ś + Îľ = d (3) The solution is given by (4) Îľ = C1 exp(Îť1t ) + C2 exp(Îť2 t ) + C3 In here, integration constant, C 3 is determined by the condition of đ?&#x153;&#x2020;đ?&#x153;&#x2020;1 and đ?&#x153;&#x2020;đ?&#x153;&#x2020;2 for an appropriate solution as follow.

C3 =

d c

(5),

where c and d are constants determine by the moduli of the model. C 1 and C 2 are needed to be determined. Thus, as initial conditions, strain and strain rate at time t = 0 was defined as đ?&#x153;&#x20AC;đ?&#x153;&#x20AC;|đ?&#x2018;Ąđ?&#x2018;Ą=0 and đ?&#x153;&#x20AC;đ?&#x153;&#x20AC;Ě&#x2021;|đ?&#x2018;Ąđ?&#x2018;Ą=0 respectively. When t = 0, K 1 and E 1 are only changed. Thus, đ?&#x153;&#x20AC;đ?&#x153;&#x20AC;|đ?&#x2018;Ąđ?&#x2018;Ą=0 can be shown as equation (6) đ??šđ??š đ?&#x153;&#x20AC;đ?&#x153;&#x20AC;|đ?&#x2018;Ąđ?&#x2018;Ą=0 = (6) đ??žđ??ž1 + đ??¸đ??¸1 In here, đ?&#x153;&#x20AC;đ?&#x153;&#x20AC;Ě&#x2021;|đ?&#x2018;Ąđ?&#x2018;Ą=0 is not affected by K 2 and E 2 because those are not changed at đ?&#x2018;Ąđ?&#x2018;Ą = 0. Thus, we derived | đ?&#x153;&#x20AC;đ?&#x153;&#x20AC;Ě&#x2021; đ?&#x2018;Ąđ?&#x2018;Ą=0 using four element model excluded K 2 and E 2 . Results are shown in equation (7). 1 1 + đ??žđ??ž1 đ??šđ??š đ??šđ??š đ??žđ??ž1 đ?&#x153;&#x201A;đ?&#x153;&#x201A; đ?&#x153;&#x201A;đ?&#x153;&#x201A; đ?&#x2018;Śđ?&#x2018;Ś đ?&#x153;&#x20AC;đ?&#x153;&#x20AC;Ě&#x2021;|đ?&#x2018;Ąđ?&#x2018;Ą=0 = ďż˝ â&#x2C6;&#x2019; ďż˝ ďż˝â&#x2C6;&#x2019; (7) ďż˝+ 1 1 đ??žđ??ž1 đ??žđ??ž1 + đ??¸đ??¸1 đ?&#x153;&#x201A;đ?&#x153;&#x201A; + đ?&#x2018;Śđ?&#x2018;Ś đ?&#x153;&#x201A;đ?&#x153;&#x201A;(đ??žđ??ž1 + đ??¸đ??¸1 ) + đ??¸đ??¸ đ??žđ??ž1 1 Then, we obtained đ??śđ??ś1 =

đ?&#x2018;&#x2018;đ?&#x2018;&#x2018; đ?&#x2018;?đ?&#x2018;?

đ?&#x153;&#x20AC;đ?&#x153;&#x20AC;Ě&#x2021; |đ?&#x2018;Ąđ?&#x2018;Ą=0 +ďż˝ â&#x2C6;&#x2019;đ?&#x153;&#x20AC;đ?&#x153;&#x20AC;|đ?&#x2018;Ąđ?&#x2018;Ą=0 ďż˝đ?&#x153;&#x2020;đ?&#x153;&#x2020;2 đ?&#x153;&#x2020;đ?&#x153;&#x2020;1 â&#x2C6;&#x2019;đ?&#x153;&#x2020;đ?&#x153;&#x2020;2 đ?&#x2018;&#x2018;đ?&#x2018;&#x2018; đ?&#x153;&#x20AC;đ?&#x153;&#x20AC;|đ?&#x2018;Ąđ?&#x2018;Ą=0 â&#x2C6;&#x2019; â&#x2C6;&#x2019; đ?&#x2018;?đ?&#x2018;?

(8),

đ??śđ??ś2 = đ??śđ??ś1 (9). If we can obtain parameters of three element model by creep test of each component fabric, then we can predict creep behavior of laminated fabric using equation (4).

3. Experimental We measured creep strains of face fabric, adhesive interlining, lamination of both fabrics without bonding (hereinafter referred to as overlapped fabric) and lamination of both fabrics with bonding (hereinafter referred to as bonded fabric) in 45Â° bias direction. Load was set as self-weight of length 80cm for each fabric assuming a dress of knee length. Dot type adhesive interlining was used. The sample was hung on the wall by fixing the upper end with a magnet bar. Dimensions of samples were measured before hanging. The sample fabrics were cut on the 45 Â° bias. The shape was long rectangle of 5cm width. It was not possible to make 80cm of fabric in bias direction without a seam due to the fabric size. Thus, the same fabric was sewn to make 80cm length of fabric. Gauge lines were drawn in 10cm interval and initial gauge length was measured before hanging. The weight of the length 80cm is applied to the center line of the gauge. Length between the gauge lines was measured. Experimental environment was 20 Âą 1Â°C, and 65 Âą 5% RH. Measurement test was carried out for 7 days and interval was 1 day. Five sheets per one kind of fabric were prepared and the average was used. For one sheet, we measured strains two times and the average was used. Adhesive interlining was bonded by a press machine under the same condition. When bonding interlining to the face fabric, press affect both adhesive interlining and face fabric. In order to make the same condition for each fabric, press treatment was carried out for sample without bonding. Overlapped fabric was made by fixing face fabric and adhesive interlining by yarn knots of eight places on gauge lines. A wool face fabric and two adhesive interlinings of different adhesive mass were used. Tables 1 and 2 show specification of experimental samples. Parameters, K 1 and E 1 were determined by load and strain at t=0. K 2 and Îˇ of face fabric and E 2 and y of adhesive interlining were determined by fitting experimental and model strains using the Excel Solver (Microsoft). Creep behaviour of bonded fabric and overlapped fabric were calculated with equation (4) of six element model substituting the obtained parameters. The calculated and experimental creep was compared.

Page 802 of 1108

Table 1 Symbol

Shear stiffness Clockwise Counterclockwise (cc)* rotation(ccw)* 0.638 0.654

Specification of face fabric

Material

Weave structure

Wool100%

Plain

Area density [g/mÂ˛] 134.3

Yarn count [tex] (warpĂ&#x2014;weft) 26.3Ă&#x2014;23.3

Weave density[N/cm] (warpĂ&#x2014;weft) 25.8Ă&#x2014;23.4

Load [gf/cm] (Length 80cm) 1.074

* Rotation direction of warp when it is seen from the face side Table 2 Specification of adhesive interlining Symbol

Material

Weave structure

Area density [g/mÂ˛]

Yarn count [tex] (warpĂ&#x2014;weft)

Polyestere100% (Dot type)

Plain

38.5

3.0Ă&#x2014;3.0

Weave density [N/cm] (warpĂ&#x2014;weft) 38.6Ă&#x2014;24.4

39.9

Adhesive dot density [/inch] (warpĂ&#x2014;weft) 23Ă&#x2014;23

Adhesive mass [g/mÂ˛]

Load [gf/cm](Length 80cm)

8.7

0.308

26Ă&#x2014;26

10.0

0.319

4. Results and Discussion Figs. 1 and 2 show the strains on time change for the all sample and those combinations. In the 45Â° bias direction of face fabric and adhesive interlining, it was found that creep occurs by fabric weight of 80cm length. Strain changes of face fabric were higher than ones of adhesive interlining. The small strain changes of interlining was due to their small weight. Overlapped fabrics showed intermediate strain between those components. However, strains of bonded fabrics in all combinations were significantly smaller than ones of overlapped fabrics. Thus, it was confirmed that bonding adhesive interlining to face fabric reduces the creep strain of face fabric. The reason of small strain changes of bonded fabrics is due to restrain of deformation by adhesive on face fabric. 3.5

3.5

A(cw) a(cw) A(cw)ď˝&#x153;ď˝&#x153;a(cw) A(cw)ď˝&#x153;a(cw) Three elements model Six elements model

3.0

3.0 2.5

Strainďźťďź&#x2026;ďź˝

2.5

A(cw) b(cw) A(cw)ď˝&#x153;ď˝&#x153;b(cw) A(cw)ď˝&#x153;b(cw) Three elements model Six elements model

2.0

1.5

1.0

0.5

0.0

0.0 0

3 4 5 Timeďźťdďź˝

Fig. 1 Strain change by time (Combination 1(Aďź?a)) Fig. 2 Strain change by time (Combination 2(Aďź?b))

Table 3 shows constant and equation for three element model for each combination. Approximated strains of face fabric and interlining using three element models are also shown in Figs. 1and 2. Approximated strains of face fabric and adhesive interlining by three element model showed good agreement with experimental ones. Thus, it was found that creep behaviour by its own weight in the 45Â° bias direction is possible to be approximated using three element model. Strain of each combination were calculated with the six element model using parameters of each component fabric. Table 3 Constant and equation for three elements model Combination Combination 1(Aďź?a) Combination 2(Aďź?b)

Constant Sample Face fabric Adhesive interlining Face fabric Adhesive interlining

đ??šđ??š [gf/cm] 1.074 0.308 1.074 0.319

đ??žđ??ž1 [gf/cm/100] 0.703 0.502 0.703 0.775

đ??žđ??ž2 [gf/cm/100] 1.402 1.428 1.402 0.808

đ?&#x153;&#x201A;đ?&#x153;&#x201A; [dă&#x192;ťgf/cm/100] 2.945 2.398 2.945 5.176

Equation đ?&#x153;&#x20AC;đ?&#x153;&#x20AC;[%] đ?&#x153;&#x20AC;đ?&#x153;&#x20AC; = 2.293 â&#x2C6;&#x2019; 0.766đ?&#x2018;&#x2019;đ?&#x2018;&#x2019; â&#x2C6;&#x2019;0.476đ?&#x2018;Ąđ?&#x2018;Ą đ?&#x153;&#x20AC;đ?&#x153;&#x20AC; = 0.829 â&#x2C6;&#x2019; 0.216đ?&#x2018;&#x2019;đ?&#x2018;&#x2019; â&#x2C6;&#x2019;0.596đ?&#x2018;Ąđ?&#x2018;Ą đ?&#x153;&#x20AC;đ?&#x153;&#x20AC; = 2.293 â&#x2C6;&#x2019; 0.766đ?&#x2018;&#x2019;đ?&#x2018;&#x2019; â&#x2C6;&#x2019;0.476đ?&#x2018;Ąđ?&#x2018;Ą đ?&#x153;&#x20AC;đ?&#x153;&#x20AC; = 0.806 â&#x2C6;&#x2019; 0.395đ?&#x2018;&#x2019;đ?&#x2018;&#x2019; â&#x2C6;&#x2019;0.156đ?&#x2018;Ąđ?&#x2018;Ą

The comparison of experimental and calculated strains was also shown in Figs. 1 and 2. Calculated strains using six element model were close to the experimental strains of overlapped fabric. Equation for six element model for 7 days were shown in Table 4. Using the experimental value of the strain of face fabric and interlining, stains of overlapped fabric was able to be predicted. As described above, the strain changes of laminated fabric was smaller than ones of overlapped fabric. The reason was considered that attached adhesive on face fabric. Therefore, if strain of face fabric with adhesive is able to be measured and creep strain of face

Page 803 of 1108

fabric with adhesive is able to be calculated using three element model, it will be able to predict strain of the laminated fabric using the six element model. However, putting adhesive on a face fabric is difficult technically. Therefore, strain of face fabric with adhesive was estimated using the experimental results. To estimate it with small number of parameters, a magnification factor n was introduced to be agreed the experimental strains at t=0 with the calculated ones. To make calculated value đ?&#x153;şđ?&#x153;ş|đ?&#x2019;&#x2022;đ?&#x2019;&#x2022;=đ?&#x;&#x17D;đ?&#x;&#x17D; and experimental value đ?&#x153;şđ?&#x153;şđ?&#x2019;&#x2020;đ?&#x2019;&#x2020;đ?&#x2019;&#x2020;đ?&#x2019;&#x2020;đ?&#x2019;&#x2020;đ?&#x2019;&#x2020; ďż˝đ?&#x2019;&#x2022;đ?&#x2019;&#x2022;=đ?&#x;&#x17D;đ?&#x;&#x17D; agree using n, from equation (6), we obtain đ?&#x153;şđ?&#x153;şđ?&#x2019;&#x2020;đ?&#x2019;&#x2020;đ?&#x2019;&#x2020;đ?&#x2019;&#x2020;đ?&#x2019;&#x2020;đ?&#x2019;&#x2020; ďż˝

đ?&#x2019;&#x2022;đ?&#x2019;&#x2022;=đ?&#x;&#x17D;đ?&#x;&#x17D;

n is calculated by equation (12). đ?&#x2019;?đ?&#x2019;? =

đ?&#x;?đ?&#x;?

ďż˝

đ?&#x2018;đ?&#x2018;

đ?&#x2018;˛đ?&#x2018;˛đ?&#x;?đ?&#x;? đ?&#x203A;&#x2020;đ?&#x203A;&#x2020;đ?&#x2019;&#x2020;đ?&#x2019;&#x2020;đ?&#x2019;&#x2020;đ?&#x2019;&#x2020;đ?&#x2019;&#x2020;đ?&#x2019;&#x2020; |đ?&#x2019;&#x2022;đ?&#x2019;&#x2022;=đ?&#x;&#x17D;đ?&#x;&#x17D;

đ?&#x2018;đ?&#x2018; đ?&#x2019;?đ?&#x2019;?đ?&#x2019;?đ?&#x2019;?đ?&#x;?đ?&#x;? +đ?&#x2018;Źđ?&#x2018;Źđ?&#x;?đ?&#x;?

(11)

â&#x2C6;&#x2019; đ?&#x2018;Źđ?&#x2018;Źđ?&#x;?đ?&#x;? ďż˝

(12)

Then, parameters đ?&#x2018;˛đ?&#x2018;˛đ?&#x;?đ?&#x;?, đ?&#x2018;˛đ?&#x2018;˛đ?&#x;?đ?&#x;? and đ?&#x153;źđ?&#x153;ź of 3 element model for the face fabric multiplied by n. In here, when all three constants are n times, the strain become 1/n. Thus, plot of three element model moves parallel. Revised six element model are shown in Table 4. The calculated behaviour of the revised six elements model was also shown in Figs.1 and 2. The strains of revised six elements model showed good agreements with the ones of bonded fabrics. Consequently, strain of laminated fabric was able to be predicted using experimental strain of face fabric and adhesive interlining, and experimental of strain of bonded fabric at time 0 (immediately after hanging). Table 4 Equation for six element model Equation for six element model

Combination 1(Aďź?a) 2(Aďź?b)

đ?&#x153;&#x20AC;đ?&#x153;&#x20AC; = â&#x2C6;&#x2019;0.489đ?&#x2018;&#x2019;đ?&#x2018;&#x2019; â&#x2C6;&#x2019;0.515đ?&#x2018;Ąđ?&#x2018;Ą â&#x2C6;&#x2019; 0.00962đ?&#x2018;&#x2019;đ?&#x2018;&#x2019; â&#x2C6;&#x2019;0.778đ?&#x2018;Ąđ?&#x2018;Ą + 1.645 đ?&#x153;&#x20AC;đ?&#x153;&#x20AC; = â&#x2C6;&#x2019;0.566đ?&#x2018;&#x2019;đ?&#x2018;&#x2019; â&#x2C6;&#x2019;0.205đ?&#x2018;Ąđ?&#x2018;Ą â&#x2C6;&#x2019; 0.104đ?&#x2018;&#x2019;đ?&#x2018;&#x2019; â&#x2C6;&#x2019;0.624đ?&#x2018;Ąđ?&#x2018;Ą + 1.612

5. Conclusion

Equation

đ?&#x153;&#x20AC;đ?&#x153;&#x20AC; = â&#x2C6;&#x2019;0.170đ?&#x2018;&#x2019;đ?&#x2018;&#x2019; â&#x2C6;&#x2019;0.487đ?&#x2018;Ąđ?&#x2018;Ą â&#x2C6;&#x2019; 0.000916đ?&#x2018;&#x2019;đ?&#x2018;&#x2019; â&#x2C6;&#x2019;0.797đ?&#x2018;Ąđ?&#x2018;Ą + 0.527 đ?&#x153;&#x20AC;đ?&#x153;&#x20AC; = â&#x2C6;&#x2019;0.104đ?&#x2018;&#x2019;đ?&#x2018;&#x2019; â&#x2C6;&#x2019;0.257đ?&#x2018;Ąđ?&#x2018;Ą â&#x2C6;&#x2019; 0.0895đ?&#x2018;&#x2019;đ?&#x2018;&#x2019; â&#x2C6;&#x2019;0.542đ?&#x2018;Ąđ?&#x2018;Ą + 0.531

Creep test of woven fabrics, adhesive interlinings and those laminated fabrics in 45 Â° bias direction under low weight was carried out for 7 days. The reduction effect on creep deformation in the bias direction by adhesive interlining was confirmed. The experimental creep strain of the face fabric and adhesive interlining was able to be predicted with three element model. The creep behavior of overlapped fabrics were well approximated with six element model using parameters of three element model of component fabrics. However, the creep behavior of bonded fabric was unable to predict with six element model because of the effect of adhesive. To take into account this effect in the six element model, the three parameters of the model for face fabric were multiplied by a factor n to make calculated strain and the experimental strain of bonded fabric at time 0 agree. The revised creep strains using the factor showed good agreements with the experimental strain of bonded fabric. The creep strains of laminated fabrics during 7 days were able to be predicted.

Acknowledgements This work was supported by JSPS KAKENHI Grant number 24220012.

6. References [1] Kim KO, Inui S and Takatera M. Verification of prediction for bending rigidity of woven fabric laminated with interlining by adhesive bonding. Text Res J 2011; 81(6): 598â&#x20AC;&#x201C;607. [2] Kim KO, Inui S and Takatera M. Prediction of bending rigidity for laminated fabric with adhesive interlining by a laminate model considering tensile and in-plane compressive moduli. Text Res J 2012; 82(4): 385â&#x20AC;&#x201C;399. [3] Kim K, Inui S and Takatera M. Bending rigidity of laminated fabric taking into account the neutral axes of components. Text Res J 2013; 83(2): 160â&#x20AC;&#x201C;170. [4] Kim K, Inui S and Takatera M. Prediction of bending rigidity for laminated weft knitted fabric with adhesive interlining. Text Res J 2013; 83(9): 937â&#x20AC;&#x201C;946. [5] Kim KO and Takatera M. Effects of adhesive agent on shear stiffness of fabrics bonded with adhesive interlining. J Fiber Bioeng Inform 2012; 5(2): 151â&#x20AC;&#x201C;162. [6] Kim KO and Takatera M. Effects of dot-type adhesive and yarn float on shear stiffness of laminated fabric with interlining. Text Res J, in printing, 2015.

Page 804 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Effect of needle-punching conditions on the fiber orientation in the nonwoven fabric characterized by X-ray micro computed tomography Tatsuya Ishikawa 1, Kengo Nakasone 1, KyoungHou Kim 1, Yutaka Ohkoshi 1,2 1

Faculty of Textile Science and Technology, Shinshu University Division of Frontier Fibers, Institute for Fiber Engineering, Shinshu University, 3-15-1 Tokida, Ueda, Nagano, 386-8567, Japan

Abstract. In the needle-punching process, fibers caught by the barb of needle are plunged into the web, and oriented along the normal-direction (ND) of fabric plane to form pillar-shaped fiber bundle, which acts as a bonding point of fabric. The size, the geometry and the density of bonding points are important to determine the properties of needle-punched nonwoven fabric. In this research, the fiber orientation change by needlepunching process was investigated by X-ray micro computed tomography (XCT). The number density of fibers and its orientation angle distribution were analyzed by the image analysis of obtained tomographic image for needle-punched nonwovens produced under several manufacturing conditions. The number density of fibers and the fraction of ND oriented fibers increased with increasing of both penetration depth and needling density. These results imply that the number density of pillar-shaped fiber bundles increases with increasing not only needling density but also penetration depth.

Keywords: Needle-punched nonwoven, X-ray computed tomography, fiber orientation.

1. Introduction In the manufacturing process of needle-punched nonwoven fabric, fibers are caught by barb of needle and plunged into the web, and oriented along to the normal-direction (ND) of fabric plane forming pillar-shaped fiber bundle, at which the fibers are entangled each other and consequently act as bonding point of fabric. The size, the geometry and the density of bonding points are largely influenced by its manufacturing conditions such as size of needle, needling density, and penetration depth of needle, from which the properties of needlepunched nonwoven fabric are determined[1–2]. To estimate the properties of needle-punched nonwoven fabric, several researches tried to evaluate the size, the geometry and the density of pillar-shaped fiber bundles [3–6]. Placing colored fibers on the web to visualize the pillar-shaped fiber bundles, they investigated the apparent and internal structure of pillar-shaped fiber bundle and the number of constituting fibers. However, the evaluation methods used in these researches were destructive and time-consuming. In addition, it has a limitation assuming uncolored fibers constituting the bulk of web were not involved in the pillar-shaped fiber bundles. Recently, a device named X-ray micro computed tomography (XCT) come to be a popular non-destructive observation tool for visualizing internal structure, and starts to be used for analyzing nonwoven fabric structure [7–10]. Jeon et al. investigated the internal structure of needle-punched nonwoven fabrics during tensile test by analyzing two-dimensional tomographic images obtained through XCT. They revealed that the constituent fibers were oriented more along tensile axis with increasing strain level of fabric. However, there is no researches investigated the change of internal structure for needle-punched nonwoven fabrics during its manufacturing process, i.e., the oriented structure of the constituent fibers along the ND of fabric plane. Therefore in this research, we have investigated the change of number density of fibers and its orientation angle distribution to ND with the change of needling density and penetration depth of needle by analyzing tomographic images obtained by XCT.

2. Experimentals Crimped polyethylene terephthalate (PET) fibers having diameter and length of 40 µm and 51 mm were used in this study. The fibers in tuft-state were opened to be sufficiently separated each other by opener, and

Page 805 of 1108

the opened fibers were carded by carding machine to obtain a homogenous web wound-up in parallel-laid. The basis weight of obtained webs was around 200 g/m2. In terms of the needle-punching machine, about 1000 needles were planted to its needle-board in the specific arrangement, and in further detail, 40 gauge needles in triangle form with regular barb spacing were planted. By this machine, the webs were needle-punched under following conditions; needling density of 20, 40, 80 punches/cm2 and penetration depth of needle of 6.4, 12.7, 19.0 mm. From each needle-punched nonwoven fabric, small pieces with 20 × 20 mm (MD × CD) were sampled for XCT measurement. The sample was set on the XCT device (Skyscan 1272, Bruker Corp), to which X-ray generated at 50 kV and 200 µA was exposed to obtain transmission images. As for transmission image, each image was obtained at 0.2 degree/image in rotation step, having 2452 × 1640 pixels (MD & CD × ND) in pixel number with 5 µm/pixel. From the obtained images, tomographic images were reconstructed by the software (NRecons, Bruker Corp) with image processing to denoise.

3. Results and discussions The tomographic image obtained from sample produced at needling density of 80 punches/cm2 and penetration depth of 12.7 mm is shown in Fig.1 (a). Fibers oriented along the fabric-plane are described as line, and the fiber orientation angle along to the ND can be estimated from its ellipsoidal shape by equation 1, as described in Fig.1 (b). The three-dimensional image rendered from the sequence of tomographic images of Fig.1 (a) is also shown in Fig.1 (c), in which 12 × 8 mm (length & width × thickness) of nonwoven fabric is displayed.

(eq. 1)

(a)

(b)

(c)

Fig.1. (a) The tomographic image of needle-punched nonwoven fabric. (b) The method to calculate the fiber orientation angle from tomographic image. (c) The three-dimensional image rendered from the sequence of tomographic images of (a). In (a, c), the fibers are described in white.

In the tomographic image obtained at the middle location in thickness of the circle-shaped sample with 10 mm in diameter, objects having minor diameter from 30 to 50 µm were extracted to calculate the number density of fibers and its orientation angle distribution. The effects of needling density and penetration depth of needle on the number density of fibers and its orientation angle distribution are shown in Fig.2.

Page 806 of 1108

(a)

(b) Fig. 2. The effects of needling density and penetration depth of needle on the number density of fibers and its orientation angle distribution. (a) The number density of fiber for each fiber orientation angle. (b) The fraction of fiber oriented along each angle. (D: (punches/cm2) in needling density, P: (mm) in penetration depth of needle) Comparing with the web sample, for most of the needle-punched samples, the number density of fibers increased more than twice. This was particularly remarkable according to increasing penetration depth of needle and needling density with the exception of penetration depth at 6.4 mm. At the penetration depth 6.4 mm, the number density of fiber did not increase with increasing needling density. At penetration depth of 12.7 and 19.0 mm the number density of fibers inclined 0-40º to ND of the fabric plane increased with increasing needling density, while the number density changed little at penetration depth 6.4 mm. In regard to its orientation angle distribution for each sample, the fraction of fibers inclined 0-40º increased with increasing penetration depth and needling density, while the fraction of fibers inclined 40-60º or 60-90º tended to decrease. The fraction of fibers inclined 0-40º was 38 % in the sample produced at penetration depth of 19.0 mm and needling density of 80 punches/cm2, whereas the fraction was only 18 % in the sample produced at penetration depth of 6.4 mm and needling density of 20 punches/cm2. On the other hand, the fraction of fibers inclined 040º in the web sample was 31 %, which was high comparing with that of needle-punched samples. Because only the 1st barb of needle went through the fabric at the penetration depth of 6.4 mm, few fibers were caught and plunged into the web, and thus bonding points where fibers were oriented along ND were

Page 807 of 1108

hardly formed. The number density of fibers with 0-40º inclined to ND also hardly increased with increasing needling density. In contrast, beyond the penetration depth 12.7 mm, more than 4 barbs of the needle went through the fabric and many fibers were plunged into the fabric. Therefore, pillar-shaped fiber bundles oriented along ND were formed, at which the movement of fibers was restricted.

4. Conclusions Changes of the number density and the orientation angle distribution with changing needling density and penetration depth of needle were investigated by analyzing tomographic images obtained using XCT. Beyond the penetration depth of 12.7 mm, the needles penetrated through the web holding enough amounts of fibers to form the pillar-shaped fiber bundles. Consequently, the number density of fibers, in particular the number density of fiber inclined 0-40º to ND, increased with increasing not only needle density but also penetration depth. Their maximum value was observed at needling density of 80 punches/cm2 and penetration depth of 19.0 mm, and it attained 7.8 times for the number density and 9.5 times for that of 0-40º comparing with web. This research demonstrated that the change of internal structure of nonwoven fabrics in the needle-punching process, at which the constituent fibers are oriented along to the ND of fabric plane, could be evaluated analyzing XCT tomographic images.

5. Acknowledgement This work was supported by a Grant-in-Aid for the Shinshu University Advanced Leading Graduate Program by the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan.

6. Reference [1] J. W. S. Hearle, M. a. I. Sultan, and T. N. Choudhari, ‘9—A Study of Needled Fabrics. Part II: Effects of the Needling Process’, J. Text. Inst., vol. 59, pp. 103–116, Nov. 1968. [2] a. Watanabe, M. Miwa, T. Yokoi, and a. a. Merati, ‘Predicting the Penetrating Force and Number of Fibers Caught by a Needle Barb in Needle Punching’, Text. Res. J., vol. 74, no. 5, pp. 417–425, May 2004. [3] J. W. S. Hearle and T. N. Choudhari, ‘35—a Study of Needled Fabrics: Part VII: the Transfer of Fibres Through the Web By Needling’, J. Text. Inst., vol. 60, pp. 478–496, Nov. 1969. [4] J. W. S. Hearle and A. T. Purdy, ‘THE STRUCTURE OF NEEDLE PUNCHED FABRIC’, Fibre Sci. Technol., vol. 4, no. 4, pp. 81–100, 1971. [5] J. W. S. Hearle and A. T. Ptmoy, ‘ON THE NATURE OF DEFORMATION OF NEEDLED FABRICS’, Fibre Sci. Technol., no. 5, pp. 113–128, 1971. [6] M. Miao, ‘An Experimental Study of the Needled Nonwoven Process Part II: Fiber Transport by Barbed Needles’, Text. Res. J., vol. 74, no. 5, pp. 394–398, May 2004. [7] S. Y. Jeon, W. R. Yu, M. S. Kim, J. S. Lee, and J. W. Kim, ‘Predicting the tensile strength of needlepunched nonwoven mats using X-ray computed tomography and a statistical model’, Fibers Polym., vol. 15, no. 6, pp. 1202–1210, 2014. [8] S.-Y. Jeon, W.-J. Na, Y.-O. Choi, M.-G. Lee, H.-E. Kim, and W.-R. Yu, ‘In situ monitoring of structural changes in nonwoven mats under tensile loading using X-ray computer tomography’, Compos. Part A Appl. Sci. Manuf., vol. 63, pp. 1–9, 2014. [9] S. S Manickam and J. R. McCutcheon, ‘Characterization of polymeric nonwovens using porosimetry, porometry and X-ray computed tomography’, J. Memb. Sci., vol. 407–408, pp. 108–115, 2012. [10] P. Soltani, M. S. Johari, and M. Zarrebini, ‘Effect of 3D fiber orientation on permeability of realistic fibrous porous networks’, Powder Technol., vol. 254, pp. 44–56, 2014.

Page 808 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Effects of Fabric Structures and Yarn Constitutions on the Functional Properties of Cooling Knitted Fabric K. B. Cheng1, 2, J. C. Chen3, J. T. Chang2*, F. L. Huang2, J. Y. Liu2, K. C. Lee4 1

Department of Fiber and Composite Materials, Feng Chia University, Taichung 407, Taiwan, R.O.C 2 Textile and Material Industry Research Center, Feng Chia University, Taichung 407, Taiwan, R.O.C 3 Graduate Institute of Materials Science and Technology, Vanung University, Chungli, Taiwan, R.O.C 4 Department of Textile Engineering, Chinese Culture University, Taipei 11114, Taiwan, R.O.C Corresponding author: K. B Cheng (kbcheng@fcu.edu.tw)

Keywords. Qmax value, thermal image temperature, ultraviolet protection factor, air permeability, moisture permeability and far infrared reflection index, cooling knitted fabric, weft and warp knitting machine.

Abstract. This paper presents the results of an experimental characterization of knitted fabrics with the different fiber constitutions and compares the functional results with cotton, regular Nylon 6, polyester, cooling Nylon 6 and interknitting fabrics. The Qmax value, thermal image temperature, ultraviolet protection factor (UPF), air permeability, and moisture permeability were conducted on knitted fabrics to assess fabric performance. The knitted fabrics were produced on Liba weft knitting machine and Tricot warp knitted fabric were produced on Carl Meyer warp knitting machine. Test results indicate that high functional weft knitted fabric with interknitting the 40d/24f cooling Nylon 6 yarns with 20d Spandex (14 wt%) which have better performance than the other seven knitted fabrics. Qmax value and thermal image temperature, ultraviolet protection factor, air permeability, and moisture permeability of cooling Nylon 6 and interknitting fabrics exhibited better performance compared to cotton, Nylon 6, polyester knitted fabrics. The functions of the cooling knitted fabrics would be improved with increasing cooling Nylon 6 content and fabric density. It can be used to produce the knitted fabric for under wear, sport wear, socks, pants, and bra materials in summer and spring seasons.

1. Introduction It is known that cotton, viscose rayon, nylon, polyester, and Tencel fibres were used as the warp or weft knitted fabric are mainly used in underwear, sport wear, socks, pants, and bra materials etc. Within the scope of this paper, the aim was to fabricate the knitted fabrics that have better air permeability, Qmax cooling property, temperature decreasing, moisture transfer, FIR reflection index and higher clothing comfort. Hence, a high added value, considering the fact that cooling yarn and weft and warp knitted fabric structures can be used for underwear. Furthermore, in the first stage of the paper, a weft knitted fabric was designed to fabricate underwear and seven different

Page 809 of 1108

fabrics were manufactured by circular knitted machine utilizing cotton, polyester, Nylon 6 DTY yarns, Nylon 6 cooling yarn, and Nylon 6 DTY and cooling yarns interknitting. Furthermore, a warp knitted fabric was also designed to fabricate underwear which manufactured by warp knitted machine utilizing regular 50d/72f Polyester DTY yarns (80%), and Spandex (20%) interknitting. Then, air permeability, Qmax cooling property, temperature decrease, and moisture transfer of the knitted fabrics were analysed, statistically reviewed and compared to each other. At the end of the paper, fabrics with optimum usage properties would be suggested. Cooling fibre materials were design and manufactured in accordance with the concept of energy saving and in response to the rapid environment change. Principle and materials properties of cooling fibre products were proposed as follows: 1.Due to moisture regain of cooling fibres to cause the wet cooling contribution; 2. Due to moisture absorption and exothermic speed of cooling fibres to cause the wet cooling contribution; 3. Due to fibre chemical modification, cause much more OH and hydrophilic groups in fibre structure to make wet cool feeling; 4. Solid and doubled-face structures of the fibre products to cause cool feeling; 5. Fibber density, fineness, porosity, and sheath/ core and side by side spun from bicomponent conjugate spinning method to make the cool feeling; 6. composite mineral stone with higher thermal conductivity and thermal diffusivity coefficient induced to cause the cool feeling;

7. Microcapsule phase change materials (PCM)

induced to make the temperature balanced; 8. Conjugate spinning method is used to fabricate the fibre after materials compounding such as Anti-UV fibres. To accomplish these demands, cooling fabrics were designed with following features: 1. Using light and thin Fabrics since have larger thermal flow capacity and better thermal diffusivity; 2. Lower density fabrics, let the hot air easy to discharge; 3. Porosity effects, cooling air convection activity between the hot air and microclimate directly; 4. Concave and protruding effects in solid structure design that would increase the capillary effects and specific surface area of the Cooling fibres; 5. Due to specific surface area, let the perspiration and quick absorption that would reduce the uncomforted feeling; 6. Adding the moisture absorbent agent and thermal diffusivity materials such as mint, microcapsule, xylitol, etc. by using padding, lamination or printing methods. In this paper, a new fibre material which contains mineral stone composite cooling powders (MSCCP) is designed for cooling fabrics. MSCCP were prepared by wet type ball grinding and through spraying dry then make the master batch (MB) and added certain amount of MB to fabricate full draw yarn (FDY) with 40d/24f by melt spinning method in this paper. Furthermore, the regular draw textured yarn (DTY) with 40d/36f and 40d/34f by Murata nip twister. Finally, the weft knitted fabric was fabricated by circular knitting machine. It is expected that the knitted fabrics exhibit the cooling, anti-UV, reflection index and water absorption properties. The cooling FDY yarns were used as the raw materials to fabricate weft knitted fabrics with the different fiber materials by circular knitted machine with Qmax value, anti-UV, temperature difference, and water absorption function properties. The MSCCP particles, cooling FDY yarns and their inter-knitted fabrics have been fabricated successfully. Furthermore, the objectives of this investigation were to

Page 810 of 1108

characterize Qmax value, thermal image temperature, ultraviolet protection factor, air permeability, and moisture permeability of knitted fabrics with the cooling knitted yarns. Finally, the end applications of the knitted fabrics will also be proposed.

2. Experimental 2.1 Materials and Process The areal weight, constitutions, knitted structure, density of wale and course yarns per unit length (WPI, CPI) were shown in Table 1. In order that the fabric codes can be apprehended easily, the codes were prepared by using the numbers of yarn codes which are used in manufacturing of the knitted fabrics. The knitted fabrics were manufactured in single jersey knitted structure (SJ) by Liba circular knitted machine and Tricot knitted structure by Carl Meyer warp knitted machine in Germany. The texture reports of the weft knitted fabrics are same. The weft knitted fabric produced by Liba weft knitting machine was configured to have an areal weight similar among these five fabrics. An interknitting of 40d/24f Nylon 6 FDY with cooling and semidull (43 wt%) and 40d/34f Nylon 6 DTY with bright (43 wt%) and 20d Spandex was used to produce weft knitted fabric SJCBS. A interknitting of 50d/72f polyester DTY with semidull (89%) and 20d Lycra (11wt%) was used to produce weft knitted fabric SJPDL. A interknitting of 40d/36f Nylon 6 DTY with semidull (86%) and 20d Lycra (14wt%) was used to produce weft knitted fabric SJNDL. A interknitting of 50d/72f polyester DTY with semidull (80%) and 20d Lycra (20wt%) was used to produce warp knitted fabric TPDS. Finally, an interknitting of 40â&#x20AC;&#x2122;S/1 cotton yarn (94%) and 20d Lycra (6 wt%) was used to produce weft knitted fabric SJCS. Table 1 Technical data of the knitted fabrics with different constitutions Article

Description

Constitutions

WPI

CPI

126.5

124

118.0

103

128.5

131

120.03

131

140

(g/m2)

No. SJCBS

Weight

40d/24f SD Cooling PA 6 DTY 43% 40d/34f Bright PA 6 DTY 43% 20D Spandex 14%

SJPDL

50D/72f Polyester DTY 89% 20D Lycra 11%

SJNDL

40d/36f SD PA 6 DTY 86% 20D Lycra 14%

TPDS

Tricot

50d/36f Polyester DTY 80% Spandex 20%

SJCS

40â&#x20AC;&#x2122;S/1 Cotton yarn 94% Spandex 6%

Note: SJ means single Jersey; Tricot: Tricot warp knitted structure; WPI: wales/inch; CPI: Course/inch; SD: Semi Dull; B: Bright

Page 811 of 1108

2.2 Testing Methods All of the experimental studies in this section were conducted in the Inorganic/ Organic Laboratories in Feng Chia University, Faculty of Engineering, Department of Fiber and Composite Materials. All of the knitted fabric samples were conditioned by keeping under the standard atmospheric conditions (20 ± 2°C temperature and 65% ± 5 relative humidity) for 24 hours before the properties and functions testing studies. The measurements are described as follows. The weight values of the knitted fabrics were identified according to ISO 5084:1997 standard, and the thickness values of the knitted fabrics were identified according to ISO 5084:1997 standard. Air permeability of the knitted fabrics was measured according to SFS-EN ISO 9237:1996 standard. Water permeability of the knitted fabrics was measured according to TS 257 EN 20811/T1–Textile Fabrics-Determination of Resistance to Water Penetration-Hydrostatic Pressure Test standard. Qmax value of the knitted fabrics was measured by KES-F7-II Thermo Labo II according to CNS 15687. Thermal image temperature of the knitted fabrics was measured according to FTTS-FA-010. The thermal absorption and diffusion capability of the cooling knitted fabrics were measured using a FLIR thermal image camera. Scientific methods of evaluating the UPF of fabrics have been developed and specified according to Australia/New Zealand (AS/NZ) standard 4399:1996.

3. Results and Discussion 3.1 Qmax Function The average Qmax value of the weft knitted fabrics with different content of Nylon 6 cooling draw textured yarn (DTY) are compared with the Qmax of warp knitted fabric with polyester DTY and Spandex yarns interknitting as well as weft knitted fabrics with cotton/Spandex, polyester/Spandex, Nylon 6/Spandex yarns interknitting in Table 2. Results indicated that the average Qmax for the four weft knitted fabrics is about 30% better than the Qmax for cotton/Spandex, polyester/Spandex, Nylon 6/ Spandex knitted fabrics, respectively. This improvement may be attributed to much more the cooling yarn content, thermal properties, and fabric density in the knitted fabric. Furthermore, analytical results indicated that the thermal conductivity and diffusivity of the cooling yarn and fabric is major contributor to initiation of cooling feeling. Table 2 Qmax comparison of knitted fabric with different constitutions and structure Test Item

Technical Face (W/cm2)

Technical Back (W/cm2)

SJCBS

0.228

0.303

SJPDL

0.192

0.244

SJNDL

0.230

0.302

TPDS

0.200

0.232

SJCS

0.182

0.192

Page 812 of 1108

3.2 Increasing and Decreasing the Temperature on the Surface of Knitted Fabrics The temperature difference of the knitted fabrics was shown in Table3. All of the knitted fabrics exhibited thermal absorption and diffusivity behaviors. Average temperature increaseddecreased for the five knitted fabrics are compared each other with the different content of Nylon 6 cooling draw textured yarn (DTY) in Table 1. Results indicated that the average temperature increaseddecreased for the SJCBS single jersey knitted fabrics is about 30% better than the temperature increaseddecreased for the lower content cooling yarn in weft knitted fabric. Table 3 Temperature Difference of the Knitted Fabrics ΔT 1

ΔT 2

ΔT 3

(T 10 -T 0 )

(T 10 -T 20 )

(T 20 -T 0 )

SJCBS

7.7℃

5.2℃

2.5℃

SJPDL

7.7℃

5.5℃

2.3℃

SJNDL

7.6℃

5.4℃

2.3℃

TPDS

9.6℃

7.0℃

2.6℃

SJCS

10.2℃

7.7℃

2.6℃

3.3 Transmission and Shielding Rate of Ultraviolet for the Knitted Fabrics The transmission and shielding rate of ultraviolet of the knitted fabrics was listed in Table 3. The SJCBS knitted fabrics exhibited 43% cooling yarn and have lower thermal conductivity and higher diffusivity, so have the UV protection effect with the other four kinds of the knitted without cooling PA6 yarns. Results indicated that his transmission and shielding rate of ultraviolet for the SJCBS single jersey knitted fabrics have not significance difference each other. It is probably because the yarns have titanium oxide and cooling powders within the knitted fabric. Table 4. Transmission and Shielding Rate of Ultraviolet for the Knitted Fabrics Transmission of ultraviolet (%)

Shielding rate of ultraviolet (%)

UVB

UVA

UVB

UVA

2.4

2.9

97.6

97.1

32301 SJPDL

2.7

2.2

97.3

97.8

32821 SJNDL

0.3

99.7

0.2

99.8

0.1

99.9

32122A SJCBS

S615136 TPDS VF0191-12 SJCS

Page 813 of 1108

3.4 The Moisture Permeability of the Knitted Fabrics The moisture permeability of the knitted fabrics was listed in Table 5. The SJCBS knitted fabrics exhibited 43% cooling yarn and have lower thermal conductivity and higher diffusivity. However, the moisture permeability for all kinds of the knitted fabrics without significance difference each other. It is probably because the yarns constitutions and fabric structure. Table 5 The Moisture Permeability of the Knitted Fabrics

Moisture permeability (g/m2/24h)

SJCBS

1675

SJPDL

1694

SJNDL

1705

TPDS

1594

SJCS

1536 Moisture permeability (g/m2/24h)

SJCBS

1675

SJPDL

1694

SJNDL

1705

TPDS

1594

SJCS

1536

4. Conclusions An experimental study has been performed in order to evaluate the performance of the cooling knitted fabrics and better understanding of the factors and testing methods influencing of these cooling knitted fabrics. The cooling fiber and regular polyester and polyamide 6 fiber materials were used to fabricate the knitted fabrics that were evaluated to establish their potential and functions for application in functional apparels. The knitted fabrics with single jersey configurations were produced on Liba circular knitting machine and one fabric was produced on a Carl Meyer warp knitting machine. All the fabrics were tested by the Qmax value, thermal image temperature, ultraviolet protection factor (UPF), air permeability, moisture permeability and far infrared (FIR) reflection index testing methods to assess fabric performance. It has been clearly demonstrated that the Qmax value, thermal image temperature, ultraviolet protection factor (UPF), and moisture permeability were conducted to compare the effects of yarn constitutions and fabric structures on the cooling knitted fabrics. The A and B fabrics Qmax value

Page 814 of 1108

were similar to the value of warp knitted fabric. The addition of cooling fiber amount increased the Qmax, thermal image temperature, ultraviolet protection factor (UPF), and moisture permeability of the knitted fabrics to the target value of 0.14W/cm2., 2℃, UPF=50+, 1500g/m2/24h and 0.90 respectfully. A more limited database was generated for the cooling knitted fabrics; their functional properties were comparable to the performance of cooling knitted fabrics. The results of this experiments indicated that cooling yarn manufacturing method is a viable process for producing the high quality and performance cooling knitted fabrics. To achieve international brand underwear quality, the knitting fabric configuration must incorporate stringent cooling yarn constitutions that will control cooling fiber content, yarn tension, alignment, and configuration stability. More details on the fabricated techniques used for these structures and the mechanical properties are described elsewhere.

Acknowledgements We appreciate the analysis equipment support from Precision Instrument Support Center and Department of Materials Science and Engineering in Feng Chia University. This study is financial support by Ministry of Science and Technology in Taiwan under NSC-96-2221-E-035-113-MY3 project.

References 1. Hepburn, C., “Polyurethane Eastomers” , Applied Science Publisher, London and New York ,1982, pp.3-6. 2. Gnter Oertel, “Polyurethane Handbook”, Hanser Publisher, Munich Vienna New York, 1985. 3. Frisch, F.C., “Polyurethane Technology”, Ed., Bruins, P.F., Interscience Publishers, New York, 1979, pp.1. 4. Dr. K. Bergmann, EMS INVENTA-FISCHER, Polyamide 2002 World Congress, Modern Polyamide-6 Production Technology, 2003. 5. M. I. Kohan, Nylon Plastics Handbook, 1995.

Page 815 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Effects of Twisting Coefficients on Properties of Coolplus/Zinc Ion Yarns and Knitted Fabrics Ming-Chun Hsieh 1, Chao-Tsang Lu 2, Ching-Wen Lou 3, Chien-Teng Hsieh 4 and Jia-Horng Lin 1,5,6 + 1

Laboratory of Fiber Application and Manufacturing, Department of Fiber and Composite Materials, Feng Chia University, Taichung City 40724, Taiwan, R.O.C. 2 Graduate Institute of Biotechnology, Central Taiwan University of Science and Technology, Taichung City 40601, Taiwan, R.O.C. 3 Institute of Biomedical Engineering and Materials Science, Central Taiwan University of Science and Technology, Taichung City 40601, Taiwan, R.O.C. 4 Department of Fashion Design and Merchandising, Shih Chien University Kaohsiung Campus, Kaohsiung City 84550, Taiwan, R.O.C. 5 Department of Fashion Design, Asia University, Taichung City 41354, Taiwan, R.O.C. 6 School of Chinese Medicine, China Medical University, Taichung City 40402, Taiwan, R.O.C.

Abstract. People have greater demands to wear amenity, following progressing technology and a higher living standard. Textiles that possess single functions have fallen behind the expectations of consumers, while products that have a great variety of functions gradually replace the shopping emphasis. This trend also causes consumer groups to shift from athletes to a wider population. This study plans to combine Coolplus yarns and zinc ion yarns by using a rotor spin device, in order to form wrapped yarns. The Coolplus yarns are combined into plied yarns, which are then wrapped in the zinc ion yarns by using a twist machine. During the process, two parameters, including the twisting coefficients as well as the twisting speeds, are varied, in order to compare the mechanical properties and antimicrobial efficacy of the different moisture absorption/antimicrobial wrapped yarns. A scanning electron microscope (SEM) is used to observe if the wrapped yarns are covered by zinc ions. Finally, the moisture absorption/antimicrobial wrapped yarns that are composed of different twisting coefficients are fabricated into knitted fabrics by using a circular hose machine, after which the mechanical properties and antimicrobial efficacy of the knitted fabrics are evaluated. Keywords: twisting coefficient, Coolplus yarn, zinc ion, antimicrobial.

1. Introduction People have an increasingly higher living standard as a result of advanced technologies. Due to their higher requirement of wearing comfort, single-function textiles can no longer satisfy consumersâ&#x20AC;&#x2122; expectations [1]. Products with diverse functions thus have appeal for the ordinary population in addition to professional users. The field of medicine has rapidly advanced in recent years, which improves the living standard, and also makes people pay more attention to hygiene. The antibacterial concepts have also been rooted in daily life. [2, 3] Staphylococcus aureus is one common pathogenic organisms, and primarily induces parasites in arms, elbows and heels of human [4]. This study incorporates Coolplus yarns and zinc ion yarns by using a rotor spin device in order to make wrap yarns. During the process, the twisting speed of the rotor spin device is changed in order to create different coefficients of twisting for the zinc ion yarns. The wrap yarns are then made into knits by using a hosiery machine. Finally, the wrap yarns and knits are tested in terms of mechanical properties and antimicrobial efficacy.

Corresponding author. Tel.: + 886-4-2451-8672. E-mail address: jhlin@fcu.edu.tw

Page 816 of 1108

2. Experimental 2.1.

Materials and Equipment

We welcome contributions from throughout the world. Papers are to be in English and submitted via the website at www.atc-13.org Please see the website for deadlines. Coolplus yarns are purchased from Everest Textile, Taiwan, R.O.C. The rotor spin device is provided by Feng Chia University, Taiwan, R.O.C. Zinc ion yarns are purchased from Tung Ho Textile, Taiwan, R.O.C. The fully computerized, high efficiency, single cylinder hosiery machine (DK-B318) is provided by Da Kong Enterprise, Taiwan, R.O.C. The Computer Universal Testing Machine (HT2402) is provided by Hung Ta Instrument, Taiwan, R.O.C.

2.2.

Experimental Procedure

Two plies of 75D Coolplus yarns are combined, and serve as the core. 180D zinc ion yarns are then used to wrap the core by using a rotor spin device. The rotor spin device is operated at speeds of 3000, 9000, and 15000rpm, which are used to provide the zinc ion yarns with twisting coefficients of 1, 3, and 5. The moisture absorbent/antimicrobial wrap yarns are then made into knits by using a hosiery machine. The influence of different twisting coefficients on the breaking tenacity and antimicrobial efficacy of the wrap yarns and knits are examined. Finally, a scanning electron microscope (SEM) is used in order to observe whether the antimicrobial wrap yarns are covered by zinc ions.

3. Results and Discussion 3.1.

Effects of Twisting Coefficient on Breaking Tenacity of Wrap Yarns and Knits

The Coolplus yarns are first combined, and are then wrapped in zinc ion yarns as indicated in Figure 1 (a). Due to the twisting by using a rotor spin device, the wrap yarns have breaking tenacity that increases as the cohesion of the yarns occurs. The breaking tenacity first increases as a result of the increasing twisting coefficients, but then decreases when the twisting coefficient is 5. This result is ascribed to the excessive twisting that causes the yarn to break, and the breaking tenacity thus decreases. Figure 1 (b) indicates that the breaking tenacity of the knits that are composed of wrap yarns that are made with different twisting coefficients. The breaking tenacity along the warp direction first increases and then decreases. In addition, the breaking tenacity along the warp direction is higher, rather than the weft direction. The knits have two times the amount of loops along the warp direction than the weft direction. There is a relatively smaller number of yarns along the weft direction to bear the externally applied force, which results in a higher breaking tenacity along the warp direction.

Fig. 1: (a) The breaking tenacity of wrap yarns with various twisting coefficients, and (b) the breaking tenacity along the warp direction and the weft direction of the knits with corresponding constituent wrap yarns.

3.2.

Effects of Twisting Coefficient on Antimicrobial Efficacy against Staphylococcus Aureus of Wrap Yarns

The antimicrobial efficacy of various wrap yarns is indicated in Figure 2. Figure 2 (a) is the control group that the yarns are not processed with twisting, and the Staphylococcus aureus is found grow surrounding the yarns, indicating the absence of antimicrobial efficacy in the non-twisted yarns. When the twisting coefficients increase from 1, 3 to 5, the shade of Staphylococcus aureus becomes lighter. This may be ascribed to a greater

Page 817 of 1108

amount of zinc ion yarns per unit area, which contributes to a higher antimicrobial efficacy of the wrap yarns. As a result, the antimicrobial efficacy of wrap yarns increases as a result of greater twisting coefficients.

Fig. 2: The antimicrobial efficacy of wrap yarns against Staphylococcus aureus as related to various twisting coefficients of (a) 0 (b) 1 (c) 3 and (d) 5.

3.3.

Effects of Twisting Coefficient on Antimicrobial Efficacy against Staphylococcus Aureus of Knits

Figure 3 indicates the inhibition zone of the knits that are composed of different wrap yarns that are made with twisting coefficients of 0, (i.e., the control group), 1, 3, and 5. The inhibition zone of the knits enlarges as a result of the increasing twisting coefficients. A high twisting coefficient means a higher amount zinc ion yarns per unit area, which also results in a greater area of knits being in contact with Staphylococcus aureus, and thereby significantly improves the antimicrobial efficacy.

Fig. 3: The antimicrobial efficacy of knits against Staphylococcus aureus. The knits are composed of wrap yarns that are made with twisting coefficients of (a) 0 (b) 1 (c) 3 and (d) 5.

3.4.

SEM Observation of the Surface of Zinc Ion Yarns

Figure 4 indicates the SEM images of zinc ion yarns, where the zinc ions are present. The wrap yarns and knits can thus obtain an antimicrobial efficacy by a balance between the positive charges of zinc ions and the negative charge of the bacterias.

Fig. 4: Surface observation of zinc ion yarns.

Page 818 of 1108

4. Conclusions This study examines the influence of twisting coefficients on the breaking tenacity and antimicrobial efficacy of the wrap yarns and the knits. A twisting coefficient of 3 results in a complete cohesion of the yarns, strengthens the breaking strength of the wrap yarn. In contrast, a twisting coefficient of 5 causes an excessive twist level that decreases the breaking tenacity of the yarns. In addition, the breaking tenacity along the warp direction of the knits is higher than along the weft direction. This result is due to the fact that the knits have twice as many yarns along the warp direction, rather than along the weft direction. Finally, the inhibition zone against Staphylococcus aureus of the knits is also significantly increased as a result of the greater twisting coefficient of the constituent wrap yarns.

5. Acknowledgements The authors would like to thank Ministry of Science and Technology of Taiwan, for financially supporting this research under Contract MOST 103-2221-E-035-028.

6. References [1] S. Perera, B. Bhushan, R. Bandara, G. Rajapakse, S. Rajapakse, and C. Bandara, Colloids and Surfaces aPhysicochemical and Engineering Aspects, 436, 975 (2013). [2] S. C. Burnett-Boothroyd and B. J. McCarthy, in "Textiles for Hygiene and Infection Control" (B. J. McCarthy, Ed., pp. 196, Woodhead Publishing, 2011. [3] K. Gad, in "Encyclopedia of Toxicology (Third Edition)" (P. Wexler, Ed., pp. 182, Academic Press, Oxford, 2014. [4] E. A. Grice, H. H. Kong, S. Conlan, C. B. Deming, J. Davis, A. C. Young, G. G. Bouffard, R. W. Blakesley, P. R. Murray, E. D. Green, M. L. Turner, J. A. Segre, and N. C. S. Progra, Science, 324, 1190 (2009).

Page 819 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Evaluation of effective permittivity of nonwoven fabrics using twolayer microstrip transmission line method Hamid Reza Sanjari 1, Ali Akbar Merati 2+ , S.Mohammad Hosseini Varkiyani 1 and Ahad Tavakoli3 1

Department of Textile Engineering, Amirkabir University of Technology, Tehran, Iran Advanced Textile Materials and Technology Research Institute (ATMT), Amirkabir University of Technology, Tehran, Iran 3 Department of Electrical Engineering, Amirkabir University of Technology, Tehran, Iran

Abstract. In the present paper, the two-layer microstrip transmission line method is used to evaluate the high frequency effective permittivity of various needle-punched nonwoven fabrics. The samples were produced using five different percent of regular and hollow polyester fibers. The overall permittivity and the operating frequency of the structure were changed by placing the samples on the line or under the dielectric substrate. Using the closed-form equations based on quasi-static analysis, the values of the effective permittivity of each sample in each arrangement were extracted from the frequency shifts. Keywords: Effective permittivity, two-layer microstrip transmission line, high frequency measurement, needle-punched nonwoven fabrics

1. Introduction Recent developments in smart textiles and wearable systems have heightened the need for electromagnetic characterization of fibrous structures, among which the permittivity is one of the most important parameters affecting the performance of these materials, especially in some new applications [1]. From practical point of view, fibrous structures in simplest form are heterogeneous mixtures of air and fibers. Usually in the case of mixtures, the overall permittivity is expressed in term of effective permittivity. Emerging of textile transmission lines and wearable antennas has revealed the need for high frequency characterization of fibrous structures from radio frequency to terahertz frequency [2, 3]. Several methods have been used for measuring high frequency permittivity of fibrous structures such as waveguide cavity and patch antenna methods1, [4]. Most of these methods are based on measuring the changes occurring in one parameter due to placing the unknown material in measurement setup. Multilayer microstrip transmission line is another method that can be used to study the permittivity of fabrics [5]. In this method, the unknown material (fabric) can be placed under or over the microstrip line. Technically, this action will change the overall permittivity and the operating frequency of transmission line. These changes will be proportional to the dielectric constant of unknown material. Several attempts have been made to derive empirical or analytical closed-form equations to predict the effective permittivity of such multilayer microstrip lines [6, 7]. The aim of the present paper is to determine the effective permittivity of different needle-punched nonwoven fabrics via two-layer microstrip transmission line method at the frequency of about 2.2 GHz. To achieve the objectives of this research, the rectangular samples of nonwoven fabrics were placed on the line and under the dielectric substrate. Afterwards, the changes occurred in the operating frequency of the microstrip line in each arrangement were related to the samples effective permittivity using the available equations presented in literature [6]. It seems that this method due to its simplicity and low fabrication cost is a good option for measuring the high frequency permittivity of textile substrates.

2. Materials and methods 2.1.

Samples preparation

To evaluate effective permittivity of textile substrates at high frequency ranges, five samples of needled fabrics were produced using regular and hollow polyester fibres. The weight fraction of hollow fibres was set

Page 820 of 1108

at intervals of 25% (i.e. 0%, 25%, 50%, 75%, and 100%). The needling process was carried out in two steps. A total needling density of 91 needle/cm and needle penetration depth of 15 mm using the Groz-Beckert felting needles. The properties of polyester fibres and the process parameters of needle-loom are shown in Tables 1 and 2. The surface density and the thickness of each sample was measured according to ASTM D6242 and ASTM D5729, respectively [8, 9]. These properties are listed in Table 3. Table 1: Geometrical properties of the polyester fibers. Fiber type Regular Hollow

Fiber inner diameter (μm) 15.26

Fiber denier 7.01 6.95

Fiber outer diameter (μm) 26.78 30.89

Table 2: Process parameters of needle-loom. Needling density Primary needling Secondary needling

60 31

The depth of needle penetration (mm) 15 15

Production speed (m/min) 2.8 4.9

The number of needles per running cm 30 30

Punches per min 580 526

Table 3: Surface density, thickness and porosity of different samples. Surface density (gr/m2)

Sample type E1 (100% hollow fibers) E2 (75% hollow fibers-25% regular fibers) E3 (50% hollow fibers-50% regular fibers) E4 (25% hollow fibers-75% regular fibers) E5 (100% regular fibers)

2.2.

Thickness (mm)

Porosity (%)

4.94 4.13 4.03 3.83 3.44

96.28 95.42 94.81 94.09 93.22

254.85 262.40 290.55 314.15 324.05

Microstrip transmission line design

Microstrip transmission lines are the most popular planar transmission structures which are mainly used at microwave frequencies [10]. For a chosen dielectric substrate thickness h 1 and a relative permittivity ε 1 , the dimensions of single-layer microstrip line are calculated from the available closed-form formulas [11]. The characteristics of this line are shown in Table 4. Table 4: Characteristics of single-layer microstrip line. L (mm) 48.032

W (mm) 30

w (mm) 2.631

h 1 (mm) 0.8128

ε r1 3.38

The microstrip line was designed in such form that is possible to place a nonwoven on the line or under the dielectric substrate (Figures 1). It should be mentioned that the described setup is previously used in such case the fabric is placed under the dielectric substrate [5]. Afterwards, Samples were cut in suitable size and the measurements of parameter S 11 were carried out using an HP 8510D Vector Network Analyser at two sets of arrangements. The measurements were repeated 5 times for each sample. All measurements were performed at a relative humidity of 37% and ambient temperature of 21 °C. The overall permittivity of these two-layer structures was calculated from the first notch of the measured S 11 curves using Equation (1.2):

ε eff

overal

c 2 ) 2Lf

(1.2)

where ε eff overal is the overall permittivity of the structure, c is the light velocity, L is the length of strip line and f is the first frequency at which the notch occurs. After calculating the overall permittivity, the effective permittivity of the nonwoven samples ( ε r 2 ) was calculated for both cases (samples placed on the line (OL) and under the dielectric substrate (UD)) using Equations (2.2) and (3.2), respectively [6]:

Page 821 of 1108

ε r 2(OL ) = ε r 2(UD ) =

q 2 (ε eff overal − ε r 1q1 ) (1 − q1 ) − (1 − q1 − q 2 )(ε eff overal − ε r 1q1 ) 2

q '1 (ε eff overal − 1 + q '1 + q '2 ) q' (q '1 + q '2 ) 2 − 2 (ε eff overal − 1 + q '1 + q '2 )

(2.2)

(3.2)

ε r1

where ε r 2 is the effective permittivity of the nonwoven samples and q 1 , q 2 , q’ 1 and q’ 2 are coefficients which are a function of the substrate thickness and microstrip line width.

(A)

(B) Fig. 1: (A) Cross-sectional view of two-layer microstrip transmission line, (a) nonwoven fabric on the microstrip line, (b) nonwoven fabric under the dielectric substrate, (B) Photograph of effective permittivity measurement setup

3. Results and discussions To verify the designed single-layer microstrip transmission line, the full wave analysis using the method of moment (MoM) was performed. Referring to Figure 2 (A), a horizontal and vertical shift in preliminary computed curve (full wave analysis curve) is observed. Considering to the mentioned setup, typically a very small gap of air is placed under the dielectric substrate. This gap can change the effective permittivity of the structure and consequently, the curve is shifted horizontally. The approximate height (about 0.37 mm) and the second curve which has a same trend and notch as the measured values are obtained by changing the height of the air gap. Also, the observed vertical difference between the modified and measured curves is due to some losses which occur at the input ports. But, this vertical shift because of same trend and notch of two curves has no significant effect on the calculation of the real part of the effective permittivity. The results of S 11 measurements for various nonwovens in up and down arrangements (Figure 1 (A)) are depicted in Figures 2 (B) and 2 (C), respectively. For the first set of arrangements, the nonwoven samples were placed on the microstrip line. As mentioned previously, because of mentioned gap, the height and the effective permittivity of the dielectric substrate should be modified. The computed results show that the air gap leads to a change in the effective permittivity of the dielectric substrate from 3.38 to 2.2. The mean values of the notches of the measured S 11 curves after placing each sample and calculated permittivity in both cases are shown in Tables 5 and 6, respectively. As expected, the obtained values are almost close to one because the fibrous materials contain a large amount of trapped air. As shown in Table 3, due to the higher porosity values of the samples containing higher amount of hollow fibres, it is expected that with increase in the proportion of hollow fibres, the effective permittivity of samples decreases. The values of effective permittivity extracted from the first set of measurements (the nonwovens placed on the line) are in good agreement with this trend. In this case, only one sample does not follow the expected trend. It seems that this contradiction is due to some non-uniformity in E5 samples. Contrary to expectations, the second set (the nonwoven placed under the dielectric substrate) does not follow this routine. Moreover, the results obtained in this case are larger than those obtained for the first ones. This inconsistency can be explained by the measurement setup instability and possible dimensional changes occurring in the samples in the second set of measurements. These fluctuations are observed in Figure 2 (C). So, with this mentioned arrangement, it is difficult to obtain good reproducibility. Considering above, it seems that for deformable structures such as textile materials, the first procedure of measurement lead to more reliable results.

Page 822 of 1108

(A)

(C)

(B)

Fig. 2: (A) S 11 parameter of single-layer microstrip line, (B) S 11 parameter of two-layer microstrip line (the nonwovens are placed on the microstrip line), (C) S 11 parameter of two-layer microstrip line (the nonwovens are placed under the dielectric substrate) Table 5: The mean values of the notches of the measured S 11 curves after placing each sample. Frequency (GHz) Sample position Nonwoven on the line Nonwoven under the dielectric substrate

2.2650 2.5050

2.2500 2.5050

2.2450 2.5050

2.2350 2.5050

2.2400 2.5150

Table 6: The mean values of evaluated effective permittivity of nonwoven fabrics. ε r2 (Effective permittivity of nonwoven fabrics) Sample position Nonwoven on the line Nonwoven under the dielectric substrate

1.1540 1.5346

1.2482 1.4986

1.2799 1.4934

1.3458 1.4822

1.3234 1.4373

4. Conclusion This paper presented the design, verification and analysis of two-layer microstrip transmission line for effective permittivity measurement of different needle-punched nonwoven fabrics. It seems that due to the deformable structure of textile substrates, placing the samples on the transmission line is more reasonable method for evaluating effective permittivity compared with the case where the samples are placed under the dielectric substrate. In general, the obtained results show that this method has desirable potential for high frequency characterization of textile materials.

5. References [1] Ouyang Y & Chappell W J, IEEE Trans. Antennas Propagat, 56 (2008) 381. [2] Salvado R, Loss C, Gonçalves R & Pinho P, Sensors, 12 (2012) 15841. [3] Sanjari H R, Merati A A, Hosseini Varkiani S M & Tavakoli A, J Text Inst, 105 (2014) [4] Hausman S, Januszkiewicz Ł, Michalak M, Kacprzak T & Krucińska I, Fibres Text East Eur. 14 (2006) 59. [5] Amaro N, Mendes C & Pinho P, 2011 IEEE International Symposium on Antennas and Propagation (APSURSI), 2011, 282. [6] Svacina J, IEEE Trans. Microwave Theory Tech, 40 (1992) 769. [7] Yoon YJ & Kim B, 2000 IEEE Conference on Electrical Performance of Electronic Packaging, 2000, 163. [8] Standard Test Method for Mass Unit Area of Nonwoven Fabrics ASTMD6242, 2004. [9] Standard Test Method for Thickness of Nonwoven Fabrics ASTMD5729, 2004. [10] Gupta KC, Garg R, Bahl IJ & Bhartia P. Microstrip lines and slotlines (Artech House Boston), 1996, 5. [11] Kirschning M & Jansen RH, Electron. Lett, 18 (1982) 272.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Exploring Phase Change Materials in Firefighter Hood for Cooling Lin 1, Boorady 2, Ashdown 3 and Chang 4 1

University of Hawaii at Manoa 2 Affiliation SUNY - Buffalo State (“Affiliation 2” style has 12 pt extra spacing after the line) 3 Cornell University 4 Chinese Culture University

Abstract. This is the Word Document template to be used for submitting a Full Paper for the 13th Asian Textile Conference Keywords: personal protective equipment (PPE), firefighter, phase change materials (PCM).

1. Introduction 1.1.

Phase Change Materials for Firefighters

There are two types of Phase Change Materials (PCMs) which have been developed and adopted in textiles: heat (energy released) and cool (energy absorbed). This paper discusses current PCM applications and explores future applications in firefighting gear.

1.2.

Manuscript requirements

Phase Change Materials (PCMs) have been suggested as latent energy storage materials. This theory derives from the use of chemical bonds to store and release heat. The thermal energy transfer occurs when a material changes from a solid to a liquid, or from a liquid to a solid [1]. This is called a change in state, or "phase." PCM, proven to possess thermal-regulating characteristics, is proposed for applications in clothing materials in conditions that require workers to face extreme temperatures. PCM is believed to conserve energy and maintain certain temperatures, therefore they have been chosen for latent energy storage materials. In some work environments, jobs require the use of heavy garments or specially designed clothing with specific functions to protect the wearer from injury, heat stress, or contamination. These specialfunction garments could prevent transfer of hazardous materials onto the skin, as well as prevent the transfer of heat and moisture out of the garment. To accomplish this, researchers have developed a way to encapsulate PCMs into clothing fibers to reduce heat loss or prevent overheating in protective clothing [2]. PCMs react instantly to temperature changes. PCMs can be used for thermal storage and thermal control because of the energy they release and absorb during these temperature changes. Theoretically, PCMs ability to preserve energy is relatively basic. When a PCMs temperature increases above its melting point, the PCM absorbs and stores heat as thermal energy as it melts. When the PCM’s temperature increases beyond the specified temperature range, the PCM is powered off and the PCM cools to below the melting point, releasing its stored energy and returning back to a solid state. As PCM absorbs heat, it provides thermal regulation to wearers, as well as enhances comfort by reducing perspiration. In this way, heat stress is prevented. Another characteristic of PCM is that it acts as a mediator between the body and the environment’s temperatures. PCM products will help people who need to protect their body during outdoor activities in severe conditions such as extreme hot or cold [3]. In agriculture, industry, and recreation, many subjects may encounter severe sun exposure, which poses a risk to their health without proper protection against ultraviolet light. Taking such cases into consideration, a secondary purpose of this project is to explore and enhance PCM product effectiveness relative to consumer needs.

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The goal of PCM textiles is to create reusable energy to maintain body temperature, as well as to optimize the performance of such protective wear. Maintaining a stable body temperature of 36.3 to 37.1Â°C is essential to maintain health. Most enzymes will function properly only within normal body temperature range, to allow the body to perform at its best. This project is intended to investigate valuable information for the product development of PCMs. The study has practical application for the inner linings of protective clothing in conditions of extreme heat.

1.3.

Important Information Phase change materials are considered latent heat storage units because as they change phase from solid to liquid, liquid to gas and vice versa, energy in the form of heat is absorbed or released. The goal of PCM textiles is to create reusable energy to maintain body temperature, as well as to optimize the performance of protective wear such as hoods. When the wearerâ&#x20AC;&#x2122;s body temperature increases or decreases, the PCMs applied to the fabric will change state helping to regulate the wearerâ&#x20AC;&#x2122;s body temperature by providing warmth or cooling. Maintaining a stable body temperature can improve working conditions and comfort. Laboratory research design was used to explore the application of PCM in the design of protective hoods to determine if there was improved thermal regulation. Prototype hoods were developed using a 35% cotton/65% polyester blend interlock material which comprised of a top and bottom layer. The middle layer was a coated PCM fabric. A final layer using PANEX, a woven carbon fabric, surrounded the other layers and formed the outer shell of the hood. This layered structure provides protection and cooling to the neck area exposed between the jacket and helmet. Preliminary tests indicate that absorbency or release of heat (energy) while changing states within this hood structure will provide a benefit for the wearer. PCMs have been found to be one of the most efficient ways of storing thermal energy and it is expected that the use of this material in hoods will provide a new use for this developing material technology. Future research will test these hoods in working conditions.

2. Discussion The results of this study show that the use of PCMs could be very beneficial to certain populations including firefighters as the material provides superior temperature control for the body. Current personal protective clothing / bunker gear is hot and heavy which can impede the work of the firefighter. Research has shown a common causal factor in both heart attacks and slips, trips and fall injuries by firefighters is heat stress [4]. Modifying personal protective equipment to reduce heat stress could drastically reduce these injuries and fatalities. Previous studies have shown that firefighters are interested in updating their personal protective equipment to take advantage of new technology but are hesitant to completely change the traditional look of their equipment [5]. The use of PCM textile can achieve increased safety through helping to regulate the body temperature without significantly changing the look of the traditional bunker gear, specifically the hood. The absorbency or release of heat (energy) of PCMs while changing states within a certain temperature range was considered beneficial by consumers. Products that include PCMs could be adopted by many customers. Clothing coated with PCM can either reduce heat loss or prevent overheating has been accepted by target consumers. Target consumers have embraced PCM as a thermal balance between heat generated by the body and heat released into the environment. PCMs have been found to be one of the most efficient ways of storing thermal energy.

3. References [1] Bendkowska, W., Tysiak, J., Grabowski, L., & Blejzyk, A. (2005). Determining temperature regulating factor for apparel fabrics containing phase change material. International Journal of Clothing Science and Technology, 17 (3/4), 209-214.

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[2] Mondal, S. (2008). Phase change materials for smart textiles: An overview. Applied Thermal Engineering, 28 (1112), 1536-1550. [3] Flouris, A., & Cheung, S. (2006). Design and control optimization of microclimate liquid cooling systems underneath protective clothing. Annals of Biomedical Engineering, 34 (3), 359-372. [4] Firefighter Life Safety Research Center. (2008) Firefighter Fatalities and Injuries: The role of heat stress and PPE. Illinois Fire Service Institute. University of Illinois at Urbana-Champaign. https://www.fsi.illinois.edu/documents/research/FFLSRC_FinalReport.pdf [5] Barker, J., Boorady, L.M., Lin, S.H., Lee, Y.A., Esponnette, B. & Ashdown, S.P. (2012). Assessing use needs and perceptions of firefighter PPE. In Performance of Protective Clothing and Equipment: 9th Volume, Emerging Issues and Technologies. Ed. A. M. Shepherd. ASTM International: West Conshohocken, PA.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Facile Synthesis of Core/Shell-like NiCo 2 O 4 -Decorated MWCNTs and its Electrocatalytic Activity for Methanol Oxidation Tae Hoon Ko 1, Ji-young Park 1, Danyun Lei2, Min-Kang Seo3, Hak-Young Kim1,2, Byoung-Suhk Kim1,2* 1

Department of Organic Materials and Fiber Engineering, 2Department of BIN Convergence Technology, Chonbuk National University, Jeonju 54896, Republic of Korea, 3Korea Institute of Carbon Convergence Technology, Jeonju 54852, Republic of Korea *E-mail: kbsuhk@jbnu.ac.kr

Abstract. The design and development of an economic and highly active non-precious electrocatalyst for methanol electrooxidation is challenging due to expensiveness of the precursors as well as processes and nonecofriendliness. In this study, a facile preparation of core/shell-like NiCo 2 O 4 decorated MWCNTs based on a dry synthesis technique was proposed. The synthesized NiCo 2 O 4 /MWCNTs were characterized by infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and selected area energy dispersive spectrum. The bimetal oxide nanoparticles with an average size of 6 Âą 2 nm were homogeneously distributed onto the surface of the MWCNTs to form a core-shell-like nanostructure. The NiCo 2 O 4 /MWCNTs exhibited excellent electrocatalytic activity for the oxidation of methanol in an alkaline solution. The NiCo 2 O 4 /MWCNTs exhibited remarkably higher current density of 327 mA/cm2 and a lower onset potential of 0.128 V in 1.0 M KOH with as high as 5.0 M methanol. The impressive electrocatalytic activity of the NiCo 2 O 4 /MWCNTs is promising for development of direct methanol fuel cell based on non-Pt catalysts.

Keywords: Nickel cobaltite; core-shell; electrooxidation; methanol oxidation; fuel cell

1. Introdution The ever growing demand for next-generation clean and high-efficiency energy has inspired considerable efforts in the development of advanced alternative energy conversion and storage devices with the features of low cost and more importantly, environmental friendliness. Among them direct alcohol fuel cells (DAFC) are attractive due to their high energy conversion efficiency. Methanol has higher energy density than hydrogen. Abundant inexpensive sources are available for production of methanol and moreover the direct methanol fuel cell (DMFC) possesses high energy conversion efficiency and stability [1]. Currently platinum (Pt)-based electrocatalysts exhibit higher energy conversion but non-preferable due to its high cost and catalytic poisoning which reduce the catalytic activity. The successful implementation of the fuel cells mainly depends on the economy, activity, and the durability of the electrocatalysts. Therefore, it is important to design highly efficient as well as economical electrocatalysts for practical applications. The development of non-Pt based electrocatalysts is still challenging mainly due to lack of high conductivity and excellent catalytic activity and stability of the catalyst. Most of the preceding researches report non-Pt based electrocatalysts using transition metal oxides, for instance, NiO, Co 3 O 4 . It has been reported that a strategy to combine both NiO and Co 3 O 4 resulted in the high electrocatalytic efficiency than their individual counterparts [2]. Among them, NiCo 2 O 4 exhibits excellent electrochemical activity due to higher electronic conductivity than either NiO or Co 3 O 4 . Several synthetic strategies, such as conventional hydrothermal, solvothermal, electrochemical synthesis were for the preparation of Ni and Co-based bimetal oxide electrocatalysts with different morphologies. However, most of them involve in use of toxic chemicals such as NH 4 F, high temperatures and other nonecofriendly solvents. In this study, we have developed an economical, environmental friendly, dry synthesis method for facile preparation of core/shell-like NiCo 2 O 4 -decorated multiwall carbon nanotubes (MWCNT). The synthesized NiCo 2 O 4 /MWCNT electrocatalyst demonstrated higher catalytic activity for electrooxidation of methanol. To the best of our knowledge, NiCo 2 O 4 /MWCNT has not been synthesized via such a simple

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grinding method followed by low temperature annealing. Further this is the first study to demonstrate the use of NiCo 2 O 4 /MWCNT as an electrocatalyst for direct methanol fuel cell.

2. Experimental Materials MWCNT (>95% in purity, 20~25 µm in length, <2 nm in diameter) was kindly provided by nanosolution Co., Korea. Cobalt (II) acetate tetra hydrate (CoAc, 99.0% assay, Sigma-Aldrich), and nickel acetate tetra hydrate (NiAc, 99.0% assay, Sigma-Aldrich) were utilized without any further modification as precursors. Methanol and potassium hydroxide were purchased from Junsei Co. Ltd. (Japan). Millipore water (Milli-Q system) was used for the preparation of solutions.

Synthesis of Core/Shell-like NiCo 2 O 4 -Decorated MWCNTs At first, 0.2 g of pure MWCNTs were treated with 3 M HNO 3 and then refluxed for 48 h to remove metal impurities. After cooling to room temperature, the solution was diluted with 500 mL of deionized water and then vacuum-filtered through a filter paper with the pore size of 0.45 µm. The resultant purified MWCNTs were further washed with deionized water until the pH became neutral and then dried in vacuum at 80 °C for 24 h. For the preparation of core/shell-like NiCo 2 O 4 -decorated MWCNTs, 0.2 g of purified MWCNT was ground using a mortar and pestle for 10 min. Then, 0.05 g of each CoAc and NiAc were added into the groundMWCNTs and ground well. The homogeneous mixture of MWNTs and CoAc and NiAc was obtained in 15 min. Finally, the mixture was calcinated at 300 °C for 4 h in air atmosphere. The composition of the CoAc and NiAc were varied at a ratio of Ni:Co = 0.2 : 0.8, 0.4 : 0.6, 0.6 : 0.4, 0.2 : 0.8, 1.0 : 1.0 with fixing the total quantity as 0.1 g. The samples before calcination and after calcination were indicated by NiAc-CoAc/MWCNT and NiCo 2 O 4 /MWCNT, respectively.

Characterization The morphologies of all the samples were observed under a JEOL JSM-5900 scanning electron microscopy (SEM) after sputtering the samples with platinum for 120 s. Energy dispersive X-ray measurements were conducted using the EDAX system attached to the same microscope. A field-emission scanning electron microscope (FE-SEM) was also used to observe the morphologies after sputtering the samples with osmium for 7 s. For TEM, the sample was prepared by dispersing in ethanol by sonication at a concentration of 0.1 mg/mL. 1 mL of sample was dropped on the Cu TEM grid and analyzed. FT-IR of spectra of the samples was recorded using a Perkin Elmer instrument. X-ray diffraction (XRD) patterns were recorded on a Rigaku X-ray diffractometer (Cu K α radiation). VersaSTAT4 (USA) electrochemical analyzer and a conventional threeelectrode electrochemical cell were utilized to investigate the electrochemical measurements. Pt wire and Ag/AgCl (saturated KC) were used as the counter and reference electrodes, respectively. The glassy carbon electrode (GCE, 3 mm diameter; area 0.07 cm2) was used as the working electrode. The MWNT/NiCo 2 O 4 powder (2 mg) was dispersed in 2-propanol (400 µL) and sonicated for 5 min. And then the mixture was added nafion solution (20 µL) and sonicated for 5 min. Then the solution was dropped on the surface of the GCE and dried at 60 °C for 15 min. Cyclic voltammetry (CV) and chronoamperometry (CA) measurements were performed to study the activity and stability of methanol oxidation reaction. The test solutions used in this study were 1.0 M NaOH solution with and without addition of various methanol concentrations. All the experiments were performed at 298 K. The electrochemical impedance spectroscopy (EIS) was recorded in the frequency range of 10 mHz to 100 kHz with a potential amplitude of 10 mV.

3. Results and Discussion

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The morphologies of the synthesized NiCo 2 O 4 /MWCNT were investigated by using FE-SEM and TEM measurements. Figure 1a&b showed the smooth surface morphologies of pristine MWCNT. On the other hand, the NiCo 2 O 4 /MWCNT exhibited a rough surface, suggesting the successful decoration of the MWCNTs with bimetal oxide nanoparticles (Figures 1c-e). It was estimated that the thickness of the MWCNT increased from ~20 nm to ~48 nm on average after decoration with NiCo 2 O 4 nanoparticles. A close examination of the HRTEM image of the NiCo 2 O 4 /MWCNT showed successful deposition of quasi-spherical NiCo 2 O 4 nanoparticles on the MWCNTs, which is similar to the core (MWCNT)/shell (NiCo 2 O 4 ) structure. The average size of the nanoparticles over the surface of MWCNTs was 6 ± 2 nm. Further, the SAED pattern (Figure 1f) exhibited well-defined rings of (511), (220), (111), (311), and (400) suggesting the polycrystalline nature of the synthesized NiCo 2 O 4 /MWCNT (JCPDS no. 73-1702).

Figure 1. FE-SEM images of pristine MWCNT (a, b), NiCo 2 O 4 /MWCNT (c, d), HR-TEM image (e) and SAED pattern (f) of NiCo 2 O 4 /MWCNT.

Figure 2a shows the electrochemical oxidation of MeOH by NiCo 2 O 4 /MWCNT with Ni:Co = 1.0 : 1.0 in 1.0 M KOH at a scan rate of 50 mV/s. It is noteworthy that the addition of even 0.5 M MeOH increased the anodic peak current density to ~3 times (97.53 mA/cm2) with a peak potential of 0.553 V. It should be noted that the heterogeneous catalysis reaction involves in adsorption of the reactant on the catalyst followed by the formation of intermediate species and then products. Thus, the anodic peak observed in the curve of forward sweep was corresponding to the oxidation of the MeOH, whereas, the peak observed in the curve of reverse sweep was attributed to the oxidation of adsorbed intermediate species produced in the forward sweep. The mechanism for electro-oxidation of methanol by NiCo 2 O 4 /MWCNT is supposed to be similar to nickel oxide and cobalt oxide catalysts as given below (Eq. 1-3).[3] NiCo 2 O 4 + OH- + H 2 O – 3e-  NiOOH + 2CoOOH Ni(OH) 2 + CO 2 + yH 2 O NiOOH + CH 3 OH + xO 2  CoOOH + mCH 3 OH + nO 2  2Co(OH) 2 + 2CO 2 + qH 2 O

(1) (2) (3)

The concentration of alcohol is one of the important parameter to determine the performance of the fuel cell. Generally, DAFCs working with highly concentrated alcohol solution is preferable, since it could dramatically decrease the size of the fuel cell and simultaneously increase the power density. Further, it is impossible to use absolute methanol as the anodic reaction (Eq. 1) because it requires water. Unfortunately, most of the preceding DMAC studies involving NiCo 2 O 4 based catalysts have been reported to use lower concentrations of MeOH such as 0.5 M to 3.0 M MeOH, which do not show any performance beyond this concentration threshold. Interestingly, in the present study, NiCo 2 O 4 /MWCNT exhibited electrocatalytic performance up to 5.0 M MeOH with a high current density of 327 mA/cm2 and peak potential of 0.675 V. For 6.0 M MeOH, the current density slightly decreases, which indicate that the concentration threshold in this study is 5.0 M MeOH. To the

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best of our knowledge, this is the highest alcohol concentration ever to be reported, especially for NiCo 2 O 4 based catalysts for methanol electro-oxidation. Onset potential is the other important parameter to demonstrate the electrocatalytic activity of the catalyst since it is the indicative measure for over potential. Pt-based catalysts perform better than non-precious electrocatalysts due to their smaller onset potential. In the present study, the onset potentials range from 0.128 to 0.262 V. The small organic molecules that were adsorbed on the catalyst and the molecules which are not fully oxidized are ascribed for the slight increase in the onset potentials. However, the onset potential reported in this study is one of the lowest values reported in the literature so far. Further to study the stability of the electrocatalytic activity, the NiCo 2 O 4 /MWCNT was subjected to longer CV cycles in 1.0 M KOH with 5.0 M MeOH. Figure 2b displays the good stability of NiCo 2 O 4 /MWCNT even after 250 cycles with retaining current density over 76%. It is noteworthy that the high performance of the synthesized core/shell-like NiCo 2 O 4 /MWCNT was due to the fine size of the metal oxide nanoparticles and their homogeneous distribution on MWCNTs.

Figure 2 (a) Electrocatalytic oxidation of methanol 1.0 M KOH by NiCo 2 O 4 /MWCNT at 50 mV/s, (b) cyclic voltammograms of by NiCo 2 O 4 /MWCNT after 50, 100, 150, 200 and 150 cycles at 100 mV/s in 1.0 M KOH with 6.0 M MeOH/

4. Conclusion In this work, we report a new and easy synthetic route to prepare core/shell-like NiCo 2 O 4 /MWNTs via a dry synthesis method. The efficient electrocatalytic oxidation of methanol on NiCo 2 O 4 /MWNTs was studied by cyclic voltammetry in 1.0 M KOH in the presence and absence of methanol. The NiCo 2 O 4 /MWNTs exhibited an impressively high electrocatalytic activity for methanol oxidation as the corresponding current increased with increasing the methanol concentration in the alkaline medium. This electrocatalyst is active for up to 5.0 to 6.0 M methanol. Remarkably this catalyst revealed a small onset potential lesser than 0.128 V vs Ag/AgCl, which is one of the superior value among the reported non-precious electrocatalyst. Overall, this work opens up opportunities for facile preparation of non-precious metal electrocatalysts via an economical, simple, and eco-friendly synthetic route with high catalytic activity.

5. References [1] Guo, Y.G., Hu . J.S., Wan . L.J. Nanostructured Materials for Electrochemical Energy Conversion and Storage Devices. Adv. Mater. 2008, 20, 2878â&#x20AC;&#x201C;87 [2] Li, Y., Hasin, P., Wu, Y. NixCo3-xO4 Nanowire Arrays for Electrocatalytic Oxygen Evolution. Adv. Mater. 2010, 22, 1926â&#x20AC;&#x201C;29 [3] Nasser A.M. Barakat., Moaaed Motlak., Ahmed A. Elzarahry., Khalil Abdelrazek Khalil., Emad A.M. Abdelghani. NixCo1-x alloy nanoparticle-doped carbon nanofibers as effective non-precious catalyst for ethanol oxidation. Int. J. Hydrogen Energy 2014, 39, 305-16

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Far-Infrared Nonwoven Fabrics Made of Various Ratios of Bamboo Fiber to Far-Infrared Fiber: Far-Infrared Emissivity and Mechanical Property Evaluations Ying-Huei Shih 1, Jia-Horng Lin 1, 2, 3, Chien-Teng Hsieh 4, Ching-Wen Lin 2 and Ching-Wen Lou 5 + 1

Laboratory of Fiber Application and Manufacturing, Department of Fiber and Composite Materials, Feng Chia University, Taichung City 40724, Taiwan, R.O.C. 2 Department of Fashion Design, Asia University, Taichung City 41354, Taiwan, R.O.C. 3 School of Chinese Medicine, China Medical University, Taichung City 40402, Taiwan, R.O.C. 4 Department of Fashion Design and Merchandising, Shih Chien University Kaohsiung Campus, Kaohsiung City 84550, Taiwan, R.O.C. 5 Institute of Biomedical Engineering and Materials Science, Central Taiwan University of Science and Technology, Taichung City 40601, Taiwan, R.O.C.

Abstract. People have growing awareness of health care as a result of progressing technology and improved living standards, which then results in a great deal of healthcare product appearing on the market. In particular, far-infrared products have been commonly explored, and are found to be capable of accelerating blood circulation of the human body, and thereby benefit a health regimen. In this study, bamboo fiber, far-infrared fiber, and low-melting polyester fiber are made into nonwoven fabrics, which are then processed by using a heat treatment in order to render the nonwoven fabrics with a smooth surface and better mechanical properties. The far-infrared fibers that are used in this study are polyester fibers that are added with powder during their spinning process, and thereby attain the far-infrared emissivity. Due to the fact that far-infrared materials display their exothermic efficacy via the vibration of water molecules, hydroscopic nature is thus indispensable to the resulting bamboo nonwoven fabrics. As a result, different fiber blending ratios of far-infrared fiber, bamboo fiber, and low-melting polyester fiber of 70 %:0 %:30 %, 60 %:10 %:30 %, 50 %:20 %:30 %, 40 %:30 %:30 %, and 30 %:40 %:30 % are used to form different nonwoven fabrics, in order to compare their far-infrared emissivity, as well as their mechanical properties.

Keywords: Far-Infrared, Bamboo Fiber, Far-infrared fiber, Low-melting-point PET, Nonwoven.

1. Introduction People increasingly pay attention to their health regimen as a result of advanced technologies and higher living standards. Thus a good diversity of healthcare products are rapidly developed in order to meet consumers’ demands. In particular, far infrared rays are widely examined in different research. Far infrared rays are also called growth rays, and are defined by the International Commission on Illumination as light waves whose wave length is 3-1000μm [1]. Far infrared rays with a wave range of 6-14 μm have a significant influence on the physiological action of human body [2]. In addition, far infrared therapy can be applied to the treatment of cancer or vessel diseases, as well as occlusion of wounds [3-7]. The far infrared rays are also in relation to the movement of water molecules, and thus affect the human health [3], and they can commonly be used for aggressive heat insulation and thereby facilitate blood circulation and capillarectasia [8]. Bamboo fibers provide a hydroscopic nature, and are thus used in this study due to the fact as water molecules are correlated with the far infrared emission [9]. In this study, far-infrared fiber (FF), low-melting polyester fiber (LPET),

Corresponding author. Tel.: + 886-4-2451-8672. E-mail address: cwlou@ctust.edu.tw

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and bamboo fibers (BF) are incorporated with different ratios in order to form nonwoven fabrics, whose mechanical properties and far infrared emissivity are finally evaluated.

2. Experimental 2.1.

Materials

Far-infrared fiber (True Young Co., Ltd., Taiwan, R.O.C.), which is abbreviated as FF, has a fineness of 6 denier (D) and a length of 64 mm. Low-melting-point PET (LPET) fiber (Far Eastern New Century, Taiwan, R.O.C.) has a fineness of 4 D and a length of 51 mm. Bamboo fiber (True Young Co., Ltd., Taiwan, R.O.C.), which is abbreviated as BF, has a fineness of 1.4 D and a length of 38 mm.

2.2.

Procedure

FF, LPET, and BF separately undergo the opening process, and are then blended with 70:0:30, 60:10:30, 50:20:30, 40:30:30, and 30:40:30.The blends are processed with carding lining, striping action, lapping, and needle-punching in order to form FF/LPET/BF nonwoven fabrics.

2.3.

Tests

Tensile Strength Tensile strength of the samples is tested by using HT2402 (Hung Ta Instrument Co., Ltd, Taiwan, R.O.C.), with a 300Âą10 mm/min pulling speed, as specified in ASTM D5035-11. Ten sample measurements are taken along the cross machine direction (CD) and machine direction (MD).

Tearing Strength HT2402 (Hung Ta Instrument Co., Ltd, Taiwan, R.O.C.) measures the tearing strength of the samples taken along the CD and the MD at a tensile speed of 300Âą10 mm/min, as specified in ASTM D5035-11.

Air Permeability The TEXTEST (FX3300, Switzerland) is used to measure the air permeability of the samples, in accordance with ASTM D373-04.

Far Infrared Emissivity A far-infrared emissivity tester (TSS-5X, Desunnano Co., Ltd., Japan) is used to measure the far infrared emissivity of various nonwoven fabrics, as specified in FTTS-FA-010. During the test, the fabrics release thermal radiation, which is compared with the intensity of radio activity of the black body that is measured under the same temperature. The far infrared emissivity of a black body is 0.94É&#x203A;.

3. Results and Discussion 3.1. Tensile Strength of FF/LPET/BF Nonwoven Fabrics as Related to Various

Blending Ratios

The tensile strength of FF/LPET/BF nonwoven fabrics increases as a result of the increasing amount of BF, as indicated in Figure 1. BF has a small denier and a short length. Therefore, at the same basis weight, there is a greater amount of BF, which gives fabrics an increasing trend in tensile strength. Another possible factor is the manufacturing process in this study. Nonwoven manufacturing involves carding lining, striping action, lapping, and needle-punching to form nonwoven fabrics. The bonding mechanism is the entanglement between fibers. The incorporation of short and fine fibers provides the more fibers with more opportunities for entanglement, which in turn fortifies the tensile strength of the nonwoven fabrics.

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Fig. 1: Influence of blending ratio on the tensile strength of FF/LPET/BF nonwoven fabrics

3.2.

Tearing Strength of FF/LPET/BF Nonwoven Fabrics as Related to Various Blending Ratios

Figure 2 indicates that 30wt% BF results in an increasing tearing strength, and the tearing strength then has a decreasing trend as a result of an excessive BF content. According to the test standard, as seen in Figure 3, samples are required to have a pre-opening of 15mm depth, where the damage is applied as the test initiates. Due to the short length of BF, there is a greater possibility for the occurring of force point in where the fibers are entangled when the nonwoven fabrics are composed of 40wt% BF. As a result, the tearing strength of FF/LPET/BF nonwoven fabrics is decreased.

Fig. 2: Influence of blending ratio on the tearing strength of FF/LPET/BF nonwoven fabrics

Fig. 3: Schematic illustration of a) pre-opening and b) force pointing in a tearing strength test.

3.3.

Air Permeability of FF/LPET/BF Nonwoven Fabrics as Related to Various Blending Ratios

As indicated in Table 1, the air permeability of FF/LPET/BF nonwoven fabrics decreases as a result of the increasing BF content. Theoretically, air permeability is dependent on the amount voids that are interconnected. BF has a small denier and short length, and thus with a specific basis weight, it also has a relative greater number count of fibers. Therefore, the pore size is small with more BF used in the nonwoven fabrics. Meanwhile, the pores in nonwoven fabrics can also be easily filled by BF, which decreases the amount of

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interconnected pores, and eventually causes the air permeability of FF/LPET/BF nonwoven fabrics to decrease accordingly. Table 1: Influence of blending ratio on the air permeability of FF/LPET/BF nonwoven fabrics Test Item Fiber Ratio 70 :0 :30 60 :10 :30 50 :20 :30 40 :30 :30 30 :40 :30

3.4.

Air Permeability

standard deviation

211.3 165.0 145.3 125.3 106.7

3.0 6.1 5.0 4.0 6.7

Far Infrared Emissivity of FF/LPET/BF Nonwoven Fabrics as Related to Various Blending Ratios

Table 2 shows that when the content of FF decreases, the far infrared emissivity of FF/LPET/BF nonwoven fabrics first increases and then decreases. This result resembles the findings of a previous study. The far infrared emissivity does not continuously increase when the radioactive body reaches a certain amount[10]. Specifically, FF/LPET/BF nonwoven fabrics that are composed of 60:10:30 or 50:20:30 have a far infrared emissivity that is beyond 0.8 and thus meets the requirement of having far infrared efficacy. Table 2: Influence of blending ratio on the far infrared emissivity of FF/LPET/BF nonwoven fabrics Test Item Far Infrared Emissivity

Standard Deviation

0.78 0.81 0.83 0.77 0.78

0.02 0.02 0.02 0.01 0.01

Blending Ratio 70 :0 :30 60 :10 :30 50 :20 :30 40 :30 :30 30 :40 :30

4. Conclusions This study incorporates far-infrared fibers, LPET fibers, and bamboo fibers to create FF/LPET/BF nonwoven fabrics that possess far infrared emissivity beyond 0.8. However, the related applications and the influence of water molecules on FF/LPET/BF nonwoven fabrics are expected for a further examination.

5. Acknowledgements The authors would like to thank Ministry of Science and Technology of Taiwan, for financially supporting this research under Contract MOST 103-2221-E-035-028.

6. References [1]

G. Ziegelberger and Icnirp, Health Physics, 91, 630 (2006).

[2]

Y. Li, D. X. Wu, J. Y. Hu, and S. X. Wang, Colloids and Surfaces a-Physicochemical and Engineering Aspects, 300, 140 (2007).

[3]

S. Hwang, D. H. Lee, I. K. Lee, Y. M. Park, and I. Jo, Cancer Letters, 346, 74 (2014).

[4]

J. Ishibashi, K. Yamashita, T. Ishikawa, H. Hosokawa, K. Sumida, M. Nagayama, and S. Kitamura, Medical Oncology, 25, 229 (2008).

[5]

C. C. Lin, M. Y. Chung, W. C. Yang, S. J. Lin, and P. C. Lee, Nephrology Dialysis Transplantation, 28, 1284 (2013).

[6]

M. Miyata and C. Tei, Circulation Journal, 74, 617 (2010).

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[7]

M. Sobajima, T. Nozawa, H. Ihori, T. Shida, T. Ohori, T. Suzuki, A. Matsuki, S. Yasumura, and H. Inoue, International Journal of Cardiology, 167, 237 (2013).

[8]

Y.-Y. Hsieh, J.-P. Lin, W.-C. Liu, and C.-C. Lin, Taiwanese Joumal of Applied Radiation and lsotopes, 3, 333 (2007).

[9]

P. Y. Wu, W. H. Hsing, Y. H. Liou, and J. M. Lin, Joumal of the Hwa Gang Textile, 16, 418 (2009).

[10] K. W. Zeng, W. H. Hsing, P. W. Hsu, Y. S. Liou, and J. M. Lin, Journal of the Hwa Gang Textile, 16, 111 (2009).

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

High Elastic-Recovery Metal/Polyester Knitting Fabric: Manufacturing Techniques and Property Evaluations Chih-Hung He 1, Ching-Wen Lou 2, Ching-Wen Lin 3, Chien-Teng Hsieh 4 and Jia-Horng Lin 1, 3, 5 + 1

Laboratory of Fiber Application and Manufacturing, Department of Fiber and Composite Materials, Feng Chia University, Taichung City 40724, Taiwan, R.O.C. 2 Institute of Biomedical Engineering and Materials Science, Central Taiwan University of Science and Technology, Taichung City 40601, Taiwan, R.O.C. 3 Department of Fashion Design, Asia University, Taichung City 41354, Taiwan, R.O.C. 4 Department of Fashion Design and Merchandising, Shih Chien University Kaohsiung Campus, Kaohsiung City 84550, Taiwan, R.O.C. 5 School of Chinese Medicine, China Medical University, Taichung City 40402, Taiwan, R.O.C.

Abstract. This study aims to propose metallic/polyester (PET) elastic knitted fabrics that can be commonly used for wearable electronic textiles. A crochet machine is used to make the metallic/PET elastic knitted fabrics with different patterns as a result of different combinations of the amounts and the types of metallic wires. The elastic knitted fabrics are then tested for stiffness, tensile strength, tensile elastic recovery, and electrical resistance of their constituent yarns. The test results show that a greater amount of metallic wires results in there being randomly and unevenly rugged elastic knitted fabrics. The stiffness of different knitted fabrics is ranked in terms of their constituent yarns as being nickel-plated, silver-plated, and then tin-plated copper wires. However, the amounts and the types of the metallic wires do not pertain to the tensile strength at break and elasticity recovery of the elastic knitted fabrics. Finally, the resistance of the constituent yarns for the elastic composite films is significantly correlated with the amounts of the metallic wires. Namely, the greater amount of the metallic wires, the lower the resistance of the elastic knitted fabrics. In comparison with stainless steel wires, the three nickel-plated, silver-plated, and tin-plated copper wires have a much lower resistance. The novel pattern design that is developed in this study provides the metallic/PET elastic knitted fabrics with a high elasticity recovery along the warp direction, as well as a low resistance.

Keywords: elastic knitted fabric, air permeability, wearable electronic, metallic wire.

1. Introduction Smart textiles can sense and adapt to the surrounding environment, and they are a result of traditional textile techniques, material technology, communication technology, and artificial intelligence. Their structure is reliant on more than the techniques that are applied to textile industry, which make it hard to classify smart textiles. Currently, they are divided into three types. Passive smart textiles can sense the stimuli from and changes in environment, but do not automatically regulate and manage their formation. Active smart textiles can trigger other devices to signal to the user to adjust the used device after receiving the stimuli from the environment. Very smart textiles can automatically adjust and manage their formation after their interior senses the stimuli from the environment [1]. Wearable electronic products are smart textiles that are derived from the combination of electronic industry and textile industry. They are a combination of electronic product and textiles, including woven fabrics, knitted fabrics, or nonwoven fabrics that are composed of staple fibers, filaments, and yarns. Wearable electronics are commonly used in medicine and sports detection [2] while wearable sensors are primarily used to monitor the individual status for men in exercise or patients that are hospitalized in any moment [3]. Electrically conductive yarns are applied to wearable sensors in order to improve the convenience and comfort of the wearable electronics. However, the relationship between the resistance of conductive yarns and textiles is more +

Corresponding author. Tel.: + 886-4-2451-8672 E-mail address: jhlin@fcu.edu.tw

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complicated than ordinary electronic circuits, which leads to a diversity of studies on sheet resistance, electromechanism, and resistive network [4-7]. As in previous studies, conductive metallic wires have been proven to be used in wearable electronic products, but such a combination does not provide the textiles with enough compatibility, flexibility, durability and intelligence according to the environment [8]. In addition, the fabrication of conductive yarns is not as easy as that of ordinary yarns. Therefore, the conductive fabrics are commonly in the form of woven fabrics or weft knitted fabrics. There are relatively fewer studies examining warp knitted fabrics. Therefore, this study uses a crochet machine to fabricate metallic/polyester elastic knits, after which their mechanical properties and resistance are simultaneously measured during the tensile tests.

2. Experimental 2.1. Materials This study uses three metallic wires that are copper and coated with silver, nickel, and tin. They are used to transmit the signal of detector, and are purchased from Yeou Chuen Wire, Taiwan, ROC. Rubber threads (Ta Yu Co., Ltd., Taiwan, ROC) are used to improve the elasticity of the fabrics. Polyester (PET) filaments (Yi Jinn Industrial Co., Ltd., Taiwan, ROC) serve as the basic material of the knits.

2.2. Metallic/Polyester Elastic Knits The illustrative drawing of metallic/polyester elastic knits is provided in Figure 1. The knits is a combination of PET filaments (in black) with a closed chain stitch structure, as well as other PET filaments (in blue), rubber thread (in red), and metallic wire (in orange) with an inlay structure. During the knitting process, the feeding gear teeth for rubber thread is varied in order to change the resistance and warp density.

red structure：Rubber threads black structure：Polyester filaments blue structure：Polyester filaments orange structure：metallic wires

Fig. 1: Diagram of metallic/polyester elastic knitted fabrics.

3. Results and Discussion 3.1. Effects of Numbers of Feeding Gear Teeth of Rubber Threads on Air Permeability of Metallic/PET Elastic Knits Metallic/PET elastic knits have an air permeability that is inversely proportional to the numbers of feeding gear teeth. This is due to fact that the a large number of feeding gear teeth results in a higher specific elongation of the rubber threads, which in turn increases the retraction force along the warp direction. Therefore, the warp density of metallic/PET elastic knits is changed accordingly. The warp density of the knits increases from 40 wales/inch to 64 wales/inch, as indicated in Table 1, which results in a decrease in the air permeability of the metallic/PET elastic knits. Table 1: The average warp density and air permeability of metallic/PET elastic knits feeding gear teeth sample control Ag1 Ni1 Sn1

20 28 36 Warp density (wales/inch) 40 48 56 40 48 56 40 48 56 40 48 56

44 64 64 64 64

28 36 44 Air permeability (cm3/cm2/s) 386 278 188 146 362 265 198 146 367 269 187 147 370 263 198 144

Page 837 of 1108

3.2. Effects of Numbers of Feeding Gear Teeth on Tensile Strength of Metallic/PET Elastic Knits The numbers of feeding gear teeth have an influence on the warp density of metallic/PET elastic knits. As indicated in Table 1, the warp density increases from 40 wales/inch to 64 wales /inch with an increase in the numbers of feeding gear teeth. However, the tensile strength along the warp direction does not significantly change, which is ascribed to the PET structure in blue (ref. Figure 1). A high number of feeding gear teeth only improves the density of this blue structure, and thereby influences the tensile strength along the weft direction. In addition, the tensile displacement along the warp direction also increases when the numbers of feeding gear teeth is increased. The optimal tensile displacement is three time that of the control group (i.e., nonstretched samples). Nevertheless, rubber threads only affect the tensile displacement along the warp direction, rather than the weft direction. The tensile strength along the weft direction increases from 266N to 550N. As the combination of metallic wires does not cause any influences on the tensile strength, samples containing metallic wires are thus excluded from Table 2. Table 2: Average tensile strength and displacement of metallic/PET elastic knits as related to various numbers of feeding gear teeth for the rubber threads numbers of feeding gear teeth wale 20 28 36 44 weft 20 28 36 44

control

Ag 1

Sn 1

Ni 1

Average tensile strength (N) 147 136 135 135

157 141 141 150

144 159 158 162

160 133 156 169 Average tensile strength (N) 266 427 449 550 -

numbers of feeding gear teeth wale 20 28 36 44 weft 20 28 36 44

control

Ag 1

Sn 1

Ni 1

Average tensile displacement (mm) 88 176 233 293

107 181 239 295

92 181 254 306

93 159 223 309 Average tensile displacement (mm) 20 23 22 22 -

3.3. Effects of Numbers of Feeding Gear Teeth on Elastic Response Rate of Metallic/PET Elastic Knits For elastic response rate test, 70% of ultimate tensile displacement at break is used as the reference. The elastic response rate of metallic/PET elastic knits is not in relation to the number of feeding gear teeth as indicated in Table 3. However, the relationship between metallic wires and the elastic response rate needs to be discussed, due to the stiffness that the metallic wires have is correlated with the morphology of metallic/PET elastic knits. Metallic wires are not as soft as PET filaments, and they are thus constricted, bended and deformed by rubber threads during the contraction of elastic knits. Table 3. Average elastic response rate of metallic/PET elastic knits as related to various numbers of feeding gear teeth for the rubber threads. feeding gear teeth sample control Ag1 Ni1 Sn1

99.4 98.8 98.8 99.7

97.2 99.1 98.3 98.6

98 98.1 97.8 98.6

97.2 97.8 98 98.1

3.4. Effects of Numbers of Feeding Gear Teeth on Resistance of Metallic/PET Elastic Knits Resistance is dependent on several factors, including electrically conductive materials, cross-sectional area of conductive fibers, and the length of the conductive fibers. In this study, the variations in the numbers of feeding gear teeth are correlated with the length of the conductive fibers. According to resistance law, resistance is proportional to the length of conductive fibers, and is inversely proportional to the cross-sectional area of conductive fibers. According to Figures 2 (a, b), the resistance of metallic/PET elastic knits increases as a result of a higher number of feeding gear teeth (i.e., a higher warp density). However, when the elastic

Page 838 of 1108

knits are stretched, their constituent metallic wires are straightened and become shorter, which in turn causes a lower resistance.

Fig. 2: Resistance of metallic/PET elastic knits a) before and b) after tensile strength test, as related to various numbers of feeding gear teeth of 20, 28, 36, and 44.

4. Conclusions This study successfully uses a crochet machine to prepare metallic/PET elastic knits that consist of metallic wires with different ductility. Various physical properties of metallic/PET elastic knits are examined in terms of the number of feeding gear teeth for rubber threads. The fabric structure is found to be dependent on the numbers of feeding gear teeth. Although an increase in warp density causes the elastic knits to have lower air permeability, it provides the elastic knits with a high elastic response that is conductive to the recovery of the stretched metallic wires by an externally applied force. In addition, the elongation along the warp direction of the elastic knits is improved by three times, while the tensile strength along the weft direction is improved by two times. Moreover, the number of feeding gear teeth also have positive and negative influences on the resistance. The resistance of metallic/PET elastic knits increases as a result of a high number of feeding gear teeth. Meanwhile, the high ductility of rubber threads disadvantageously shortens the length of metallic wires per unit area, which subsequently results in a decrease in resistance per unit length. This study proposes metallic/PET elastic knits that can be equipped with different elastic responses and resistances by adjusting their structure, in order to meet the requirements by different products. The elastic knits are expected to be used in livelihood textiles, professional textiles, and wearable textiles.

5. Acknowledgements The authors would like to thank Ministry of Science and Technology of Taiwan, for financially supporting this research under Contract MOST 103-2221-E-166-009.

6. References [1]

M. Stoppa and A. Chiolerio, Sensors, 14, 11957 (2014).

[2]

S. Lee, W. Du Preez, and N. Thornton-Jones, "Fashioning the future: tomorrow's wardrobe", Thames and Hudson, 2005.

[3]

T. Tamura, in "Wearable Sensors" (E. Sazonov and M. R. Neuman, Eds.), pp. 85, Academic Press, Oxford, 2014.

[4]

B. Kim, V. Koncar, and C. Dufour, Journal of Applied Polymer Science, 101, 1252 (2006).

[5]

P. Xue, X. M. Tao, K. W. Y. Kwok, M. Y. Leung, and T. X. Yu, Textile Research Journal, 74, 929 (2004).

[6]

C. Cochrane, V. Koncar, M. Lewandowski, and C. Dufour, Sensors, 7, 473 (2007).

[7]

L. Li, W. M. Au, K. M. Wan, S. H. Wan, W. Y. Chung, and K. S. Wong, Textile Research Journal, 80, 935 (2010).

[8]

P. Gould, Materials Today, 6, 38 (2003).

Page 839 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Investigating the dimensional properties of the spectral reflectance of the woolen yarns used in Persian Carpet Sarvenaz Ghanean 1, Mansoureh Ghanbar Afjeh 1 1

Textile Engineering Department, Amirkabir University of Technology

Abstract. In this paper the diversity of wool yarns used in Persian carpet and its effect on resulted shades is studied. Therefore different samples of woolen yarns that are commonly used for carpet weaving in Iran were collected. The reflectance of all samples was measured and the well-known Principal Component Analysis (PCA) was implemented in order to determine the basis functions and actual dimensional sizes of the reflectance spectra of the raw selected woolen yarns. Moreover, the analysis was extended to Munsell color chips for comparison. Results show that the collected dataset of woolen yarns has three dimensions, which could be decreased to two by eliminating the virgin and pre-treated samples, while the Munsell series has at least seven dimensions. The spectral reflectance of both datasets was reconstructed by employing the first 2, 3, 4 and 5 PCs. Then the RMS and deltaE errors between actual and recovered reflectance were calculated and reported. Afterward all samples were dyed with a specific kind of Iranian Madder in the same pre-mordanting and dyeing process and the spectral reflectance as well as K/S of undyed and dyed woolen yarns was studied. For further comparison, the colorimetric specifications of all samples were also calculated and have been discussed. As expected, the color of the virgin samples was clearly different from the others. Keywords: Persian Carpet, woolen yarns, principal component analysis, dimensional sizes

Introduction

The term Persian has become synonymous with oriental rugs, since in the 19th and early 20th centuries Persia became the largest exporter of rugs to the West [1]. By studying the oldest carpet of the world, Pazyryk, which was found in Altai Mountains, Siberia, many researchers date it back to the 6th century BC and believe that undoubtedly Iran is the origin of this opulence craft [2]. Handmade Persian carpet, one of the most important manifestations of the Iranian art, is famous for its unique design, artistic structure, vivid color harmony and also for its matchless raw materials. Wide range of unrepeatable shades on woolen yarns is obtained using various natural dyes accompanied by different mordants. This valuable product is weaved knot by knot by the artistic hands of the traditional weavers in a very long production period [3]. The envied quality of Persian wool used in the exotic carpet has pivotal role in making Persian woolen carpet known worldwide. Various kinds of woolen yarns are used in creating this artwork, which differs in geographical origin, animal breeds, color, yarn spinning and twisting process, pre-treatment and etc. In this paper the diversity of wool yarns used in Persian carpet and its effect on resulted shades is studied. Thus the Principal Component Analysis (PCA) was implemented to determine the basis functions and actual dimensional sizes of the reflectance spectra of the collected woolen yarns. The PCA technique is widely used to reduce the dimensionality of dataset by capturing the variance in a dataset and highlight the most important directions. The extracted bases that are called principal components (PCs) are a set of variables, which encapsulates the maximum variation in the desired dataset [4]. Among diverse conventional natural dyes used for Persian carpets, Madder is widely used for centuries due to its accessibility in Iran, acceptable general fastness properties and besides; it provides extensive range of various reds, oranges, browns and etc [5]. Thus all samples were dyed with a specific kind of Iranian Madder in the same dyeing procedure and then their colorimetric specifications were evaluated.

2. Experimental 36 different samples of woolen yarns were collected in the form of hank. Specimens included hand-spun yarns, pre-treated (with fluorescence whitening agent) samples, yarns in different color (white, untreated and even virgin wools), singled, doubled and also winder pled. Some were gathered from several parts of Iran such as Azerbaijan, Fars, Khorasan, Kurdestan, Kerman provinces and etc.; while a number of woolen yarns were imported from News land, Uruguay and Australia. All samples were scoured with 3 g/lit non-ionic detergent

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at 50-60Ë&#x161;C for 20 min and then rinsed thoroughly with tap water. Afterward the samples were mordanted with 2% (o.m.f) Alum, AlK(SO 4 ) 2 , in a bath including formic acid for adjusting the pH at 5. The L:G of the mordanting was kept at 40:1. The mordanting was started at 40Ë&#x161;C and gradually raised to the boiling point over 45 min and finally the bath was boiled for 75 min. For dyeing step 40% powdered Madder from Ardakan, Yazd province, was used. The pH of dyebath was kept at 5.5 by adding acetic acid and the L:G was the same as the mordanting. The dyeing process was started at 40Ë&#x161;C and raised to the boiling point over 30 min and dyebath was boiled for an hour. All undyed and dyed woolen yarns were wounded over a 2cmĂ&#x2014;4cm cards. A ColorEyeXTH spectrophotometer from GretagMacBeth Company was used for the reflectance measurements of samples. The specular component of reflectance was excluded. Samples were measured at four different rotational positions and the average was reported from 400 to 700 nm at 10 nm intervals. The reflectance spectra of 1269 colored chips of Munsell Book of ColorMatt Finish Collection were downloaded from the website of the University of Joensuu [6]. Matlab, the well-known mathematical software from Mathworks, was operated for all computational calculations [7].

3. Results & Discussion The spectral reflectance of 36 undyed woolen samples is shown in Figure 1(left). The two lower curves are reflectance of virgin yarns which could be eliminated to create a more level 34 samples dataset. Among other spectral reflectances, two thicker curves have different shapes which are pre-treated yarns so by omitting them the most level dataset with 32 samples is made. The mean reflectance of three sets were calculated and plotted together in Figure 1(right). As expected, ignoring the virgin samples shifted the mean reflectance to the higher position. Wool 0.7

0.6

0.5

0.5 reflectance

reflectance

Wool - 36 type 0.7

0.4 0.3

0.2

0.1

0 400

450

500

550 wavelength(nm)

600

650

0 400

700

36 samples 34 samples 32 samples 450

500

550 wavelength(nm)

600

650

700

Fig. 1: The spectral reflectance of 36 undyed woollen yarns (left) and mean reflectance of 3 datasets (right).

The dimensional sizes of the three mentioned datasets and Munsell dataset were determined by applying the PCA method on their spectral reflectance. Hereof the cumulative percentage of variance (cv%) of Munsell datasets as well as 36, 34 and 32 sample selections were computed and shown in Table 1. Results show that the original collected dataset of woolen yarns has three dimensions (cv=99.96), which could be decreased to two dimensions by eliminating the virgin and pre-treated samples (cv=99.94), while the Munsell series has at least seven dimensions (cv=99.89). It is obvious because the Munsell set includes a variety of colors with high diversity that leads to a bigger size in comparison with the three woolen yarns sets with limited range of colors. The spectral reflectance of four datasets was reconstructed by employing the first 2, 3, 4 and 5 PCs. For evaluating the spectral and colorimetric reconstruction error the mean, maximum, minimum and median RMS as well as deltaE between actual and recovered reflectance were calculated and reported in Table 2. It is evident that again reconstruction error by using 2 PCs for woolen yarn set with 32 samples is less than original set by 3PCs and in all cases error for Munsell dataset even by 5PCs is more than three woolen yarn sets. These results are in agreed with previous results. In order to investigate the effect of wool type on final shades, the spectral reflectance and K/S of undyed and dyed woolen yarns were studied. The spectral reflectance of 36 dyed samples is plotted in Figure 2(left). The mean reflectance of three dyed and undyed datasets were calculated and then the K/S of each average reflectance was computed from the well known Kubelka-Munk equation (equation 3.1) [8] and is shown in Figure 2(right). đ??žđ??ž đ?&#x2018;&#x2020;đ?&#x2018;&#x2020;

(1â&#x2C6;&#x2019;đ?&#x2018;&#x2026;đ?&#x2018;&#x2026;)2 2đ?&#x2018;&#x2026;đ?&#x2018;&#x2026;

Table 1: The Cumulative Percentage of Variance of Datasets for different numbers of PCs.

(3.1)

Page 841 of 1108

Number of PCs 1 2 3 4 5 6 7 8 9 10

36 samples

34 samples

32 samples

Munsell

96.4603 98.9756 99.9593 99.9910 99.9972 99.9991 99.9996 99.9997 99.9998 99.9999

96.5607 98.8290 99.9623 99.9874 99.9952 99.9985 99.9993 99.9995 99.9997 99.9998

98.4377 99.9446 99.9747 99.9900 99.9967 99.9990 99.9994 99.9997 99.9998 99.9998

76.7657 92.5978 98.5583 99.3150 99.6841 99.8029 99.8927 99.9318 99.9638 99.9787

Table 2: The RMS and DeltaE errors between actual and reconstructed reflectance for four datasets.

32 samples

34 samples

36 samples

Munsell

Dataset

Num of PCs

mean

max

RMS min

med

0.0576

0.0961

0.0245

0.0550

3 4 5 2 3 4 5 2 3 4 5 2 3 4 5

0.0260 0.0179 0.0120 0.0015 3.999×10-4 1.882×10-4 1.024×10-4 0.0015 2.913×10-4 1.640×10-4 1.020×10-4 3.313×10-4 2.109×10-4 1.454×10-4 8.315×10-5

0.0412 0.0291 0.0289 0.0074 7.144×10-4 3.784×10-4 2.297×10-4 0.0037 5.227×10-4 3.473×10-4 2.260×10-4 9.656×10-4 8.075×10-4 3.354×10-4 1.693×10-4

0.0149 0.0086 0.0057 4.207×10-4 1.561×10-4 6.498×10-4 3.887×10-5 3.952×10-4 1.645×10-4 6.498×10-5 4.904×10-5 1.814×10-4 6.444×10-4 6.004×10-4 3.525×10-5

0.0251 0.0183 0.0111 8.033×10-4 3.871×10-4 1.885×10-4 9.217×10-5 0.0015 2.736×10-4 1.461×10-4 9.368×10-5 2.920×10-4 1.850×10-4 1.387×10-4 7.068×10-5

Madder on differrent wools - 36 type

mean 15.0626 -0.0689i 3.4506 1.3892 0.8144 0.8818 0.4864 0.1180 0.0522 1.7004 0.2877 0.0815 0.0492 0.2914 0.1545 0.0911 0.0521

DeltaE max min 74.955039.3498i 30.2988 12.6329 5.1747 5.0159 1.4748 0.4361 0.1888 4.2836 0.7911 0.2287 0.2090 0.7251 0.5368 0.2811 0.2435

med

0.4313

10.3616

0.0752 0.0257 0.0067 0.1792 0.0282 0.0113 0.0030 0.0154 0.0076 0.0064 0.0060 0.0254 0.0163 0.0084 0.0057

2.6854 0.9607 0.6579 0.6054 0.4240 0.0787 0.0348 1.6247 0.2453 0.6930 0.0372 0.2522 0.1291 0.0872 0.0367

0.7 0.6

reflectance

0.5 0.4 0.3 0.2 0.1 0 400

450

500

550 wavelength(nm)

600

650

700

Fig. 2: The spectral reflectance of 36 dyed woollen yarns (left) and K/S of mean reflectance of 3 datasets (right).

Considering the reflectance of dyed samples it is clear that virgin samples have less reflection, but the pretreated species are not discernible. Analysing K/S of dyed samples leads to the same results. As it can be seen in Fig2 (right) eliminating the virgin samples cause a small decrease in K/S values while there is no significant difference between K/S of 34 and 32 sample collections. The colorimetric data were calculated under D65 illuminant for 1964 standard observer and reported in Table 3. As expected, results have reasonable agreement with previous discussion; which is prominent difference between color specifications of virgin samples (No 2 and 3) with all other 34 dyed woolen yarns so their chroma are smaller than others. Table 3: Colorimetric specification of dyed samples under D65 illuminant and 1964 standard observer.

Page 842 of 1108

sample

h˚

sample

h˚

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

32.16 26.46 25.92 32.99 32.16 29.06 33.05 32.34 32.09 31.66 30.47 31.07 35.94 35.94 35.53 34.56 35.07 34.68

32.90 22.43 21.14 32.08 31.88 29.49 31.83 30.87 31.22 30.54 29.89 30.86 32.40 32.40 31.70 32.31 32.41 32.31

24.31 17.11 15.16 24.31 23.59 22.33 24.58 23.62 22.52 23.44 23.04 22.96 25.03 24.96 23.32 25.92 24.70 24.01

40.90 28.21 26.01 40.25 39.66 37.00 40.22 38.86 38.49 38.50 37.74 38.46 40.94 40.90 39.32 41.42 40.75 40.25

36.47 37.33 35.65 37.15 36.50 37.13 37.68 37.42 35.80 37.50 37.62 36.64 37.68 37.61 36.37 38.73 37.31 36.62

19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36

34.26 34.26 34.99 35.59 34.80 34.47 34.73 36.36 36.16 34.19 35.37 36.36 33.63 34.51 34.77 31.76 30.48 32.96

32.07 30.99 32.93 32.76 31.45 33.36 31.98 33.31 32.74 33.95 33.00 33.74 32.78 33.55 33.05 30.92 32.49 31.12

24.32 25.68 24.97 25.22 25.03 25.09 24.95 26.05 26.39 25.29 26.03 26.76 24.69 24.14 26.33 22.67 23.49 22.25

40.25 40.25 41.33 41.34 40.19 41.74 40.56 42.29 42.05 42.33 42.03 43.06 41.04 41.33 42.26 38.34 40.10 38.26

37.17 39.65 37.17 37.60 38.51 36.9 37.96 38.03 38.86 36.68 38.27 38.41 36.98 35.74 38.54 36.25 35.86 35.57

4. Conclusion To investigate the diversity of wool yarns used in Persian Carpet, the Principal Component Analysis was applied to collected samples that are commonly used in Iranian carpet production. Results show that the collected dataset of woolen yarns has three dimensions, which could be decreased to two dimensions by eliminating the virgin and pre-treated samples, while the Munsell series has at least seven dimensions. Reconstruction error by using 2 PCs for woolen yarn set with 32 samples is less than original set by 3PCs and in all cases error for Munsell dataset even by 5PCs is more than three woolen yarn datasets. To study the effect of the woolen yarn type on final shade, all samples were dyed with madder in the same pre-mordanting and dyeing process. Spectral and colorimetric properties of dyed samples were discussed and results show that the virgin samples have clearly different color from the others.

5. References [1] Nemati, P. The Splendour of Antique Rugs and Tapestries. Woodbridge: PDN Communications, 2001. [2] Burkel, J.; Burkel, D. Carpets of Iran: weaving and techniques of nowadays. 1st ed. Tehran, Iran: Gooya House of Culture and Art, 2010. [3] Ghanbar Afjeh, M.; Ghanean,S.; Mazaheri, F. “Colorimetric and Spectral Properties of Natural Colorants Used in Handmade Traditional Persian Carpets”. Journal of Textiles and Polymers. 2013 (1), pp. 99-105. [4] Tzeng, D. Y.; Berns, R. S. “A review of principal component analysis and its applications to color technology”, Colot Res Appl. 2005 (30), pp. 84-98. [5] Maghsoudi, M.; Ghanbar Afjeh, M.; Ghanean, S. “Optimizing Wool Dyeing with Madder and Effect of the Mordant Type on its Spectral and Color Data”, 14th National & 1st International Recent Developments, Textile Technology and Chemistry Symposium (May 8-10), Bursa, Turkey, 2013. P

[6] University of Joensuu Color Group. Spectral Database. Available, http://www2.uef.fi/en/spectral/munsell-colorsmatt-spectrophotometer. [7] MATLAB (2013), The Math WorkInc, Version R2013a (8.1.0.604). [8] McDonald, R. Recipe prediction for textile, in Colour Physics for Industry. 2nd ed. Bradford: The Society of Dyers and Colourists, 1997.

Page 843 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Investigation of Electromagnetic Shielding Effectiveness of the Nonwoven Carbon Mat Produced by Wet-Laid Technology Mustafa Sabri Özen, Mehmet Akalin, Erhan Sancak, İsmail Usta; Ali Beyit University of Marmara, Faculty of Technology, Department of Textile Engineering, Istanbul, TURKEY

Abstract. The usage of electrical and electronic devices all over the world as a result of the development of technology has increased. Operating all electrical, electronic devices, radars, household appliances, base stations emit electromagnetic radiation. The radiation is harmful to human health and sensitive electronic devices. The electromagnetic radiation can be shielded by using conductive textile materials including carbon, steel, silver and copper. In this paper, electromagnetic shielding effectiveness (EMSE), absorption and reflection properties of nonwoven Optimat® Carbon Mat produced from short chopped engineered carbon fibres by using wet-laid technology was investigated. The carbon mat is manufactured from short chopped carbon fibres and small amount of poly vinyl alcohol (PVA) binder for bonding and has exceptionally even fibre distribution. The production was carried out at wet-laid machine which consist of headbox, web forming wire system, dryer and bonding cylinder. The carbon mat is bonded with thermal method by using cylinders. The key benefits of Optimat® nonwoven include high electrical conductivity, high temperature resistance, high thermal stability, EMI shielding, static dissipation and chemical resistance. The surface resistivity, EMSE, absorption and reflection properties in addition to physical properties such as weight, thickness and breaking strength of Optimat® carbon mat were measured. The surface resistivity measurement of carbon mat nonwoven fabric specimen was done accordance with ASTM D 257-07 standard, using a Keithley6517A Electrometer/ and Keithley8009 resistivity test fixture. The electromagnetic shielding effectiveness of Optimat® carbon mat was determined using a network analyzer as specified in ASTM D4935-10 in the frequency range 15-3000MHz. These kinds of materials can be used for EMI shielding in a variety of applications including tent, building and composite enclosures in order to isolate electrical devices and protect human health. Keywords:

electromagnetic

shielding,

nonwoven,

carbon,

wet-laid,

carbon

mat

1. Introduction Electromagnetic radiation caused electromagnetic waves emitted from electrical and electronic devices is a form of energy and is considered as a type of pollution such as air, water, soil and noise pollutions. Electromagnetic (EM) pollution has negative effect on health of environment, humans and other living organisms. In order to protect environment, humans and other living organisms against EM pollution, electromagnetic shielding is necessary. Communication devices such as mobile phone, pagers, radio/TV broadcasting, satellites, base stations, TV stations and high voltage lines are main EM pollution sources emitting electromagnetic waves. As the electromagnetic waves cannot be seen or felt, they are not considered important by people and are mostly neglected. The effects of electromagnetic waves on human nerve cells, brain tissue, DNA, genes, the immune system and the metabolism have been investigated by many researchers and it is expressed that these EM waves have direct and indirect effects on both living tissues. This problem can be solved by using conductive textile materials containing steel, carbon and silver materials. Electromagnetic shielding is the process of reducing the electromagnetic fields in a space by blocking the field with barriers made of conductive or magnetic materials. The conductive textile materials can be produced directly from conductive staple or filament fibres by using nonwoven

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production technologies and can be used in garments and buildings as interlining or lining material for protecting people from electromagnetic waves.

2. Material and Method 2.1. Material Wet-laid nonwoven fabric consisting of staple carbon fibres was used. The weight of the wet-laid nonwoven fabric is 80gram per square meter. The thickness of the fabric is measured as 1.15mm. First, wet-laid web was formed from staple carbon fibres, and then the web was bonded by chemical spray and thermal bonding methods. Polyvinyl alcohol, polyester, styrene acrylic, co-polyester and polyurethane resin are generally used as chemical binder materials. This kind of nonwoven fabric can be used in aerospace, automotive, defence, electronics, industrial, energy and infrastructure applications. Typical applications of the carbon wet-laid nonwoven fabrics can be said as surfacing veils, EMI shielding, resistive heating, static control, fuel cell, adhesive carriers and supports. The nonwoven fabric offers the advantages of superior fibre distribution, excellent resin uptake and suitability for all common composite manufacturing techniques.

Fig. 1: SEM Images of Carbon Staple Fibres (a-120x, b-1800x, c-2300x, d-8500x)

2.2. Method Wet-laid is one of the nonwoven web forming methods. The principle of wet-laid is similar to paper manufacturing. Speed and production capability are important advantages of such a process. [1] The wet-laid nonwoven line requires a very large investment, perhaps as much as ten times the cost of a carding line. [2] Such a process involves mixing fibres in water, preparing the dilute slurry from these materials, transporting the suspension to a continuous moving wire belt, depositing the fibres on a moving wire screen, separating and draining the water from the fibres, finally drying and consolidation to form a uniform sheet of material.[3,4] These wet-laid webs are generally bonded by chemical spray or thermal calendering methods. Wood pulps, cotton linters, short natural fibres and PAN carbon, pitch carbon and recycled staple carbon fibres are commonly used in wet-laid processes. [1,5]

2.3. Characterization Surface resistivity measurement of the wet-laid carbon nonwoven fabric was carried out in accordance with ASTM D 257-07 standard by using Keithley 6517A Electrometer/High Resistance Meter instrument and Keithley 8009 resistivity test fixture. Surface resistivity (p s ) was measured by applying a voltage potential across the surface of the specimen, measuring the resultant current and then performing the following calculations: 53.4đ?&#x2018;&#x2030;đ?&#x2018;&#x2030; đ?&#x2018;&#x153;đ?&#x2018;&#x153;â&#x201E;&#x17D;đ?&#x2018;&#x161;đ?&#x2018;&#x161;đ?&#x2018;&#x161;đ?&#x2018;&#x161;(đ?&#x203A;şđ?&#x203A;ş) (1) đ??źđ??ź Where "đ?&#x2018;?đ?&#x2018;?đ?&#x2018; đ?&#x2018; " is the surface resistivity of the wet-laid carbon nonwoven fabric specimen, â&#x20AC;&#x153;Vâ&#x20AC;? is the applied voltage, and â&#x20AC;&#x153;Iâ&#x20AC;? is the current reading from the instrument. [6] The EMSE, absorption and reflection measurements of the wet-laid carbon nonwoven fabric were carried out in 15-3000MHz the frequency range based on ASTM D4935-10. The sample was cut into circular plates with dimension 138.85cm2 and placed between flanges. The measurement area was 37cm2. The measurement set-up consists of two coaxial adapters (Electrometrics, EM-2107A), two 10 dB attenuators, and a network analyzer (ROHDE& SCHWARZ, ZVL 9 kHz-13GHz). The EMSE calculations were performed by using Equation2, as specified in ASTM D4935-10. Where Ei and Et are electrical fields of incident and transmitted radiation, respectively during shielding and no shielding periods. Absorption and reflection values of the samples were also calculated đ?&#x2018;?đ?&#x2018;?đ?&#x2018; đ?&#x2018; =

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by using Equation3, where, Ab and Re are absorbance and reflection of incident radiation, respectively during shielding, and T is transmittance of incident radiation. Re and T was calculated by using S parameters according to Equations 4 and 5. E

Ab = 1 â&#x2C6;&#x2019; đ?&#x2018;&#x2021;đ?&#x2018;&#x2021;r â&#x2C6;&#x2019; đ?&#x2018;&#x2026;đ?&#x2018;&#x2026;e (3),

3. Results

EMSE = 20 log ďż˝E đ?&#x2018;&#x2013;đ?&#x2018;&#x2013; ďż˝ (2) đ??¸đ??¸ 2

đ?&#x2018;Ąđ?&#x2018;Ą

đ?&#x2018;&#x2026;đ?&#x2018;&#x2026; e = ďż˝ đ??¸đ??¸đ?&#x2018;&#x;đ?&#x2018;&#x; ďż˝ = |đ?&#x2018;&#x2020;đ?&#x2018;&#x2020;11 (đ?&#x2018;&#x153;đ?&#x2018;&#x153;đ?&#x2018;&#x153;đ?&#x2018;&#x153; đ?&#x2018;&#x2020;đ?&#x2018;&#x2020;22 )|2 (4), đ?&#x2018;&#x2013;đ?&#x2018;&#x2013;

đ??¸đ??¸ 2

đ?&#x2018;&#x2021;đ?&#x2018;&#x2021;r = ďż˝đ??¸đ??¸đ?&#x2018;Ąđ?&#x2018;Ą ďż˝ = |đ?&#x2018;&#x2020;đ?&#x2018;&#x2020;21 (đ?&#x2018;&#x153;đ?&#x2018;&#x153;đ?&#x2018;&#x153;đ?&#x2018;&#x153; đ?&#x2018;&#x2020;đ?&#x2018;&#x2020;12 )|2 (5) đ?&#x2018;&#x2013;đ?&#x2018;&#x2013;

The surface resistivity of wet-laid carbon nonwoven fabric is measured as 2.05E+03ohm. The result clearly shows that the wet-laid carbon nonwoven fabric is conductive. The lower surface resistivity value indicates higher conductivity for the wet-laid carbon nonwoven fabric. EMSE, reflection and absorption results for the wet-laid nonwoven fabric consisting of staple carbon fibres are presented in Figures8 and 9.

Fig.2: EMSE Result of Wet-Laid Carbon Nonwoven Fabrics in 15-3000MHz Frequency Range

Fig.3: Absorption and Reflection Behaviour of WetLaid Carbon Nonwoven Fabrics in 15-3000MHz Frequency Range

In this study, EMSE properties in addition to reflectance and absorbance behaviours of wet-laid carbon nonwoven fabric in the 15-3000MHz frequency range were investigated. It was seen that the wet-laid nonwoven fabric consisting of staple carbon fibres with diameters of 7.5Âľm has obtained high EMSE values over 45dB in the 15-3000MHz frequency range. It was understood that wet-laid nonwoven fabric has showed horizontal EMSE behaviour in the 15-3000MHz frequency range. In the frequency 15MHz and 3000MHz, over 45dB EMSE value was obtained. First, it was seen that the absorbance and reflectance behaviours of wet-laid fabric are opposite to each other. In the low and high frequency range, absorbance values of wet-laid carbon nonwoven fabric are higher than that of reflectance values of the wet-laid carbon nonwoven fabric. The reflectance values of wet-laid carbon nonwoven fabric are only higher in the medium frequency range. It was found that the electromagnetic waves by wet-laid carbon nonwoven fabric was shielded about 99.9% at low, medium and high frequencies. [7,8] The specific EMI shielding efficiency was calculated on the basis of the rate of total EMI shielding efficiency and the fabric density. As shown in Fig.4, the wet-laid carbon nonwoven fabric was compared to needle punched nonwoven fabrics produced from stainless steel fibres and silver coated polyamide fibres. It was seen that the needle punched nonwoven fabric produced with carding and needle punching technologies from silver coated polyamide fibres has higher EMSE value than that of wet-laid carbon nonwoven fabric and needle punched nonwoven fabric with stainless steel fibres. The comparison results were shown at dB/g/cm3 unit.

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Fig.4-Specific EMI Shielding Efficiency (dB/g/cm3)

4. Conclusion Electromagnetic shielding effectiveness, absorbance and reflectance behaviours in addition to surface resistivity property of wet-laid nonwoven fabric produced from staple carbon fibres were investigated. The following conclusions were reached from test results of this study.  The wet-laid carbon nonwoven fabric has excellent EMSE values higher than 45dB in 153000MHz frequency range.  The highest EMSE value was found at 2100MHz frequency as 49.58dB.  The reflectance values are only higher in medium frequency between 1200MHz and 1800MHz frequency range.  It was seen that the absorbance values are higher in low and high frequency range.

5. Acknowledgements This work was supported by Research Fund of Marmara University in the framework D type scientific projects.

6. References 1. Purdy, A.T.: “Developments in Non-woven Fabrics, The Textile Institute, (1983) 2. Bhuvenesh, C.; Goswami; Rajasekar, D.: “Nonwovens:An Important Segment of the Textile Scene”, International Conference on Nonwovens, The Textile Institute North India Section, (1992), p.28-29 3. Williamson, J.E.: “Wet-Laid Systems, Nonwovens: Theory, Process, Performance, and Testing, Editor:Albin F. Turbak, Tappi Press, (1993), p.139. 4. http://www.edana.org/discover-nonwovens/how-they're-made/formation 5. Akalın, M.; Özen, M.S.: “Tülbent Esaslı Dokunmamış Kumaşlar-Nonwoven Fabrics”, (2010), ISBN: 978-605-61602-0-2, Istanbul, TURKEY 6. Özen, M.S.; Sancak, E.; Soin, N.; Shah, T.; Siores, E.: “Investigation of Electromagnetic Shielding Effectiveness of Needle Punched Nonwoven Fabric Produced From Conductive Silver Coated Staple Polyamide Fibre”, The Journal of Textile Institute, (2015), DOI: 10.1080/00405000.2015.1070604. 7. Özen, M.S.; Sancak, E.; Beyit, A.; Usta, I.; Akalın, M.: “Investigation of Electromagnetic Shielding Properties of Needle Punched Nonwoven Fabrics with Stainless Steel and Polyester Fibre”, Textile Research Journal, Vol.83 (8), (2013), pp.849-858. 8. Özen, M.S.: Investigation of the Electromagnetic Shielding Effectiveness of Carded and Needle Bonded Nonwoven Fabrics Produced at Different Ratios with Conductive Steel Fibres”, Journal of Engineered Fibers and Fabrics, Vol.10, Issue:1, (2015), pp.140-151.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Knitted strain sensors for monitoring body movements Juan Xie1,2,3, Hairu Long2,3, Menghe Miao1 + 1

CSIRO Manufacturing Flagship, P.O. Box 21, Belmont, Victoria 3216, Australia College of Textiles, Donghua University, 2999 North Renmin Road, Shanghai 201620, China 3 Key Laboratory of Textile Science & Technology, Ministry of Education, China

Abstract. Smart garments can be fabricated by integrating flexible electro-active devices into knitted fabrics to detect human body movements and to perform posture classification. We present a systematic study on the fabrication and electro-mechanical behaviours of knitted strain sensors under unidirectional and strip biaxial elongation and the application of such knitted strain sensors in detecting body movements. It has been found that resistances of both smart shirt and knee cap respond closely to body motions. Keywords: knitted strain sensor, body movements, conductive blended yarn, stainless steel fibre.

1. Introduction Smart garments can be fabricated by integrating flexible electro-active devices into knitted fabrics to detect human body movements and to perform posture classification 1-4. These strain sensors work on the principle of resistance variation. Their sensing mechanisms in relaxed state and unidirectional extension have been studied by a number of research groups 5-7. However, wearable sensors at elbows, knees and other curved parts of smart garments are under two-dimensional forces, including bending, shear and in-plane tensile stresses, which are essential to maintain body comfort during movement. Therefore, the main objective of this contribution is to systematically study the fabrication and electro-mechanical behaviours of knitted strain sensors under unidirectional and strip biaxial elongation and the application of such knitted strain sensors in detecting body movements.

2. Experimental 2.1 Materials Polyamide/spandex core-spun nonconductive yarn and 78dtex/48F polyamide elastic nonconductive filament and 110 dtex/40F silver-coated conductive multifilament yarn with resistance of 0.5 Ω/mm were utilized for fabricating knitted sensor and smart shirt and knee cap. Another conductive yarn used in the investigation was made from cotton and stainless steel (SS) slivers. The mean length and linear density of cotton fibre are 32.7 mm and 1.7 dtex, respectively. The length, diameter and breaking strain of stainless steel fibre are 50 mm, 8 μm and 2%, respectively.

2.2. Fabrications of strain sensors To achieve cotton/SS 50/50 conductive blended yarn, two ends of cotton slivers (5,65 ktx) and two ends of stainless steel slivers (5.7 ktex) were blended in the first passage of drawing using a SHIRLEY PLANT type SD drawframe. After being drawn five times, a roving was produced on a speedframe. Finally, a cotton/SS blended yarn of 50 tex was spun using a spinning frame SER.MA.TES FILAT010. Figure 1(a) and (b) show the cross sectional and longitudinal views of the conductive blended yarn. The Cotton/SS blended yarn and a 50tex pure cotton yarn were knitted on SHIMA SEIKA SES-SWG knitting machine. The course density and wale density of fabric sample are 67 wales/100mm and 79 +

Corresponding arthor. Tel: +61 3 5246 4055

E-mail address: menghe.miao@csiro.au

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courses/100mm, respectively, with a conductive area of 15mm×35mm, as shown in Figure 1(c). Figure 1(d) is a magnified view of the conductive area. The conductive knitted sensors for strip biaxial elongation and garment were manufactured using the twocolor plating jacquard knitting technique on knitting machine SANTONI SM8 Top 2, at densities of 160 wales/100mm and 280 courses/100mm. The size of the central conductive area is 30mm×30mm, as shown in Figure 1(e) and its magnified view in Figure 1(f).

Fig.1: (a) cross section and (b) longitudinal surface of cotton/SS blended yarn; (c) knitted sensor made of cotton/SS blended yarn and (d) its magnified view; (e) knitted sensor from silver coated multifilament yarn and (f) its magnified view.

2.3. Unidirectional tensile testing The cotton/SS blended yarn sensor and its knitted fabric sensor were stretched at a speed of 10mm/min on Instron 5500R. The jaw width was 35mm, and distance between the jaws was 500mm and 35mm, respectively. The resistance traces were recorded continuously using a DIGITECH QM1571 digital multi-meter via wireless connection. The same condition was used for resistance-strain test of the silver-coated multifilament conductive yarn and its knitted fabric sensor.

2.4. Strip biaxial elongation testing The load and strain of silver-coated multifilament yarn knitted sensor was measured on a DRong X-Y Biaxial Material Tester, where two pairs of clamp were utilized to fix sample in both course and wale directions. The resistance was recorded on a Rigol Digital Multi-meter 3068 using the four-wire sensing method. Specimens were first stretched in course direction while being fixed in wale direction (strip biaxial elongation in x direction, SBE-X). Specimens were then tested under SBE-Y direction (stretching in y direction and fixed in x direction). In both experiments, the speed of clamps was 60mm/min and the pre-load was 0.1N. The tests were stopped when ε x under SBE-X and ε y under SBE-Y reached 30%.

2.5. Body movements detecting Front and back sides of the seamless knitted shirt and knee cap were displayed in Figure 2. By using the same electrical resistance testing method as in the SBE test, resistance variations of smart T-shirt and knee cap were recorded during body movements at elbow, shoulder and knee parts. A video camera SONY DCRSR200E was utilized to record body movements.

Fig.2: (a) and (b) front and back sides of knitted shirt and (c) knee cap.

Figure 3 shows body movements at elbow, knee and shoulder sensors. The angle between the forearm and the axis of upper arm is θ e , changing from zero to maximum value and then back to the initial position

by bending forearm upwards and downwards (Figure 3a). Besides, angle θ k between calf and axis of thigh increases to maximum value with calf bending backwards, and then returns to initial condition with leg stretching forwards. During this test, the subject did a series of step and squat movements, as shown in Figure 3(b). To test the shoulder sensors, the left arm stretches horizontally in front of body (initial position) and then performs chest extending exercise slowly. The variation of angle θ s

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between arm and its initial position are shown in Figure 3(c) and (d) with same body movements in both front and back shoulder sensors tests, respectively.

Fig.3: Body movements for sensor tests at elbow (a), knee (b), front shoulder sensor (c) and back shoulder sensor (d).

3. Results and discussion 3.1. Electro-mechanical properties of yarn and knitted strain sensors In the first stretching stage with strain less than 1%, SS fibres in blended yarn start to straighten and contact pressure between fibres starts to rise. Increasing contact area between metallic fibres contributes to the drastically decrease of yarn resistance, as shown in Figure 4 (a). SS short fibres have breaking strain 2%, much lower than cotton fibres. As yarn strain further increases, SS fibres starts to experience extension in length, slippage and breakage, leading to increment of resistance, and the cotton//SS blended yarn becomes nonconductive after 3% when SS fibres are broken into short lengths and continuous connections between SS fibres are lost. The resistance of knitted sensor made from cotton/SS blended yarn decrease sharply within the first 5% strain, shown in Figure 4 (b). The main reason is that the reduction of yarn-to-yarn contact resistance as the contact force between two interlocking loops grows due to fabric strain. The fabric resistance decreases at a much slower rate during further fabric extension at strain levels between 10% and 30%.

Fig.4: Relationship between resistance and strain of blended yarn sensor (a), knitted sensor made of blended yarn (b) and silver-coated multifilament yarn knitted sensor (c).

The relationship between resistance and strain of silver-coated multifilament yarn knitted senseor under strip biaxial elongations are depicted in Figure 4 (c). During SBE-X testing, resistance grows almost linearly and quickly with strain rising. By contrast, resistance increases only slightly in SBE-Y test. Unlike the cotton/SS blended yarn, the contact between the silver coated multifilament yarns is through the direct contact of silver particles, which means much smaller contact resistance. Yarn segments in each conductive loop transfer much more significantly and more SBE-X deforamtion occurs in each stitch than that under SBE-Y. Therefore, equivelant resistance of fabric sensor based on length-related resistance of yarn segments shows more evident growth under strip biaxial elongation in course direction8. This nearly linear relationship between resistance and deformation makes it suitable kntted construction for smart garments.

3.2. Body movements detection Changes of angle and resistance versus time of elbow sensor are shown in Figure 5 (a). The maximum angle values in each bending movement contribute to the most deformation and the highest resistance results. On the other hand, the lowest resistance values occur at minimum angles. The deformation of knitted sensor makes similar effect on the resistance of knee sensor during step and squat movements, shown as Figure 5(b). When arm moves from back to front, deformation of front shoulder sensor reduces. The negative angle values in Figure 5(c) represent the arm reaching initial position and moving further forwards causing the fabric sensor to buckle. As a result, the resistances at the lowest angles are not in accordance with arm movements. Tight garment fit (good contact between body and the back shoulder sensor) improves above-mentioned inconsistency between resistance of back shoulder sensor and body angles. Above-mentioned results demonstrate that resistances of both smart shirt and knee cap respond closely to body motions.

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Fig.5: response of resistance to angle of elbow sensor (a), knee cap (b), and front shoulder sensor (c) and back shoulder sensor (d).

4. Conclusion We have conducted a systematic investigation on the fabrication and electro-mechanical behaviours of knitted strain sensors under unidirectional and strip biaxial elongation and on the application of such knitted strain sensors in detecting body movements. The resistance of knitted sensor made from cotton/SS 50/50 blended yarn reduces sharply and then smoothly as a result of contact force change between conductive fibres in the yarn. The strain sensor knitted from silver-coated multifilament yarn has almost linear resistance-strain relationship under strip biaxial elongation, which is desirable for detecting body movements. The resistance responses of both smart shirt and knee cap respond closely to body motions.

5. Reference [1]. Wijesiriwardana R. Inductive fiber-meshed strain and displacement transducers for respiratory measuring systems and motion capturing systems. IEEE Sensors Journal. 2006; 6: 571-9. [2]. Paradiso. R, Loriga. G and Taccini. N. A wearable health care system based on knitted integrated sensors. IEEE Transactions on Information technology in biomedicine. 2005; 9: 337 - 44. [3]. A. T, Bartalesi R, Lorussi F and Rossi. DD. Body segment position reconstruction and posture classification by smart textiles. transactions of the instritute of measurement and control. 2007; 29: 215-53. [4]. Helmer RJN, Farrow D, Ball K, Phillips E, Farouil A and Blanchonette I. A pilot evaluation of an electronic textile for lower limb monitoring and interactive biofeedback. Procedia Engineering. 2011; 13: 513-8. [5]. Zhang H. Electro-Mechanical Properties of Knitted Fabric Made From Conductive Multi-Filament Yarn Under Unidirectional Extension. Textile Research Journal. 2005; 75: 598-606. [6]. Li L, Liu S, Ding F, Hua T, Au WM and Wong KS. Electromechanical analysis of length-related resistance and contact resistance of conductive knitted fabrics. Textile Research Journal. 2012; 82: 2062-70. [7]. Wang J, Long H, Soltanian S, Servati P and Ko F. Electro-mechanical properties of knitted wearable sensors: Part 2 - Parametric study and experimental verification. Textile Research Journal. 2013; 84: 200-13. [8]. Xie J and Long H. Equivalent resistance calculation of knitting sensor under strip biaxial elongation. Sensors and Actuators A: Physical. 2014; 220: 118-25.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Manufacture of PAN-based anode fibers for lithium ion battery through wet spinning Ho-Sung Yang1 and Woong-Ryeol Yu1, * 1

Department of Materials Science and Engineering and Research Institute of Advanced Materials, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul, 151-744, Korea *woongryu@snu.ac.kr

Abstract. Carbon materials have been widely used as lithium ion battery anode. A strong demand on wearable devices has emerged recently, promoting various researches into flexible and bendable energy source. Carbon nanofibers (CNF) manufactured by electrospinning and heat treatment have been intensively studied thanks to high surface area and electrochemical properties. Due to small size of the nanofibers (2 ~ 800 nm), however, their processibility is not sufficient for developing stand-alone anodes or cathodes. We report on carbonized wet-spun carbon fibers containing active anode nanoparticles, which can be used as an anode themselves, thus enabling to develop one of critical elements for fiber-type and flexible lithium ion battery. Poly(acrylonitrile) (PAN) co-polymer with methacrylic acid and silicon (Si) nanoparticles were used as carbon precursor and active material, respectively. Si-encapsulated PAN fibers were then thermally treated for their carbonization. The electrical conductivity of the Si-encapsulated carbon fibers was 1.4 S/cm and their tensile strength and modulus were about 100 MPa and 2.4 GPa.

Keywords: Wet spinning, Carbon fiber, Lithium-ion battery, Anode

1. Introduction Carbon materials have been widely used as the electrode of energy storage devices [1]. For example, carbon nanofibers (CNF) manufactured by electrospinning and heat treatment have been intensively studied thanks to high surface area and electrochemical properties arising from small size of the nanofibers [2, 3]. Recently, a strong demand on wearable devices has emerged recently, promoting various researches mostly into flexible and bendable energy source [4]. Various materials can be candidates for the electrode of wearable energy device: CNT yarns with active materials such as silicone (Si) or tin [5, 6], CNF web [7], and conductive materials-coated textiles [8]. Carbon fibers have been used as electrode materials [9, 10] because carbon fiber has high mechanical properties and stable electrochemical properties by ion intercalation. However, carbon fiber has low capacity and the improvement of low electrochemical properties is necessary. Therefore, in this study, active nanoparticles such as Si were incorporated into carbon fibers. A wet spinning system was set up, by which poly(acrylonitrile) solution containing Si nanoparticles was spun. After stabilization and carbonization processes, the mechanical, and electrochemical properties of Si-encapsulated carbon fibers were characterized.

2. Experimental 2.1. Spinning solution Poly(acrylonitrile) co-polymer with 6 % methacrylic acid (termed as the PAN below, Mw=80,000 g/mol, Polyscience, Inc), Silicon nanoparticles (Si, D<50 nm, Nanoshel), and N,N-dimethylformamide (DMF, purity 99.5%, Daejung chemical) were used without further purification. Si (1 g) were ultirasonicated in DMF (7.9 g) for 5h and then PAN was added to the solution by controlling to be 21 wt%. The solution was stirred at 90 째C for 24h.

2.2. Wet spinning process

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The wet spinning process is described in Fig. 1. The spinning system consisted of a syringe pump, a coagulation bath, the first roller, a hot bath, and the second roller. The solution coming from the syringe at 5 ml/h flow rate was wet-spun into a coagulation bath consisting of 60:40 DMF/H 2 O at room temperature and o the fibers went through silicon oil hot bath at 105 C. The process conditions were set up: syringe tip diameter – 0.41 mm, the first roller speed – 1.67 m/min, the second roller speed – 9.42 ~ 15.70 m/min respectively. The o length- fixed wet-spun fibers were dried in vacuum oven at 60 C for 8 h. Fig. 1 Schematic diagram of a wet spinning process

2.3. Heat treatment The precursor fibers were clamped between two tungsten blocks at 25 MPa and then thermally treated for o their stabilization and carbonization. The stabilization was carried out at 270~300 C under air atmosphere, during which the removal of hydrogen in PAN started, transforming PAN into ladder structured PAN. The o carbonization was carried out a 1000 C under nitrogen atmosphere, increasing carbon purity in the fiber. The o o increasing rates of temperature were 0.16 C /min and 5 C /min for the stabilization and carbonization processes, respectively.

2.4. Characterization The morphology of the wet spun fiber and the carbonized fibers were analyzed using a field emission scanning electron microscope (FE-SEM) (JSM-7600F, JEOL). The mechanical properties of the wet-spun fiber were measured with universal testing machine (ML802, RNB). Thermogravimetric analysis, wide-angle X-ray diffraction, Raman spectroscopy, and cell test were carried out.

3. Results and discussions PAN solution without Si nanoparticles was firstly wet spun at 9.42 and 15.70 m/min, respectively. The SEM image (Fig. 2(a)) of the wet-spun PAN fiber shows the fibril structure in fiber axis direction. The mechanical properties of the wet-spun fibers are shown in Fig. 2(b) and Table 1. As the drawing speed increased, the diameter of the fiber decreased and the mechanical properties increased.

140

9.42 m/min 15.70 m/min

120

Stress (Mpa)

100 80 60 40 20 0 0

(a)

Strain (%)

(b)

Fig. 2 (a) SEM image of the wet spun PAN fiber and (b) stress-strain curve of the wet spun PAN fiber at 9.42 m/min and 15.70m/min drawing speed

After the wet-spun PAN fiber drawn at 15.70 m/min was thermally treated and their diameter decreased from 55.4 to 40.67 (5.85) nm. Carbonized PAN fibers were observed by SEM image (Fig. 3(a)) and the

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encapsulation of Si nanoparticles in the fibers was confirmed through EDS (Fig. 3(b)). The electrochemical performance of the manufactured carbon fibers containing Si nanoparticles will be evaluated and discussed at the conference.

(a)

(b)

Fig. 3 (a) SEM and (b) EDS images of carbonized wet-spun carbon fibers

Table 1 Diameter and mechanical properties of the wet spun PAN fibers

Sample

Diameter (Îźm)

Strength (MPa)

Modulus (GPa)

Strain (%)

The wet spun PAN fiber (9.42 m/min)

71.6 (13.1)

85.9 (3.4)

2.1 (0.16)

11.1 (1.6)

The wet spun PAN fiber (15.70 m/min)

55.4 (2.9)

128.6 (15.2)

2.34 (0.14)

13.1 (1.7)

4. Summary A wet spinning process was set up, by which pure PAN solution was firstly wet spun. The fibril structure of spun fiber was confirmed via SEM, showing relatively good mechanical properties: the strength and modulus are 129 MPa and 2.3 GPa, respectively. After carbonization process, Si particles were confirmed encapsulated in the carbon fibers. More experiments including the cell test are under progress.

5. References [1] [2] [3] [4] [5] [6]

Wu, Y.P., E. Rahm, and R. Holze, Carbon anode materials for lithium ion batteries. Journal of Power Sources, 2003. 114(2): p. 228-236. Lee, B.-S., et al., Anodic properties of hollow carbon nanofibers for Li-ion battery. Journal of Power Sources, 2012. 199: p. 53-60. Lee, B.-S., et al., Effect of Pores in Hollow Carbon Nanofibers on Their Negative Electrode Properties for a Lithium Rechargeable Battery. ACS Applied Materials & Interfaces, 2012. 4(12): p. 6702-6710. Zeng, W., et al., Fiber-Based Wearable Electronics: A Review of Materials, Fabrication, Devices, and Applications. Advanced Materials, 2014. 26(31): p. 5310-5336. Lin, H., et al., Twisted Aligned Carbon Nanotube/Silicon Composite Fiber Anode for Flexible Wire-Shaped Lithium-Ion Battery. Advanced Materials, 2014. 26(8): p. 1217-1222. Ren, J., et al., Twisting Carbon Nanotube Fibers for Both Wire-Shaped Micro-Supercapacitor and MicroBattery. Advanced Materials, 2013. 25(8): p. 1155-1159.

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[7] [8] [9] [10]

Kim, B.-H., et al., Solvent-induced porosity control of carbon nanofiber webs for supercapacitor. Journal of Power Sources, 2011. 196(23): p. 10496-10501. Hu, L., et al., Stretchable, Porous, and Conductive Energy Textiles. Nano Letters, 2010. 10(2): p. 708-714. Jost, K., et al., Knitted and screen printed carbon-fiber supercapacitors for applications in wearable electronics. Energy & Environmental Science, 2013. 6(9): p. 2698-2705. Sawangphruk, M., et al., High-performance supercapacitor of manganese oxide/reduced graphene oxide nanocomposite coated on flexible carbon fiber paper. Carbon, 2013. 60: p. 109-116.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Manufacturing Techniques and Property Evaluations of PVA/LE Nano-fibrous Membranes Zong-Han Wu 1, Ching-Wen Lou 2, Chiung-Yun Chang 3, Chih-Kuang Chen 4 and Jia-Horng Lin1, 5, 6 + 1

Laboratory of Fiber Application and Manufacturing, Department of Fiber and Composite Materials, Feng Chia University, Taichung City 40724, Taiwan, R.O.C. 2 Institute of Biomedical Engineering and Materials Science, Central Taiwan University of Science and Technology, Taichung City 40601, Taiwan, R.O.C. 3 Department of Dental Technology and Materials Science, Central Taiwan University of Science and Technology, Taichung City 40601, Taiwan, R.O.C. 4 The Polymeric Biomaterials Lab, Department of Fiber and Composite Materials, Feng Chia University, Taichung City 40724, Taiwan, R.O.C. 5 School of Chinese Medicine, China Medical University, Taichung City 40402, Taiwan, R.O.C. 6 Department of Fashion Design, Asia University, Taichung City 41354, Taiwan, R.O.C.

Abstract. Electrospinning has been proven to be a relatively simple method to produce nonwoven nanofibrous mats. The diameter of the electrospun fibers can be as fine as micro- or nano-meter sizes. In addition, electrospun fibers have a high specific surface area and resembles a natural extracellular matrix (ECM). These features qualify the nanofibers to be used in tissue engineering and for drug delivery. Shikonin is a naturally occurring compound, and can be extracted from the roots of Boraginaceae, such as Lithospermum erythrorhizon (LE), Alkanna tinctoria, and Arnebia euchroma. Due to its anti-inflammatory activities, proliferation of granulation tissue, and being wound healing anti-tumor, antioxidant, and antibacterial, Shikonin has been commonly studied in different fields. In this study, a polyvinyl alcohol (PVA) solution and an LE extract solution are blended with various ratios (100/0, 80/20, 70/30, 60/40 and 50/50 v/v %), after which blends are electrospun into PVA/LE membranes. The viscosity, conductivity, fiber diameter, and cytocompatiblity of the PVA/LE membranes are then evaluated in order to determine the optimal PVA/LE blending ratio. PVA and ethonal are blended with different ratios of 100/0, 78/22, 67/33, 57/43 and 50/50 v/v %, followed by being electrospun into PVA/Ethonal nanofibrous membranes. A scanning electron microscope is used to observe the morphology of fibers in order to evaluate the optimal PVA/Ethonal ratio. Next, the PVA solution and LE solution are blended with an optimal ratio, and are then electrospun into PVA/LE nanofibrous membranes. Finally, the fiber morphology is evaluated in terms of different applied voltages. Keywords: Electrospinning, polyvinyl alcohol (PVA), Lithospermum rythrorhizon (LE), membrane, wound dressing

1. Introduction Electrospinning is a technique that suits the production of nano-fibers the best, due to its relative ease process, low cost, pervasive material options, versatility, and potential uses in diverse fields[1]. Nanofibrous membranes that are incorporated electrospinning have a porous nature and a large surface that can absorb wound exudate, and it prevents microbial invasion that helps avoiding infection. In addition, it is also featured by having interconnected porous structure and ultrafine fibers, which enhance cell attachment and provide extracellularmatrixc-like (ECM) scaffolds that are required by the regeneration of tissues [2-4]. The formation and morphology of electrospun nano-fibers depend on diverse parameters, including setup parameters (e.g., applied voltage, volume feed rate, tip-to-collector distance, and collector type), solution parameters (e.g., +

Corresponding author. Tel.: + 886-4-2451-8672. E-mail address: jhlin@fcu.edu.tw

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polymer concentration, molecular weight, solvent electrical conductivity, solution viscosity, and surface tension), and environmental conditions (e.g., temperature and relative humidity)[5]. Shikonin is phytochemically derived from Lithospermum erythrorhizon (LE), and it has been proven to possess diverse biological and pharmacological activities, and thus has anti-inflammation, antibacterial activities, wound-healing function, and antitumor properties [6-8]. This study uses PVA electrospun fibers as drug carriers. As Shikonin is not water-soluble, it is dissolved in ethanol, organic solvents and vegetable oils. Ethanol is used as the solvent for the extraction of LE in order to obtain its Shikonin and its derivatives. PVA/ethanol nanofibrous membranes and PVA/LE nanofibrous membranes are evaluated in order for a purpose obtaining their optimal parameters. PVA/Ethonal mixtures that are composed of ratios of 100/0, 78/22, 67/33, 57/43 and 50/50 v/v % are tested for their viscosity and electrical conductivity. The mixtures are then electrospun into PVA/Ethona nanofibrous membranes, whose morphology is observed by using an SEM in order to obtain the optimal PVA/Ethonal ratio. Next, PVA solution and LE solution are blended with an optimal ratio, and are then electrospun in conjunction of voltages of 15, 20, and 25kv into PVA/LE nanofibrous membranes. An SEM is used to observe their morphology of fibers, and an image software is used to compute the diameters of fibers, and thereby determine how the difference in voltage in relation to PVA/LE nanofibrous membranes.

2. Experimental 2.1 Materials PVA (Sigma Chemical Co., USA) has a molecular weight between 89000-98000, and is 99+% hydrolyzed. Lithospermum erythrorhizon is purchased from Xin Long, Taiwan, R.O.C. Shikonin (≥ 98% HPLC, S7576), phosphate buffered saline (PBS), and Tween-80 are purchased from Sigma-Aldrich. Ethanol (Union Chemical Works Ltd., Taiwan, R.O.C.) has a purity of 95 %.

2.2 Preparation of PVA/ethanol and PVA/LE nanofibrous membranes The extraction of LE is referred to a previous study[8]. PVA powder and deionized water are formulated into a 12 wt% PVA solution. This PVA solution is blended with a 95% ethanol with a blending ratios of 100/0, 78/22, 67/33, 57/43 and 50/50 v/v %, and different mixtures are electrospun into PVA/ethanol nanofibrous membranes with the voltage of 15, 20 and 25 kV. The collection distance between the jet and the collector plate is 10 cm, and a velocity is 1.0 ml/hr. The parameters for nanofibrous membranes are indicated in Table 1. The optimal blending ratio is determined by the SEM observation of PVA/ethanol nanofibrous membranes. PVA solution and LE extract are blended with an optimal ratio. The mixture is electrospun with the voltage being being 15, 20 and 25 kV, a collection distance between the jet and the collector plate being 10 cm, and a velocity of 1.0 ml/hr, thus forming PVA/LE nanofibrous membranes.

3. Results and discussion The influences of PVA/ethanol ratios of 100/0, 78/22, 67/33, 57/43 and 50/50 v/v % on the PVA/ethanol nanofibrous membranes are indicated in Fig. 1 and Table 1. A PVA/ethanol ratio of 100:0 or 78:22 leads to a desired fiber morphology in PVA/ethanol nanofibrous membranes, as indicated in Fig. 1 (a-f). However, the nanofibrous membranes initially exhibit a great deal of bead formation, rather than a fiber formation, as indicated in Fig. 1 (g-l). The possible factors are viscosity and electrical conductivity. According to Table 1, the viscosity and electrical conductivity with the corresponding PVA/ethanol ratio are 544 ± 38.6 mPa•s and 656 µS (100:0) and 230 ± 0.92 mPa•s and 190µS (50:50). The PVA/ethanol mixtures that are composed of a 50:50 ratio thus have 42.2% lower viscosity and 28.9% lower electrical conductivity. Therefore, the incorporation of ethanol significantly dilutes the PVA concentration, which in turn considerably decreases the viscosity and electrical conductivity. The viscoelastic properties of polymers are a key factor to the electrospinning because a critical amount of chain entanglements is needed for fiber formation [9]. In addition, a high viscous system contributes to fabricate less defective fibers, but an excessive viscosity results in high cohesiveness of the solution, which is responsible for the flow instability [5]. Zong et al. indicated that a polymer solution containing a higher net charge density could yield finer and bead-free fibers [10]. Therefore, PVA/ethanol mixture containing 33~50% ethanol have a low viscosity and a low electrical conductivity. The density of the polymers is too low to create chain entanglement, and eventually fails in supporting a continuous electrospinning for fiber formation. The discontinuous spinning solution thus results in a great amount of beads. This phenomenon gets obvious when

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the ethanol content is increased. In contrast, different voltages of 15, 20, and 25kV are not correlated with the fiber morphology of PVA/ethanol nanofibrous membranes. In sum, according to the optimal fiber morphology of PVA/ethanol nanofibrous membranes in Table 1 and Fig. 1, the optimal PVA/ethanol ratio is 78:22, which is used for subsequent discussions.Afterwards, PVA/LE extract are blended with a 78:22 ratio, and are electrospun with three voltages of 15, 20, and 25kV into PVA/LE nanofibrous membranes. PVA/LE nanofibrous membranes are then observed by using an SEM, and are examined in terms of diameters. The viscosity and electrical conductivity of PVA/LE mixtures of 78:22 are comparable to the viscosity and electrical conductivity of PVA/ethanol. This result is ascribed to the low amount of Shikonin and its derivatives in LE extract (6.24mg/ml). In addition, the solvent (i.e., ethanol) in LE extract plays a dominant role in affecting the viscosity and electrical conductivity of PVA solution. Therefore, PVA/ethanol mixture and PVA/LE mixure have comparable viscosity and electrical conductivity. Fig. 2 and Table 2 indicate the effects of applying different voltages on PVA/LE nanofibrous membranes. As indicated in SEM images and fiber diameter distribution, an increasing voltage from 15 to 25kV causes the diameter distribution from 243-495 nm to 178-379 nm. The average diameter of fibers becomes finer, which is from 359 ± 64 nm to 266 ± 57 nm. This result is attributed to the fact that with a specified volume feed rate of 1.0 ml/hr, a tip-to-collector distance of 10 cm, and a constant collector type, the electrical field between the needle to the collector is strengthened as a result of a higher applied voltage. The polymer solution is extended to a greater extent, and thereby decreases the diameter of nanofibers. 15 kV

20 kV

25 kV

(a)

(b)

(c)

(d)

(e)

(f)

(g)

(h)

(i)

(j)

(k)

(l)

100/0

80/20

67/33

57/43

Fig. 1: SEM of PVA/ethanol nanofibrous membranes with different combinations of PVA/Ethanol ratios and voltages. The scale bar is 10 um. Table 1: Properties of PVA/ethanol nanofibrous membranes. Amount of water Amount of ethanol Viscosity, mPa·s Electrical Conductivity, Samples based 12% based 95 % ethanol µS PVA solution, % solution, % PVA 100 544 ± 38.6 656 PVA/ethanol 78 22 454 ± 26.7 376 PVA/ethanol 67 33 384 ± 19.2 300 PVA/ethanol 57 43 300 ± 12.0 249 PVA/ethanol 50 50 230 ± 0.92 190

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(b)

(a)

(c)

(e)

(d)

(f)

Fig. 2: SEM of PVA/LE nanofibrous membranes of a) PVA/LE-I, b) PVA/LE-II, and c) PVA/LE-III with a scale bar being 10 um. Their corresponding fiber diameter distributions are d) PVA/LE-I, e) PVA/LE-II, and f) PVA/LE-III. Table 2: Properties of PVA/LE nanofibrous membranes. Amount of water based Amount of ethanol based Samples PVA solution, % LE solution, % PVA/LE-I PVA/LE-II PVA/LE-III

78 78 78

22 22 22

Voltage, kV

Fiber Diameter, nm

15 20 25

359 ± 64 271 ± 60 266 ± 57

4. Conclusion This study has successfully developed and manufactured PVA/LE nanofibrous membranes. According to the viscosity, electrical conductivity, and SEM evaluations, the optimal blending ratio for PVA/ethanol mixture is 78：22 that can be electrospun into bead-less nanofibers. In comparison of different PVA/LE nanofibrous membranes, PVA/LE-III is the most stabilized as its fiber diameter distribution is narrow and the fiber diameter is finest ( 266 ± 57 nm). PVA/LE nanofibrous membranes will be evaluated in terms of drug release and in vitro test for their applications to wound healing and nursing.

5. Acknowledgements The authors would like to thank Ministry of Science and Technology of Taiwan, for financially supporting this research under Contract MOST 103-2622-E-166-001-CC2.

6. References [1] [2] [3]

S. Homaeigohar and M. Elbahri, Materials, 7, 1017 (2014). A. C. Brignier and A. M. Gewirtz, Journal of Allergy and Clinical Immunology, 125, S336 (2010). X. L. Hu, S. Liu, G. Y. Zhou, Y. B. Huang, Z. G. Xie, and X. B. Jing, Journal of Controlled Release, 185, 12 (2014). [4] M. C. L. C. W. Lou, C. T. Lu, C. L. Huang, J. H. Lin, Applied Mechanics and Materials, 457-458, 371 (2013). [5] A. Luzio, E. V. Canesi, C. Bertarelli, and M. Caironi, Materials, 7, 906 (2014). [6] S. Y. Yin, A. P. Peng, L. T. Huang, Y. T. Wang, C. W. Lan, and N. S. Yang, Evidence-Based Complementary and Alternative Medicine, (2013). [7] I. Andujar, J. L. Rios, R. M. Giner, and M. C. Recio, European Journal of Pharmaceutical Sciences, 49, 637 (2013). [8] C. W. Lou, C. Y. Chang, Z. H. Wu, and J. H. Lin, Materials Science & Engineering C-Materials for Biological Applications, 48, 165 (2015). [9] H. Fong, I. Chun, and D. H. Reneker, Polymer, 40, 4585 (1999). [10] X. H. Zong, K. Kim, D. F. Fang, S. F. Ran, B. S. Hsiao, and B. Chu, Polymer, 43, 4403 (2002).

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Moisture Management and Thermo-physiological Properties of the Multi-layered Clothing System Containing Super-absorbent Materials Shadi Houshyar, Rajiv Padhye and Rajkishore Nayak, School of Fashion & Textiles, RMIT University, Brunswick, Victoria 3056, Australia

Abstract: Extensive research has been done to improve the comfort properties of protective clothing system worn by fire fighters. In this research, new inner-layer construction has been developed with high liquid and vapor absorption capacity that could assist in retaining the moisture and vapor away from the skin, and in addition, provide a dry microclimate close to the skin. These new inter layers were tested for mechanical and thermo-physiological properties, such as thermal and water vapor resistance. The results indicated that it is possible to improve the comfort properties of the protective clothing by the incorporation of super absorbent materials into the internal layer. However, tensile and tear strength of the final product was reduced significantly. Further investigation is required to optimize the SAF content into the inner layer fabric. Keywords: super absorbent fiber, comfort, absorbency, water vapour resistance, thermal resistance

Introduction Fire-fighters encounter a range of hazards during structural as well as wild-land fire-fighting. Therefore, wearing protective clothing is essential to protect them from thermal exposures and other life threatening risks [1-3]. In general, the standard protective clothing is a multilayer construction, which is heavy and bulky, to provide the desired thermal protection, while reduces the ability of the protective clothing to transfer internal heat to the surrounding atmosphere and creates heat stress to the fire-fighters [2,3-6]. Hence, the moisture produced by sweating remains inside the clothing system resulting in a sensation of wet clinginess and thermal discomfort to the wearer. Consequently, optimizing the thermal protection and comfort properties of these clothing have been the major area of research in recent years [4,7-9]. In this study, we developed new internal layers for the protective clothing by incorporating super absorbent materials (SAF) and high wicking polyester (Coolmax速) into the inner layer of the protective clothing. These internal layer have the high capacity to absorb sweat and vapor, and assist in retaining the absorbed sweat intact even under the pressure of the outer garment. The sweat absorption and the transport properties of the fabrics were recorded and compared with the existing material currently in the market.

Materials and Methods Materials Nomex, Superabsorbent and Coolmax 速 yarn were provided by Bruck Textiles, Technical Absorbent, UK and Invista, respectively. The Tests were carried out on one layer, inner layer, 1/3 Twill fabric made by Bruck Textiles. The specifications of developed fabrics were listed in Table 1. Fabric contains Nomex yarn in the warp direction and weft direction has various composition of Nomex/SAF/Coolmax. Table 1. Specifications of produced fabrics

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Sample code A

Fibre composition (%)

Thickness (mm)

Construction

GSM

DuPont™ Nomex® Comfort

131±1

Woven (Rip stop)

135

60/40% Nomex® / Coolmax

115±5

A2 A3 A4 A5

88/12% Nomex® / Coolmax 55/45% Nomex® / SAF yarn 67/33% Nomex® / SAF yarn 75/25% Nomex® / SAF yarn

130±5 165±5 165±5 155±5

110-120 Woven (Rip stop)

125-135 160-170 160-170 150-160

Physical and Mechanical properties All the fabrics were conditioned and tested for thickness and mass in in accordance with ASTM D3776-1990 and ISO 5084. Five specimens of 0.2 m (l) x 0.05 m (w) were cut parallel to each direction, warp and weft, respectively. The samples were tested according to ISO 13934-1 and D1424 - 09(2013), using an Instron Universal Testing Machine (3300 Single Column) under standard conditions.

Thermo-physiological properties The thermal resistance (R ct ), and water vapour resistance (R et ) or the breathability of the fabrics, were evaluated in accordance with ISO 11092: 1993 under steady-state conditions using the Atlas Sweating Guarded Hot Plate (SGHP, ). The R ct and R et results were used to calculate the water vapour index (i mt ) and the thermal insulation (Clo) values of the fabrics following the equations below: i mt = 60*R ct /R et

(1.1)

Thermal insulation (Clo) = (R ct + 0.087)/0.155

(1.2)

Results and Discussion Fabric with Coolmax yarn in the structure, (A 1 & A 2 ) dried off much quicker than A, Nomex, due to the structure of the fabric which changed from compact packaging to looser structure. While, the fabric with high SAF content dried off longer than the 100% Nomex fabric due to SAF high water absorbency. Figure 1 showed that water absorbency of the Coolmax/SAF/Nomex versus time. BY incorporation of SAF into the fabric the amount of absorbed water increased significantly, while incorporation of Coolmax did not have any effect on water absorbency of the fabric.

Water absorbency (%)

90 80

60 A3

50 A4

40 30

10 0 0

120

Time (min)

Fig. 1: Water absorbency of fabrics with Coolmax/SAF/Nomex composition

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Tear and tensile properties of the fabrics were recorded and the results showed in Figure 2. There is a reduction in tear and tensile properties of the fabric, by incorporating Coolmax/SAF into the fabric structure. The highest reduction belonged to the fabrics with the highest percentage of SAF, due to the lower mechanical properties of SAF yarns compared with Nomex and Coolmax. Also it should be noted that fabrics, A 3 , A 4 and A 5 have high percentage of PE into their structure in addition to SAF which can led in reduction of mechanical properties of the fabric. Load @ Break (N)

Max Load (N)

1000 800 600 400 200 0 A

Extension (mm) 100 90 80 70 60 50 40 30 20 10 0 A5

Extension @ Max load (mm)

1200

(a) Warp Weft

120

Tear strength (N)

100 80 60 40 20 0 A

(b) Fig. 2: Tensile and tear properties for Nomex/Coolmax/SAF fabric

On the basis of the results which were presented in figure 3, it can be stated that there is not much difference in thermal and water vapour resistance of the fabrics by changing the composition from Nomex to Nomex/Coolmax or Nomex/SAF. However the fabric with high percentage of Coolmax showed lower thermal resistance due to the fact that the property of the fabric has been governed partially by Coolmax and the lower thickness for this type of fabric.

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3.5

0.03

Ret (m2Pa/W)

0.02

2 0.02 1.5 0.01

Rct (m2K/W) & imt

2.5

Ret 0.01

0.5 0

0.00 O1

Water permeability index Rct

Fig. 4: Mean thermal resistance, water vapour resistance and water permeability index for Nomex/Coolmax/SAF fabrics

Therefore there is no advantage or disadvantage of adding SAF or Coolmax (low percentage) into the composition of the fabrics. Selection of the final fabric should be established base on the results from the other properties of the fabrics, such as physical properties, liquid transfer and heat transfer flame and radiant. However, it has to be considered that the addition of SAF into the inner structure of protective clothing can reduce the humidty and dampness of theair trapped inside the clothing.

Conclusion This results from this investigation showed that incorporating SAF/Coolmax into the internal layer of protective clothing had negligible effect on thermo-physiological properties of the final fabric. Water vapour resistance, thermal resistance and water permeability indices values of the all ensembles were close. It indicated that there was not any major improvement of comfort properties of the internal layer by changing the composition of the woven internal layer from Nomex to Nomex/SAF/Coolmax. While there is a significant reduction in tensile and tear strength of the Nomex/Coolmax/SAF fabric, due to the low mechanical properties of SAF/Coolmax, which has an effect on the mechanical propeties of the final fabric. Another reason for reduction in mechanical properties of the final fabric was that the used SAF yarn was a blend of polyester and SAF, which has low mechanical properties. Further investigation is required to optimised the SAF content while eliminating polyester fibers from the final product.

Acknowledgements Thanks to the Commonwealth government for funding this project under Strategic Capability Program (SCP).

References [1] [2] [3] [4] [5] [6] [7] [8] [7]

Scott, R.A., Textiles for protection. 2005: Woodhead Publishing, Cambridge, UK Nayak, R; Houshyar, S; Padhye, R; Fire Science Review 3, 4 (2014), 1. Kilinc, F.S., Handbook of fire resistant textiles. 2013, Cambridge, UK: Woddhead Publishing A. D. Ellison, T. M. Groch and B. A. Higgins; â&#x20AC;&#x153;Thermal Manikin Testing of Fire Fighter Ensemblesâ&#x20AC;?, Major Project, Worcester Polytechnic Institute (2006) S. Jing, S. F. Chang, S. T. Yang and G. T. Jou: The 6th Asian Textile Conference (2011) Houshyar S, Padhye R; Troynikov O; Nayak R and Ranjan S; The Journal of The Textile Institute (2015),1. H. S. Yoo, G. Sun and N. Pan: American Society for Testing and Materials (2000) G. Bartkowiak Fibres & Textiles in Eastern Europe 18, 4 (2010), 82 G. Bartkowiak Fibres & Textiles in Eastern Europe 14, 1 (2006), 55.

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[9] [10] [11]

A. Marszalok, G. Bartkowiak and K. Tezak: International Journal of Safety and Ergonomics 15, 1 (2009), 61. S Nazare, R. Davis, J Peng and J. Chin: NIST Technical Note 1746 (June 2012) GJ Carlsson, LH. Gan and DM. Wiles: Canadian Journal of Chemistry 53 (1975), 2337

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Composite Knitted Fabrics and Woven Fabrics : Electromagnetic Shielding Effectiveness and Far-infrared Emissivity Jan-Yi Lin 1, Ting-Ting Li 2, 3, Mei-Chen Lin 1, Ching-Wen Lou 4, and Jia-Horng Lin 1

1, 5, 6 +

Laboratory of Fiber Application and Manufacturing, Department of Fiber and Composite Materials, Feng Chia University, Taichung City 40724, Taiwan. 2 School of Textiles, Tianjin Polytechnic University, Tianjin 300387, China. 3 Tianjin and Education Ministry Key Laboratory of Advanced Textile Composite Materials, Tianjin Polytechnic University, Tianjin 300387, China. 4 Institute of Biomedical Engineering and Materials Science, Central Taiwan University of Science and Technology, Taichung City 40601, Taiwan. 5 Department of Fashion Design, Asia University, Taichung City 41354, Taiwan. 6 School of Chinese Medicine, China Medical University, Taichung City 40402, Taiwan.

Abstract. In order to reduce harms from electromagnetic (EM) radiation to human health, as well as to remedy the defects of current anti-electromagnetic radiating composites, study on EM shielding composites are progressed positively. This study prepares BC/CF woven fabric and BC/CF knitted fabric using bamboo charcoal (BC) filament as sheath material to give its added-value of far-infrared emissivity, and carbon fiber (CF) as core material because of its electric conductivity merely inferior to metal material and its EM shielding effect. The processing performance, far-infrared emissivity, surface resistance and EM shielding effectiveness (SE) of prepared woven fabric and knitted fabric were evaluated respectively. Result shows that, BC/CF knitted fabric has better EM SE; and its EMSE largely improves with number of layers. BC/CF fabric which was made in the study has a broadening application of electromagnetic shielding and conductive heating fields in the future. Keywords: Electromagnetic shielding, woven fabric, knitted fabric, carbon fiber, bamboo charcoal.

1. Introduction In recent years, science and technology advancement prompts communication technology booming. For example, smartphone, television, micro-wave oven and AM/FM radios, notebook computer, and Wi-Fi bring some negative effects although some great convenience, especially when electromagnetic waves radiation from smartphone becomes a health hazard issue and then a focus to the public [1-3]. Carbon fiber is a common material in the current industry and livings, and has kinds of carbon element related excellent properties, such as good electric conductivity, low specific gravity, good thermal resistance, corrosion resistance, high thermal conductivity and small thermal expansion coefficient. In addition, it has fibrous-structure flexural property and can be further knitted and processed. However, the excellent performance is that its specific strength and specific modulus both surpass the general reinforcing fibers, and these values are 3 times higher than steel and aluminium after it composites with resin forming carbon-fiber reinforced composites. These carbon-fiber reinforced composites have the broad application. In the aerospace industry, they reduce weight obviously, increase effective load and improve the performance, and become the important structural materials in aircraft and spacecraft. Moreover, due to the low cost, they widely uses in automobile industry and sports apparatus [4]. This study prepared bamboo charcoal (BC)/carbon fiber (CF) wrapped yarns via rotor-twisting machine which were made by BC filament as the sheath and CF as the core, and BC/CF woven fabric and knitted fabric via weaving and knitting processes.

Corresponding author. Tel.: + 886-4-2451-8672 E-mail address: jhlin@fcu.edu.tw

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2. Experimental 2.1.

Materials

3K Carbon filament (CF) was provided by Tory Industries, Japan. 70 D/36f bamboo charcoal /Nylon (BC/NY) yarn provided by Formosa Taffeta Co., Ltd, Taiwan, had a BC content of 3%.

2.2.

Sample Preparation

Preparation of BC/CF wrapped yarn BC/NY filament used as sheath material, and CF as core material were fabricated into BC/CF wrapped yarn using rotor-twisting machine. The rotating speed was set as 15000 rpm.

Preparation of BC/CF woven fabric The prepared BC/CF wrapped yarn was used as weft yarn and 1000 D high-strength PET was as warp yarn. Those two directional yarns were woven into BC/CF woven fabrics using a rapier loom.

Preparation of BC/CF knitted fabric BC/CF wrapped yarns were made into BC/CF knitted fabric using knitting machine. The number of threads was 70.

2.3.

Testing Method

Surface observation The structure pattern of different fabrics was observed by stereomicroscopy (SMZ-10A, Nikon Instruments Inc., Japan) attached with Motic Images Plus 2.0 software (Motic Group Co., Ltd., USA).

Far-infrared emissivity According to FTTS-FA-010, far-infrared emissivity of BC/CF fabrics was tested by Far Infrared Emissivity Tester (TSS-5X, Desunnano Co., Ltd., Japan). Ten positions of each fabric were measured for the mean value.

Surface resistance According to JIS L1094-2014, surface resistance of BC/CF fabrics was tested by surface resistance meter (RT-100, OHM-STAT, Static Solutions Inc., USA). The sample was first placed on the Teflon plate to insulate from the airs. Then, meter loaded by 5 pounds weights was put on the surface of samples to make them contact well with each other. 20 positions of each fabric were measured for the mean value.

Electromagnetic shielding effectiveness (EMSE) According to ASTM D4935-10, EM shielding clamper (E-Instrument Tech Ltd., Taiwan) attached with frequency analyzer (Advantest R3132A, Burgeon Instrument Co., Ltd., Taiwan) was to conduct the EMSE of BC/CF fabrics. Before testing, the control sample which has the same thickness with testing sample was considered as the reference, and its EMSE was measured as SERef. This is the adjusting process for analyzer. The number layers and lamination angle of samples also changed and then their EMSE was measured as SEload. The actual SE of sample was SEload subtracting from SERef. The testing frequency was 300 kHz~3 GHz. Each fabric had a size of 150Ă&#x2014;150 mm2. The number of layers was 1~3. The lamination angles were 0/0/0, 0/90/180and 0/45/90 respectively.

3. Results and Discussion 3.1.

Surface Observation

This part purposes to observe structure of different patterns of fabrics. In Figure 1(a), red circles show the 1000 D polyester (PET) filament, carbon filament, BC/NY yarn. It is found that the fabric has the woven structure. Red circle in Figure 1(b) shows the carbon fiber, and also knitted structure is observed.

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Fig. 1: Stereoscopic images of different structure of fabrics (20×) (a) BC/CF woven fabric; (b) BC/CF knitted fabric.

3.2.

Far-infrared Emissivity

This part shows the effect of fabric structure on far-infrared emissivity. Figure 2 shows that BC/CF woven fabric and knitted fabric both have far-infrared emissivity of above 0.8. This is because carbon fiber has been wrapped with BC filament which has far-infrared effect before weaving. It reflects that whatever the fabric structure, the samples have far-infrared releasing effect.

Fig. 2: Far-infrared emissivity of different structures of fabrics.

3.3.

Surface Resistance

This section shows effect of fabric pattern on surface resistance. Table 1 displays that warp-wise woven fabric cannot detect the surface resistance, because 1000 D PET filaments were selected as warp yarn and had not electrical conductivity. However, weft yarn, BC/CF wrapped yarn, cannot connect each other and thus worse electro-conductivity. For knitted fabric, weft-wise fabric displays small surface resistance, indicating better electric conduction. This is because knitted fabric was shaped by connective loops during knitting process, and its weft-wise yarn which was composed of conductive carbon fibers had a good continuity. Table 1: Surface resistance of different structure of fabrics. Warp-wise(Ω) Weft-wise(Ω)

3.4.

Woven fabric

209.40±5.32

Knitted fabric

46.88±0.71

7.15±0.20

Electromagnetic Shielding Effectiveness (EMSE)

This section shows different fabric pattern, lamination number and lamination angle influencing on EMSE. Figure 3(a) shows that with the same lamination angle, increasing from one-layer to three-layer has not a significant influence on EMSE. Comparatively, Figure 3(b) shows that with three layers, lamination angle significantly affects EMSE of woven fabrics. Woven fabrics plied at 0/45/90° have better EMSE, and the EMSE reaches 38 dB at high-frequency (1800-3000 Hz). It is attributed to the fact that changing lamination angle makes more carbon fibers contained at per unit area.

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Fig. 3: Effects of number of layers and lamination angle on EMSE of BC/CF woven fabrics. (a) number of layers: 1-3 layers; (b) lamination angles: 0/0/0, 0/90/180, 0/45/90.

Figure 4(a) shows that number of layers significantly increases the EMSE, and the EMSE value reaches 48 dB at high-frequency (1800-3000 Hz) up to the industrial protection level. It is because knitted fabric was formed by continuous loops, and thus carbon fiber as conductor generated relatively complete shielding network and hence better EM shielding effect. Figure 4(b) shows that lamination angle cannot reinforce the EMSE, which is because knitted loops connected each other and thus three layers had already reached the best shielding effect.

Fig. 4: Effects of number of layers and lamination angle on EMSE of BC/CF knitted fabrics. (a) number of layers: 1-3 layers; (b) lamination angles: 0/0/0, 0/90/180, 0/45/90.

4. Conclusions This study successfully prepared different patterns of multi-functional fabrics using bamboo charcoal(BC)/carbon fiber(CF) wrapped yarns. Result shows that the resultant BC/CF fabrics have excellent far-infrared emissivity and electromagnetic shielding effectiveness. Comparatively, BC/CF knitted fabric has smaller surface resistance and thus better electromagnetic shielding efficiency up to 48 dB at frequency of 1800-3000 Hz.

5. Acknowledgements The authors would like to thank Ministry of Science and Technology of Taiwan, for financially supporting this research under Contract MOST 103-2221-E-035-027.

6. Reference [1] [2] [3] [4]

Repacholi, M. H. (1998). Low~ level exposure to radiofrequency electromagnetic fields: health effects and research needs. Bioelectromagnetics, 19, 1~ 19. Goldsmith, J, R. (1997). Epidemiologic evidence relevant to radar (microwave) effects, Environ Health Perspect, 105, (6), 1579~ 1587. Hyland, G. J. (2000). Physics and biology of mobile telephony, The Lancet, 356, 1833~ 1836. Klitzing, L. (1995). Low~ frequency pulsed electromagnetic fields influence EEG of man, Physica Medica, 11, 77~ 80.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Performance Evaluation of Commercial and Test Textiles and Analysis of Their Behavior against Washing Machine Parameters during Laundering Muhammed Heysem Arslan1, İkilem Göcek1, İlkan Erdem2, Umut Kıvanç Şahin1, Hatice Açıkgöz Tufan1 1

Istanbul Technical University, Faculty of Textile Technologies and Design, Department of Textile Engineering, Gumussuyu-Beyoglu Istanbul, TURKEY, 2 ARCELIK Incorporation Washing Machine Plant, Product Development Department, System Design & Development Unit, TURKEY

Abstract. In daily life during wear and use, textiles are exposed to continuous effects of many external factors. Apart from these, textiles require to be cleaned periodically depending on their frequency of use. The laundering process with its inherent parameters creates a medium with severe physical and chemical effects on textiles. Different textiles possess various properties according to their inherent structures, and due to their unique structures they exhibit different behaviors against many external factors. Revealing the relationship between the commercial textiles and the test textiles will enable better comprehension of the behavior similarities and differences of the textiles included in those two groups against washing parameters of the laundering process. Therefore, the aim of this study is to investigate the behavior of commercial textiles such as men’s shirt, trousers, men’s and women’s T-shirts and a pair of socks as well as that of test textiles such as Swissatest 304 Fraying fabric, Swissatest 252 Pilling fabric and Swissatest 106 Mineral oil/Carbon Black Soil towards the most remarkable two washing machine parameters during laundering such as temperature and load quantity by focusing on pilling, shrinkage, collar abrasion, sewing defects, the other defects other than sewing, whitening and overall properties of textiles. Moreover, the study focuses on exploring and analyzing the relationship between commercial textiles and test textiles depending on statistical analysis conducted by utilizing MINITAB® package program. During investigation, the behaviors of both groups of textiles towards washing machine parameters were visually and quantitatively evaluated in dry state, i.e. after laundering and drying processes were over.

Keywords: performance evaluation of textiles, washing machine parameters, laundering, durability against laundering, test textiles

1. Introduction By the investments made on the textile sector, novel textile products have been entering into our daily lives and being utilized continuously. With the increase in the use of these new textiles, users and producers have encountered with numerous parameters to be dealt with due to diversification of these textiles in terms of their inherent properties. Moreover, since textiles and fibers are amenable to environmental stresses, a number of studies have been conducted on the effects of external factors on textile materials [1]. Especially, the laundering process which can impact most of the textile qualities has been taken into consideration in these studies in terms of its mechanical and chemical effects on aesthetics, physical properties and durability of textiles [1, 2]. Sawhney et al. investigated the effects of household laundering machine from the point of the predetermined textile features such as weight, thickness, tearing strength, tensile strength, elongation, absorbency, and dimensional changes on hydro-entangled cotton nonwoven fabrics which had different quality characteristics such as micronaire, upper half mean length, uniformity index, short fiber content, strength, breaking elongation, and trash count. Basically, the aim of their study was to reveal why textiles lose their fabric tensile strength in laundering after numerous washing cycles. They found that mechanical quality of greige cotton which was long-lasting for up to 15 washing and drying cycles could be taken as a reference suitable for manufacturing nonwoven fabrics [3]. Quaynor et al. demonstrated the effects of temperature in terms of alteration of surface and dimensional properties of cotton and polyester knitted fabrics during laundering process, and made a comparison based on silk; for that, silk filament yarns, combed, ring-spun, and

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mercerized cotton yarns, and polyester yarns were all utilized for knitting. In their investigation, each sample was washed 10 times with a special laundering cycle having three profiles in terms of washing conditions as 20°C, 35°C and 50°C. According to the findings, surface friction of cotton decreased after a while with increasing shrinkage due to the increase in water temperature. On the other hand, fabrics’ cover factors showed a negative correlation with them [4]. In the current study, the behavior of both commercial and test textiles against washing machine parameters were visually and quantitatively evaluated in dry state after laundering and drying processes in order to analyze the relationship between commercial textiles and test textiles depending on statistical analysis conducted by utilizing MINITAB® package program.

2. Experimental 2.1. Materials and Equipment In this study, cotton fabrics were preferred mostly as commercial textiles in order to benefit from the advantages they provide in terms of both their performance against chemical conditions especially organic solvents and their inherent properties such as durability, strength, color retention, absorbency, machinewashability, drape-ability and resistance to pilling. In addition, textile products made of cotton can reply to many specified conditions under strong chemicals and high temperature during laundering processes. White hand towels were utilized instead of polyester ballast fabric. Furthermore, one kind of a shirt with black color and two different kinds of t-shirts with variety of colors such as black and red were selected to evaluate their color changes. These colors were selected since they are the most preferred colors by the customers, and changes in color can be easily observed with these colors, namely black and red. Trousers with dark blue color dyed with dark indigo dyestuff were utilized to examine deformation on their structure. A pair of socks having a very similar structure and quality as Falke socks were produced with 98% cotton and 2% elastane. Swissatest 106 Mineral Oil / Carbon Black Soil fabric was utilized to observe color changes, since this type of fabric is really sensitive to the amount of detergent and the level of agitation. Moreover, evaluation of pilling during laundering and drying processes was performed by utilizing Swissatest 252 Pilling fabric. The measurement of mechanical action was conducted with the Swissatest 304 Fraying Fabric. Commercial home laundering machine that is a front-loaded type with a loading capacity of 11 kg, maximum speed of 1400 rpm and multi-sensors for loading weight, water amount, rinsing and rotational speed etc. was used in this study in order to benefit from its variety of programmable properties for different types of textiles and washing durations. The spectrophotometer Datacolor 650® was utilized to detect rate of the color change for each fabric with its quantitative assessment standard.

2.2. Methods and Processes For each of the profiles, commercial home laundering machine was utilized in order to investigate the effects of the parameters i.e. load quantity and temperature on textiles, which were chosen for each of the four profiles with different values (see Table 1). Each profile always consisting of men’s shirt, trousers, men’s and women’s T-shirts, a pair of socks, Swissatest 304 Fraying fabric, Swissatest 252 Pilling fabric and Swissatest 106 Mineral oil/Carbon Black Soil fabric were washed for 20 cycles. For washing process, a modified version of ‘‘IEC 60456 Test Method - Clothes Washing Machines for Household Use – Methods for Measuring the Performance’’ was used. Full factorial experimental set-up was utilized while designing the experimental procedure. The amount of detergent was changed as 0.5 % gram per liter depending on varying load quantity levels. Mechanical action was taken as constant with a value of 45%. Table 1: Parameters chosen for testing Parameters

Levels

Load Quantity

2 kg

5 kg

Temperature

20°C

40 °C

2.3. Test For revealing the relationship between the commercial textiles and the test textiles, the effects of variations of load quantity and temperature during laundering were analyzed by subjective and objective assessment

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criteria, which would enable better understanding of the behavior similarities and differences of the textiles included in these two groups by leading to a relation between the customer perception of commercial textiles and standard test results of standard test textiles. After 20 washing cycles, four different profiles that were created for the appraisement of color changes, pilling, shrinkage, collar abrasion, sewing defects, other defects other than sewing, whitening and overall properties of textiles were evaluated by using both visual point scoring assessment system as a qualitative method for color changes, pilling, shrinkage, collar abrasion, sewing defects, other defects other than sewing and whitening and overall properties of textiles, and spectrophotometer Datacolor 650® as quantitative method for color changes. “The other defects other than sewing” as an assessment parameter was defined as the defects such as holes, tears, worn and torn areas on textiles, loss of buttons and accessories and problems with zippers. “Whitening and overall properties of textiles” as an assessment parameter was defined as the preference of the customers whether they wear the textiles or not, and evaluated according to the whitening and color loss of textiles caused by surface abrasion and fiber loss due to wear during mechanical action in laundering process. Spectrophotometer Datacolor 650® was used to explore almost all differentiation in color of textiles. Degree of pilling was determined by the EMPA Photographic Standards for Pilling Test (3 x 4 knitted) and EMPA Photographic Standards for Pilling Test (3 x 4 woven) with 1 to 5 point system according to the existence of more or less pilling. Shrinkage, collar abrasion, sewing defects, whitening and overall properties, and other defects other than sewing were evaluated visually according to the standards customized specifically for this study. According to the visual assessments, four different profiles were evaluated by six qualified evaluators that gave points from 1 to 5, after these profiles being performed under both mechanical and chemical action during laundering process were completed.

3. Results & Discussion In this study, it was aimed to investigate the behavior of commercial and standard test textiles against laundering parameters such as load quantity and temperature. Therefore, mainly the correlation between these two groups of textiles were analyzed by benefitting from the MINITAB® statistical analysis package program in order to show the relationship between commercial textiles and test textiles in terms of their behaviour against laundering parameters. Table 2 shows the correlation found between Swissatest test textiles and commercial textiles according to the statistical analysis. According to the findings, temperature was found as the main effect for commercial textiles, while load quantity was found as the main effect for Swissatest standard test textiles. Table 2: Correlation Swissatest Test Textiles & Commercial Textiles Red Tshirt Durability Pearson Swissatest304 correlation factor P value Pearson Swissatest252 correlation factor P value Pearson Carbon Black correlation factor P value

Black Tshirt Durability

Shirt Durability

Jeans Durability

Socks Durability

-0,011

-0,180

-0,398

-0,565

0,523

0,984

0,733

0,435

0,243

0,287

-0,234

-0,019

0,182

0,376

-0,713

0,655

0,971

0,730

0,463

0,112

-0,165

0.003

0,266

0,450

-0,614

0,754

0,995

0,611

0,371

0,195

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4. Conclusion The laundering process with its unique parameters builds a medium with heavy physical and chemical effects on textiles. Different textiles have variety of properties related with their inherent structures, and due to their structures they show different behaviors towards many parameters of laundering. In this study, by revealing the relationship between the commercial textiles and the test textiles, behavior similarities and differences of the textiles included in these two groups towards parameters of the laundering process were better understood.

5. Further Work This study can become more apparent with the results of many different laundering parameters such as mechanical action, level of water amount etc. and many different types of standard test textiles which are not yet considered in the context of this study, since this is a kind of ongoing project. Therefore, different and interesting results are going to be obtained by considering these parameters.

6. Acknowledgement This work was supported by the ARCELIK Incorporation Washing Machine Plant, TURKEY. The authors would like to sincerely express their highest appreciations and gratitudes to the members of the system improvement team of ARCELIK Washing Machine Plant, ARCELIK Washing Efficiency Laboratory and ARCELIK Textile Technologies Laboratory.

7. References [1] Was-Gubala, J. Textile and Fiber Damage, Encyclopedia of Forensic Sciences, 2013, pp. 138â&#x20AC;&#x201C;142. [2] Laurent, St. B. J. Laundry Cleaning of Textiles. Handbook for Cleaning/Decontamination of Surfaces, 2007, Vol.1, pp. 57-102. [3] Sawhney P., Reynolds M., Allen C., Effect of Laundering Hydroentangled Cotton Nonwoven Fabrics, Journal of Engineered Fibers and Fabrics, Vol.7 No. 3, (2012), pp. 103- 110. [4] Quaynor L., Takahash M., Nakajima M., Effects of Laundering on the Surface Properties and Dimensional Stability of Plain Knitted Fabrics, Textile Research Journal, (2000, January), pp. 28- 35.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Performance of UV Protection Finish with HTUV100 on Knitted Cotton Fabric for Summer Clothing Gehui Wang1, Jing Dai1, Jiajing Cai1, Ron Postle2 1 Fashion and Art Design Institute, Donghua University, Shanghai, China 2 School of Chemistry, The University of New South Wales, Sydney, Australia Abstract: The effect of UV protection finish with HTUV100 on cotton single jersey knitted fabric was studied. Based on single factor and orthogonal experiments, a bleached cotton single jersey fabric for summer clothing was treated with anti-UV finishing agent HTUV100. The UV protection property of the fabric was tested by using the UV–visible spectrometer Lambda 35 before and after the application of UV protection finish. The optimum technological conditions for anti-UV finish were established as follows: the concentration of HTUV100 50g/l，the solution temperature 70℃ and baking temperature 110℃. It was found that UV protection finish with HTUV100 under the optimized technological conditions could significantly improve the UV protection properties of the fabric. The UPF value of the finished fabric reached a value of 30 while the ultraviolet transmittance was always lower than 6.7% after the finish. Accordingly, the application of HTUV100 finish had reached the level of good protection as defined by the UV protection standard of Australia/New Zealand. This contrasts with the UPF value of the fabric which was as low as 2 before the finish. The comfort properties of the cotton knitted fabric, such as air permeability, the moisture permeability, wicking effect and softness, were also tested before and after the UV protection finish under standard atmospheric conditions. The results showed that the moisture permeability, wicking effect and softness of the fabric were improved to some extent after the finish, while the air permeability of the fabric was reduced slightly. Keywords: UV protection, knitted cotton fabric, anti-UV agent HTUV100, comfort properties

1. Introduction The increased incidence of skin cancer in recent years has resulted in more and more attention on the research of UV-protective clothing fabrics.[1-10] In recent year, the influence of fabric construction on the fabric UV-protection has been studied by several research groups. [2,8,10] Both the influence of fabric colour on the fabric UV-protection[1-2] and the effect of some new UV-protective finish have also been studied. [4,5,7,9] In actual use, the UV-protection is more important for summer clothing fabrics because of the stronger UVR in the summer sunlight. In addition, because the ambient temperature is high in summer, thin and light colour fabrics are usually used for summer clothing. From the point of view of clothing comfort, a light colour and thin knitted cotton fabric is very suitable

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for summer clothing. However, it may only provide inadequate UV-protection. The aim of this paper is to find a kind of finish processing technology, which can provide good UV-protection to thin knitted cotton fabric and won’t reduce the fabric comfort at the same time.

2. Experimental details Materials In this study, a desized, scoured and bleached thin single jersey knitted fabric was chosen as the base fabric. The specifications of the fabric were listed in Table 1. Table 1 The specifications of the fabric. Fabric weight （g/m2）

Fabric thickness （mm）

Vertical density （loop/5cm）

170

0.58

120

Horizontal density （loop/5cm） 82

UV protective finish Based on the comparative experimental work, HTUV100 was chosen as the UV protective agent. The finish process is as following: dipping (liquor ratio: 1:50)→padding→drying. The optimal finishing conditions were obtained by using orthogonal experiments as shown in Table 2. Table 2 The optimal conditions of the UV protective finish HTUV100 dosage （g/l） 50

Finishing bath temperature （℃） 70

Baking temperature （℃） 110

Baking time (min) 8

3. Test methods Assessment of ultraviolet protection factor UPF (Ultraviolet Protection Factor) is commonly used to express the UV protective ability of fabrics. The UPF of fabric specimens was measured by using a Lambda 35 (UV-Vis) spectrophotometer equipped with an integrating sphere. UPF measurement was conducted corresponding to the Australian/New Zealand Standard AS/NZS4399:1996. Fabric specimens were tested in a flat and tensionless state. All fabric specimens were conditioned under standard atmospheric conditions for 24 hours prior to assessment. The transmittance over a wavelength range of 290 ～ 400nm with 5nm intervals was measured using the spectrophotometer for calculating the UPF of fabric specimens using Equation (1):

∑ UPF = λ λ ∑λ

λ = 400

= 290 = 400

Eλ × Sλ × ∆λ

E × Tλ × Sλ × ∆λ = 290 λ

(1)

Where Eλ is the relative erythemal spectral effectiveness, S λ is solar spectral irradiance in Wm-2nm-1, Tλ is the spectral transmittance of the fabric, λ is the wavelength in nm

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and â&#x2C6;&#x2020;Îť is the bandwidth in nm. Scanning electron microscope The scanning electron microscope (SEM) images of the original fabric and the fabric finished using HTUV100 were obtained by using a FESEM(S-4800) microscope. Fabric specimens were mounted onto an aluminum stub and coated with gold by means of thermal evaporation in a vacuum-coating unit and then examined in the SEM at an accelerating voltage of 5 kv. The SEM photographs were obtained with a magnification 2000.

Assessment of fabric comfort properties The air permeability of fabrics was tested by YG461E air permeability tester according to China standard GB/T 5453-1997. The average of the ten measurements for each fabric was used as the air permeability for that fabric. The fabric water vapor permeability was determined using the cup method (the water method) according to China standard GB/T 12704.2-2009. The average of the three specimens for each fabric was used as the water vapor permeability for that fabric. The wicking effect of fabrics was evaluated by measuring the height of liquid wicking into vertically hanging strips of fabric after fixed time periods according to China standard FZ/T 01071-2008. Three vertical specimens and three horizontal specimens were tested for each fabric. The average of them was used as the wicking effect of that fabric. The fabric stiffness was measured using YG(B)022D automatic fabric stiffness tester.

4. Results and discussion The effect of HTUV100 finish on fabric UV protection property Figure 1 shows the effects of HTUV100 finish on fabric UV transmittance. It can be seen that all the UVA, UVB and UVC transmittance of the bleached cotton single jersey fabric decreased greatly after the HTUV100 finish at optimal conditions. The values of UVA, UVB and UVC transmittance were 4.87, 3.45 and 4.5 respectively after the UV protection finish. 80

69.54

Transmittance (%)

70 60 46.41

50 40

28.31

30 20 10

4.87

3.45

4.50

0 UVA

UVB

UVC

UV ranges Original fabric

HTUV100 finished fabric

Fig.1 The effect of HTUV100 finish on UVA, UVB and UVC transmittance The UPF values of the original fabric and the UV protection finished fabric were calculated according to equation 1 and shown in Figure 2. It indicates that the UPF value of the original fabric is as low as 1.95 and has almost no UV protection at all. While after the

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UV protection finish with HTUV100 at optimal conditions, the fabric obtained a high UPF value 28.96 and this means that the finished fabric has good UV protection property. 35 28.96

UPF

25 20 15 10 5

1.95

0 Original fabric

HTUV100 finished fabric

Fabric type

Fig.2 The effect of HTUV100 finsh on fabric UPF Scanning electron microscopy Scanning electron microscopy was used to observe surface morphology of the fabrics (Figure 3). The SEM images of the original fabric (Figure 3(a)) showed its smooth longitudinal ďŹ bril structure. However, after coating the fabric with HTUV100, the surface morphology changed, as shown in Figure 3(b). It is suggested that the UV protection agent has been combined to the fabric and provides the good UV protection of the finished fabric.

(a) Original fabric

(b) UV protection finished fabric

Fig. 3 SEM images of the original fabric and the finished fabric The effect of HTUV100 finish on fabric comfort properties The test results of the fabric comfort properties are listed in Table 3. It can be seen from Table 3 that the fabric water vapor permeability improved and the fabric wicking effect improved greatly after the UV protection finish, and these will increase the thermal-wet comfort of the fabric. From Table 3, it can also be seen that the bending length of the fabric decreased after the UV protection finish, and this means that the fabric became softer (or more flexible) after the UV protection finish and thus will improve the touch comfort of summer clothing. Table 3 shows that the permeability of the fabric was decreased to some extent after the UV protection finish. Table 3 The test results of the fabric comfort properties

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Performance indicator

Permeability (cm2·s)

Water vapor permeability (g·m-2·d-1)

Wicking effect （cm/30min）

Bending length （mm）

Original fabric

453.12

5353

2.5

18.98

HTUV100 finished

429.01

5713

8.3

15.54

Conclusions

The UV protection finish with HTUV100 under the optimized technological conditions provided good UV protection property (according to Australian/New Zealand Standard AS/NZS4399:1996 ) to a thin and bleached cotton single jersey fabric. In addition, the comfort properties of the finished fabric improved to some extent.

6. References 1.

Wilson, C.A., Gies, P.H., Niven, B.E., McLennan, A. and Bevin, N.K., The Relationship Between UV Transmittance and Color –Visual Description and Instrumental Measurement. Textile Research Journal. 78(2), 128–137(2008).

Dubrovski, P. D. and Golob, D., Effects of Woven Fabric Construction and Color on Ultraviolet Protection. Textile Research Journal. 79(4), 351–359(2009).

Stankovic, S. B., Popovic, D., Poparic, G. B. and Bizjak, M., Ultraviolet Protection Factor of Gray-state Plain Cotton Knitted Fabrics. Textile Research Journal. 79(11), 1034–1042(2009).

Paul, R., Bautista, L., Varga, M. D., Botet, J. M., Casals, E., Puntes, V. and Marsal, F., Nano-cotton Fabrics with High Ultraviolet Protection. Textile Research Journal. 80(5), 454–462(2010).

Kursun1, S. and Ozcan, G., An Investigation of UV Protection of Swimwear Fabrics. Textile Research Journal. 80(17), 1811–1818(2010).

Kan, H., Zhang, L., Xu, H. Mao, Z. and Cao, H., Optimization of Conditions for Nanocrystal ZnO in-situ Growing on SiO 2 -Coated Cotton Fabric. Textile Research Journal. 80(7), 660–670(2010).

Mahmoudifard M. and Safi, M., Novel study of carbon nanotubes as UV absorbers for the modification of cotton fabric. The Journal of The Textile Institute. 103(8), 893–899 (2012).

Wong, W., Lam,J. K., Kan, C. and Postle, R., Influence of knitted fabric construction on the ultraviolet protection factor of greige and bleached cotton fabrics. Textile Research Journal. 83(7), 683–699(2013).

Yasukawa, A., Ruike,S., Gotoh, K. and Kandori, K., Ultraviolet shielding properties of cotton fabric supported by cerium-calcium hydroxyapatite solid solution particles. Textile Research Journal. 84(15), 1578–1585(2014).

10. Zhang, Y., Kan, C. and Lam., J., A study on ultraviolet protection properties of 100% cotton knit fabric: effect of fabric structure. The Journal of The Textile Institute.

106(6), 648–654(2015).

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Physical Properties and Manufacturing Process Evaluation of Complex Stainless Steel Wire/Bamboo Charcoal Nylon/Spandex Piled Yarn and Knitted Fabric Chin-Mei Lin1, Pei-Chen Hsiao2 1

Department of Fashion Design, Asia University, Taichung 41354, Taiwan. PhD student, College of Creative Design, Asian University, Taichung 41354, Taiwan.

Abstract. Under the quick development of modern technology, electronic machine, precision machine and petrochemical industry, the quality of people’s lives is much better than before. With the convenience brought by the development come the issues regarding static electricity and electromagnetic wave. In order to reduce the harm of electromagnetic wave on the human body, the 50μm stainless steel wire (core yarn) and the 70D bamboo charcoal nylon yarn (wrapped yarn) were processed (11~15 turns/cm) to make the complex stainless steel wire/bamboo charcoal nylon yarn by Electrical Covering Machine in this research. The 70D elastic yarn (Spandex) (core yarn) was then added to the complex stainless steel wire/bamboo charcoal nylon yarn (wrapped yarn). Together the two underwent the wrapping process twice (wrapped yarn with variable number of turns from 1~3 turns/cm) using the rotor twister machine to make the bi-layer-structure complex flexible wrapped yarn. During the research, the twisting speeds of the rotor twister were altered to control the number of twists to discuss the the effects of changing the number of twists of the complex yarn on the tensile strength. Based on the tensile strength, the complex stainless steel wire/bamboo charcoal nylon/Spandex wrapped yarn with the optimum experimental parameters was obtained. The Computer Jacquard Hose Machine was applied to circular knit the complex wrapped yarn to gain the complex electromagnetic shielding/heat preservative/Spandex knitted fabric. The knitted fabric was tested and evaluated regarding its physical properties and anti-static properties. From the result of the yarn elongation and tensile strength tests, it is known that the optimum elongation and tensile strength for the bi-layer-structure complex flexible wrapped yarn of 11 turns/cm (NB/SS) (wrapped yarn) and 1 turns/cm (SP)(core yarn) are 31.58% and 748.84N, respectively. In terms of the electromagnetic shielding effectiveness test, the EMSE is the best (36.71 dB) for NB/SS yarns (wrapped yarn) (12 turns/cm)/ 2 turns/cm /SP (core yarn) when the incident frequency is low (203MHz). Under the laminated angles 0°/90°, the electromagnetic shielding effectiveness of the 2-layer yarns in average was better than the effectiveness when laminated angles are 0°/0°. The EMSE for the 2-layer NB/SS yarn (wrapped yarn) (12 turns/cm)/ 1 turns/cm /SP (core yarn) was 23.44 dB when the incident frequency was medium (1290MHz), which means the shielding rate was as high as 99.49%.

Keywords: Stainless Steel Wire, Bamboo Charcoal Nylon Yarn, Spandex, Complex Wrapped Yarn, Knitted Fabric

1. Introduction Under the quick developments of modern technology, electronic machine, precision machine, and petrochemical industry, the quality of people’s lives is much better than the past. With the convenience brought by the development come the issues regarding static electricity. Electronic and communication devices emit high electromagnetic waves. For instance, electrical cables emit electromagnetic radiation while receiving electromagnetic radiation from other devices. Therefore, if electromagnetic waves cannot be isolated effectively, the devices may interact one another and be malfunctioned. Moreover, exposing under electromagnetic radiation for long periods of time may harm the human body Electromagnetic waves damage the nervous system, cardiovascular system, and temperature physiologically [1,2]. control system of the human body and inhibit many functions of other systems as well as reducing the number of platelets and white blood cells in the blood [3,4]. In order to slow down or reduce the damages, functional yarns and knitted fabrics that shield electromagnetic waves have been produced and introduced to minimize the negative effects.

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2. Experiment 2.1. 1. 2. 3.

2.2.

Materials The diameter of stainless steel filament (304 types) was 50Îźm, supplied by Yuan Company Limited. The bamboo charcoal nylon yarn was 70D, supplied by Hua Mao Nano-Tech Co., Ltd The Spandex filament was 70D, supplied by DuPont.

Method

The manufacturing process for the complex yarn was divided into two stages in this experiment. In the first stage, 0.05mm stainless steel filament (SS) (core yarn) and 70D bamboo charcoal nylon yarn (NB) (wrapped yarn) underwent wrapping processing in the electronic control wrapping machine. The wrap numbers were changed to produce 5 sets of NB/SS complex wrapped yarns with the wrap number 11, 12, 13, 14 and 15 turns/cm, respectively. The tests and evaluations regarding the elongation and tensile strength of these 5 sets of wrapped yarns were conducted then. In the second stage, spandex (SP) was added to the optimum NB/SS complex yarn (wrapped yarn) before undergoing the second wrapping processing in the rotor twister. The twist number of the rotor twister was changed to reform the complex flexible NB/SS wrapped yarns with the wrap numbers from 1 to 3 turns/cm. Then, the first 9 sets of the complex flexible yarns with the best performance were obtained to undergo tests and evaluations regarding elongation and tensile strength. Later, weft-knitted fabrics were produced and the electromagnetic shielding effectiveness was tested and evaluated.

2.3. 1. 2. 3. 4. 5.

Apparatus Electronic Control Yarn Wrapping Machine: DH-CR20, Dah Heer Industrial Co., Ltd. Rotor Twister, Self-assembly. Automatic tensile tester for yarns, STATIMAT ME, Automatic, TEXTECHNO Herbert Stein GmbH. Fully Computerized Hosiery Machine, DK-B318-8ďź&#x152;Da Kong Enterprise Co. Ltd. Electromagnetic Shielding Effectiveness Testing Equipment, E-INSTRUMENT TECH LTD.

3. Test Method

Elongation(% )

Elongation and Tensile Strength Test for Yarns: The tensile strength and elongation were measured by Instron 5566 at the rate of 300 mm/min. The yarn was clamped with a distance of 25 cm in between. Electromagnetic Shielding Effectiveness Test: Electromagnetic Shielding Effectiveness (Shielding Effectiveness Test Sample Holder, EM-2107A), the testing system of electromagnetic shielding effectiveness adopts the electromagnetic shielding effectiveness test sample holder (EM-2107A), with the incident frequencies from 300k to 3G Hz. The electromagnetic filed of this testing method is a far-field plane wave. The standard of test sample is as shown in Figure 1. In addition, a hollow test lamination (Washer Type) with the same thickness is needed as the referential test lamination, and the electromagnetic shielding effectiveness value (SERef) was measured to calibrate this measuring device. 40

Fig.1: Test Sample of Electromagnetic Shielding Effectiveness

35 30 25 20 15 10 5 0

Fig.2: Effect of changing the wrap numbers of the wrapped yarn on the elongation

4. Results and Discussion Effect of changing the wrap numbers of NB/SS complex yarn on the elongation and tensile strength of the wrapped yarn Fig. 2 shows the elongation test results of the wrapped yarn as the wrap number was changed from 11 to 15 turns/cm. As the wrap number increased, the overall differences were not significant. However, when the wrap number was 12 turns/cm, the elongation was the greatest. After that, the elongation declined. Moreover, the elongation decreased only when the tensile strength was at the largest and during the manufacturing process, the elongation was only affected when the yarn collecting speed was low. The largest elongation (32.04%) was gained when the wrap number was 12 turns/cm. Fig. 3 shows the tensile strength test results of the wrapped yarn as the wrap number was change from 11 to 15 turns/cm. As the wrap number increased, the tensile strength was the largest when the wrap number was 12 turns/cm. After that,

Page 879 of 1108

the tensile strength declined as the yarn was over-twisted. The cohesion between the fibers began to lower which caused the decline in the tensile strength. From the figure, it is known that when the wrap number was 12 turns/cm, the tensile strength was the largest (699.60N).

Effect of changing the wrap numbers of NB/SS complex yarn on the tensile strength of the wrapped yarn

800 700 600 500 400 300 200 100 0

11-13(NB/SS)/1/(SP) 11-13(NB/SS)/3/(SP)

11-13(NB/SS)/2/(SP)

30 Elongation(% )

Tensile strength(N)

Fig. 2 and Fig.3 show the elongation and tensile strength tests results of NB/SS complex wrapped yarns with the wrap numbers from 11 to 15 turns/cm. The results were not significantly different. At the wrap number 12 turns/cm, both the elongation and the tensile strength were the greatest. From the test results, it is known that the NB/SS complex wrapped yarns with the wrap numbers from 11 to 13 turns/cm have the best elongation and tensile strength. Next, the second stage where SP with the wrap numbers from 1 to 3 turns/cm were added to the NB/SS complex wrapped yarns with the wrap numbers from 11 to 13 turns/cm, respectively. In total, 9 sets of parameters were used to undergo the elongation and tensile strength tests.

25 20 15 10 5 0

Fig.3: Effect of changing the wrap number of the wrapped yarn on the tensile strength

11(NB/SS)/1-3/(SP)

12(NB/SS)/1-3/(SP)

turns cm

13(NB/SS)/1-3/(SP)

Fig.4: Effect of changing the wrap number of the complex flexible wrapped yarn on the elongation

Effect of changing the wrap numbers of NB/SS yarns (11-13 turns/cm) (wrapped yarn)/spandex (1-3 turns/cm) (core yarn) on the elongation and tensile strength of the complex flexible wrapped yarn Fig. 4 shows the test results. As the wrap number increased, the largest elongation (31.58%) was gained when the wrap number for the complex wrapped yarn [NB/SS yarn (wrapped yarn) (11 turns/cm)/SP (core yarn)] was 2 turns/cm. However, the elongation was the lowest (24.66%) after adding SP to change the wrap number of the wrapped yarn. Moreover, when the wrap number for the complex wrapped yarn [NB/SS yarn (wrapped yarn) (12 turns/cm)/SP (core yarn)] was 2 turns/cm, the elongation was 31.51%. The results from the set [NB/SS yarn (wrapped yarn) (12 turns/cm)/SP (core yarn)] were also significant. However, when the wrap number for the complex wrapped yarns [NB/SS yarn (wrapped yarn) (11-13 turns/cm)/SP (core yarn)] was 3 turns/cm, the elongations were poor in average. Fig. 5 shows the test results. As the wrap number increased, the largest tensile strength (748.84N) was gained when the wrap number for the complex wrapped yarn [NB/SS yarn (wrapped yarn) (11 turns/cm)/SP (core yarn)] was 1 turns/cm. The second largest tensile strength (741.19N) was gained when the wrap number for the complex wrapped yarn [NB/SS yarn (wrapped yarn) (12 turns/cm)/SP (core yarn)] was 1 turns/cm. The results from the set [NB/SS yarn (wrapped yarn) (12 turns/cm)/SP (core yarn)] were also significant. However, when the wrap number for the complex wrapped yarns [NB/SS yarn (wrapped yarn) (11-13 turns/cm)/SP (core yarn)] was 3 turns/cm, the tensile strengths were poor in average. The follow-up test applied the above-mentioned 9 parameters to manufacture the weft-knitted fabrics and conduct electromagnetic shielding effectiveness test and evaluation. 11-13(NB/SS)/1/(SP) 11-13(NB/SS)/3/(SP)

11-13(NB/SS)/2/(SP)

750 700 650

EMSE (dB)

Tensile strength(N)

800

600 550 500 450

11(NB/SS)/1-3/(SP)

12(NB/SS)/1-3/(SP)

turns cm

13(NB/SS)/1-3/(SP)

Fig.5: Effect of changing the wrap number of the complex flexible wrapped yarn on the tensile strength

11(B/SS)/1(SP)

11(B/SS)/2(SP)

11(B/SS)/3(SP)

12(B/SS)/1(SP)

12(B/SS)/2(SP)

12(B/SS)/3(SP)

0 -5 -10 -15 -20 -25 -30 -35 -40 3.00E+05

7.50E+08 Frequency 1.50E+09 (MHz) 2.25E+09

3.00E+09

Fig.6: Effect of changing the wrap number of the complex flexible wrapped yarn on the electromagnetic shielding effectiveness

Effect of changing the wrap numbers of NB/SS yarns (11-13 turns/cm) (wrapped yarn)/spandex (1-3 turns/cm) (core yarn) on the electromagnetic shielding effectiveness

Page 880 of 1108

Fig. 6 shows the test results. Even as the wrap number increased, the electromagnetic shielding effectiveness was not significantly affected. However, when the wrap number for the complex wrapped yarn [NB/SS yarn (wrapped yarn) (12 turns/cm)/SP (core yarn)] was 2 turns/cm, the optimum EMSE (36.71 dB) was gained when the incident frequency was low (210 MHz). In the follow-up test, the appearances of the knitted fabrics were observed by eyes and the optimum NB/SS yarns (wrapped yarn) (11-13 turns/cm)/spandex (core yarn) (1-2 turns/cm) sets were evaluated. Six sets of parameters underwent the lamination changes for the electromagnetic shielding effectiveness test.

Effect of changing the laminated angles (0°/0°) and laminated angles (0°/90°) of the 2-layer NB/SS yarns (wrapped yarn) (11-13 turns/cm)/spandex (core yarn) (1-2 turns/cm) on the electromagnetic shielding effectiveness Fig. 7 shows the test results. Under the laminated angles 0°/0°, the electromagnetic shielding effectiveness of the 2-layer yarns in average was better than the 1-layer yarns. The EMSE for the 2-layer NB/SS yarn (wrapped yarn) (12 turns/cm)/ spandex (core yarn) (1 turns/cm) was 41.06 dB when the incident frequency was low (135MHz). Fig. 8 shows the test results. Under the laminated angles 0°/90°, the electromagnetic shielding effectiveness of the 2layer yarns in average was better than the effectiveness when laminated angles are 0°/0°. The EMSE for the 2-layer NB/SS yarn (wrapped yarn) (12 turns/cm)/ spandex (core yarn) (1 turns/cm) was 23.44 dB when the incident frequency was medium (1290MHz), which means the shielding rate was as high as 99.49%.

0 -5 -10 -15 -20 -25 -30 -35 -40 -45 3.00E+05

11(B/SS)/1/(SP)*2 layer 0°/90° 12(B/SS)/1/(SP)*2 layer 0°/90° 13(B/SS)/1/(SP)*2 layer 0°/90° 0

11(B/SS)/2/(SP)*2 layer 0°/0° 12(B/SS)/2/(SP)*2 layer 0°/0° 13(B/SS)/2/(SP)*2 layer 0°/0°

11(B/SS)/2/(SP)*2 layer 0°/90° 12(B/SS)/2/(SP)*2 layer 0°/90° 13(B/SS)/2/(SP)*2 layer 0°/90°

-5 -10 EMSE (dB)

EMSE (dB)

11(B/SS)/1/(SP)*2 layer 0°/0° 12(B/SS)/1/(SP)*2 layer 0°/0° 13(B/SS)/1/(SP)*2 layer 0°/0°

-15 -20 -25 -30 -35

7.50E+08

1.50E+09

2.25E+09

3.00E+09

Frequency (Hz)

Fig.7: Effect of changing the wrap number of the wrapped yarn of the 2-layer complex flexible knitted fabric for the laminated angles (0°/0°)

5. Conclusions

-40 3.00E+05

7.50E+08

1.50E+09 Frequency (Hz)

2.25E+09

3.00E+09

Fig.8: Effect of changing the wrap number of the wrapped yarn of the 2-layer complex flexible knitted fabric for the laminated angles (0°/90°) on the electromagnetic shielding effectiveness laminated angles (0°/0°)

In terms of the elongation and tensile strength tests, the double layered complex flexible wrapped yarn of NB/SS yarns (wrapped yarn) (11 turns/cm)/1 turns/cm/SP (core yarn) are the best, which are 31.58% and 748.84N, respectively. Also, the elongation for NB/SS yarns (wrapped yarn) (12 turns/cm)/ 1 turns/cm /SP (core yarn) is 31.51%. The tensile strength for NB/SS yarns (wrapped yarn) (12 turns/cm)/ 1 turns/cm /SP (core yarn) is 741.19N. In terms of the electromagnetic shielding effectiveness test, the EMSE is the best (36.71 dB) for NB/SS yarns (wrapped yarn) (12 turns/cm)/ 2 turns/cm /SP (core yarn) when the incident frequency is low (203MHz). The test results for 2-layer knitted fabric with laminated angles 0°/0° shows the EMSEs are better than those of the 1-layer knitted fabric. The EMSE for the 2-layer NB/SS yarn (wrapped yarn) (12 turns/cm)/ 1 turns/cm /SP (core yarn) was 41.06 dB when the incident frequency was low (135MHz). Under the laminated angles 0°/90°, the electromagnetic shielding effectiveness of the 2-layer yarns in average was better than the effectiveness when laminated angles are 0°/0°. The EMSE for the 2-layer NB/SS yarn (wrapped yarn) (12 turns/cm)/ 1 turns/cm /SP (core yarn) was 23.44 dB when the incident frequency was medium (1290MHz), which means the shielding rate was as high as 99.49%.

Acknowledgements The authors would especially like to thank Ministry of Science and Technology of the Taiwan, for financially supporting this research under Contract MOST 104-2221-E-468-019 -

References [1] [2] [3]

[4]

Goldsmith JR: Epidemiologic evidence relevant to radar (microwave) effects. Environ Health Perspect;105 Suppl 6:1579-87 (1997) Hyland GJ: Physics and biology of mobile telephony. Lancet;356:1 833-6 (2000) L. M. Green. A. B. Miller, P. J. Villeneuve, D. A. Agnew, M. L. Greenberg, J. H. Li, and K. E. Don – nelly, A case-control st Udy of childhood leukemia in Southem Ontario , Canada , and exposure to magnetic fields in residences , International Journal of Cancer，82, 161-170 ( 1999 ). R. W. Habash, Electromagnetic the uncertain health risks, IEEE, 22, 23 - 26 ( 2003 ).

Page 881 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Preparation and Characterization of wet-laid nonwoven for secondary battery separator Seung woo Han 1, Sung won Byun1*, Chang Whan Joo 2 1

Research Institute of Industrial Technology Convergence Technical Textile & Materials R&D Group, Korea Institute of Industrial Technology, Korea 2

Organic material & textile system, Chungnam National University, Korea *byunsw@kitech.re.kr

Abstract. Secondary batteries application is expanded such as smart mobile devices, electric vehicles, and energy storage systems which were demanded high energy density, high power density and good safety. Wet-laid nonwoven has an excellent homogeneity and easily handles thin fibers. The secondary battery separator was manufactured by wet-laid nonwoven with meta-aramid fibril, m-aramid floc and RM PET short-cut fiber because aramid and RM PET have good electrolyte wettability, ionic conductivity and thermal resistance. Properties of wet-laid nonwoven were enhanced as RM PET melted by calendaring process. Also, PVDF (polyvinylidene fluoride) was coated in the wet-laid nonwoven for controlling the pore size, porosity, thickness and tensile strength. The manufactured nonwovens were evaluated in terms of various physical and electrochemical properties including tensile properties, pore diameter, air permeability, thickness, electrolyte absorption and electrolyte stability. Keywords: wet-laid, m-aramid, secondary battery, separator

1. Introduction The characteristics of wet-laid nonwoven are easy to fabrication of thin films, and flexible in choosing raw materials and excellent uniformity. Due to the high energy and power characteristics, Lithium-ion batteries are widely used in smart mobile devices, electric vehicles and high-power tools applications [1-3]. Separators are a valuable part of all batteries. Their main function is to keep the electrodes apart to prevent electrical short circuits and at the time allow rapid transport of ion. Recently, polyolefins such as PP and PE are widely used separators in lithium-ion battery because of thin thickness, small pore size, long cycle life, high voltage and good electrochemical stability [4-5]. But polyolefin separators are difficult to fully ensure electrical isolation between electrodes for reason of poor thermal shrinkage and weak mechanical strength. Non-woven materials have been developed for lithium-ion batteries because non-woven materials have more choices in the compositions and structure. Also, they show uniform basis weight, thickness, porosity and resistance to degradation by electrolytes.

2. Experimental Experimental materials Meta-aramid fibril, meta-aramid floc(diameter 2 ă&#x17D;&#x203A; and length 6mm) and RM PET (0.5de and 0.5 mm) short-cut fiber were used as raw materials. Also, PVDF 20 wt% solution was used as wet-laid nonwoven coating materials that enhance the properties. Manufacturing of wet-laid nonwoven

Page 882 of 1108

Meta-aramid fibril and meta-aramid floc and meta-aramid fibril and RM PET were mixed with 3L water (beating) and dispersed with 15L water (suspension) using mechanical stirrer. And then, the wet-laid non-wovens (7g/m2) were manufactured by lab-scale wet-laid hand sheet former (200mm x 200mm). These were dried in hot air drying machine at 80 â&#x201E;&#x192; for 30min. The calendering process with temperature 180â&#x201E;&#x192; and linear pressure 90.48 kg/cm was performed to reinforce strength, decrease thickness and control pore size and gurley number. Table1 shows the production conditions of wet-laid non-wovens using meta-aramid and RM PET. Table 1 Producing conditions of wet-laid non-wovens using meta-aramid and RM PET Content(%)

Content(%)

Sample

Sample Floc

Fibril

Floc

RM PET

Basis Weight(g/m2)

7 g/m2

And then, the prepared samples were coated with PVDF 20wt% solution for the better improvement of wet-laid nonwovens.

3. Results and discussion Pore dimensions The pore size of separators for lithium batteries must be small enough to prevent dendritic lithium infiltration and internal short circuits. Fig. 1 shows the pore size of wet-laid non-woven separators. Mean flow diameter and bubble point diameter became smaller as an increase of the content of fibril. Also, nonwoven separators of floc have a little smaller pore diameter than non-woven separators of RM PET.

Fig. 1 Pore size of separators

Gurley number and Thickness Gurley number (air permeability) is defined as the time necessary for a specific amount of air to pass through as specific area of the separator under a specific pressure. The separator with uniform permeability is essential for the long cycle life of a battery. Gurley number of the eight kinds of separator was summarized in fig. 2. In general, as the contents of fibril increase, so do value of gurley number. Thickness in secondary battery separator is significant factor for high energy and power densities. By contrast, thin thickness of separators causes properties degradation of mechanical strength and safety. Also, Fig. 2 indicated that thickness of all samples is under 25 ă&#x17D;&#x203A;. This means that thickness of samples is standard thickness of rechargeable batteries.

Page 883 of 1108

Fig. 2 Gurley number and thickness of samples

Tensile strength The tensile strength of separators has large influence on solar cell manufacture process such as winding. The samples are damaged with the electrodes under tension. So, high tensile strength is required. Tensile strength at max load of separator samples is shown in Figure 3. It is showed that tensile strength is increased as an increased of the content of fibril. Although thickness of sample is increased after PVDF coating process, tensile strength of samples is increased.

Fig. 3 Tensile strength at max load of samples

Electrolyte absorption of separators Separators are required wet easily in the electrolyte and retain the electrolyte consistently which helps to fill electrolyte in battery assembly and increase cycle life of battery. Electrolyte absorption of wet-laid non-woven separators is shown in Table 2. It is proved that all samples have moderate electrolyte absorption performance. Table 2 Electrolyte absorption of separators Weight (g) Sample

Content(%)

Uptake (wt%)

Sample

Before

After

0.0067

0.0203

302

0.0072

0.0176

0.0044

0.0059

Uptake (wt%)

Before

After

0.0058

0.0207

356

244

0.0096

0.0258

268

0.0184

418

0.0057

0.0199

349

0.0171

289

0.0053

0.0210

396

Page 884 of 1108

Separator is the one of the most important component in battery. Main function of separator is to prevent physical contact between the electrodes and allows the free flow of ions. The separator itself does not participate in any reaction. For high energy and power densities, thin thickness and highly porous of separator are demanded whereas it adversely influences the safety and cycle life of the battery as a result of the reduced mechanical strength. But it in battery has an important function in determining the safety and performance. In this study, separator samples consisted of meta-aramid fibril, meta-aramid floc RM PET was manufactured by wet-laid hand sheet former process. It was proved that wet-laid non-woven separator using meta-aramid and RM PET possessed good properties of gurley number, thickness, electrolyte absorption. On the other hand, tensile strength and mean pore diameter are slightly dropping mechanical properties. If some of the physical properties are improved, wet-laid non-woven separators using meta-aramid and RM PET are expected to growth for the high-energy lithium ion battery.

References [1] H. Li, Z. Wang, L. Chen, X. Huang, Research on advanced materials for Li-ion batteries, Adv. Mater. 21 (2009). [2] J. Hassoun, S. Panero, P. Reale, B. Scrosati, A new, safe, high-rate and high energy polymer lithium-ion battery, Adv. Mater. 21 (2009). [3] C. Liu, F. Li, L.P. Ma, H.M. Cheng, Advanced materials for energy storage, Adv.Mater. 22 (2010). [4] S.S. Zhang, A review on the separators of liquid electrolyte Li-ion batteries, J. Power Sources 164 (2007).

Page 885 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Preparation and Property Evaluations of Conductive Composite Wrapped Yarn Ting An Lin 1, Ching-Wen Lou 2 and Jia-Horng Lin 1

1, 3, 4 ď&#x20AC;Ť

Laboratory of Fiber Application and Manufacturing, Department of Fiber and Composite Materials, Feng Chia University, Taichung City 40724, Taiwan. 2 Institute of Biomedical Engineering and Materials Science, Central Taiwan University of Science and Technology, Taichung City 40601, Taiwan. 3 Department of Fashion Design, Asia University, Taichung City 41354, Taiwan. 4 School of Chinese Medicine, China Medical University, Taichung City 40402, Taiwan.

Abstract. Stainless steel wires and polyester filaments are examined into this study. An electronic wrapping machine is used to fabricate composite wrapped yarns with PET filaments as the core, and stainless steel/PET wrapped yarns as the sheath. The composite wrapped yarns are then tested for their tensile properties and electrical resistance in relation to different wrap counts and number of wrapped layers. The wrapped yarns are then made into composite woven fabrics and knitted fabrics via a weaving/knitting process. The completeness of the fabric structure is then observed by using a stereoscopic microscope. The tensile properties of the composite wrapped yarns with the corresponding combination of wrap counts and number of wrapped layers are an optimal breaking strength of 1493cN (a low wrap count/double wrapped layers), an optimal tenacity of 1.59cN/dtex (a low wrap count/single wrapped layer), and an optimal elongation of 19.5% (a high wrap count/single wrapped layer). According to the electrical resistance results, the resistance is small when the distance between probes is small, which indicates an optimal electrical conductivity. The low resistance is largely due to stainless steel wires. The stereomicroscopic observation indicates that the composite wrapped yarns and woven fabrics have a satisfactory formability.

Keywords: stainless steel wire, wrapped yarn, woven fabric, knitted fabric, conductive.

1. Introduction Since the nineteenth century, technology has been confronting the rapid revolutionary changes, demonstrating a profound influence on human history. It has also brought tremendous advancement in the textile and clothing industries [1]. Specifically, the development of high technology textiles is dependent on the original application of materials and commercialization of smart textiles. Smart textiles integrate the advantages of both the electronic industry and the textile industry in order to develop functional products that meet consumersâ&#x20AC;&#x2122; demands, including the ability to receive body signals, to alert users to environmental changes, and to acquire data. Related literature sources and studies on the development of smart textile have been published by many researchers [2, 3]. Castano and Flatau reviewed literature source, and submitted incorporating basic principles and approaches of electronic textiles with textile substrates in order to develop fabric sensors [4]. Stoppa and Chiolerio proposed wearable electronic textiles with conductive materials as sensors that consisted of conductive fibers and treated conductive fibers, conductive fabrics, conductive inks, and electrically conductive materials for user ends [5]. The wearable electronic textiles can be applied to longterm care, sport management, and telemedicine fields. In this study, electrically conductive stainless steel filaments and PET filaments are combined with a wrapping process in order to form composite wrapped yarns. The influence of wrap count and the number of wrapped layer on the tensile properties and electrical resistance are examined. The wrapped yarns are then made into composite woven and knitted fabrics, which are observed by using a stereomicroscope in order to examine their formability.

ď&#x20AC;Ť

Corresponding author. Tel.: + 886-4-2451-8672. E-mail address: jhlin@fcu.edu.tw

Page 886 of 1108

2. Experimental 2.1. Materials

Polyester (PET) filaments (Yi Jiun Industrial Co., Ltd., Taiwan, R.O.C.) and 316L stainless steel wire (Yuen Neng Co., Ltd., Taiwan, R.O.C.) and other materials are introduced in Table 1. Table 1: Basic properties of materials Materials Polyester Filament Stainless Steel Wire 7-SS/PET wrapped yarn 14-SS/PET wrapped yarn

Diameter(mm) 0.08 -

Fineness(D) 75D/144f 445 D 464 D

Force(cN) 315.55 417.07 587.04 654.34

Elongation (%) 18.39 25.56 11.94 24.46

Tenacity(cN/dtex) 3.79 1.18 1.27

2.2. Manufacturing Process Composite Wrapped Yarn This study administers an electronic wrapping machine and a wrapping process to prepare composite wrapped yarns. The core is the 75D PET filaments and the sheath is the SS/PET wrapped yarns. The wrap count is expressed as twists per centimeter (cm). The wrapped yarns are denoted as 7-S, 7-D, 14-S, and 14-D, where the numbers refer to 7 or 14 twists per centimeter, while S means a single-wrapped layer and D means double-wrapped layers. These composite wrapped yarns are then tested for tensile properties (ASTM D2256) and electrical resistance. In addition, strength efficiency is computed with equation (1). The schematic illustrations are indicated in Figure 1. Strength Efficiency =

breaking strength of the yarns Ă&#x2014; the sum of strength of all constituent yarns

100%

(1.1)

Fig. 1: Schematic illustration of composite wrapped yarns of (a) 7-S and (b) 7-D.

Composite Woven Fabric and Knitted Fabric 7-S, 7-D, 14-S and 14-D composite wrapped yarns are then made into woven and knitted fabrics. The composite woven fabrics are composed of 1000D PET filaments as the warp yarns with composite wrapped yarns as the weft yarns. They are denoted as 7-S-W, 7-D-W, 14-S-W and 14-D-W where W refers to woven fabrics. The composite knitted fabrics that are made of four composite wrapped yarns are denoted as 7-S-K, 7-D-K, 14-S-K and 14-D-K, where K refers to knitted fabrics.

3. Results and Discussion 3.1. Stereomicroscopic Observation of Composite Wrapped Yarns

7-S, 14-S, 7-D and 14-D are the composite wrapped yarns with different wrap count and number of wrapped layers, and are indicated in Figure 2 (a-d), respectively. A high wrap count results in a greater amount of sheath, which causes a larger angle between the sheath and the axial direction. In addition, when the composite wrapped yarns are double-wrapped, stainless steel wires from the sheath (i.e., the SS/PET wrapped yarn) are exposed to the surface of the composite wrapped yarns as a result of the twisting process, as indicated by the red arrows. Moreover, composite wrapped yarns appear to be curly when the wrap count is greater, as indicated in Figure 2 (d), which is disadvantageous for the subsequent manufacturing.

Page 887 of 1108

Fig. 2: Stereomicroscopic images (15Ă&#x2014;) of (a) 7-S, (b) 14-S, (c) 7-D, and (d) 14-D.

3.2. Tensile Properties of Composite Wrapped Yarns

The breaking strength, tenacity, and elongation of composite wrapped yarns are indicated in Figure 3 (ac). Figure 3 (a) shows that 7-D has a breaking strength of 1493cN, which is 1.54 times that of 7-S. 7-D is double-wrapped with two sheaths of SS/PET wrapped yarn. Therefore, the twisting process gives 7-D a higher cohesive force between yarns when compared to 7-S. In addition, the equation (1) is used to compute the strength efficiency of composite wrapped yarns, which the results are shown in Table 2. Strength efficiency of 7-S and 7-D which reach above 100% are both indicating that all materials are fully exploited to their maximum efficiency. In contrast, there are no significant differences in the breaking strengths of 14-S and 14-D. A high wrap count of 14 twists/cm excessively twist the yarns, as indicated in Figure 2 (d), and the composite wrap yarns thus exhibit over-twist. Figure 3 (b) indicates the tenacity, which is a ratio of breaking strength to fineness of yarns (cN/dtex), and it indicates the strength per unit length that the yarns can bear. 7-S has an optimal tenacity of 1.59cN/dtex. When the composite wrapped yarns have a high wrap count, there is a greater amount of sheath. The angle between the yarn and axial direction is enlarged accordingly, which undermines the yarnâ&#x20AC;&#x2122;s tenacity and ability to bear the axial stress. Figure 3 (c) shows that 14-S has an optimal elongation of 19.52%. A higher wrap count means more sheath, which positively influences the elongation of the yarns, as proven by the comparison of the elongation of 7-S and 14-S. In addition, a double wrap causes a higher elongation of composite wrapped yarns, compared with a single wrap. The elongation of 7-D is higher than that of 7-S, which is ascribed to the double wrap of the sheath that extends perpendicular to the axis and increases the extension range of yarns. However, 14-D has a lower elongation. Because a high wrap count prevents the yarns from slipping, the composite wrapped yarns rapidly break after small parts of fibers from the cutting section are damaged, which is called shorter breakage. Table 2: Strength efficiency of composite wrapped yarns Strength Efficiency(%)

7-S 102.71

7-D 100.23

14-S 91.55

14-D 54.41

Fig. 3: Tensile properties of (a) breaking strength, (b) tenacity, and (c) elongation of composite wrapped yarns.

3.3. Electrical Resistance of Composite Wrapped Yarns

Figure 4 indicates the electrical resistance of composite wrapped yarns measured with probes that are 1, 3 or 5cm apart. Regardless of the wrap counts and number of layers, the electrical resistance is proportional to the distance between probes. All wrapped yarns have a sheath that is a combination of electrically conductive stainless steel wires and non-conductive PET filaments. Stainless steel wires play an important role in giving the composite wrapped yarns a low electrical resistance, which means a high electrical conductivity.

Page 888 of 1108

Fig. 4: Electrical resistance of composite wrapped yarns as related to various probe distances.

3.4. Stereomicroscopic Observation of Composite Woven Fabrics and Knitted Fabrics

Figure 5 (a-d) indicates the composite woven fabrics, composed of 7-S, 7-D, 14-S, and 14-D as the weft yarns and 1000D high strength PET filaments as the warp yarns, while Figure 6 indicates the composite knitted fabrics, composed of 7-S, 7-D, 14-S, and 14-D. In comparison of Figures 5 and 6, composite woven fabrics have a greater formability than composite knitted fabrics. In particular, the loops in the knitted fabrics of 14D-K are poorly formed, as indicated in Figure 6 (d). The composite wrapped yarns of 14-D are rigid due to their high wrap count, which also hampers the formability. In addition, the composite woven fabrics have a stabilized pore size, a phenomenon absent in the composite knitted fabrics. The loop structure of knitted fabrics is dependent on the rigidness of their constituent yarns.

Fig. 5: Stereomicroscopic images (10Ă&#x2014;) of composite woven fabrics (a) 7-S-W (b) 7-D-W (c) 14-S-W (d) 14-D-W.

Fig. 6: Stereomicroscopic images (10Ă&#x2014;) of composite knitted fabrics (a) 7-S-K (b) 7-D-K (c) 14-S-K (d) 14-D-K.

4. Conclusions This study successfully fabricates composite wrapped yarns, composite woven fabrics, and composite knitted fabrics. The tensile properties with the corresponding composite wrapped yarns are a maximum breaking strength of 1493cN for 7-D, a maximum tenacity of 1.59 cN/dtex for 7-S, and a maximum elongation of 19.5% for 14-S. The composite wrapped yarns have the smallest electrical resistance when the probes are 1cm apart. In addition, composite woven fabrics, with their stable pore sizes, have better formability than composite knitted fabrics. From this study, it is believed that the weave pattern can replace circuits to be used as a precursor in future products. Therefore, textile techniques and electronic elements can be combined in order to create smart textile products, whose integral structure can be adjusted based on the requirements of the end products that suit consumer demands.

5. Acknowledgements The authors would like to thank Ministry of Science and Technology of Taiwan, for financially supporting this research under Contract MOST 103-2221-E-035-028.

6. References

Page 889 of 1108

[1]

X. Tao, "Smart fibres, fabrics and clothing", The Textile Institute, CRC Press LLC and Woodhead Publishing Ltd, North and South America, 2001.

[2]

T. Kinkeldei, C. Zysset, N. Munzenrieder, and G. Troster, Sensor Actuat B-Chem, 174, 81 (2012).

[3]

Y. Cheng, R. R. Wang, J. Sun, and L. Gao, Acs Nano, 9, 3887 (2015).

[4]

L. M. Castano and A. B. Flatau, Smart Mater Struct, 23 (2014).

[5]

M. Stoppa and A. Chiolerio, Sensors-Basel, 14, 11957 (2014).

Page 890 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Property Evaluations of Sodium Chloride/Polyvinyl Alcohol Hydrogels Prepared by Different Drying Methods Jia-Horng Lin 1,2,3, Po-Ching Lu 1, Wen-Yu Fu 1, Chien-Lin Huang 4 and Ching-Wen Lou 1

5 +

Laboratory of Fiber Application and Manufacturing, Department of Fiber and Composite Materials, Feng Chia University, Taichung City 40724, Taiwan, R.O.C. 2 School of Chinese Medicine, China Medical University, Taichung City 40402, Taiwan, R.O.C. 3 Department of Fashion Design, Asia University, Taichung City 41354, Taiwan, R.O.C. 4 Department of Fiber and Composite Materials, Feng Chia University, Taichung City 40724, Taiwan, R.O.C. 5 Institute of Biomedical Engineering and Materials Science, Central Taiwan University of Science and Technology, Taichung City 40601, Taiwan, R.O.C.

Abstract. When a large area of the skin is burned or incised, a shorter healing can be achieved with the dressings. An ideal dressing requires good biocompatibility, non-toxicity, healing acceleration, good air permeability, and good moisture permeability. This study aims to examine the influences of different drying methods and different concentrations of sodium chloride (NaCl) on the polyvinyl alcohol (PVA) hydrogels. Different concentrations of NaCl powders are added to PVA solution, after which the mixtures are made into PVA hydrogels by using a freezing-thawing method. Next, NaCl is removed from PVA hydrogels, and the hydrogels are dried by using different methods. Finally, the dried PVA hydrogels are then evaluated for their properties. The test results show that with a high NaCl concentration, the PVA hydrogels that are dried by using the freezing-and-thawing method have greater the degradation, swelling, and tensile strength than the PVA hydrogels that are dried at room temperature. However, the influences of different NaCl concentrations and different drying methods on the water retention of the PVA hydrogels are negligible.

Keywords: polyvinyl alcohol, freezing-thawing, hydrogel.

1. Introduction Polyvinyl alcohol (PVA) is a synthetic polymers that is hydrophilic, biodegradation, and it is commonly used in different fields. In addition, PVA is a semicrystalline polymer with flexure, hydrophilicity, chemical stability, and resistance, which qualifies their applications in organ solvents, and tissue scaffolds, filter membranes, wound dressings [1-10], and hydrogels that are in relation to textile, food, building, printing, agriculture industries [4]. Gel is a three-dimensional network, which is a result of the cross-linked polymerization while water is refrained in the reticular structure and causing the gel to swell. Studies on gels have been caught a great deal of attention, and gel is a reticular structure containing a large amount of water, which swells the non -water soluble polymers. Gel has been pervasively used in biological medicine and biological engineering, due to having softness, elasticity, swelling, and biocompatibility [11-17]. In this study, pure PVA hydrogels with different concentrations are first evaluated for degradation and water retention. Sodium chloride (NaCl) is then added to PVA gels, after which the mixtures are dried in a room temperature and then freeze-dried in order to form PVA hydrogels. Finally, the effect of NaCl concentrations are investigated in relation to degradation ratio, swelling ratio, water retention, tensile strength, and the functional groups are examined via a Fourier transform infrared spectroscope (FTIR).

2. Experimental 2.1. +

Materials

Corresponding author. Tel.: + 886-4-2451-8672 E-mail address: cwlou@ctust.edu.tw

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Polyvinyl alcohol (PVA, Sigma-Aldrich, US) of molecular weight of 89000-98000 Da is hydrolyzed to be 99+ %.

2.2.

Preparation of PVA hydrogels

PVA powder is blended with deionized water at 90°C for four hours until a complete dissolution, in order to form a 3 wt% PVA solution. Different concentrations of 1, 2, 3, 4, and 5 wt% NaCl powder is then added to the PVA solution in order to formulate NaCl-contained PVA solutions. These solutions are infused onto a plate, which is freezed at -18 °C for six hours, and thawed at room temperature. Next, one batch of these solutions are freeze-dired while the other batch is dried at room temperature. Finally, the PVA hydrogels are processed with an ultrasonic cleaner (UC-80, Double Eagle Enterprise, Taiwan, ROC) for ten minutes in order to remove the NaCl. Finally, the PVA hydrogels are divided into two batches that are once again dried at room temperature and freeze-dried, respectively.

2.3.

Tests

Swelling Test The PVA hydrogels are placed in test tubes after which 30ml PBS is added. The materials are placed in a shaking bath at 37 °C for different times, and are then removed to dry the moisture from the surface. The hydrogels are weighed in order to obtain the wet weight, after which they are dried in an oven for 24 hours in order to obtain their dry weight. The swelling of the PVA hydrogels is computed with the equation as follow. Swelling (%) = (wet weight – dry weight)/dry weight×100% (1.1)

Water Retention Test The PVA hydrogels are placed in test tubes, after which 30 ml PBS is added. The materials are placed in a shaking bath at 37 °C for different times, and are then removed to dry the moisture from the surface. Afterwards, the water retention of hydrogel is computed with the equation as follows. Water Retention (%) = (W w -W t ) / (W w -W 0 )×100% (1.2) where W 0 is the initial weight of hydrogel, W w is the weight of hydrogel that is fully saturated with water, and W t is the weight of the hydrogel that is dried for different length of time (t).

Tensile Strength Test The PVA hydrogels are cut into a rectangle of 1 cm × 3 cm, followed by being placed in a PBS solution. Samples are then tested by using a universal testing machine (HT2402, Hung Ta Instrument, Taiwan, ROC). The distance between the clamps is 1cm, and the tensile speed is 5 mm/min.

3. Results and Discussion 3.1.

Swelling Rate b Swelling (%)

Swelling (%)

Time(min)

Fig. 1: The swelling of PVA hydrogels that are (a) dried at room temperature (b) freeze-dried. The hydrogels are composed of NaCl concentrations of 0, 1, 2, 3, 4, and 5 wt%. The hydrogels are soaked in water for 2, 4, 6, 8, 10, and 360 minutes.

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Figures 1(a) and (b) indicate that the swelling of PVA hydrogels that are freeze-dried is higher than the swelling of PVA hydrogel that is dried at room temperature. When made via the freeze-drying process, the hydrogels have a greater number of pores, allowing it to retain more water. In other words, the freeze-dried PVA hydrogels exhibit a high swelling. In addition, the freeze-dried PVA hydrogels also have a shorter saturated rate of swelling as the freeze-drying process provides PVA hydrogels with a porous structure that can cause the capillary phenomenon. As a result, the swelling of PVA hydrogels that are made via freezedrying is more efficient that the swelling of PVA hydrogels that are made at room temperature.

3.2.

Water Retention Rate

There are no significant differences in the water retention rate between PVA hydrogels that are dried at room temperature and those that are freeze-dried, as indicated in Figures 2 (a) and (b). This result is due to the fact that PVA hydrogels cannot retain water, therefore, regardless of the drying methods, PVA hydrogels have a water retention rate that is close to zero after being immersed in water for twelve hours. Figure 3 indicates that the NaCl concentrations are not in relation to the water retention rate. Water retention of PVA hydrogels depends on their structure caused by the freeze-thaw process; however, the reticular structure is unable to retain water. As a result, the water retention of PVA hydrogel is irrelevant to the NaCl concentration. b

Water retention (%)

Time(hour)

Fig. 2: The water retention of PVA hydrogels that are (a) dried at room temperature (b) freeze-dried. The hydrogels are composed of NaCl concentrations of 0, 1, 2, 3, 4, and 5wt%. The hydrogels are soaked in water for 2, 4, 6, 8, 10, and 360 minutes.

3.3.

Tensile Strength Test

Fig. 3: The tensile strength of PVA hydrogels as related to being dried in a room temperature and by freeze drying. The hydrogels are composed of NaCl concentrations of 0, 1, 2, 3, 4, and 5wt%.

The tensile strengths of PVA hydrogels that are made with NaCl concentrations of 0, 1, 2, 3, 4, and 5 wt% are indicated in Figure 3. The optimal tensile strength of 0.17 MPa occurs when the PVA hydrogels are made with 3 wt% NaCl. During the process of hydrogels, the infusion of NaCl in water allows for a condensate phenonmeon of PVA hydrogel, which leads a great deal of small-sized gels. A high NaCl concentration thus results in a greater size of hydrogels. The freeze-thaw process results in the attraction among the hydroxyl

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groups in PVA molecular chains, the physical cross-linking in turn forms a reticular structure. However, gels prevent the attraction among the hydrogen bonds, and influences the strength of PVA hydrogels. The strength of the hydrogel is higher when the NaCl concentration is higher than 3 wt%, as this 5 wt% causes a greater volume of the hydrogels. When PVA hydrogels are dried at room temperature, they transform from hydrogels, then solutions, to membranes. This process gives NaCl a higher concentration, and the condensate action is thus strengthened. The bond force between hydrogen in PVA hydrogels is then strengthened as a result of a high NaCl concentration. As a result, PVA hydrogels that are dried at room temperature have a maximum tensile strength when 1wt% NaCl is administered. In contrast, the moisture in freeze-dried PVA hydrogels is direction sublimated from being at a frozen status, and the PVA hydrogels thus have pores and a desired spacial structure as a result of sublimation. Without being transformed into solutions, freeze-dried PVA hydrogels do not contain a relatively high NaCl concentration that increases the condensate action.

4. Conclusions This study successfully examines the influence of NaCl concentration and drying methods on the properties of PVA hydrogels. The test results indicate that regardless of the NaCl concentrations, the PVA hydrogels have a water retention that is close to zero after being immersed in water for twelve hours. The degradation level swelling, and tensile strength of the PVA hydrogels that are freeze-dried are all higher than the degradation level and swelling of PVA hydrogels that are dried at room temperature. Specifically, a maximum tensile strength of PVA hydrogels that are dried at room temperature or freeze-dried occurs with an optimal NaCl concentration of 3wt%.

5. Acknowledgements The authors would like to thank Ministry of Science and Technology of Taiwan, for financially supporting this research under Contract MOST-2622-E-166-001-CC2.

6. References [1] S. R. Prakash, H. Ramakrishna, S. Rai and A.V. Rajulu, J. Appl. Polym. Sci., 90(1), 33, 2003. [2] M. Roohani, Y. Habibi, N.M. Belgacem, G. Ebrahim, A.N. Karimi and A. Dufresne, Eur. Polym. J., 44(8), 2489, 2008. [3] B. Ding, E. Kimura, T. Sato, S. Fujita and S. Shiratori, Polymer, 45(6), 1895, 2004. [4] C.K. Chua, K.F. Leong, K.H. Tan, F.E. Wiria and C.M. Cheah, J. Mater. Sci. Mater. Med., 15(10), 1113, 2004. [5] C.J. Shuai, Z.Z. Mao, C.D. Gao, J.L. Liu and S.P. Peng, J. Mech. Med., 13(03), 12, 2013. [6] R.K. Nagarale, V.K. Shahi and R. Rangarajan, J. Membr. Sci., 248(1-2), 37, 2005. [7] S.A. Paralikara, J. Simonsen and J. Lombardi, J. Membr. Sci., 320(1-2), 248, 2008. [8] Y. Wang and Y.L. Hsieh, J. Membr. Sci., 309(1-2), 73, 2008. [9] H. Serincay, S. Ozkan, N. Yilmaz, S. Kocyigit, I. Uslu, S. Gurcan and M. Arisoy, Polym.-Plast. Technol., 52(13), 1308, 2013. [10] N. Rescignano, E. Fortunati, S. Montesano, C. Emiliani, J.M. Kenny, S. Martino and I. Armentano, Carbohydr. Polym., 99(2), 47, 2014. [11] A.S. Hoffman, Adv. Drug Deliv. Rev., 54, 3, 2002. [12] D. Seliktar, Science 336 (2012) 1124â&#x20AC;&#x201C;1128. [13] N.A. Peppas, J.Z. Hilt, A. Khademhosseini and R. Langer, Adv. Mater. 18, 1345, 2006. [14] N. Sahiner, Prog. Polym. Sci., 38, 1329, 2013. [15] D. Buenger, F. Topuz and J. Groll, Prog. Polym. Sci., 37, 1678, 2012. [16] C. GoncÂ¸ alves, P. Pereira and M. Gama, Materials, 3(2), 1420, 2010.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Strength Forecasting of Spun Yarns at Different Gauge Lengths Using Weibull Distribution Parameters Anindya Ghosh1 + 1

Government College of Engineering & Textile Technology, Berhampore, West Bengal, India-742101

Abstract. This article addresses the strength forecasting of different spun yarns at other gauge length from a knowledge of the strength distribution at a given gauge length. From the Weibull distribution parameters at 10, 50, and 500 mm gauge lengths, yarn strength at other gauge lengths have been predicted. The results show that the yarn strength at shorter gauge lengths can be well predicted from the distribution parameters of short gauge length. Similarly, yarn strength at longer gauge lengths can be fairly predicted from the distribution parameters of long gauge length. However, the strength distribution parameters of long gauge lengths cannot able to predict the yarn strength at shorter gauge length and vice versa. The data of yarn tenacity follows the Weibull distribution at longer gauge lengths and follow a different Weibull distribution at shorter gauge lengths.

Keywords: Gauge length, scale parameter, shape parameter, Weibull distribution, yarn strength

1. Introduction The strength of a spun yarn depends on the gauge length and extension rate employed during its measurement [1, 2]. The standard measurement of yarn strength is accomplished at 500 mm gauge length. However, in actual practice, the yarns of different lengths experience stresses. For instance, during warping, sizing and weaving, yarns longer than 500 mm length experience stresses. Hence, the measurement of yarn strength only at 500 mm gauge length is not adequate. Also, it is not practical to determine yarn strength at a number of possible gauge lengths. Therefore, any attempt to predict the yarn strength at various gauge lengths from theoretical model is worth mentioning. The present work is endeavored to predict strength of different spun yarns at other gauge length from the Weibull distribution parameters of yarn strength at a given gauge length.

2. Experimental The ring, rotor, air-jet and open-end friction (Dref-11) yarns of 20â&#x20AC;&#x2122;s Ne nominal count were spun from viscose staple fibres of 1.5 denier and 44 mm length. The twist multipliers for ring and rotor spun yarns were 3.75 and 4.2 respectively. Lakshmi LG 5/1 ring frame and Rieter M 2/1 machines were employed to produce ring and rotor yarns respectively. The air-jet and open-end friction yarns were made on MJS-802 H and DrefIII spinner respectively. The yarns were conditioned at 65% RH and 25Â°C for 24 h prior to the tensile testing. An lnstron tensile tester was used for testing the yarns at a wide range or gauge lengths, viz. 0, l, 3, 5, 10, 15, 20, 25, 30, 35, 40, 44, 50, 75, 100, 200 and 500 mm, keeping the extension rate constant at 200 mm/min. For each set of experiment, 100 tests were conducted.

3. Weibull distribution of Spun yarn strengths Similar to the approach of Realff et al. [3] the spun yarn strengths at other gauge lengths are predicted from the Weibull distribution parameters of yarn strength at a given gauge length. If the yarn strength at a given gauge length l 0 , follows a two-parameter Weibull distribution [4], then its distribution function have the following form +

Anindya Ghosh. Tel.: + 03482-250142. E-mail address: anindya.textile@gmail.com.

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  x r  (3.1) Fl0 ( x ) = 1 − exp −      x 0   where x 0 and r are scale parameter and the shape parameter respectively. The distribution function of yarn strength at any other gauge length l is given by   x r  (3.2) Fl ( x ) = 1 − exp −      x l   where l = m l o and x l = x 0 m-1/r. The parameters x 0 and r are positive constants. The mean and coefficient of variation for the data following a two-parameter Weibull distribution are given by

µ = x0 Γ(1 + 1 / r )

(3.3)

{

σ 2 = x 0 2 Γ(1 + 2 / r ) − [Γ(1 + 1 / r )]2

}

(3.4)

Therefore, the coefficient of variation is CV =

 σ  Γ(1 + 2 / r ) = − 1 2 µ  {Γ(1 + 1 / r )} 

1/ 2

(3.5)

where μ, σ2, and CV are the mean, variance, and coefficient of variation (fraction), respectively, and Γ(.) is the gamma function. The expression of Γ(n) is given by ∞

Γ(n) = ∫ exp(−t )t n −1 dt

(3.6)

The scale parameter x 0 is related to the strength of the flaw in a yarn. Typically the scale parameter is numerically close to the mean yarn tenacity. It is noticed from the Equation 3.5 that the coefficient of variation of yarn tenacity depends only on shape parameter r. The shape parameter r represents the dispersion of yarn strength per unit length of yarn. A greater value of r indicates a small yarn strength variation. If the yarn follows the weakest-link theorem in the Weibull setting, we expect that the shape parameter r for strength will be constant for each yarn as the gauge length changes and the scale parameter x 0 changes according to Equation 3.2. If these two conditions are satisfied with a change in gauge length, then this suggests the same sort of flaw and its distribution may be associated with all the samples [3]. The Matlab 7.11 package was employed to determine the values of shape and scale parameters using Equations 3.3 and 3.5. Using a Kolmogorov-Smirnov [5] goodness-of-fit at a significance level α ≥ 0.05, the tenacity data for all the spun yarns at different gauge lengths were found to fit a two-parameters Weibull distribution. Fig. 1 illustrates the two-parameters Weibull plots for the tenacity of ring spun yarns at 10, 50, and 500 mm gauge lengths. (a)

(b)

(c)

Fig. 1: Weibull distribution for ring spun yarn (a) at 10 mm gauge length, (b) at 50 mm gauge length, (c) at 500 mm gauge length.

4. Prediction of Yarn Strength at Different Gauge Lengths In case of ring spun yarn, the scale parameters based on the experiments at 15, 20, 35, 40, 44, and 50 mm gauge lengths are very well predicted by the 10 mm distribution parameters (Fig. 2, a). The scale parameters based on actual tensile test at 3, 35, 40, 44, and 75 mm are almost accurately predicted from 50 mm parameters. But from the 500 mm distribution parameters, except 3 mm, the experimental scale parameters at higher gauge lengths (200 and 100 mm) can only be predicted without much error.

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(a)

(b)

(c)

(d)

Fig. 2: Predicted and experimental scale parameters for spun yarns at different gauge lengths (a) ring spun yarn, (b) rotor spun yarn, (c) air-jet spun yarn, (d) OE friction spun yarn.

For rotor yarn, the shorter gauge test performances based on the 500 mm distribution parameters are underestimated (Figure 2, b). But the parameters of 500 mm gauge length give a fairly better prediction of scale parameters at 40, 50, 75, 100, and 200 mm gauge lengths. The 10 mm distribution parameters can only predict the performance at 15, 20, 200, and 500 mm gauge lengths without much error. Whereas the scale parameters of 1, 35, 40, 44, 75, 100 and 200 mm gauge lengths are well predicted based on the 50 mm distribution parameters. In general, the average prediction errors from all three-gauge lengths (10, 50, and 500 mm) are higher in case of rotor spun yarns than that of ring spun yarns. In case of air-jet yarn, the scale parameters at 5, 15, 30, and 35 mm gauge lengths can be fairly predicted from 10 mm strength distribution parameters (Figure 2, c). The distribution parameters of 50 mm gauge length results in a comparatively better prediction of the scale parameters at 75 and 100 mm gauge lengths, whereas, the predicted scale parameters at all gauge lengths from the strength distribution parameters of 500 mm are significantly underestimated. This strengthen the perception that in case of air-jet spun yarns, a change in gauge length causes the yarn failure mechanism to shift from one dominated by fibre slippage at a longer gauge length to one dominated by fibre breakage at shorter gauge lengths especially below the fibre staple length. Overall, the mean prediction errors from all three-gauge lengths are much higher in case of air-jet spun yarns than the remaining yarns. For OE friction yarn, scale parameters at 35, 40, 44, and 75 mm gauge lengths are fairly well predicted from 50 mm distribution parameters (Figure 2, d). The scale parameters at 200 and 500 mm gauge lengths can only be well predicted based on the 10 mm parameters. However, 500 mm parameters give a reasonably better prediction of data at 20, 30, 35, 40, 44, 50, 75, and 200 mm gauge lengths. For all the samples, the decrease of Weibull shape parameter r with the decrease of gauge length indicates higher strength variability at shorter gauge length. This clearly indicates a change in yarn failure mechanism when the gauge length varies. Furthermore, the Weibull scale parameter diminishes with increasing gauge length in a manner that it deviates from the weakest-link scaling theories. From the Weibull distribution

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analysis, it generally suggests that the data of yarn tenacity follow the Weibull distribution at longer gauge lengths and follow a different Weibull distribution at shorter gauge lengths. If the classical weakest-link theory [6] were to satisfy, the shorter gauge test performance would have been accurately predicted based on the strength distribution parameters of longer gauge length and the reverse would have also become true. However, the results generally show that the strength distribution parameters for long and short gauge lengths cannot predict the strength distributions at shorter and longer gauge lengths respectively. This deviation from the weakest-link theory obviously suggests that the mechanism of yarn failure changes significantly when the yarns are tested at shorter and longer gauge lengths. These results also confirm the findings by Realff [3].

5. Conclusion It has been observed that the data of yarn tenacity are well fit to two-parameter Weibull distribution. The Weibull shape parameter r diminishes as the gauge length decreases. The results show that the yarn strength at shorter and longer gauge lengths can be predicted with reasonable degree of accuracy from the distribution parameters of short and long gauge lengths respectively. However, the strength distribution parameters for long and short gauge lengths cannot predict the same at shorter and longer gauge lengths respectively. From the analysis of the results, an inference may be drawn that none of the yarns considered in this study strictly follows the classical weakest link theory and there is a considerable change in failure mechanism for all the yarns as the gauge length is varied.

6. References [1] Ghosh, A., Ishtiaque, S. M., and Rengasamy, R. S. (2005), Analysis of Spun Yarn Failure; Part I: Tensile Failure of Yarns as a Function of Structure and Testing Parameters, Text. Res. J., 75(10), 731-740. [2] Ghosh, A., Ishtiaque, S. M., Rengasamy, R. S., Mal, P., and Patnaik, A. (2004), Spun Yarn Strength as a Function of Gauge Length and Extension-Rate: A Critical Review, J. Text. & Appl. Tech. Management, 4(2), 1-13. [3] Realff. M. L., Pan, N., Seo. M., Boyce, M. C., and Backer, S. (2000) A Stochastic simulation of the Failure Process and Ultimate Strength of Blended continuous Yarns, Text. Res. J., 70 (5), 415-430. [4] Weibull, W. (1951), A Statistical Distribution Function of Wide Application, J. Applied Mech., 18, 293-297. [5] Thoman, D. R., and Bain, L. J. (1969), Two Sample Tests in the Weibull Distribution, Technometrics, 11 (4), 805-815. [6] Peirce, F. T. (1926), Tensile Tests for Cotton Yarns, Part V: The Weakest Link Theorems on the Strength of Long and Composite Specimens, J. Textile Inst. 17, T355-T368.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Study on the influence of tight-fitting sports socks on human leg’s pressure distribution Ling Chen1, Xiu-E Bai2 1,2

College of Textile and Clothing Engineering, Soochow University, GanJiang East Road No.178, Suzhou, 215021, China

Abstract: Two kinds of tight-fitting sports socks with different lengths of their legs were collected. Three subjects were recruited and pressure values on their legs applied by these socks were tested under different states of motion (standing, walking, running), using an objective test system on human physiological clothing comfort. And then we further analyzed the influence of motion states, body-shape and the length of socks’ legs on the pressure. The results show that the pressure distribution is related to the relative movement of joints, the deformation of subcutaneous soft tissue, the body circumference, the surface curvature, and the clothing covering area. Such results will provide a theoretical reference for the study on the pressure comfort of tight-fitting sports socks.

Keywords: tight-fitting sports socks, pressure comfort, states of motion, human body shapes, lengths of sports socks’ legs

1. Introduction With the improvement of people’s living standards, their requirements for sportswear’ functionality and comfort are becoming higher and higher. Sports socks, as a kind of sportswear, are usually thick and durable. Meanwhile, sports socks also can protect human feet and legs [1]. Tight-fitting sports socks, as a special kind of socks, mainly play a role of protecting human body, improving sports performance, and reducing fatigue within a certain range of pressure. But, when the pressure exceeds a certain range, not only its positive effects no longer exist, but also it will hinder the sport, and even do harm to human body. So, controlling the pressure of tight-fitting sports socks in an appropriate range can guarantee its functionality, meanwhile, it can ensure the pressure comfort. Clothing comfort is increasingly becoming one of the main features of modern consumer’s demands [2]. Clothing comfort contains three potential independent factors: thermal-wet comfort, tactile comfort and pressure comfort [3]. Because of the prominent characteristics of tight-fitting sports socks, namely pressure, the pressure comfort is the most important index to evaluate its comfort.

2. Experiment

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2.1. Experimental materials A certain brand’s middle and long tube tight-fitting sports socks with same fabric and size were selected, and the specifications are shown in table 1. Table 1: The specifications of tight-fitting sports socks Number

Type

Tube length (cm)

middle tube socks

long tube socks

Size

Fabric

23.5

chinlon /spandex

2.2. Experimental subject Three male college students aged between 20 to 23 years old were selected as experimental subjects, and their basic information are shown in table 2. Table 2: The basic information of three subjects Number

Height

Weight

Calf length

(cm)

(kg)

(cm)

183.5

82.4

40.8

29.5

178

172

64.5

38.2

23.1

Calf circumference

ankle circumference (cm)

Three points on their shank as test points were selected, namely, the back point of ankle P1, 1/3 of the shank’s back point P2, the back point with the biggest circumference on the shank P3, which have obvious differences in the thickness of soft tissue .

2.3. Experimental method The experiment was conducted in the Japanese ESPEC walk-in artificial climate chamber and it adopts the objective test system on human physiological clothing comfort developed by Japanese AMI Technology Co. Ltd. Each of the subjects was required to wear two kinds of socks respectively. Firstly, they needed to stand on the ground for one minute, then the pressure values applied by socks were recorded by the experimental apparatus, and then they would rest for 15 minutes. Secondly, the subjects needed to walk on the treadmill at the speed of 3.0 km/h for one minute, then the pressure values of test parts were recorded, and then they had another 15 minutes to rest. Finally, the subjects were required to run on the treadmill at the speed of 7.5 km/h for one minute, the pressure values were recorded.

3. Results and discussion 3.1. The influence of human motion states on human leg’s pressure The figure1, figure2 and figure3 are the pressure distributions on the legs of three subjects wearing tight-fitting sports sock B respectively, under different motion states.

3 2.5 2 1.5

0.5

pressure values (kPa)

Page 900 of 1108

0 standing

walking

2.5 2 1.5

0.5

0 standing

running

walking

running

state of motion

2.5 2 1.5

0.5

0 standing

walking

Fig. 2: Pressure distribution of subject S2 in B

pressure values (kPa)

Fig. 1: Pressure distribution of subject S1 in B

state of motion

3 2.5 2 1.5

0.5

running

S3 subjects

state of motion

Fig. 3: Pressure distribution of subject S3 in B

Fig. 4: Pressure distribution in B under standing

From figure 1 to figure 3, it can be seen that, when all subjects wear the tight-fitting sports sock B, the pressure values at the points of P1 and P3 are greatly affected by the motion states, while the influence of the motion states on the pressure value of point P2 is relatively small. Because of the ankle relative movement, the pressure value of P1 is greatly affected by the motion states. And because of the shift of gastrocnemius muscle, the pressure value of P3 is greatly affected by the motion states. While P2 is located on the fibula and achilles tendon. The fibula does not produce relative movement and the achilles tendon almost do not produce deformation, resulting in the pressure value at P2 is hardly affected by the motion states.

3.2. The influence of human body shape on human legâ&#x20AC;&#x2122;s pressure

2.5 2 1.5

0.5

0 S1

pressure values (kPa)

Figure 4, figure 5 and figure 6 are respectively the pressure distribution on subjectsâ&#x20AC;&#x2122; legs under different motion states, when they wear tight-fitting sports sock B. 2.5 2 1.5

0.5

0 S1

subjects

Fig.5: Pressure distribution in B under walking

S3 subjects

Fig. 6: Pressure distribution in B under running

From figure 4, we can see that when subjects were in the state of standing, the impact of body-shape on the pressure distribution is relatively large. And the descending order of pressure

Page 901 of 1108

values at P1 and P3 is S1, S3, S2, which is consistent with the descending order of three subjects’ ankle circumference and calf circumference. Furthermore, from figure 4 to figure 6, it also can be seen that the pressure distribution at P2 is greatly affected by human body-shape under all kinds of motion states. And the descending order of pressure values at P2 is S2, S1, S3.

3.3. The influence of length of tight-fitting sports sock’s leg on human pressure

3 2.5 2 1.5

0.5 0

3.5 3 2.5 2 1.5

0.5 0

test points

Fig. 7: Pressure distribution on S3 under standing

test points

pressure values (kPa)

3.5

pressure values (kPa)

Figure 7, figure 8 and figure 9 are respectively the pressure distribution on the leg of subject S3, who wear two kinds of tight-fitting sports socks in different movement states. 4 3.5 3 2.5 2 1.5 1 0.5 0

A B P1

test points

Fig. 8: Pressure distribution on S3 under walking

Fig. 9: Pressure distribution on S3 under running

Form figure 7 to figure 9, it can be seen that, the trend of pressure is consistent. The pressure values decrease from the bottom of human shank to its top when subjects wear sock A. However, the pressure values decrease first and then increase from the bottom of human shank to its top when subjects wear sock B. By contrast, when subjects wear sock B, the pressures values at the point of P1 decrease greatly, and it decrease slightly at the point of P2, while the pressures values at the point of P3 increase significantly compared to that of sock A.

4. Conclusion (1) Clothing pressure is affected by human motion states. This influence is essentially caused by joint movement and soft tissue deformation. Because of the movement of ankle joint, the influence of motion states on the pressure of the back point of ankle is relatively great, and because of the deformation of gastrocnemius muscle, the influence of motion states on the pressure of the back point with the biggest circumference on the shank is also relatively great. While the pressure at 1/3 of the shank’s back point is hardly affected by the motion states. (2) When human body shapes are different, the pressures from tight-fitting sports socks on human legs are different too. The pressure values are consistent with human ankle circumference and calf circumference. Under the same binding condition, the greater curvature the human body has, the greater pressures human body can feel. (3) When the lengths of tight-fitting sports socks’ legs are different, the pressures from tightfitting sports socks to human legs are different too. The long tube tight-fitting sports socks covers more area than that of the middle tube socks, thus it can disperse partial pressure on the legs. So, wearing stockings can improved the pressure comfort of the ankle, but the pressure comfort of the parts close to stocking welt is decreased obviously.

Page 902 of 1108

5. Reference [1] http://baike.baidu.com/view/1178883.htm. [2] Li Y. Clothing comfort and product development [M]. Beijing: China Textile Press, 2002, 10. [3] Meng XL, Zhang WY. The research progress of clothing pressure comfort [J]. Journal of Textile Research, 2006, 27(7):109-112.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Study on warm moisture heating UNIQLO brand thermal underwear ZHENG Jingjing,JI Xiaofeng,DONG Jinchang (College of Fashion Zhejiang Sci-Tech University, Zhejiangďź&#x152;Hangzhou 310018, China)

Abstract.UNIQLO brand famous for its superior functional fabrics, is popular among consumers, especially moisture heating thermal underwear series in autumn and winter. This study selected the UNIQLO brand HEATTECH series moisture heating underwear, and test its thermal properties ,while compared with the blended thermal underwear, wool thermal underwear, cotton thermal underwear. It tested the thermal conductivity of each underwear, warm-cool feeling; And using infrared thermography test device to test and analysis various underwear fabric warmth retention property. Experiments prove that the warmth retention property of UNIQLO HEATTECH series moisture heating underwear slightly less than wool thermal underwear, but better than pure cotton thermal underwear and blended thermal underwear, although the warmth retention property is not advertised so magical, but the underwear have high cost performance, it is worth consumers to buy.

Keyword: Thermal underwear;

moisture heating; infrared thermography;

sense of touching well-being;

thermal conductivity

With the development of science and technology and people's living standards improve, people's requirements for practical function of fabric and clothing tends to be diversified, especially in recent years, a variety of new functional textiles gradually entered people's daily lives. In terms of underwear products, the main tend to be "light, thin" "moisture absorption and perspiration", "air breathing", "thermal insulation." Among these, "moisture heating material" is particularly popular. This kind of underwear fabric can absorb the water vapor of the human body, and make the temperature rise, to achieve the effect of keeping warm; while temperature rises, it can accelerate the dissipation of water vapor, which makes people feeling more dry and comfortable after wearing, so using the fiber that sustained and strong hygroscopicity, we made underwear fabric with durability heating and warming function [1].

1. Experiment 1.1 Experiment Purpose Moisture heating underwear with excellent performance come into the public view and win good graces. A variety of functions of the thermal underwear on the market let the consumers do not know how to choose. Besides too many category of thermal underwear fabrics which makes it difficult for consumers to choose, the main reason why consumers feel tangled is that some businesses have a false propaganda on fabric and pass away the sham as the genuine. UNIQLO brand famous for its superior functional fabrics, is popular

Page 904 of 1108

among consumers, especially moisture heating thermal underwear series in autumn and winter. We hope that through this study uncovered the veil of the UNIQLO brand for consumers, and test whether the moisture heating underwear fabric has good thermal property.

1.2 Experiment Instrument In the experiment, we using the precision thermal physical property of KES-F7 to directly get the data of warm-cool feeling when the underwear contacting with the human body,and the thermal conductivity of each underwear fabric. At the same time we use infrared thermography DL700C+ which has a two dimensional planar imaging infrared system, the infrared radiation energy is gathered in the infrared detector by the optical system and converted to the electronic video signals, after the electronics processing, forming the infrared thermal image of the measured target [2].

1.3 Experimental Subject The experimental subjects were 5 healthy male students, the average age was 22 years old, the average height was 172 cm, the average weight was 55kg.

1.4 Experiment Sample The experiment selected UNIQLO HT thermal underwear, UNIQLO HT EXW thermal underwear, wool thermal underwear, cotton underwear, blended thermal underwear for basic performance test. Table 1-1 the test sample and the basic performance parameters of the sample.

2. Test results and analysis Fabric Name

Ingredient Content/

Weight/

Thickness/

Warp Density/

(%)

(g)

(mm)

(No./5cm)

223

0.68

160

Zonal Density/ Fabric Weave

UNIQLO HT

Acrylic fiber 55%，

EXW thermal

Viscose fiber 23%，

underwear

(No./5cm) 180

Plain

Polyester fiber 18%， Polyurethane fiber 4%

UNIQLO HT

Acrylic fiber 27%，

thermal

Viscose fiber 33%，

165

0.41

125

140 Plain

underwear

Polyester fiber 35%， Polyurethane fiber 5%

Wool thermal

Wool100%

244

0.70

100 Plain

underwear Cotton

Cotton 100%

181

0.50

120 Plain

underwear, Blending thermal underwear

Modal fiber47.5%、

155

0.54

120

150

Cotton47.5%、

Plain

Polyurethane fiber5%

Table 1-1 the test sample and the basic performance parameters of the sample

2.1 Test and analysis of sense of heat well-being in contact with fabric The sense of well-being is simulate The maximum number of transferring heat from the skin to the fabric, when the fabric just contact with human skin In an instant，and the moment the heat flow value is called Qmax.

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The greater the value of .

Qmax, the heat flow from the skin to the fabric is larger, it indicates that the fabric cold feeling is stronger ; conversely, explain fabric warm feeling stronger[3]. Table 2-1 shows each underwear Qmax value. From table 2-1 ,we can draw the following conclusion: Table 2-1 Each underwear Qmax value（W/m） Test

Number

EXW

Wool

Cotton

Blending

0.064

0.142

0.120

0.158

0.145

0.087

0.145

0.116

0.156

0.147

0.081

0.146

0.113

0.154

0.149

Average

0.077

0.144

0.116

0.156

0.441

Value

(1) The UNIQLO HT EXW thermal underwear warm feeling is the strongest which is far more than other thermal underwear; (2) Wool underwear warm feeling slightly worse than HT EXW UNIQLO thermal underwear； (3) The warm-cool feeling of UNIQLO HT thermal underwear and cotton underwear is closer. In comparison, UNIQLO HT thermal underwear is slightly better； (4) Blending warm underwear feeling is the most cold； (5) The sort of warm-cool feeling from hot to cold：UNIQLO HT EXW thermal underwear> Wool thermal underwear> UNIQLO HT thermal underwear> Cotton thermal underwear> Blending thermal underwear.

2.2

Test analysis of thermal conductivity

The higher the thermal conductivity is, the worse warmth retention property；On the contrary，the lower the value of the thermal conductivity is, the better the warmth retention property. From the table 2-2, according to the value of the thermal conductivity we can get the following conclusions： Table 2-2 The thermal conductivity of each underwear HT HT

Wool

Cotton

Blending

8.245

4.744

9.397

8.937

EXW Thermal Conductivity K/(W/cm·

℃

4.380

0-4

（1）The UNIQLO HT EXW and wool thermal underwear warmth is the best, and UNIQLO HT EXW thermal underwear is more warm than wool thermal underwear；（2）The warmth retention property of cotton thermal underwear is the worst；（3）UNIQLO HT thermal underwear warmth is better than blending thermal underwear；（4）The sort of warmth retention property：UNIQLO HT EXW thermal underwear> Wool thermal underwear> UNIQLO HT thermal underwear> Blending thermal underwear> Cotton thermal underwear.

2.3 Test and analysis of infrared thermal image

Page 906 of 1108

The experimental subjects entered the artificial climate chamber that the temperature is 25 ℃±2℃ and humidity is 40%±2%,sitting quietly in for 15 minutes in order to adapt to the environment；after that they put on thermal underwear and sit for 5 minutes, we take infrared thermal images of their upper back；then they run on the treadmill for 5 minutes, after the exercise, we immediately take infrared thermal images of their upper back；After 5 minutes sitting of the experimental Subjects, the infrared thermal image of the upper back was taken again. After shooting once every five minutes, a total of 25 minutes after the rest of the exercise is required to shoot 5 the infrared thermal image of front and back of upper body. In order to observe the temperature distribution on the picture more intuitive，we used Dali Infrared report analysis system to do isothermal treatment for the the obtained infrared thermal image. We set the three temperature ranges, that respectively is 33 ℃ to 34 ℃, temperature is 33.5 ent ℃, green, 32.5 ℃dark and 31.5 ℃, the blue, lake blue. The temperature range of above 34℃ is basically shown as a bright yellow, and the temperature range of less than 31℃ is shown as purple. Figure 2-1 shows the surface temperature distribution of clothes taken by infrared thermal image after the test subjects wearing thermal underwear five minutes. When the subjects just wear the thermal underwear, Because of underwear blocking temperature on the surface of the skin, so the photographed human body temperature distribution is significantly lower than normal human body temperature at 37 ℃, at this tim standard of judging the warmth of the thermal underwear is that the lower the overall temperature distribution of the infrared thermal image after processing,the better the ability of underwear to prevent heat through,The better the performance of thermal underwear to keep warm[4-5].

混纺保暖内衣

图 3-1 穿上 5 分钟后的红外热像图 UNIQLO HT thermal underwear

UNIQLO HT EXW thermal underwear

Cotton thermal underwear

Wool thermal underwear

Blending thermal underwear

Figure 2-1 The infrared thermal image after the subjects wearing underwear 5 minutes.

The following conclusions can be made from Figure 2-1： (1) UNIQLO HT thermal underwear warmth is the worst； (2) Wool thermal underwear warmth is the best； (3) The warmth of Cotton thermal underwear、UNIQLO HT EXW thermal underwear、Blending thermal underwear is closer，The cotton warm underwear warm slightly higher than the UNIQLO HT EXW thermal underwear; the UNIQLO HT EXW thermal underwear warm higher than blending thermal underwear； (4) Eventually sort：Wool thermal underwear> Cotton thermal underwear≥ UNIQLO HT EXW thermal underwear> Blending thermal underwear> UNIQLO HT thermal underwear. Figure 2-2 shows that the human body in the motion did not sweat a lot, but 5 minutes after exercise, the body began to sweat,and resulting in a lower temperature display of sweating area.In addition to UNIQLO HT thermal underwear, the regional distribution of temperature for other four thermal underwear are relatively close. Figure 2-3 shows that besides there are some sweat in blending thermal underwear and UNIQLO HT

Page 907 of 1108

EXW thermal underwear, other thermal underwear are already in dry state. To exclude the influence of sweat on the temperature, so we compare this group of infrared thermography as a standard for determining the level of fever of the thermal underwear after moisture absorption[5-6]. From figure 2-3, the heating performance of the thermal underwear after moisture absorption is summarized as follows： (1)The moisture absorption and heat performance of wool thermal underwear is the best. (2)The moisture absorption and heat performance of blending thermal underwear is the worst. (3)The moisture absorption and heat performance of UNIQLO HT thermal underwear is better than Cotton thermal underwear. (4)The moisture absorption and heat performance of Cotton thermal underwear is better than UNIQLO HT EXW thermal underwear. (5)The sort of moisture absorption and heat performance：Wool thermal underwear> UNIQLO HT thermal underwear> Cotton thermal underwear> UNIQLO HT EXW thermal underwear> Blending thermal underwear.

After exercise

5 min after exercise UNIQLO HT thermal underwear

UNIQLO HT EXW thermal underwear

Figure 2-2

UNIQLO HT thermal underwear

Cotton thermal underwear

Wool thermal underwear

Blending thermal underwear

The infrared thermal image after exercise and 5 minutes after exercise

UNIQLO HT EXW thermal underwear

Cotton thermal underwear

Wool thermal underwear

Blending thermal underwear

Figure 2-3 The infrared thermal image for 25 minutes of rest after exercise

3. Experimental test results and Revelation 3.1 Experimental results In Table 3-1,The experimental results of warm-cool feeling, thermal conductivity and infrared thermal imaging test were cross-comparison. Table 3-1 shows the sort of comprehensive warm performance of the thermal underwear：Wool thermal underwear＞ UNIQLO HT EXW thermal underwear＞ UNIQLO HT thermal underwear＞ Cotton thermal underwear＞ Blending thermal underwear.

Page 908 of 1108

Table 3-1 The sort of warmth of each thermal underwear Rank

Warm-cool

feeling

EXW>

Wool>

HT>

Cotton>

Blending

EXW>

Infrared thermography Wool>

Cotton>

Warm of just wear Thermal

Blending

HT Wool>

Conductivity

Cotton

HT > >

EXW> Warm Infrared Cotton

thermography Wool> Warm after

HT Blending

HT> >

EXW>

moisture

There is no doubt that the wool has always been known for its excellent moisture absorption and heat performance, and the warmth is also the bestďź&#x203A;UNIQLO uses acrylic materials known as "artificial wool" to guarantee a certain moisture absorption and heat property and also reduces the cost of raw materials. In the HEATTECH EXW series thermal underwear, the acrylic fiber content reached about 55%. Its good warm sensibility also thanks to its fabric design, which the inner layer thin fleece texture brings more warm feeling than smooth warm a lot. Its thermal conductivity is also the lowest in some of the underwear, so the warmth is better than pure cotton thermal underwear and blending thermal underwear [7-8].

3.1 Experimental Revelation Through experimental verification, we prove that the moisture absorption and heat property of UNIQLO HEATTECH EXW series thermal underwear of indeed better than HEATTECH series, but its moisture absorption and heat property is not advertised so magical. When the weather is not very cold, it has a level of thermal effect, which is better than cotton fabrics of the same thickness of thermal underwear and no acrylic or ordinary thermal underwear, but in the north or low temperature environment the warm effect may not be quite satisfactory. At the same time, the experimental results show that the warm of the wool fabric is the highest in common fabrics. But because the price of wool is relatively expensive, the price of thermal underwear made of wool is also rising. In the condition of fabric thickness is close to and the ambient temperature is not very cold, we can choose UNIQLO HEATTECH series thermal underwear because it is more cost-effective than the wool thermal underwear.And HEATTECH series compared with HEATTECH EXW series, the HEATTECH EXW series warmth retention property is better. Consumers should not be confused by some publicity when choose to purchase, but should be more rational to consider the fabric composition, handle, and fabric weaving characteristics.

References [1] Hu haibo, Qi Lu. Development and application of

moisture absorption and heating fiber [J]. Synthetic fiber: China

Page 909 of 1108

Textile Press, 2006. [2] Li Hongyun, Sun Xiaogang, Yuan Jiabin. The accurate temperature measurement technology of infrared thermal imager [J]. Optical precision engineering, 2007, 15(9): 1336-1341 [3] Yuan Zhilei, Li Fangxue. Test methods for moisture absorption and heat of textile fabrics[J]. Textile Leader, 2011, (8): 105-106 [4] Zheng Jingjing, Yan Fei. Measurement and evaluation of thermal performance of underwear based on infrared thermal imaging technology[J] .Modern Textile Technology, 2010, (3) [5] Jie Lu, Meng Jiaguang, Liu Xian. Taking performance and evaluation of softwarm heat fiber knitted fabric[J]. Knitting Industry, 2013, (6): 29 [6] Wu Yingjie, Qi Lu. Research progress of moisture absorption and heating materials[A]. New Chemical Material, 2012, 1(40): 47 [7]

Luo Hong. Thermal insulation testing of knitted thermal underwear and its influence factors[J]. Chinese Xianjian, 2001, (9): 35-36

[8] Li Ling, Meng Jiaguang. Development and application of warm fiber and heating fiber[R]. The Sixteenth National Fancy Yarn And Fabric Technology Progress Seminar, 2010

Page 910 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

The Characteristic Evaluation of Electric Yarn Coated with Electroconductive Material Un-Hwan Park 1, In-Sung Lee1, Kwang-Nyun Cho2, Dae-Gyu Park1, Jae-Won Lee1 1 2

KOTMI(Korea Textile Machinery Research Institute KRIFI(Korea Research Institute for Fashion Industry

Abstract. In the smart fiber parts fused with IT and textile, electric yarn is the most important key components. The use of electric yarn is different according to the degree of electrical resistance. For a highresistance, it is used as anti-static garment. For a low-resistance, it is used as IT device for signal transduction. In this study, we experimentally verified the electric characteristic of yarn coated with conductive material(Ag, Cu) on the yarn produced by the spinning technology of multi-filament to study the conditions for the development of the IT device for signal transduction, And we evaluated its performance and electric characteristic as measuring consumption power of IT device manufactured in the study

Keywords: Electric Yarn, Coating, Electro-conductive

1. Introduction The smart fiber has been widely developed as sensors to recognize human body and wearable computing systems to comfortable life[1]. The smart fiber is required by several devices such as sensors, wearable electronic circuit, display etc[2]. To transmit the power and signals, there are two possible methodologies for implementation of sensors and wearable computing systems. One is the wired system using conventional electrical wires and the other is the wireless system which is fabricated with electronic conductive yarns[3]. The wired system has a few problems in applying to clothing. Because it is relatively heavier than wireless system and it is hard to arrange the physical layout of the devices. Therefore, electronic conductive yarn is preferred to be used in smart fabrics[4]. Smart fiber that fused with IT and textile, is being highlighted as one of the future growth engines. Specially, electric yarn for signal transmission is essential component and technology of smart fiber[5,6]. In this study, we measure and evaluate analyze the electrical characteristic of IT complex composed of the electrical properties.

2. Experimental Result and Discussion 2.1 The characteristic analysis of existing electric yarn

Figure 1. schematic diagram for resistance test

In order to measure the resistance of the electric yarn and the copper is being sold on the market, as shown in the schematic view of Figure 1, a probe of an LCR meter (HIOKI 3532-50) was fixed at both ends of the copper wire and the resistance were measured. As shown in Table 1, while resistance for the two kinds of copper is showing a low value as about 26立/m and 38立/m, that of Cu Coated yarn is so high that it is

Page 911 of 1108

inappropriate for IT device. For Ag Sputter Fiber, the resistance is showing 200Ω/m. it is appropriate to use for IT device. but it is expected to limit the fine circuit design because of the thickness of 280D. Table1. the resistance of the existing electric yarn Ag Sputter Fiber (280D)

Sample

Resistance (Ω/m)

169.1

Cu Coated Fiber (75D)

1.08~1.1M

Cu Coated Fiber (150D)

223~225k

Cu wire (0.025mm)

37.9~38

Cu wire (0.030mm)

26.7~26.8

2.2 The characteristic analysis of developed electric yarn On the other hand, the developed electric yarn is under 200Ω/m with thickness 50D as shown in Table 2. It is appropriate electric yarn for IT device. Tabel 2. the resistance of developed electric yarn Developed Sample

Resistance (Ω/m)

Ag Coated Fiber(50D)

Cu Coated Fiber(50D)

148.0±2

174.0±2

2.3 The characteristic analysis with change of stretch for the developed electric yarn

Figure 2. schematic diagram for stretch resistance test

To measure the electric resistance value according to stretch rate, the electrical resistance of the electric yarn was measured as to movement of fixing jig with LCR meter(HIOKI 3532-50) as shown in Figure 2. Table 3. The resistance of electric yarn as to stretch rate

Stretch rate

Ag Coated Fiber(50D)

Cu Coated Fiber(50D)

156.1±2Ω/m

174.0±2Ω/m

10%

162.3±2Ω/m

203.5±2Ω/m

15%

192.3±2Ω/m

Disconnection

20%

256.1±2Ω/m

Disconnection

It was possible for Ag Coated Fiber(50D) to stretch up to about 20% Elongation. The resistance value for the elongation was increased from 156Ω/m to 256.1Ω/m by 100 Ω as shown in Table 3. But Cu Coated Fiber(50D) was possible to stretch up to 10% elongation. The resistance change for the elongation was from 174Ω/m to 203.5Ω/m.

Page 912 of 1108

2.4 The characteristic analysis with change of temperature for the developed electric yarn

Figure 3. schematic diagram of resistance test by temperature

To measure electric resistance value by the change of the external temperature, The developed electric yarn was fixed on the Hot-Plate and we measured electrical resistance with change of the temperature from 20oC to 120oC.

Temperature

Ag Coated Fiber (50D)

Cu Coated Fiber (50D)

20oC

148.0±2Ω/m

174.0±2Ω/m

50oC

142.0±2Ω/m

170.9±2Ω/m

80oC

135.9±2Ω/m

165.3±2Ω/m

100oC

127.5±2Ω/m

161.4±2Ω/m

120oC

119.0±2Ω/m

157.1±2Ω/m

We confirmed that the resistance for electric yarn was decreased according to increasing of the temperature as shown in the Table 4. By increasing by 100oC, the resistance of Ag Coated Fiber (50D) was decreased from 148.0Ω/m to 119.0Ω/m and Cu Coated Fiber(50D) was from 174.0Ω/m to 157.1Ω/m. The Ag Coated Fiber for the electrical properties is more sensitive to the change of temperature compared to the Cu Coated Fiber

2.5 The design of IT device for simulation

Figure 4. The manufacturing and design of textile touch sensor using of Embroidering machine

Page 913 of 1108

A 12-channel touch sensor pad was manufactured by embroidery process of electric yarn. It was implemented such that a number is displayed on the computer screen by the change of the capacitance value when touched.

[Power supplier]

[multi-meter and sample]

Figure 5. Measuring of power consumption for the textile touch sensor

Applying a voltage of 3.3V in the fiber sensor, the voltage at both ends of the fiber sensor and electric current of fiber sensor were measured repeatedly. the power consumption using verage value was calculated by its formula(power consumption = electric current ✕ Voltage)

3. Conclusion Newly developed electric yarn Ag Coated Fiber and Cu Coated Fiber was a less than 200Ω/m for resistance. So these can be used for the IT device in the thickness of the 50D. As a result of measuring the resistance value changes according to the stretch rate of the two kinds electric yarns, Ag Coated Fiber (50D) and Cu Coated Fiber(50D) could be up to about 20% and 10% elongation and were increased from 156Ω/m to 256.1Ω/m and from 174Ω/m to 203.5Ω/m. The resistance was confirmed to be increased by about 100Ω and 30Ω. This is because the resistance is generally inversely proportional to the cross-sectional area. In addition, As a result of measuring the resistance according to the temperature for development electric yarn, Ag Coated Fiber (50D) and Cu Coated Fiber(50D) were decreased from 148.0Ω/m to 119.0Ω/m by about 30Ω and from 174.0Ω/m to 148.0Ω/m by abut 17Ω. It was confirmed that Ag Coated Fiber is more sensitive compared to Cu Coated Fiber

4. References th

[1] E. Wade and H. H. Asada; Proceedings of the 26 Annual International Conference of the IEEE EMBS San

Francisco, CA, USA·September 1-5; pp.5376-5379, 2004. [2] S. M. Lobodzinski and M. M. Laks; Journal of Electrocardiology, 39, pp. 41-46, 2006. th

[3] J. Akita, T. Shinmura, T. Murakami, M. Y. Kanazawa and M. Toda; Proceedings of the 7 International

Conference on Mobile Data Management(MDM’06), 2006. [4]

J. Akita, T. Shinmura, T. Murakami, M. Y. Kanazawa and M. Toda; Proceedings of the 26 IEEE International Conference on Distributed Computing Systems Workshops(ICDCSW’06), 2006.

[5] M. Amberg, K. Grieder, P. Barbadoro, M. Heuberger and D. Hegemann; Plasma Processes and Polymer, 5,

pp. 874-880, 2008. [6] S. Bosselman; TECHNICAL Report Natick /TR-07/022, 2007.

Page 914 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

The Comparative Evaluation of Car Carpet Material Including Hollow Fiber for Sound Absorbing Performance In-Sung Lee 1, Un-Hwan Park 2 , Yong-Won Jin 3 and Dae-Kyu Park4. 1,2,4 3

Korea Textile Machinery Research Institute Gumho NT Co., LTD Central R&D Center

Abstract. In general, the floor carpet is one of soundproof parts in vehicle. It is used for the absorption of the noise and vibration generated from the lower part of vehicle body. So, it is required absorption, antivibration, flame resisting, compressive elasticity characteristic etc. In this study, we developed the multi-pore hollow fiber added functional inorganic particle to polyester material. And conducted comparative evaluations of the sound absorbing performance for use as automotive carpet material

Keywords: absorbing, soundproof, multi-pore hollow fiber, floor carpet.

1. Instruction From the 1970s until recently, in the automotive industry, the weight of the vehicle is underway for the purpose of improving fuel efficiency and reducing exhaust emissions car by using lightweight material of vehicle. In general, the floor carpet is one of soundproof parts in vehicle. It is used for the absorption of the noise and vibration generated from the lower part of vehicle body. So, it is required absorption, anti-vibration, flame resisting, compressive elasticity characteristic etc. According to aspire to car lighters, cottonizing of PET material used in the Needle Punching carpet is progressing. And the structure of the carpet is progressing diversification Cord type, Loop type, and Velour type, etc in Plain type to. The hollow fibers are more excellent in thermal insulation, sound absorption and lighter than general fiber by the air filled in the hollow portion of the inner. Also, they are greater recovery of the fold or compression. Because flexural stiffness and rebound resilience is excellent successfully compared to general fiber. So, in this study, we selected 2 kinds of the hollow fibers those are possible to reuse or biodegradation on the purpose of environmentally friendly and lightweight for automobile seat cushion material. and we were suing the binder fiber of the other components for thermal bonding between the fibers. Currently, polyester (PET) fiber has accounted for more than 90 percent of the material of the car seat cover. So, if the cushion material is fabricated PET hollow fiber, it is possible to recycle without separation step. And if we are using the poly-lactic-acid (PLA) hollow fibers, it can be expected biodegradability. In this study, we developed the multi-pore hollow fiber added functional inorganic particle to polyester material and conducted comparative evaluations of the sound absorbing performance for use as automotive carpet material.

2. Evaluation Development of hollow fiber of multi-pore type for vehicle carpet 2.1.

Web lamination applied hollow fiber and construction for carpet

2.1.1. Technology of uniform thickness for Base Web of flame resisting hollow fiber Number

Type

Fiber Composition

Weight

NP-T101

Plain

R-PET 100% (6D, 51mm)

800 gsm

NP-T102

Plain

R-PET 100% (6D, 51mm)

1000 gsm

NP-T103

Plain

NP-T104

Plain

H-PET 70% R-PET 30% (7D, 51mm) H-PET 70% R-PET 30%

800 gsm 1000 gsm

Page 915 of 1108

(7D, 51mm)

Figure 1 Control of Areal density according to Carding condition for Hollow fiber

2.1.2. Conditions of Needle punching suitable for the physical properties of flame resisting hollow fiber Result of Needle evaluation, in case of production used hollow fiber and recycle yarn, Bob of 2, the thickness of 1.8mm, length was confirmed that the 3.5mm is most suitable.

2.2.

Development of floor carpet non-woven improved sound absorption

2.2.1The Internal-pore structure control in accordance with Crimp form and number Crimp number (ea/inch) #1

W-form

S-form

Result of selection test, optimal crimp form and number is W-form and 11~13ea/inch. In this case, we can confirm that it is having a highest internal pore structure. 2.2.2. Selection of Optimal ratio for fiber material The higher the mixing ratio of Hollow Fiber in order to have an optimal sound absorbing performance, it has been confirmed that the sound absorbing performance is increased.

2.3.

Evaluation of absorption sound insulation performance in accordance with the construction conditions of the non-woven fabric material

2.3.1. Sound absorbing performance test in accordance with the Denier of thread weight : 400gsm, thickness : 3mm

Figure 2 Sound absorbing performance in accordance with Denier

At the lower Denier, it has been confirmed that the sound absorbing performance is increased.

Page 916 of 1108

2.3.2. Sound absorbing performance test in accordance with the Hollow fiber. NP-T102 (R-PET 100%), NP-T104 (H-PET 70%) / weight : 1,000gsm

Figure 3 Sound absorbing performance of Regular PET vs Hollow Fiber

In the case of H-PET, the sound absorption rate is increased average 21% higher than R-PET. 2.3.3. Sound absorbing performance test in accordance with the Hollow fiber weight NP-T103 (H-PET 800gsm), NP-T104 (H-PET 100gsm)

Figure 4 Sound absorbing performance in accordance with Hollow Fiber weight

The more the weight of the hollow fiber is heavy sound absorption rate also increases. Its weight, in order to obtain a high sound absorption rate, it is necessary to laminate structures having high sound absorbing performance.

2.4.

Evaluation of absorption sound insulation performance in accordance with the type of the non-woven

2.4.1 Absorption sound insulation performance of each type Plain and Velour Sample

thickness(mm)

weight(gsm)

Plain Type+PE Coating

2.36

917

Velour Type+PE Coating

2.28

947

Page 917 of 1108

Figure 5 Absorption sound insulation performance in accordance with each Type

Velour Type is better than Plain type in terms of sound absorption and sound insulation. 2.4.2 Absorption sound insulation performance in accordance with the presence or absence of PE Coating. Sample

thickness(mm)

weight(gsm)

Plain + Latex + PE Coating

917

Plain Type only

874

Figure 6 Absorption sound insulation in accordance with the presence or absence of PE Coating

Sound absorption when there is a PE Coating structure is low, but it is exhibited excellent sound insulation effect.

2.5.

The results of the performance evaluation utilizing development hollow fiber

Sound absorbing performance evaluation of non-woven applied the hollow fiber that has been developed (NP-T2) Regular PET (100%) : HP-01(100%) -> Comparison of the same weight(500gsm)

The result of comparing the sound absorbing performance, by fabricating sample using the hollow fiber has been developed, the hollow rate is being verified at about 5% or more, sound absorption rate elevated about 10% to 15%. Moreover, it was possible to confirm the hollow rate and sound absorbing rate proportional.

2.6.

Development of a structure having a optimal sound absorption and insulation performance(NP-P1)

2.6.1Configuration of optimum working conditions and structure

Page 918 of 1108

The development of the non-woven fabric of composite structure

Class

thickness(mm

weight(gs

)

Velour Type + Latex 100gsm + PE Coating

4.11

985

Plain Type + Latex 100gsm + PE Coating + Felt Interleave

4.96

1129

Plain Type + Flet Interleave + PE Coating

3.98

1050

Plain Type + Mesh + Flet Interleave

4.13

1185

NP-

Plain Type + Latex 100gsm / Felt + Mesh Interleave

4.91

1276

P105

PE Coating + Felt Interleave

NP-

NP-P101 + Evolon(Heating)

4.52

1081

NP-

Development history

P101 NPP102 NPP103 NPP104

P106

2.6.2. Sound absorption and sound insulation performance by the development structure

Figure 7 Sound absorption performance evaluation Figure 8 Sound insulation performance evaluation

The evaluation results of sound absorption and sound insulation performance, sound absorbing performance of development products as compared with the general products are high about 24%. and in the case of sound insulation has a degree of about 18% lower sound insulation performance.

3. Conclusion In the development of carpet material for vehicle using the hollow fiber, the higher mixing ratio of the hollow fiber and the less Denier of original material, sound absorbing performance is increased. Also, if it is possible to be applied to the surface of the hollow Inc. carpets, it is possible to expect a high sound absorption coefficient, The weight of the hollow fiber can be increased higher sound absorption rate. In addition, Velour Type has sound absorption, excellent performance in terms of sound insulation than Plain Type. In the case of PE Coating, to reduce the sound-absorbing , but shows excellent sound insulation effect . Therefore , the result have developed a non-woven composite structure having the structure such as Plain Type + Flet Interleave + PE Coating, it was confirmed to have a conventional than 24% higher sound absorption performance and 18% lower sound insulation performance.

Page 919 of 1108

4. References [1] R. Shishoo, “Textile Advances in the Automotive Industry”,Woodhead Publishing Limited, Cambridge, 2008, pp.21-29. [2] Y. Choi and D. Lim, “Light Weight Textile Materials for Automotive Industry”, Fiber Tech Ind, 2010, 14, 18-26. [3] 小林稔, “自動車輕量化技術の開發動向”, 東レリサ一チセンタ一調査硏究部, 東京, 2010, pp.1-11. [4] T. Nishimatsu, H. Kanai, T. Nishioka, H. Kimura, and T. Yamamoto, “Influence of Hardness of Seat Pad on Sitting Comfort of Automotive Seat”, Sen-i Gakkaishi, 2010, 66, 20-25. [5] T. Nishimatsu, T. Takahashi, H. Kanai, H. Ishizawa, Y. Matsumoto, and E. Toba, “Influence of Combination of Covering Fabrics and Seat Pad on Sitting Comfort of Automotive Seat”, J Text Mach Soc Japan, 2009, 57, 47-52. [6] M. M. Verver, R. de Lange, J. van Hoof, and J. S. H. M. Wismans, “Aspects of Seat Modeling for Seating Comfort Analysis”, Applied Ergonomics, 2005, 36, 33-42. [7] M. Matsudaira and Y. Kondo, “The Effect of a Grooved Hollow in a Fiber on Fabric Moisture and Heat Transport Properties”, J Text Inst, 1996, 87, 409-415. [8] H. J. Shm, K. A. Hong, and H. S. Kim, “Comparison of Hand and Thermal Properties of Woven Fabrics Made from Hollow and Regular Fibers”, J Korean Fiber Soc, 2000, 37, 280-285. [9] Y. Na and G. Cho, “Sound Absorption and Viscoelastic Property of Acoustical Automotive Nonwovens and Their Plasma Treatment”, Fiber Polym, 2010, 11, 782-789.

Page 920 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

The design of new Jacquard fabric Based on four-needle jacquard technology Md. Anwar Jahid1, Deng Zhongmin2 Wuhan textile university, P. R. China Correspondence to: Deng Zhongmin e-mail-hzcad@163.com

Abstract. The paper studies the new jacquard needles election technique which includes four-needle jacquard technique and compares the pattern knitting principle and lapping diagram with the traditional processďź&#x17D;It studies out the jacquard warping CAD system and develops the new warp knitted fabric with two colorďź&#x17D;It also studies out the law of developing aperture in new fabric with two color. The result shows that the face and back of jacquard guidance make both under lapping and over lapping through the new jacquard technology which makes the pattern structure very plentiful. The design project about aperture also multifarious and different pattern structure could form the same aperture. The rationality of pattern combination as well as the raw material density and product usage should be considered in design. The new jacquard needles election technique helps to enrich the pattern and design project. The new fabric with two colors is a great innovative solution.

Keywords: jacquard warp knitting technology, four- needles jacquard election technique, CAD design software, etc.

1. Introduction Jacquard warp knitting technology has rapidly developed in recent years. Digital jacquard technology includes aided-design technology representative of the jacquard CAD system and digital production technology represented by electronic jacquard machine[1] and the use of a new generation piezo jacquard system makes Jacquard warp knitting technologies are maturing and more detailed perfect product the successful application of the machine's increased 50% speed by piezo jacquard system and further development of the Jacquard principles. Market faster With the changes while electronics applications (such as warp knitting CAD systems) effectively shorten the production cycle, also contributed to the development of warp knitting technology. Four-needle technology not only provides more design options for fabric design pattern, while improving the production efficiency is important. The two-color jacquard fabric design provides a solution for further simplify the design process. Expect to improve and enrich organizational design on the basis of Jacquard warp knitting technology provides the enterprises to develop new products[2].The general aim of CAD system is to provide fast, easy designing and realistic simulation of structures on a computer screen to enable manufacturers to assess their designs before actual production[3].

2. New process of four-needle Jacquard Four-needle jacquard technology has 16 kinds of lapping combinations. The same can be formed of four different effects that thick organizations, sub-thick organization, thin organization and mesh organization[4]. Summarizes the basic stiches of four-needle jacquard technology in Figure 1:

(0)HHHH

(12) HHTT

(3)TTHH

(15) TTTT

(8) HHHT

(11) TTHT

(4) HHTH

(7) TTTH

Page 921 of 1108

(2)HTHH

(1)THHH

(14) HTTT

(13) THTT

(10) HTHT

(9) THHT

(6) HTTH

(5) THTH

Fig. 1: basic stitch of Four-needle jacquard technology

Float stitch is formed (9) THHT odd row did not nodules. Chain stitch is formed the four needle law is (1) THHH (8) HHHT (11) TTHT (13) THTT, the principle of jacquard unit to form a float nodule into the column but due to the starting point there are four different needle. THHH and THTT are even row nodules, HHHT and TTHT is odd row nodules because of different starting points the directions is opposite. Three kinds of thin organization (3) TTHH (5) THTH (10) HTHT, these three organizations across a pitch, (3) TTHH is an odd row before yarn lapping needle guide and needle back pad yarn are sliding to the left of the needle And THTH, HTHT is inclined in the opposite direction of the float organization, THTH is even course before the formation of two needle lapping nodule formed float odd row to the left, HTHT odd row in front of the needle to form a two- needle lapping nodules and even-row form the floating line toward the right. Thick organization (0) HHHH (2) HTHH (7) TTTH (15) TTTT, Such organizations form a three-needle lapping range, HHHH basic organizational odd row is not offset. HTHH and TTTH the odd row and even row from the offset but not change over the needle number and TTTT is offset while the odd row of a needle to the left, so the starting point for HHHH changed. Such Organization has thickness (4) HHTH (6) HTTH (12) HHTT (14) HTTT. Forming a four-needle lapping range and even row needle are offset to the left, odd row is not shifted, except that the front needle sliding. HHTH has no front needle sliding, HTTH course there is odd front needle sliding, HHTT course there is even before the needle sliding and HTTT odd row front needle has traversed. These 16 kinds of basic stitch organization can be combined with each other. It also can be combined yarn materials, color and luster with a variety of styles of fabric. Jacquard fabric compared with the traditional Jacquard pattern greatly increasing the variations.

3. The design process of new warp knitted Jacquard fabric 3.1. Two-color fabric design methods Design an appropriate pattern, a pattern may be embossed to achieve expression of the difference between concave and convex, two-color pattern effect can be achieved. Select a local pattern area (repeat) and then determine the pattern height and pattern width. Then determine the cycles of pattern according to the machine width.  Machine technology

Fig. 2: input parameters

To draw a pattern we need to set machine model is used MRSJF53/1/24, machine gauge is 24 and we need to know Horizontal density and Vertical density. We need to set Pattern height and pattern width, its calculation formula is: pattern height = vertical density × number of centimeters in a repeat in high direction, pattern width = Horizontal density × number of centimeters in a repeat in wide direction.

Page 922 of 1108

 Jacquard drafted pattern design Before designing the pattern need to give input parameters , here Ground is set to rectangular and set pattern layer parameters, yarn parameters, set Jacquard yarn layer color 11 or 12, here 11-layer is set for white, 12-layer set for blue then click OK and exit. Set the appropriate parameters

for the

four should have RT = 0, three for the corresponding RT = 0 two states. Note: The design process attention must be appropriate. Then Jacquard design can be carried out. Draw Jacquard drafted pattern there are three methods, the first one is to use the scan function

. Click to open and upload the bmp

format images then scanned in CAD systems. Using the selection function Circle the unit organization cycle then drawing the various parts of the Jacquard. After drawing click save. The second: Click to open and upload the bmp format images then click on the "jacquard Design" and then click on the "color clustering" and then click on the "take Bmp jacquard 2" the resulting picture will be saved to a folder. Re-open CAD software to save the last step file called Jacquard then click on "jacquard Design" and then use the color can be represented jacquard organizational structure, we can use these three methods for replace the design is complete "shows jacquard yarn"→" display jacquard "correct and then save. The third is direct input process parameters according to graphics rendering different organizations use different colors to represent different color Jacquard as shown fig. 3 and then use this organization function successively is relatively flexible.

to replace the filled such method

Fig. 3: jacquard renderings

 CAD simulation Click the function key this function can be visual the design to quickly see the effect of pattern and facilitate changes timely.  Jacquard save file. In operation there will be a variety of organizations for different regions can be filled a similar effect but the style is different than you can choose to save a different file name.

4. four-needle jacquard technology design different mesh organizations 4.1. The four-needle jacquard technology design simple mesh organizations The single thick organization, sub-thick organization connections make chain stitch to form a square mesh, mesh ramp. Thick organization (No. 4,6,12,14 organization) with the (8,9,11,13 different effect) chain stitch, sub- thick organization (0,2,7,15,) with the (8, 9, 11, 13 different effect) chain stitch. The following example is in Figure 4.

Fig. 4: simple mesh organizations

Page 923 of 1108

Figure7. First picture shows two adjacent vertical lines form two cells form a larger square mesh and large mesh between rows is staggered connective tissue for the second thick organization. Figure7. Second picture shows small mesh is formed together to form a slightly larger gap adjacent tissue in a single oblique mesh. Staggered mesh and adjacent to each other, for the thick connective organization.

4.2. The four-needle technology design complex mesh organizations Increase the number of matching color, this approach may be appropriate to increase the thickness of the connective organization make the connection more secure.

Fig. 5: complex mesh organizations

4.3. Design sense of color fabric The traditional two-color fabric mostly achieved by jacquard or multi-bar jacquard while the traditional twocolor Jacquard fabric consume more raw materials and low efficiency with respect to four-needle jacquard technology. Four-needle jacquard technology design Two color fabrics are more flexible to changes the organizational design, greater variety of organization, wider pattern with respect to the traditional two-color fabric comb. The process of simplification makes greatly improved production efficiency and application of new technologies to increase the value of color fabric products can better meet the market needs.

5. Conclusions Four-needle jacquard technique used to make flower design, reduced limitations of diverse pattern and reduced limitations of design flexibility and greater flower design can be achieve. from the perspective of design process four needle technology to achieve the needle sliding back before to enrich the organization, the same style of design has a variety of options to choose while raw materials more effectively saved compare with conventional four-needle technology and Four-needle jacquard design fabric is thinner. The CAD design software can greatly shorten the production cycle and convenient. But the design need to consider the connection problems and pay attention to the different stitch laws otherwise the design prone to leaking needle, attention to design and after checking make the appropriate organization. Monochromatic color fabric and mesh fabric design various programs based on the need to make the best choice, making mesh diverse organizational transformations by applying four needle technology, essentially four-needle technology can Different organizational design to achieve the same effect mesh. This pattern design process will provide the basis for enterprising.

6. References [1.] [2.] [3.] [4.]

Ng, zhou, and jiu. Merging digitization technology into jacquard fabric creation. In International association of socities of design research. 2007. The hong kong polytechnique university. G.-m. Jiang., Design & Technology of Warp Knitting Products. 2002, Beijing: China: Textile & Apparel Press. O.Goktepe and S. C. Harlock, Three dimensional computer modeling of warp knitted structres. Textile research journal, 2002. 72(3): p. 266-272. G. Shuai, Jacquard warp knitted Analysis and Application. Textile Science and Technology 2010.

Page 924 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

The effect of elastic strain on tribological characteristics of fabrics suitable for therapeutic gloves S. H. Nasir1+ and O. Troynikov1 1

School of Fashion and Textiles, RMIT University, 25 Dawson Street, Brunswick 3056, Australia.

Abstract. Therapeutic gloves are constructed to have a negative fit, where the size of the glove is 10% to 20% smaller than the actual size of the hand. Thus, the inner surface of these gloves is in full contact with the wearerâ&#x20AC;&#x2122;s skin with some amount of interface pressure generated to the hand. The fabric-skin interactions play an important role in maintaining the overall physiological comfort because sensorial properties of fabrics are closely related to their surface properties. The objective of this study is to investigate the influence of fabric elastic deformation on its surface characteristics under conditions similar to practical extension when therapeutic gloves are worn. Keywords: therapeutic gloves, compression garment, sensorial comfort, friction, roughness

1. Introduction Tight-fitting therapeutic gloves are designed to relieve pain, reduce swelling and improve hand function for arthritis patients, prevent or flatten developing hypertrophic scars on burned skin, maintain edema swelling and controlling the pain for lymphedema patients. Different fiber content, fabric density and structure influence the interface pressure generated by these gloves as well as the comfort level of the wearer [1]. Therapeutic gloves are constructed to have a negative fit, where the size of the glove is 10% to 20% smaller than the actual hand. Thus, the inner surfaces of these gloves are in full contact with the wearerâ&#x20AC;&#x2122;s skin with some amount of interface pressure generated to the hand. Due to the negative fit, textile fabric comprising the glove is stretched over the hand which leads to the change of the inner surface topography of the fabric. Since most manufacturers and health professionals recommend that therapeutic gloves are worn for up to eight hours a day, it is important that the gloves do not cause physiological discomfort to the wearer. The fabric-skin interactions play an important role in maintaining the overall physiological comfort because sensorial properties of fabrics are closely related to their surface properties [2]. The skin sensorial comfort characterizes the sensations when the fabrics are in direct mechanical contact with skin. These sensations may be pleasant when the fabric feels smooth or soft; or unpleasant if it is too stiff or scratchy. Fabrics with poor skin sensorial wear comfort may also lead to skin irritations when worn next to skin [3]. The friction between fabric and skin, and the surface roughness of fabric are the two components that are often considered in evaluation of fabric surface properties. It appears that numerous investigations have been focused on the tribological studies of sports compression garments and medical compression stockings. However there is limited research on the tribological attributes of the therapeutic gloves. Therefore, detailed investigation in this area is needed. As the fabric surface topography of therapeutic gloves changes during practical wear through practical extension, it is important to investigate how the topographical changes induced by varying elastic strain influence the friction between the fabric and the skin. Therefore surface characteristics and physical attributes of the fabric are important in determination of the overall aspects of fabric sensorial comfort. The objective of this study is to investigate and compare the surface properties of four knitted fabrics suitable for therapeutic gloves. _______________________________ +

Corresponding author. Tel.: +61 03 99259484

E-mail address: sitihana.nasir@rmit.edu.au

Page 925 of 1108

The study quantitatively examines and evaluates the effect of fabric elastic strains on the fabric surface characteristics under conditions similar to practical extension when therapeutic gloves are worn.

2. Experimental details The surface properties of the experimental fabrics were investigated in relaxed state (0% strain) and under elastic strains of 10% and 20%. These ranges of strains were determined based on the reduction factors which are commonly used for making therapeutic gloves. In most therapeutic gloves, the fabric is oriented so that the warp is in widthwise direction of the glove. However, there are some therapeutic gloves where the fabric is oriented so that the warp is in lengthwise direction of the glove. In this study, fabric samples were cut from commercial therapeutic gloves. They were tested in lengthwise direction and widthwise direction as shown in Fig. 1, irrespective of their warp and weft directions

Lengthwise direction

The standard deviation for coefficient of friction (MIU) and surface roughness mean deviation (SMD) of fabric samples was calculated to demonstrate the variation in their individual surface properties. The data of each group for MIU and SMD are presented using bar charts with error bars presenting standard deviation (at 95% confidence interval). One-way ANOVA was performed to determine statistical significance differences between the strains of each group of fabric being studied.

Widthwise direction

Fig. 1: Fabric test directions.

Fig. 2: Experimental setup when fabric sample stretched over the plate.

2.1. Materials and sample preparation Four commercial samples were selected for this study. One sample was cut from commercial fabric commonly used for making therapeutic gloves and the other three samples were cut from commercial therapeutic gloves. All samples were cut in the directions mentioned earlier which is shown in Fig 1. Each sample was tested in its relaxed state (0% strain) and two more elastic strains of 10% and 20%. A plate measuring 50 mm width, 50 mm length and 2 mm thickness was used to strain the fabric across it to apply experimental elastic strains in lengthwise and widthwise directions (Fig. 2). The fabrics were cut to the size that provides strains of 0%, 10% and 20% in both directions when placed and fixed on the plate. The experimental fabric samples were conditioned for 24 hours under standard conditions at 20Âą2Â°C and 65Âą2% relative humidity to eliminate the influence of atmospheric moisture content according to AS2001.11995 [4]. The fabric parameters such as number of wales and courses per unit length [5], fabric thickness [6], and fabric mass per unit area [7] were determined. All the experiments were carried out under similar standard conditions for conditioning of the fabrics.

2.2. Fabric surface properties Fabric surface properties were measured in next-to-skin side using Kawabata evaluation system, KESFB4A, Kato Tech Co. Ltd. Evaluation system. The MIU is calculated by averaging the output over the distance between 0 and 20 mm and is defined as:

Page 926 of 1108

đ?&#x2018;&#x20AC;đ?&#x2018;&#x20AC;đ?&#x2018;&#x20AC;đ?&#x2018;&#x20AC;đ?&#x2018;&#x20AC;đ?&#x2018;&#x20AC; =

đ??šđ??š đ?&#x2018; đ?&#x2018;

(1.1)

Where F is the frictional force and N is the sensor load. The constant N of 0.5N is a standard set load that mimics general pressure of garments against the skin and was used as a constant to reduce the number of variables being studied. The SMD is the value obtained by eliminating the low frequency waviness by filtering the measurement data with a high-pass filter, extracting the waviness profile of wave lengths greater than 1 mm (frequencies smaller than 1 Hz) and by numerically integrating over the absolute value of the distance moved from the standard position along the path taken by the sensor. It is expressed as:

đ?&#x2018;&#x2020;đ?&#x2018;&#x2020;đ?&#x2018;&#x2020;đ?&#x2018;&#x2020;đ?&#x2018;&#x2020;đ?&#x2018;&#x2020; = đ??żđ??ż

đ?&#x2018;&#x161;đ?&#x2018;&#x161;đ?&#x2018;&#x161;đ?&#x2018;&#x161;đ?&#x2018;&#x161;đ?&#x2018;&#x161;

đ??żđ??ż đ?&#x2018;&#x161;đ?&#x2018;&#x161;đ?&#x2018;&#x161;đ?&#x2018;&#x161;đ?&#x2018;&#x161;đ?&#x2018;&#x161;

â&#x2C6;Ť0

|đ?&#x2018;?đ?&#x2018;?0 â&#x2C6;&#x2019; đ?&#x2018;?đ?&#x2018;?|đ?&#x2018;&#x2018;đ?&#x2018;&#x2018; đ??żđ??ż

(1.2)

Where L max is the distance travelled by the sensor over the fabric, and Z 0 is the standard sensor position. The value of MIU, the mean deviation of the coefficient of friction (MMD), and the roughness signals (SMD in Âľm) are recorded individually and simultaneously for the â&#x20AC;&#x2DC;go and returnâ&#x20AC;&#x2122; stroke. Measurements were taken on each fabric sample three times in the lengthwise direction and then three times in the widthwise direction. The evaluation of the fabrics was carried out having particulars as follows. 1. The increase in value of MIU is interpreted as indication of the increasing friction between the fabric and the skin. 2. The increase in value of SMD is interpreted as an increase in the surface roughness and surface irregularities.

3. Results and discussion The physical properties of the experimental fabrics are summarized in Table 1. The results demonstrate that therapeutic glove fabrics widely vary in their physical properties. Fabric F2 had the highest mass per unit area and this is due to its construction which is laminated fabric. Fabric F1 and F3 had almost similar thickness and fabric mass per unit area, with slight difference in the number of wales and courses per unit length. Fabric F1 and F3 were made of sharkskin warp knitted structure which is commonly used for producing a fabric with high elastic modulus and smooth surface on its technical back. The long floats of yarn which were made by the back guide bar were exposed on the technical back providing smooth surface and high elastic modulus. The mean fabric thickness and mass per unit area for Fabric F4 were 0.77 mm and 270.67 g/m2 respectively. Fabric F4 was the lightest fabric among all the sample fabrics of this study. This is due to the lower stitch density of the fabric. It is expected that when fabric is strain under various elastic strains, fabric structure will change resulting in lower thickness and stitch density. This will lead to the considerable change in the fabric surface topography that will influence the surface characteristics relevant to human sensorial comfort. Table 1: Fabric physical properties (mean Âą standard deviation) Sample fabric code

Mean no. of wales per cm

Mean no. of courses per cm

Thickness mean (mm)

Fabric mass per unit area mean (g/m2)

0.84Âą0.006

356.00

2.12Âą0.05

612.00Âą0.139

F3 F4

31 16

55 28

0.86Âą 0.77Âą0.012

300.00 270.67Âą0.006

Mean value of MIU of the fabrics at different elastic strains, and in various directions and their corresponding p-values are plotted in Fig. 3. All four fabrics had relatively low MIU (below 0.30) which means that these fabrics would present a smooth sensation. The MIU of Fabric F2 was slightly higher than the other fabrics due to the mechanical raised finish of the fabric. This finish improves the physical bulk of the fabric, which will create more contact points between the fabric and the skin. Higher stitch density could also contribute to higher MIU between the fabrics. This can be seen between fabrics F1 and F3 where higher number of courses per cm was the reason of higher MIU at widthwise direction. The change in surface topography due to elastic strains would influence the surface characteristics relevant to human sensorial comfort. There was a clear difference observed in the change of the MIU under 20% strain in comparison to the relaxed state. The friction of fabrics under 10% and 20% strains becomes lower in

Page 927 of 1108

comparison to 0% strain, ranging between 0.2% and 1.4% at 10% strain and between 0.5% and 5.7% at 20% strain. This is due to fewer yarns available per surface area resulted in less contact points in the fabric surface and led to lower MIU. It was observed that significant differences exist between the values of MIU at different elastic strains for almost all fabrics except for fabric F3 at lengthwise direction. This indicated that elastic strains do influence the MIU of the fabrics. Surface roughness mean deviation (SMD) of four fabrics in relaxed and under various elastic strains is plotted in Fig. 4. The SMD of fabrics under strain become lower in comparison to relaxed state. Once again fabric F2 recorded higher SMD at lengthwise direction compared to the other fabrics. The reason for this would be due to the mechanical raised finish of the fabric. Furthermore, our results show that significant differences exist between the values of SMD at different elastic strains for all fabrics indicating that elastic strains influence the SMD of the fabrics.

Fig. 3: MIU of fabrics at various strains.

Fig. 4: SMD of fabrics at various strains.

4. Conclusion This study investigated the influence of fabric elastic strain on its surface characteristics under conditions similar to practical extension when therapeutic gloves are worn. The changes in fabric surface topography due to elastic strain significantly influence the surface characteristics of the fabrics. The loops became widened and there were larger spaces between the rows of wales and courses thus affecting the contact points between the fabric and the surface which can be observed in the MIU and SMD values. The fabrics under investigation showed significant differences in the values of MIU and SMD at different elastic strains for almost all fabrics. The results of this study also suggest that the fabric under strain may be perceived to be smoother when worn next-to-skin compared when it is in relaxed state. The findings of this study can provide guidelines in selecting material for therapeutic glove in terms of sensorial comfort. Future studies on moisture management properties of therapeutic glove fabric are also important to enhance the comfort characteristic of the gloves.

5. References [1] Yu, A., et al., The effect of pressure and fabrication of pressure therapy gloves on hand sensitivity and dexterity. Journal of Burn Care & Research, 2014. [2] Derler, S., U. Schrade, and L.C. Gerhardt, Tribology of human skin and mechanical skin equivalents in contact with textiles. Wear, 2007. 263(7â&#x20AC;&#x201C;12): p. 1112-1116. [3] Nawaz, N., O. Troynikov, and C. Watson, Evaluation of Surface Characteristics of Fabrics Suitable for Skin Layer of Firefightersâ&#x20AC;&#x2122; Protective Clothing. Physics Procedia, 2011. 22(0): p. 478-486. [4] Australian standard, Method of test for textiles; Conditioning procedures. 1995. [5] Australian standard, Method of test for textiles; Method 2.6 physical test; Determination of the number of wales and courses per unit length of knitted fabric. 2001. [6] Australian standard, Method of test for textiles; Method 2.15 physical test; Determination of thickness of textile fabrics. 1989. [7] Australian standard, Method of test for textiles; Physical test; Determination of mass per unit area and mass per unit length of fabrics. 1987.

Page 928 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

The effect of structural parameters on air permeability of bifacial fabrics Licheng Zhu 1, Maryam Naebe 1, Ian Blanchonette 2 and Xungai Wang 1, 3 + 1

Australian Future Fibres Research & Innovation Centre, Institute for Frontier Materials, Deakin University, Geelong, Australia 2 CSIRO Manufacturing, Geelong, Australia 3 School of Textile Science of Engineering, Wuhan Textile University, Wuhan, China

Abstract. In our recent study, a bifacial fabric with a knitted structure on one side and a woven structure on the other side of the fabric was designed and manufactured for apparel applications. The physical properties of the bifacial fabrics were previously reported. In this study, bifacial fabrics with two different weft densities of 18 and 22 picks per cm in the woven structure and loop lengths of 10 and 11 mm in the knitted structure were prepared, then the air permeability of the fabrics was analyzed. The extension of the analysis of variance techniques was applied to the data. It was found that there were highly significant differences in the air permeability of bifacial fabrics with different weft densities and loop lengths, while the interaction between these two factors was not statistically significant in their effects on the air permeability. Briefly, increasing loop length increased air permeability, while air permeability decreased with an increase in weft density. This finding shows that fabricâ&#x20AC;&#x2122;s parameters can be manipulated to affect air permeability of the bifacial fabrics, and further to influence comfort properties of such novel fabrics.

Keywords: bifacial fabric, weft density, loop length, fabric structure, air permeability.

1. Introduction Enhancing functionalities of fabrics has attracted considerable interest among textile researchers in recent years, and research on applications of functional fabrics has been extended to almost every area, such as industrial, domestic and apparel fields. In order to obtain these fabrics, researchers attempted to use various methods, from novel materials to chemical finishing. However, changing structures of fabrics without any harmful treatments is a preferred approach to improve fabric properties or achieve unique functionalities. Since woven and knitted fabrics have their own advantages and disadvantages, a combination of these two structures, so called co-woven-knitted (CWK), has been reported to improve the properties of traditional fabric structures. The applications of such fabric structures have been focused on protective materials [1] and reinforcement composites [2-6]. We have recently developed novel bifacial fabric structures for apparel applications [7]. The bifacial fabrics showed unique appearance: an obvious knitted structure on one side and a woven structure on the other side of the fabric. It had a smooth surface on the woven side and an uneven surface on the knitted side. The tensile properties of the fabrics showed two peaks in the stress-strain curves along both the warp and weft directions representing the breakage of the woven and knitted structures in bifacial fabrics, respectively. The fabrics also showed strong wear resistance, combining the performance of woven and knitted fabrics in abrasion resistance. Moreover, their thickness was less than that of the woven and knitted fabrics combined, and the fabric density was similar to the woven fabrics. Air permeability influences the process of transmission of heat and water vapour between skin and the environment. Therefore, it performs a vital role in comfort properties of fabrics for apparel use. For example, knitted fabrics usually have higher air permeability and feel warmer than woven fabrics.

Corresponding author. Tel.: + 61 3 5227 2894. E-mail address: xungai.wang@deakin.edu.au

Page 929 of 1108

Although there were several process and structural parameters affecting air permeability of novel bifacial fabrics (e.g. gauge of the bed on the knitting machine, gauge of the reed on the weaving machine, warp density, weft density, loop length), weft density and loop length of fabrics were selected in this study based on preliminary experiments and the condition of the modified machine for producing the bifacial fabrics. Since the modified machine was a combination of a weaving and a flat knitting machine, there must be good compatibility between gauges of the reed on the weaving machine and the bed on the flat knitting machine, which determines the warp density in the woven structure as well as the course density in the knitted structure when a desirable match of the reed and the bed is selected. Hence, weft density and loop length of the novel bifacial fabrics were selected as two parameters that can be changed at this stage. In order to obtain a better understanding of the relationship between structural parameters and properties of the bifacial fabrics, the effects of weft density, loop length and their interactions on air permeability were investigated. Significance tests were carried out to examine these effects and their interactions.

2. Experimental 2.1.

Design and material

Schematics of the novel bifacial fabrics are shown in Fig. 1. The fabrics were prepared with the same warp yarns of pure polyester (56 tex) and weft yarns of 35% acrylic and 65% wool (65 tex). All fabrics were manufactured on a modified weaving machine with loop lengths of 10 and 11 mm, 18 and 22 picks per centimetre for weft densities.

Fig. 1: Three dimensional sketches of the novel bifacial structure (warp yarns: green, weft yarns: red, loop yarns: grey). a) knitted side; b) woven side.

2.2.

Measurement

All fabrics were washed according to standard method ASTM D5489-14 [8] in the Kenmore Washer (Sears, USA) and conditioned at a standard condition (20Âą2 Ě&#x160;C and 65Âą2% relative humidity, ASTM D1776 - 08e1) [9] prior to testing. The air permeability of different fabrics was measured according to ASTM D737-04 (2012) [10] using the air permeability tester (Textest FX3300, Switzerland), with a test area of 5 cm2 and an air pressure of 98 Pa. Ten measurements were made on each side of the specimens, and the average of ten readings was reported.

2.3.

Statistical analysis

An extension of the analysis of variance was applied to the data using IBM SPSS Statistics 22. F-tests were used to evaluate the effect of weft density and loop length on fabric thickness and interactions between these two factors. Differences of weft density and loop length were determined using a p-value = 0.05. The post hoc multiple comparison using least significant difference (LSD) was carried out to compare all possible pairs of factor levels. Linear regression modelling was built to determine the effect of significant attributes.

3. Results and discussion Table 1 shows the details of loop length and weft density along with mean and standard deviation (S.D) of air permeability for each bifacial fabric. Since there was no statistically significant difference in air permeability on two sides of the bifacial fabrics (p>0.05), only the average results from two sides of the fabrics are presented here.

Page 930 of 1108

The analysis of variance of air permeability is summarized in Table 2. Both weft density and loop length had an independent effect on air permeability (p<0.001). The interaction between weft density and loop length was not significant (p=0.600>0.05). Table 1: Mean and standard deviation (S.D) of air permeability of bifacial fabrics. Fabric

Loop length (mm)

Weft density (picks per cm)

11 11 10 10

18 22 18 22

1 2 3 4

Air permeability (cm3/cm2/s) (mean ± S.D) 34.87 ± 2.57 29.72 ± 2.17 24.67 ± 2.07 19.04 ± 1.03

Fabric weight (g/m2) (mean ± S.D) 330 ± 6.7 400 ± 4.5 311 ± 3.6 383 ± 3.8

Table 2: Analysis of variance results for effects on air permeability of bifacial fabrics at two weft densities and loop lengths. Source Model Loop length Weft density Interaction

Sum of Squares 61394.609 2179.872 579.965 1.152

Degree of freedom 4 1 1 1

f-value 3688.518 523.857 139.374 0.277

p-value <0.001 <0.001 <0.001 0.600

The LSD results for air permeability are presented in Table 3. It can be found that there were significant differences in air permeability between all pairs (p<0.05). Table 3: LSD’s post hoc comparisons of bifacial fabrics (loop length, weft density) for the main effects on air permeability. Fabric (I) 1 (11,45)

Fabric (J) 2 (11,55) 3 (10,45) 4 (10,55) 2 (11,55) 3 (10,45) 4 (10,55) 3 (10,45) 4 (10,55) *The mean difference is significant at the 0.05 level.

Mean difference (I-J) 5.145* 10.200* 15.825* 5.055* 10.680* 5.625*

p-value <0.001 <0.001 <0.001 <0.001 <0.001 <0.001

The multiple regression modelling of the air permeability value included weft density and loop length, and the final model was in the form of (R2=0.897): Air permeability value = constant + β 1 × weft density + β 2 × loop length, (1) Where β 1 and β 2 are the coefficients of the model as shown in the Table 4. Table 4: A list of the regression coefficients and statistical significance of included terms in the final model for air permeability values of bifacial fabrics. β

Standard Error

t-value

p-value

(Constant)

-55.623

5.285

-10.525

<0.001

Loop length

10.440

0.454

22.996

<0.001

Weft density

-0.538

0.045

-11.862

<0.001

Adjustment to final model

The results showed that bifacial fabrics with a higher weft density had a lower air permeability, which was similar to the performance of conventional woven fabrics. Adding the number of weft yarns in a unit length and reducing the space or distance between weft yarns increased weft density. This, therefore, decreased the air movement through fabrics. Increasing the loop length in a knitted fabric increased the course or wale density, resulting in a looser structure with higher air permeability. However, the course density and wale density in the knitted structure of bifacial fabrics did not change when the loop length increased, because the loop yarns were fixed by the warp

Page 931 of 1108

and weft yarns in the woven part of bifacial fabric structures. It was observed that thickness of bifacial fabrics increased when loop length increased, which increased the softness of the knitted side of bifacial fabrics. Air permeability is a parameter used to evaluate the ability of air transferring through fabrics, which is presented as the amount of air transferring through fabrics in a unit area per second. Air flows through a fabric when there is an air pressure gradient between two sides of the fabric, and it is affected by the fabric porosity. It should be noted that the fabric porosity depends on fabric structures, weft density in the woven structure and loop length in the knitted structure of bifacial fabrics. Specifically, increasing weft density or decreasing loop length will reduce size of pores in bifacial fabrics and thus negatively affect the air permeability when the fabrics are prepared using the same materials without treatments.

4. Conclusion There were highly significant differences in the air permeability of bifacial fabrics with different weft densities and loop lengths, although the interaction of these two factors was not statistically significant. Increasing the loop length increased air permeability, but air permeability decreased with an increase in weft density. This finding shows that fabric parameters can be manipulated to affect air permeability of the bifacial fabrics, and further to influence comfort properties of such novel fabrics.

5. References [1] Chen, H-C, Lee, K-C and Lin, J-H. Electromagnetic and electrostatic shielding properties of co-weaving-knitting fabrics reinforced composites. Composites Part A: Applied Science and Manufacturing 2004; 35(11): 1249-1256. [2] Xu, Y, Yuan, X and Hu, H. A uniform multilayer weft insertion co-woven-knitted structure and its produce equipment. Patent 200810039656.9, China, 2008. [3] Xu, Y, Yuan, X and Hu, H. A co-woven-knitted structure and its produce equipment. Patent 200920039593.7, China, 2010. [4] Xu, Y, Yuan, X and Hu, H. Tensile properties of co-woven-knitted fabric with basalt fibre reinforced composites. Journal of Textile Research 2011; 32(2): 48-52. [5] Ma, P, Hu, H, Zhang, Y, Sun, B and Gu, B. Frequency features of co-woven-knitted fabric (CWKF) composite under tension at various strain rates. Composites Part A: Applied Science and Manufacturing 2011; 42(5): 446-452. [6] Xu, Y, Hu, H and Yuan, X. Geometrical analysis of co-woven-knitted preform for composite reinforcement. Journal of The Textile Institute 2011; 102(5): 405-418. [7] Zhu, L, Naebe, M, Blanchonette, I & Wang, X. Physical properties of novel co-woven-knitted fabrics. The 89th Textile Institute World Conference; Wuhan, China, 2-6 November 2014. [8] ASTM D5489-14: 2014. Standard guide for care symbols for care instructions on textile products. [9] ASTM D1776-08e1: 2008. Standard practice for conditioning and testing textiles. [10] ASTM D737-04: 2012. Standard test method for air permeability of textile fabrics.

Page 932 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

The interaction between UV light and fibres with different crosssectional shapes within the yarns Yao Yu 1, Christopher Hurren 1, Keith Millington 2 Lu Sun 1, 3 and Xungai Wang 1, 3 + 1

Australian Future Fibres Research & Innovation Centre, Institute for Frontier Materials, Deakin University, Geelong, Australia 2 CSIRO Materials Science and Engineering, Geelong Technology Precinct, Deakin University, Australia 3 School of Textile Science and Engineering, Wuhan Textile University, Wuhan, China

Abstract. High ultraviolet radiation (UVR) protection from a textile structure alone will reduce or remove the need for chemical UV absorber usage. Therefore, research on UVR protection of fibres, yarns and fabrics themselves is necessary for exploiting the capacity of UV absorption, reflectance, scattering and transmittance of textiles. This study was to maximise UVR protection of textiles using fibre selection and structure alone by setting theoretical models. Fibre type, refractive index, fibre cross-sectional shape, fibre diameter, porosity and fibre layers were involved in the model. Under the assumption that the fibres were from the same material, and the fibre mass, cross-sectional area, and the areal coverage were kept constant, three shapes (circle, triangle, and rectangle) were studied based on the models to investigate the best shape to provide the highest UV protection. Several situations were discussed, including a single fibre, a row of fibres, several layers of fibres with the same thickness, a single yarn and a row of yarns (the yarns being arranged parallel in a row is the simplest structure form of fabrics). Keywords: theoretical model, fibre diameter, fibre cross-sectional shape, UV protection.

1. Introduction Textiles are widely used to make UV protective products, hence to improve the UV protection of textiles is essential. With the development of technological innovation, fabrics achieve UVR protection by two main ways: chemical treatments and physical structure. However, there are some potential hazards from the chemical treatments. If UV protection of textiles by the structure of the fabric alone is sufficient, chemical usage would be reduced or eliminated. The physical method of protection is achieved by the placement of fibres and yarns within a fabric structure to maximise UV protection. Parameters that influence physical protection include fibre type, fibre diameter, the arrangement of fibres within the yarns, yarn linear density, yarn twist, fabric thickness, mass cover factor and structure (the arrangement of yarns). There is a hypothesis that fibre cross-sectional shapes would have effect on UV absorption, reflectance, scattering and transmittance of textiles. Theoretical models are helpful to analyse the interaction between UV light and textiles. In this work three specific fibre shapes (circle, triangle, and rectangle) were modelled to determine what effect fibre cross-sectional structure would have on UV protection. The situations for a single fibre and a bundle of fibres with fixed fibre layers (thickness) have been discussed in the published paper [1]. Based on the fixed mass model in the previous study [2], this work will discuss the situations for a single yarn and a row of yarns. The aim is to determine the best shape for the fibres within the yarns in order to improve UV protection by structure alone, and to investigate how the differences in the UV protective properties caused by fibre cross-sectional shapes are transferred from the fibre level to the yarn level.

2. Model description 2.1.

Assumptions

An optical model for a single yarn simulating the interaction of UV light and fibres was developed based on the fibre model (a bundle of fibres with fixed mass) [2]. A two-dimensional optical process was simplified +

Corresponding author. Tel.: + 61 3 52272894 (X. Wang) E-mail address: xungai.wang@deakin.edu.au

Page 933 of 1108

in the model at the fibre cross section. According to the yarn cross section in the references [3, 4pp.198-193], a single yarn was assumed to be as a cylinder that was filled with a bundle of fibres with a certain number of layers. The effect of yarn twist angle (Îł, gamma) was assumed to be transferred into the included angle between the incidence light direction and the yarn axis. The incidence light energy was divided into the components of parallel and perpendicular to the yarn axis, and the component of incidence energy with perpendicular direction (Ă&#x2014; sinÎł). In Fig. 1, x-y plane was the plane of incidence, z axis was the yarn axis direction. In this case, based on the range of twist for knitted fabrics (200 T/m to 800 T/m), the range of sinÎł was 0.128 to 0.460. When the yarn was without twist, the incident light energy was assumed to be 1.

Fig. 1: Optical model for a bundle of fibres with a fixed mass (two-dimensional view) [2].

The light interaction between two adjacent yarns and the effect of yarn twist were discussed at the yarn level in this work. A light ray after being transmitted and reflected from one yarn could reach its neighbouring yarn. After the analysis based on both optical and geometrical knowledge, and calculation using MatlabÂŽ software, there were two combined intervals of the incidence angle (Î¸) range 0â&#x2030;¤Î¸â&#x2030;¤0.429495 and 0.785398â&#x2030;¤Î¸â&#x2030;¤1.5708. In these ranges, both the reflection and refraction from one yarn could cause the interaction to its adjacent yarns. The percentage of reflectance and transmittance through this yarn was acquired for the calculation of the interactive energy.

2.2.

Calculations

The calculation methods for this work are the same as the fixed fibre mass model [2]. After one, two and three internal reflections and refractions, the energy summation of all the reflections and transmissions was obtained as the interactive energy. The interactive energy was assumed to impact an adjacent yarn. Hence, for any yarn in a row, the reflected and transmitted light from it should depend on the summation of incident and interactive energy, rather than only incident energy (=1). Fibre volume percentage (100-Îľ)% in a single yarn determines the number of fibres within the yarn, so that it controls the fibre layers. It was assumed that all the space was occupied by air instead of fibres, and the air volume percentage (porosity) was Îľ%. Since the model assumed the fibres were packed as filaments, combining with the packing fraction equation from Petrulisâ&#x20AC;&#x2122; study [5], fibre volume percentages were calculated from Equation 1.1.

(100 â&#x2C6;&#x2019; đ?&#x153;&#x20AC;đ?&#x153;&#x20AC;)% =

đ?&#x2018;&#x2030;đ?&#x2018;&#x2030;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C; đ?&#x2018;&#x2030;đ?&#x2018;&#x2030;đ?&#x2018;Śđ?&#x2018;Śđ?&#x2018;Śđ?&#x2018;Śđ?&#x2018;Śđ?&#x2018;Śđ?&#x2018;Śđ?&#x2018;Ś

đ?&#x153;&#x17D;đ?&#x153;&#x17D;đ?&#x2018;Śđ?&#x2018;Śđ?&#x2018;Śđ?&#x2018;Śđ?&#x2018;Śđ?&#x2018;Śđ?&#x2018;Śđ?&#x2018;Ś

Ă&#x2014; 100% = đ?&#x203A;żđ?&#x203A;ż

đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;

Ă&#x2014; 100%

(1.1)

where, m fibre was the total mass of fibres in volume V fibre (V fibre =m fibre /Î´ fibre ), m yarn was the total mass of yarn in volume V yarn (V yarn =m yarn /Ď&#x192; yarn ), and m fibre = m yarn for a yarn of fixed fibre length [5]. Ď&#x192; yarn was the yarn bulk density, and Î´ fibre was the specific gravity of the fibre. Determining the number of fibre layers in a single yarn was essential to determine the number of reflections from following fibre layers.

đ?&#x2018;&#x203A;đ?&#x2018;&#x203A;đ?&#x2018;&#x203A;đ?&#x2018;&#x203A;đ?&#x2018;&#x203A;đ?&#x2018;&#x203A;đ?&#x2018;&#x203A;đ?&#x2018;&#x203A;đ?&#x2018;&#x203A;đ?&#x2018;&#x203A;đ?&#x2018;&#x203A;đ?&#x2018;&#x203A; đ?&#x2018;&#x153;đ?&#x2018;&#x153;đ?&#x2018;&#x153;đ?&#x2018;&#x153; đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C; =

đ??´đ??´đ?&#x2018;Śđ?&#x2018;Śđ?&#x2018;Śđ?&#x2018;Śđ?&#x2018;Śđ?&#x2018;Śđ?&#x2018;Śđ?&#x2018;Ś â&#x2C6;&#x2122;(100â&#x2C6;&#x2019;đ?&#x153;&#x20AC;đ?&#x153;&#x20AC;)% đ??´đ??´đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;

(1.2)

where, the cross-sectional area of yarn was A yarn =ÂźÂˇĎ&#x20AC;ÂˇD yarn 2, the cross-sectional area of single fibre was A fibre =Ď&#x20AC;/4Âˇd fibre 2, and D yarn and d fibre are the diameters of a single yarn and fibre. D yarn =0.03568Ă&#x2014;â&#x2C6;&#x161;(T t /Ď&#x192; yarn )

Page 934 of 1108

(mm) [4 pp.178], where T t was yarn linear density (tex) and σ yarn was mass per volume of the yarn (the yarn bulk density, g/cm3). Since a single yarn was composed of a mixture of fibres and air, the refractive index of the yarn should be recalculated with refractive indexes of both fibre and air, using the Heller equation [6].

3. Results and discussion The effect of cross-sectional shape in a row of yarns on UV protection is important for UV protective fabric design, since a row of yarns is the simplest arrangement for the yarns, and a fabric is made up from a regular arrangement of yarns. It was assumed that the filaments were all made from one material, so it meant that specific gravity, refractive index, and transmittance index at a certain wavelength were constant. The filament mass, length and fibre cross-sectional area were assumed constant. Also, the areal coverage (areal coverage of 2r* for single fibre) was constant (Fig. 2 (a)). Fibre cross-sectional shapes (circle, triangle and rectangle) were varied to investigate which shape had the best UV protection. The value for calculation is shown in Table 1.

(a)

(b)

Fig. 2: (a) a row of fibres with different cross-sectional shapes (keeping fibre type, mass, area, areal coverage constant) [1]; (b) a row of yarns composed by different cross-sectional shape fibres (keeping yarn diameter, number of yarns and areal coverage constant). Table 1: Parameters for fibres with different shapes [1]. Shape

r* (μm)

b* (μm)

Area

Circle

2r*

πr*2

0.9

1.54

Triangle

πr

0.9

1.54

Rectangle

½π2r*

πr*2

0.9

1.54

Notes: r* is a half of the x-length, b* is the y-length of the of the fibre cross-sectional shape, Area is cross-sectional area, a is the transmittance index, and m equals to the refractive index of fibre (because n air = 1).

In Fig. 2, the three fibre cross-sectional shapes had the same fibre type, mass, cross-sectional area, and areal coverage, and they were assumed to comprise a single yarn with the same yarn diameter. As shown in Fig. 3(a), the different fibre cross-sectional shapes presented significant differences in UV absorption, transmittance and reflectance at a single yarn level. The transmittance differences of (circle-triangle) and (rectangle-triangle) were 0.33 and 0.27, respectively. For a single yarn, the triangular shapes were superior to the other shapes examined, and the circular one provided the lowest UV protection.

Page 935 of 1108

Fig. 3: Comparison of UV protection of yarns with different fibre cross-sections: (a) a single yarn; (b) a row of yarns.

In contrast, as shown in Fig. 3(b), under the situation: a row of yarns with the same areal coverage (100%), same number of yarns and same yarn diameter made from fibres with each of the cross-sectional shapes, the difference in transmittance was negligible. After calculation, the transmittance difference of (circle-triangle) and (rectangle-triangle) were 0.08 and 0.06 respectively. The triangular shape still provided the higher UV protection of the three fibre cross-sectional shapes considered, however the differences in UV properties among the three shapes at the level of a row of yarns tended to be much smaller than that for a single yarn level. Previous work [1] showed that at the fibre level, different cross-sectional shapes presented differences in UV protection properties of fibres. In addition, the differences caused by fibre cross-sectional shapes increased in UV protection from the situation of a single fibre to the situation of a single yarn. However, from this work, it was found that the differences caused by fibre cross-sectional shapes decreased in UV protection when transitioning from a single yarn to a row of yarns. This was due to an increased complexity of the model caused by factors including yarn twist and the light interaction between two adjacent yarns. The impact on UV protection of both twist and light interaction between yarns is significantly higher than the effect of fibre crosssectional shape. This causes the UV protection effect of cross sectional shape to lose its significance when in a layer of yarns. Yarns arranged parallel in a row are the simplest structure form of fabrics. For fabrics with more complex structures, the various arrangements of yarns will play an important role for the UV protection of fabrics. Therefore, it can be inferred that the differences in the UV protection caused by cross-sectional shapes would be negligible at the fabric level.

4. Conclusion Based on the predictive results from the shape model and yarn model, differences caused by fibre crosssectional shapes were enlarged in the UV protection from a single fibre to a single yarn (a bundle of fibres with a certain number of fibre layers). However, when a row of yarns was studied, the differences caused by fibre cross-sectional shapes were decreased much in the UV protection of yarns. Therefore, the fibre crosssectional shapes would be hardly cause the differences in the UV protection at the fabric level.

5. References [1] YU, Y., HURREN, C., MILLINGTON, K., SUN, L. & WANG, X. 2015. UV protection performance of textiles affected by fiber cross-sectional shape. Textile Research Journal. Published online: 24 March 2015, doi: 10.1177/0040517515578335. [2] YU, Y., HURREN, C., SUN, L., MILLINGTON, K. R. & WANG, X. 2015. Effects of fibre parameters on the ultraviolet protection of fibre assemblies. The Journal of Textile Institute. Published online: 23 June 2015, doi: http://dx.doi.org/10.1080/00405000.2015.1054144. [3] YANG, K., TAO, X., XU, B. & LAM, J. 2007. Structure and Properties of Low Twist Short-staple Singles Ring Spun Yarns. Textile Research Journal, 77, 675-685. [4] YAO, M. 2009. Textile Material (The third edition), Beijing, China, China Textile & Apparel Press, 333-363. [5] PETRULIS, D. & PETRULYTE, S. 2003. Properties of close packing of filaments in yarn. Fibres & Textiles in Eastern Europe, 11, 16-20. [6] TASIC, A. Z., DJORDJEVIC, B. D., GROZDANIC, D. K. & RADOJKOVIC, N. 1992. Use of mixing rules in predicting refractive indexes and specific refractivities for some binary liquid mixtures. Journal of Chemical & Engineering Data, 37, 310-313.

Page 936 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

The life test and analysis of fabric switch Meiling Zhang1, Mengnan Gu1 +, Lijing Yuan2 and Lei Xu1 + 1 2

School of Textile,Tianjin Polytechnic University, Tianjin, 300387, China.

National clothing quality inspection & supervision center, Tianjin, 300384, China.

Abstract. This paper establishes the 3D through-interlocking structures for realizing the fabric switches. Life for the fabric switch is an important performance which is a new study field. The 17 kinds of fabric switch samples are woven by changing three kinds of structural parameters such as the key width, the conductive yarn roots of the lower layer of the key and the yarn fineness of the support part. Using the composite life tester, the life of the fabric switches is measured. Pressing the key for 24000 times, the closing rate and bouncing rate of each key are worked out. It can be concluded that when the weft conductive yarns for the key is 4 roots, the key width is 6 to 8 cycles in the weft direction, and the yarn fineness of the support part is 50tex,80tex or 110tex, the closing rate of key can keep more than 98%.

Keywords: fabric switch, life, closing rate, bouncing rate.

1. Introduction Taking advantage of the characteristics of fabric structure and the effective distribution of conductive yarns, the basic function of fabric switch is achieved. In order to realize it, first every layer is weaved separately, and then multilayer must be combined together. It is beneficial to maintain the switchâ&#x20AC;&#x2122;s performance, however it is time consuming and costly[1]. Second, some metal accessories are woven into the fabric, whereas the switchâ&#x20AC;&#x2122;s flexibility will be highly affected[2]. Third, two layers or less than two layers are adopted. This type of switch is light and thin. Yet the security of the switch will be a big problem[3]. In this paper the throughinterlocking fabric switch is adopted [4]. Life prediction of cotton woven fabric was discussed by Xian Zhang in 2013[5]. The above paper researched the fabric life, but life research is still less for the fabric switch. So this paper tested and optimized its life.

2. Materials and structure 2.1. Materials Stainless steel metal filament is used as the conductive material. The technical parameters are showed in Table 1. Polyester staple is used as the insulating yarn. The technical parameters are listed in Table 2.

Corresponding author. Tel.: + 86-13820406285. E-mail address: zhangmeiling@tjpu.edu.cn.

Page 937 of 1108

Table 1: Technical parameters of metal wire Yarn diameter(mm） 0.090

Tolerance

Strength of extension

（mm）

（N/mm2）

±0.003

878

Tensile elongation（%）

Electrical resistivity （Ω/m）

100.23

Table 2: Technical parameters of polyester staple Material

Fineness（tex）

Breaking strength

Elastic recovery(%)

Twist（twist/10cm）

0.67

（cN） Polyester

2340.6

2.2. Through-interlocking structure Through-interlocking structure is shown in Fig.1. It includes the support part and the orifice part[4]. The orifice part includes the upper conductive layer and the lower conductive layer. The support part can keep the upper and lower conductive layer of the orifice part to be separated when no press. When pressed by a suitable force, the upper and lower conductive layer can contact with each other and the circuit will be conducted.

Fig.1: Through-interlocking structure

2.3. Weaving process The fabric is woven by using semi-automatic sample loom. Straight arrangement is adopted. The first part and the second part draws in 9~16 harness and 1~8 harness, respectively. The reed number is 65. Every 8 warps were fed into a dent gap.

3. Experiment and testing Connection pressure is one of the important performance index for fabric switch. Using the single factor analysis, it can be concluded that three factors are significant such as the key width named A, the conductive yarn roots of the lower layer of the key named B and the yarn fineness of the support part named C. According

Page 938 of 1108

to the design principle of Box-Behnken, three factors three levels experiments are designed. 17 kinds of experiments are designed. If the upper conductive layer can contact with the lower conductive layer at a fixed pressure, the closing times can automatically add one time, otherwise, the closing times don’t add. The closing times is merely pressed times multiple of the closing rate. At a fixed pressure, the upper conductive layer can contact with the lower conductive layer well. When the pressure is released, the upper conductive layer can leave the lower conductive layer well. Then the bouncing times are added. The bouncing times are merely the closing times multiple of the bouncing rate. In experiment, sample is first tested 2500 times, and the data is recorded. Then the second 2500 times are tested until it is 24000 times. 17 kinds of samples are tested for 24000 times or more. The closing times, the closing rate, the bouncing times and the bouncing rate of each kind of sample are worked out. The experiments and the testing results are shown in Table 3. Table 3: 17 kinds of experiments scheme Sample A(number)

B(number)

C(tex)

Closing times

Closing rate

Bouncing times

Bouncing rate（%）

（%） 1

24000

100

5406

22.52

5116

23.31

5116

100

23578

98.24

23576

99.99

110

20087

83.69

20087

100

15899

66.24

15898

99.99

Failure

14560

60.66

14560

100

110

Failure

21231

88.46

21228

99.99

25678

98.76

25669

98.72

110

13656

56.90

13642

99.98

110

19960

83.16

19856

99.47

23554

98.14

23551

99.98

23697

98.73

23694

99.98

23587

98.15

23546

99.93

23539

98.07

23431

99.54

13566

56.52

13562

99.99

The key width named A refers to cycle numbers of the first part woven. The key width is changed through cycle number of the first part in the weaving process. When the first part is woven and cycled for six times, the key width is noted as 6. The cycle number is 7 which shows that the cycle number of the first part is seven times. The meaning of 8 is the same. The conductive yarn roots of the lower layer of the key named B is changed in order to alter the interlacing point contacting with each other between the warp metal filament and the weft metal filament in the orifice part. When the number of the warp metal filament of the first part remains the same, the more the number of the weft metal filament, the more the interlacing point of conductive material in the lower conductive layer. Three kinds of conductive yarn roots are altered. For example, the weft “56, 61” represent the number 2. The weft “53, 56, 61, 64” represent the number 4. The weft “48, 53, 56, 61, 64, 69” represent the number 6.

Page 939 of 1108

The yarn fineness of the support part named C is changed such as the third and the fourth weft in the through-interlocking structure.

4. Results and analysis The closing rate of the sample 1 was always 100%. Bouncing rate continued to decrease. This showed that the upper and lower conductive layer of fabric switch adhered to each other so that not to bounce off after the 5406th times. The data of sample 2, 4, 5 and 7 showed that the key can bounce off in a certain number of times of closing. The bouncing rate is good. However, after that times, the upper and the lower conductive layer wouldn’t contact with each other. The closing rate is low, this is mainly because the metal filaments of the upper and lower conductive layer were embedded into the insulating yarn. The sample 9, 11, 12 and 17 stop testing halfway because they have not closed completely before the end. The sample 6 and 8 showed that they almost didn’t work. The closing rate and bounce rate of sample 3, 10, 13, 14, 15 and 16 are both high. In the processing of testing, some error occur by chance. If these accidental error can be avoided, the life of fabric switch will be greatly improved. About these samples, the key width named A and the yarn fineness of the support part named C are not completely the same. However, the conductive yarn roots of the lower layer of the key are the same, 4 weft metal filaments were woven into the fabric switch, such as “53, 56, 61, 64” weft. The bouncing rate and the closing rate of these samples are more than 98%.

5. Conclusion It was known to us that a few samples have no life at all. Some samples were easy to be embedded into the insulating yarn because the number of the weft metal filaments was less. The conductive yarn of the upper and lower layer couldn’t easily contact with each other. However, when the weft metal filaments were 4 roots, the closing rate and bouncing rate of fabric switch would reach more than 98% when pressed 24000 times. This work would help the switch fabric to further research and development.

6. References [1] Li Guo.A kind of flexible fabric keyboard[P].Hubei:CN102478964A,2012-05-30. [2] Ridao G M, Garcia U D,Escudero G J, et al.Torsion and/or Tension and/or Pressure Textile Sensor: EP,2040053(A1) [p].2009-03-05. [3] Qiao Li,Xin Ding.The analysis of fabric switch[J].Journal of Donghua University(Natural Science Edition),2009(35):161-166. [4] Meiling Zhang.The optimization and prediction of three dimensional structure and parameter of flexible fabric keyboard switch[D].Tianjin:Tianjin Polytechnic University, 2011. [5] Xian Zhang,Yanrong Wang.Life prediction of purified cotton woven[J].Journal of Textile Research, 2013, 34(3): 40-43.

Acknowledge: The financial support for this investigation given by Tianjin Research Program of Application Foundation and Advanced Technology(13JCYBJC16800), China National Funds for Distinguished Young Scientists(51303131), China National Funds for Distinguished Young Scientists(61307094) and CSC is gratefully acknowledged. At the same time, I honestly acknowledge Deakin University’s assistance for my visiting appointment.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

The Research on Feature Recognition of Raw Cotton Defects and Impurities based on Image Processing Technology ZhangYong1, Md. Anwar Jahid1 and Deng Zhongmin1 Wuhan textile university, P. R. China Correspondence to: Deng Zhongmin e-mail-hzcad@163.com

Abstract. The main research content of this paper is the computer detection and feature recognition of raw cotton defects and impurities, the paper studies and analysis the method of computer image processing technology and completes the task of detection and identification about these raw cotton defects and impurities by testing and debugging many detection algorithms. Then the paper puts forward a kind of adaptive threshold image segmentation algorithm which based on Mean Shift by experimental measurement and analysis and in the part of profile extracting about flaw and impurity it introduces a scanning method based on morphological and makes the break point in the contour line link. This paper extracts four kinds of shape features of images and analysis their correlation and ultimately determines their matching method and finish the task of detection and identification about these raw cotton defects and impurities. Key words: Raw Cotton Defects and Impurities, Image Segmentation, Edge Detection, Image Recognition, etc.

1. Introduction Cotton is the main natural fiber who solves the mankind wearer needs. china is the largest country for global cotton consumption and trade [1] .The harmful defects and impurities of Cotton including sterile seeds, plastics, seeds soft skin with fiber SCN, stiff sheets, naps and chemical fiber, silk, hair, plastic rope, hemp and colored fibers. Most of the cotton spinning enterprises is still using manual sorting and removing methods for raw cotton impurities and defects need to rely on the workers one by one pick split bales its heavy workload, time-consuming, inefficient and influence human factors. Generally manual sorting of cotton impurity and defects requires larger space thus increased the financial investment and workers suffer from the high-intensity [2]. The current cotton inspection mostly used system is HVI (High Volume Instrument) high capacity instrument for rapid detection and its standardization degree is relatively high. it can analyze the data based on cotton condition and comprehensive evaluation of cotton fiber spinning performance [3]. Computer digital image processing means converts the image into a digital format and use the computer to process it. It is rich in content including image distortion, image compression, image segmentation, shape description, morphological analysis, Fourier analysis technique image, color image processing, edge extraction [4]. Using digital image processing techniques to detect defects and impurities in raw cotton it also can improve the accuracy rate, improve the test efficiency but also reduce the workload of workers, the release of surplus labor and factory space and enhance practical benefit.

2. The pretreatment of raw cotton images 2.1. Image collections of raw cotton impurities and defects After picking of raw cotton then acquisition and processing was done for identifying defects. Discomfort due to human touch and stacked prone to dry the "three wire" (such as hair, chemical fiber, hemp, feathers, plastic rope and cloth and some non-cotton impurities) and it is difficult to remove completely after the machine ginning. Under normal circumstances color format images collected from camera and the threedimensional data storage making computer color image will occupy a large amount of data and the image processing speed weaken the system but the detection process of raw cotton impurities color concept is involves so in order to improve the processing speed of the computer you need a color image into a gray-

Page 941 of 1108

scale

image.

2.2. Histogram Enhancement Image histogram is the most basic and important characterization of gray image it reflect the appears of each frequency and measure the number of pixel level for each gray image. In the histogram the abscissa represents the gray scale, the ordinate represents the frequency of the gray-scale and histogram clearly illustrates the distribution of each level of gray image [5]. After a predetermined histogram image is a clearer, enhanced contrast, highlighting the objectives of gray-scale image and facilitate subsequent image processing.

3. Cotton image segmentation technology In this paper the Mean-Shift adaptive thresholding method is used. This concept was first proposed by Fukunaga in 1975. Mean-shift algorithm it has own unique advantages. Mean-shift algorithm movement is relatively smooth and it can promote the image processing speed segmentation operations to achieve clear and stable image target area information needed for the description and analysis. This paper based on Mean-shift adaptive threshold selection segmentation algorithm compared to different threshold segmentation Mean-shift algorithm can segment the target raw cotton image [6]. Fig.4. shows the three types of impurities segmentation effects first is raw cotton image, the second is the use of Mean shift segmentation algorithm, third is acts between Otsu. We can clearly see the advantages of segmentation of the adopted subject. A series of experiment we have done by using Otsu Segmentation method to find the optimal threshold value to facilitate.

Fig.1: different types of impurities segmentation effects

4. Image Identification 4.1. Feature Extractions Feature extraction is a decisive prerequisite for image analysis and recognition. Image characteristic values reflect the goals contained in the image and it represents a lot of useful information about its performance in the graphical representation of the target value. Target image Contents is different means its features also different there are four commonly used image features are: shape features, color characteristics, spatial relations and texture characteristics. Texture which describes the structure of the image, gray scale space it is within a region of space, distribution of image pixels with a certain degree. At present the scientific definition of a uniform texture is not an accurate statement. Special Texture extraction methods typically: statistical method (gray scale difference and run-length statistical method), auto-correlation function, spectral method and the joint probability matrix method [7].

4.2 features identification and Classification The subject is selected with fiber SCN, stiff piece of cotton, Neps class, shell leaf impurities, plastics and hair line type to do the experiment, analysis and classification. Through these various shapes of feature values extracted defects, impurity and the shape of each feature correlation analysis parameters. Eccentricity, height and width ratio, rectangle degree, circumference area use of these parameters we can identify raw cotton impurities and defects. height and width ratio - due to impurities cotton are varied and their shapes are not the same may be approximately elliptical, irregular, or curved but the concept of the height and width ratio is represented the value of r is less than a certain value then the area is elongated. Experimental data shown in the Table 1 and Table 2:

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Table 1: fiber seed coat, stiff cotton sheets and Neps (filament mass) defects with height and width ratio fiber seed coat

Nep (filament mass)

stiff Cotton sheet

0.9013

0.8041

0.6302

0.8011

0.8842

0.9217

0.8499

0.5537

0.8417

0.7498

0.8346

0.8482

0.6398

0.6472

0.8796

0.8799

0.8960

0.7366

0.6690

0.9100

0.8546

0.7966

0.6534

0.7022

0.8664

Table 2: shell leaf impurities, plastics and hair line class with height and width ratio Shell leaf impurity

plastics

Hair line class

0.7541

0.3999

0.4322

0.1521

0.0039

0.6324

0.3785

0.5396

0.1637

0.0142

0.5739

0.6722

0.7721

0.2355

0.1325

0.4366

0.8322

0.1015

0.4609

0.0128

0.3699

0.8917

0.0324

0.5217

0.0547

from the Table 1 and Table 2 we can Analysis the data of fiber seed coat, stiff cotton sheets and Neps (filament mass) with height and width ratio is about [0.5093], shell leaf impurities [0.3609] , plastics [0.01078] , the hair line class [0.003055]. The elongated shape of the hair line and some data is 0.2 but some data between 0.5-0.6 because of hair line class and cotton line.

Fig. 2: data analysis chart of height and width ratio Table 3: fiber seed coat, stiff cotton sheets, and Neps (filament mass) Defects with rectangle degree Fiber seed coat

Nep (filament mass)

Stiff Cotton sheet

0.7831

0.8327

0.7853

0.8666

0.8026

0.7642

0.8146

0.7800

0.9009

0.7915

0.7655

0.8159

0.8346

0.7954

0.7934

0.8215

0.9013

0.9012

0.7853

0.8215

0.7854

0.9237

0.7960

0.8016

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Table 4: shell leaf impurities, plastics, hair line class with rectangle degree Shell leaf impurity

Plastics

Hair line class

0.6015

0.9036

0.2032

0.8344

0.9191

0.7800

0.8245

0.1337

0.8567

0.8977

0.7154

0.6691

0.1935

0.7749

0.8054

0.6213

0.6927

0.6653

0.3022

0.8925

0.6482

0.8906

0.8302

0.1496

0.8434

Fig. 3: data analysis chart of rectangle degree

Through more than six samples of rectangle degree is calculated to find these values tends to extract impurities into two directions some in between [0.6092] and the other parts in between [0.35]. The goal of rectangle degree is to reflect the impurities area of image and its share MER area because MER object is the minimum bounding rectangle so this value also indirectly reflects the general shape of the target image. More than six impurities accept the hair type and plastics thin strips the remaining five is generally elliptical. Among them fiber and cotton stiff seed coat and hair line classes mostly similar after the end of image processing is an elliptical shape. The impurity appearance of shell leaves is not same because of the size. But the binary image generally tends to be treated rectangular or elliptical. Plastics and hair line impurities is different such cotton impurities is generally erratic bend or folded so the rectangle changes relatively large when itâ&#x20AC;&#x2122;s bending is minor and natural. When it is bending or folded substantially reduces the rectangular degree 0.4 or less and no regularity. The target profile substantially represented in nearly circular and large curved shape curvature but that does not do the matching with the real appearance of the object.

5. Conclusions The main direction of this paper is detection of defects and impurities of raw cotton by computer image processing technology. The various methods and principles of image processing are used through the raw cotton image containing defects and impurities were pretreated, image segmentation, edge extraction and a description of the characteristic parameters. The final completion of the work is to identify defects and impurities. The detection of raw cotton defect and impurities based on computer image processing technology is relatively successful, there is certain practical significance but the equipment can be improved- if high quality lighting and camera methods work in this task will be more effective.

6. References 1. 2. 3. 4. 5.

A., T.R., Estimating the size of cotton trash with video images. Textile Research Journal, 1990. 60(4): p. 185193. K, T.J. and K.S. C., Objective evaluation of the trash and color of raw cotton by image processing and neural network. Textile Research Journal, 2002. 72(9): p. 776-782. G, X.B., F. C, and H. R, Chromatic image analysis for co tton trash and color measurements. Textile Research Journal, 1997. 67(12): p. 881-890. J, L.Y., L. K, and B.H. Y. Key technology in detecting and eliminating isomerism fibre in cotton. in International Conference on Electronic Measurement & Instruments. 2007. Xi.an,China. D., F.B. Measurements of trash contents and grades in cotton using digital image analysis. in International Conference on Signal Processing Proceedings. 1996.

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K, P.S., D.M. S, and S.-S. H. Segmentation and classification of four common cotton contaminants in X-ray micro-tomographic images. in Proceedings of SPIE,Machine Vision Applications in Industrial Inspection XII. 2004. San Jose,CA,USA. J, K.T. and K.S. C, Objective evaluation of the trash and color of raw cotton by image processing and neural network. Textile Research Journal, 2002. 72(9): p. 776-782.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Unsupervised fabric defect segmentation using local dictionary approximation Zhou Jian1, Gao Weidong1, 2 + 1

School of Textile & Clothing, Jiangnan University, Wuxi, 214122, China Key Laboratory of Science & Technology of Eco-textiles Ministry of Education, Jiangnan University, Wuxi, 214122, China

Abstract. Automated detect detection in woven fabrics for quality control is still a challenging novelty detection problem. This work presents a new method based on local dictionary approximation to address automated defect segmentation on fabrics. The proposed method adopts unsupervised scheme without the need of reference images or any other prior information. Local dictionary is learned from a testing sample in the least squares sense to represent fabric texture. By assuming that the learned dictionary only captures normal background texture, the defective texture not found in the learned dictionary cannot be approximated well, causing substantial difference on the defective regions. With this clue, the patch-level approximation residuals is computed to construct abnormal map of defects. For defect segmentation, the 2D maximum entropy with neighborhood considered is applied to segment defective regions from the abnormal map. The experiments on various defective samples demonstrate that our method yields a robust and good overall performance in locating fabric defects.

Key words: fabric defect; novelty detection; unsupervised segmentation; approximation

1. Introduction Unlike the technical textiles, measuring visual quality of raw woven fabric is highly important to the textile manufacturers before reaching to customers. Traditional visual quality inspection relies on trained human inspectors. Limited by factors such as tiredness, and inattentiveness, currently manual inspection process can hardly provide a consistent, reliable and accurate detection results. Thus, most research has moved towards developing automated fabric inspection system to response the shortcomings of manual inspection as well as provide consistent and objective results. In the related work, Lu and Tsai have applied singular value decomposition to identify defects on TFT (Thin Film Transistor) panel surfaces [1]. They assumed that the background information of a TFT panel image lies in the space spanned by columns associated with large singular values (SVs), while those related to smaller SVs contain localized irregularities; Rall贸 et al proposed an unsupervised novelty detection algorithm for defect segmentation using Gabor wavelets [2]; Zhou and Wang presented an unsupervised dictionary approximation based method for fabric defect segmentation [3]. However, this method performs poorly on those defects sharing anomalies with normal regions, e.g. thin bar, due to the absence of neighbouring information used. In this work, we present a novel detection method for fabric defect segmentation using local dictionary approximation. It is devised to identify defects in a fully unsupervised manner without reference images and any prior information. Specifically, our method firstly attempts to represent fabric texture in patch-level with a learned dictionary in sense of least squared error. By assuming that the learned dictionary only captures

Corresponding author. Tel.: + 86-13806185321. E-mail address: gaowd3@163.com.

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normal background texture, the defective texture not found in the learned dictionary cannot be approximated well, causing substantial difference on the defective regions. Then, the patch-level approximation residuals is computed to construct abnormal map. For defect segmentation, the thresholding technique based on 2D maximum entropy is performed on the abnormal map.

2. Dictionary learning Considering the significant structural redundancies in fabric texture among the repetitive spatial structures, learning a linear basis (called atoms or dictionary elements) from image patches is effective for representing training samples even in a very lower dimensional subspace, i.e. the linear combination of the learned dictionary elements can approximate the signal as close as possible subject to certain constraints. Give a data matrix X =[x 1 , x 2 , ..., x n ], x i∈ Rm where m is the dimensionality of data points and n is the number of data points. Seeking such a linear basis D=[d1, d2, ..., dk], di∈Rm, (potentially with k < n) can be formulated as follows: R

min ∑ xi − Dα i D, α

i =1

2 2

(2.1)

where αi is called coefficient vectors for each xi with dimensionality of k. The solution of Equation (2.1) will yield a dictionary D that can represent every point in X in sense of least squared error. It is noted that minimize the objective in Equation (2.1) is a non-trivial task, as it is not a convex function due to the multiply of D and α. But if one of variables, either D or α, is known, Equation (2.1) is a convex problem with respect to the other unknown.

3. Methodology of the proposed method The overall unsupervised detection scheme is illustrated in Fig. 1, consisting of the following stages:

Fig. 1: Overall unsupervised detection scheme.

3.1. Image patch extraction The key idea of our unsupervised method is to represent fabric images based on image patches in least squares sense. Given an image, the image patches are obtained in both overlapping and non-overlapping ways. Non-overlapping division means the patches are divided sequentially without overlap, while patches from the overlapping way share partial regions with their neighbors in column or/and row directions.

3.2. Outlier remove To trim abnormal patches, we assume that they are distant from those normal patches. Thus, the key idea of our outlier remove method is simply based on distance comparison, where those with larger Euclidean distance to the data center are considered to be abnormal patches. Let the image patches collected from testing

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sample be {xi} and data matrix X =[x1, x2, ..., xn]. The Euclidean distances E(i) to the data center can be computed as:

E (= i)

xi − x

(3.1)

where x is the mean value of {xi}. An image patch in data matrix X will be removed, if its distance E(i) is larger than the threshold Th that needs to be estimated dynamically. Considering the small proportion of defective regions, we empirically trim one fourth of the total number of patches to guarantee as many as possible potential abnormal patches being removed. Thus, the 3rd quartile (75th percentile) can be used as the threshold Th to trim outliers straightforwardly.

3.3. Learning dictionary and constructing abnormal map The proposed method is assumed that the learned dictionary will only capture the normal texture structures of the fabric sample, and it is not able to model the defective patches well, due to the absence of the abnormal elements. Intuitionally, the difference (e.g. approximation error) derived from the approximation with Dt for normal and abnormal patches can be used as a clue for defect identification, i.e. the approximation operation will cause substantial approximation error on defective regions. Suppose that y is an image patch, and its approximation yˆ can be computed by solving the following least square problem:

yˆ = Dtα * = α * arg min y − Dtα

（3.2）

With the assumption above, it is not difficult to understand that the approximation error between y and yˆ will be quite small if y is a non-defective patch, which is a possible metric to discriminate defective patches from normal ones. But, this patch based scheme for defect identification is only able to locate the defective regions in patch-level precision. In order to segment defects in pixel-level precision, we need to highlight the differences for each pixel in the testing sample. To do this, one simple way is first to divide the testing sample into patches without overlap, and then to approximate all the patches to create the approximated version of the testing sample. Thus, we will take the neighborhood pixels into consideration, and construct an abnormal map using weighted patch-level approximation error. Let i be the center pixel of patch yi, and the difference for this pixel is defined as, 2

S (i ) = 1 − exp(−γ wT ( yi − yˆi ) ) ,

(3.3)

where, yˆ is the approximation of yi, w is a weighting term and γ is a user-defined parameter controlling sensitivity. The use of weight term w is to reduce the influence of those pixels distant from the center pixel, improving the robustness of our method. Here, the weight w is computed from the two-dimensional symmetric Gaussian function.

3.4. Segmentation In this section, segmentation operation will be performed to segment the defective regions from the abnormal map calculated from Equation (3.3). Apparently, the thresholding technique is the most suitable for obtaining a binary segmentation of the abnormal map, as the regions with larger magnitude in abnormal map are doomed to be defects. For threshold method, the most critical thing is to find a decent threshold value. Although there is a variety of methods to determine a threshold value, our experiments demonstrated that the 2D maximum entropy method was found to result in the best performance. The major reasons are: (1) gray level of defective and background regions change gradually in same manner; (2) 2D maximum entropy method takes the neighborhood information into consideration.

4. Experiments

Page 948 of 1108

We apply the proposed method described in the preceding sections to the real-world samples with a total of six defective images containing various defect types. All the testing samples have a size of 512Ă&#x2014;512 with 256-gray levels. The ground truth defective regions were annotated manually for objective evaluation.

4.1. Results and discussion Fig. 2 shows the segmentation results for the six defective fabric samples, where the dictionary size is set to 7 and the patch size is set to 32Ă&#x2014;32. From Fig. 2, it can be see that the defective regions can be well segmented, although there have a few of false detected regions that maybe removed via connectivity analysis. It also demonstrates the effectiveness of the proposed method in segmenting fabric defects.

Fig. 2: Segmentation results.

5. Conclusions In this work, we have presented an unsupervised algorithm for the problem of detecting local defects on textile fabrics using local dictionary approximation. Different from the existing defect segmentation methods with reference samples needed, our method is able to work under a fully unsupervised manner. Benefiting from the repeating texture, the dictionary learned in the least squares sense can admit a decent approximate to the local fabric texture in patch-level, providing a foundation of discriminating the defective regions using approximation error. For performance evaluation, our experiments on six defective samples demonstrate that the proposed method can well segment defective regions on fabric textures.

6. Acknowledgements This wok was supported by Doctoral Fund of Ministry of Education of China (Grant No. 20120093130001).

7. Reference [1] Lu C, Tsai D. Automatic defect inspection for lcds using singular value decomposition. Int J Adv Manuf Tech 2005; 25: 53-61.

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[2] Rall贸 M, Mill谩n M S, Escofet J. Unsupervised novelty detection using Gabor filters for defect segmentation in textures. J Opt Soc Am A 2009; 26: 1967-1976. [3] Zhou J, Wang J. Fabric defect detection using adaptive dictionaries. Text Res J 2013; 83: 1846-1859.

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The 13th Asian Textile Conference Geelong, Australia, November 3–6, 2015

Visual impression of fabrics at different viewing distances Aya GOTO 1, Aki KONDO1, Sachiko SUKIGARA1 1

Department of Advanced Fibro-Science, Kyoto Institute of Technology, Kyoto, Japan

Abstract. The aim of this study was to examine the effect of viewing distance on visual evaluations of fabrics. We collected 11 cotton-blended fabrics that differed in weave structure, color, weight, and thickness, and measured their mechanical and surface properties using the KES-F system. Fifteen students assessed the visual feel of fabrics at distances of 150 and 15 cm. Some fabrics showed large impression changes between those distances for surface evaluations such as “transparent” and “thin” and for value evaluations such as “feels beautiful,” “like,” and “elegant.” Impression changes for “transparent” and “thin” were correlated with fabric weight. These results suggest that light weight and transparency of fabrics can change impressions depending on the viewing distance.

Keywords: textile, viewing distance, texture

1. Introduction Visual impressions of fabrics are not always the same from one person to the next, even when viewing the same piece of fabric. For example, impressions may change when fabric is examined from a long or short distance. Further changes may occur if the fabric is held in the hands. It is interesting that the amount of information obtained from fabric is not always the same and can be related to the viewing distance. In this study, we choose viewing distance as a parameter influencing the impressions of fabrics. The fabric density, yarn thickness, and weave pattern of fabrics are considered as parameters affecting detailed impressions. Mechanical properties were also taken account to consider the contribution of fabric shape. The aim of this study was to ascertain the effect of these parameters on impressions of fabrics with respect to viewing distance.

2. Experiment 2.1 . Samples 2.2 Eleven cotton and cotton-blended fabrics that differed in weave structure, color, weight, and thickness were used to produce various appearances (Table 1). The fabric sample size was 20 × 20 cm. 2.3 Subjective evaluation of visual feel of fabrics Seven male and eight female students assessed the visual feel of the selected fabrics. Participants were asked to evaluate the visual feel of fabrics displayed on a gray spherical stand (diameter 12 cm), based on only sensations arising from the material appearance. The evaluation categories were “feels beautiful/doesn’t feel beautiful,” “like/dislike,” “elegant/not elegant,” “new/old,” “glossy/not glossy,” “natural/artificial,” “soft/hard,” “coarse/fine,” “thin/thick,” “smooth/rough,” “transparent/opaque” (Table 2). Evaluations were performed using a scale from 1 (“very much”) to 7 (“not at all”) according to the semantic differential method. Participants evaluated each fabric from a distance of 15 cm, and then from a distance of 150 cm. The viewing angle from the object was 73° at a distance of 150 cm, and 18° at a distance of 15 cm. All participants had normal color vision and normal or corrected-to-normal visual acuity.

Corresponding author. Tel.: + 81-75-724-7365. E-mail address:sukigara@kit.ac.jp.

Page 951 of 1108

Table 1: Samples No.

Color

Material

Thickness (mm)

(10-7g/m2)

Ends /cm

Picks /cm

Texture

L* (D65)

a* (D65)

b* (D65)

Black

C100

1.04

12.4

emboss

12.91

0.33

-1.00

2 3 4 5 6 7 8 9 10 11

Black Black Black Navy Red Blue Gray White Beige Pink

C100 C100 C74 Pe26 C99 Pe1 C62 Pe38 C33 Pe67 C76 Pe24 C76 Pe24 C100

0.60 0.43 0.57 0.45 0.50 0.46 0.29 0.48 0.60 0.34

21.4 13.3 8.0 11.6 6.3 14.9 8.1 8.4 16.8 7.2

55 73 40 20 53 49 88 47 70 32

39 46 40 40 42 53 93 45 52 27

twill twill plain twill plain twill twill plain twill plain

17.23 17.96 18.99 23.24 34.65 37.40 49.04 74.99 77.32 90.90

-0.10 0.22 -0.14 0.11 36.75 -1.89 1.26 0.72 2.74 3.36

-0.78 -1.96 -0.77 -3.82 11.00 -16.19 -2.52 1.62 12.16 10.28

C51 Pe42 N7

Weight

C: cotton; Pe: polyester; N: nylon Table 2: Evaluation term pairs Feels beautiful Like Elegant New Glossy Natural Soft Fine Thin Smooth Transparent

Doesn’t feel beautiful Dislike Not elegant Old Not glossy Artificial Hard Coarse Thick Rough Opaque

2.4. Measurement of mechanical and surface properties Mechanical and surface properties and air resistance were measured using the Kawabata Evaluation System for Fabrics (KES-F)1. Fabric colors were assessed using a colorimeter (CM-3600d, Konica Minolta) under D65 illuminant conditions with a 10° field of vision. To consider differences in information obtained from the cloths (e.g., weave structure, color, and pattern) depending on viewing distance, we took photographs of all 11 fabrics from distances of 16 and 150 cm. Note that a 16-cm distance was adopted instead of 15 cm because we could not focus on the fabrics at 15 cm. Photography was carried out in a dark room with a D65 light against a neutral-gray background. Photographs were taken with a digital camera (D5100, Nikon), which was placed perpendicular to the front of the fabrics. Photographs were taken under the same shooting conditions from both distances. We used a DX AF-S Nikkor lens (Nikon) at focal length 35 mm, ISO 100, f-number f/3.5, shutter speed 1 s, and luminance 56.9 lx.

3. Results and Discussion 3.1. Effect of the viewing distance on visual evaluation The effect of the viewing distance on visual evaluation was evaluated by subtracting the evaluation values at 150 cm from those at 15 cm (Fig. 1). Three samples (Nos. 4, 6, and 9) showed large impression changes (more than 1 point difference) between 15 and 150 cm for surface evaluation characteristics such as “transparent/opaque” and “thin/thick.” When the distance was shorter (15 cm), these evaluation values increased. For these samples, the viewing distance also dramatically affected value evaluation characteristics such as “feels beautiful,” “like,” “elegant,” and “new.” When the distance was shorter (15 cm), evaluation

Page 952 of 1108

values for “like,” “new,” “glossy,” “feels beautiful” for No. 4 and “glossy” for No. 9 increased, but those for “elegant,” “like,” and “feels beautiful” decreased for No. 6. For the No. 4 fabric, we could observe weave structure and yarn more clearly from 15 cm than from 150 cm. The additional information such as fabric thickness and yarn fineness obtainable at short distances might increase the scores for surface evaluation characteristics such as “transparent” and “thin” as well as value evaluation characteristics such as “feels beautiful,” “like,” “elegant,” and “new.” Also, the No. 9 fabric has very little pattern, which might lead to a large influence of distance for surface evaluation characteristics such as “transparent,” “thin,” “soft,” and “glossy,” more than value evaluation characteristics. On the other hand, the No. 6 fabric is very thin and lightweight, so the appearance of the red fabric mixed with the background gray, which might decrease the value evaluation scores at a short distance.

Fig. 1: Effects of viewing distance on visual evaluation

3.2. Effect of viewing distance on the information obtained from fabric surfaces The photographed data were analyzed using photo editing software (Adobe Photoshop CS6). Table 3 shows RGB and L*a*b* values for each sample. Differences in color and lightness between 16 and 150 cm was larger for No. 6 than that for Nos. 4 and 9. At a 16 cm distance, the lightness of the No. 6 surface was darker than that at a 150 cm distance, which may lead to the decreased evaluations for “elegant,” “like,” and “feels beautiful.” However, we found no clear difference in weave structure appearance or fabric pattern between 16 and 150 cm in the photographed data. Table 3: RGB and L*a*b* values of photographed data for fabrics and background color R Sample No.4 No.6 No.9 background color

150 cm 46.8 156.4 210.2 166.0

G 16 cm 42.6 131.2 203.2 158.6

51.8 57.6 213.6

16 cm 46.6 19.6 206.4

166.2

161.4

150 cm

50.8 76.0 216.0

16 cm 42.4 54.8 209.4

168.2

164.4

150 cm

19.0 43.6 85.8

16 cm 16.6 33.3 82.8

68.8

66.6

150 cm

-3.8 52.4 -1.4 0.0

-1.2

150 cm

3.3. Relation between mechanical properties and impression changes

b* 16 cm -3.8 54.2 -1.0

-0.6 18.6 -2.0

16 cm 2.2 19.2 -1.8

-1.0

-2.0

150 cm

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Figure 2 shows the mechanical and surface properties of the No. 4, 6, and 9 fabrics. The impression changes for “transparent/opaque” and “thin/thick” were correlated with fabric weight (r = 0.77 and 0.57, respectively). This suggests that the light weight and transparency of fabric can change its visual impression depending on the viewing distance.

Fig. 2: Mechanical and surface properties of the No. 4, 6, and 9 fabrics (Mi: mean value; σi: standard deviation)

4. Conclusion We examined the effects of viewing distance on visual evaluations of fabrics. For lightweight fabrics (those with weight lower than 1.0 × 10-6 g/m2), impressions for “transparent/opaque” and “thin/thick” were strongly influenced by distance. Additional information such as fabric thickness and yarn fineness affected not only surface evaluations but also value evaluations at a short distance. Fabric weight and transparency are thus thought to be key parameters that can change visual impressions depending on viewing distance.

5. Acknowledgements We thank M. Tatsumi of Tatsumi Weaving Co., Ltd. for help in choosing theses samples and K. Maeda for assistance in taking the photographs. This work was supported by JSPS KAKENHI Grant Nos. 15H01764 and 15K16008.

6. References [1] Kawabata S. (1980), “The Standardization and Analysis of Hand Evaluation”, 2nd ed. Textile Machinery Society of Japan, pp 23-34.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

A Study of one-direction-moisture-conducting laminated fabric Qiuyun Li1，Zhong Zhao1，Jihong Wu1 + 1

School of Textile Science and Engineering, Wuhan Textile University, Wuhan 430073, China

Abstract. In this study, one-direction-moisture-conducting laminated fabric was made by bonding the knitted fabric proceeded by hydrophlic finishing and the woven fabric processed by hydrophil finishing together with an adhesive (consists of polyester adhesive, isocyanate and cross-linking agent, GLA-7 in a mass ratio of 10:3:2 ) at 150℃. One-direction-moisture-conducting index，gas permeability and moistureresistance index were measured to assess the one-direction-moisture-conducting ability of the laminated fabrics. Results show that the laminated fabric possesses relatively excellent moisture conducting ability.

Keywords: one-direction-moisture-conducting, laminated fabric, gas permeability test, heat and moisture resistance, functional finishing

1. Preparation of laminated fabric 1.1.

Basic parameters of fabric

Three kinds of fabrics, including yellow knitted fabric, black knitted fabric and gray woven fabric, numbered as Sample 1, Sample 2 and Sample 3 were used in this study. Basic parameters of these three pieces of fabrics are listed in Table 1. Table 1 Basic parameters of the three pieces of fabrics Basic parameters of yarns Number

1.2.

Fiber

Linear density

Sample 1

Polyester

Sample 2

Polyester

Sample 3

Polyester

Structure Plain stitch Laying-in stitch Cobourg

Grams per square meter(g/m2)

Thickness (mm)

163

0.88

310

1.46

327

0.70

Hydrophilic treatment and hydrophobic treatment of fabrics

The single layer of the laminated fabric need to be treated with hydrophilic agent or hydrophobic agent before laminating. Sample 1 and Sample 2 were treated with hydrophilic agent while Sample 3 was treated with hydrophobic agent in this study. Process of hydrophobic treatment: Sample 1 and Sample 2 were cut in dimensions of 35cm*35cm before they were placed in the solution of hydrophobic agent for 10 min. Then it was dried in the air and placed in an oven at 160℃ for 5 min. Process of hydrophilic treatment: Sample 3 was cut in dimensions of 35cm*35cm. It was placed in the solution of hydrophilic agent for 10 min, then dried and heated in an oven at 160℃ for 5 min [1-2].

1.3.

Laminating of single layers

The adhesive used to bond the fabrics together was made by mixing three ingredients: polyester composite adhesive, isocyanate and cross-linking agent 75 in a mass ratio of 10:3:2.Then a certain amount of mixed adhesive was coated on the right side of Sample 3 before the reverse sides of Samples 1 and Sample 2 were bonded to it. After that, the bonded fabrics were squeezed through two rotating cylinders at the pressure of 3kgf/cm2 and a rotational speed of 1m/min. The laminated fabric was heated and cured from the +

Corresponding author. Jihong Wu. Tel.: + 86 13006196389. E-mail address: jihong-wu@wtu.edu.cn

Page 955 of 1108

temperature of 140℃ to 170℃ in an oven for 1 hour. Two pieces of laminated fabric were made, following these procedures, and named laminated fabric 1 and laminated fabric 2. Basic parameters of the two pieces of fabrics are listed in Table 2. Table 2 Basic parameters of laminated fabrics 1 and 2 Number

Inner layer

Outer layer

Grams per square meter (g/m2)

Thickness (mm)

Laminated fabric 1

Sample 1

Sample 3

580

1.68

Laminated fabric 2

Sample 2

Sample 3

680

2.14

In addition to the laminated fabrics[3] described above, 12 pieces of laminated fabric were made by bonding Sample 1 , 2 and 3. Sample 1 and 2 were treated with hydrophobic agent solution at concentration of 0, 1, 2, 3, 4, 5 g/L, respectively. Other 12 pieces of laminated fabrics were also made by bonding untreated Sample 1, 2 and 3. Sample 2 and 3 were treated with hydrophilic agent solution at different concentration of 0, 10, 20, 30, 40, 50 g/L. The moisture conducting ability of the 24 pieces of laminated fabrics were characterized by MMT (moisture managing test), in order to understand the impact of different treatment process on the moisture conducting ability of laminated fabric.

2. Testing The properties of the laminated fabrics were tested by several methods, among which the moisture conducting[4] ability was examined by MMT while the heat resistance, moisture resistance and gas permeability tests were conducted on Sample 1, 2 and 3, laminated fabric 1 and 2. Moisture managing tests were conducted by placing the Samples on the platform of MMT machine with the inner layer face upwards. NaCl solution at the concentration of 0.2 g/L was dripping onto the fabric surface from a nozzle while the weight of liquid that the fabric absorbed was recording by a computer. One single test approximately lasted for 2 min. All of the 24 pieces of laminated fabrics were tested in the dimensions of 9cm*9cm. Heat and moisture resistance of the Samples were tested by a YG606G High-Precision Heat and Moisture Tester. All the Samples were cut in the dimensions of 35cm*35cm and placed under the conditions of the ambient temperature of 20℃ and the ambient humidity of 65% for 24 hours before the test[5]. Gas permeability of the Samples were tested by YG461E-Ⅲ Gas Permeability Tester under the standard atmospheric pressure.

3. Results and analysis 3.1.

MMT results

The one-direction conducting index of the laminated fabric, which represents the ability of conducting moisture from the contact point to the opposite side of the fabric, was tested. Results of laminated fabrics made of Sample 1 and 2 treated by hydrophilic agent solution are shown in Fig. 1. Those of laminated fabrics made of Sample 3 treated by hydrophobic agent solution are presented in Fig. 2.

Fig. 1 MMT results of laminated fabric with treated Sample 1 and 2

Fig. 2 MMT results of laminated fabric with treated Sample 3

Page 956 of 1108

It can be seen from Figure 3-1 that the on-direction conducting index increases at first stage but then decreases as the concentration of hydrophilic agent solution is raised. The reason why the trend of onedirection conducting index changed is probably because the conduction of water alongside the axial direction of the yarn was restricted due to the hydrophobic surface of the knitted layer while the conduction of water through the fabric was not affected because of the low concentration of the hydrophobic agent .However, when the concentration of the hydrophobic agent reached at a certain level, water on the surface of laminated fabric was prevented from permeating because of the strong hydrophobic property of the surface of knitted layer, which resulted in the fabric was completely saturated by hydrophobic agent. The results of one-direction conducting index which shown in Figure 3-2 are similar with those of Figure 3-1. The one-direction conducting index rises as the concentration of hydrophilic agent solution was raised within limits while it declined when the concentration reached higher levels. One possible reason for the change of the trend is that water absorbed by the surface of knitted layer was then rapidly transferred to the surface of woven layer due to the strong hydrophilic property which was treated by hydrophilic agent solution. When the concentration of hydrophilic agent solution exceeded the optimal level, water absorbed by the surface of knitted layer was then conducted along the interface between the knitted layer and woven layer rather than being transferred to the surface of woven layer.

3.2.

Heat and moisture resistance

Results of heat and moisture resistance tests of laminated fabric are listed in Table 3 and Table 4. Table 3 Indexes of heat resistance tests Sample 1

Index Heat resistance thermal conductivity CLO value Thermal insulation ratio

Sample 2

Sample 3

Laminated fabric 1 Front Back

Laminated fabric 2 Front Back

Front

Back

Front

Back

Front

Back

0.0197

0.0198

0.02

0.0202

0.0183

0.0198

0.0206

0.0203

0.0209

0.021

50.67

50.47

49.87

49.27

54.39

50.49

48.37

49.22

47.82

47.46

0.127

0.129

0.13

0.118

0.127

0.133

0.131

0.134

0.135

22.70

22.98

23.20

21.48

22,76

23.53

23.22

23.74

23.87

Values of indexes in table 3 show that there are not distinct differences of both heat resistance and thermal conductivity between the two sides of all of the Samples, which implies that heat resistance and thermal conductivity would be much more likely related to the material of single layer rather than its structure and thickness. It could also be concluded that the adhesive cured between the layers of laminated fabric would not likely affect the thermal properties of laminated fabric, by comparing the figures of indexes of single layers with those of laminated fabric. One possible reason for this result is that the active ingredient of adhesive used in this study is polyester which is same with those of all of the Samples. Compared with the CLO value and thermal insulation ratio of single layer, those values of laminated fabrics increased by a small amount, which may cause by the change of thickness, coupled with blockage in the interstices of fabric caused by cured adhesive. This may weaken the air convection through fabric due to the decline in its air permeability and form an effect of heat preservation. The thermal conductivity diminished slightly because of its opposite feature of definition of thermal insulation ratio. Table 4 moisture resistance, moisture permeability and moisture permeability index of the fabrics

Index

Sample 1

Sample 2

Sample 3

Laminated fabric 1

Laminated fabric 2

Moisture resistance

3.40

5.40

5.00

8.30

11.10

Moisture permeability

0.4600

0.2947

0.3185

0.1914

0.1435

Moisture permeability index

0.34

0.22

0.24

0.15

0.10

Moisture resistance of laminated fabric, unlike unapparent change of heat resistance, increased dramatically and therefore resulted in the decrease of moisture permeability and moisture permeability index.

Page 957 of 1108

These changes of moisture permeability, are probably caused by the blockage in the interstices of fabric. It can be suggested the cured adhesive, may shed light on the importance of dosage of the adhesive because of its dramatic impact on the properties of laminated fabric, especially for moisture permeability.

3.3.

Results of gas permeability test

Each Sample was tested repeatedly for five times, all the results are listed in Table 5. Table 5 Permeability test results of all Samples Number

Sample 1 Sample 2 Sample 3 Before laminating Laminated After fabric 1 laminating Before laminating Laminated After fabric 2 laminating

1109 430.7 79.98

1089 419.9 80.11

1047 421. 8 76.15

1027 415.6 71.55

1048 431.0 72.68

Average value 1064 423.8 76.09

77.41

72.88

70.4

77.29

75.04

74.60

54.97

51.82

53.84

51.83

50.71

52.63

65.59

60.48

61.92

63.97

64.30

63.25

44.84

45.21

46.72

44.70

47.50

45.79

Air permeability of fabric is associated with its structure and thickness. Sample 1 possesses the highest property of air permeability due to its lighter thickness and larger loops, than Sample 2 and 3. Air permeability of Sample 3 is the lowest among these three single layer fabrics because of its high thickness and covering factor. The two single layers were laid together and tested before laminating. Results show that air permeability of two single layers without adhesive are better than that of laminated fabric. This was also caused by the blockage-effect of adhesive. In summary, it might be concluded that the thickness of fabric has significant effect on air permeability of laminated fabric while the introduction of adhesive has relatively less importance impact on air permeability.

4. Conclusions The concentrations of both hydrophilic agent and hydrophobic agent solution has dramatic influence on moisture-one-direction-conducting property of laminated fabric. That property will be enhanced when the concentration remains in a proper range, and it will be weakened once the concentration exceeds that limit. Thermal property of laminated fabric was not changed significantly before and after laminating. Thickness and introduction of adhesive have dramatic influence on moisture conducting property of laminated fabric. Air permeability would deteriorates as thickness increases, the introduction of adhesive also worsen air permeability of laminated fabric.

5. References [1] Wang J H，Yasuda H．Dynamic water vapor and heat transport through layered fabrics Part I：Effect of surface modification[J]．Textile Research Journal。1991，61(1)：10-20． [2] Volkmar T，Bartels and Karl Heinz Umbach．Water vapour transport through protective textiles at low temperatures[J]．Textile Research Journal，2002，72(10)：899—905． [3] Margrent Drinkmann J Coated Fabrics．1992：21(1)：199～2ll [4] Kim J O．Spivak S M．Dynamic moisture vapor transfer through textiles Part II：Further techniques for microclimate moisture and temperature measurement[J]．Textile Research Journal，1994，64(2)；112—121． [5]

PU Zheng Xiang．A dynamic model of the human/ cooling system /clothing/environment system[D]．Orlando： University of Central Florida，2005

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Regenerablity and Stability of Antibacterial Cellulose Containing Triazine N-halamine Lin Li 1, Kaikai Ma1, Xuehong Ren 1 + 1

Key Laboratory of Eco-textiles of Ministry of Education, College of Textiles and Clothing, Jiangnan University, Wuxi, Jiangsu 214122, China

Abstract. A reactive triazine derivative, 2,4-dichloro-6-hydroxy-1,3,5-triazine (DCHT), was prepared through the controlled hydrolysis of cyanuric chloride in water solution. The reaction was characterized with 13C NMR study. The reaction solutions could be directly used to treat cellulose fibers. A pad-dry-cure method was employed to immobilize the triazine derivative onto cotton. The covalently bound triazine moieties on cotton could be transformed into N-halamine structure after a chlorine bleaching treatment. The biocidal efďŹ cacies of the treated samples with different chlorine loadings were further examined. The storage and release testing showed that the antimicrobial function of the N-halamine modified cotton fabrics was durable and rechargeable. These advantages make the triazine N-halamine modified cotton as an attractive candidate in a broad range of application fields. Keywords. Antibacterial, Cellulose, Triazine, N-halamine

1. Introduction Bacterial infection from medical care related materials is responsible for the increasing number of morbidities and large medical costs1-4. Many different methods have been developed to reduce the incidences of the infection. One of the most effective methods is to produce antimicrobial fabrics by incorporating biocidal agents into the fibers of the fabrics. Quaternary ammonium salts3-7, nano silver8, N-halamines9-23, and others have been used in the development of antimicrobial textiles. Among these biocidal agents, N-halamines have been demonstrated to be a powerful, durable and reachargeable antimicrobial agents with low toxicity to human. These advantages render N-halamines considerable potential materials for medical, hospital, hygienic, and other related applications. During the past two decades, N-halamines have been successfully applied to a variety of surfaces such as cellulose, polystyrene, polyethylene, and polyurethane for antimicrobial purposes. Cellulose containing abundant hydroxyl groups is easy to obtain antimicrobial property through chemical modification11-29. A series of siloxane N-halamine precursors were successfully prepared and tethered onto cellulose, and organic solvent is used in the treating solution due to the poor solubility of the siloxanes in water19-22. But, the siloxane Nhalamines are not very stable for storage21. Some water-soluble N-halamine epoxides were synthesized to prepare antimicrobial cotton fabrics23. The relative low reactive and not high enough chlorine loading of epoxides limit their applications. A reactive melamine derivative, 2-amino-4-chloro-6-hydroxy-s-triazine (ACHT) was developed and coated onto cotton, which rendered fabrics powerful antibacterial function26-28. Most recently, a high reactive triazine derivative, 2,4-dichloro-6-hydroxy-1,3,5-triazine (DCHT) has been prepared through controlled hydrolysis of cyanuric chloride and used to treat cotton fabrics directly, and the triazine treated fabrics were rendered antimicrobial through exposure to diluted bleach29. The triazine derivative was high reactive and easy to be attached onto cellulosic materials through nucleophilic substitution reactions. The enol structures in triazine ring could transform to amide structure by tautomerism (SCHEME 1). After a bleach treatment, the covalently bound amide groups in triazine moieties were transformed into Nhalamine derivatives, which demonstrated antimicrobial functions against gram-negative and gram-positive bacteria.

Corresponding author. E-mail address: xhren@jiangnan.edu.cn

Page 959 of 1108

Scheme 1. Synthesis of DCHT and the attachment of DCHT to cellulose.

2. Experimental methods 2.1.

Preparation of DCHT grafted fabrics

The preparation of cotton fabrics modified with DCHT was followed the method in a previous report29. A calculated amount of cyanuric chloride and NaOH with a mole ratio of 1:2 were added in distilled water and stirred for 5 min to get an aqueous solution. Additional NaOH (2% to the solution) was added and dissolved in the solution. Then, cotton fabrics were dipped into the solution, padded through a laboratory wringer (100% wet pick-up), and cured in an oven at 110 °C for 10 min. Afterward, the fabrics were washed thoroughly with a large amount of distilled water, and dried at 60 °C for 1 h.

2.2.

Chlorination

Chlorination was processed through the immersion of DCHT grafted cotton fabrics in 10% bleach solution, pH 7 at room temperature for 60 min. After chlorination, the samples were washed thoroughly with distilled water, and dried at 45 °C for 1 h to remove any unbonded chlorine from cotton fabrics. The active chlorine content of the fabric was determined by an iodometric/thiosulfate titration method as reported previously23-25.

3. Results and discussion 3.1.

Characterization of DCHT and cotton modified with DCHT

The preparation of the treatment solution is processed at normal pressure and ambient temperature using water as the solvent, and easy to scale up in practical applications. The 2,4-dichloro-6-hydroxyl-1,3,5-triazine sodium salt can be grafted onto cotton cellulose through nucleophilic substitution with a regular pad-dry-cure ﬁnishing process. The reaction was characterized by FTIR study as shown in Fig. 1. The FTIR spectrum of triazine-treated cotton shows two sharp peaks at 1713 and 1610 cm-1, which are caused by the planar triazine ring stretching vibrations.26 As expected, another park at 767 cm-1 is detected as a characteristic band of C-Cl bond of triazine ring26,28.

Fig. 1: FTIR spectra of (A) cotton and (B) triazine-treated cotton and (C) their difference spectrum (spectrum A subtracted from spectrum B).

The XRD spectra of the samples are shown in Fig. 2. There is no remarkable change in the XRD peaks of cotton, unchlorinated triazine-treated cotton and chlorinated triazine-treated cotton cotton. The 2θ peaks at 23.00°, 16.45° and 14.63° are attributable to the[002], [101] and [101-]lattice planes of cellulose I. The crystallinity of the cotton is 72.3%. While the triazine-treated cotton before and after chlorinated are 73.6% and 67.5%, respectively. The slightly decrease of crystallinity of the treated cotton after chlorinated might be due to the oxidation of cellulose by sodium hypochlorite, which is consistent with the small tensile strength loss after chlorinated12,24.

Page 960 of 1108

Fig. 2: X-ray diffraction diagrams of (A) cotton, (B) unchlorinated triazine-treated cotton cotton and (C) chlorinated triazine-treated cotton cotton.

3.2.

Chlorination of the Triazine-treated Samples

The active chlorine loadings of the samples were also quantitatively measured by the iodometric/thiosulfate titration analysis. The relationship of cyanuric chloride concentration and active chlorine content is shown in Fig. 3. Increasing cyanuric chloride concentration in the coating solution (from 1% to 8%) leads to the increase of active chlorine of the coated cotton fabrics (from 0.05% to 0.55%), which indicates that more N-halamine precursors are covalently bound onto the cotton. Previous studies have proved that N-halamine modified cotton with a chlorine loading over 0.05% is sufficient for rapid disinfection and feasible for practical applications16,17,28. The relationship between the chlorine loading and antimicrobial efficiency was discussed in the followed antimicrobial efficacy study section.

Fig. 3: InďŹ&#x201A;uence of the cyanuric chloride concentration on active chlorine content of the treated cotton fabrics.

3.3.

Antimicrobial efficacy study

The antibacterial functions of the amide halamines modified fabrics were challenged with108 cfu per 2 in2/sample of E. coli and S. aureus. The antimicrobial efďŹ cacies against E. coli and S. aureus are summarized in Fig. 4. The results of the treated fabrics showed 3 log reduction (99.9%) of both E. coli and S. aureus with 1 min (need a space between 1 and min) contact. After 30 min of contact time, the treated fabrics could provide a complete kill of E. coli and S. aureus with 8 log reduction. The prolonged contact time resulted in a complete inactivation of the bacteria by transferring more active chlorines to bacterial cells.

Page 961 of 1108

Fig.4: Antimicrobial efďŹ cacy against E. coli and S. aureus of the N-halamine modified fabrics with different contact times. (The chlorine loading of the fabrics is 0.35%. The original bacteria concentration was 108 CFU per 2 in2 sample.)

3.4.

Storage stability and Renewability study

Durability and renewability are very important features of N-halamine modified biocidal fabrics. The storage stability results of the chlorinated fabrics are shown in Fig. 5. After 1 month storage, cotton swatches retained 66% of the initial chlorine loading. The fabrics still had a chlorine loading about 0.11% after 7 month storage, which still have a very good antimicrobial efficacy according to the results of antimicrobial testing as shown in antimicrobial efficacy study. The fabrics with chlorine loading of 0.11% could inactivate 8 log bacterial within 1 h. All of the lost chlorine could be restored after rechlorination, which indicated that the antimicrobial activity of the N-halamine modified fabrics is regenerable. The chlorine losses were primarily due to the dissociation of the N-Cl bonds rather than the breaking of the bonds between N-halamine precursors and cotton. The storage stability of triazine N-halamines was better than hydantoin and piperidine N-halamines studied previously21. To further test the renewability, the chlorinated triazine modified fabrics were treated with 1% of sodium thiosulfate solution for 10 min to quench the active chlorine completely, and then rechlorinated in a diluted bleach solution at pH 7 for 1 h. After 30 cycles of the quenching-rechlorinating treatment, all of the original active chlorine was retained, indicating that the antimicrobial properties were fully rechargeable.

Fig. 5: Storage stability of the active chlorine on fabrics at room temperature.

4. Conclusion 2,4-Dichloro-6-hydroxy-1,3,5-triazine (DCHT), a triazine derivative was successfully synthesized through the controlled hydrolysis of cyanuric chloride in water solution . A simple pad-cure method was used to graft DCHT triazine rings onto cotton cellulose without using organic solvent. After chlorination, the amide groups on triazine rings can be transformed into N-halamines and provide powerful, durable, and rechargeable antimicrobial activities against E. coli and S. aureus. Due to the easy production, long-term and excellent antimicrobial efficacy, and the controlled release of active chlorine, the DCHT modified cellulose materials may have great potential for practical applications.

5. Acknowledgements The financial supports were provided by the Project for Jiangsu Scientific and Technological Innovation Team, the research fund from the Science and Technology Department of Jiangsu Province of China (BY2014023-09), the National Thousand Young Talents Program, and the Scientific Research Foundation for Returned Overseas Chinese Scholars, Ministry of Education, China.

6. References [1] Binder, S.; et al.; Science 1999, 284, 1311-1313. [2] Tokarczyk, A. J.; et al.; Crit Care Med 2009, 37, 2320-2321. [3] Turnidge, J.; et al.; Med J Aust 2009, 191, 368-373. [4] Olsen, M. A.; et al.; Arch Surg 2008, 143, 53-60. [5] Colak, S.; Tew, G. N.; Macromolecules 2008, 41, 8436â&#x2C6;&#x2019;8440. [6] Klibanov, A. M.; J Mater Chem 2007, 17, 2479â&#x2C6;&#x2019;2482.

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[7] Pernak, J.; Branicka, M.; Ind Eng Chem Res 2004, 43, 1966-1974. [8] El-Shishtawy, R. M,; Asiri, A. M.; Abdelwahed, N. A.; et al.; Cellulose 2011, 18, 1−8. [9] Sun, Y.; Sun, G.; J Appl Polym Sci 2003, 88, 1032-1039. [10] Liu, S.; Zhao, N. and Rudenja, S,; Macromol Chem Phys 2010, 211, 286−296. [11] Liu, S.; Sun, G.; Ind Eng Chem Res 2006, 45, 6477−6482. [12] Ren, X.; Kocer, H. B.; Worley, S. D.; et al.; Carbohydr Polym 2009, 75, 683−687. [13] Liu, S.; Sun, G.; Ind Eng Chem Res 2009, 48, 613−618. [14] Sun, Y.; Sun, G.; J Appl Polym Sci 2002, 84, 1592−1599. [15] Sun, G.; Xu, X.; Text Chem Color 1999, 30, 26−30. [16] Qian, L.; Sun, G.; J Appl Polym Sci 2003, 89, 2418−2425. [17] Sun, G.; Xu, X.; Text Chem Color 1999, 31, 21−24. [18] Sun, Y.; Sun, G.; J Appl Polym Sci 2001, 81, 617−624. [19] Worley, S. D.; Chen, Y.; Wang, J. W.; et al.; Patent 6969769 B2, USA, 2005. [20] Worley, S. D.; Chen, Y.; Wang, J. W.; et al.; Surf Coat Int B 2005, 88, 93−99. [21] Ren, X. H.; Kou, L.; Liang, J.; et al.; Cellulose 2008, 15, 593−598. [22] Liang, J.; Chen, Y.; Barnes, K.; et al.; Biomaterials 2006, 27, 2495−2501. [23] Kocer, H. B.; Cerkez, I.; Worley SD. Appl Mater Interfaces 2011, 3, 2845−2850. [24] Liang, J.; Chen, Y.; Ren, X.; et al.; Ind Eng Chem Res 2007, 46, 6425−6429. [25] Ren, X.; Kou, L.; Kocer, H. B.; et al.; Colloids Surf A 2008, 317, 711−716. [26] Sun, Y.; Chen, Z.; Braun, M.; Ind Eng Chem Res 2005, 44, 7916−7920. [27] Chen, Z.; Luo, J.; Sun, Y.; Biomaterials 2007, 28, 1597−1609. [28] Martha, B.; Sun, Y.; J Polym Sci A: Polym Chem 2004, 42, 3818−3827. [29] Cerkez, I.; Kocer, H. B.; Worley, S. D.; et al.; J Appl Polym Sci 2012, 124, 4230−4238. [30] Ma, K. K.; Xie, Z. W.; Jiang, Q. Y.; et al.; J Appl Polym Sci 2014, 131, 40627.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Application of genetic algorithm optimization in bleaching treatment of cellulosic fibers Ahmad Hivechi1, S. Hajir Baharmi*1, Mokhtar Arami1, Afzal karimi2 1

Department of textile engineering, Amirkabir University of Technology, Tehran, Iran Department of chemical and petroleum engineering, University of Tabriz, Tabriz, Iran

Abstract. In this article we have proposed a new optimization technique for bleaching of cured cellulose. In the curing process due to removal of impurities, fiber color will change into yellowish hue. So bleaching will be needed to produce high quality alpha-cellulose. In this research we have bleached cured cellulose fibers at 75 â&#x20AC;&#x201C; 95 oC in 1 â&#x20AC;&#x201C; 4 % hydrogen peroxide solution. Whiteness index and degree of polymerization (DP) was measured in order to investigate the effect of bleaching parameters on final products properties. Statistical analysis showed that both parameters had significant effect on whiteness and DP of final product. Increasing the temperature and hydrogen peroxide will enhance whiteness but reduce the DP of cellulose. In the first stage the normality of the data was evaluated. Normality diagrams stated that our results are completely normal, so we have normalized data via Z conversion. Because we want to maximize both whiteness and DP, Z whiteness and ZDP was added to each other to make a new parameter named Z score. Next the best function was fit to the data using MATLAB curve fitting tool. Finally Genetic Algorithm (GA) was used to optimize curing conditions. GA is inspired by the evolutionist theory explaining the origin of species. In nature, weak and unfit species within their environment are faced with extinction by natural selection. The strong ones have greater opportunity to pass their genes to future generations via reproduction. In the long run, species carrying the correct combination in their genes become dominant in their population. Calculated optimum condition was bleaching at 82 oC in 3.5% hydrogen peroxide solution.

1. Introduction Cellulose is one of the most abundant and widely used natural polymers in the world. Since cellulose is the major consistence of the plants, a large amount of this substance produces annually through photosynthesis. Cellulose can be produced from a variety of sources which differ in some features, and generally classified into two main sources of wood and cellulosic fibers [1]. Impurities presented in cellulose depend on the source from which cellulose has been produced from[2]. Lignin, pectin, hemicellulose, proteins and waxes are cellulose impurities [1-4].Because of this reason, cellulose will need curing process in order to raise cellulose purity. cellulosic fibers get brownish shade after curing treatment, so they need bleaching treatment [5]. In order to produce high quality cellulose, optimizing the bleaching conditions is valuable. Genetic Algprithms (Gas) are a heuristic solution-search or optimisation technique, originally motivated by the Darwinia nprinciple of evolution through (genetic) selection. A GA uses a highly abstract version of evolution ary processes to evolve solutions to given problems. Each GA operates on a population of artificial chromosomes. These are strings in a finite alphabet (usually binary). Each chromosome represents a solution to a problem and has fitness, a real number which is a measure of how good a solution is to the particular problem. Starting with a randomly generated population of chromosomes, a GA carries out a process of fitness based selection and recombination to produce a successor population, the next generation. During recombination, parent chromosomes are selected and their genetic material is recombined to produce child chromosomes. These are then passed into the successor population. As this process is iterated, a sequence of successive generations evolves and the average

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fitness of the chromosomes tends to increase until some stopping criterion is reached. In this way, a GA “evolves” a best solution to a given problem[6]. In this research we have proposed a new method to optimise the bleaching conditions of cured cellulosic fibers which is performed by MATLAB GA optimising tool.

2. Experimental 2.1. Materials Chemicals used in this research were analytical grade. Sodium hydroxide was purchased from Aldrich, hydrogen peroxide were prepared from Merck and used without further purification.

2.2. Fiber pretreatment and bleaching Cotton linter waste was collected from Vashdasht cotton cleaning company. It was processed in a carding machine to remove solid impurities. Curing was performed at 130 oC for 2 hours in 20 g/L sodium hydroxide aqueous solution. Hanau HT dyeing machine was used for curing. Then, cotton linter rinsed twice for complete effluent removal. Bleaching was carried out using 1-4% (w/w) H 2 O 2 for 90 minutes at 75-95 oC. The final product was washed by distilled water and finally dried in an oven at 100 oC for 1 hour.

2.3. Cellulose characterization To measure whiteness, fibers were mixed together by shirly fiber opener until the fibers become fully homogeneous. The reflection spectrum of the fiber was measured by reflectance spectrophotometer. Yellowness index of fibers also calculated according to the standard ASTM E313. Cellulose degree of polymerization (DP) was determined through one point viscosity measurement of 0.3 g/dL cellulose in cellulose-cupperammonium solution at 25oC using these equations:

ηspe = t 1 − t 0 t

(3) 0

[= η ] 1.37 × DP 0.72

(4)

c [η ] + 0.29 [η ]ηsp ηsp =

(5)

Where, c is the polymer solution concentration (g/dL), t 0 and t 1 are efflux time of solvent and polymer solution respectively, [η ] is intrinsic viscosity and ηsp is specific viscosity[2].

3. Results and discussion 3.1. Bleaching treatment Bleaching process performed according to method mentioned at various hydrogen peroxide concentration and temperature. Whiteness index and degree of polymerization of bleached cellulose have been measured and reported in table 1.

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Table 1. Whiteness index and Degree of polymerisation of cellulose in different conditions Whiteness index Degree of Polymerisation H 2 O 2 Concentration (%) 75 oC 85 oC 95 oC 75 oC 85 oC 95 oC 1 2 3 4

37.90 41.31 47.03 46.41

41.97 46.00 52.64 53.10

45.83 47.67 54.48 60.81

5899 5768 5671 5511

5539 5506 5441 5359

5457 5362 5072 4937

According to the presented results it can be seen that cellulose DP will decrease by increasing the temperature and H 2 O 2 concentration. This phenomenon occurs due to the cellulose oxidation in alkali medium. On the other hand whiteness index increases which is due to more oxidative reagent with increasing temperature or concentration. In this case development of new way to optimize both the DP and whiteness index will be valuable.

3.2. Statistical study In this step we focus on normality test and normalization of our data. SPSS statistical software was used for statistical studies. Normality test and distribution have been shown in table 2 and figure 1 respectively. Table 2. Normality test data (obtained from SPSS statistical software)

DP WI

Kolmogorov-Smirinov Statistic df Sig 0.186 12 0.200 0.183 12 0.200

Statistic 0.956 0.962

Shapiro-Wilk df 12 12

Sig 0.719 0.818

(a) (b) Figure 2. Normality distribution for (a) DP and (b) whiteness index Both the Kolmogorov-Smirinov and Shapiro-Wilk normality test methods shows the normality of data for both DP and WI due to higher Sig value (>0.05). Also Normal plots show fine distribution over normal line, so it can be seen that experimental data are normal. Z conversion method was used to normalize experimental data. Normalized data have been shown in table 3.

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H 2 O 2 Concentration (%) 1 2 3 4

Table 3. Normalized data of bleaching treatment Whiteness index Degree of Polymerisation o o o 75 C 85 C 95 C 75 oC 85 oC 95 oC -1.5698 -1.0360 -0.1407 -0.2377

-0.9327 -0.3019 0.7373 0.8093

-0.3285 -0.0405 1.0253 2.0161

1.6402 1.1506 0.7880 0.1900

0.2946 0.1713 -0.0716 -0.3781

-0.0118 -0.3669 -1.4509 -1.9555

Our purpose is to maximize both whiteness and DP, so, a new factor introduced named score which is calculated using equation 1.

score = DP + YI

(1)

Data related to score is shown in table 4. Table 4. calculated data for score H2O2 Concentration (%) 1 2 3 4

75 oC 0.0704 0.1145 0.6473 -0.0477

score 85 oC -0.6380 -0.1306 0.6657 0.4312

95 oC -0.3404 -0.4075 -0.4255 0.0606

Then using MATLAB curve fitting the best curve is fitted on score data. Equation 2 is the fitted function and figure 3 is the fitted curve.

f (x , y ) = 47.54 − 1.158x − 19.18 y + 0.007076x 2 + 0.4891xy − 0.3751y 2 − 0.003323x 2 y + 0.01616xy 2 − 0.1434 y 3 (3)

Figure 3. Fited curve for score Finally fitted function was optimised using MATLAB Genetic algorithm optimising tool. Optimized conditions were bleaching at 82.5 oC using 3.5 % H 2 O 2 concentrated solution.

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4. Conclusions In this research we have bleached cured cellulosic fibers to remove their brownish shade. During the bleaching process by increasing the temperature and H 2 O 2 whiteness of fibers increased, but on the other hand degree of polymerisation was decreased. So optimisation is required to produce the high DP cellulose fibers with fine whiteness. Genetic optimising technique was used to optimise the process. Optimised condition was bleaching in 3.5% H 2 O 2 solution at 82.5 oC.

1. 2. 3. 4. 5. 6.

Ott, E., H.M. Spurlin, and M.W. Graffline, Cellulose and Cellulose Derivatives. second ed. Vol. 1. 1954: Interscience. Klemm, D., et al., Comprehensive Cellulose Chemistry. Vol. 1. 1998: Wiley-VCH. Kalia, S., B.S. Kaith, and I. Kaur, Cellulose Fibers: Bio- and Nano-Polymer Composites. 2011: Springer. Nevell, T.P. and S.H. Zeronian, Cellulose Chemistry and Its Applications. 1987: Ellis Horwood. Woodings, C., Regenerated cellulose fibres. 2001, Cambridge, England: Woodhead. McCall, J., Genetic algorithms for modelling and optimisation. Journal of Computational and Applied Mathematics, 2005. 184(1): p. 205-222.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6

Catechinone Hair Dyestuff Preparation by Chemical Oxidation Method in Water/Alcohol Mixed Solution -Solvent Effect and Reaction MechanismTakanori Matsubara 1, Isao Wataoka 2, Hiroshi Urakawa 2 and Hidekazu Yasunaga 2 1 2

Department of Mechanical Engineering, College of Industrial Technology, Japan Faculty of Fibre Science and Engineering, Kyoto Institute of Technology, Japan

Abstract. Catechinone hair dyestuff was prepared in (+)-catechin/O2/monoethanol amine (base) reaction system, which is in aqueous solution and into which alcohols is added, in order to improve the efficiency of the dye production. The concentration of (+)-catechin greatly increases by adding alcohol into aqueous solution. The efficiency of the dye formation increases with an increase of the base concentration, and the optimum temperature for the dyestuff producing is 30 °C. For preparing the dyestuff, other water-soluble alcohols such as methanol, 1-propanol, 2-propanol and tert-butyl alcohol are available. The water/alcohol mixing ratio strongly affects the dye formation efficiency. The amount of dyestuff obtained is maximum at alcohol molar fraction being 0.45 for water/methanol, 0.25 for water/ethanol, 0.15 for water/1-propanol, 0.20 for water/2-propanol or 0.10 for water/tert-butyl alcohol.

Keywords: Catechinone, (+)-Catechin, Water/alcohol mixed solution.

1. Introduction The authors have been studying safer hair colouring and found that the oxidation product of (+)-catechin, “catechinone,” works as hair dyestuff [1]. Catechinone does not cause erythema or oedema on skin of rabbits. It dyes hair orange, reddish orange or deep yellowish brown, and the colour fastness of the dyed hair to washing and light is high enough. Catechinone is useful as hair dyestuff and the OH improvement of the efficiency of the dye production is the issue for its OH practical application. O HO The dyestuff is obtained enzymatically [1] or chemically [2] and the oxidation reactions proceed at the catechol (o-dihydroxybenzene) group OH of (+)-catechin to give a corresponding o-quinone as shown in Fig. 1. OH The enzymatic technique is superior in terms of the reactivity and selectivity, whereas the chemical method is more useful and practical for industrial production because the chemical reaction is easier to Ox. control than the enzymatic one. Catechinone is chemically prepared by introducing O2 into (+)-catechin basic aqueous solution. Bases and O2 O are necessary for the catechinone formation and the higher pH and O higher concentration of O2 are favourable to forming the dye. O HO Furthermore, the mass yield of catechinone per one batch greatly increases by adding ethanol into the reaction aqueous solution [3]. OH Interestingly, catechinone is obtained little in pure ethanol, whereas the OH dyestuff is formed in water/ethanol mixed solution and its amount is over 20 times higher than that of the dyestuff formed in aqueous Fig. 1: Catechinone formation solution. By optimising the reaction conditions such as concentration reaction by the oxidation of the of (+)-catechin, base and ethanol and temperature, the amount is over 50 catechol part in (+)-catechin. times higher than that in water [4]. Especially, the water/ethanol mixing 

Corresponding author. E-mail address: matsubara@cit.sangitan.ac.jp.

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ratio affects strongly the dye formation efficiency. Water and ethanol should play a crucial role in catechinone formation. In this research, the relation between the efficiency of catechinone production and the preparation conditions such as basicity, temperature or the alcohol type/content of solution was studied. The reaction mechanism in water/alcohol mixed solution is discussed.

2. Experimental (+)-Catechin and monoethanol amine as base were dissolved in water/alcohol mixed solvent. O2 gas was introduced continuously into the reaction solution through porous glass ball filter (pore size: 40 - 50 μm), and the solution was stirred at a fixed constant temperature ( T ). The reaction solution was sampled at several time intervals and diluted by water with a dilution ratio ( f ). The absorbance at 430 nm (A430) of the diluted solution was measured by a Hitachi U-3900H spectrophotometer at 25 °C. The dye formation behaviour was monitored by using f · A430, which corresponds to the concentration of the formed dyestuff.

3. Results and Discussion 3.1.

Effect of base concentration and temperature

The colour of reaction solution turns from pale red to deep reddish brown with reaction time and that shows the formation of catechinone dyestuff. Catechinone is hardly obtained in acidic and neutral reaction solution without base (pH < 8). The amount of dye formed in the water/ethanol mixed solution increases with increasing the monoethanol amine concentration. This is because that catechinone formation proceeds via the deprotonation of OH group of the catechol part in (+)-catechin. The T dependence of the dye formation was examined at 20-50 °C. As shown in Fig. 2, the amount of produced dye at 140 min of reaction time (( f · A430)140 min) in water/ethanol mixed solution slightly increases with increasing T up to 30 °C and it notably decreases over 30 °C. This may be related with the formation of colourless products and/or the precipitation of colourants which is caused by the further reaction of catechinone formation.

3.2.

Effect of alcohol added and reaction mechanism

( f ・A430)140 min / 10

Fig. 3 shows the relationship between the alcohol molar fraction of the solvent (xA) and f · A430)140 min in each water/alcohol mixed solution from (+)-catechin at high concentration (0.17 mol kg-1). In ethanol mixed system, the ( f · A430)140 min increases steeply from xA = 0.10 to 0.25 and decreases from 0.28 to 0.97 and the catechinone is little obtained at xA = 0.97. The maximum of ( f · A430)140 min is also observed in every alcoholadded system as shown in Fig. 3. The optimum xA (xA,max) for each system depends on the type of 1.5 alcohols and it is 0.45 for water/methanol system, 0.25 for water/ethanol system, 0.15 for water/1propanol system, 0.20 for water/2-propanol system or 0.10 for water/tert-butyl alcohol 1.0 system. On the other hand, the differential enthalpy of mixing between water and alcohol (ΔmixH) changes by changing the xA as shown in Fig. 4 [914]. The ΔmixH for methanol and ethanol show 0.5 negative value in any xA and ΔmixH for others show negative value in lower xA. Thermodynamically, the mixed solution is stabilised by interaction between water and alcohol molecules. The phenomenon is known to 0.0 20 30 40 50 be caused by microstructure such as micro phase separation generating water phase and alcohol T / °C phase [5-7]. Comparing between Fig. 3 and Fig. Fig. 2: Relationship between solution temperature ( T ) 4, both ( f · A430)140 min and ΔmixH have a peak for and (( f · A430)140 min) for catechinone preparation in each the alcohol system, and the xA values for water/ethanol mixed solution with 0.50 mol kg-1 of ( f · A430)140 min and ΔmixH at the peak position are monoethanol amine at x = 0.28. A

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0.4

1.5

-1

mixH / kJ mol

( f ・A430)140 min / 10

0.2

1.0

0.5

0.0 -0.2 -0.4 -0.6 -0.8

0.0 0.0

-1.0

0.2

0.4

0.6

0.8

1.0

Fig. 3: Relationship between the alcohol molar fraction of the solvent (xA) and the amount of the dyestuff (( f · A430)140 min) prepared in the water/methanol (), water/ethanol (), water/1-propanol (), water/2propanol () or water/tert-butyl alcohol () mixed solution at 30 °C and 140 min.

0.0

0.2

0.4

0.6

0.8

1.0

Fig. 4: Relation of mixing enthalpy (ΔmixH) for water and alcohols with xA [9-14]. The values are for water/methanol (), water/ethanol (), water/1propanol (), water/2-propanol () or water/tert-butyl alcohol () mixed solution at 25 °C.

near each other. The xA,max, 1-octanol/water partition coefficient of pure alcohol (log POW) which is the index of hydrophobicity of organic compounds [8] and the alcohol molar fraction at the minimum of differential enthalpy of mixing between water and alcohol (xA,Hm) are summarised in Table 1. Table 1 shows that xA,max depends on the type of alcohols and the order of the value is methanol > ethanol > 2-propanol > 1-propanol > tert-butyl alcohol. The xA,max order follows the reverse order of log POW and the order of xA,Hm. The hydrophobicity of alcohols would be correlated with the ΔmixH and further the xA,max for the alcohol, water and (+)-catechin system. The catechinone formation reaction hardly proceeds in pure alcoholic solution and water is necessary for the oxidation of (+)-catechin to give catechinone. This is because the proton dissociation of hydroxyl group of (+)-catechin as described is indispensable for promoting the reaction. In contrast, the solubility of (+)catechin in an alcohol is much higher than that in water. (+)-Catechin prefers to dissolve in alcoholic phase rather than in aqueous phase. Therefore, a large amount of (+)-catechin molecules exist in the alcoholic phase. The (+)-catechin molecule oxidised to give catechinone may be at interface between the both phases sticking the hydroxyl groups into water phase like surfactants. Consequently, the reaction proceeds most efficiently, when the amount of such the water-alcohol Table 1: List of the parameters for producing catechinone interface and (+)-catechin being at the interface is in water/alcohol mixed solvents or pure solvents and their the largest. solvent itself. The proposed schematic illustration of the Alcohols xA,max a log POW b xA,Hm c reaction field for the dye formation as changing Methanol 0.45 – 0.70 0.3 xA is shown in Fig. 5. The model exhibits Ethanol 0.25 – 0.25 0.16 instantaneous local microstructure. In 2-Propanol 0.20 0.13 0.11 water/alcohol mixture, micro-phase separation 1-Propanol 0.15 0.28 0.06 occurs to generate water-rich phase (blue part) tert-Butyl alcohol 0.10 0.36 0.05 and alcohol-rich phase (orange part) [5-7]. At a a The optimum alcohol molar fraction of water/ alcohol lower xA (i), most (+)-catechin molecules are mixed solution for dye producing at concentration of (+)dissolved in alcohol-rich phases and form catechin is 0.17 mol kg-1 and 30 °C. clusters. Some of (+)-catechin molecules are far b The 1-octanol/water partition coefficient of pure alcohol from the interface in the cluster. It may take long at 25 °C [8]. time for (+)-catechin to move to the interface at c The alcohol molar fraction at the minimum of differential which the reaction proceeds and resulting enthalpy of mixing between water and alcohol at 25 °C catechinone remains. As increasing xA (i → ii), [9-14]. the number of alcoholic-rich phase increases

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(i) Lower xA (< xA,max)

(ii) xA = xA,max

(iii) Higher xA (> xA,max)

Fig. 5: Schematic illustration of proposed instantaneous local microstructure in the reaction solution. R ≡ 3,4-dihydro-2H-1-benzopyran-3,5,7-triol.

and/or the volume of the phase enlarges, and then the interface increases. This increases the reactivity. The number of (+)-catechin at the interface reaches maximum at xA = xA,max (ii) and the reaction proceeds most efficiently. Water interacts with alcohol at the most and the maximal interface forms at xA,Hm. However, the xA,max is larger than the xA,Hm as shown in Table 1. The ΔmixH values shown here are for pure water/alcohol mixture. When (+)-catechin is introduced into the system, more alcohol may be required to form the maximal interface. The interface becomes small and the reactivity decreases with the further increase of xA (iii). The alcoholic phase is too large and most of (+)-catechin molecules are far from the reaction interface. As the hydrophobicity of the alcohols (log POW) increases, the xA,max decreases. It can be said that the hydrophobicity order of the five kinds of alcohol plays an important role in the order of the reactivity.

4. References [1] Yasunaga, H.; et al., J. Cosmet. Dermatol. Sci. Appl., 2(3), 158-163 (2012). [2] Matsubara, T.; et al., Int. J. Cosmet. Sci., 35(4), 362-367 (2013). [3] Matsubara, T.; et al., Sen’i Gakkaishi, 70(1), 19-22 (2014). [4] Matsubara, T.; et al., Adv. Chem. Eng. Sci., 4(3), 292-299 (2014). [5] Egashira, K.; et al., J. Phys. Chem. B, 102(21), 4054-4057 (1998). [6] Matsumoto, M.; et al., Bull. Chem. Soc. Jpn., 68(7), 1775-1783 (1995). [7] Wakisaka, A.; et al., J. Mol. Liq., 129(1-2), 25-32 (2006). [8] Kalmet, M.J.; et al., J. Phys. Chem., 92(18), 5244-5255 (1988). [9] Lama, R.F.; et al., J. Chem. Eng. Data, 10(3), 216-219 (1965). [10] Friese, T.; et al., J. Chem. Eng. Data, 44(4), 701-714 (1999). [11] Benjamin, L.; et al., J. Phys. Chem., 67(4), 858-861 (1963). [12] Boyne, J.A.; et al., J. Chem. Eng. Data, 12(3), 318-318 (1967). [13] Bertrand, G.L.; et al., J. Phys. Chem., 70(3), 699-705 (1966). [14] Koga, Y.; et al., J. Phys. Chem., 94(19), 7700-7706 (1990).

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Comparison of Dyeing Behaviors of Reactive Dyes According to Different Neutral Salt Addition Method SeokIl Hong1 and HeeCheol Cha + 1

ICT Textile & Apparel Group, Korea Institute of Industrial Technology, Korea

Abstract. Reactive dyes are most widely used when dyeing cotton fabric, have reactive groups which can have a chemical reaction with hydroxyl groups of the cotton fabric, and are very different in reactivity and dyeing temperature according to reactive groups of the dyes. When dyeing cotton fabric with the reactive dyes, this process includes three steps such as adsorption step, reaction step, and soaping step for removing hydrolyzed dyes to make excellent quality products. Cotton fabric have very high negative potential in their surfaces when immersed in water, and the negative potential of the cotton fabric acts as an electrostatic repulsive force against anionic reactive dyes, thereby hindering adsorption of the reactive dyes to cotton fabric. If the reactive dyes are not adsorbed in the cotton fabric, the fixation ratio of reactive dyes is reduced remarkably in the reaction step, and therefore we should try to increase the amount of dyes to be adsorbed in the cotton fabric as much as possible in the adsorption step. Exhaust dyeing methods used for dip dyeing are dyeing methods used most frequently in dyeing & finishing companies, and are sensitive to dyeing conditions. 1,2 In this study, dyeing behaviors are measured according to methods of adding the large amount of neutral salt (50-100g/L) which are used to reduce the negative potential in the surface of cotton fabric in the adsorption step. Especially, dyeing behaviors are measured and compared according to different neutral salt addition methods (one-addition or split-addition, and dye pre-addition (dye addition-neutral salt addition) or dye afteraddition (neutral salt addition-dye addition), etc.) due to difference between a dyeing laboratory condition and a plant dyeing condition (dyeing machine, dyeing method, etc.). In the case of adding neutral salt, the splitaddition is more effective than the one-addition and the dye after-addition is more effective than the dye preaddition for the reduction of an initial dye adsorption speed, thereby reducing uneven dyeing remarkably. Keywords: reactive dye, neutral salt, dye-o-meter, dyeing behavior

1. Introduction Dyeing industry is located in the middle stream of textile industry and has processes that pursue added value to all textile processes. Variety of conditions and several technologies manifoldly combine to complete the dyeing industry. The dyeing industry requires more standardized dyeing method between the laboratory and field site compared to other fabric because dyeing industry respond to the market by pairing the laboratory and the producing site. If the dyeing was proceeded with standardized dyeing method for both laboratory and field site, the dyeing can be proceeded with not color difference. In particular, cotton fabric dyeing using reactive dye can be divided into first adsorption step between reactive dye and cotton fabric and second reactive step between the absorbed reactive dye and cotton fabric. The compound used in absorption step is neutral salt which helps to reduce negative potential of fabric surface, moves the reactive dye to the fabric surface and help the adsorption. The compound used in reactive step is alkali which helps the violent reaction of covalent bond between the reactive dye moved to fabric surface and cotton fabric to happen. In this study, dyeing behaviors are measured according to methods of adding the large amount of neutral salt (50-100g/L) which are used to reduce the negative potential in the surface of cotton fabric in the adsorption step. Especially, dyeing behaviors are measured and compared according to different neutral salt addition methods (one-addition or split-addition, and dye pre-addition (dye addition-neutral salt addition) or dye afteraddition (neutral salt addition-dye addition), etc.) due to difference between a dyeing laboratory condition and a plant dyeing condition (dyeing machine, dyeing method, etc.). +

Corresponding author. Tel.: + 86-31-8040-6145. E-mail address: redstone@kitech.re.kr

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2. Experimental 2.1 Test samples and reagents 100% mercerized cotton fabric were used for dyeing, and were treated with hot water, scoured, or bleached according to the kind of experiments. Sodium sulfate anhydrous(Na 2 SO 4 ) was used as a neutral salt, and sodium carbonate anhydrous(Na 2 CO 3 ) was used as an alkali and they were first class reagents. Sunfix Red S3B 100% was produced by Ohyoung Industrial Co., Ltd. and is a bi-functional reactive dyestuff having 2 reactive groups of monochloro-triazine and vinysulfone.

2.2 Dyeing For dyeing, uses 100% mercerized cotton fabric. Set up the dyeing concentration to 1.5%o.w.f to each dyes, and used 50g/l of sodium sulfate anhydrous(Na 2 SO 4 ) and 20g/l of sodium carbonate anhydrous(Na 2 CO 3 ). At 30℃, put in the liquid and stir, then divided addition sulphate of soda and absorb about 10 minutes. Then set the temperature rising speed at 1℃/min until 60℃. At 60℃, divided insert Alkali and check the reactive process for 60minutes. Liquor ratio 1:10, set the total dyeing time to100minutes.

Fig. 1: Dyeing and soaping process of reactive dyes

2.3 Measurement of dye liquor state To measure absorbancy of dye liquor in a real time during dyeing, dye-o-meter(DyeMax, KITECH, Korea) was used as shown in Figure 2. Dye-o-meter included a liquor flow dyeing machine that was similar to a reactive dyeing machine for cotton fabrics, a measuring equipment for measuring absorbancy of dye liquor in a predetermined interval, and an analysis program to analyze measured data and show them on a monitor screen. The measuring equipment included a circulation frame for circulating dye liquor, light source and detector. The circulation frame was used to measure absorbancy in a wave length range of UV/VIS 200-750nm and had resistance to heat, pressure, and chemicals. The light source was a pulsed Xenon lamp and was used to measure absorbancy in a wave length range of 220-750nm. The detector was used to measure by expanding channels to maximum 8 sets and was used for precise measurement having high resolution(0.3-1.5 nm FWHM) by using 25 ㎛ slit in a wave length range of 200 - 1100nm. Dye-o-meter was used to measure and analyze absorbancy of dye liquor circulating through the circulation frame at the interval of 1 ~ 2 min. to show exhaustion ratio.

3. Results and Discussion 3.1. Methods of adding of neutral salt Generally, since substantivity of reactive dye is low, the exhaustion rate is around 10%; however if neutral salt is added, the dye’s adsorption rapidly increases reaching around 80%. However, if a large amount of neutral salt was put into in the same time, the rate of initial adsorption increases which affects the unlevel dyeing and worsens the reproducibility. Therefore, neutral salt must be inserted in partition. If the neutral salt is inserted partition, unlevel dyeing due to initial adsorption rate can prevented.

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Fig. 2: Dye-o-meter used in this experiment.(Dyeing MC, Detector, Analysis program)

Figure 3 shows the exhaustion curve change according to the neutral salt concentration of Sunfix Red S3B 100% dye(Initial conc. 1.5% owf, liquor ratio 10:1). It can be seen that as the amount of neutral salt increased in 20g, 30g, 40g, 50g, 60g , 70g, 80g the exhaustion rate also increased. However the exhaustion rate growth width decreased after the amount of neutral salt added was above 40g. In the case of reactive dyes, when the alkali is added, the ion radical ionization increases, exhaustion no longer increases, and only the amount of dye reacting with fabric increases.

Fig. 3: Exhaustion curve change according to the neutral salt concentration

Fig. 4: Exhaustion curve change according to the neutral salt concentration

Figure 4 shows the exhaustion curve change of Sunfix Red S3B 100% dye according to insertion method of neutral salt (initial conc. 1.5%owf, liquor ratio 10:1, neutral salt 50g/l). It represents the exhaustion curve

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change from first inserting all the neutral salt at the very start, second adding in partition every 1 minute and lastly adding in partition every 9 minutes. When the neutral salt is inserted in partition, the adsorption rate slows down which prevents unlevel dyeing according to initial adsorption rate. In addition, by controlling the initial adsorption rate with neutral salt, it can be seen that exhaustion rate before insertion of alkali will all reach the same concentration.

3.2. Procedures of adding of neutral salt In addition, in order to improve the color reproducibility of laboratory and field site, according to the order of adding dye and neutral salt, dye pre-addition (dye addition-neutral salt addition) or dye after-addition (neutral salt addition-dye addition) methods are used to dye. Figure 5 shows the exhaustion curve change according to the order of adding dye and neutral salt. Compared to dye pre-addition (dye addition-neutral salt addition), Dye after-addition (neutral salt addition-dye addition) does have the same final exhaustion rate, but because the initial adsorption rate is faster, unlevel dyeing may occur. If the dye was inserted after the neutral salt is fully dissolved, unlevel dyeing may occur because the substantivity is high.

Fig. 5: Exhaustion curve change according to the order of adding dye and neutral salt.

4. Conclusions In this study, dyeing behaviors are measured according to methods of adding the large amount of neutral salt (50-100g/L) which are used to reduce the negative potential in the surface of cotton fabric in the adsorption step. Especially, dyeing behaviors are measured and compared according to different neutral salt addition methods (one-addition or split-addition, and dye pre-addition (dye addition-neutral salt addition) or dye afteraddition (neutral salt addition-dye addition), etc.) due to difference between a dyeing laboratory condition and a plant dyeing condition (dyeing machine, dyeing method, etc.). In the case of adding neutral salt, the splitaddition is more effective than the one-addition and the dye after-addition is more effective than the dye preaddition for the reduction of an initial dye adsorption speed, thereby reducing uneven dyeing remarkably.

Acknowledgement This work was supported by the Ministry of Strategy and Finance of Republic Korea (Kitech JC-15-0032).

5. References [1] P. S. Collishaw, D. A. S. Phillips and M. J. Bradbury, J. Soc. Dyers. Colour., 109, 284(1993). [2] K. Parton, J. Soc. Dyers. Colour., 110, 4(1994).

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Design of Safer Flame Retardant Textiles through Inclusion Complex Formation with Cyclodextrins Nanshan Zhang, Jialong Shen, Melissa A. Pasquinelli, David Hinks and Alan E. Tonelli + Fiber and Polymer Science Program, North Carolina State University Campus Box 8301, Raleigh, NC 27695-8301, USA

Abstract. Flame retardants (FRs) are utilized to reduce the ignition time and spread of burning in materials. They are applied to many products that have the potential to burn, including apparel, furniture upholstery and foams, drapes, floor coverings, plastics and insulation. FRs are a prime example of the challenge presented by industrial chemicals that are intended to benefit society, yet pose substantial environmental and toxicological impacts. Many current FRs lead to adverse effects on health and the environment because they are often applied as a finishing treatment, and thus are not integrated into the structure of the material in such a way that the chemicals remain within the material during its intended lifetime. Through an experimental effort, we demonstrate an alternative approach involving the formation of an inclusion complex (IC) between halogenated FRs and β-cyclodextrin (β-CD). These FR-CD-ICs are easily melt-processed into polymer materials and retain flame retarding properties of polymer materials with the FR-CD-IC incorporated. They also eliminate the unnecessary loss of FRs, especially volatile FRs, and are expected to only be released from the IC when they are actually needed during burning protection. In this manner, FR-CD-ICs also reduce the potential toxicological effects of the included guest FRs.

Keywords: flame retardant (FR), triphenyl phosphate (TPP), β-cyclodextrin (β-CD), inclusion complex (IC), poly(ethylene terephthalate) (PET)

1. Introduction According to the data provided by the ‘International Association of Fire and Rescue Services’, 2.5 million fires were reported from thirty-two countries worldwide, causing 21,700 deaths in 2013 (1). In the U.S., home structure fires led to an average of 2,570 civilian deaths and $7.2 billion of property damage per year during the five-year-period (2007-2011). ‘NFPA Fire Analysis and Research’ claimed that upholstered furniture and mattresses and bedding fires are the primary causes of home fire deaths (2). To minimize fire loss, flame retardants (FRs) have been actively used in a wide variety of combustible products, including apparel, drapes and furniture upholstery. Flame retardants are chemicals added to materials with an aim to prevent combustion and delay the spread of fire. Conventional FRs such as polybrominated diphenyl ethers (PBDEs) were found to be bioaccumulative, persistent and endocrine disruptive, and thus are being phased out. As one of the potential replacements for PBDEs, Firemaster 550 (FM 550) is extensively applied in polyurethane foams. Triphenyl phosphate (TPP) (See Fig. 1 (a)), a phosphorus flame retardant, is one of the four components of FM 550. However since it is also an additive, TPP can migrate out of the flame retarded product over time. It has been detected in U.S. house dust, with concentrations as high as 1.8 mg/g of dust (3). Furthermore, TPP is associated with a R50/53 label in Europe and the use of TPP has been restricted due to its toxicity to aquatic organisms (4).

Corresponding author. Tel.: + 1-919-515-6588. E-mail address: alan-tonelli@ncsu.edu.

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The resemblance between the structures of TPP and triphenyl tin chloride (TPT chloride) makes TPP also a potential endocrine disruptor. A recent work demonstrated that TPP diverted osteogenesis to adipogenesis in primary mouse bone marrow cultures, which may result in an enhanced transcriptional activity of PPARγ in human (5). By taking the mass production and the potential endocrine disrupting properties into consideration, the environmental exposure of TPP needs to be significantly reduced. Cyclodextrins (CDs) are cyclic oligosaccharides with different numbers of α-(1,4)-linked glucopyranose units. The three most well-known members are alpha- (α-), beta- (β-) and gamma- (γ-) cyclodextrins, which are also called natural CDs. The structures of CDs are visualized as truncated cones and the chemical structure of β-CD is illustrated as Fig. 1 (b). The unique structure of CDs endows them with a hydrophilic outside and a hydrophobic inner cavity. As a result, CDs can act as containers where a series of ‘guest’ molecules can be embedded. This is probably the most striking feature of cyclodextrins. β-CD is the most widely used CD due to its low-cost and moderate size (6). Therefore it is chosen in the current work. Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), 1H-nuclear magnetic resonance (1H-NMR) and wide-angle X-ray diffraction (WAXD) were applied to verify the formation of the TPP-β-CD-inclusion complex. Inspired by an idea from Tonelli and coworkers, it is expected that by including FRs into CD-ICs, the guest molecule (FR) will not be discharged under normal conditions, but only when adequate heat is provided (7). Consequently, flame retardants can retain their flame-resistant properties, without the usual environmental and health concerns.

2. Methodology 2.1.

Preparation of physical mixture (PM) and inclusion complex (IC) of β-CD and TPP

2.2.

Preparation of PET films by a hot-press technique

2.3.

Film thickness test

The inclusion complex of β-CD and TPP (TPP-β-CD-IC) was prepared by a co-precipitation method. TPP was dissolved in methanol and added dropwise to an aqueous solution of β-CD. The mixture was heated at 50 ºC for 3 hours with stirring. The system was then rested overnight, following by filtration and vacuum drying. The physical mixture of β-CD and TPP (TPP-β-CD-PM) was made by mixing the two substances mechanically.

Four groups of film samples including pure PET films, PET films with 10 wt. % β-CD (PET-β-CD), PET films with 10 wt. % neat TPP (PET-TPP) and PET films with 10 wt. % TPP-β-CD-IC (PET-IC) were prepared by using a Carver Laboratory Press (Model B). All film samples were made at 250 ºC under fixed pressure and time. Finally the whole system was quenched in ice water. A Thwing-Albert Electric Thickness Tester (Model II) was employed to measure film thicknesses according to ASTM D 1777 (8). For each individual film the thickness was measured at 10 different locations, and an average thickness was reported for each film.

2.4.

Flame retardancy test

Flame-resistant properties of PET film samples were evaluated by a modified ASTM D 6413 (9). Here the standard method was slightly adjusted due to the restriction of film sample size. The specimen was mounted in the specimen holder and their bottoms leveled with each other. Then each film specimen was exposed to the flame for 3 seconds and the ignition source was moved away. Char length and after ignition flame time were recorded. OH

3. Results and Discussion

3.1.

Characterization of TPP-βCD-IC

O HO

HO O

OH O OH

FTIR is a useful tool in verifying the O presence of the host and guest molecules O P in expected IC products. Characteristic O O vibrational bands from both β-CD (for -1 instance, at ~ 3347.1 cm ) and TPP (for (a) TPP (b) β-cyclodextrin instance, at ~ 1589.6 cm-1) are probed in the spectrum of IC (Fig. 2 (a)). Changes in Fig. 1: Chemical structures of (a) TPP and (b) β-cyclodextrin. frequencies of the corresponding peaks may indicate the interaction between the host and the guest. On the contrary, the physical mixture (PM) spectrum is a simple combination of β-CD and TPP spectra, with no observed host-guest interaction. O

O OH

Page 978 of 1108

From TGA thermograms (Fig. 2 (b)), the difference between PM and IC is observed. Three separate weight loss stages, including thermal degradation of water, TPP and β-CD are displayed in PM curve. However, degradation of TPP disappears in the IC thermogram, indicating the improved thermal stability of the volatile compound, TPP. This can likely be attributed to the host-guest interaction. TPP has a melting temperature of around 50 ºC, so if it forms an inclusion complex with β-CD, no endothermic melting peaks will be observed near 50 ºC in the IC thermogram. In Fig. 2 (c), an intensive peak appears at 49 ºC in the neat TPP thermogram, however it is absent in that of IC. In combination with FTIR and TGA findings, results from DSC analysis demonstrate there is no free TPP in the IC and an inclusion complex has been successfully formed. DMSO-d 6 was chosen as the solvent to dissolve β-CD, TPP and IC samples and their NMR spectra are presented in Fig. 2 (d). By integrating specific featured peaks from β-CD and TPP in the IC spectrum, a stoichiometry of β-CD:TPP~2:1 is obtained for the inclusion complex. Though not presented there, WAXD further reveals the distinct features between the PM and IC. This fact indicates that IC is a new type of crystal, which is different from a simple combination of β-CD and TPP crystals present in the PM. However it is hard to draw a conclusion whether the obtained IC adopts the cage or columnar crystal structure.

(a) FTIR

(b) TGA

(c) DSC (d) NMR Fig.2: Proof of the formation of TPP-β-CD-IC, including (a) FTIR, (b) TGA, (c) DSC and (d) NMR results. Figures are reused with permission from Ref. (10).

3.2.

Flame retardancy test

Results of film thickness tests exhibit that film samples have comparable thicknesses. At 3 seconds after removing the ignition source, untreated PET (Fig. 3 (a)) and PET-β-CD (Fig. 3 (b)) films combusted vigorously and dripping behavior was noticed. In contrast, PET-TPP (Fig. 3 (c)) and PET-IC (Fig. 3 (d)) samples became self-extinguishing at this time point. PET (Fig. 3 (e)) and PET-β-CD (Fig. 3 (f)) films continued to flame and at 20 seconds (after the removal of the burner), both films were almost entirely consumed by burning. At the same time, the majority of PET-TPP (Fig. 3 (g)) and PET-IC (Fig. 3 (h)) films remained unaffected since combustion had stopped earlier. Through the comparison of char length and after ignition flame time, PET-IC is comparable to PET-TPP in flame-resistant properties. However, considering the fact that β-CD by itself did not offer enhanced flame retardancy to the substrate, PET-IC sample should attribute its superior performance to the advanced thermal stability of TPP included in the host CD. It should

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be noted that the amount of TPP (in mass) in PET-IC was only one eighth of that in PET-TPP, according to the stoichiometry calculated from NMR results. As a result, use of IC is more efficient with potentially longer standby time than using TPP alone.

Fig. 3: Photographs of films at 3 and 20 s after the removal of ignition source. Figures are reused with permission from Ref. (10).

4. Conclusions In the current work, an inclusion complex formed between β-cyclodextrin and TPP flame retardant is reported. Formation of IC has been verified via a series of characterization techniques. Vertical flame tests demonstrate that PET-IC films own superior flame-resistant properties in spite of containing a lower concentration of effective FR. At the same time, it is expected that the exposure and release of TPP will be reduced, thus lessening environmental and health concerns associated with it and other FRs. Further work on the study of toxicity and other biological effects of TPP-β-CD-IC should now be conducted.

5. Acknowledgments The authors are grateful to North Carolina State University for funding and support through the Research Innovation and Seed Funding (RISF) program.

6. References [1] Brushlinsky NN, Ahrens M, Sokolov SV, Wagner P. World Fire Statistics. International Association of Fire and Rescue Services; 2015. [2] Ahrens M. Home Structure Fires. U.S.: National Fire Protection Association; 2013. [3] Stapleton HM, Klosterhaus S, Eagle S, Fuh J, Meeker JD, Blum A, et al. Detection of Organophosphate Flame Retardants in Furniture Foam and US House Dust. Environ Sci Technol. 2009 OCT 1;43(19):7490-5. [4] Brooke D N, Crookes M J, Quarterman P and Burns J. Environmental risk evaluation report: Triphenyl phosphate. United Kingdom: Environment Agency; 2009. [5] Pillai HK, Fang M, Beglov D, Kozakov D, Vajda S, Stapleton HM, et al. Ligand Binding and Activation of PPAR gamma by Firemaster (R) 550: Effects on Adipogenesis and Osteogenesis in Vitro. Environ Health Perspect. 2014 NOV;122(11):1225-32. [6] Szente L, Szejtli J. Cyclodextrins as food ingredients. Trends Food Sci Technol. 2004 0;15(3–4):137-42. [7] Huang L, Gerber M, Lu J, Tonelli A. Formation of a flame retardant-cyclodextrin inclusion compound and its application as a flame retardant for poly(ethylene terephthalate). Polym Degrad Stab. 2001;71(2):279-84. [8] ASTM D1777-96(2011)e1, Standard Test Method for Thickness of Textile Materials, ASTM International, West Conshohocken, PA, 2011. [9] ASTM D6413 / D6413M-15, Standard Test Method for Flame Resistance of Textiles (Vertical Test), ASTM

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International, West Conshohocken, PA, 2015. [10] Zhang N, Shen J, Pasquinelli MA, Hinks D, Tonelli AE. Formation and characterization of an inclusion complex of triphenyl phosphate and Î˛-cyclodextrin and its use as a flame retardant for polyethylene terephthalate. Polym Degrad Stab. 2015 10;120:244-50.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Development of New AOX-free Processing Method Extended to Wool Masukuni Mori1* and Illya Kulyk2 1

Mori Consultant Engineering Office, 36-1 Kaimei, Ichinomiya, Aichi, 494-0001 Japan Veneto Nanotech SpA, via delle Industrie 5 I-30175 Marghera (VE) Italy

Abstract. Wool fabric has a lot of excellent physical properties, outstanding functionality and soft handling that are rarely realized by any other fibers and fabrics. Now some fields are composed of garments made of only wool fabrics and fibers. But unfortunately, the most disadvantageous point of wool fabrics is to cause felt-shrinkage accompanied by home washing, and besides, pill generation during wearing the fabrics cannot be avoided. Accordingly, though processing by Kroy Hercosett and/or water-soluble urethane resin processes has been industrially executed even now, it has been well-known that chlorine induces the environmental problem and resin finishing destroys fabric handling characteristic of wool fabrics. In this work, improved ARS (US Agricultural Research Service) process, improved sodium hypochlorite process, cationic polyamide resins assisted process, and so on, were compared with each other regarding the adaptability for the underwear use.

Keywords: Anti-felting, Anti-pilling, Super black effect, Eco-friendly process, Wool.

1. Introduction Chlorine-free (AOX (Adsorbable Organic Halogen)-free) shrink-proofing for woolen fabrics is an important subject to be solved even now. Researches on chlorine-free shrink-proofing began more than twenty years ago. Now the chlorinefree shrink-proofing has still been an urgent subject among persons concerned with wool in the world over. Currently, the chlorination process is a principal one for the purpose of anti-felting (shrink-proofing) for wool, and particularly in Japan, this process has been adopted as the pretreatment process for super-black formal wear production as well as the shrinkproofing one. Actually, any other deep dyeing methods have not been available yet. In view of such a situation, the present author proposed only one processing method by means of low-temperature plasma exposure in 2005 [1-4]. The plasma method attained satisfactory anti-felting effect, but unfortunately, it was found to be inferior to the chlorination process with respect to deep dyeing and soft handle of processed fabrics. The low-temperature plasma process has not been put into practice because of low productivity and high equipment cost. After that, the author concentrated on searching for safe and shrink-proofing agents replacing with chlorine, and presented some alternative technologies [5-7], wherein the ARS method [4], was opened to the public in 2010, and it was found to be a promising method. Experiments have been continued for the sake of putting into practice. Meanwhile, a demand of the wool material for high-class sweaters increases even now, but the pill generation problem is not solved. It became clear in 2014 that the ARS process had a high anti-pilling effect as compared with chlorination and also had a marked deep-black effect [9, 10]. However, the ARS method had only low anti-felting effect as compared with the chlorination process. Thereby, it is judged that wool fabrics treated with the ARS process cannot stand for machine washing. Thus, in order to compensate such anti-felting properties of ARS method, the present author thought a combined use of aqueous solution of cationic polyamide resin.

2. Experimental 2.1. Materials Fabric samples to be used for experiments were decreased by about 20% in both warp and weft directions as compared to the standard density in order to facilitate the degree of felt-shrinkage during washing and pill generation during wearing. Sample fabric was 2/2-twill fabric made of 2/48 100% merino wool yarn. Also the number of twist of yarn, the lower twist is Z500 and the upper twist was S260 in warp and weft directions. The density was 170/10 cm in warp and 165 pick/10 cm

Page 982 of 1108

in weft. The fabric weight was 158 g/cm2.

2.2. Outlines of various kinds of chemical anti-felting methods The present author has been searching for a shrink-proofing method for ages, and a combined method of NARS with cationic polyamide resin has been concluded as the best shrink-proofing method for wool. The permonosulphate method was a representative non-chlorine shrink-proofing one. The chlorination process has been executed even now because of anti-felting effect, high machine washable effect and super-black realization, though it is not a eco-friendly process. For the purpose of comparison, atmospheric pressure plasma treatment with no liquid effluent and no chemicals was added.

2.2.1. NARS＋Resin A ARS method refers to the processing described in US Agricultural Research Service (Wyndmoor, PA 19038). First, 20 to 25 degrees C water was put into the dyeing bath at a liquor ratio of 1 : 20 to 1 : 30. A solution of 0.05% nonionic surfactant as a penetrating agent was added into it. Then, according to a modified ARS method (ARS method excluding enzyme processing is called NARS method), treatments to wool fabrics were carried out at conditions of pH 10.2, 30 degrees C, period of 10 min and liquor to wool ratio of 20 : 1 using a laboratory dyeing machine containing 3 g/L sodium hydroxide, 1 g/L gluconic acid, 5 g/L dicyandiamide and 12 mL/L H2O2 (35%). After such treatments, the fabrics were rinsed with water until reaching neutral pH. Following NARS method described in 2.2.1, cationic polyamide resin process is executed; using a 15% solution of , the sequence Padding- Squeezing (100% pick-up) -Drying at 130 degrees C, Curing for 2 min. pick-up - Drying - Curing was taken.

2.2.2 NARS＋Poylamide Resin B This processing is the one in which Resin A in 2.2.1 is replaced with Resin B. Components and compositions of Resin A and Resin B have not been opened to the public by manufacturers. Both of them are imagined to be mainly composed of hydroxy-cation monomer, and at least, compositions of them seem to be different from each other.

2.2.3. Permonosulfate＋Resin A Permonosulfate method is the treatment executed by a standard prescription using a 6.0% o.w.f. solution of permonosulfate (KHSO5). Afterward, resin finishing using Resin A was performed like in 2.2.1

2.2.4. Chlorination treatment Chlorination is the treatment executed by a standard prescription using a 3% o.w.f. (active chlorine conversion) solution of DCCA (Dichloroisocyanuric acid)

2.2.5. Atmospheric pressure plasma Fabric was treated by DBD (Dielectric barrier discharge) in air with the energy of 60 J/cm2 applied (Veneto Nanotech, Italy).

2.3. Evaluation and measurement methods 2.3.1. Evaluation of felt-shrinkage of wool fabric and measurement of tensile strength Washing tests were performed according to the following cycle using a full-automatic drum-type washing machine. One cycle of washing is composed of 5 min washing, 5 min rinsing and 5 min dewatering. After 5 cycles were repeated, air-dried was executed. After such 5 times washing and spontaneous drying, the degree of felt-shrinkage of the sample was measured in warp and weft directions. The ratio of felt-shrinkage area, Sa (%), was obtained from equation (1), Sa (%) ＝〔{(L01＋L02)－(L1＋L2)}/ (L01＋L02)〕× 100 (1) where L01 is the length of original fabric in the warp direction, L02 is the length of original fabric in the weft direction, L1 the length of fabric in the warp direction after washing, L01 is the length of original fabric in the warp direction and L2 the length of fabric in the warp direction after washing.

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Tensile (Breaking) strength, elasticity and Young’s modulus were measured based on JIS L-1095

2.3.2. Evaluation of fabric handle Changes of mechanical properties and handling for treated and untreated fabrics were determined by an objective evaluation method using KES [11, 12]. Tensile, bending and shearing properties were measured for warp and weft yarns, and both compressive and surface properties for fabrics were measured together with thickness and weight.

2.3.3. Dyeing method Each sample was dyed with 4.0% o.w.f. Lanasol Black CVR (Reactive) for 20 min at 100 degree C. Then, a 2.0% solution of maleic acid was added, and the dyeing bath was maintained at a boiling state for 10 min. After complete washing, the dyed fabrics were dried.

2.3.4. Color measurement Color of sample was measured by spectro-colorimetry: Minolta CM-3600D. Power source was D65, visual angle was 10 degrees, and sample size was 5 cm×5 cm. Dyeing intensity was determined from the reflection ratio at maximum absorption wavelength, and K/S was calculated using Kubelka-Munk equation. L*, a* and b* on CIELAB system were obtained for dyed samples, where L* was used for the reference value of dyeing yield.

2.3.5. Evaluation of yellowing Reflectance of untreated and 7 treated wool was measured, and L* was calculated according to Kubelka-Munk equation. The yellowing index was obtained from the change to the untreated wool fiber.

2.3.6. Pilling test method Pilling conditions for treated and untreated fabric samples are based on JIS L-1076-1992 (ISO 12945-1) method. The measurements for treated fabrics were compared with those for untreated fabric. According to the method, the ranking of pill generation was determined from the first to the fifth rank.

2.3.7. Hydrophilic property Hydrophilic property was determined according to Byreck method of JIS-1907: water-absorbancy test. The fabric sample with 10 mm wide and 200 mm long was dipped in a 2% solution of C.I. Acid Red 116, and water absorption height was measured after 1 h had passed. Water-absorbancy, H (%), was calculated by equation (2), H (%) ＝ h/hmax ×100 (2) where hmax is the maximum height (mm), and h water absorption height of each sample (mm).

2.3.8. Observation of fiber surface morphology SEM (Hitachi S-2150 Type) was used for observation of wool surface at direct magnification ranging from 100 to 3000. 3D profile microscope (Keyence KK 9800) was used on the direct magnification of 1000 at a plane special resolution of 0.13 μm and with the repetition accuracy of 0.02 μm.

3. Results and Discussion 8 items of performance for fabrics treated by shrink-proofing and an untreated fabric were compared, and they are summarized in Table 1. Process 2 (NARS＋Resin A) is proven to exhibit satisfactory characteristics in anti-felting, color intensity, yellowing, anti-pilling, hydrophilicity, etc. Table 1: Comparison of performance in five sorts of non-chlorine anti-felting processing No.

Method No. Evaluation item

Numerical value 1

Order 5

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Anti-felting (%)

Area shrinkage (%) Appearance (1-5) THV (Total Hand Value) B (Bending rigidity) 2HG5 (Share hysteresis)

Fabric Handle

3 4 5

Color intensity (K/S) Yellowing (%) Anti-pilling (1 to 5 Grade) Number of fluff balls dropped out

6 7 8

Hydrophilicity (cm) Tensile strength (N) Elongation (%) Degree of damage by methylene blue (K/S) (

57.5 1 2.60 0.080 0.39 6 80 1 0 6.0 198.4 15.7 5

8.0 4 3.06 0.081 0.63 22 85 3-4 0 3.5 223.1 22.6 12

4.5 4 2.59 0.140 0.94 18 83 3 10 7.2 235.8 20.6 24

40 4 3.26 0.100 0.66 14 81 2-3 0 9.5 199.8 20.8 18

12.5 2-3 3.04 0.099 0.50 24 75 2 15 12.0 185.6 12.0 37

15.0 2 2.05 0.089 1.43 10 80 1 50 11.0 199.5 16.3 10

3.>2>5>6>4>1 2=3=4>5>6>1 4>2>5>3>1>6 1>2>6>5>4>3 1>5>2>4>3>6 5>2>3>4>6>1 2>3>4>1=6>5 2>3>4>5>1=6 1=2=4>3>5>6 3>2>6>4>1>5 2>4>3>6>1>5 3>1>2>6>4>5 1>2>6>4>3>5

*Sample 1: Untreated, 2: NARS+Resin A treated, 3: NARS+Resin B treated, 4: Permonosulphate+Resin A treated, 5: Chlorination treated, 6: DBD plasma treated

Fiber surface morphology observed by SEM is shown in Figure 1 for untreated fabric 1 and treated fabrics 2 - 6. In Figure 2, anti-felting effects were compared for untreated and treated fabrics 1 - 6. Typical basic physical properties, bending rigidity B and shear hysteresis 2HG5 of untreated and treated fabrics representing fabric handle are compared for untreated and treated fabrics 1 â&#x20AC;&#x201C; 6 in Figure 3. Figure 4 shows hydrophilic properties of untreated and treated fabrics.

Fig. 1: Observation of fiber surface morphology (1:1000).

Fig. 3: Comparison of typical basic physical properties representing fabric handle for untreated and treated fabrics.

Fig. 2: Comparison of Anti-felting effects.

Fig. 4: Hydrophilic properties of untreated and treated fabrics.

It is obvious in Figure 1 that the scale edge opens for untreated sample, whereas in samples 2 â&#x20AC;&#x201C; 4, the surfaces are covered with resins. In Sample 5, only the trace of complete removal remains. Scale edge on Sample 6 appears close as compared to Sample 1. This evidence suggests that scale edge should be related to anti-felting and anti-pilling natures. It is confirmed from Figure 2 that anti-felting nature is improved by resin processing. Figure 3 indicates that both bending rigidity B and shear hysteresis 2HG5 of Sample 3 are larger than those of Sample 2, which result in stiff handling. Accordingly, Sample 3 cannot be used practically, though being superior in shrink-proofing nature.

4. Conclusion Process 2 had satisfactory effects on both anti-felting and anti-pilling which was the main purpose of this work. Process 3 is also superior in anti-felting. However, 2HG5 is large, and hence, fabric handling is stiff. The process 2 is superior in color intensity, and is characterized by the fact that there is little change in fabric handle. Therefore, synthetically the process 2 is recognized as an AOX-free prescription. It is clear from the numerical value of shear hysteresis in KES that the polyamide resin used in this work is effectively cross-linked with wool fibers. However, as for Sample 2, the fabric handle

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becomes a little stiff. The optimum amount of resin to be used and the optimum prescription must be established as early as possible.

Acknowledgements The authors thank Dr. Hidehiro Kumazawa, Professor Emeritus, University of Toyama, for his kind and suggestive discussion and critical reading of the manuscript.

References [1] M. Mori and N. Inagaki, SEN-I GAKKAI SHI, 61, 267-275 (2005) [2] M. Mori and N. Inagaki, Research Journal of Textile and Apparel, 10, 33-45 (2006) [3] M. Mori, M. Matsudaira and N. Inagaki, Journal of Textile Engineering, 52, 19-27 (2006) [4] M. Mori and N. Inagaki, Textile Research Journal, 83, 208-215 (2006) [5] M. Mori and M. Matsudaira, Fibers and Polymers, 10, 182-1921-8 (2009) [6] M. Mori, V.V. Arim, D. Alberecht, M. Matsudaira and T. Wakida , Journal of Textile Institute, 102(6), 534-539 (2011) [7] M. Mori and M. Matsudaira , Textile Research Journal, 83, 208-215 (2013) [8] M. Cardamone and J. Yao, Textile Research Journal, 74, 555-565 (2004) [9] M. Mori, T. Fujimoto and M. Murakami, International Conference on Kansei Engineering and Emotion Research, Sweden (2014) [10] M. Mori, ISF 2014 Conference, SEN-I GAKKAI, Tokyo (2014) [11] Textile Machinery Society of Japan, â&#x20AC;&#x153;Manufacturing Performance and Mechanical Properties of Fabricâ&#x20AC;?, Amagasaki-Insatsu, Osaka, pp. 15-29 (1998) [12] S. Kawabata:"The Standardization and Analysis of Hand Evaluation, 2nd Ed.", HESC, Textile Machinery Society of Japan, 28 (1980)

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Discoloration of Kapok Indigo Denim Fabric by Using Carbon Dioxide Laser with Different parameters Wei Du1, Ting-ting Li2, Zheng-lei He3, Hou-lei Gan4, Xun-gai Wang3,4, Chang-hai Yi1,2,3 ∗ 1

School of Materials Science and Engineering, Wuhan Textile University, Wuhan, China 2 School of Fashion, Wuhan Textile University, Wuhan, China 3 School of Textile Science and Engineering, Wuhan Textile University, Wuhan, China 4 Australian Future Fibres Research & Innovation Centre, Institute for Frontier Materials, Deakin University, Geelong, Australia

Abstract: The kapok fiber is a kind of hollow fibers, its hollow degree is 90%. In this study, a CO 2 laser machine was used for the color-fading treatment of kapok denim fabric in the conditions of different laser power and movement speed. To analyze the color fading of denim fabrics, surface morphology and chemical molecular structure were tested by SEM and FTIR. Moreover, the properties of denim fabrics including tensile strength, air permeability and thickness were measured, as well as color changing (K/S value). The result demonstrates that K/S value of kapok denim fabric was reduced dramatically, while the thickness kept stable, air permeability and tensile strength of denim fabric were decreased slightly. Furthermore, with the laser power increasing and the speed decreasing, the K/S values and the strength reduced significantly, but the changes in thicknesses and the permeability of the kapok denim fabrics were changed fractionally.

Key words: Kapok; Denim fabric; Laser technology; Color-fading; Air permeability.

Introduction Kapok fiber is a natural fiber, apart from being more environmentally-friendly than manmade fibers. It is the best warm natural fiber material which keeps hollow degree 90％ [12] . Kapok also has a good natural anti-bacterial and drive mite effect, the driving mite rate can reach to 87.54％, and the anti-bacteria rate is 99.4％[3]. CO 2 laser treatment has been used in different areas of textile industry for several years, because it allows short-time surface designing of patterns with good precision, desirable effect, various size and intensity without much damaging the bulk properties of the textile materials [46] . In the case of denim fabric, CO 2 laser treatment is proved to be an effective method for fading the color from denim fabric surface in a short time depending much on the laser process parameters [7].

1. Experiments 1.1 Materials ∗

Corresponding author. Tel.: + 86-02759367652; fax: + 86-02759367572. E-mail address: yichanghailaoshi@163.com.

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Denims were provided from Guangdong Jun’an Denim Research Institute, fiber components of the denim were 70％cotton and 30％ kapok, the gram weight of the denim was 322.42 g/m2, the weft density(strips/10cm) was 198, the warp density( strips/10cm) was 338. The E-400 laser engraving machine was provided from Wuhan Golden Laser Co., Ltd. The laser power was from 0 to 500w, the speed was from 0 to 20000mm/min.

1.2 Preparation of samples The denim fabrics were cut 20 pieces with the size of 300mm × 300mm, and were numbered sample0 to sample9. The different parameters of laser were used to process the kapok fabrics, as shown in Tab.1. The laser process formulated as follows: a fixed length of 1650mm, the start delay time 300μs, end of the delay time 300μs, the power and speed were varied from 225w to 255w and from 10000mm/min to 12000mm/min. Tab.1. P (w)

Orthogonal experimental factors 225

240

255

10000

Sample 1

Sample 4

Sample 7

11000

Sample 2

Sample 5

Sample 8

12000

Sample 3

Sample 6

Sample 9

V(mm/min)

(Untreated is Sample 0)

1.3 Methods The morphology of three samples was observed using a Scanning Electron Microscopy (SEM) (JSM-6510LV, Japan). The surface composition of three samples was measured by FTIR (TENSOR-27. German) with the scan time of 256s and wave number 500-4000/mm-1. The color strength (K/S) was determined by X-rite Color I 7 spectrophotometer. The load and elongation at break (tensile strength) was measured by mechanical properties tester (YG026H, China). The air permeability was tested by air permeability tester (YG461E, China). The fabrics’ thicknesses were researched by thickness tester (YG (B) 141D, China) [8].

2. Result and discussion 2.1 Influence of laser washing on permeability and thickness The different samples' corresponding (air permeability and thickness) for laser were reported in Tab.2. As seen, the thicknesses of denim fabrics almost kept stable, while the number of air permeability was lower than before. The reason was the fabrics were washed by laser, so that the surface of the yarn was worn-out, the hairiness was generated, the gap between the yarns was reduced, and the rate of permeability was decreased. What’s more, after the laser processing, some residue of the dye would be left on the the fabric surface, it would also cause the decrease of permeability. Compared with the air permeability changed obviously, the thicknesses of the fabrics were not changed markedly after the laser washing treatment. The reason was that laser washing for denim without mechanical action, and just used high temperature to etch the dye on the surface of the fiber.

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Tab.2. Different laser parameters processed kapok denim permeability and thickness Sample Permeability /mm/s

34.62

33.21

33.80

34.00

32.21

32.93

33.11

31.60

31.72

32.14

0.44

0.41

0.42

0.41

0.42

0.45

0.43

0.42

0.44

Thickness/mm

2.2 Influence of laser washing on K/S value The different samples' corresponding (K/S) for laser were reported in Tab.3. As shown, the K/S values of the denim fabrics had been obviously decreased. As a common, the K/S value is smaller, the color is lighter. In this experiment, the effect of laser washing was very obvious. Laser washing was to use the heat produced by laser energy to etch the dye on the fabric surface, the power was higher, the speed is slower, the K/S values was smaller, so the Sample7’s K/S values was smallest 3.378. What’s more, the rates of decline were all more than 53.56％, it indicated the method of laser processing was a suitable way to bleach the kapok/cotton denim fabrics. Tab.3. Different laser parameters processed kapok denim K / S values Sample K/S Value

14.252

5.577

5.967

6.618

4.219

5.342

5.112

3.378

3.867

4.113

60.87

58.13

53.56

70.40

62.52

64.13

76.30

72.87

71.14

Rate of decline /％

2.3 Influence of laser washing on tensile strength The different samples' corresponding (tensile strength) for laser is reported in Tab.4. The results revealed that the denim fabric without treatment had a higher tensile strength. The kapok fiber is a natural hollow fiber with 90％ hollow degree. So the mechanical property of kapok denim fabric was poor, but the tensile strength of it would not change sharply after laser washing. The power was higher, the speed is slower, the tensile strength was smaller,so the Sample7’s tensile strength were smallest (warp: 1450.70N, weft: 229.90N). The loss rate was between 0-41.85％, if the laser parameters were suitable, the loss of tensile strength with denim fabrics could be controlled. Tab.4. Different laser parameters kapok denim washing Brad tensile strength Sample

warp

weft

BS/N

BE/％

LR/％

BS/N

BE/％

LR/％

1450.70

127.30

384.60

37.80

1139.78

109.50

21.43

322.32

35.80

16.19

1154.28

113.02

20.43

311.34

38.18

19.05

1183.25

124.12

18.44

340.42

29.12

11.49

1030.44

109.50

28.97

278.20

35.24

27.67

962.44

104.62

33.66

288.52

29.72

24.98

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1031.66

107.28

28.89

306.64

27.82

20.27

843.58

94.14

41.85

229.90

22.04

40.22

863.06

106.32

40.51

250.48

28.86

34.87

957.62

115.56

33.99

261.96

27.70

31.89

Note: BS: Breaking strength

BE: Breaking elongation

LR: Loss rate

2.4 Characterization of FTIR Fig.1. is an infrared spectra of the Samples. It could be found that there were no new organic function groups generated, although a number of fibers were etched by laser. The absorption peaking of kapok fiber is 1595.8 cm-1. The absorption peak at 3352.19cm -1 is the hydroxyl, the peak at 1000-1500 cm-1 is the absorption of C-O-C, it is the typical cellulose absorption peaking. It means that the laser washing is an environmental way to treat the denim fabrics.

2.5 Scanning electron microscope We used SEM technique to investigate the morphology of the fiber both before and after laser treating. As shown of the Fig.2.,the fibers of both treated samples had been partially removed and the surfaces of these fibers had lots of porous. The surface of these samples was smoother than treated sample. It depicted that the laser had also broken the fiber and the dyes had been degraded.

Fig.1. IR spectra of Samples

Fig.2. SEM photographs of denim samples a: Sample1,b: Sample2,c: Sample3,d: Sample4.

3. Conclusion Laser washing is a good method to bleach denim fabrics because the indigo on surface of denim fabrics was faded distinctly through laser. During the process, there were no new organic function groups generated, although a number of fibers were etched by laser. The thicknesses of denim fabrics almost kept stable, while the number of tensile strength, air permeability and K/S values of the fabrics were lower than before. Kapok fiber is a natural hollow fiber with 90ďź&#x2026; hollow degree, the mechanical property of kapok is poor, but it would not change sharply after laser washing.

References [1] L. P. Tan, F. M. Wang, W. Liu, Text. Res. J. , 28, 38-44 (2007).

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[2] W. j. Yi, H. Xiao, J. Xiâ&#x20AC;&#x2122;An Univ. Eng. Sci. Tech. , 19, 236-239 (2005). [3] J. Fang, Texleader. , 10, 97-100 (2006). [4] Z. Ondogen, O. Pamuk, E. N. Ondogen, and A. Ozguney, Opt. Laser Technol., 37, 631 (2005). [5] V. N. Wijayathunga, C. A. Lawrence, R. S. Blackburn, M. P. U. Bandara, E. L. V. Lewis, H. M. ElDessowky, and V. Cheung, Opt. Laser Technol., 39, 1301 (2007). [6] O. N. Hung, L. J. Song, C. K. Chan, C. W. Kan, and C. W. M. Yuen, Fiber. Polym., 12, 1069 (2011). [7] C. W. Kan, C. W. M. Yuen, and C. W. Cheng, Coloration Technology, 126, 365 (2010). [8] W. Du, C. H. Yi, X. G. Wang, D. Y. Zuo, L. Liu, H. L. Gan, The 89th TIWC Conference Proceedings 1068-1071 (2014).

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Durability of Antibacterial Efficacy against Laundering for Atmospheric Plasma-Treated Knitted Fabrics with Metal Salts İkilem Göcek1, Muhammed Heysem Arslan1, Umut Kıvanç Şahin1, Hatice Açıkgöz Tufan1, Fatma Banu Uygun Nergis1 and Cevza Candan1 1

İstanbul Technical University Faculty of Textile Technologies and Design

Abstract. Antibacterial efficacy is one of the most demanded characteristics for textiles by the consumers since nowadays textiles with antibacterial functionality are being increasingly utilized in daily life not only in the field of medical textiles and disposable personal hygienic textiles but also in home textiles and various kinds of apparels including military textiles and other industrial textiles. Many textile finishing treatments and techniques have been being utilized for imparting antibacterial efficacy as a functionality to textiles. However, the main issue to consider is to provide prolonged durability of antibacterial efficacy for textiles since the finishes implemented on textiles can easily be removed with everyday use and repetitive laundry. Hence, durability of antibacterial efficacy of textiles is required to be enhanced. To improve antibacterial efficacy of textiles, various surface modification techniques and treatments have been utilized up-to-now. Atmospheric plasma technique is one of the surface modification processes for maintaining durability of finishing of fabrics with the advantage of its applicability to the conventional continuous textile processes by allowing it to be integrated with other textile finishing processes in the industry which is one of the novel subjects recently studied by the researchers. In this study, enhancement of the endurance of presence of metal salts on the fabric surface during washing cycle and improvement of the antibacterial efficacy obtained by implementing metal salts such as copper sulphate and zinc acetate individually and in combination on knitted fabrics consisting of man-made fibers such as polyamide, polyester and viscose by atmospheric plasma technique as a pre-treatment and/or post-treatment are tried to be achieved. Antibacterial functionality analyses were conducted on the fabrics with and without metal salt treatments and after washing process in order to evaluate the performance of antibacterial efficacy with metal salt treatment on the knitted fabrics and to investigate the alteration of antibacterial efficacy depending on washing cycle.

Keywords: antibacterial efficacy, atmospheric plasma, metal salts, knitted fabrics, durability against laundering

1. Introduction As the textile sector’s perspective alters day by day with the consumer demands, different functions for different kind of fabrics with different features have been created for the current needs. Nowadays, when this development in the textile sector is taken into consideration, it can be easily stated that conventional textile treatments run short to respond the need. Therefore, variety of fabrics depending on fiber type such as cotton, wool, viscose etc. are exposed to different treatments in product line for various properties desired for the product. Finishing process ranks as the last operation step in the fabric product line offering wide range of properties for the fabric. The process parameters are deterministic factors to define the effects to be obtained on the inherent structure of the fabrics by altering the mechanical and chemical properties and visual appearance of the fabrics [1]. The conventional finishing processes have some kind of limitations requiring a specified solution which can be possible with the modification techniques for obtaining stabilized visual appearance, increased finishing durability and improved efficiency etc. [2]. As aforementioned, the requirement for the applicable modification techniques is undeniable for contributing to the conventional finishing processes to extent the limits of these processes. Numerous surface modification techniques have been developed up-to-now in order to enhance wettability, adhesion and other properties of textile surfaces by means of forming reactive groups in the structure of the textiles, altering the surface roughness of the substrate fabric etc. [3]. With the development of plasma technology hence, it has become one of the most widely used one in textile treatments. The plasma technique,

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one of the physicochemical methods, has become the state-of-the-art of the scientific researches in recent years with the outstanding advantages it possesses. Therefore, the surface modification applied on the fabrics with the intention of obtaining a final product with desired characteristics including prolonged durability and sufficient efficiency can be accomplished by the plasma technique [4]. Recently, many scientific studies include imparting one or more plasma processes for examination of its applicability on different textiles and its effects on the resulting properties of textiles. Considering the UV- protection and antibacterial functionality of fabrics, Ibrahim et al. examined the effect of atmospheric pressure dielectric barrier discharge plasma in advance of metal salt treatment followed by dyeing [2]. Virk et al. processed nonwoven fabrics prevalently utilized for surgical gowns with antimicrobial finishes and plasma, and assessed them according to the alterations in physical and functional characteristics [5]. Mekewi et al. aminated viscose and acrylic fabrics to improve metal chelation of Cu, Zn and Ni in order to impart fabrics antimicrobial activity against E. coli and S. aureus [6]. The goal of the study of Ilic et al. was to investigate the antimicrobial efficiency and color changes of cotton fabrics treated with colloidal silver nanoparticles synthesized without any stabilizer [7]. Many other studies exist regarding using silver salts or nanoparticles as well as nanocomposites, showing synthesis and applicability of silver on cellulosic fibers [8-11]. The aim of this study is to prolong the duration of remaining of metal salts on the fabric surface during washing cycle and enhance the antibacterial efficacy acquired by applying copper sulphate and zinc acetate individually and in combination on knitted fabrics made of polyamide (PA), polyester (PET) and viscose by atmospheric plasma technique as a pre- and/or posttreatment. Antibacterial activity tests were conducted on the fabrics with and without metal salt treatments and these tests were also performed after laundering process to assess the performance of antibacterial efficacy with metal salt treatment on the fabrics and observe the change of antibacterial efficacy with washing.

2. Experimental 2.1.

Materials and Equipment

The structure of functional knitted fabrics with antimicrobial characteristics acquired by using atmospheric plasma modification along with metal salt application in the context of this study is given in Table 1. The fabrics were washed for 1 hour at 400C in water without any chemical solvents to remove any dust included in the fabrics that may affect the results and then they were all dried in room temperature. Copper sulphate (Copper (II) sulfate, 249,69g/mol, RPH, Carlo Erba Group Reagents) and zinc acetate (zinc acetate dihydrate for analysis, 219.49g/mol, Emsure Acs, Merck) were used individually and in combination in metal salt solutions (Table 1). A non-ionic fatty alcoholetoxylate modified wetting agent was used with for removing oil from the fabric structure and giving high hydrophilic property to the fabrics. Table 1: The Structure of Knitted Fabrics and the Metal Salt Solutions Prepared Fabric Type PET

Basis Weight (g/m2)

Pattern

238.75

Single Jersey

PA Viscose

146 177.89

Interlock Single Jersey

Metal Salt Solution Copper Sulphate Zinc Acetate Mixture

Copper Sulphate (g/L) 5 2.5

Zinc Acetate (g/L) -

Wetting Agent (g/L) 2

5 2.5

2 2

Laboratory scale atmospheric plasma jet machine, OpenairÂŽ, was used for the plasma treatments by utilising RD1010 plasma jet mechanism including two plasma jets that rotate on a 100 mm diameter circle with 3000 revolutions per minute.

2.2.

Methods and Processes

The decision of the numerous parameters was firstly made in accordance with the literature search mainly followed by the results of trial-and-error method. Throughout the whole experimental process, series of tryouts were conducted for variety of parameters in order to obtain optimum results. The procedure used was divided into three major categories as pre-treatment, metal salt application, and post-treatment. According to the literature search 2-8 g/L of metal salt concentration values were found to be commonly used. Therefore, the metal salt concentration and bath ratio parameters were tried with different levels in this range. The concentration of 5 g/L and bath ratio of 1:20 were decided for metal salt treatments. PET, PA and viscose fabric samples were impregnated with 100% pick-up ratio. Various drying temperatures with different durations were tried for metal salt treated samples not to observe any unwanted color changes and/or defects on the surface of the fabrics. Drying for 10 minutes at 100Â°C with oven was chosen as the optimum value. As

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it is known that bonding between metal salt and fiber requires certain amount of energy to occur and exist, which is generally provided with heat in conventional curing process. Oven curing was conducted on PET, PA and viscose fabric samples. For oven curing, 140°C, 150°C, and 160°C were tried at 2, 5 and 10 minute durations. 10 minutes resulted in color change and burning smell regardless of fabric type and metal salt applied. 160°C of temperature resulted in defects on viscose fabric. Therefore, 150°C and 5 minutes were chosen as process conditions for oven curing. In this study, plasma treatment was not only chosen as pre-treatment process but also as an alternative method to conventional curing process benefitting from the plasma energy. Plasma machine runs depending on two variables that are jet-to-substrate distance and travel speed of tray. The desired intensity of the treatment without any defects can be obtained by setting different parameter values since for the fabrics, burning behaviour/smell and yellowness are the main limitations of adjusting the parameters for the desired intensity. Considering these facts, variations of 5 mm, 8 mm, and 10 mm as jet to substrate distances and 5 m/min, 8 m/min, and 10 m/min of tray travel velocities were determined as trial parameters. The optimum parameters were determined after these trials for pre- and post-treatments as 10 mm of distance and for PET fabric samples as 10 m/s and for PA and viscose fabric samples as 8 m/s. of speed.

2.3.

Tests and Characterization

In this study FTIR-ATR technique was used to study the effects of plasma treatment on the surface of the fabrics and the effect of metal salt presence on the fabric surface. AATCC 100 standard test method was used for the determination of the fabric samples’ antibacterial efficacy. Two different bacteria namely E. coli ATCC 25922 and S. aureus ATCC 6538 were used.

3. Results & Discussion 3.1.

FTIR- ATR

The FT-IR results of PET, PA and viscose fabric samples show no significant differences between the nonplasma-treated samples and the plasma treated samples in the case of no metal salt treatment, indicating that the modification effect of plasma process is temporary unless the substrate was exposed to a chemical/material that promotes bonding between the substrate and the chemical/material. On the other hand, when the FTIR spectra of the PET, PA and viscose fabric samples treated with metal salts and the non-treated ones are compared, slight difference is observed implying the effect of metal salt presence.

3.2.

Antibacterial Efficacy

The antibacterial activity tests were conducted to observe if any increase or change in antibacterial efficacy was obtained after pre- and/or post-plasma treatment for PET fabric samples. The antibacterial efficacy can be clearly assessed with the analysis of logarithmic reduction values for E. coli and S. aureus. According to the findings, it is obvious that the results for metal salt treatment with zinc acetate are significant regardless of the plasma application. On the other hand, it was apparently seen that the fabric samples treated with zinc acetate with application of only both pre- and post-plasma treatments together show antibacterial efficacy with a logarithmic reduction value over 4.48 for E. coli. The results obtained for S. aureus all exhibit antibacterial efficacy regardless of the plasma application. Furthermore, in the case of antibacterial activity against E. coli, all of the fabric samples treated with a mixture of zinc acetate and copper sulphate were found to have sufficient antibacterial efficacy. Also, all of the fabric samples have sufficient antibacterial efficacy against S. aureus. For the copper sulphate treated samples, the only significant result was found for the one with both pre- and post-plasma application and no antibacterial efficacy was found against E. coli for the other fabric samples. When pre-plasma is applied, sufficient antibacterial efficacy can only be reached with post-plasma treatment against S. aureus and without post-plasma the results can be accepted as only significant, but when pre-plasma is not applied the fabric samples have all antibacterial efficacy whether post-plasma is applied or not. When logarithmic reduction values for S. aureus are considered, without metal salt treatment at least pre-plasma is required to obtain sufficient antibacterial efficacy. However, no antibacterial activity was found against E. coli in any case. Five fabric samples were chosen out of all of the PA knitted fabric samples and tested to show if any gain or alteration in antibacterial efficacy was obtained after plasma treatment. According to the results depending on the logarithmic reduction values for both E. coli and S. aureus, it is clear that pre- and postplasma treatment together with metal salt application in combination and with zinc acetate lead to antibacterial efficacy. For E.coli loaded fabrics, pre- and post-plasma and metal salt application resulted in a logarithmic reduction rise from 1.32 to <3.11 for both of the salts in combination and to >4.48 for zinc acetate, showing a significant and acceptable antibacterial activity. In addition to this for S. aureus loaded fabrics, again an increase was obtained from 0.99 to <3.94 for both of the salts in combination and to >4.12 for zinc acetate

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leading to a very significant and high antibacterial efficacy. However, for zinc acetate metal salt application without pre-plasma application, when post-plasma application is not performed, the logarithmic reduction increases from 1.32 to 1.83 for E. coli resulting in significant antibacterial results and 0.99 to >4.12 for S. aureus resulting in considerable antibacterial efficacy and when post-plasma application is performed, the logarithmic reduction increases 1.32 to 1.89 for E. coli resulting in significant antibacterial results and 0.99 to 3.48 for S. aureus resulting inconsiderable antibacterial efficacy. For viscose knitted fabrics, two fabric samples were selected and tested. According to the test results depending on the logarithmic reduction values for both E. coli and S. aureus, it is apparent that pre- and post-plasma treatment together with metal salt application leads to antibacterial efficacy with an increase from 1.40 to >3.11 and from 1.34 to >4.51 logarithmic reduction values against E. coli and S. aureus, respectively. When durability of metal salt loading in fabric structure against laundering is considered by focusing on the results of “after 5 washing cycles”, it can be concluded that for all of the four samples of PA fabric no antibacterial efficacy was obtained against both E. coli and S. aureus. On the other hand, no antibacterial efficacy was obtained against E. coli for the PET fabric samples with copper sulphate and with both of the salts in combination. In addition to this, significant results were obtained for antibacterial efficacy against E. coli for only the PET fabric samples with zinc acetate with only post plasma application. Moreover, antibacterial efficacy against S. aureus was obtained for the PET fabric samples with copper sulphate without any plasma application and with only post plasma application, with both of the metal salts in combination with only post plasma application, and with zinc acetate with only post-plasma application.

4. Conclusion The plasma technique was shown to be effective as a pre-treatment and also as a post-treatment step in textile finishing processes in order to enhance durability of finishes on fabric substrates.

5. Acknowledgement The authors would like to sincerely express their highest appreciation to Mr. Oktay Aydın, Mr. Hakan Sağkal (Plasmatreat GmbH), Ms. Başak A. İlkiz and Burcu Yakartaş (Arcelik Inc.), F.B. Demirel, M.Ö. Dobur.

6. References [1] Ceria, A. et. al., The effect of an innovative atmospheric plasma jet treatment on physical and mechanical properties of wool fabrics, Journal of Materials Processing Technology, 2010, Vol. 210, pp.720-726. [2] Ibrahim, N.A. et al., Functionalization of cellulose-containing fabrics by plasma and subsequent metal salt treatments, Carbohydrate Polymers, 2012, Vol. 90, pp. 908-914. [3] Costa, T.H.C., et al., Effects of gas composition during plasma modification of polyester fabrics, Journal of Materials Processing Technology, Vol. 173, 2006, pp. 40-43. [4] Garg, S. et. al., Improvement of adhesion of conductive polypyrrole coating on wool and polyester fabrics using atmospheric plasma treatment, Synthetic Metals, 2007, Vol. 157, pp.41-47. [5] Virk, R.V. et al., Plasma and Antimicrobial Treatment of Nonwoven Fabrics for Surgical Gowns, Textile Research Journal, 2004, vol.74, pp.1073 [6] Mekewi, M. et al., Imparting permanent antimicrobial activity onto viscose and acrylic fabrics, International Journal of Biological Macromolecules, 2012, vol. 50, pp.1055-1062 [7] Ilic, V. et al., The influence of silver content on antimicrobial activity and color of cotton fabrics functionalized with Ag nanoparticles, Carbohydrate Polymers, 78, 2009, pp. 564–569. [8] El-Rafie, M.E. at al., Bio-synthesis and applications of silver nanoparticles onto cotton fabrics, Carbohydrate Polymers, 90, 2012, pp. 915– 920. [9] Kozicki, M. et al., Facile and durable antimicrobial finishing of cotton textiles using a silver salt and UV light, Carbohydrate Polymers, 91, 2013, pp. 115-127. [10] Zhang, D. et al., Antibacterial cotton fabric grafted with silver nanoparticles and its excellent laundering durability, Carbohydrate Polymers, 92, 2013, pp. 2088– 2094. [11] Breitwieser, D. et al., In situ preparation of silver nanocomposites on cellulosic fibers – Microwave vs. conventional heating, Carbohydrate Polymers, 94, 2013, pp. 677-686.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Dyeing and Fastness Properties of Wool Yarns Dyed with Sunflower Seed Hulls Fateme Gholami 1, Zahra Ahmadi * 12 1- Master student, 2- assistant professor of Tehran University of Art

Abstract. As a literature review shows it was possible to replace synthetic dyes with ones of echo-friendly as natural dyes. Natural dyes and dyeing are as old as textiles themselves. Although plants exhibit a wide range of colours, not all of these pigments can be used as dyes directly. Sunflower seed is one of the popular vegetal cooking oil source used in Iran, but also in the world. The main colorants in the sunflower seed hulls (SFSH) are anthocyanin. Anthocyanin dyestuffs are used in the food industry mainly. Most of the purple, blue and black fruits are the anthocyanin source. Anthocyanins can be used as pH indicators because their color changes with pH. . Sunflower seed hulls are by-product of the sunflower seed oil extraction process. A large amount of SSH are produced annually in the world, causing environmental concern. In spite of being a serious ecological problem, there is an important question. Can SFSH, contain anthocyanin dyestuff, represent a possible resource for the dyeing materials It contains a valuable source of abundant natural coloring substances. The aim of this study understands the effect of effectual parameters in natural dyeing process in order to finding a suitable method for dyeing. Effects of two kinds of sunflower seed, kind of textile, mordant (kind, concentration and method), liquor ratio and antibacterial effect and dyeing in waste water have studied. The range of color developed on dyed materials are evaluated in terms of (L*, a*, b*) CIE LAB coordinates and the dye absorption concentration on the woolen yarn dyed by SSH is studied by using K/S values. Fastness tests on dyed samples for light and washing fastness are carried out. The antibacterial property of samples was evaluated using, AATCC 100-1993 method, two pathogenic bacteria including Escherichia coli and Staphylococcus aurous as outstanding barometers in this field. CIELab coordinates of the samples change in the different dyeing process. The best results were obtained at respectively cupper mordant and Meta mordanting. Also woolen yarn has better dyeing properties with SFSH than silk or cotton. On the other hand, the effect of reuse and dyeing in the waste water on the dyeing quality revealed the SFSH extract contained huge quantities of natural dyes which can be exploited in dyeing wool.

Key Words: Sunflower seed hulls, dyeing, wool

1. Introduction In recent years, there has been a growing tendency towards the use of natural dyes in textile coloration because of the increasing awareness of environment, ecology, pollution control and sustainability. The main colorant in sunflower seed hulls is anthocyanin. Its chemical structure has been shown in Fig 1. Anthocyanins, also known as anthocyans, are water soluble flavonoid pigments that, depending on pH, and in some cases complexing agents, can contribute diverse colors such as red, purple and blue [1-4]. Sunflower is one of the major oilseed crops ranking fourth with a worldwide production of about 15.6 million Metric tons in 2007 [2] the share of Iran was 45000metric tons. The purpose of this study was to 1

ahmadi@art.ac.ir, +982166463482

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use anthocyanins from purple-hulled sunflower genotypes to determine if such pigments were qualitatively and quantitatively competitive with other sources of natural pigments for textiles. The present study focuses on the valorization of sunflower seed hulls (SFSH) in dyeing and fastness properties of wool yarns.

Figure1- Schematic chemical structure of anthocyanin [1]

1.1 Experimental Anthocyanin compounds extracted from the sunflower seed hulls are used as natural dyes. Pre scoured wool pile yarn 20 metric, different mordant, acetic acid were laboratory reagents grade from Merk, Germany. Dyeing was performed using a liquor ratio of 1:40, started at 40 Ě&#x160; C and, temperature was raised to boiling temperature in open beakers. The constitution of dyeing bath has been explained in the table 1. Table 1- constitution of dyeing procedure Sample Constitution

Mordant Acid Mordant method Goods L/R Temperature

FeO acetic Meta 2% Wool 40 65Â°C

Fe 2 O 3 acetic Meta 2% wool 40 65Â°C

CuSO 4 acetic Meta 3% wool 40 65Â°C

alum acetic Pre 5% wool 40 100Â° C

alum acetic Post 5% wool 40 100Â°C

M 7 =L 2

alum acetic Meta 5% wool 40 100Â°C

alum acetic Pre 10% wool 40 100Â°C

alum acetic Meta 10% wool 40 RT

alum acetic Meta 5% wool 30 R.T

alum acetic Meta 5% wool 50 100Â°C

alum acetic Meta 5% silk 40 100Â° C

alum acetic Meta 5% cotton 40 100Â°C

All samples dyed by 50% SSHF

1.1.2 Colour strength Relative colour strengths (K/S values) were determined using the Kubelkae Munk equation [2]. 2

đ??žđ??žďż˝ = ( 1â&#x2C6;&#x2019;đ?&#x2018;&#x2026;đ?&#x2018;&#x2026;) (1.1) đ?&#x2018;&#x2020;đ?&#x2018;&#x2020; 2đ?&#x2018;&#x2026;đ?&#x2018;&#x2026; Where R is the decimal fraction of the reflectance of dyed woolen yarn, K is the absorption coefficient, and S is the scattering coefficient. The L*, a*, b* were calculated for light source D65. The color properties of samples have been mentioned in the table 2.

Page 997 of 1108

2.1.2Fastness testing The dyed woolen yarns were tested according to ISO standard methods. The specific tests were as follows: ISO 105-C02 (1989), color fastness to washing and ISO 105-B02 (1988), color fastness to light (xenon arc) [3]. Fastness properties of dyed samples have been mentioned in the table3. The results show that although the use of mordant cause to improve light fastness and washing fastness but the improved results are not satisfied. More research and study need in this area.

2. Results and discussion CIELab coordinates of the samples change in the different dyeing process. This could be explained with presence of anthocyanin components that are sensitive to pH and temperature. The mordant (concentration, kind and method) affected considerably color yield and also fastness. The best results were obtained at respectively 3% cupper mordant and meta mordanting method. On the other hand, the effect of reuse and dyeing in the waste water on the dyeing quality revealed the SFSH extract contained huge quantities of natural dyes which can be exploited in dyeing wool. No antibacterial effect for SFSH has been evaluated. Our Study shows that SFSH can be used as valuable natural source for dyeing artistic textile.

Table 2- Color properties of woolen yarn dyed with SFSH sample

K/S

1.349 位 max

610 L*

38.61 a*

42.9 3

2.347

0 3.98

44.67

0.215 16.81

M7= L2

0.45

0.61

0.31

560

580

40.2

34.7

45.5 6

0.916

550

0.63

2.735

CIEL*a*b*

0.84

2.08

0.02

5.78

4.00

0.52 6

0.27 5

0.18 8

580

46.4 1

52.5 0

0.21

59.6 8

1.03 7

0.03 5

3.77 4

3.83

18.9

5.55

1.41 -1.1

3.03 3.6

Table 3- Various color fastness of woolen yarn dyed with SFSH sample

M7 =L2 3-4

3-4

4-5

3-4

4-5

3-4

Light Fastness

Washing

stain on cotton

stain on wool

Fastness

Page 998 of 1108

3. Acknowledgements This work was supported by Tehran University of Art.

4. References 1. Nabhan, G., Sunflower of Indians of the southwest, The Sunflower, January1982:30-3 2. 2. Zahra Ahmadi, Narges Shayegh broujeni, Effectual parameters on the natural dyeing process, j. of Textile & polymers, Vol.1, No.3, (2013), 15-18 3. AATCC, AATCC Technical Manual, Vol.75.American Association of Textile Chemists and Colorists, Research Triangle Park, NC (2000). 4. Z. Ahmadi, F. Gholami, Evaluation of Effectual Parameters in the Natural Dyeing of Woolen Yarns with Sunflower Seed Hulls, Academic Dissertation, University of Art Tehran, winter 2015 5. Z. Ahmadi, F. Gholami, M. Aftabi, Different behavior of some natural dyes in the wool dyeing process , proceeding of 12th ATC, China Shanghai,22-24 October, 2013.

Page 999 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Dyeing Properties and Energy Saving Ratios According to Dyeing Conditions of S Type Disperse Dyes SeokIl Hong1 and BeomSoo Lee  1

ICT Textile & Apparel Group, Korea Institute of Industrial Technology, Korea

Abstract. Disperse dyes are most widely used when dyeing polyester fibers and are generally classified into azo type and anthraquinone type in terms of a chemical structure. Also, disperse dyes are classified into three types such as E type, SE type, and S type according to dyeing properties due to high temperature dyeing and are used properly according to dyeing conditions. Especially, S type dyes have an excellent sublimation fastness and are suitable for high temperature dyeing but they have a poor even-dying property. In the case of S type having such a high temperature-dependence, a large amount of energy is consumed due to high dyeing temperature and long dyeing time. In this study, polyester fibers are dyed with S type dyes according to various dyeing conditions. Additionally, dyeing behaviors are measured in real time to set optimal dyeing temperature and time. In this study, energy consumptions according to dyeing processes are compared using an energy consumption calculation program and we found that 15% of the energy is saved in a range in which dyeing properties of polyester fibers are not influenced..

Keywords: s type, disperse dye, dye-o-meter, automatic dilution

1. Introduction Environment and energy problems became challenges that can no longer be delayed because global warming is assuming an acute phase all around the world. Environment and energy problems have a dual nature of ‘regulation’ and ‘market’, in which failing to respond to environment regulation may risk to be pulled away from the market from blockage of trade barrier of developed countries. In addition, a new environment market is forming to overcome the environment and energy problems. Textile industry has a characteristic of having manufacture stream that have high pollution load and energy guzzling. Therefore, there is a possibility for the existing market to shrink according to the environment regulation. Exhaust dyeing methods used for dip dyeing are dyeing methods used most frequently in dyeing & finishing companies, and are sensitive to dyeing conditions. 1,2 In particular, one of the major stream of fabric industry, dye manufacturing process is a process that removes impurities and grant aesthetic colors. In addition, it is a step for granting suitable function according to its purpose of use, and for granting the highest added value in the fabric manufacturing process. However dye manufacturing process uses high temperature water and large quantity of various chemical agents and has a high treatment temperature (above 100℃), so it is the main process that pours out waste and is energy guzzling. Disperse dye widely used for dyeing polyester fabric has a low solubility to water, and as such exist in soluble form from dispersant effect and is a dye that can be for dyeing. In addition, since disperse dye has low solubility to water, unlike the water soluble dye that has fiber movement through the fabric pore, it will move through the free volume of the fabric formed by heat. Therefore, polyester fabric that have high glass transition temperature (Tg) requires high temperature. Disperse dye’s dyeing temperature changes according to molecular weight. And the dyeing behavior reacts sensitively to dyeing temperature. The table 1 below shows the types of disperses dye and dyeing temperature of polyester fabric.



Corresponding author. Tel.: + 86-31-8040-6145. E-mail address: redstone@kitech.re.kr

Page 1000 of 1108

Table 1. The types of disperses dye and dyeing temperature

Type

Molecular weight

Dyeing temperature (℃)

S type

High energy

More than 400

140

SE type

Middle energy

300 - 400

130

E type

Low energy

Less than 300

120

Water soluble dye usually show L-shape absorption curve. Disperse dye’s absorption behavior for polyester fabric has a typical S-shape absorption curve that very sensitively absorbs in certain temperature as shown in the picture. In this study, polyester fibers are dyed with S type dyes according to various dyeing conditions. Additionally, dyeing behaviors are measured in real time to set optimal dyeing temperature and time.

2. Experimental 2.1 Test samples and reagents 100% polyester fiber(interlock) were used for dyeing, and were treated with scoured, or bleached according to the kind of experiments. Acetic Acid(CH2COOH) was used as a pH agent, and Dispergen CTN(Snogen cooperation, Korea) was used as dispersing agent and they were first class reagents. Synolon Blue S-GS was produced by kyungin.Co., Ltd. and is a S type dyes. And dilution solution was used to DMF (N,N-Dimethyl Formamide)

2.2 Dyeing For dyeing, uses 100% polyester fiber. Set up the dyeing concentration to 2.0%o.w.f to each dyes, and used 1.5g/l of Acetic Acid(CH2COOH) and 1.0g/l of dispersing agent. At 40℃, put in the liquid and stir, then set the temperature rising speed at 1.5℃/min until 130℃. Keep for 60 minutes At 130 ℃. Liquor ratio 1:20, set the total dyeing time to180minutes.

Fig. 1: Dyeing process of disperse dyes(130℃)

Page 1001 of 1108

liquor in a predetermined interval, and an analysis program to analyze measured data and show them on a monitor screen. The measuring equipment included a circulation frame for circulating dye liquor, light source and detector. The circulation frame was used to measure absorbancy in a wave length range of UV/VIS 200-750nm and had resistance to heat, pressure, and chemicals. The light source was a pulsed Xenon lamp and was used to measure absorbancy in a wave length range of 220-750nm. The detector was used to measure by expanding channels to maximum 8 sets and was used for precise measurement having high resolution(0.3-1.5 nm FWHM) by using 25 ㎛ slit in a wave length range of 200 - 1100nm. Dye-ometer was used to measure and analyze absorbancy of dye liquor circulating through the circulation frame at the interval of 1 ~ 2 min. to show exhaustion ratio. Finding process parameter from analyzing absorption behavior of disperse dye is completely different from typical water soluble dye. In addition, disperse dye has a low solubility to water, so quantitative analysis in water soluble state is almost impossible. Therefore, in order to quantify the disperse dye remaining in dyeing solution per dyeing time, sampling should be done for dyeing solution in dyeing machine per dyeing time. In order to this auto sampling and dilution system (Dilution, KITECH, Korea) was used.

Fig. 2: Dye-o-meter used in this experiment.(Dyeing MC, Detector, Analysis program, Diluter)

3. Results and Discussion Figure 3 shows a measure of the spectrum of the disperse dyes(Synolon Blue S-GS, 2.0%owf) by the dilution solution. When using a diluter(DMF solution ) can measure the precise spectrum and dyeing behavior. Figure 4 shows the exhaustion curve change of Synolon Blue S-GS dye according to dyeing temperature (initial conc. 2.0%owf, liquor ratio 20:1) The polyester fibers are dyed with S type dyes according to various dyeing conditions(dyeing temperature 110℃ , 120℃ , 130℃ , 140 ℃ , dyeing time 60min). The dyeing behaviors are measured in real time to set optimal dyeing temperature 130℃.

Fig. 3: Spectrum change according to the dilution solution

Page 1002 of 1108

Fig. 4: Exhaustion curve change according to the dyeing temperature

Table 2. Energy consumptions according to dyeing processes Item Liquor ratio (T/R, 1:X)

PET Rayon

Water (kg) Treatment time(min) Electricity (kwh) Gas(m3) Steam(kg) Energy expenditure (kcal)

Before

After

10 8 45,600 293 0 0 874 471,250

5 5 32,000 252 0 0 499 398,520

Energy Reduction (%) 50.00 37.50 29.82 13.99 0.00 0.00 15.10 15.43

4. Conclusions Disperse dyes are classified into three types such as E type, SE type, and S type according to dyeing properties due to high temperature dyeing and are used properly according to dyeing conditions. Especially, S type dyes have an excellent sublimation fastness and are suitable for high temperature dyeing but they have a poor even-dying property. In the case of S type having such a high temperature-dependence, a large amount of energy is consumed due to high dyeing temperature and long dyeing time. In this study, energy consumptions according to dyeing processes are compared using an energy consumption calculation program and we found that 15% of the energy is saved in a range in which dyeing properties of polyester fibers are not influenced.

Acknowledgement This work was supported by the Ministry of Strategy and Finance of Republic Korea (Kitech JC-15-0044).

5. References [1] P. S. Collishaw, D. A. S. Phillips and M. J. Bradbury, J. Soc. Dyers. Colour., 109, 284(1993). [2] K. Parton, J. Soc. Dyers. Colour., 110, 4(1994).

Page 1003 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Dyeing Properties of Poly(ethylene terephthalate)/Poly(ethylene glycol) Block Copolymer Fibers Shekh Md. Mamun Kabir + and Joonseok Koh Department of Organic and Nano System Engineering, Konkuk University, Seoul 143-701, South Korea

Abstract. Dyeing properties of the easy dyeable polyester(EDP), which was prepared through copolymerization of PET and polyethylene glycol, was compared with that of PET in a comparative manner. The easy dyeable polyester was successfully dyed with disperse dyes at temperatures below 100째C under normal pressure without using dye carriers. The enhanced deyability of EDP over PET especially at lower dyeing temperature is generally advantageous with respect to costs associated with dyestuff, carriers, energy consumption, and environmental control.

Keywords: easy dyeable polyester, low temperature dyeing, disperse dye, color fastness

1. Introduction Polyethylene terephthalate(PET) fiber is one of the major synthetic fibres widely used in textile applications for apparel owing to its unique properties of easy care, toughness and dimensional stability. However, some of the problems associated with polyester fiber are its hydrophobic nature and hence the difficulties encountered during dyeing. As the fiber has no dye sites, it is dyed mainly with disperse dyes, which require high temperature and high pressure to facilitate dye penetration. Therefore, to improve the dyeability of polyester without affecting its bulk properties, a chemcal modification of PET through copolymerization has been adopted. The introduction of flexible long chain glycol or chemically modified glycol structure to the PET structure can result in significant property enhancements without sacrificing the desirable attributes of the PET homopolymer. The chemical modification lowers the glass transition and melting temperature of PET and improve the dyeability especially at lower temperature. In this study, the dyeing properties of block copolymers (easy dyeable polyester, EDP, Fig. 1) made from Poly(ethyleneterephthalate) (PET) and polyethylene glycol(PEG) was investigated. O C

O C

O C O CH2CH2O

O C OCH2CH2

OCH2CH2O x1 n

Fig. 1: Chemical structure of EDP

2. Experimental 2.1.

Materials

Easy dyeable polyester (EDP, 75d/72f) and regular PET (RP, 75/72f) were obtained from HUVIS Corporation(South Korea). Circular-knitted fabrics was then prepared by using laboratory-scale circularknitting machine (single jersey, 28 gauge) and used to investigate their dyeing properties. Commercial samples of the two disperse dyes were used without purification prior to use; C.I. Disperse Red 60 (Figure 2, Ohyoung Chemicals, South Korea). All other reagents were of general purpose grade. +

Corresponding author. Tel.: + 82-2-450-3512. E-mail address: s.mamunkabir@yahoo.com.

Page 1004 of 1108

NH2

Fig. 2: Chemical structure of C.I. Disperse Red 60

2.2.

Determination of crystallinity(%)

Mass fraction crystallinity was determined from density of the polymers (PET and EDP) by density gravity column test according to Equation (1.1) (ASTM D1505).

(1.1) where, ρ s : sample density ρ a : theoretical 100% amorphous PET density (=1.3335g/cm3) ρ c : theoretical 100% crystalline PET density (=1.4550g/cm3) Also, the fusion enthalpy that was obtained from DSC was used to calculate the degrees of crystallinity of neat PET and the EDP, according to Equation (1.2). (1.2) where, ΔH m : fusion enthalpy of the polymer sample ΔH i : fusion enthalpy of the completely crystallized neat PET (=140.1J/g)

2.3.

Dyeing

Polyester fabrics were dyed in a laboratory dyeing machine (DLS-6000, Daelim Starlet Co. Ltd) at a liquor ratio of 1:20. A 50ml dyebath comprised of disperse dyes and a dispersing agent (Lyocol RDN liquid, 1.0 ml/l, Clariant Chemicals Ltd). After adjusting to pH 4.5, polyester fabric (2.0 g) was immersed in the dyebath and the temperature was increased to the dyeing temperature (90, 100, 110, 120 and 130°C) at a rate of 2.0°C/min. Dyeing was carried out at this temperature for 60 min. After dyeing, all the samples were rinsed and dried at 60 °C. The color strength (f k ) and CIELAB values of the dyed fabrics were measured using a spectrophotometer interfaced with a personal computer.

2.4.

Color fastness test

In order to evaluate the color fastness properties of the polyester fabrics, the dyed fabric was reductioncleared (sodium dithionite, 2.0 g/l; sodium hydroxide, 2.0 g/l; soaping agent 2.0 g/l; 80 °C, 20 min) followed by heat-setting at 180 °C for 45 seconds in a laboratory tenter (Tex-dryer, Daelim Starlet Co. Ltd.). Color fastness was determined according to the respective international standards: fastness to washing (ISO 105-C06 A2S), fastness to perspiration (ISO 105-E04), fastness to rubbing (ISO 105-X12), fastness to sublimation (ISO 105-P01) and fastness to light (ISO 105-B02). Change in shade and staining of adjacent multifiber (Multifiber DW, adjacent fabric, BS EN ISO 105-F10) were assessed using grey scales.

3. Results and Discussion 3.1.

Crystallinity determination Table 1: Crystallinity(%) of PET and EDP Density gravity column test

DSC

Density (ρ, g/cm3)

Crystallinity (%)

PET

1.3865

45.78

ΔH m (J/g) 58.1

EDP

1.3715

33.18

41.4

Sample

Fusion Enthalpy

Crystallinity (%) 46.5 33.1

Page 1005 of 1108

Both the degree of crystallinity from density gravity column test and DSC shows that EDP has lower crystallinity than PET (Table 1). This result is consistent with their dyeing properties.

3.2.

Dyeing properties

Figure 2 shows that the exhaustion(%) of EDP is higher than that of PET and the gap was higher in lower temperature such as 90 and 100Ë&#x161;C. The higher dye uptake of EDP is probably ascribed to the lower T g and crystallinity due to the flexible PEG chain in its structure.

PET EDP

Color strength (fk)

100

0 90

100

110

120

130

Dyeing temperature ( C)

Fig. 2: Dye exhaustion(%) properties of PET and EDP

Again in Figure 3. it is clear that the color strength of EDP is higher than PET at each dyeing concentration. In case of PET, the highest dyeing temperature exhibited the highest color strength. However, in case of EDP, 100oC are the most preferable temperature for achieving the higher color strength: the color strength of the EDP significantly decreases as the dyeing temperature increases. 300

200

130oC 130oC

150

120oC 110oC

100

100oC

300 PET EDP

250

Color strength (fk)

250

Color strength (fk)

100oC 110oC 120oC 90oC

PET EDP

200

150

100

50 90oC 0 1

Dye concentration (%owf)

0 90

100

110

120

130

Dyeing temperature (oC)

Fig. 2: Dyeing properties of PET and EDP. (a) separate dyeing (b) competitive dyeing in the same bath (4%owf)

In case of competitive dyeing in one bath, the performance difference in color strength between PET and EDP is even higher than the separate dyeing. EDP showed 16 times higher color strength than PET at 90oC and 2 times higher color strength than PET at 130oC, respectively. The highest color strength of EDP was achieved at 100oC.

3.3.

Color Fastness properties

Overall color fastness properties of PET and EDP were almost identical level. Table 3 shows wash fastness results of PET and EDP.

Page 1006 of 1108

Table 3: Color fastness to washing (ISO 105-C06 A2S) Sample

Dyeing Temperature (˚C)

PET EDP

130 100

Staining

Color change

Acetate

Cotton

Nylon

Polyester

Acrylic

Wool

4-5 4-5

3-4 3-4

4-5 4

3 3

4 4

4-5 4-5

4. Conclusions In this study, the dyeing properties of block copolymers (easy dyeable polyester, EDP, Fig. 1) made from Poly(ethyleneterephthalate) (PET) and polyethylene glycol(PEG) was investigated. Dyeing properties of EDP was higher than that of PET and the gap was even higher in lower temperature such as 90 and 100oC. Especially in case of EDP, 100oC are the most preferable temperature for achieving the higher color strength. The higher dye uptake of EDP is probably ascribed to the lower T g and crystallinity due to the flexible PEG chain in its structure. Both the degree of crystallinity from density gravity column test and DSC shows that EDP has lower crystallinity than PET. The lower degree of crystallinity of EDP obtained from density gravity column test support the higher dyeing properties at lower temperature. Overall color fastness properties of PET and EDP were almost identical level.

5. Acknowledgement This work was supported by the Technological Innovation R&D Program (S2220477) funded by the Small and Medium Business Administration (SMBA, Korea)

6. References [1] W. Albrecht in Tomorrows Ideas and Profits; Polyester 50 years of Achievement (Ed. D. Brunnschweiler and J.W.S Hearle), Textile Institute, Manchester, 52, 1993. [2] F Francalanci and F D'Andolfo, Chem. Fibers Int., 53, 99 (2003) [3] Dawson Tim, “Progress towards a greener textile industry’ Color. Technol., 128 (2012) 261-269. [4] K H Park, M Cassetta and V Koncar, Color. Technol., 118, 319 (2002). [5] Dyeing of Polyester/Wool Blends Fabrics, in Bayer’s Products Applicable to the Wool Industry, Bayer China Company Limited, Shanghai, China, pp.1-6, 1998. [6] Zhao L. G and Wu R. Textile Res.J., 74 (1), 27 (2004). [7] Wang, J.P., and Asnes, H., J. Soc. Dyers Colour, 107, 274 (1991). [8] Sherril, W.T., Text. Chem. Color. 10, 210 (1978).

Page 1007 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Dyeing Textiles by Using Extracts from Mulberry Branch/Trunk I. Dyestuff Fluorescence Property Akihiro Kuroda, Isao Wataoka, Hiroshi Urakawa, Hidekazu Yasunaga + Kyoto Institute of Technology, Faculty of Fibre Science and Engineering, Kyoto, Sakyo-ku, 606-8585, Japan

Abstract.

In the research, the dyeing and functional finishing by using the extracts from the mulberry branches and trunks were studied in order to invent the efficient use of the wastes. Brown powder is obtained by extracting from the crushed and ground mulberry branches and trunks with water. The wool, nylon and silk textiles are dyed yellow at 40 °C, and brown at higher dyeing temperature. The wool and nylon textiles dyed at high temperature show high colour fastness to washing. The colour of the wool textile dyed by the mulberry extracts in combination with Fe(II), Fe(III), Cu(II) or Al(III) chloride is dark brown, brown, dark yellow or bright yellow, respectively. The wool textile treated with Al(III) chloride and dyed with the mulberry extracts shows fluorescence by the irradiation with ultraviolet light in the vicinity of 310 nm. Key words: Dyeing, Mulberry, Fluorescence

1. Introduction The mulberry branches and trunks have been discarded as agricultural waste in the sericultural industries, although the mulberry fruits are used for food and the leaves are utilised in the sericultur. However the wood portion of the mulberry contains useful substances such as flavonoids, diarylheptanoids and so on. They show unique properties, for example, the reducing ability, absorption of ultraviolet light and physiological functions. The utilisation of the substances is important from the viewpoint of the efficient recycle of the wastes. In the research, the dyeing and functional finishing by using the extracts from mulberry branches and trunks were studied. The fabrics used for the dyeing experiments were natural ones such as the wool, silk, flax, cotton, and chemical ones such as nylon, acrylic fibre and polyester. The dyeing by the combination of the mulberry extracts and metal compounds was also tried and the dyeability was estimated.

2. Experimental 2.1.

Extraction and dyeing

The mulberry branches and trunks crashed with a mill were extracted with distilled water at 100 °C for 4 h. The extract was concentrated and dried. The obtained powder was dissolved into distilled water to 2.0 wt% solution. Each textile sample was immersed in the solution at solution 30-90 °C for 3 h. The liquor rations were 1:66.0 for wool, 1:179 for silk, 1:80.1 for flax, 1:90.6 for cotton, 1:160 for nylon, 1:108 for acrylic fibre and 1:157 polyester. The each textile was washed with 50 ml of 2.0 wt% marseille soup solution at 40 °C for 10 min, as rinsed with 100 ml of distilled water at 40 °C for 5 min twice and was air dried. The obtained colour of the fibre sample was measured by a spectrocolourimeter (CONICA MINOLTA, CM-2600d). T he obtained values were expressed in the L*a*b* standard colour system (CIE 1976). L* is lightness index, a* is red-green chromaticity coordinate and b* is yellow-blue chromaticity coordinate.

2.2.

Colour fastness to washing

Wool, silk and nylon dyed at 40, 50, 90 °C were washed with 100 ml of 0.50 wt% marseille soup solution at 40 °C for 30 min and were rinsed with 100 ml of distilled water at 30 °C for 1 min twice and was air dried. +

Corresponding author. Tel.: +81-75-724-7562 E-mail address: yasunaga@kit.ac.jp

Page 1008 of 1108

The same procedure was repeated 15 times and the colour of the sample textiles was measured every after the procedure.

2.3.

combination

with

metal

The wool textile was immersed in 0.10 M of Fe(II)Cl 2 , Fe(III)Cl 3 , Cu(II)Cl 2 or Al(III)Cl 3 at 40 °C for 1 h. The treated samples were them immersed in the 2.0 wt% mulberry extracts solution at 40 °C for 3 h. The washing, rinsing and drying procedures were the same as described in §2.1.

Dyeing in compounds

30 20 10

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

n / times

3. Results and discussion 3.1.

Dyeability and colour fastness to washing

Only wool, silk and nylon fibres are dyed among the natural and chemical fibres. The obtained colour of the textile samples is summarised in Table 1. As shown in Table 1, the L* of the wool dyed by the mulberry extracts at 40 °C is 81.8, that of the silk is 82.2 and that of the nylon is 86.5. The b* of the wool, silk and nylon is 27.7, 25.8 and 43.3, respectively. These b* values are high enough. The results show that wool, silk and nylon fibres are dyed yellow by the mulberry extracts. The dyeability for the wool fibre is highest as dyed at 90 °C. That for the silk fibre is highest at 90 °C and for the nylon is at 50 °C. The results show that the higher dyeing temperature is preferable for the wool and silk and the middle one is preferable for the nylon. Table 1 Sample

L*, a*, b* values of textiles dyed by mulberry extracts at each temperature. Wool Silk Nylon

Colourimetric Parameter

Initial

87.6

-0.260

13.1

95.7

-0.0926

2.45

95.1

-1.14

7.75

30 °C

84.0

-2.32

24.6

86.2

1.18

21.9

92.5

-7.09

37.7

40 °C

81.8

-1.95

27.7

82.2

2.41

25.8

86.5

-4.94

43.3

50 °C

80.1

-1.14

30.8

78.3

3.64

27.5

82.8

-0.388

50.9

60 °C

76.9

0.545

32.8

75.3

4.04

26.4

77.4

2.09

49.2

70 °C

72.9

2.88

33.0

72.3

5.19

26.7

72.4

5.11

47.5

80 °C

67.8

5.81

32.8

68.5

5.85

26.1

66.9

6.67

43.2

90 °C

64.2

7.96

34.9

69.4

5.43

27.0

64.0

7.89

42.6

60 50

The colour fastness to washing for the textile dyed by the mulberry extracts was estimated. Here, the change in b* 40 values is shown for the evaluation of the colour fastness. Fig. 1(a)-(c) show the b* for the wool, silk and nylon samples 30 as a function of the number of washing. The samples were dyed by the mulberry extracts solution at 40, 50 or 90 °C. 20 The change in b* values between for the textile samples in the initial state and at after 15 times washing is 6.1 for wool, 10 2.8 for silk and 3.1 for nylon, which were dyed at 90 °C. 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 The changes are small enough for practical uses. The n / times changes for the samples dyed at lower temperatures than 90 °C are larger. It is concluded that the higher colour fastness (a) to washing is obtained by dyeing at higher temperature. Fig. 1 (a) Change in b* for wool textiles dyed at 40 °C (○), at 50 °C (□) or at 90 °C (△), as a function of the number of washing (n).

Page 1009 of 1108

3.2.

Dyeing with metal compounds

The obtained colour of wool textile treated with metal chlorides and dyed with mulberry extracts is brown for Fe(II)Cl 2 , dark brown for Fe(III)Cl 3 , dark yellow for Cu(II)Cl 2 or bright yellow for Al(III)Cl 3 . The L*, a*, and b* values measured for the samples are summarised in Table 2. The L* is lowest for the wool treated with FeCl 2 and the extracts and the b* is extremely highest for that treated with AlCl 3 . It was found that the wool textile treated with Al(III)Cl 3 and dyed with the mulberry extracts shows fluorescence by the irradiation with ultraviolet light in the vicinity of 310 nm. The fluorescence spectrum (b) of mulberry extracts in Al(III)Cl 3 ethanol solution shows the maximum signal at 364 nm when the solution is irradiated with excitation light of 310 nm. The mulberry extracts may contain materials which form complexes with the aluminum ion and this complex fluoresce.

4. Conclusion

The wool, nylon and silk textiles are dyed yellow and brown by the extracts from the mulberry branches and trunks. The wool and nylon textiles dyed at high 60 temperature show high colour fastness to washing. The colour of the wool textile dyed by the mulberry extracts in 50 combination with Fe(II), Fe(III), Cu(II) or Al(III) chloride (c) is dark brown, brown, dark yellow or bright yellow, 40 respectively. The wool textile treated with Al(III) chloride and dyed with the mulberry extracts shows 30 fluorescence by the irradiation with ultraviolet light. 20 10

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

n / times Fig. 1 (b) and (c) Change in b* for silk (b) and nylon (c) textiles dyed at 40 °C (○), at 50 °C (□) or at 90 °C (△), as a function of the number of washing (n).

Table 2 L*, a*, b* of wool samples treated with each metal chloride aqueous solution (0.10 M) and, treated by the metal solution and then dyed with the aqueous solution of mulberry extracts. Wool sample

Initial

87.3

-0.130

13.6

Dyed

81.3

-2.33

36.5

Treated with FeCl 2 solution

70.1

6.12

23.7

Treated with FeCl 2 solution and dyed

60.9

1.92

24.8

Treated with FeCl 3 solution

70.0

6.25

20.2

Treated with FeCl 3 solution and dyed

58.0

1.68

22.2

Treated with CuCl 2 solution

78.1

-11.4

10.4

Treated with CuCl 2 solution and dyed

67.1

-1.88

31.1

Treated with AlCl 3 solution

89.4

0.06

13.0

Treated with AlCl 3 solution and dyed

83.0

-4.37

46.8

Page 1010 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Effects of Roller Drafting and Twisting on the Structural and Mechanical Properties of Nano-fibrous Bundles Ganbat T.1, Jung H. Lim 2 and You Huh3 + 1

Department of Mechanical Engineering, Graduate School, Kyung Hee University, Yongin, Gyunggi-Do, 446-701, Korea (Republic of) 2 Department of Textile Engineering, Graduate School, Kyung Hee University, Yongin, Gyunggi-Do, 446-701, Korea (Republic of) 3 Department of Mechanical Engineering, College of Engineering, Kyung Hee University, Yongin, GyunggiDo, 446-701, Korea (Republic of)

Abstract. This study introduces a novel method to produce continuous nano-fibrous web and nano-fibrous bundle including drafting and twisting to improve the mechanical properties of the bundle. The bundle made with nano-fibrous web is roller drafted under elevated temperature surroundings. Twisting is generated on the so called Two-For-One (TFO) principle. The nano-fibrous yarns herewith produced show excellent TFO twisting performance in the “twist generation zones”. This novel method caused the structure and shape of the bundle to change, while not only the bundles got thinned by roller drafting, but the constituent nano-fibers also became thinner. The transformation from the ribbon shaped nanofibrous bundle to the cylinder-shaped twisted yarn took place. Using a scanning electron microscope (SEM), the inner structure of the bundle was assured, that is, the change of the loops that occurred during the formation of nano-fibrous web, while the distribution of the fiber orientation angle also was measured. The tensile strength of the bundle before twisting and after twisting were tested and compared to see how much the strength of the nano-fibrous bundle could be improved by drafting and twisting. A considerable improvement of the mechanical performance in tensile strength and strain at breakage was achieved for the twisted. Finally effects of the process variables for roller drafting and twisting on the changes in the structural and mechanical properties of the bundles are introduced. Keywords: nano-fibrous web, bundles, roller draft, elevated temperature, loops, two-for-one twisting, structure, twist angle, mechanical properties.

1. Introduction Electrospun nanofiber yarns are an ordered structure of assembled electrospun nanofibers. Recently, many researchers have developed technologies to obtain continuous nanofibrous bundle and twisted nanofiber yarns, by using a rotating mandrel, a water reservoir collector, two oppositely located metallic spinneret and selfbundling, etc [1-2]. Although these methods have the advantage of being able to produce nanofibrous yarns and bundles directly, there are critical disadvantages such as a low productivity and insufficient reproducibility for the application. The process of manufacturing electrospinned nanofiber yarns can be divided into two parts: (1) production of preferably aligned states of nanofibers like ordered bundles and taking of them by a proper mechanism of device such knife-edged disc, collecting them on a rotation drum, and (2) drawing and twisting them simultaneously or in following steps. In the latter, by drawing process the order of fibers along the yarn axis would be improved and by twisting the cohesion between nanofibers would be increased and acceptable mechanical properties can be achieved just like the same for ordinary yarns[3-4]. The objectives of this study to investigate (1) the influence of various drawing conditions on the tensile properties, especially for various draw ratios and heating temperatures (Table 1), in order to establish the feasible operation conditions and (2) to confirm how far the mechanical properties of the yarns can be improved by “Two-for-One” (TFO) twisting technology. To achieve the goals robbin-shaped nano-fibrous bundles which produced by the electrospinning and the heat-drawing processes were used. The bundles were tested by the tensile mechanical properties and fiber configurations. The yarns were made from the bundles by twisting TFO technology.

Page 1011 of 1108

Results of this experimental research shown that the most acceptable condition with improved mechanical properties of the bundle is the drawing ratio of 3 while in the drawing temperature of 90Â°C. and it was investigated that if use this condition for producing of nanofiber bundles with consequent TFO twisting technology, the resulted nanofiber yarns could be produced with enhanced mechanical properties.

2. Experiments 2.1 Material Preparation As the raw material, poly(vinylidene fluoride) (PvDF) was used to produce the nanofibers. PvDF with the molecular weight of 107,000 was dissolved in a mixture of 60% N,N-dimethylacetamide (DMAc) and 40% acetone, and then heated up to 60oC to give a concentration of 20 wt%.

2.2 Experimental rig The experimental equipment consists of an electrospinning device with multi-headed syringes, an endless moving collector, nanofiber bundle heat-drawing and TFO twisting devices. Figure 1 shows the total system of the experimental rig that was set up in this research. The electrospinning in the experimental rig was conducted by supplying an electric voltage of 15 kV. The spinneret, a syringe with needles, was installed with a distance of 120 mm from needle tip to the moving collector. The nano-fiber web produced on the collector surface was transported to the drawing zone and transformed into a nano-fiber bundle. Figure 2a shows the electrospinning process of the nanofibers.

Fig.1: Schematic of experimental rig

2.3 Nanofiber bundle drawing process The heat-drawing device consisted of two roller pairs and a home-made heating chamber. The heating chamber was located between the two roller pairs. Drawing was implemented by the speed difference between the front roller pair and the back roller pair, and the fiber bundle was heated simultaneously by hot air injection, of which the temperature was controlled. Figure 2b shows that heat-drawing process of nano-fibrous bundle. Material

PVDF

Table 1: Process conditions for the Heat-drawing process Undrawn bundle CV% Front roller speed Temperature width (mm) m/min â °C

3.796

0.62

0.2

70,90,120

Draw ratio

Heating zone mm

2-4

2.4 TFO twisting process Figure 2c shows a photo view of the novel design for continuous TFO spinning system. After passing through a front rollers, ribbon shaped nano-fibrous drafted bundle is delivered to the hollow flyer. Each rotation of the flyer, therefore, inserts one turn of twist in the bundle within the roller-flyer zone. Then, the yarn balloon generated by the whirling flyer inserts further one turn of twist simultaneously to the other end of the balloon in the bundle that is running through the hole of the bottom disc. Thus, two turns of the yarn are created for every flyer revolution. The operating principle is illustrated in Figure 2d, which shows how the strand undergoes a first twist zone between its entry into guide exit from the flyer and a second twist zone between insert to balloon exit from the hole of bottom disc. Material

PVDF

Table 2: Process conditions for the TFO twisting Heat-drawn bundle width CV% Spinner rotation (mm) rpm

1.5853

1.44

100

Bobbin speed/take-up/ m/min

0.2

Page 1012 of 1108

Fig. 2: Photograph of a) electrospinning, b) heat-drawing, c) TFO twisting processes, d) schematic description of 1st and 2nd twisting zones

3. Results and Discussion 3.1 Heat-Drawn nano-fibrous bundles and their mechanical properties Figure 3 and Figure 4 shows SEM images of nano-fibrous bundle and nanofibers under different heat-drawing conditions. The fibers arranged in a random fashion in the input bundle, and with increasing of temperature and drawing ratio, the fibers are reoriented more parallel to one direction corresponding to the bundle axis and the fiber thickness reduces. Therefore, increasing of the temperature and drawing ratio assures that the bundle drawing process and the process may consist of two phases: (i) loop release and arrangement of the nanofibers in bundle, and (ii) reduction of the nanofiber diameters. a) b) c) d)

Fig.3: SEM images of a) undrawn bundle, b) temperature 70⁰C, draw ratio 2, c) temperature 90⁰C, draw ratio 3, d) temperature 120⁰C, draw ratio 4, nano-fibrous bundles

Fig.4: SEM images of a) undrawn bundle, b) temperature 70⁰C, draw ratio 2, c) temperature 90⁰C, draw ratio 3, d) temperature 120⁰C, draw ratio 4, of nanofibes in bundle

Experimental results show the width changes of the nanofibrous bundles and the constituent fibers before and after the drawing operations for various levels of temperature and drawing ratio are given in Figure 5a-b. As temperature and draw ratio increased, the width of the nanofiber bundle and the diameter of constituent nanofibers reduced. However, the thinning points for the nanofiber bundle and that for constituent nanofibers seemed to be different. This experiment showed that the nanofiber bundle width was firstly thinned by according to the drawing ratio regardless (independently) of the temperature effect due to the fiber rearrangement along to the bundle axis. Then, the diameter of constituent nanofibers got thinned when the drawing ratio and temperature exceeded some levels.This explains that the nanofiber bundle drawing had the effects that firstly the nanofibers are rearranged then they are stretched. a) b)

Fig.5: a) Relationship between the fiber diameter and drawing ratios for various levels of temperatures, b) relationship between the bundle width and drawing ratios for different levels of temperature

Figure 6a-c shows the breaking tenacity and the breaking strain of heat drawn nano-fibrous bundles. It is shown that the breaking tenacity of nano-fibrous bundle increases from 1.33 to 5.48 cN/tex with increasing of heating temperature and draw ratios. This heat-drawing leads to a considerable descreases from 46 down to 9%

Page 1013 of 1108

in the bundle breaking strain. It can be explained by the increasing of structural orientation of the chains in the nanofiber due to heat-treatment. a) b) c)

Fig.6: Influence of the different heat-drawing condition on mechanical properties of nano-fibrous bundle a) temperature 70⁰C, b) temperature 90⁰C ,c)temperature 120⁰C

3.2 Twisted nano-fibrous bundles and their mechanical properties SEM images were used to investigate the TFO twisting on nanofiber morphology and bundle structure. The SEM images of the nano-fibrous yarn were obtained at flyer spinner rotation speed of 100 rpm, as it is shown Figure 7a, b. A uniform twist distribution was observed on the surface of the twisted bundle. The twisted bundle, which was obtained at take-up bobbin speed of 0.2m/min, showed a diameter 0.383mm ( CV 2.6%) , twist angle of 27⁰ (CV 16%). As shown in Figure 7c, the undrawn nano-fibrous bundle showed a breaking tenacity of 5.48 cN/tex and a breaking strain of 11% at break; however, nano-fibrous bundle with a twist angle of 27⁰ showed a tenacity of 8.82 cN/tex and strain of 126% at break because of the cohesive force between the nanofibers. The breaking tenacity and strain at broken point were significantly improved for twisted bundle. a) b) c)

Fig.7: SEM images of a) twisted nanofibrous bundle, b) nanofibers in twisted bundle temperature 90⁰C, draw ratio3, c) Stress-strain curves of twisted nano-fibrous bundle and undrawn nano-fibrous bundles.

Conclusion This study demonstrated that a nano-fibrous bundle can be prepared by consecutive processes of heatdrawing and TFO twisting technique. SEM images of undrawn and heat-drawn nano-fibrous bundles confirmed that nanofiber alignment in the bundle axis direction increased by heat-drawing process and this resulted better compactness of bundle structure and decrease bundle width. However, heat-drawing increase the breaking tenacity, but it decrease the breaking strain. The nano-fibrous yarns shows excellent twisting performance at “Twist generation zones” in TFO. The TWO twisting process improve the yarn and fiber uniformity in the yarn structure, bundle tenacity and strain at break, while decreasing of the bundle and fiber diameters.

Acknowledgement This research was supported by a Korea-Germany mobility PROGRAMME through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (NRF-2013K1A3A1A04075431).

4. References [1] Doshi, J and Reneker, D. H., ‘Electrospinning Process and Applications of Electrospun Fibers’. J.

Electrostatics., 35, 151-160, 1995. [2] Smit E, Buttner U and Sanderson R. D., ‘Continuous yarns from electrospun fibers’, Polymer., 46, 2419-

2423, 2005. [3] Teo W E, Gopal R, Ramaseshan R, Fujihara K and RamakrishnaS., ‘A dynamic liquid support system for

continuous electrospun yarn fabrication’ Polymer 48, 3400–5, 2008. [4] Yousefzadeh M, Latifi M, Teo W E, Amani-Tehran M and Ramakrishna. S., ‘Producing continuous

twisted yarn from well-aligned nanofibers by water vortex’ Polym. Eng. Sci., 51, 323–9, 2007.

Page 1014 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Effects of Variety, and Scouring Treatments on Dyeability of Cotton Fabric Genevieve Crowle 1, 2, Stuart Gordon 1 and Christopher Hurren 2 1

CSIRO Manufacturing Flagship Institute for Frontier Materials, Deakin University

Abstract. Dyeing of cotton is influenced by a range of chemical and physical interactions between dye molecules and fibres. To ensure consistency dyers select cotton varieties based on similar high volume instrument (HVI) properties, yet despite this control there are still many instances where dyed appearance of cotton products differs on a time/batch basis. Reported in this paper are the results of investigation into the effects of cotton variety, and scouring pre-treatments on dye uptake. These experiments represent the prelude to examinations of differences in cotton fibre structure concomitant with differences in dye uptake. The results showed the effects of varietal differences within a species can be eliminated by ensuring consistency of fibre properties, such as Micronaire and fibre maturity. There was also minimal dyeability difference evident as a result of different scouring pre-treatments.

Keywords: cotton, natural fibres, dyeing

1. Introduction Cotton is the most widely used natural textile fibre, however recent decades have seen a steady decline in the proportion of cotton used per capita as a consequence of the rise in synthetic textiles. It is therefore critical for the cotton industry to optimize the fibre properties that influence textile processing, including dyeing, so that cotton remains competitive with synthetic fibres. Dyeing of cotton is influenced by a range of chemical and physical interactions between dye molecules and fibres, many of which are not well understood. To ensure consistency dyers select cotton varieties based on similar high volume instrument (HVI) properties, yet despite this control there are still many instances where dyed appearance of cotton products differs on a time/batch basis. Of the four domesticated species of cotton, over 90% of cotton produced is Gossypium hirsutum, otherwise known as Upland cotton. About 8% of the remaining cotton is from the Gossypium barbadense species, an extra long staple cotton. Pima cotton is of the Gossypium barbadense species. Cotton fibre from all species has a layered structure consisting of a waxy outer cuticle, and the cellulosic primary and secondary cell walls, surrounding a hollow lumen. The extent of secondary cell wall development, or maturity of the fibre, is known to have profound effects on dyed appearance, with differences seen between fibres with as little as an 0.05 maturity difference [1]. Effects on dyeability due to Micronaire, a measure of specific surface area of which maturity is a factor, are also well documented with recommendations that blended fibres ought not vary by more than 0.2 Micronaire units to avoid issues of differential dye uptake and dyed appearance [2]. The cuticle must be removed prior to dyeing as it serves as a waterproof barrier, preventing the penetration of dyes and other chemicals into the fibre. This layer is removed by scouring prior to dyeing, typically under alkaline conditions. Growing environment is thought to affect both the amount and composition of wax on the fibre, as well as the colour of the fibre. The genetic variety of cotton has not been found to have a significant impact on raw cotton colour, but has been shown to have an effect on the dyed appearance of cotton fibre [3]. Reported in this paper are the results of a preliminary investigation into the effects of cotton variety, and fabric pre-treatments on dye uptake. Dye uptake was measured in terms of fabric colour differences before scouring, after scouring, and after dyeing. These experiments represent the prelude to examinations of differences in cotton fibre structure concomitant with differences in dye uptake.

Page 1015 of 1108

2. Experimental Fibres frin seven different varieties each grown on two plots at the Australian Cotton Research Institute (ACRI) in Narrabri, NSW was spun into Ne 30 (20 tex) ring spun yarn with a twist factor (αe) of 4.0. Single pieces of single jersey fabric (24 gauge) were knitted from each yarn to give 14 fabric samples representing 20 tex carded yarns spun from 14 cotton samples representing the seven different varieties (6 Upland and 1 Pima) in two replicates (Table 1). These samples were scoured, dyed and the colour measured according to the procedures described below. Sample 1 2 3 4 5 6 7 8 9 10 11 12 13 14

Table 1: Fibre Properties of Australian Cotton Varieties Variety Strength (gf/tex) Micronaire Sicot 71BR 29.4 4.48 Sicot 71BR 29.6 4.42 Sicot 70BRF 28.7 4.12 Sicot 70BRF 29 4.12 CHQX12B 32.5 3.99 CHQX12B 32.1 4.19 CHQX90 31.5 3.97 CHQX90 30.6 4.08 CHQX377 33 4.2 CHQX377 32.5 4.3 Sicala 350B 31.8 4.22 Sicala 350B 31.8 4.32 Sipima 280 46 3.45 Sipima 280 46.4 3.4

Maturity 0.87 0.87 0.86 0.86 0.87 0.87 0.86 0.86 0.87 0.87 0.88 0.87 0.87 0.87

The scouring trial was performed using a commercial woven griege cotton fabric of Chinese origin. Scouring was performed under the conditions listed in Table 2. After scouring the samples were conditioned under standard conditions, i.e. 20°C and 65% relative humidity for 24 hours before the fabric colour was measured. Scouring was performed in either a SDM2-140 rotary dyeing machine (Fong, Australia) or a H24-C rotary dyeing machine (Rapid, Taiwan). Scouring was performed for 1 hr at 95°C in a solution of NaOH (1 g/L), Hostapal FAZ (2 g/L), and Leonil JDZ (1 g/L). The samples were rinsed warm in fresh water, then rinsed cold in fresh water, and excess water removed before being oven dried at 105°C for 10 mins. Sample

Alkali

1, 2, 3 4 5, 6, 7 8 9, 10, 11 12 13, 14, 15 16 17, 18, 19 20 21, 22, 23 24 25, 26, 27 28 29, 30, 31 32

NaOH NaOH NaOH NaOH NaOH NaOH NaOH NaOH Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3

Table 2: Scouring Conditions Alkali Detergent concentration concentration (g/L) (g/L) 0, 1, 4 0.5 1 0.5 0, 1, 4 0.5 1 0.5 0, 1, 4 2 1 2 0, 1, 4 2 1 2 1, 2, 4 0.5 1 0.5 1, 2, 4 0.5 1 0.5 1, 2, 4 2 1 2 1, 2, 4 2 1 2

Temperature (°C)

Time (hr)

80 80 100 100 80 80 100 100 80 80 100 100 80 80 100 100

1 3 1 3 1 3 1 3 1 3 1 3 1 3 1 3

Dyeing was performed in the same equipment as scouring. The samples were held in a solution of NaCl (70 g/L), Verolan NBO (1 g/L), and Albaflow FFW (0.5 g/L) for 10 mins at 30°C, after which time Procion Yellow HE-6G (0.1% w/w) was added. The dye bath was raised to 90°C at 1°C/min and held for 30 mins. The bath was cooled to 70°C and Na2CO3 (10 g/L) added. The samples were held at 70°C for 35 minutes

Page 1016 of 1108

before being cold rinsed in a fresh bath. The samples were removed from the bath and excess water removed before being oven dried at 105°C for 10 mins. Colourimetry was performed using a Gretag Macbeth Color-Eye 7000A UV/Vis reflectance spectrophotometer (X-rite, USA) using the large (25.4 mm) aperture, D65 light source and a 10° collection angle with the spectral component included. Colour was measured in the CIELAB colour space from the average of 3 readings of L* (lightness), a* (red/green), and b* (yellow/blue) values. ΔE values were calculated to appraise colour differences between samples using the formula below, although because there were no evident differences in the varietal treatments these values are not reported.

ΔE = √(ΔL*2 + Δa*2 + Δb*2) Difference in lightness ΔL were calculated using the following formula:

ΔL = √(L1 – L2)2 Where, depending on the comparison L1 represents raw or scoured fabric and L2 represents scoured or dyed fabric.

3. Results and Discussion No visible difference in colour could be observed between the 6 Upland cotton varieties, although a large difference was observed between the Upland samples and the Pima cotton. A review of ΔE values indicated minor colour differences, i.e. ΔE < 1.0 between the Upland samples. Figure 1 shows the relationship between L* values for scoured and dyed fabric colour for each sample in the varietal set. The strong linear correlation (R2 = 0.99, p = 0.01) shows a one-to-one relationship between scoured and the dyed colour for this set with a ΔL between scoured and dyed colour of 3. This result indicates there is no significant difference in the dye uptake by any of the samples and that the observed colour difference in L* values is attributable to the base colour of the fibre. A large colour difference is seen between the Upland and Pima cottons. These results suggest that when HVI and fibre maturity values are held constant, genotype has minimal impact on the dye uptake of cotton within species.

L* scoured

y = 1.0387x - 3.0146 R² = 0.9873

L* dyed

Fig. 1: The L* values of the dyed fabrics plotted against the L* values of the scoured fabrics.

The scouring experiments on a commercial fabric found colour differences that were visible with the naked eye between the differentially treated (scoured) cotton fabrics. These differences, while more subtle, could also be seen within the dyed fabrics. The differences were attributed to differential base colour caused by the scouring treatment and not due to structural change to the fibre caused by the treatment. The ΔL between the dyed and scoured samples followed a mostly linear progression according to chemical concentration, time, and temperature (see Figure 2.). The largest differences in ΔL were seen for fabric

Page 1017 of 1108

subjected to extended scour treatments with NaOH at higher temperatures. The variation in ΔL values as a result of the various scour treatments highlights the importance of applying consistent conditions in scouring.

Delta L*

80°C 0.5g/L Hostapal 80°C 2g/L Hostapal 100°C 0.5g/L Hostapal 100°C 2g/L Hostapal

Treatment Fig. 2: The difference in lightness (ΔL) between the scoured and dyed samples plotted against treatment conditions.

4. Conclusion This work showed no marked differences in dyed appearance of cotton fibres based on varietal effects within Upland cotton, despite a wide range of Micronaire values represented within the samples. Although maturity values were largely constant. A range of scour treatments on a griege cotton fabric produced differences in dyed appearance which were attributed to the differential base colour of the fabric after scouring. Future work aims to study the effect of bleaching and storage conditions on cotton dyeability and the effect of changes brought by these treatments to cotton’s surface and/or cellulose structure on dye uptake. The authors gratefully acknowledge the funding by the Cotton Research and Development Corporation, Australia

5. References [1] 1. Gordon, S., et al. Using Siromat to Distinguish Fiber Maturity Related Issues in the Mill. in Proceedings of the Beltwide Cotton Conference. 2008. Nashville, TN: National Cotton Council. [2] 2. Choudhury, A., Textile Preparation and Dyeing, 2006, Science Publishers: Enfield, NH. [3] 3. Bradow, J. and P. Bauer. How Genotype and Temperature Modify Yarn Properties and Dye Uptake. in World Cotton Research Conference-2. 1998. Athens, Greece.

Page 1018 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Efficacy of Torque Adjustment to the Roller Draft Process You Huh1 +, Jung H. Lim2, Ganbat T.3, E. Schulte-Suedhoff4, and M. Wischnowski4 1

Department of Mechanical Engineering, College of Engineering, Kyung Hee University, Yongin, GyunggiDo, 446-701, Korea (Republic of) 2 Department of Textile Engineering, Graduate School, Kyung Hee University, Yongin, Gyunggi-Do, 446701, Korea (Republic of) 3 Department of Mechanical Engineering, Graduate School, Kyung Hee University, Yongin, Gyunggi-Do, 446-701, Korea (Republic of) 4 Institut für Textiltechnik (ITA) of RWTH Aachen University, Otto-Blumenthal-Str. 1, 52074 Aachen, Germany

Abstract. Roller drafting is a mechanical process to attenuate the linear density of slivers or rovings for the yarn formation process. The quality of drafted staple fiber bundles is evaluated in terms of irregularity in linear density and openness of the fibers, which determine the mechanical performance of the produced yarn. Therefore the roller drafting operation has been adjusted to improve the evenness of the drafted bundle; i.e., controlled by the draft ratio, which is realized by controlling the speed difference of roller pairs, while the distance between two roller pairs, that is, the draft gauge is considered. Since the effect of draft ratio on the sliver evenness is not clear yet theoretically, practical application is limited. Thus an optimization of the draft ratio and the sliver thickness as well is not yet established, even though a big body of research has been conducted. This research focuses on a search for a variable that can be used to lead the roller drafting operation to an easy optimization. The torque to drive the draft roller was chosen as the variable. And the torque was measured for variable draft gauge settings to derive the torque-evenness relationship. Based on the dynamics of sliver movement in a draft zone, simulation also was conducted and its results were compared with those from experiments so that the efficacy of the torque as an accessible variable for roller drafting was examined.

Keywords: roller drafting, draft ratio, torque, access variable, draft gauge, sliver movement, simulation.

1. Introduction Roller-drafting is a mechanical unit operation making the material in the draft zone attenuated by the speed difference between the two roller pairs. Yarn formation process is composed of a series of drafting operations that are applied to thick laps of fibres downwards to the thin and narrow fibre fleece through several steps. Especially for the drawing process that is a process using the roller drafting, slivers are doubled, and drawn along the sliver axis. During the drafting operation, the slivers are disturbed by extraneous factors so that the output sliver contains thickness irregularities. In order to enhance the quality of the product slivers, much effort has been made in the last century. However, the sliver consists of many fibres in cross-section, and its thickness changes along the length. Therefore a description of the fibre movement in the drafting zone is very complicated and in actual scarcely achieved, which indicates why the roller drafting operation has been adjusted manually according to the expert experience. In this research, we chose motor torque to drive a draft roller pair as an access point for the draft operation and to see the feasibility to use the torque as a real-time variable. Based on the theoretical model from Huh et al. [1], the draft force can calculated by solving the sliver draft dynamics. Also the torque was measured experimentally. Comparisons of the torques would suggest us how to take advantage of the torque for the roller drafting operation.

2. Theoretical model of the sliver movement in the drafting zone For the slivers in a drafting zone, the continuity equation is expressed [1] as (lb )t = −(lb ⋅ v )x and the equation of motion is

(1)

Page 1019 of 1108

(lb ⋅ v )t = −(lb ⋅ v 2 )x − (lb ⋅Var[vi ])x − ( f )x

(2)

lb and v are the linear density and speed of the sliver that are dependent on time t and position x from the nip point of the input roller pair. f stands for the momentum transferred into the control element surface of the sliver at time t and position x . The subscription means a partial derivative with respect to the subscript variable and Var[ ] is the variance of the speed of the constitutional fibers at ( t, x ). Assuming a constitutive behavior of the sliver expressed with µ for the kinematic viscosity as where

f ∝ −lb ⋅ (v )x = − µ ⋅ lb ⋅ (v )x and the speed variance of fibers modeled as 2π   Var [vi ] = a0 ⋅ v ⋅ 1 − cos x L   where a0 is a speed variance constant, Eqs. (1) and (2) can yield to

(l ) + (l *

) (

)

(

⋅ v*

)

(3) (4)

)

( ( ))

(5)

⋅ v * t * + lb ⋅ v x* + ae ⋅ lb ⋅ v * ⋅ (1 − cos( 2π ⋅ x * )) x* = µ e ⋅ lb ⋅ v * x* x* while dimensionless variables are introduced such as * L * x = x* ⋅ L , t = t * ⋅ , v = v ⋅ v0 , lb = lb ⋅ lb 0 v0 a The dimensionless model parameter are defined as µ e = µ , and ae = 0 . v0 L ⋅ v0 The boundary conditions can be given as * * * v0 = 1, lb 0 = 1 at x * = 0 for all t * , v L = DR (draft ratio) at x * = 1 for all t * *

(6) (7)

(8)

3. Experiments The motor torque required to draft the sliver was measure on a factory-driven 4/3 draw frame (Fig. 2), of which the roller pairs are driven by individually.

Fig. 2 Schematic representation of the draw frame to measure the torque.

At first the power of the driving motor was measured and then the toque was calculated. The torque was measured for the main draft zone under different draft ratios, while the break draft conditions were maintained unchanged. Thus the torque was measured for the middle roller motor and the front roller motor. The measurement conditions were summarized in Table 1. Table 1. Draft conditions for measuring the torques to drive the middle and front rollers Staple length of the sliver 27.92 mm

U% of the sliver 2.91%

Sliver thickness 4.99 tex

Draft Ratio (Main/Break) 6.25/1.1

Gauge length 38 - 46 mm

4. Results and Discussions 4.1. Motor torques The motor torques measured for various draft gauge lengths are given in Fig. 3.

Draft speed 500 m/min

No. of doublings 5

Page 1020 of 1108

Fig. 3 Relationship between motor torque and draft zone length measured from experiments.

For a given input, the motor torque for the front roller decreases as the gauge length increases, especially, in the level of small gauge length, i.e., from 38 mm to 42 mm (1.36-1.5 times average fibre length). However, further increase of the gauge length from 42 mm up to 46 mm (more than 1.5 times average fibre length) causes no significant change in motor torque. On the other hand, the motor torque for the middle roller increases almost linearly to the gauge length. Since the draft force in the main draft zone becomes smaller as the draft zone gets wider, the pull-out force acting on the sliver near the middle roller decreases, which would lead to the result that more torque must be brought up to the middle roller to maintain the break draft as required. This indicates that the break draft can be more strongly coupled with the main draft, when the draft gauge becomes longer.

4.2. Simulations Dynamics of the bundle flow, described by the governing equations of Eqs. (5) and (6), was discretized by the FTBS (Forward-Time Backward-Space) principle combined with Crank-Nicholson method to achieve the numerical stability and a minimal calculation time. The initial condition for simulation was set as * * * * (9) lb = 1, v* = 1 at t * = 0 and v L = DR (draft ratio) at x = 1 for t = 0 According to Eqs. (5) and (6) together with the boundary conditions given in Eq. (8) and the initial condition in Eq. (9), the behaviour of the sliver thickness and speed in the draft zone was simulated for different draft gauge lengths. For the simulation the parameter values are the same as given in Table 2. The slivers under draft operation are stretched in the process direction, but not shrunk or pushed back because fibers are easily bent and folded. Therefore the bundle in the draft zone can be treated as an extensional flow. The parameter µ was determined by experiments [2], revealing that the value had the order of 108 (mm2/s), depending on the draft ratio but not so much on the sliver thickness and the draft gauge length, except the gauge length near the mean fiber length. Therefore we assumed the viscosity had values of 108 order in (mm2 /s) for simulation. The model parameter a0 was adjusted by trial and error. Simulation results for the dynamic behaviour of the draft force are given in Fig. 4, where various combinations of the model parameters a e and µ e are adopted for a given draft gauge length of 38 mm. a) b)

Fig. 4 Dynamic behaviours of the draft force in the main draft zone obtained from the model for a given draft gauge length of 38 mm:

a) a e =4167, µ e =2.0559.104,

b) a e =3125, µ e =4.1118.105.

Page 1021 of 1108

Draft force responses very fast to the initial condition in low levels of a e and µ e , as shown in Fig. 4 a), while high levels of a e and µ e cause some delay in the draft force response as given in Fig. 4 b). The greater the sliver viscosity, the more delayed the draft force response ! The draft force behaviour from Fig. 6 can be observed also in Fig. 7 where draft gauge length was 46 mm; the greater the sliver viscosity, the more delayed the draft force response. It can be concluded that draft gauge has no influence on the dynamic behavior of draft force as far as the parameter values remain in the same level (Pleas compare Fig. 4 and Fig. 5). a) b)

Fig. 5 Dynamic behaviours of the draft force in the main draft zone obtained from the model for a given draft gauge length of 46 mm:

a) a e =4037, µ e =1.7756.104, b) a e =3125, µ e =3.3967.105.

When focusing on the dynamic behavior of the linear density of the output sliver, simulation revealed that the linear density of the output sliver had some underdamped behavior with time, even for the very small values of the parameter a e =4037, µ e =1.7756.104. Simulation results obtained so far indicate that the draft process is sensitive to the parameter of dimensionless viscosity that is defined as µ /( L ⋅ v0 ) . The speed variance of the fibres in the draft zone defined as a 0 / v 0 seems to have minor effect on the output sliver. The draft force or the motor torque are very effective variables in that they can reflect the state of the draft dynamics very fast in comparison with the linear density of the output sliver, which is more effective, when the sliver viscosity becomes lower.

5. Conclusions In this research we investigated the possibility to take advantage of the draft force or motor torque for the roller draft operation Results turned out that the motor torque could be a good measurement variable for the draft operation, in that it is including the state information more precisely than the linear density of the output sliver. As the draft gauge length increases, the motor torque to the front roller decreases fast in a certain range of the draft gauge. The draft gauge longer than 1.5 times average fibre length has no impact on the motor torque. The break draft is more strongly coupled with the main draft, when the draft gauge becomes longer. Simulation analysis showed that the draft force, corresponding to the motor toque by the factor of the roller radius, was very sensitive to the sliver viscosity. As the sliver viscosity becomes smaller, the draft force contains more precise dynamic information on the draft process than the linear density of the output sliver. Results from this research indicate that the motor toque can be used more effectively than the linear density of the output sliver for monitoring the roller draft operation.

Acknowledgement: This research was supported by Korea-Germany Mobility Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (NRF-2013K1A3A1A04075431).

6. References 1. 2.

Huh, Y. and Kim and Jong S., “Modeling the Dynamic Behavior of the Fiber Bundle in a Roll-Drafting Process”, Textile Res. J. 74, 872-878 (2004). Jong S. Kim and You Huh, ’Kinematic Viscosity of Fiber Bundle Flow and Draft Stability’, J. Korean Fiber Soc. 46. 215-221 (2009).

Page 1022 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Elimination of dyestuff using scCO 2 ○Yao Chen1, Satoko Okubayashi1, Teruo Hori2, Ryoma Fukumoto3 Toya Banno3 (1Kyoto Institute of Technology, 2University of Fukui, 3Fujix Ltd.)

Abstract. Supercritical carbon dioxide (scCO 2 ) dyeing is an ecological new type of dyeing process. With the development of scCO 2 dyeing, how to remove dyestuff from the vessel after scCO 2 dyeing is becoming a new problem. Organic solvent is the conditional solvent to remove the dyestuff from the vessel, but it is not environmentally friendly. Supercritical carbon dioxide including surfactant, were applied to remove dyestuff from dyeing vessel. The removed dyestuff ability of the surfactant were evaluated by the results of color difference of polyethylene terephthalate (PET) fabrics which were treated by supercritical carbon dioxide in the vessel after removing dyestuff. This study reports that the relationship between solubility of surfactant and its elimination ability for dyestuff in scCO 2 .

Keywords: supercritical carbon dioxide, elimination dyestuff, surfactants.

1. Introduction Supercritical carbon dioxide (scCO 2 ) dyeing technology is going to be considered as an ecological new type of dyeing process because the traditional textile dyeing industry is becoming to be a big consumer of water. Nowadays, scCO 2 dyeing technology which uses the recycled carbon dioxide to replace water and drying process is used to dye polyester fabrics without water in some sports apparel brand’s manufacturer. With the development of scCO 2 dyeing technology, how to elimination dyestuff from the vessel after scCO 2 dyeing is becoming a new problem. Organic solvent, which are poisonous if inhaled in sufficient amount, and can cause dermatitis after long time skin expose, is the conditional solvent to clean the dyestuff from the vessel, but it is not environmentally friendly and bad for human’s body. Finding a new ecological way to replace this dangerous eliminating dyestuff way is become a new topic in textile dying industry. Dry cleaning using supercritical carbon dioxide

Page 1023 of 1108

as solvent is more environmentally friendly than traditional organic solvents such as hydrocarbon to eliminate dyestuff which remains in the vessel after scCO 2 dyeing. In this study, scCO 2 including surfactant, were applied to remove dyestuff from dyeing vessel. Polyethylene terephthalate (PET) fabrics, a conventional disperse dyestuff, solvent and several types of surfactant were used in this research. The capability of the surfactants as cleaning agent of dyestuff was evaluated by measuring lightness chromaticity L of PET fabrics which were treated by scCO 2 in the vessel after removing dyestuff. The Î&#x201D;L which was the difference of L between untreated PET fabric and the one treated in the vessel including residue dyestuff after CO 2 treatment. The solubility of the surfactants was estimated from its weight decrease of before and after CO 2 treatment. This study reports that the relationship between quantity, hydrophile-lipophile balance and solubility parameter of surfactant and its elimination ability for dyestuff in supercritical carbon dioxide. The influences of CO 2 conditions such as temperature, pressure, time were also investigated.

2. Expeimental 2.1 Materials PET fabrics samples were purchased from Shikisensha CO., LTD (warp yarn count: 75d-36f; weft yarn count: 75d-36f ; warp yarn density 120yarn/inch; weft yarn density: 90yarn/inch). A red disperse dyes (C.I. Disperse Red 60) was supplied excluding dispersing agent and any other additives. Moreover, the acetone (purity: 99.5%), was purchased from NACALAI CO., LTD. The 7 types of surfactant were supplied by OHARA PARAGIUM CO., LTD. The chemical structure of the disperse dye are given in Fig. 1.

Fig.1 Chemical structure of C.I. Disperse Red 60

2.2 Procedure

Page 1024 of 1108

The 1.25mg of dye in acetone was absorbed in glass filter and dried. One gram of each surfactant was wrapped by glass filter and weighed (Wb). Both glass filters were placed into a high-pressure vessel which was mounted in an oven (JASCO SCF-Sro) and heated up to 125℃ for 1 hour. Then CO 2 was injected in to the high-pressure vessel by using PU-2086 intelligent HPLC pump (JASCO Corporation) until 25MPa. After keeping supercritical carbon dioxide treatment for 1hour, the CO 2 was released out from the vessel to remove the dyestuff. The glass filters wrapping the dye stuff and the surfactant were taken out from the high-pressure vessel and weighed (Wa), then 1g of PET fabric was placed into the high-pressure vessel and treated by supercritical carbon dioxide at 125℃ and 25MPa for 1 hour to exhaust the reside of dyestuff to the fabric. The capability of the surfactants as cleaning agent of dyestuff was evaluated by measuring color depth L

of PET fabric. The ΔL∗ which was difference between untreated PET fabric and one treated in the vessel

including residue dyestuff after CO 2 treatment. The solubility of the surfactants was estimated from the weight change of glass filter before and after CO 2 treatment according to the equation (1).

3. Results and Discussion

Weight loss (%) =

Wb−Wa Wb

× 100

（1）

Table 1 Color change of PET fabric and weight loss of surfactant Surfactant

ΔL

Weight loss (%)

Cont.

38.65

32.90

25.00

29.78

9.26

34.70

0.81

27.73

8.73

19.75

4.01

12.78

1.28

10.98

1.68

Table 1 shows the color change of PET fabric and the weight loss of surfactant before and after treatment with the residue dyestuff in CO 2 . The control experiment was carried out without surfactant. The weight loss

Page 1025 of 1108

which indicates the solubility of surfactant in CO 2 was higher in the order of S1 > S2> S4 > S5 >> S6= S7 > S3. However, the elimination ability of the surfactant which gives smaller Î&#x201D;L, was higher with usage of S6 and S7. That says Î&#x201D;L of PET fabric showed smaller value with lower solubility of surfactant in scCO 2 , and more dyestuff was remained in vessel because higher affinity of surfactant for CO 2 would reduce the affinity for dyestuff including the elimination ability of surfactant. It could be considered that S3 does not have elimination ability as surfactant because it almost does not dissolve in scCO 2 .

4. Summary In this study, the relationship between solubility of surfactants and their elimination ability for disperse dye was investigated. Consequently, the surfactant with not too high and not to low solubility excluded the largest amount of residue dye in scCO 2 .

Page 1026 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Enhancing UV protection of Green Bamboo Textiles during bio-processing Shah J.N. The M. S. University of Baroda, Vadodara – 390 001, Gujarat, INDIA

Abstract. Bamboo, a woody-stemmed green grasses, can be converted into bio-degradable textile fibre. Exploring bamboo and its bio-processing is an innovative approach towards green environment. Conventionally hazardous chemicals are employed in processing of this fibre. In this study an effort has been made to preserve the green status of this fibre through bio-processing and to enhance its UV protection characteristic. Bio-pretreatment of Bamboo fabric had been performed with enzymes having various activities on noncellulosic constituents (hemicelluloses, pectin, lignin, fat & waxes) of bamboo fibre under various process parameters. Pretreatment conditions were optimized with respect to weight loss (6.3%). Optimized sample was dyed with natural dye Turmeric at different conditions. Aloe Vera extract applied as finishing agent to impart better handle and to enhance UV protection of Bamboo fabric. Comparative evaluation of conventional and bio-processed bamboo and cotton fabric revealed that Ultraviolet protection reported in terms of UPF rating enhanced from 18 to 32 units in case of bamboo, whereas the same in case of cotton fabric was negligible. UV transmission reduced drastically in UV-A as well as UV-B regions as a result of enzyme pretreatment and finishing with Aloa vera in case of Bamboo. This indicates that as a result of bioprocessing some structural changes occurred in Bamboo which is responsible for reduction in transmittance of UV rays. Keywords: UV protection, Bamboo textiles, enzymes, bio-processing, pretreatment, noncellulosics

1. Introduction Bamboo is known for its unique characteristics; natural anti-bacterial, ultra-violet protection, moisture absorption, antistatic, excellent wicking property, soil release, breathable and cool, temperature adaptability, Green & biodegradable. Bamboo is abundant and vigorous plant so it should be harvested in a sustainable way to get maximum ecological benefit1-3. The conventional processing of bamboo textiles employs hazardous chemicals, thereby the green status of bamboo is lost. In this study an effort has been done to preserve this status and to enhance UV protection of bamboo. Though cellulosic, bamboo fibre contains various noncellulosic constituents, namely, hemicelluloses, pectin, lignin etc4. In the present study, during pretreatment, the major stage of wet processing of bast fibre (bamboo), these noncellulosic constituents are removed to certain extent using different enzymes. Enzyme with a particular activity removes a particular constituent for example xylanase is supposed to remove hemicelluloses5. This enzymatic pretreatment is evaluated for its efficiency and compared with conventional process and optimized. At optimized conditions, combination of various enzymes eliminates these constituents to desired level and imparts the best performance. Compared to cotton, bamboo fibres exhibit better protection against Ultraviolet rays. When dyed with natural turmeric dye and application of Aloe vera, transmittance in UV range is much more reduced in case of bamboo fibre. This enhances UV protection factor of bamboo.

2. Materials & methods 2.1 Materials Grey fabric manufactured from 100% bamboo fibre in warp & weft having 54 reeds/inch, 50 ends/inch and procured from local supplier in India was used for the study. Three different types of enzymes coded “A”, “B” & “C” was used for the study (table 1). Table 1: Details of Enzymes Used

Page 1027 of 1108

Code

A B C

Trade Name BGLU BIO-SOFT PALCOSCOUR

Acts On

Optimum Conditions

Activity(u/g)

Hemicellulose & Pectin

Temp.50ͦ C & pH 5

Cellulose Fat,wax,pectin & lignin

Temp. 55ͦ C & pH 5-5.5 Temp.50-55ͦC & pH5-5.5

75000 25000 120000

Procured From Rossari Biotech Rossari Biotech Maps(India)Ltd

Natural dye Turmeric (Curcuma Longa, mole. wt. 368.33) was used after purification. Aloe Vera gel (Aloebarbandensis miller, mole. wt. 418.39) used as finishing agent.

2.2 Methods Grey bamboo fabric sample of about 2 grams conditioned for about 24 hours under standard conditions and subjected to treatment after weighing accurately on electronic weighing balance.

2.2.1 Pretreatments Sample was chemically pretreated using 2 gpl sodium hydroxide 2 gpl soda ash at 90oC for 1 hr in a shaker bath, keeping MLR at 1:60. The sample was thoroughly washed with hot and cold water and neutralized with acetic acid. This sample was used as control sample for comparison with bio-processed fabric. Fabric samples were bio-pretreated with enzymes “A”, “B” and “C”. To study the effect of enzyme, concentration of enzymes “A”, “B’’ and “C” were varied and so also the time of treatment(2,4,6 and 9 hrs). A temperature of 50-55 oC and pH 5-5.5 was maintained in all cases, keeping MLR at 1:60 in a shaker bath.

2.2.2 Dyeing Fabric samples after pretreatment were dyed with natural dye Turmeric ( 10% concentration) by exhaust dyeing technique using simultaneous mordanting (10% Alum) in a water bath machine at temperature 80oC for 1 hr keeping MLR at 1:60.

2.2.3 Finishing with Aloe Vera Selected dyed fabric samples both control and bio-processed were subjected to finishing with natural finishing agent Aloe Vera using pad-dry-cure technique on Laboratory Pad-Dry-Cure machine(RBE Make)6. The fabric samples were padded at a pressure of 2.5 psi, temperature 50oC resulting 60% wet pick-up. Samples then dried at 80ºC for 2 minutes followed by curing at 180ᵒC temperature for 3 minutes.

2.2.4 Test methods Fabric samples grey as well as treated were analyzed for their chemical composition using standard scheme proposed by A. J. Turner (1949)7. Standard prescribed methods were used to analyse weight loss percent and physical characteristics, namely, absorbency, tensile strength, whiteness and yellowness index etc of samples to study efficiency of pretreatment 8-10. Evaluation of color fastness to washing was carried out using ISO-3 method11. Ultraviolet protection factor (UPF) of control and bio-processed samples was analyzed as per standard method on UV-2000F instrument (Labsphere make) wavelength range 290 to 400nm at interval 2 to 5 nm. The results were reported as per AS/NZS 4399 Sun protective clothing standards12.

3. Results and Discussions Conventional wet processing of bamboo fibre produce harmful effect to environment and also green status of bamboo is lost. In present work an effort has been done to save environment and to preserve green status of bamboo through bio-processing.

3.1 Pretreatment performance Multicellular bamboo fibre along with cellulose contains significant quantity of non cellulosic constituents (Ncs). Bamboo under study contains 26.21% non cellulosic constituents (Ncs) which is in agreement with the reported values (table: 2).

Page 1028 of 1108

Table 2: Chemical Composition of Bamboo Sr. no.

Constituents

1 2 3 4 5

Cellulose Hemicellulose Lignin Pectic matter Water soluble

Reported

Grey fabric

73.83 12.49 10.15 0.37 3.16

73.79 12.98 7.23 0.89 5.11

Composition in percent Conventionally (optimum) pretreated 80.59 10.20 5.12 o.73 3.36

Enzymatically (optimum) pretreated 79.40 9.98 5.05 0.68 4.89

These Ncs may largely affect the physical properties of the substrate13. In the preparatory process a portion of these Ncs are removed resulting in weight loss and thereby affects the physical properties. Conventional alkaline pretreatment at various conditions resulted in weight loss from 2.80 to 9.76 percent. As a result of removal of Ncs, characteristics of fibre altered and change in whiteness, yellowness, tensile strength and absorbency observed. This effect is studied as a function of weight loss. Results reveal that at weight loss level of 6.8% optimum pretreatment performance is achieved. At this optimum condition various Ncs are removed selectively to desired level (table 2). Enzymes having different activity as alone or in combination removed various Ncs to different level depending on their activity and treatment conditions. Enzymatic pretreatment was optimized to achieve performance at par with conventional process. At optimum conditions with weight loss 6.84, various Ncs removed to desired level (table 2). Improvements in absorbency, whiteness, brightness obtained which is at par with conventional (figure 1).

Fig. 1 : Comparison of Optimally Pretreated Samples

3.2 Dyeing Bamboo with Turmeric In order to study the complete bio-processing, optimally pretreated samples were dyed with Turmeric dye. Dyeability was assessed in terms of K/S value for comparison of conventional and bio-processed samples. Higher K/S value 2.165 observed in bio-processed sample compared to conventional (table 3). Higher dye uptake in case of enzymatic pretreated sample may be due to increase in surface area due to cellulose etching. Fastness properties found to be satisfactory in both cases. Table 3: Dyeing Performance of Selected Sample Dyed With Turmeric Dye Sample

K/S value

Washing fastness

Rubbing fastness Dry Wet

Light fastness

Conventional

1.727

3-2

Enzyme pretreated

2.165

3-4

3.3 Finishing with Aoe Vera Ultraviolet rays (280-400 nm) when strike human skin, it causes harmful effect. The ultraviolet protective factor (UPF) is a numerical value which represents the degree of protection against UV rays provided by clothing. The transmission, absorption and reflection of UV radiation are responsible for the UV protection ability of a fabric next to skin. Such fabric acts as a barrier to harmful effect on skin (figure 2). The UPF of textiles can be improved by the integration of metal particles, dyes, pigments or the application of a UV-absorbing finish to the fabric as per Vigneshwaran, 2007 14. Aloe Vera is used in this study to serve as UV-absorbing natural finish. The result of UV transmittance from various fabric samples is illustrated in figure 3. From these results UPF rating were reported in table 4 as per AS/NZS 4399 Sun protective clothing standards12.

Page 1029 of 1108

Transmittance (%)

20 15

E17

10 5 0 260 280 300Wevelength 320 340 360 (nm)380 400 420 440

Fig. 2 Schematic Representation of a Textile as a Barrier to UV Radiation

Fig. 3 UV Transmission Percentage of various fabric sample

Results clearly indicate that cotton fabric have no protection to ultraviolet radiation compare to bamboo fabric. Considerable reduction in UV transmittance in case of conventionally and enzymatic treated bamboo fabric imparts protection against UV radiation from category good to very good. Table 4: UV Transmission Analysis of Various Fabric Sample UV-A UV-B UPF Protection category (330-400 nm) (280-320 nm) Rating CC 17.40 17.10 ------No protection C7 5.00 4.55 18 Good E17 3.05 2.80 32 Very good CC :- Cotton C7:- Conventionally pretreated ,dyed and finished sample E17:- Enzymatically pretreated, dyed and finished sample Sample code

In case of enzymatically pretreated sample transmittance of UV rays drastically reduced compared to conventional sample. The reduction of UV transmittance may be due to selective removal of lignin, waxes and pectins during enzymatic treatment and also change in fabric structure due to shrinkage. The UPF is further enhanced with colorant of dark hues and with high concentration of the colorant in the fabric15. Increase in UPF value of sample finished with Aloe Vera may be because aloe vera extract contain vitamins (A,C,B12), metals, sugars compounds which decreases UV transmissittance16-17. Also some molecular structural features may act as UV blocking sites when applied on fibre and reduce UV transmittance.

4. Conclusions In this study conventional pretreatment has been successfully replaced by green pretreatment using enzymes of various activities. The pretreatment performance in terms of various physical properties of optimized enzymatic pretreatment (weight loss i.e. 6.86%) found to be well comparable with that of conventional pretreatment. In order to complete the green processing, the finishing was also carried out using natural Aloe Vera. The satisfactory results were obtained in this era. UPF rating of conventionally pretreated fabric was found to be 18 corresponding to good protection category where as in case of green processed sample this value drastically increased to 45 correspond to excellent protection category, thus, UV protection factor also found to improve during this green processing. The object of this work has been successfully achieved by green processing of bamboo fabric and found to be well comparable or even better than that of conventional processing. Outcome this study can be explored in garment industry for manufacturing sun protective clothing especially for the regions prone to UV radiation.

5. References 1.

Dr Shah J N and Dr Shah S R. ˝Bamboo: The Green Fibre of 21st Century; Characteristics and Structure”. Bangladesh Textile Today.Dec.2012, 39

2. 3. 4. 5.

Afrin T, Tsuzuki T, and Wang X. “Bamboo Fibers and Their Unique Properties”. Bamboo Bulletin.2009; 11(1), 36-39 Afrin T, Tsuzuki T, and Wang X. “UV absorption property of Bamboo”, Journal of The Textile Institute,2012,103(4),394-399 Wang Y. “Structure of Bamboo Fibre for Textiles”. Textile Research Journal. March 2010,80(4), 334-343 Chakraborty J N, Patra A K, and Madhu A. “Studies on Enzymatic Pretreatment of Linen”. Indian Journal of Fibre and Textile Research. December 2010; 35:337-341.

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Dr. Khan F A. “Extraction, Stabilization and Application of Antimicrobial Agents from Aloe Vera”. Pakistan Textile Journal. April 2012; 1:6.

7. Textile Laboratory Manual Vol.5 by W. Garner, Third Edn. 8. ISI Handbook of Textile Testing (1981) 221,31,44,399 9. ASTM Standards on Textile Materials, ASTM, Philadelphia (1994). 10.J.E Booth. “Principles of Textile Testing” 1stEdn. (1996) 353. 11.Umbreen Saima, Ali Shaukat, Hussai Tanveer and Nawaz Rakhshanda.ʽʽDyeing Properties of Natural Dyes Extracted from Turmeric & Their Comparison with Reactive Dyeing”.RJTA.2008; 12:4.

12.http://www.arpansa.gov.au/pubs/upf/UPF_TestingInfoPack.pdf dt. May 20,2015 13.Bhattacharya S D and Shah J N. “Enzymatic Treatments of Flax Fabric”. Textile Research Journal.2004; 7:622-628. 14.Saravanan D. “UV Protection Textile Materials”. Autex Research Journal.2007;7:53-62 15.Das D. “Bio-Chemistry”. Academic Pub. Calcutta.1995; 8:96. 16.Joshi M, Ali W and Purwar R. “Ecofriendly Antimicrobial Finishing of Textiles Using Bioactive Agents Based on Natural Products”. Indian Journal of Fibre and Textile Research.2009; 34:295-304.

17.Hu Y, Xu J, And Hu QJ. “Aloe Vera for Skin Care”. Agric Food Chem.2003; 51:7788-7791.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Evaluation on Dyeability and the Reproducibility of Natural Indigo Dyeing Ching-Wen Lin 1+, Chia-Chia Wu 1, Ching-Wen Lou 2 and Jia-Horng Lin 3,4 1

Department of Fashion Design, Asia University, No. 500, Lioufeng Rd., Wufeng, Taichung 41354, Taiwan, Republic of China 2 Institute of Biomedical Engineering and Material Science, Central Taiwan University of Science and Technology, Taichung, Taiwan, Republic of China 3 Department of Fiber and Composite Materials, Laboratory of Fiber Application and Manufacturing, Feng Chia University, Taichung, Taiwan, Republic of China 4 School of Chinese Medicine, China Medical University, Taichung, Taiwan, Republic of China

Abstract. People expect to have beautiful clothes to show themselves, and thus resulting in booming fashion industry and the textile industry. Synthetic dyes are most commonly used for dyeing, but many dyes were found to cause human disease, and often serious pollution problems. The use of non-toxic and eco-friendly natural dyes on textiles has become a matter of significant importance because of the increased environmental awareness in order to avoid some hazardous synthetic dyes. Dyeing effect of natural indigo dyeing is not reproducible, so that indigo dyed apparel with only unique, but not had the popularity and fashion. In this study, a modified indigo dyeing procedure has been introduced and the color strength, color difference and reproducibility of dyed fabrics dyed with natural indigo dyes have been evaluation. The result indicates the modified indigo dyeing procedure suitable for reproducibility of natural indigo dyeing.

Keywords: Dyeability, Reproducibility, Color difference, Natural indigo dyeing

1. Introduction Natural dyes are known for their use in colouring of food substrate, leather, wood as well as natural fibers like wool, silk, cotton and flax as major areas of application since ancient times. Natural dyes may have a wide range of shades, and can be obtained from various parts of plants including roots, bark, leaves, flowers, and fruit. Since the advent of widely available and cheaper synthetic dyes in 1856 having moderate to excellent colour fastness properties, the use of natural dyes having poor to moderate wash and light fastness has declined to a great extent. However, recently there has been a revival of the growing interest in the application of natural dyes on natural fibers due to worldwide environmental consciousness. Although this ancient art of dyeing with natural dyeing with natural dyes withstood the ravages of time, a rapid decline in natural dyeing continued due to the wide availability of synthetic dyes at an economical price. However, even after a century, the use of natural dyes never erodes completely and they are still being used. Thus, natural dyeing of different textiles and leathers has been continued mainly in the decentralized sector for specialty products along with the use of synthetic dyes in the large scale sector for general textiles owing to the specific advantages and limitations of both natural dyes and synthetic dyes [1]. Recently there has been growing interest in the use of non-toxic and eco-friendly natural dyes in textile applications. This is a result of the stringent environmental standards imposed by many countries in response to the toxic and allergic reactions associated with synthetic dyes. Natural dyes exhibit better biodegradability and are generally more compatible with the environment. In spite of their inferior fastness, natural dyes are more acceptable to environmentally conscious people around the world. Indigo is insoluble in water, but soluble in polar organic solvents. Prior to the dyeing process, it has to be reduced into its leuco form (soluble in water). Currently, the dye reduction step is carried out with sodium dithionite in alkaline medium [2]. +

Corresponding author. Tel.: + 886-4-2332 3456 #1870.

E-mail address: chingwen@asia.edu.tw.

Page 1032 of 1108

The main disadvantage of indigo is the fast oxidation of its leuco form in contact with air. For this reason, some of the industrial dyeings are performed in the nitrogen atmosphere. In order to ensure the reproducibility and regularity of dyed yarns, it is also important to evaluate the indigo concentration in the dye baths during the dyeing process. The concentration of leuco form should be constant and it is regulated by means of sodium dithionite addition [2]. Because natural indigo dyes come from native plants and do not purify, the concentration of the dyes can’t be quantified and dyeing effect is controlled only empirically. The effect of dyeing is almost different to each other. That is to say the color difference between two fabrics dyed from a similar process. The effect of indigo dyeing is not reproducible. Therefore, even if there is a good fashion style design, it is difficult to have the same two sets of natural indigo dyed apparel. This apparel is impossible to form widespread and fashion. In order to reduce environmental pollution and to satisfy the demand of fashion, to improve the dyeing reproducibility of natural indigo dyeing is necessary.

2. Experiments 2.1.

Materials and Methods

Four types, a plain weave and three twill weaves, scouring and bleaching cotton fabric were used. The plain woven fabric was dyed for evaluating effects of dye parameter on dyeability and effects of dye concentration on dyeing reproducibility. Three twill woven fabric was dyed for evaluating dyeing reproducibility of different fabric structure. The native indigo clay purchased from Tennii Studio was used as dyes source. Sodium hydroxide and Sodium hydrosulfite made by Showa Kako Corporation were of general laboratory grade and obtained from Echo Chemical Co., Ltd. were used for the indigo dyeing. Screen fabrics with 200, 300, and 400 meshes/ inch2 and hydrophobic PTFE membrane with 0.2μm pore size were used for filtering the impurity and larger particle of the native indigo clay. Polypropylene (PP) box with auxiliary apparatus is used as dyeing bath. The apparatus was designed for rotating the dyeing fabric and for improving dyeing evenness. The X-Rite SP-62 spectrometer was used to assess reflectivity, K/S value and color difference of dyed fabrics.

2.2.

Preparation of Indigo Dyes

Indigo dyes used in the dyeing process were purified from commercial native indigo clay in advance. The native indigo clay was reduced in the presence of alkali by sodium hydrosulfite. Then it dissolves in water. The mixed solution consists of water soluble indigo, lime powder, impurity and so on. It was filtered by the screen fabrics and a hydrophobic PTFE membrane successively. The filtered solution was then exposed to air, which oxidizes the dye molecule back to its insoluble form. The insoluble dye powders are then used to subsequent dyeing process.

2.3.

Dyeing

The effects of the main experimental conditions (dye concentrations, sodium hydrosulfite concentrations and dyeing duration on the quality of this dyeing process were studied. A plain woven fabric, two dye concentrations (18% and 36%), three sodium hydrosulfite concentrations (1.5, 3 and 4.5 times molecular weight than indigo powder) and three dyeing duration were used to assess the effect on dyeability. Then the important conditions obtained from the above-mentioned experiment were used to dye fabric for reproducibility evaluation. The 10% and 30% o.w.f dye concentrations and the other dye condition were selected for evaluating effects of dye concentration on dyeing reproducibility. Plain woven cotton fabrics were dyed at 10 and 30% o.w.f. (on the weight of fabric) indigo powder and Sodium hydrosulfite with 1.5 times molecular weight than indigo powder for 15 min at 25℃, in the Sodium hydroxide solution, using a 200:1 liquor ratio in PP box. The pH of dyeing solution was maintained at 13. The indigo dyeing solution was progressed reduction reaction for 1 hour. At the end of dyeing, the dyed fabrics were then exposed to air to progress oxidizing reaction. When the oxidizing reaction is completed, the dyed samples were scoured using 5 g/l C 17 H 35 COONa and 550ml water at 50 ℃ for 30 min. The scoured sample was rinsed thoroughly with tap water and allowed to dry in the open air. In order to understand the dyeing reproducibility of different fabric structure, three type twill fabrics are used. The 50% o.w.f. dye concentration was used for evaluating effect of fabric weave on dyeing

Page 1033 of 1108

reproducibility. Two cotton fabrics of each fabric structure were dyed in two different solution baths that prepared in same dyeing condition.

2.4.

Measurement of Color

The dyeing quality of dyed samples was evaluated by light reflectance technique using X-Rite SP-62 Spectrometer (D65 illuminant, specular included, 10° observer angle). The spectrometer was equipped with software, which was able to calculate color strength (K/S values) from the reflectance values at the appropriate λ max for each dyeing automatically. The color strength of fabrics was assessed using the Kubelka–Munk formula, which is shown below. K/S = (1-R)2/2R Where K is the scattering coefficient, S is the absorption coefficient, and R is the reflectance. Colour-difference formula ΔE CIE (L*, a*, b*): The total difference ΔE CIE (L*, a*, b*) was measured using the X-Rite SP-62 spectrometer. The total difference ΔE CIE (L*, a*, b*) between two colors each given in terms of L*, a*, b* is calculated from: ΔE*=[(ΔL*)2 + (Δa*)2+ (Δb*)2 ]1/2 Where: ΔE* value: is a measure of the perceived colour size of the colour difference between the standard and sample and cannot indicate the nature of that difference. ΔL*value: indicates any difference in lightness, (+) if the sample is lighter than standard, (-) if darker. Δa* and Δb* values: indicate the relative positions in CIELAB space of the sample and the standard, from which some indication of the nature of the difference can be seen.

3. Results and Discussion 3.1.

Effect of dye parameter on dyeability

The color strength of fabrics that dye in different conditions is shown in Table 1. The color strength increases with increasing dye concentration or Na 2 S 2 O 4 concentration or dyeing duration. In order to obtain high color strength and to reduce the technical problems of dithionite processes related to the difficulty of controlling processes and the non-reproducibility of the obtained shades[3], the dye concentration is used as the main parameter of the evaluation of reproducibility. Table 1: Effect of different dyeing condition on color strength Dye concentration Na 2 S 2 O 4 concentration Dyeing duration Color strength Fabric No. (o.w.f) (time than Dye) (min) (K/S value) A1B3C2 18% 4.5 10 1.08 A1B3C3 18% 4.5 15 1.89 A2B1C3 36% 1.5 15 1.99 A2B2C3 36% 3 15 5.69 A2B3C1 36% 4.5 1 2.15 A2B3C2 36% 4.5 10 7.3 A2B3C3 36% 4.5 15 9.4

3.2.

Effects of dye concentration on dyeing reproducibility

Two dye concentrations, 10% and 30% o.w.f., were used for evaluating effect of dye concentration on dyeing reproducibility. Two cotton fabrics were dyed in two different solution baths that prepared in same dyeing condition. The reflectivity of dyed fabrics is given in Figure 1 and Figure 2. Color strengths, K/S, of dyed fabrics are 0.79 and 2.90 for 10% and 30% dye concentrations respectively. The reflectivity of fabrics that dyed in the same dye concentrations and different solution baths is similar regardless of the dye concentration. This can show that the native indigo clay is purified effectively and the dyeing condition is suitable for dyeing reproducibility.

Page 1034 of 1108

Figure 2: The reflectivity of fabrics that dyed in the same Figure 1: The reflectivity of fabrics that dyed in the same dye concentrations (10% o.w.f.) and different solution baths dye concentrations (30% o.w.f.) and different solution baths

3.3.

Dyeing reproducibility of different fabric structure

The color strength and color difference of three dyed twill fabrics are given in Table 2. As similar as the effects of dye concentration on dyeing reproducibility, the color strength and color difference of fabrics that dyed in the same dye concentrations and different solution baths is similar and acceptable regardless of the fabric structure. Though theΔE is not small for the 325g/m2 fabric, it is acceptable for industrial application[4], particularly in natural dyeing. Table 2: Color strength and color difference of different fabric structure

Fabric 3/1 left hand twill (164 g/m2) 2/1 left hand twill (200 g/m2) 3/1 left hand twill (325 g/m2)

Sample 1-1 1-2 2-1 2-2 3-1 3-2

K/S 4.29 4.24 4.08 4.19 2.74 2.81

dL*

da*

db*

ΔE

0.05

-0.03

0.27

0.28

-0.62

0.14

0.10

0.64

-0.82

0.34

0.16

0.91

4. Conclusions The native indigo clay is purified effectively by the purify process that is designed in this research. The purified indigo powder and the dyeing condition are suitable for dyeing reproducibility regardless dye concentrations and fabric structures. The color difference of natural indigo dyed fabrics is acceptable. The dyeing reproducibility of modified natural indigo dyeing procedure designed by this research is suitable for industrial application.

5. Acknowledgement The authors of this article thank the Ministry of Science and Technology of the Republic of China, Taiwan, for financially supporting this research under Contract 103-2815-C-468-017-H.

6. References [1] Rungruangkitkrai, N. and R. Mongkholrattanasit. Eco-friendly of textiles dyeing and printing with natural dyes. in RMUTP International Conference: Textiles & Fashion. 2012. [2] Buscio, V., M. Crespi, and C. Gutiérrez-Bouzán, A critical comparison of methods for the analysis of indigo in dyeing liquors and effluents. Materials, 2014. 7(9): p. 6184-6193. [3] Etters, J. and M. Hou, Equilibrium sorption isotherms of indigo on cotton denim yarn: Effect of pH. Textile research journal, 1991. 61(12): p. 773-776. [4] Yang Xiaohong, computer color matching, in Color Matching Applications. 2010, China Textile Press.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Robust Superhydrophobic Surfaces by Modification of Chemically Roughened Fibers via Thiol-Ene Click Chemistry Chao-Hua Xue 1, 2, +, Xiao-Jing Guo 1, Mingming Zhang 1 and Shun-Tian Jia 1 1

College of Resource and Environment, Shaanxi University of Science and Technology, Xi’an 710021, China Shaanxi Research Institute of Agricultural Products Processing Technology, Shaanxi University of Science and Technology, Xi’ an 710021, China

Abstract. Superhydrophobic fabrics were fabricated by creation of roughening structures through alkali etching of fibers, modification with mercapto silanes and hydrophobization via thiol-ene click chemistry. Alkali etching resulted in nanoscale pits on the fiber surfaces roughening the fabrics with hierarchical structures, and improved the affinity of fibers for mercapto silanes. Click reaction between dodecafluoroheptyl methacrylate and sulfhydryl fibers lowered the surface energy, making the fabrics superhydrophobic with superoleophilicity. The as-obtained superhydrophobic fabrics maintained superhydrophobicity after 4500 abrasion cycles, 200 laundering cycles. The fabrics could be applied in oil/water separation due to the superhydrophobic and superoleophilic properties.

Keywords: superhydrophobic, fabrics, alkali treatment, click chemistry, oil/water separation

1. Introduction The fabrication of superhydrophobic surfaces is a fast growing area in both the scientific community as well as the industrial world due to their unique water-repellent and self-cleaning properties.1-3 Their emerging applications include oil-water separation,4 anti-icing,5 protection of electronic devices,6 and avoiding fluid drag in macrofluidic devices.7 It is well known that a superhydrophobic surface generally has a low surface energy material combined with a particular micro/nano structural roughness.8-10 Using this principle, numerous artificial superhydrophobic surfaces have been prepared on different substrates adopting various methods/techniques. Among these artificial superhydrophobic surfaces, water-repellent fabric is considered to be the most promising one. Despite the significant progress made in developing superhydrophobic fabrics, it is still a great challenge to sustain the superhydrophobicity through laundering and abrasion during applications. Strategies that have been developed to improve the mechanical stability of surface superhydrophobicity include cross-linking the coating layer,11 creating multiscaled roughness on the substrate,12, 13 introducing a bioinspired self-healing function,14, 15 endowing the coating with an elastomeric nanocomposite structure,16 or establishing chemical bonds between the coating and substrate.17, 18 Forming covalent bonds between fibers and low surface energy compounds is a critical point to enhance the stability of superhydrophobic fabrics. In this work, we report the superhydrophobic poly(ethylene terephthalate) (PET) fabrics fabricated by creation of roughening structures through alkali etching of fibers, modification with 3mercaptopropyltriethoxysilane (MPTES) and hydrophobization with dodecafluoroheptyl methacrylate (DFMA) via thiol-ene click chemistry, as shown in Fig. 1. The wettability tests showed that the superhydrophobic fabrics were robust to different chemicals and maintained superhydrophobicity after severe abrasion, laundering, as well as long time exposure to UV irradiation. And the superhydrophobic fabrics showed excellent oil/water separation property.

2. Experimental section +

Chao-Hua Xue. Tel.: ＋86-029-86132768 E-mail address: xuech@zju.edu.cn

Page 1036 of 1108

2.1. Chemical Etching of PET Fabrics Chemical etching of PET fabrics was conducted through a modified procedure reported by our previous work. The original fabrics were cleaned with deionized water at 80 ℃ for 30 min to remove the impurities and dried at 80 ℃ for 10 min. The cleaned fabrics were dipped into 380 g/L sodium hydroxide solution for 5 min. Then the soaked fabrics were doubled-side covered in a polyethylene film and heated at 110 ℃ for 3 min. Finally, the fabrics were rinsed with abundant water until the pH of the fabric surfaces reached 7 and dried at 80 ℃ in an oven. Thus, chemically etched PET fabrics were obtained and denoted as E-PET.

2.2. Mercapto Silane Modification of the Etched PET Fabrics Chemical vapor deposition was used to form mercapto silane monolayer on the E-PET fabrics. Firstly, the E-PET fabrics were placed into a container with 0.1 mL MPTES added. Then the container was sealed and mounted in an infrared-rays heating machine, followed by heating according to a heating program to 90 ℃ and held for 1.5 h. Finally, the samples were taken out, washed successively with anhydrous ethanol and deionized water, then dried at 80 ℃ to obtain mercapto silane modified fabrics, denoted as E-PET-SH.

2.3. Hydrophobization of Fabrics via Thiol-Ene Click Chemistry Fabrics were immersed in a conical flask added with DMF (150 mL), DFMA (12 g, 30 mmol), and DMPA (0.03 g, 0.12 mmol). Then the conical flask was sealed and irradiated with UV light with an intensity of 300 W/m2 at 370 nm from the top side for a given time. After the reaction, the samples were washed with anhydrous ethanol and deionized water. The resultant fabrics were dried at 80 ℃ and denoted as E-PET-S-F.

Fig. 1: Schematic illustration of the fabrication of superhydrophobic fabrics.

3. Results and discussion 3.1. Characterization of the Thiol-Ene Click Chemistry Modified Fabrics The surface morphology of the original and the modified fabric were characterized by a Hitachi S-4800 field emission scanning electron microscope (SEM). It was found that the fibers of the pristine PET fabrics were smooth with average diameter of about 11.5 μm reduced to about 8.5 μm and the fiber surface became extremely rough, as shown in Fig. 2(a) and (b). Fig. 2(c) shows that modification with mercapto silane did not cause obviously changes in the roughening morphology of the etched fibers. Also importantly, the surface morphology of E-PET-S-F fabrics was similar to that of E-PET and E-PET-SH, as shown in Fig. 2(d). Maintaining of the fiber morphology helps to complement the microscale roughness inherent in the textile weave, directing to proper roughness for superhydrophobic surfaces. The chemical composition of the fabric surfaces obtained by K-alpha thermo Fisher Scientific X-ray photoelectron spectra (XPS) was shown in Fig. 2(e). The surface of pristine PET fabric shows the C 1s and O 1s signals, while the surfaces of E-PET-SH and E-PET-S-F dominate new Si, S and F signals. This demonstrated that MPTES and DFMA were successfully incorporated onto the surface of the PET fibers. Meanwhile, surface wettability examination showed that the water maintained spherical on the E-PET-S-F fabric (Fig. 2f).

3.2. Stability of the Superhydrophobic Fabrics The influence of ambient force on the stability and robustness of the surfaces of superhydrophobicity is one of the most important factors that need to be considered for daily applications. Such resistance against mechanical damage was further evaluated by laundering samples of the E-PET-S-F in water with 0.37 wt% of detergent. It was found that the CAs measured at 25 ℃ with deionized water of 5 μL using a video optical

Page 1037 of 1108

contact angle system (OCA 20, Data physics, Germany) changed only slightly after laundering for 40 cycles, approximate to 200 cycles of commercial laundering. However, SA increased from 7°±2º to 45.2°±2º, as shown in Fig. 3(a). There are two reasons for this phenomenon. On the one hand, as laundering cycles increases, the roughness on the E-PET-S-F fiber surface decreased (Fig. 3c) due to mechanical action. On the other hand, with severe mechanically laundering, some protruding fuzzes appeared on the surface of the sample, causing some force or adhesion to the water on the fabric. Thus, the SA increased with increasing the laundering cycles.

Fig. 2: SEM images of (a) pristine PET, (b) E-PET, (c) E-PET-SH and (d) E-PET-S-F fabrics. (e) XPS spectra of the pristine PET, E-PET-SH and E-PET-S-F fabrics, (f) Digital images of dyed water droplets on E-PET-S-F fabrics.

Fig. 3: Changes of CA and SA of E-PET-S-F fabrics with (a) laundering cycles, (b) abrasion cycles, SEM image of EPET-S-F fabrics after (c) laundering test of 200 cycles (d) abrasion test of 4500 cycles.

In order to measure the durability against the mechanical stress, a standard procedure of the abrasion test was performed on the samples of E-PET-S-F according to a modified procedure based on the AATCCA Test Method 8-2001. The applied pressure was 45 kPa and the results were shown in Fig. 3(b). It was found that the CA of the E-PET-S-F fabrics decreased from 163.5°±2º to 157°±3º, indicating excellent durability of superhydrophobicity against abrasion. As for SA, it increased from 7°±2° to 60°±2°, which might be due to the formation of surface protrusions and lowering of fiber roughness (Fig. 3d).

Page 1038 of 1108

3.3. Oil/Water Separation Superhydrophobic fabrics are promising oil/water separation materials for practical applications. Based on the different behavior of the E-PET-S-F fabrics towards oil and water, a bench-scale oil/water separation apparatus was built up (Fig. 4). As shown in Fig. 4, E-PET-S-F fabrics were rolled as a part of the conduit. After turning on the self-priming pump, water can successfully pass through the rolled fabrics as a tube to the water collector and the n-hexane will leak at the part of E-PET-S-F fabrics to the oil collector due to the superhydrophobicity and superoleophilicity special wetting properties. Importantly, this process is repeatable.

Fig. 4: Photographs of the oil/water separation apparatus with n-hexane (dyed in red)

4. Conclusion In summary, we have demonstrated a simple and novel strategy to fabricate superhydrophobic surfaces, namely, combination of chemical etching of PET fibers with thiol-ene click chemistry hydrophobization of PET fabrics. It was shown that the superhydrophobicity of the modified fabrics is resistant mechanical laundering and abrasion. Importantly, the surface of the superhydrophobic fabrics showed potential application in water/oil separation. This method might be suitable for other hydrophobic monomers for fabrication of superhydrophobic fabrics, paving a way for generating durable and robust superhydrophobic surfaces through chemical bonding between the hydrophobic substances and the substrates. Importantly, the method is simple and suitable for large-scale production.

5. References [1] H. Bellanger, T. Darmanin, E. Taffin de Givenchy and F. Guittard, Chem. Rev., 2014, 114, 2694-2716. [2] C.-H. Xue and J.-Z. Ma, J. Mater. Chem. A, 2013, 1, 4146-4161. [3] B. Deng, R. Cai, Y. Yu, H. Jiang, C. Wang, J. Li, L. Li, M. Yu, J. Li, L. Xie, Q. Huang and C. Fan, Adv. Mater., 2010, 22, 5473-5477. [4] Y. Si, Q. Fu, X. Wang, J. Zhu, J. Yu, G. Sun and B. Ding, ACS Nano, 2015, 9, 3791-3799. [5] M. Ruan, W. Li, B. Wang, B. Deng, F. Ma and Z. Yu, Langmuir, 2013, 29, 8482-8491. [6] F. Su and K. Yao, ACS Appl. Mater. Interfaces, 2014, 6, 8762-8770. [7] J. Ou and J. P. Rothstein, Phys. Fluids, 2005, 17, 103606. [8] A. Cavalli, P. BĂ¸ggild and F. Okkels, Langmuir, 2012, 28, 17545-17551. [9] T. Liu, B. Yin, T. He, N. Guo, L. Dong and Y. Yin, ACS Appl. Mater. Interfaces, 2012, 4, 4683-4690. [10] S. G. Lee, D. S. Ham, D. Y. Lee, H. Bong and K. Cho, Langmuir, 2013, 29, 15051-15057. [11] Y. Zhao, Z. Xu, X. Wang and T. Lin, Langmuir, 2012, 28, 6328-6335. [12] C.-H. Xue, P. Zhang, J.-Z. Ma, P.-T. Ji, Y.-R. Li and S.-T. Jia, Chem. Commun., 2013, 49, 3588-3590. [13] C.-H. Xue, Y.-R. Li, P. Zhang, J.-Z. Ma and S.-T. Jia, ACS Appl. Mater. Interfaces, 2014, 6, 10153-10161. [14] H. Wang, Y. Xue, J. Ding, L. Feng, X. Wang and T. Lin, Angew. Chem., Int. Ed., 2011, 50, 11433-11436. [15] H. Wang, H. Zhou, A. Gestos, J. Fang and T. Lin, ACS Appl. Mater. Interfaces, 2013, 5, 10221-10226. [16] C.-H. Xue, Y.-R. Li, J.-L. Hou, L. Zhang, J.-Z. Ma and S.-T. Jia, J. Mater. Chem. A, 2015, 3, 10248-10253. [17] C.-H. Xue, X.-J. Guo, J.-Z. Ma and S.-T. Jia, ACS Appl. Mater. Interfaces, 2015, 7, 8251-8259. [18] H. Zou, S. Lin, Y. Tu, G. Liu, J. Hu, F. Li, L. Miao, G. Zhang, H. Luo, F. Liu, C. Hou and M. Hu, J. Mater. Chem. A, 2013, 1, 11246-11260.

Page 1039 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Glycerol 1,3-diglycerolate diacrylate â&#x20AC;&#x201C; A unique surface modifier for keratin fibres Jackie Y. Cai1*, Dan Yu2, Jeffrey S. Church1, Lijing Wang3 1

CSIRO Manufacturing, PO Box 21, Belmont, Victoria, 3216, Australia College of Chemistry, Chemical Engineering & Biotechnology, Donghua University, Shanghai 201620, China 3 School of Fashion and Textiles, RMIT University, 25 Dawson Street, Brunswick, Victoria 3056, Australia

Abstract. This paper reports on a unique surface modifier, glycerol 1,3-diglycerolate diacrylate (GDA), identified for keratin fibres, and its facile application method based on thiol-ene click chemistry. The modified fabric substrates were characterized and evaluated for their changes in fibre properties. The results demonstrate that the GDA modified keratin fabrics exhibit significantly altered surface properties and functionalities including improved liquid moisture management and antistatic properties as well as a remarkably improved shrink-resistance coupled with good fibre strength retention.

Keywords: keratin fibre, thiol-ene, diacrylate, click chemistry, surface modification

1. Introduction Keratin fibre is an important group of fibrous materials for both textile and medical applications. There has been considerable interest in surface modification and functionalization of keratin fibres for added value and enhanced end-use performance. The presence in the fibre of free thiol groups and cystine disulfide bonds which readily turn into cysteine thiols by reductive cleavage [1-3], have offered great opportunities for keratin fibres to be modified and functionalised through facile thiol-ene reactions. Recently, we have reported on the controlled tris(2-carboxyethyl)phosphine hydrochloride (TCEP) reduction of keratin fibres, followed by grafting of surface modifiers, such as acrylate sulfonate, acrylamide sulfonate or quaternary ammonium compounds onto the keratin cuticle structure through thiol-ene click chemistry [4, 5]. This has shown to be an effective and powerful method for improving keratin fibreâ&#x20AC;&#x2122;s characteristics and performances. In this paper, we report a new and unique surface modifier identified for keratin fibres, namely, glycerol 1,3-diglycerolate diacrylate (GDA), and its resultant impact on fibre properties. GDA is a water soluble diacrylate which is capable of reacting with the cysteine thiol residues in keratin fibres at room temperature. The previously established TCEP reductive pre-treatment [4] was applied to generate more of these reactive residues for enhanced grafting density and treatment effect. Wool, as one of the most widely used keratin fibres, was used as a representative keratin substrate in this study. The modified substrates were characterized and the treatment effects were evaluated.

2. Results and discussion 2.1.

Grafting of GDA onto the keratin structure GDA is a highly reactive diacrylate monomer with multiple hydroxyl and ether groups. Grafting this hydrophilic monomer onto the cuticle structure of keratins would be expected to significantly alter the surface properties. The two diacrylate groups in GDA also have potential to form crosslinks within the keratin fibre. The possible chemical reactions involved are shown in Scheme 1, where the cysteine residues in keratin fibres generated through TCEP reduction react with the acrylate groups in GDA through the thiol-ene click reaction, resulting in the grafting of GDA onto the keratin structure. Crosslinks can be formed when both acrylate groups of the GDA react with keratin cysteine residues.

S S

TCEP

GDA

CH2

Keratin peptide chain

Page 1040 of 1108

O O

CH2

S O

Scheme 1. The grafting of GDA onto keratin through TCEP reduction and thiol-ene reactions.

-1717

- 2567

B A

- 508

-3037

D -3105

Relative Counts

To investigate the reaction details on the fibre surfaces, in particular, the extent of thiol reaction (grafting) and the reformation of disulfide bonds, the TCEP-GDA treated wool samples were analysed by Raman spectroscopy (Fig 1). Compared to the TCEP treated fabric (Fig. 1, Trace B), the S-H stretching mode (2657 cm-1) reduces by 86% and 91% in the fabric treated with 1% and 10% GDA (Traces C and D), respectively. These losses are accompanied by increases in intensity of the S-S stretching vibration (508 cm-1). In the case of the 1% GDA treated fabric (Trace C), 51% of the S-S bonds are being reformed while only 5% are being reformed after the 10% GDA treatment (Trace D).

A 3050

2850

2650

Raman Shift (cm-1)

2450

1800

1600

1400

1200

1000

800

600

400

Raman Shift (cm-1)

Fig. 1. Raman spectra obtained from wool fabrics: A) untreated, B) TCEP reduced, C) TCEP-1%GDA treated and D) TCEP-10%GDA treated.

Further analysis of the Raman spectra of both the treated fabrics show that the acrylate carbonyl stretching vibration can be observed at 1717 cm-1 (Traces C and D). The relative intensity increase in this feature is more evident in the 10% GDA treated, which is consistent with the higher level of treatment. H 2 C=CH- group bands are observed in the Raman spectrum obtained from the parent compounds at 3105 (CH 2 symmetric stretch) and 3037 (C-H stretch) cm-1 [6]. The Raman spectra in Fig. 1 show that when treated with 1% GDA, there is little vinyl (C=C) detected on the treated substrate, indicating that both acrylate groups in GDA have reacted with wool, and thus crosslinking might have occurred, as illustrated in Scheme 1. In the treatment with 10% GDA however, residual vinyl groups are still present on the treated sample. It is likely that this is due to excess amount of the acrylate groups relative to the avalible â&#x20AC;&#x201C;SH sites, resulting in some GDA molecules having only one of the acrylate groups react with â&#x20AC;&#x201C;SH in the fabric.

2.2.

Liquid moisture management and surface resistivity of TCEP-GDA treated fabrics Liquid moisture transport behaviours of the fabrics in multi-directions were evaluated by using a moisture management tester according to AATCC test method 195-2009. The surface resistivities of the fabrics were assessed using a surface resistivity tester developed by CSIRO in accordance with European Standard EN 1149-1. The results in Table 1 show a significantly improved liquid moisture transfer capability for the TCEPGDA treated fabric compared to the control. This is evidenced by a shorter wetting time, higher water spreading speed, and 5 mm wetted radius on the bottom surface of the treated fabric, indicating a good water transfer capability in the vertical direction, while no wetted radius appeared on the bottom surface of the untreated fabric. It is also noted that although TCEP treatment alone (for 4h) provided a certain degree of

Page 1041 of 1108

improvement due to the cystine disulfide cleavage in the cuticle region, further improvement was achieved by the introduction of the hydrophilic groups of GDA onto the fibre surface. The TCEP-GDA treatment also resulted in a reduced surface resistivity of the fabric, i.e. improved antistatic property. Table 1: Liquid moisture management and surface resistivity of treated and untreated fabrics Surface Resistivity (Ω/sq)

Sample

Wetting Time (sec)

Wetted Radius (mm)

Water Spreading Speed (mm/sec)

Top

Bottom

Top Max

Bottom Max

Top

Bottom

Untreated

1.5×1012

15.6

120.0

0.62

0.00

TCEP only

‒

7.8

120.0

0.60

0.00

7.7

70.4

0.60

0.20

TCEP-GDA

6.7×10

2.3.

Shrink-resist performance of TCEP-GDA treated fabrics It is known that cystine is mainly located in the cuticle of keratin fibres [1]. The TCEP induced cystine reduction and the subsequent GDA grafting are therefore expected to occur mainly in the cuticle region of the fibre. This surface modification has changed the keratin fibre surface from hydrophobic to hydrophilic (Table 1) and increased the aqueous swelling potential of the surface proteins. In addition, GDA, with two acrylate groups and multiple polar functional groups, has been shown to form crosslinks (Raman analysis in Fig. 1) and maybe also extensive hydrogen bonding networks in the keratin fibres, which would likely reduce fibre movement and friction. All of these changes would be expected to have a direct impact on the shrinkage behaviour of keratin fabrics during wet processing and domestic laundering. The shrink-resist effect of the treatment was therefore assessed according to the IWTO TM 31 standard in a Wascator, where fabric samples were subjected to a program 7A (relaxation cycle) and five consecutive program 5A wash cycles, each followed by tumble drying. The percent felting shrinkage after each 5A wash and tumble-dry cycle was recorded. The results in Fig. 2 (a) demonstrate that a TCEP-GDA (10% GDA) treated 100% wool fabric (plain weave, 190g/m2) exhibited excellent shrink-resist performance. The total felting shrinkage after 5 consecutive cycles of 5A washing and tumble drying was only about 3% for the treated fabric, compared to about 24% for the untreated control. For comparison purposes, 1,4-butyl diacrylate (BDA), a hydrophobic analogue of GDA, was applied in an identical manner as GDA, and the shrink-resist effects of the treated fabrics were evaluated. In this comparative experiment, a wool fabric of an extremely low density (1/2 of the previous fabric) with a much greater shrinkage tendency was used. It can be seen from Fig. 2 (b) that the shrink-resist effect obtained with this hydrophobic diacrylate is far inferior to that obtained with GDA.

Fig. 2. Felting shrinkage of treated and untreated fabrics as a function of wash cycle.

2.4.

Wet burst strength of TCEP-GDA treated fabrics Wet burst strength was used to assess the effect of the chemical treatments on the fabric mechanical properties. The results in Fig. 3 show that the wet burst strength of the TCEP pre-treated fabric is about

Page 1042 of 1108

39% lower than that of the untreated fabric. The strength loss is likely caused mainly by cystine disulfide bond cleavage. However, after subsequent treatment with 10% GDA, the ultimate strength loss was reduced to 11%. This can possibly be attributed to covalent GDA crosslinks formed between peptide chains of the TCEP reduced wool. These results have indicated that the GDA treatment is able to compensate for some of the strength loss caused by the TCEP pre-treatment, resulting in overall higher fibre strength retention. This will maximize the anti-felting effect attainable while minimizing the fibre strength loss.

Wet Burst Strength (kPa)

350

300

250

200

150

100

Untreated

TCEP

TCEP-GDA

Fig. 3. The effect of chemical treatment (10% GDA solution applied) on fabric wet burst strength.

3. Conclusions GDA is a highly reactive, water soluble diacrylate monomer with multiple hydroxyl and ether groups. This study has demonstrated that grafting of GDA into the cuticle structure of a keratin fibre can be readily achieved by thiol-ene click reactions at room temperature. The acrylate groups of GDA are coupled with the cysteine thiols of TCEP reduced keratins, resulting in the formation of GDA crosslinks. The modified keratin substrate exhibits significantly altered fibre surface properties and functionalities including improved liquid moisture management, improved antistatic property, and remarkably improved shrink-resistance to washing. The ability to offer higher strength retention as a result of crosslink formation is another significant benefit of the GDA modification. In addition, the shrink-resist performance of the GDA modified keratin substrate is significantly superior over that treated with a hydrophobic diacrylate, 1,4-butyl diacrylate, under the identical conditions.

4. References [1] A.N. Parbhu, W.G. Bryson, R. Lal, Disulfide Bonds in the Outer Layer of Keratin Fibers Confer Higher Mechanical Rigidity:â&#x20AC;&#x2030; Correlative Nano-Indentation and Elasticity Measurement with an AFM, Biochemistry, 38 (1999) 11755-11761. [2] P. Liu, B.W. O'Mara, B.M. Warrack, W. Wu, Y. Huang, Y. Zhang, R. Zhao, M. Lin, M.S. Ackerman, P.K. Hocknell, G. Chen, L. Tao, S. Rieble, J. Wang, D.B. Wang-Iverson, A.A. Tymiak, M.J. Grace, R.J. Russell, A Tris (2-Carboxyethyl) Phosphine (TCEP) Related Cleavage on Cysteine-Containing Proteins, Journal of the American Society for Mass Spectrometry, 21 (2010) 837-844. [3] J.A. Burns, J.C. Butler, J. Moran, G.M. Whitesides, Selective reduction of disulfides by tris(2carboxyethyl)phosphine, The Journal of Organic Chemistry, 56 (1991) 2648-2650. [4] D. Yu, J.Y. Cai, J.S. Church, L. Wang, Modifying Surface Resistivity and Liquid Moisture Management Property of Keratin Fibers through Thiolâ&#x20AC;&#x201C;Ene Click Reactions, ACS Applied Materials & Interfaces, 6 (2014) 1236-1242. [5] D. Yu, J.Y. Cai, X. Liu, J.S. Church, L. Wang, Novel immobilization of a quaternary ammonium moiety on keratin fibers for medical applications, International Journal of Biological Macromolecules, 70 (2014) 236-240. [6] N.B. Colthrup, L.H. Daly, S.E. Wiberley, Olefin Groups, Introduction to Infrared and Raman Spectroscopy, Academic Press, San Diego, 1990, pp. 247-260.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Hemin-fixed non-woven fabrics for removing a trace of CO gas contained in H 2 gas Teruo Hori 1+ and Koji Miyazaki 2 1

Headquarters for Innovative Society- Academic Cooperation, University of Fukui Frontier Fiber Technology and Science, Graduate School of Engineering, University of Fukui

Abstract. As a driving force of next-generation's cars, fuel cell is expected because the cell produces no CO 2 and other toxic gases by combustion. H 2 gas uses for driving the cell, but H 2 gas produced by most of industrial methods contains at least 10 ppm of CO gas. To drive fuel cell efficiently, the removal of such small amount of CO is important in the view point of keeping the long life of fuel cell catalyst. In this paper, an attempt has been done to prepare a unique non-woven fabric filter for removal of CO contained H 2 gas. Mainly, polypropylene (PP) non-woven fabrics were used as base material fiber. Various kinds of Feporphyrin derivatives, which is well known as a useful CO catcher, were grafted on non-woven PP fabrics by electron beam grafting method. First, it was confirmed that the aqueous solution of Fe-porphyrin derivatives act as good CO catcher after reduction treatment. The Fe-porphyrin grafted non-woven PP fabrics were activated by treating with an appropriate reducing agent before CO absorption. Hemin-grafted polypropylene non-woven fabric shows sufficient CO catching effect. Keywords: fuel cell, contaminant in H 2 gas, electron beam grafting, porphyrin, polypropylene

1. Introduction It is well known that haemoglobin can catches not only the oxygen gas, but also carbon dioxides (CO). Using the characteristic an attempt has been done to prepare a useful filter to remove CO gas containing hydrogen gas produced in industrial scale. Such kinds of filters are expected to drive fuel cell motors as next generationâ&#x20AC;&#x2122;s cars, efficiently and with keeping the long life time of the catalysis. To give CO-adsorption property, some kinds of Fe-porphyrin derivatives are grafted on polypropylene non-woven fabric by using electron beam grafting method.

2. Experimental 2.1 Materials As base fabrics, polypropylene, PP and poly(ethylene terephthalate), PET nonwoven fabrics were selected. They were used after normal scouring. They are normally inactive against chemicals. However, the PP fabric is better than PET fabric for electron beam grafting, because radicals are formed much easier on PP materials. As Fe-porphyrin derivatives, Fe-porphyrins having carboxyl, amino or hydroxyl groups were first tried to graft on nonwoven fabrics with or without crosslinking compounds. Secondly, hemin having two reactive vinyl groups was used (Fig.1). To reduce the Fe-porphyrin derivatives, different kinds of reducing compounds such as ascorbic acid, hydrazine were used without further purification.

Corresponding author. Tel.: + 81-776-27-8641.

E-mail address: hori@u-fukui.ac.jp.

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Fig.1: Structure of Hemin

2.2 Electron beam graft polymerization of porphyrin-derivatives Electron beam grafting of porphyrin derivatives were carried out using a laboratory machine, CURETRON, NHV Corporation. Accelerating voltage of the machine was 250keV. Electron dose was varied from 20kGy to 100kGy. Mainly two methods were examined; one of them is pre-irradiation method and the other one is mutual (direct) method shown in Fig.2 (a) and (b), respectively. In the pre-irradiation method, first, the nonwoven fabric was irradiated by EB to produce radicals in/on fabric. After then the fabric was immersed in a solution of Fe-porphyrin derivatives and heated up to the appropriate temperature to proceed the graft polymerization. In the mutual method, the nonwoven fabric was immersed in a solution of Fe-porphyrin derivatives and then the fabric was irradiated by EB to proceed the graft polymerization. In both cases, the fabric was kept in a PET bag to avoid exposure by air. (a)

(b)

Fig.2: Two different methods for EB-grafting of nonwoven fabrics (a) Pre-irradiation method, (b) Mutual(direct) method

2.3 Estimation of CO absorption CO gas absorption by the prepared nonwoven fabric was carried out using a simple apparatus prepared by our self (Fig.3). Sample was put in a tetra bag and a certain amounts of CO gas was introduce to the bag. After a certain time the concentration of the bag was determined using CO gas detector tube.

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Fig.3: Schematic illustration for following CO absorption by the nonwoven

3. Results and discussion 3.1 The effect of solvent on graft polymerization Fig.4 shows the effect of the solvent to prepare Hemin solution is shown. Relatively high grafting was obtained in the cases of DMSO and DMSO/H 2 O(50/50) by pre-irradiation method. In the case of direct method, it ws recognized that DMSO/H 2 O(50/50) was best.

Fig.4: Effect of solvent on grafting

3.2 The effect of solvent on graft polymerization First, CO absorption experiments were carried out in an aqueous solution of hemin after reduction by ascorbic acid. From Fig.5 it is clear that a pure solution of hemin acts quite good CO absorber, while pure water cannot absorb CO. On the other hand, reduction of porphyrin derivatives on/in fabric by ascorbic acid did not succeed. Only using hydrazine the hemin on/in fabrics could be reduced. However a certain amounts of hemin was eliminated from the fabric and decomposed. Therefore, the effect of reduced hemin on/in fabric on CO absorption was not very high (Fig.6).

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Fig.5 CO gas absorption by hemin

Fig.6: CO gas absorption by hemin-fixed fabrics

4. Conclusion It was shown that hemin-fixed nonwoven fabric by EB grafting was absorb CO gas. To prepare more effective fabrics we are continuing grafting hemin together with 1-allylimidazole and ethyl 2-(hydroxymethyl)acrylate.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Investigation on Structural and Physical Properties of N/CoPET and PET Nonwovens by Processing Steps Jung Soon Jang and Chang Whan Joo + Dept. of Advanced Oraganic Materials and Textile System Engineering, Chungnam National University, Daejeon, 305-764, Korea

Abstract. Composite nonwovens can be designed the various structure by combination of different materials, manufacturing methods and processing conditions to meet the properties required for the special end-uses such as filter media, clean wiper, artificial leather substrate and so on. In this study, the composite nonwovens composed of nylon/copolyethylene terephthalate (N/CoPET) sea-island fibers and high shrinkage polyethylene terephthalate(PET) fibers have been fabricated by a needle-punched technique, and carried out at two steps as alkali treatment and calender process to control the thickness, porous size and density of nonwovens. And the structures and physical properties of the composite nonwovens were evaluated to obtain the information of the influence of the processing steps with theoretical calculation and experiments. For the structural analysis of nonwovens, the packing density, porosity and pore characteristics were calculated in terms of fiber fineness, fiber length and fiber orientation distribution under the basic assumptions. The composite nonwovens were characterized using morphological analysis (SEM), tensile (Instron速), pore (capillary flow porosimeter) and air permeability (Frazier) test. From the calculated and experimental results, the structural characteristics of composite nonwovens can be controlled by processing steps and applied to performance design for expanding end-uses and adding high-values of nonwovens.

Keywords: sea-island fiber, composite nonwoven, needle-punch, NaOH treatment.

1. Introduction In the nonwoven manufacturing, the use of bicomponent fiber has been increased continuously, which expand the applications of nonwoven products ranging from cheap disposable products to high performance products. Micro-denier nonwovens using bicomponent fibers provide specific properties such as soft feel and high absorption by the large specific surface area and high filtration efficiency. Bicomponent fibers has been used for nonwovens manufacturing to enhance the properties that are not expressed by limits of singlecomponent fibers [1,2]. Especially, sea-island type microfibers have a number of advantages including large specific surface area, softness and drapability. In alkali treatment, CoPET component of bicomponent fiber is removed through hydrolysis, which leads the reduction of fiber diameter, and the decrease of nonwoven thickness, weight and density [3]. Among a variety types of nonwovens, needle-punched nonwoven is a popular technique and is used in a variety of engineering applications, including geotextiles, agriculture textiles, sports, automotive, filtration, clothing, medical, thermal and sound insulation [4]. Vertical punching motion creates rearrangement of fiber bundles in the thickness direction by barb and fiber to fiber interlocking, which influences to the structure and mechanical properties. In addition, numerous studies have been attempted to optimize the manufacturing process and meet the requirements of end-use while reducing the manufacturing cost. Thermal bonding is one of the widely used bonding techniques, one of them, calendaring method is that nonwovens is passed through the nip of heated rollers. Main parameters of calendaring process are roller temperature, speed and pressure [5]. Structure and physical properties of final product depend significantly on the selecting material and manufacturing process, and in order to predict the performance of the product, it is important to analysis the structure of materials according to each process [6]. Whereas, the study for needle-punched nonwovens

Corresponding author. Tel.: + 82-42-821-7696. E-mail address: changjoo@cnu.ac.kr.

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composed of sea-island and shrinkage fibers is insufficient state in literatures, and the relations among the process parameters, structural and physical properties are not clear. Thus, the purpose of this study was to analysis the structure and physical properties of composite nonwovens consisted of Nylon/CoPET sea-island fibers and PET shrinkage fibers with different process steps. This paper deals with the needle-punched composite nonwovens consisted of N/P sea-island fibers and PET shrinkage fibers, and the structural and physical properties along with different process steps are discussed.

2. Experimental 2.1 Materials The materials used in this study was needle-punched nonwovens manufactured by PET shrinkage fibers and Nylon/CoPET (N/P) sea-islands fibers were supplied from each ‘S’ and ‘K’ company. The web was prepared with fiber mixtures composed of weight ratio 8:2 (N/P and PET). Nonwoven sample (N) was punched 5 times, because the punching density increased and contraction of shrinkage fiber was reduced. Based on our previous study, the samples were alkali treated with 1wt% NaOH at 95℃ for 30min. After treatment, they were washed with water to remove NaOH and were dried for 48h at room temperature. Calendering temperature was set to between the glass transition temperature and below the melting point of both fibers. 125℃ top roll and 145℃ bottom roll were used, and the calender speed and pressure were 3m/min and 15kgf/ ㎠, respectively. (Table 1) Sample ID N NA NAC NC NCA

Table 1: Basic characteristics of nonwoven samples Basic Weight Thickness Density Process (g/㎡) (㎜) (g/㎤) None 382.2 2.61 0.15 Alkali treatment 349.5 2.13 0.16 Alkali treatment → Calendering 326.3 0.76 0.43 Calendering 415.6 1.41 0.30 Calendering → Alkali treatment 317.1 1.30 0.24

Shrinkage (%) 0 7.7 6.6 3.0 6.7

2.2 Measurements The samples were cut into square pieces (200×200 ㎟) and measured length, thickness and weight, then the percent of shrinkage was calculated. The thickness of sample was measured using a thickness gauge (CS55, USA), and the density was calculated .The samples were weighted before and after alkali treatment, then the weight loss (%) was calculated. Electron scanning microscope(S-4800, Hitachi, Japan) was used to observe the morphological structure of nonwoven samples with different process steps. Pore size and distribution of nonwovens were analyzed with a capillary flow porosimeter (CFP1200-AEL, PMI, USA) according to ASTM F316. The air permeability was measured using a Frazier type air permeability tester (No. 415, YASUDA, Japan). The sample were cut with 200 ㎠ and tested three times at different locations. Tensile test was performed on a tensile tester (Instron 4467, Instron, USA), according to ASTM standard (ASTM D 5035). The specimen size were cut with 125×15 ㎟, and 5 pieces of specimen were tested in both machine and cross direction. Tensile tests were carried out using 500N load cell and 75 ㎜ gauge length at extension rate of 300 ㎜/min. Tearing test was performed three times for each sample following ASTM D 5735. The specimen was cut from the nonwovens (200×75 ㎟) in MD and CD. The gauge length was 100 ㎜ and extension rate was 50 ㎜/min.

3. Results and discussion 3.1 Structural properties Fig. 1 shows the basic weight and density of samples (N) with different process steps. The basic weight of alkali treated sample (NA) was reduced about 15% and shrinkage was 7.7%, while the calendering sample

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(NC) had a basic weight increase of about 6% and shrinkage of 3.0%. The results indicate that the alkali treated sampled (NS) had a greater shrinkage and weight loss than sample (NC). In the case of calendering process, the density of nonwovens was increased with reducing the thickness by thermal pressing. Also, alkali treatment made a decrease of density with weight reduction by dissolving of sea components. Air permeability of nonwovens decreased with the progress of two process steps. The results showed that the treated samples exhibited lower air permeability than a non-treated sample due to the small fiber diameter and low porosity. As shown in Fig. 1, air permeability of untreated sample (N) had the highest value. The results indicated that sample (NAC) applied with calendaring after alkali treatment had high value of basic weight and density than that of sample (NCA). 0.35

0.30 400 0.25 350 0.20

Density(g/cm3)

Basic weight(g/m2)

Basic weight Density

300 0.15

250

NAC

NCA

Air permeability(cc/cm2·sec)

450

0.10

Sample ID

NAC

NCA

Sample ID

Fig. 1: Basic weight, density and air permeability of samples with process steps

3.2. Pore diameter and distribution The pore diameter and distribution of samples with process steps were measured by using a capillary flow porosimeter. Based on the measured values, the maximum, minimum, mean and most probable pore diameter were calculated and shown in Table. 2. After the alkali and calendaring process, pore diameter was significantly decreased, and the diameter distribution showed a tendency to narrow. The mean pore diameter of the samples (NAC and NCA) is reduced 73.4% and 57.6%, respectively. It is that the fiber diameter decreased by separating of sea-island fibers and the reduced distance between the fibers due to the shrinkage and thermal compression. Sample ID N NA NAC NC NCA

Table 2: Pore diameter of samples Most probable Maximum Minimum Mean distribution (㎛) (㎛) (㎛) (㎛) 88.53 75.89 31.25 56.51 39.64

10.94 11.93 2.27 9.29 10.62

36.33 28.84 9.67 24.44 15.41

21.00 20.08 6.72 19.24 11.88

3.3. Tensile properties Fig. 2 shows tensile properties of samples. For comparison, tensile strength was normalized with nonwoven density. When the samples were treated with alkali solution, tensile strength and modulus increased with dissolving of sea components in both machine and cross directions. These results indicate that alkali treatment has a large effect on tensile properties of samples (NA and NCA). Furthermore, the process sequence was little effect on the tensile strength of sample (N). Breaking elongation was found to be higher in the cross direction than in the machine direction, since the fibers were more oriented in MD.

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25 MD CD

NAC

Tensile modulus(MPa)

Tensile strength(MPa/ρ)

MD CD 20

NCA

NAC

NCA

Sample ID

Fig. 2: Tensile properties of samples with process steps

Whereas, the tear strength of samples showed a rapid decrease with the dissolving of the sea component by alkali treatment, the influence of the calender was insufficient. In case of alkali treatment after calendering, the tear strength in the MD and CD was reduced by 31.6% and 33%, respectively. Further, the tear strength and work of rupture in the MD showed relatively high values compared to CD. Therefore, it was confirmed that the process sequence of alkali treatment after calendering is to prevent a reduction in strength. 20

Tearing strength(kgf)

NAC

Sample ID

NCA

Work of rupture(kgf·mm)

5000 MD CD

MD CD 4000

3000

2000

1000

NAC

NCA

Sample ID

Fig. 3: Effects of process steps on tearing strength and work of rupture

4. Conclusion The structure and physical properties of composite nonwovens consisted of Nylon/CoPET sea-island fibers and PET shrinkage fibers with alkali treatment and calendering process were conducted to control the thickness and density of nonwoven, and obtain the following conclusion. (1) Effects of alkali treatment: Sea-island fiber with about 20 ㎛ diameter was changed to approximately 3 ㎛ after alkali treatment since the sea-component was dissolved. Besides, the basic weight was reduced by about 15% and showed a 7.7% shrinkage ratio. It led to the decrease in air permeability. After the alkali process, pore diameter was significantly decreased, and a wide diameter distribution narrowed. Air permeability of samples(NA) decreased from 64.7 to 28.0 ㎠/cc/sec due to the dense structure by the separated fibers. Whereas, since the weight reduction and shrinkage occurred at the same time, the density was not significantly increased from 0.15 to 0.16g/㎤. Tensile strength and modulus of samples showed a tendency to increase in both MD and CD after alkali treatment. However, tearing strength and work of rupture were significantly decreased due to the dissolved sea-components. (2) Effects of calendaring: Calendering samples showed a 46.2% reduction in thickness, and the density was improved about 100%. The surface of samples was changed to a relatively uniform structure. Calendering also led to decrease of air permeability. The value of air permeability was reduced from 64.7 to 24.0 ㎠/cc/sec with decrease of distance between the fibers. Tearing strength and work of rupture did not show a notable change.

5. References

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[1]

E. Shim, B. Pourdeyhimi, and M. Latifi, “Three-Dimensional Analysis of Segmented Pie Bicomponent Nonwovens”, JTI, 2010, 101(9), 773-787

[2]

Baker, B. “Bicomponent fibers: A personal perspective”, International Fiber Journal, 1998, 13(3), 26–35.

[3] V.K. Midha and A Mukhopadyay, “Bulk and Physical Properties of Needle-punched Nonwoven Fabrics”, Indian J of Fibre & Textile Research, 2005, 30, 218-229

[4] S. Michielsen, B. Pourdeyhimi and P. Desai, “Review of Thermally Point-Bonded Nonwovens: Materials, Processes, and Properties”, J of Applied Polymer Science, 2006, 99, 2489-2496

[5] A.V. Dedov, “Air Permeability of Calendered Needle-Punched Materials”, Fibre Chemistry, 2009, 41, 43-45 [6] D. Kopitar, Z. Skenderi and B. Mijovic, “Study on the Influence of Calendaring Process on Thermal Resistance of Polypropylene Nonwoven Fabric Structure", Journal of Fiber Bioengineering and Informatics, 2014, 7(1), 1-11

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Manufacturing the Continuous Electro-spun Bundle and its Battery Application Jung H. Lim1, Ganbat T.U. 2 and You Huh3 1

Department of Textile Engineering, Graduate School, Kyung Hee University, Yongin, Korea Department of Mechanical Engineering, Graduate School, Kyung Hee University, Yongin, Korea 3 Department of Mechanical Engineering, College of Engineering, Kyung Hee University, Yongin, Korea 2

Abstract. Electro-spun nano-fibers have remarkably high volume to mass ratio, and the web form products have a great potential in various industrial fields. But due to the extremely low mechanical strength of the web and difficulties in handling, the usage of the electro-spun nano-fibers is restricted. Therefore it is urgent and important to develop the technologies that can make post-processes of the electro-spun web possible. In this research, we suggest a novel mechanism for manufacturing round-shaped continuous composite bundle using the nano-fibrous web by combining the electro-spinning and friction bundling technologies, and based on the experimental trials, we prepared the round shaped Zinc-Carbon primary battery with electrospun nano-fibers in order to investigate its feasibility as an energy storage device. According to the results the method that we suggested could be well applied to produce the bundle which is characterized multi-layered structure and also could be applied to produce the batteries. The discharging test results show that bundle type battery which was produced in this research has a good flexibility and can generate a voltage, but the voltage level is relatively lower than commercial batteries. Keywords: electro-spun bundle, composite bundle, bundle battery, flexible battery

1. Introduction In textile industries, nanotechnology has been one of the main topics in R&D stream. Especially, spinning the ultra-thin fibers even having a nano-metric scale size is a great concern to many engineers. In the last a few decades, many researches have been conducted for manufacturing the nanometer scaled fibres in various ways. Among them to produce ultra-thin fibers, electro-spinning which was using the electrostatic force is considered as the most effective way to produce nano-scaled fibres. The advantages of electrospinning method are 1) easy to build up the manufacturing apparatus, and 2) easy to obtain the nano-fibers from the organic polymer or inorganic metal oxide material, finally, 3) relatively inexpensive than other processes. The electro-spun fibers have a great potential in high performance industries, for instance, filtration, optoelectric industries or in energy storage such as batteries. But in many cases, electro-spun fibers were produced in a non-woven web which is difficult to handle. In spite of many application possibilities, usage of this fiber is strongly limited. To overcome this disadvantage, several researchers have developed methods to obtain continuous single nanofibers or to manufacture the uniaxial nano-fibrous bundle by using the liquid bath or funnel shape collector recently [1,2]. Lim et al [3] suggested a process to transform the electro-spun web into a uniaxial bundle using the friction spinning method. In this research we report experimental results from a feasible process, where the electro-spun web is transformed to a uniaxial bundle, to find the possibility to use the nano-fibrous bundle as battery.

2. Experiments 2.1 Experimental rig. A structured yarn can be defined as a composite bundle consisting of various kinds of material. In generally, constitutive material of this type of product is constrained according to the function required and must have specific properties. This type of bundle appears in various forms according to the manufacturing methods and application purposes. In this research we adopted the friction method to transform the electro-spun web into a

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composite bundle, while several kinds of material are used. Figure 1 shows a schematic representation of the experimental rig and the mechanism for generating a bundle in our experimental system. a)

Fig. 1: Schematic representation of a) experimental rig and b) mechanism for producing composite bundle using by friction method.

When different materials are parallel-aligned and transported by an endless belt to an operation zone, i.e., friction bundling zone in our research, consisting of two friction drums, the material located at the far end from the drum exit (material 1 in Fig. 1a) will be positioned inside (central) and the material near the drum exit (material 3 in Fig. 1a) will wrap the bundle, so that the output bundle can have a multi-layered structure consisting of different materials (Fig. 1b). In this research, purposing to produce 3 types of nano-fibrous web with a proper thickness simultaneously, we engaged a parallel-aligned multi-nozzle system to electro-spin nano-fibers. The nozzles for electrospinning were arrayed in a linear form in the direction of the collector movement. As the process advanced, the ejected fibers from the nozzles were stacked on the web that had already been formed prior to the nozzle on the moving belt. Then, the nano-fibrous web on the moving collector was delivered to the friction zone. The bundle produced by the friction drums in the bundling zone was took-up by a winding unit. All the experimental parts were driven individually by servo-motors and controlled by a computer. If we choose the materials 1, 2 and 3 in Fig. 1a for the anode, separator and the cathode, the resulting bundle has the same structure as batteries. In this research, employing the manganese dioxide/graphite and zinc as an active material, we tried to produce Leclanche´ primary batteries.

2.2 Preparation the electrospun web For preparing electro-spun nanofibrous web that is used as an electrode of the battery yarn, we used MnO 2 powders as active positive material, zinc powders as active negative material. PVDF (M n : 107,000) was used as a binder, PVDF-co-HFP(M n : 130,000) for the separator. To enhance the conductivity of MnO 2 , we mixed synthetic graphite with MnO 2 powders. To prepare each solution of PVDF and PVDF-HPF they were dissolved in a mixture of 60 % N,N-dimethylacetamide (DMAA) and 40 % acetone, and heated up to 60℃ to give a concentration of 10 and 20 wt.% respectively. Slurries for anode and cathode were made by adding each active material into the 10 wt% PVDF/DMAA/Acetone solution slowly and stirring the solution more than 48 hours at 60℃. The slurry for anode was composed of 80 wt% of MnO 2 , 10 wt% of graphite and 10 wt% of PVDF. In case of slurry for cathode, 90 wt% of zinc and 10 wt% of PVDF were used. Because we added the in-organic powders to PVDF solution for slurries, 18-gauge nozzles with the inner diameter 0.033 inches were used, while for producing web electrodes and the separator 23-gauge nozzle with the inner diameter 0.013 inches were used. During the process, we maintained the tip-to-collector distance as 12 cm, and an electric voltage was set at 19 kV. Aqueous electrolyte was prepared by dissolving 45 g ammonium chloride and 12 g zinc chloride into 100 mL distilled water. This aqueous electrolyte was sprayed onto the electrospun web on the moving collector periodically. All the process were conducted at temperature 26 ℃ and 78% of relative humidity.

3. Results and Discussion 3.1 Web formation and bundling the web Figure 2 shows photographs of the bundling zone displaying the friction drum and the moving collector with the component materials delivered (Fig. 2a) and of the produced yarns (Fig. 2b). Because we used 3 parallelaligned multi nozzle systems, there are 3 types of nanofiber web were collected on the moving collector and transported to friction bundling zone. At the initial state of the friction bundling process, we used a guide yarn for take up the in-process bundle, but after the steady state, the guide yarn was cut and removed from the bundling zone. The output bundle has a mean diameter of 1.586 mm with a CV. of 9.56%. a) b)

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Fig. 2: Photographs of a) moving collector and friction drum, and b) output bundles.

3.2 Morphological characteristics of output bundle Figure 3 demonstrates images of the scanning electron microscope for several samples produced. From Figs. 3a and 3b, we can notify that active materials are good pasted upon the electro-spun web. a)

Fig. 3: SEM images of a) anode (MnO 2 /C-PvDF), b) cathode (Zinc-PvDF), c) separator (PvDF-HFP) in a magnification ratio of 5,000 d) cross-section of output battery yarn magnified by 120.

In the case that the battery circuit becomes electrically shorted, the battery will be rapidly discharged and heated up due to the high electron current. This could cause the battery to be permanently damaged. To avoid the short circuit between electrodes, a permeable membrane, called separator is located between anode and cathode. Fig. 3d shows the cross-section image of the produced battery yarn, demonstrating that cathode material is located in the yarn center and anode material is located on the outer surface. Both of the electrodes are solidly separated by a thin membrane, that is, by a separator. a)

Fig. 4: X-ray diffraction pattern of a) anode (MnO 2 -PVDF web) and b) cathode (Zinc-PVDF web)

The x-ray diffraction patterns obtained from PVDF nano-fibers doped with MnO 2 and Zinc are shown in Fig. 4. For the MnO 2 doped specimen (Fig. 4a), the diffraction peaks occur at 2θ = 28.72, 37.39 and 56.69 degrees and for the Zn doped specimen, the diffraction peaks at 36.35, 43.30, 54.39 degrees. This means that the positive and negative active materials are well dispersed in the electro-spun web. These results agree well with literature [4,5].

3.3 Discharge performance of battery yarn

The discharge curve with a constant resistance (100 Ω) of the battery yarn is represented in Fig. 5. The specimen was 35 cm long, 1.52 g weight. Normally the initial discharge voltage of commercial zinc-carbon batteries is approximately 1.5 volts, but in the case of our specimen it is 0.87 volts, a relatively low level of

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the initial discharge voltage than the commercials. We infer the reasons of the low initial discharge voltage as 1) low packing density of output yarn, 2) high resistance of the electrodes, and 3) no substrate involved to act as a current collector. In a trial, where the planar battery cell (flexible sheet) which employed current collector material was rolled up to a bundle, we could achieve the initial discharge voltage much improved up to 1.24 volts.

Fig. 5: Discharge curve of the battery produced in experiments.

3.4 Flexibility test of the battery yarns a)

Fig. 6: Photographs of flexibility test of battery yarns: a) normal state, b) bent state and c) tied state.

The most advantageous trait of textile material, especially, yarns or bundles, is that it can transform to any shape for products. However, the post-process requires a certain extent of deformability to endure the fabrication process such as weaving or knitting. If a battery has an enough flexibility, it has a great potential to be used in many industrial areas such as roll-up electric devices or wearable components. Fig. 6 is showing results from flexibility tests for the battery yarns that we produced. As shown in Fig. 6, even though the initial discharge voltage is lower than the conventional zinc-carbon batteries, it’s discharge voltage remains almost unchanged when the battery yarn is bent or tied, which demonstrates a good enough battery characteristics under shape-flexible conditions.

4. Conclusion In this research, we suggested a novel method for producing a continuous bundle with electro-spun web through surface friction force. By introducing active materials we investigated the possibility to use the friction bundle as a battery. According to the results, the friction bundling system could be applied to bundle the nanofiber web. With three bands of nano-fibrous web as anode and cathode electrodes and a separator delivered to the friction zone, battery yarns were produced that could be characterized by multi-layered structure. The results of discharging test showed that the novel primary battery could generate an electric voltage, but the discharge voltage level was relatively low in a reference to the conventional batteries due to a low packing density and a high electrode resistance. However the battery performance could be maintained under flexible deformation conditions.

5. Reference [1] Amalina M. Afifi, Shigeyuki Nakano, Hideki Yamane, Yoshigaru Kimura, ‘ Electrospinning of Continuous Aligning Yarns with a ‘Funnel’ Target’, Macromol. Mater. Eng., 295, 660-665, 2010. [2] Usman Ali, Yaqiong Zhou, Xungai Wang and Tong Lin,’ Direct electrospinning of highly twisted, continuous nanofiber yarns’, The Journal of Textile Institute, 103(1), 80-88, 2012. [3] Jung H. Lim, G. Tumenulzii, and you huh, ‘Transform of Nano-fibers to Bundle by Surface Friction and Features of the Nano-fibrous Bundle’, Fibers and Polymers, 16(6), pp.1378-1383, 2015.

Page 1056 of 1108

[4] Howard E. Swanson, Howard F. McMurdie, Marlene C. Morris, Eloise H. Evans, and Boris Paretzkin, ‘Standard Xray Diffraction Powder Pattern-Section 10’, pp. 39, 1953 [5] Muhammad Mehboob, Abdul Wasay, Sadaf Ramzan and Fiaz Ahmed, ‘ Synthesis of Electrolytic Zinc Powder for Zinc Silver Oxide Batteries’, ARPN Journal of Science and Technology, 5(6), pp.295-298, 2015

Page 1057 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Multi-objective self-optimization of the weaving process Saggiomo +, Gloy and Gries Institut fĂźr Textiltechnik der RWTH Aachen University (ITA), Aachen, Germany

Abstract. Textile producers in high-wage countries have to cope with the trend for smaller lot sizes in combination with the demand for increasing product variations. One possibility to cope with the dilemma scale vs. scope consists in manufacturing with cognitive machinery [1]. This paper focuses on woven fabric production and presents a method for multi-objective self-optimization of the weaving process. Setup of weaving machines is done, in general, by relying on the experience of machine operators. In case the operator cannot find a stable setting point, trial and error strategies are used to find adequate settings for the process parameters. This process can take up to several hours in the worst case (e.g. unknown material) and depends highly on the knowledge of the operator. Especially in connection with small lot sizes, this procedure leads to uneconomic fabric production. The self-optimized weaving process handles small lot sizes by reducing changeover time and set-up costs [2]. A weaving machine is transformed into an intelligent self-optimizing production system which is aligned to the trend towards the Internet of Things and Industry 4.0. The control unit of the weaving machine knows about the general conditions of the production environment, namely customer requirements, fabric properties, machine condition and energy efficiency. The weaving machine automatically calculates its optimal settings with algorithms solving a multi-objective optimization problem [3]. As a result, the algorithms reduce changeover time of the weaving machine by 75 %. Faster machine reconfiguration leads to decreasing manufacturing costs of the fabric by 10 % per mÂ˛. Keywords: Industry 4.0, multi-objective self-optimization, weaving process, fabric production

1. Introduction The development towards Industry 4.0 is based primarily on modern production machines in conjunction with digital technologies [1]. Today, setting-up a manufacturing process is mainly done by relying on the experience of experienced operators. This paper suggests multi-objective self-optimization of the weaving process to enable the machine to find an optimized set of parameters autonomously. The capability to decide autonomously which operating point is optimal forms one of the first steps towards a weaving machine as a Cyber-Physical System in the sense of Industry 4.0. Thus, the optimization algorithm assists especially unexperienced operators with settingup weaving machines and helps to reduce set-up and changeover time.

2. Experimental In case the operator cannot find a stable setting point, trial and error strategies are used to find adequate settings for the process parameters. This process can take up to several hours in the worst case (e.g. unknown material) and depends highly on the knowledge of the operator [3]. Moreover, fabric production in different weaving mills is subject to various requirements. Multi-objective self-optimization of the weaving process has been developed to avoid time-consuming trial and error strategies to set-up weaving machines through an optimization algorithm. To consider the requirements of different

Corresponding author. Tel.: + 49-241-80 23 444. E-mail address: Marco.Saggiomo@ita.rwth-aachen.de

Page 1058 of 1108

operators or plant managements, user-defined preferences regarding the objective functions can be integrated into the optimization procedure. The algorithm optimises the machine parameters static warp tension, vertical position of warp stop motion and revolutions per minute. The objective functions warp tension, air consumption, active power consumption and fabric quality are taken into account [4]. The algorithm consists of the steps shown in Fig. 1.

Fig. 1: Steps of multi-objective self-optimization of the weaving process [3]

In the first step an experimental design is calculated automatically. Within this design, the three setting parameters static warp tension, vertical position of warp stop motion and revolutions per minute are varied. In the second step, the test procedure, the weaving machine realises every test point and data describing the objective functions is recorded for the respective parameter setting. In the third step, the obtained data is used to calculate models which describe the objective functions in dependence of the setting parameters. In the last step, an optimised set-up of the weaving machine based on predefined quality criteria is calculated by application of desirability functions and Nelder/Mead - Algorithm. Before execution of the optimization procedure, user-defined preferences regarding the objective functions can be integrated through target weights. The equipment used for multi-objective self-optimization is shown in Fig. 2.

Airjet weaving machine

ibaMS16xAI-20mA (signal input)

air consumption sensor

trigger signal

ibaMS16xAl-10V (signal input)

yarn tension sensor

PC with ibaLogicV4

control program

Fieldbus controller

ibaPADU-S-IT-16 (runtime platform)

active power measurement

programme (runtime platform)

vision based fabric inspection

switch

Fig. 2: Equipment used for multi-objective self-optimization of the weaving process [4]

3. Results of long-term test

Page 1059 of 1108

Before multi-objective self-optimization, the following parameters were extracted from a weaving machine from an exemplary German weaving mill for technical textiles: • static warp tension = 4 kN • vertical position of warp stop motion = 0 mm • revolutions per minute = 900 RPM The optimization algorithm calculated an optimal setting of parameters as follows: • static warp tension = 3.71 kN • vertical position of warp stop motion = 20 mm • revolutions per minute = 522 RPM The measurement data of the objective functions gathered during the long-term test is shown in Fig. 3.

2,5 2 1,5 1 -15 %

0,5 0

Active power consumption[kW]

360

720 1080 1440 1800

155 150 145 140

-14 %

135 130

360

Machine angle [°]

5 4 3 2

-46 %

1 0 0

360

720 1080 1440 1800

Machine angle [°]

720 1080 1440 1800

Machine angle [°] Fabric quality category [-]

Warp tension [kN]

After self-optimisation

Air consumption [m³/h]

Before self-optimisation

4 3 2 1 -40 % 0 0

360

720 1080 1440 1800

Machine angle [°]

Fig. 3: Results of multi-objective self-optimization of the weaving process [4]

It becomes obvious from Fig. 3 that the characteristic of every objective function is improved after selfoptimization of machine parameters. The y-axis of fabric quality shows category values between 0 and 4 where 0 stands for perfect fabric quality and 4 means the fabric quality is not suitable [4].

4. Acknowledgement The authors would like to thank the German Research Foundation DFG for the kind support within the Cluster of Excellence „Integrative Production Technology for High-Wage Countries”.

5. References [1] Saggiomo, M.; Wischnowski, M.; Gebert, T.; Winkel, B.; Nierhaus, M.; Gloy, Y.-S.; Gries, T.: Industry 4.0 in the field of Textile Machinery - First steps of implementation. Melliand International (2) 2013. [2] Löhrer, M.; Lemm, J.; Gloy, Y.-S.; Gries, T.: Adaptive Supporting System For a Competence-Enhancing humanMachine-Interaction in new Production Processes. 9th International Technology, Education and Development Conference. Madrid, 2nd-4th of March, 2015 [3] Gloy, Y.-S.; Sandjaja, F.; Gries, T.: Model-based self-optimization of the weaving process. Journal of Manufacturing Science and Technology (CIRP). Volume 9, May 2015, Pages 88–96

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[4] Saggiomo, M.: Entwicklung und Implementation eines Konzeptes zur mehrdimensionalen Selbstoptimierung des Webprozesses. Master Thesis. Aachen, Rheinisch Westf채lische Technische Hochschule. 2014.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Novel Oxidation Hair Dyeing by Using Bio-Catechol Materials Takanori Matsubara 1 +, Chinami Seki 2, Isao Wataoka 2, Hiroshi Urakawa 2 and Hidekazu Yasunaga 2 1 2

Department of Mechanical Engineering, College of Industrial Technology, Japan Faculty of Fibre Science and Engineering, Kyoto Institute of Technology, Japan

Abstract. Three kinds of hair dyeing methods using biobased materials having catechol part, bio-catechol materials, were examined and compared with one another in order to improve the dyeability for hair. The first dyeing method is dyeing hair by a redissolved dyestuff, which is preliminarily obtained by the oxidation of raw materials (redissolution dyeing). The second one is dyeing hair in solution containing a raw material and the dyeing is accompanied by the oxidation reaction (simultaneous oxidation dyeing). The third one is dyeing hair, which adsorbs preliminarily a raw material, by the oxidation treatment (post-oxidation dyeing). The enzymatic or chemical technique was used as the oxidation treatment of bio-catechol materials to get colourants. It was found that the dyeability of the simultaneous oxidation and post-oxidation dyeing methods is higher than that of redissolution dyeing method for the (+)-catechin (Cat) system at 30 °C. The (−)-epicatechin (EC), tea extract Sunphenon EGCg (EGCg, main component is (−)-epigallocatechin gallate), L-3,4dihydroxyphenylalanine (DOPA), hematoxylin (HX), brazilin (BZ), rosmarinic acid (RA), caffeic acid (CA), chlorogenic acid (ChA) or ellagic acid (EA) was used as a raw material and hair dyeing by using them was tried. The results show that EC, EGCg, HX and BZ are available for hair dyeing. In the simultaneous enzymatic oxidation dyeing, the colour of hair dyed with EC is yellowish brown, with EGCg is dull yellowish brown, with HX is dark yellowish brown and with BZ is reddish brown. The colour of hair dyed with EC, EGCg, HX or BZ by post-chemical oxidation dyeing is yellowish brown, deep yellowish brown, slightly reddish brown or reddish brown, respectively. The deepest colour of dyed hair is obtained by dyeing with HX using the post-chemical-oxidation dyeing technique. The hair dyed with EGCg by the post-chemical-oxidation dyeing method shows also deeper colour. The hair dyed with Cat by the simultaneous enzymatic oxidation dyeing method shows the highest chroma.

Keywords: Catechinone, (+)-Catechin, Bio-Catechol, oxidation hair dyeing

1. Introduction Some of the components in the human hair dyeing products based on oxidation dyes and by-products formed during the dyeing process work as strong allergens and cause sensitisation symptoms and severe dermatitis in a certain case. The authors have been studying novel hair dyeing techniques by using biobased materials obtained from plants in order to invent safer ones. It was found that the oxidation product of (+)catechin, “catechinone,” works as hair dyestuff and catechinone does not cause erythema or oedema on skin of rabbits [1]. It dyes hair orange, reddish orange or deep yellowish brown, and the colour fastness of the dyed hair to washing and light is high enough [1, 2]. The catechinone is obtained enzymatically [1] or chemically [3], and the oxidation reactions are made at the catechol (o-dihydroxybenzene) group of (+)-catechin (Cat, Fig. 1 (a)) to give a corresponding o-quinone. The enzymatic technique is superior in terms of the reactivity and selectivity, whereas the chemical method is more useful and practical for industrial production of the catechinone dyestuff because the chemical reaction is easier to control than the enzymatic one. In the research, the dyeing technique that dyeing hair by a redissolved dyestuff, which is preliminarily +

Corresponding author. E-mail address: matsubara@cit.sangitan.ac.jp.

Page 1062 of 1108

(a)

(b)

(d)

(e) O HO

OH OH

(f)

OH OH O

(h)

O OH

O HO

HO OH

(g)

OH O

NH2

OH O

(i)

O O

(j)

OH OH

Fig. 1: Chemical structure of bio-catechol materials. (a) (+)-Catechin (Cat), (b) (−)-epicatechin (EC), (c) (−)-epigallocatechin gallate (EGCg), (d) L-3,4-dihydroxyphenylalanine (DOPA), (e) hematoxylin (HX), (f) brazilin (BZ), (g) rosmarinic acid (RA), (h) caffeic acid (CA), (i) chlorogenic acid (ChA) and (j) ellagic acid (EA).

obtained by the oxidation of raw materials, “redissolution dyeing,” was compared with two types of dyeing methods in order to find better technique showing higher dyeability. First one is colouring hair with (+)catechin solution during oxidation reaction, “simultaneous oxidation dyeing”. Another one is colouring hair, which was treated with Cat, by oxidising the absorbed materials, “post-oxidation dyeing”. The other biocatechol materials, such as (−)-epicatechin (EC), tea extract (main component is (−)-epigallocatechin gallate (EGCg)), L-3,4-dihydroxyphenylalanine (DOPA), hematoxylin (HX), brazilin (BZ), rosmarinic acid (RA), caffeic acid (CA), chlorogenic acid (ChA) and ellagic acid (EA) were used to dye hair by the three kinds of dyeing techniques and their dyeabilties were estimated.

2. Experimental (+)-Catechin (Cat), (−)-epicatechin (EC), tea extract Sunphenon EGCg® (EGCg, chemical composition: (−)-epigallocatechin gallate 92.1 wt%; (−)-epicatechin gallate 3.9 wt%; residual is other catechin derivatives and water), L-3,4-dihydroxyphenylalanine (DOPA), hematoxylin (HX), brazilin (BZ), rosmarinic acid (RA), caffeic acid (CA), chlorogenic acid (ChA) and ellagic acid (EA) were used as the dyestuff precursors. Fig. 1 shows their chemical structures. Dyeing hair was made as follows: 1) Redissolution Dyeing Method: Catechinone was produced by the oxidation of the precursor enzymatically [4] or chemically [5]. The precursor/tyrosinase/O2 reaction system was used in former process and the precursor/base/O2 reaction system in latter one. The obtained dye was dried out to be powder. Decolourised hair (0.8 g) was immersed in the 0.29 wt% redissolved dye 0.1 M phosphate buffer aqueous solution (pH = 7.0) at 30 °C for 40 min. 2) Simultaneous Oxidation Dyeing Method: The 10 mM precursor phosphate buffer solution with 70 U ml-1 tyrosinase at pH = 7.0 or the 10 mM precursor solution with 0.1 M Na2CO3 at pH = 10 ~ 11 was prepared. Hair was dyed in each the solution with O2 gas introducing at 30 °C for 40 min. 3) Post-Oxidation Dyeing Method: After hair was treated in the 10 mM precursor solution at 30 °C for 40 min, the hair was dyed in 70 U ml-1 tyrosinase solution at pH = 7.0 or 0.1 M Na2CO3 at pH = 11.6 at 30 °C for 40 min under O2 gas introducing. The dyed hair was washed with 0.8 wt% sodium dodecyloxypolyoxyethylene (n = 2) sulphate aqueous solution and rinsed twice with distilled water at 35 °C. The hair was air-dried at room temperature. The colour of hair was measured by a Konica Minolta CM-2600d spectrocolourimeter and the resulting colour was expressed in L*a*b* standard colourimetric system (CIE 1976). The colour measurements were made employing 10°-view angle, CIE standard illuminant D65 and SCI mode. All the reflection light from the sample including the regular reflection is integrated under the SCI mode. The L* is the lightness index, and a* and b* are the chromaticity coordinates. The positive values of a* indicate red and its negative values indicate green, and the positive values of b* indicate yellow and its negative values indicate blue. The C* is the chroma calculated by C* = {(a*)2 + (b*)2}1/2.

3. Results and Discussion

Page 1063 of 1108

(a)

40 20

(b)

Fig. 2: Colour measurement results of hair samples undyed (ď&#x201A;Ł) and dyed by redissolution dyeing method with catechinone obtained by enzymatic oxidation ( ) or chemical oxidation ( ), simultaneous oxidation dyeing method enzymatically ( ) or chemically ( ), and post-oxidation dyeing method enzymatically ( ) or chemically ( ) by using (+)-catechin. (a) Chromaticity coordinates relationship (a* - b*), (b) chroma lightness index relationship (C* - L*).

In the redissolution dyeing method, the colour of the hair dyed with catechinone by enzymatic oxidation or chemical oxidation is yellow or reddish brown, respectively. As shown in Fig. 2, the colour of enzymatically-dyed hair shows high b* (more yellowish) and that of chemically-dyed hair is lower L* (deeper colour). The difference of the dyeability may be due to the composition of the small amount of by-products. Hair is dyed with Cat by both the simultaneous enzymatic oxidation dyeing method and post-enzymatic oxidation dyeing method. The dyeability of the two techniques is higher (higher a* and lower L*) than that of the redissolution dyeing method as shown in Fig. 2. The b* of the hair dyed with Cat by the simultaneous enzymatic oxidation dyeing method shows relatively high value. In contrast, the a* and b* of the hair dyed by simultaneous chemical oxidation dyeing method or post-chemical oxidation dyeing method are higher than those of the redissolution dyeing method. The L* for the hair dyed with Cat by the simultaneous enzymatic oxidation dyeing method is higher than that for the post-enzymatic oxidation dyeing method. The hair dyed with Cat by the simultaneous enzymatic oxidation dyeing method shows the highest C*. The hair dyed with Cat by post-chemical oxidation dyeing method shows the deepest colour (lowest L*). Moreover, the L* of the hair dyed with Cat by post-chemical oxidation dyeing method decreases to ~ 35 at 30 Â°C for 50 min of immersing time in Cat solution with 0.15 M calcium (II) chloride and for 20 min of oxidation time. Furthermore, other bio-catechol materials, which are biobased materials having catechol part like (+)catechin, are applied to the novel oxidation dyeing. Used bio-catechols are materials as shown in Fig. 1. EA is unable to use for hair dyeing because EA is little soluble in water and its solubility is very low. The aqueous solutions of EC, EGCg, DOPA, RA, CA and ChA are colourless and slightly coloured. The colour of the solution of HX or BZ is wine red. All solutions of bio-catechols expect for EA are oxidised to turn deeper colour. Fig. 3 shows dyeing results of the oxidation dyeing by using bio-catechols. In the enzymatic oxidation dyeing, the hair dyed by the simultaneous oxidation dyeing method and using EC, EGCg, DOPA, HX or BZ is coloured, and its colour is yellowish brown, dull yellowish brown, grey, dark yellowish brown or reddish brown, respectively. The hair dyed by post-enzymatic oxidation method is slightly coloured with them. RA, CA or ChA is not available for enzymatic oxidation dyeing. In the chemical oxidation dyeing, hair is little dyed by the simultaneous oxidation dyeing method. Meanwhile, hair is dyed by the post-chemical oxidation dyeing using EC, EGCg, HX, BZ or RA. The colour of the dyed hair with EC, EGCg, HX, BZ or RA is yellowish brown, deep yellowish brown, slightly reddish brown, reddish brown or dull yellowish brown, respectively. Chemical oxidation dyeing by using DOPA, CA or ChA cannot colour hair. The hair with most vivid colour or the deepest colour is obtained by simultaneous enzymatic oxidation dyeing with Cat (C* ~ 58) or post-chemical oxidation dyeing with HX (L* ~ 24). The L* of the hair dyed by post-chemical oxidation dyeing with EGCg (tea extract mixture) is ca. 23.

Page 1064 of 1108

30 20

0 -10

(a)

(c)

0 -10

(b)

(d)

Fig. 3: Colour measurement results of hair samples undyed () and dyed by simultaneous enzymatic oxidation dyeing method ((a),(b) green symbol), post-enzymatic oxidation dyeing method ((a),(b) orange symbol), simultaneous chemical oxidation dyeing method ((c),(d) cyan symbol) or post-chemical oxidation dyeing method ((c),(d) magenta symbol) with bio-catechol materials. Used bio-catechols are (+)-catechin (Cat, ), (−)-epicatechin (EC, ), tea extract Sunphenon EGCg (EGCg, ), L-3,4-dihydroxyphenylalanine (DOPA, ), hematoxylin (HX, ), brazilin (BZ, ), rosmarinic acid (RA,

), caffeic acid (CA,

) and chlorogenic acid

(ChA, ) (a),(c) Chromaticity coordinates relationship (a* - b*), (b),(d) chroma - lightness index relationship (C* - L*).

The oxidation dyeing proceeds accompanied with dyestuff formation and its adsorption. The differences of the dyeability between the dyeing and oxidation method may be caused by the differences in the oxidising reactivity, the composition of the formed dyestuffs, their adsorption behaviour onto hair, and so on. The biocatechols showing high dyeability are Cat, EC, EGCg, HX and BZ. The materials have dihydrobenzopyran (chroman) structure and catechol part. They should play important roles in the dyestuff formation and its adsorption onto hair.

4. References [1] Yasunaga, H.; et al., J. Cosmet. Dermatol. Sci. Appl., 2(3), 158-163 (2012). [2] Matsubara, T.; et al., J. Cosmet. Dermatol. Sci. Appl., 5(2), 94-106 (2015). [3] Matsubara, T.; et al., Int. J. Cosmet. Sci., 35(4), 362-367 (2013). [4] Yano, A.; et al., Proc. 11th Asian Text. Conf., 1081-1084, 1PS-067, EXCO, Daegu, Korea, 1-4 November (2011). [5] Matsubara, T.; et al., Sen’i Gakkaishi, 70(1), 19-22 (2014).

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Production Technology Selection for the Development of Technical Fabrics Beer 1+, Schrank 1, Gloy 1, Gries 1 1

Institut fĂźr Textiltechnik (ITA) der RWTH Aachen University, Aachen, Germany

Abstract. Textiles, especially technical textiles are used in various fields of applications. Different technologies for the production thereof exist, like weaving and braiding. These technologies are available in different versions. Each technology version possesses advantages and disadvantages for the desired fabric application. Often, a technology for new products is selected without considering the other production technologies. This is due to habit or nescience of the other technologies within the development team. The consideration of alternative production technologies may create economic advantages. The technology selection is an important step during the development of new textile products. This paper shows an overview of possible textile technologies for the processing of new technical products. Moreover, it is a guideline for the systematic selection of suitable technologies. Starting from known product requirements, the technology selection enables textile manufacturers to make other technologies accessible and to popularize non considered technologies. This way, new products can be developed, especially for manufacturers who are new in the textile sector or manufacturers who want to enter a new textile field to broaden their product range. The technology overview covers the textile production technologies weaving, warp and weft knitting, braiding and non-wovens. These technologies as well as their sub-categories (e.g. weft knitting: circular â&#x20AC;&#x201C; flat) are considered and evaluated.

Keywords: Technical Fabrics, Design Method, Technology Selection, Textile Fabric Structures

1. Introduction The selection of suitable textile machinery for new ways of producing textile products is difficult. With different technologies, similar textile characteristics of possibly be achieved. However, the production technology selection is often influenced by habit or nescience of other technologies. Different factors need to be considered when choosing an alternative production machine. The first and most important factor is the technical feasibility of the production of the desired product. If e.g. a new bed sheet is developed, a narrow weaving machine is not suitable for the final product due to its fabric output dimension. Another important factor is the economic efficiency. Depending on the field of application it can be important that low invest and high productivity are more important than perfect realisation of mechanical properties. Following, the step of technology selection as part of a design method for technical fabrics is described.

2. Technology selection Technical fabrics can either be produced on weaving, warp knitting, weft knitting, non-woven, braiding or multi-non crimp machines. All these technologies can be further sub divided dependent on resulting dimensions (2D, 3D), structure (velvet, tubular, etc.), configuration (weft insertion technology, weft and warp yarns, plush).

Sub-Category

TECHNOLOGY

Page 1066 of 1108

Weaving

Warp Knitting

Weft Knitting

Braiding

Nonwoven

Multi Non-Crimp

Ribbon

Tricot

Small Circular

Radial

Warp Knitted Fixation

Standard

Raschel

Large Circular

Flat

Broadloom

Crochet

Seamless

3D-Hexagonal

Mechanical Bonding Chemical Bonding Thermal Bonding

Flat

Binder Fixation

Fig. 1: Overview of fabric production technologies and the sub-categories, based on [1, 2, 3, 4, 5, 6]

Part of the technology selection is a detailed overview of all standard fabric production technologies and its typical characteristics, possibilities and limitations. The fabric production technologies and the main subcategories are given in Fig. 1 [1, 2, 3, 4, 5, 6]. The major focus of the technology selection step is to support a product development by outlining possible production options. The main aspects to consider are: • Production aspects (Dimensions, Cost, Time, Quantity, …) • Material aspects • Mechanical properties Depending on the product development strategy, a different aspect can be the main focus. In the following, the steps of procedure for each aspect are described.

2.1.

Production aspects

For any new product idea typically some boundary conditions are already given. These boundary conditions are e.g. product dimensions, maximum production costs, maximum production time or the quantity needed to saturate the market. For each new product development, the priority of these boundary conditions may vary. For example if within a new development the economic efficiency is of main importance, the productivity of the machine technology has more weight within the selection than the structure characteristics. In another case scenario, the dimension of the product may be of major importance (e.g. tubular stent structure in medical application) but the production costs within a niche market may become insignificant. All of the product aspects need to be taken into consideration and rated for the desired product.

2.2.

Material aspects

Fineness Strength



 Machine Type A



Machine Type B



Processable Material Strength [N]

Yarn material requirement

Processable Yarn Fineness [dtex]

Another important factor to consider is the material process ability. If a special yarn material is needed for the planned product development but cannot be processed on some of the existing machine technologies, these technologies have to be sorted out in a pre-selection. Two major yarn characteristics are typically taken into consideration to select a fitting fabric production technology - the yarn fineness and the yarn strength (Fig. 2). Brittle or weak yarns for example typically cannot be processed by air jet weaving looms, as the charged forces on the yarn are too high resulting in yarn failure during process. The fineness of the yarn typically defines dimensions of used machine components (e.g. machine gauge).

Selection Machine Type A to process required yarn material

Machine Type C

Fig. 2: Relevant material aspects for the selection of a suitable machine technology

Page 1067 of 1108

2.3.

Mechanical properties

The third major aspect category, that may be the focus within development of a product are specific material properties, the product has to achieve (e.g. customer demands regarding air permeability for a breathable textile). The mechanical properties of the resulting product are majorly influenced by the selected machine technology. Based on a requirement list from the product development team with fixed requirements (F) and wishes (W), standard material test are selected to evaluate target areas. The structure characteristics that can be determined using the material tests can be linked to production parameters (e.g. the weft density of a woven fabric has a significant influence to the air permeability). Not all production parameters can be varied in all processes. This leads to a pre-selection of suitable machine technology types that can be used to address the requirements of major importance for the product development (see Fig. 3).

Requirement List Characteristic A Characteristic B Characteristic C Characteristic D Characteristic E Characteristic F Characteristic G … … …

F W W F F W F

Material Tests DIN EN xyz ISO xyz CEN xyz ETSI xyz ASE xyz … … … …

Production Parameters Parameter A Parameter B Parameter C Parameter D … …

Machine Type Knitting Mach. A Weaving Mach. B Knitting Mach. F Braiding Mach. A … …

 X X 

Fig. 3: Machine selection regarding mechanical properties of the developed product

3. Results and Conclusion The selection of suitable machine technologies, ranging from knitting over weaving, braiding, non-wovens to multi-non crimp fabrics, is a complex and challenging task. Multiple aspects need to be taken into consideration and their interdependencies. To reduce the complexity within the technology selection, an overview of the currently available textile production technologies with their sub-categories was given. These technologies are correlated to the main selection aspects: production, material and mechanical properties. For each technology these aspects are elaborated in detail to support the development of new textile products.

Page 1068 of 1108

4. References [1] Gries, T.; Veit, D.; Wulfhorst, B.: Textile Fertigungsverfahren – Eine Einführung 2. Aufl.; München: Hanser Verlag: 2014 [2] Adanur, S.: Handbook of weaving Boca Raton; London; New York: CRC Press (2001) [3] Head, A; Ko, F.; Pastore, C: Handbook of Industrial Braid 1. Ed.; Covington KY: Atkins & Pearce (1989) [4] Spencer, D. J.: Knitting technology - A comprehensive handbook and practical guide 3. Ed.; Lancaster, Pa, Cambridge, UK: Technomic; Woodhead (2001) [5] Horrocks, A.R.; Anand, A.C.: Handbook of technical textiles Cambridge: Woodhead Publishing Limited (2000) [6] Fuchs, H.; Albrecht, W.: Vliesstoffe: Rohstoffe, Herstellung, Anwendung, Eigenschaften, Prüfung 2. Ed.; Weinheim: Wiley-VCH Verlag (2012)

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Research of the electroless copper-plating on wool fabrics through supercritical CO 2 pretreatment Guang Hong Zheng 1*, Jianhua Ren1,Xugui Zhang1,Rong Hui Guo2, Feng Long Ji3 1 2

School of Materials and Environment, Chengdu Textile College, Chengdu, Sichuan, P.R.China, College of Light Industry, Textile and Food, Sichuan University, Chengdu, Sichuan, P.R.China, 3 College of Textile and Clothing, Wuyi University, Jiangmen, Guangdong, P.R.China

Abstract: In this study, the supercritical CO 2 impregnation process was employed before electroless copper plating of wool fabrics. It was found that as compared with traditional immersing fabrics into reduction agent, the supercritical CO 2 impregnation favored the deposition of reduction agent on wool fabrics. In addition, using ethanol as co-solvent in the supercritical CO 2 impregnation favored the impregnation of reduction agent into wool fabrics. It was experimentally proved that the wool fabrics plated with copper exhibited good antistatic properties.

Key words：Electroless plating, Copper, Wool fabric, Supercritical CO 2 pretreatment

1. Introduction Recently, the metallization of textile is a new technology attracted great attention from industry and academia. The metallized textile can meet extensive applications such as UV protective clothing, curtains for energy-saving and light-blocking, heat shielding material, space and military fields, and so forth[1-2]. In this study, copper films were plated onto the surface of wool fabric by electroless plating. Before electroless plating, a process, i.e. surface sensitization, was conducted by coating the fabric with reduction agent [3]. A traditional method commonly used is simply immersing fabric into reduction agent solution. However, the reduction agent hardly permeates into the inner parts of the fibers . Recently, the supercritical carbon dioxide (scCO 2 ) technique has drawn increasing attention in the dyeing and finishing of textile because of the high diffusion rate and low viscosity of scCO 2 fluid as well as its swelling effect for fibers [4-5]. In order to promote the absorption of wool fibers to the reduction agent, the scCO 2 technique was also employed to conduct the surface sensitization of the wool fabric in this study.

2. Experimental 2.1.

Materials

A sort of plain weave fabric (210counts/10cm in warp, 180counts/10cm in weft, 125.6g/m2) made of 100% Austrilian Merino wool fibers were used in this study. The fabric samples were cut to the size of 20cm×20cm for electroless plating. The chemicals including silver nitrate, ammonium solution, glucose, sodium hydroxide, stannous chloride, palladium chloride, copper sulfate, sodium hypophosphite, boric acid, nickel sulfate, sodium citrate were all used as purchased from Sinopharm Chemical Reagent Co.,Ltd.

2.2.

Fabric pretreatment

All wool fabric samples were rinsed with 5% detergent solution at room temperature for 20 min in order to remove the fat chemicals and other contaminants on wool fibers. The samples were then rinsed in deionized water for 3 times. Afterwards, they were dried in an oven at 60oC for using.

2.3.

Surface sensitization

Before electroless plating, a traditional surface sensitization process was conducted by immersing the samples into an aqueous solution containing 10g/l stannous chloride and 5 ml/l hydrochloric acid (38%) at 1 * Corresponding author：Guang Hong Zheng, Tel.: 86-13981765160, E-mail address: zhenggh53@163.com

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room temperature for 10 minutes. The samples were then rinsed in a large volume of deionized water for more than five minutes to prevent the contamination of plating bath. The fabric samples were then dried in a vacuum oven at 80 oC for 2h. In order to enhance the absorption of the reduction agent by the fibers, a supercritical CO 2 (scCO 2 ) equipment was also employed for the surface sensitization of the wool fabric samples. Supercritical fluids have a higher diffusion rate and a lower viscosity and can result in the significant swelling of the fibers, which is favorable for the absorption of the fibers to the reduction agents. In this study, Palladium (II)-hexafluoroacetylacetonate (Pd(hfa) 2 ), as a sort of sensitization agent, was injected into the wool fibers with a scCO 2 equipment. As demonstrated in Fig1, the treatment of the wool fabrics was conducted in a 10cm3 sample cartridge. The CO 2 was injected into the stainless-steel vessel via the high-pressure syringe pump to the desired pressure. A testing sample was then treated for a 30min at 100oC and under the pressure of 25MPa. Afterwards, the sample was heated to 150oC and a layer of Palladium catalyst formed on the fibers. Then the samples were taken out after decompression and rinsed thoroughly before drying for the use of electroless plating.

Fig.1: Illustration of the scCO 2 equipment. (A) cooling unit. (B) high-pressure pump. (C) pressure gauges. (D) thermometer. (E) heater and high-pressure stainless-steel vessel. (F) sample cartridge. (G) sample. (H) cleaning pump.

2.4.

Electroless plating

As shown in Fig2, the copper-plating bath containing 10g/L copper sulfate, 30g/L sodium hypophosphite, 0.8g/L nickel sulfate, 30g/L Boric acid and 20g/L sodium citrate was prepared in advance (Fig 2 (a)). Then the solution was adjusted to pH=10 with sodium hydroxide and sulfuric acid. The wool fabric samples coated with the reduction catalyst either via the traditional simple immersion surface sensitization or by the scCO 2 injection was then immersed in the electroless silver plating bath at 10oC for 20 min. A layer of copper formed on the fabric quickly (Fig 2 (b)). After thoroughly rinsing, the copper plated fabric samples were dried in a vacuum oven. The copper plated fabric samples were chocolate brown in color ( Fig 2 (c)).

(a)

(b)

(c)

Fig.2: Demonstration of the electroless plating of wool fabrics

2.5.

Characterization and measurement

The surface of the treated and untreated wool fibers were observed by a JSM-6335F field emission scanning electron microscope (SEM). The copper-plated wool fabrics were analyzed by X-ray photoelectron spectroscopy (XPS). An ULVAC Φ5500 spectrometer with Mg-Kα excitation (15.0 kV, 300 W, φ:100 μm) under a vacuum pressure of 1×10−8 Pa was used. The antistatic properties of the fabric samples were explored using a Static Voltmeter R-1020 (Rotchschild, Swiss).

3. Results and discussion 3.1.

The influences of scCO2 impregnation conditions

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Pd(hfa) 2 can be easily dissolved in scCO 2 due to its hydrophobic feature. Because of low viscosity and high diffusiveness of scCO 2 , the Pd(hfa) 2 contained in the scCO 2 fluid can be impregnated into the polymers.[2] In this study, the impregnation of Pd(hfa) 2 into wool fabrics were conducted at 150oC and 20MPa for 10min or 40min in scCO 2 fluid. In addition, CO 2 is non-polar and thus is difficult to diffuse into hydrophilic natural fibers. Some polar co-solvents such as methanol (MeOH), ethanol (EtOH), acetone, etc., were reported to be effective for increasing the solubility of polar substance in scCO 2 fluid [3]. The atomic compositions of the surface of the wool fabrics impregnated with Pd(hfa) 2 under different conditions were investigated by XPS. As shown in Fig 3 (A) and (B), two intense peaks at ca. 561eV and ca. 335eV are ascribed to the emission from the 3p1 level and 3d level electrons of the Pd atoms, indicating the presence of Pt catalyst on both of the two samples. In Fig 3 (A), the peak at ca. 686eV is ascribed to the emission from the 1s level electrons of F atoms whereas the peak disappears in Fig 3(B). The atomic compositions of the wool fabrics treated under different conditions were summarized in Table 1. It can be seen that that the presence of EtOH in the scCO 2 greatly raised the Pd content and reduced the F content. This suggests that EtOH promoted the impregnation of Pd(hfa) 2 into wool fibers since EtOH enhanced the compatibility of wool fibers and scCO 2 .

(A)

(B)

Fig. 3: XPS spectra of the wool fabrics impregnated with Pd(hfa) 2. (A) Treated for 15min without ethanol being employed; (B) Treated for 60 min with ethanol being employed. Table 1: Atomic compositions of wool fabrics treated with Pd(hfa) 2

Impregnation conditions Time (min) EtOH (wt%) 10 10 6.2 40 6.2

3.2.

Atomic composition of the fabric impregnated with Pd(hfa) 2 Pd/C (Ă&#x2014;10-2) F/C (Ă&#x2014;10-2) 3.56 1.49 4.97 0.37 6.89 0

The surface morphology of copper-plated wool fabrics

Fig 4 shows those SEM images of the original and the copper-plated wool fibers. It can be seen that the surface of the original wool fibers was rather smooth (see Fig4 (a)). In contrast, a lot of particles were attached on the surface of the copper-plated wool fibers prepared through the traditional simple immersion surface sensitization (see Fig4 (b), indicated the presence of copper on the fiber surface. In addition, the amount of the particles viewed on the copper-plated wool fibers made through the scCO 2 impregnation process was even larger (see Fig 4(c) ). This verifies that the scCO 2 injection process could enhance that copper amount deposited on the wool fabrics.

(a)

(b)

(c)

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Fig.4: SEM views of the original and the copper-plated wool fibers

As expected, with the increase of impregnation time the Cu content increased and the surface electric resistance decreased(see Table 2 ). When the impregnation of Pd(hfa)2 was conducted with EtOH as co-solvent the resultant copper-plated fabric exhibited higher Cu content and lower surface electric resistance. Table 2: Influences of scCO 2 impregnation conditions on copper-plating effect

Impregnation conditions Time (min) EtOH (wt%) 10 10 40

3.3.

6.2 6.2

Copper-plating effect Cu content (g/m2) 15.6 17.9 19.5

Surface resistance (Ω/cm2) 0.81 0.61 0.54

The antistatic properties of the copper-plated wool fabrics

Table 3 presents the changes of fabric weight and antistatic properties of the wool fabrics before and after electroless plating. It can be seen that the copper-plated fabric prepared via the scCO 2 process showed more increase of fabric weight, which is consistent with conclusion drawn from the SEM experiments, namely, the scCO 2 process for surface sensitization is favorable the copper formation of wool fabric. In addition, after copper plating, the average static half-life values of the fabrics decreased significantly due to the presence of copper deposition on the fabrics. Moreover, the copper-plated fabric prepared via the scCO 2 process showed smaller Average static half-life value. Table 3: The fabric weight and antistatic properties of the fabrics

Sample

Fabric weight (g/m2)

Original Prepared via traditional process Prepared via scCO 2 process

125.86 136.48 142.06

Average static half-life (second) warp weft 694 712 139 138 122 126

4. Conclusions The traditional simple immersion process and the scCO 2 process were respectively employed for surface sensitization of wool fabrics, and the copper-plated wool fabrics were prepared via electroless plating. It was found that the scCO 2 process was favorable for the absorption of the fibers to the reduction agent and thus increased the amount of the copper deposited on wool fibers. In addition, using ethanol as co-solvent in the supercritical CO 2 impregnation favored the impregnation of reduction agent into wool fabrics and enhanced the efficiency of copper-plating.

5. Reference [1] Bula, K, Koprowska, J, Janukiewicz, J, ‘‘Application of Cathode Sputtering for Obtaining Ultra-Thin Metallic Coatings on Textile Products.’’ Fibers Text. East. Eur., 14 (5) 75– 30179 (2006) [2] Zhao, X., Hirogaki, K., Tabata, I., Okubayashi, S. and Hori, T. “A new method of producing conductive aramid fibers using supercritical carbon dioxide.” Surf. Coat. Tech, 201, 628–636 (2006 ). [3] Jiang, SQ, Newton, E, Yuen, CWM, Kan, CW, ‘‘Chemical Silver Plating on Cotton and Polyester Fabrics and Its Application on Fabric Design.’’ Text. Res. J., 76 (1) 57–65 (2006) [4] Montero, G. A., Smith, C. B., Hendrix, W. A. and Butcher, D. L. “Supercritical Fluid Technology in Textile Processing: An Overview.” Ind. Eng. Chem. Res. 39, 4806-4812 (2000). [5] Kongdee, A., Okubayashi, S., Tabata, I. and Hori, T. “Impregnation of Silk Sericin into Polyester Fibers Using Supercritical Carbon Dioxide.” J. Appl. Polym. Sci. 105 , 2091–2097(2007). [6] Sawadaa, K., Takagia, T. and Uedab, M. “Solubilization of ionic dyes in supercritical carbon dioxide: a basic study for dyeing fiber in non-aqueous media”. Dyes Pigments 60 129–135(2004 ).

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Study on Water-repellent Property of multi-layer fabric by using Melt-blown Nonwovens Ki-Sub Lim, Do-Kun Kim, In-Woo Nam and Byeong-Jin Yeang+ Korea Institute of Industrial Technology

Abstract. For replacing vapor permeable and water-repellent material, melt-blown nonwoven was produced by inserting microporosity. Melt-blown process was conducted for nonwovens by using several materials such as Polypropylene, hot melt PET and Elastomer. The nonwoven web was applied by multi-spinning process with cross section of S/S (side by side) type by using hot melt PET and PP. Each webs that fabricated by meltblown process were reprocessed for 3-layer fabric with mesh of PET material by using roll calender and laminator,. Structure and properties of obtained 3-layer multi fabrics were analyzed by measurements of air permeability tester, porosity pressure and diameter test and field-emission scanning electron microscope. Keywords: Melt-blown, Water-repellent, Laminate. Roll calender.

1. Introduction Recently, Textile material of apparel is demanded a lot of useful functions from body protection and esthetic satisfaction to clothing comfort. People are increasing interest in leisure life with improvement of income level. And demand for outdoor clothing is growing explosively. Products of water-repellent function today have used by several materials such as Nano web and hydrophobic-poriferous PTFE. Also the research and development is making progress with clothing part as well as interior and transport steadily. In the study, melt-blown process was conducted for nonwovens by using several materials such as Polypropylene, Hot melt PET and Elastomer. The webs were applied by multi-layer fabric with PET material after. This process was experimented so as to make up for fault of film and make use of easy machinability and production efficiency. For replacing water-repellent material, melt-blown nonwoven was produced by inserting microporosity. The nonwoven web was applied by multi-spinning process with cross section of S/S(side by side) type by using Low melting PET and PP. We used the nozzle with diameter of 0.3Đ¤, 35HPI(Hole per inch) and L/D of 30:1. Each webs that fabricated by melt-blown process were reprocessed for 3-layer fabric with mesh of PET material by using roll to roll calender and laminator. Structure and properties obtained 3-layer multi fabrics were analyzed by measurements of air permeability tester, automated filter tester, porosity pressure and diameter test and Scanning electron microscope(FE-SEM). In the result, the fabricâ&#x20AC;&#x2122;s average pore size and dispersion was changed, depending on different polymer material, Temperature, belt speed and pressure. This affected in permeability and resistance to water pressure. Also this correlation was confirm by morphology image of FE-SEM. Therefore, we could confirm the possibility of product as apparel material on the basis of excellent permeability in comparison with the existing material.

2. Experimental 2.1.

Material

The material of nonwoven web was used with Elastomer (Vistamaxx2330 of Basf), Hot-melt PET (EH700 of SK chem.) and Poly propylene (Polymirae) in order to produce the one of multi-layer fabrics. Elastomer

Corresponding author. Tel.: + 82-31-8040-6065. E-mail address: yeang777@kitech.re.kr

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and Hot-melt PET have adhensive property with low temperature process. Therefore this material adhered well among multi-layer fabric..

2.2.

Melt-blown process

The Melt-blown process was used in order to design 1 ㎛ of micropore and replace water-repellent material. The nonwoven web was applied by multi-spinning process with cross section of S/S(side by side) type by using Low melting PET and PP. We used the nozzle with diameter of 0.3Ф, 35HPI(Hole per inch) and L/D of 30:1. Nonwoven weight (g/m2) was had by 20 and 40gsm , the ratio of sample was 100% , 70%:30% and 30%:70% in order to confirm the different diameter and air permeability.

2.3.

Adhesive process

We had 2 kinds of adhesive processes with roll to roll calender and laminator. Firstly, nonwoven web that produced by melt-blown system with multi-spinning was reprocessed by roll to roll type calender in the form of 3-layer multi fabric with PET fabric and mesh. the process was conducted for air permeability and adhesive property between PET fabric and mesh. the temperature was set from 95℃ to 110℃ and the roll speed was 3m/min. also the pressure was 50kg/cm2. Secondly, laminator was used for reprocessing multi-layer fabric with PET fabric, mesh and nonwoven to thermal bonding after the Melt-blown process. The factors with heat temperature and belt speed proceed in order to confirm the change of bonding strength and porosity. The temperature was set of 150℃ and the belt speed was set from 0.7m/min to 1.3m/min without roll to roll pressure.

2.4.

Characterization

The porosity properties of multi-spinning nonwovens and multi-layer fabric were investigated by air permeability tester, air resistance & penetration tester and porosity pressure & diameter tester. The morphology of that was measured with Field-Emission Scanning Electron Microscopy in a ratio of from x50 to x600 for fiber diameter and bonding appearance of surface.

3. Results and Discussion We produced 7-types of nonwoven webs by using multi-spinning melt-blown with different ratios of materials. The materials had different properties because of hydrophilic and hydrophobic properties. So each web was different surface form and fiber diameter through melt-blown process. In figure1, we confirmed the morphology of Hot-melt70/PP30. The web used 2 types of polymers had fiber of different sizes and this average diameter was 7.28 ㎛. Other materials also had similar average diameter.

Figure 1. Morphology of surface form and diameter of nonwoven web (Hot-melt 70/PP 30)

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After the melt-blown process and morphology analysis, roll to roll calender and laminator was used for reprocessing multi-layer fabric for air permeability and adhesive property between PET fabric and mesh. In the roll to roll calender system, the higher 3-layer fibric applied temperature, The lower this had the value of air permeability. In the laminating system, the higher 3-layer fabric applied belt speed, The higher this had the value of air permeability. Also the material (including the nonwoven of hot-melt 70/elastomer 30) used elastmer 30% with hydrophilic property was higher a value of air permeability than others. In comparison with roll to roll calender and laminator, laminating system was high value of air permeability, even though it had lower adhesive property than other. Therefore we measured the pore diameter in the condition of mean flow and 16dynes/cm (surface tension). The material used 3-layer fabric with nonwoven (hot-melt 70/elastomer 30) because this had high value of air permeability. By increasing the belt speed, pore diameter was decreased. This result show similar tendency with air permeability. We mersured FE-SEM image in order to confirm the adhesive property of 3-layer with several multispinning nonwoven. all materials were formed well between PET fabric and mesh by measuring a cross section of that. In the result, we could make eco-friendly multi-layer fabrics without the harmful adhesive. And manufacturing process was simplified for outdoor material development. This could improve the productivity and save the cost. Lastly, fiber material with melt-spinning nonwoven could diversify multi-layer technical development.

4. References [1] F. Martinez-Hergueta, A. Ridruejo, C. Gonzalez and J. LLorca, International Journal of Solids and Structures, Vol. 64-65, Page 120-131 (2015) [2] Farukh Farukh, Emrah Demirci, Baris Sabuncuoglu, Memis Acar, Behnam Pourdeyhimi and Vadim A. Silberschmidt, Computational Materials Science, Vol. 94, Page 8-16 (2014)

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Switchable Directional Liquid Transport across a Single Layer Fabric Having Gradient Wettability Hua Zhou 1, Hongxia Wang 1, Haitao Niu 1, and Tong Lin 1 + Australian Future Fibres Research and Innovation Centre, Institute for Frontier Materials, Deakin University, Geelong, VIC 3217, Australia

Abstract: We herein report a functional single-layer fabric showing directional liquid transport ability to either water or oil fluids, just from one side to the other but not the opposite way. The fabric was prepared by asymmetrical irradiation of a superamphiphobic fabric with strong UV light. Depending on the irradiation time, the fabric showed directional liquid transport to different fluids. 24 hours UV treatment permits the fabric to directionally transport water. 14 hours UV treatment renders the fabric a directional transport ability to cooking oil, and 12 hours UV treatment gave the fabric transport ability to lower surface tension liquid, e.g hexadecane. More interestingly, the fabric’s original superamphiphobic effect can be restored by simply heating treatment at 130°С for 10 minutes. Such a “smart” fabric may find novel applications for functional clothing, catalysis, healthcare and environmental protection. Keywords: Directional liquid transport, Wetting gradient, Fabric

1. Introduction Along with the increased interest in durable super liquid-repellent technologies, multifunctional superhydrophobic surfaces have emerged with the purposes of meeting a variety of applications needs. “Smart” superhydrophobic surfaces being able to switch between superhydrophobicity and hydrophilicity triggered by an external stimulus, such as thermal, electrical, light, or redox reaction have been reported.[1-5] When superhydrophobicity, or even hydrophobicity, is combined regionally with hydrophilicity, remarkable ability to direct the motion of water drops may result. On natural surfaces where hydrophobicity and hydrophilicity exist alternately, water drops are inclined to move and coalesce in the hydrophilic areas.[6, 7] This phenomena has inspired the development of innovative water harvesting devices.[8] More controllable directional fluidmotion has been achieved on artificial surfaces through the formation of a wettability gradient [9-11]. However, most of the work has focused on water guidance across flat, open surfaces. Directional oil transport through thin porous membranes based on wettability heterogeneity is more desirable than that of only directional watertransport membranes, due to the expanded applications, such as oil/water separation and storage. We have reported that a fabric, after being treated by a wet-chemistry coating technique, can have a superdurable, self-healing superamphiphobic surface [13]. In this study, more interesting phenomenon has been found that the coated fabric can be switched to show a directional fluid-transport function for not only water but also oil fluids when it is irradiated with strong UV light. The fluid-transport function can be removed by a heating treatment, which in turn, restores the full superamphiphobicity of the surface. In this paper, we report on this novel fabric and its remarkable directional fluid-transport performances. A plain weave polyester fabric (thickness 520 µm) has been used as a sample porous membrane. Our method is based on a two-step solution coating technology to form a superamphiphobic layer containing PVDF-HFP/FAS/silica [13], and subsequent exposure of the one side of the superamphiphobic fabric to a multi-wavelength ultra-violet (UV) beam to make the irradiated fabric side hydrophilic, leading to the formation of cross-section wettability gradient.

2. Experimental section +

Corresponding author. Tel.: + 61-3-5227 1245. E-mail address: tong.lin@deakin.edu.au

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Materials: 1H,1H,2H,2H-perfluorodecyltriethoxysilane (C 16 H 19 F 17 O 3 Si) supplied by Sigma, and poly(vinylidene fluoride-co-hexafluoropropylene), dimethylformamide, tetraethylorthosilicate (98%), ammonium hydroxide (28% in water), oil red and oil blue obtained from Aldrich were used as received. Commercial polyester fabric (plain weave, 168 g/m2, thickness = 520 µm) was purchased from local supermarket. The preparation of superamphiphobic fabric: The superamphiphobic coating solution was prepared according to our previously reported method [18]. The fabric substrate was immersed in the silica particulate solution for 1 minute. After drying at room temperature for 10 minutes, the coated fabric was immersed in PVDF-HFP/FAS solution for 1 minute and finally dried at 130 °C for 1 hour. Other characterizations: Contact angle measurements were carried out on a contact angle goniometer (KSV CAM 101) using liquid droplets of 5 µL in volume. X-ray micro-Tomography (micro-CT) is a non-destructive technique for visualizing features in the interior of 3D solid objects. The breakthrough pressure was measured using customer-built equipment comprising a fluid-feeding system with a flow rate controller, a pressure gauge and a fabric holder.

3. Results and Discussion Upon irradiating with UV light (middle-pressure Hg lamp 450W) from one side of the coated fabric, the fabric showed a decrease in liquid-repellent property. As shown in Fig. 1a, after 10 hour UV treatment, the fabric can be wetted by hexadecane, while the soybean oil and water droplets can stay on the irradiated surface. And the 14 hours treated fabric can repel water only, and be wetted by soybean oil and hexadecane. After 24 hour UV irradiation, the irradiated fabric surface is hydrophilic. Once the irradiated fabric was heated at 130 °C for 10 minutes, its original superamphiphobicity reappeared as seen in Fig. 1a. Fig. 1 (b & c) show the SEM images of the coated fabric of before and after 24 hours of UV irradiation, which indicates that the UV irradiation did not change the surface morphology. More interestingly, when liquid was dropped on the back side of the UV irradiated fabric, depending on the irradiation condition and the liquid used, the droplet showed different wetting behaviors. For 10 hour UV irradiation fabric, hexadecane can spread on the front surface of the fabric, it did not penetrate through the fabric and wick to the other side. When hexadecane was dropped onto the back side which did not receive the UV irradiation directly, it moved through and spread on the front side immediately. For soybean and water, they cannot wet the fabric from either side. After 14 hour UV irradiation treatment, however, the cooking oil can spread on the front surface, but did not penetrate through the fabric, and the soybean oil can move through and spread on the front side immediately when it dropped from the back side. Fig. 1d shows the series of frames taken from video of cooking oil transport on either side of the coated fabric after 14 hour UV irradiation treatment. The coated fabric showed directional wetting effect to water, when it was subjected to a UV irradiation for 24 hours under the same condition as shown in Fig.1e, but the irradiated fabric can be wetted by both hexadecane and soybean oil on both sides. These results clearly demonstrate that the coated fabric develops unique directional fluid transport ability after an asymmetric UV irradiation treatment. The ability to directionally transfer fluids is determined by the UV irradiation time. Shorter irradiation time favors fluids of lower surface tension.

Fig. 1 a) photos of blue colored water droplets, red colored hexadecane droplets and clear soybean oil droplets on the coated polyester fabric and after 10 hours, 14 hours and 24 hours UV irradiated fabrics, and the heated fabric (10 µL for each drop; The small amount of dye used, reactive blue in water, oil red in hexadecane, had no influence on the contact angles), b & c) SEM images of the coated polyester fabric of b) before and c) after

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24 UV irradiation treatment, d & e) still frames taken from videos showing dropping soybean oil (45 µl) on the parallel placed polyester fabric (after 14 hours of UV irradiation), d) dropping from top to bottom, on front side (1~5, time interval, 0.13s) and back side (1’~5’, time interval, 0.7s), e) dropping water on front side (top, time interval 0.65s) and back side (bottom, time interval 0.2s). To understand the novel wetting effect, the CA on the front and back side of the UV irradiated surface was measured. The CA of front fabric surface after different UV irradiation time is shown in Fig. 2a. After 10 hours UV irradiation, the front side CA is 0° for just hexadecane, the irradiated surface is still amphiphobic for water and soybean oil. Long UV irradiation time, i.e. 14 hours, the CA of the front surface to soybean oil and hexadecane became 0°, however, the CA to water was still 120°. After 24 hours of UV irradiation, the irradiated front surface was wettable to all the three liquids with a CA of 0°. This suggests that the UV irradiation decreases the liquid repellency of the coated fabric, and the wettability increases with increasing the irradiation time. Due to the directional fluid-transport effect, directly measuring the CA on the back side of the UV-irradiated fabric was difficult. Alternatively, an indirect method was employed by irradiating two layers of the same fabric, which were closely in contact with each other, and testing the front surface of second fabric layer. As shown in Fig. 2a, after 10 hours of UV irradiation, the CA changed to 166°, 158° and 150° for water, soybean oil and hexadecane, while after 24 hours of UV treatment, the CA decreased to 160°, 130° and 80° for these liquids, respectively. This result also demonstrates that the UV irradiation completely penetrates the fabric layer but is significantly absorbed and weakened. To further characterize the directional fluid-wetting effect, the initial pressure required to make the fluids breakthrough the fabric was measured. As shown in Fig. 2b, at least 1.96 kPa of pressure was needed for water to break through the coated fabric from the UV irradiated side when the fabric was subjected to 24 hours of UV irradiation, whereas the breakthrough pressure on the back side was only 0.29 kPa. Lower pressure of 1.76 kPa and 1.57 kPa were measured for soybean oil and hexadecane to break through the front side of the coated fabric after it was UV irradiated respectively for 14 and 10 hours. However, the corresponding pressures on the back side were only 0.29 kPa and 0.25 kPa, respectively (Fig. 2b). For comparison, the breakthrough pressure of the un-coated pristine polyester fabric was measured to be 0.29 kPa, 0.26 kPa and 0.24 kPa for water, soybean oil and hexadecane, respectively, with no difference shown on either side. X-ray microtomograph (micro-CT) is a non-destructive method to observe the space morphology of 3D objects. It was to understand the wetting state of the fabric to different fluids. Fig. 2c shows a typical 3D image of the coated fabric after 14 hours UV irradiation from one side. 3D photos obtained from the 3D image at different layer inside the fabric showed different degrees of wetting. One side of the fabric was totally wetted by soybean oil, while the opposite was dry. The wetting thickness is around 268 µm. The wicking portion of the wetted fabric can be calculated from the cross-section of the partially wetted fabric, the results are shown in the Fig. 2d. After 10 hours UV irradiation, the wicking portions are 0%, 20% and 74% to water, cooking oil and hexadecane, with increasing the UV irradiation time, the liquid wicking portions increased, after 24 hours UV irradiation, the wicking portions are 62%, 100% and 100% to water, soybean oil and hexadecane. This confirmed that increasing UV irradiation time can decrease the fabric liquid repellent property, so that, the fabric treated with different time of UV irradiation will show the directional transport effect to different liquids.

Fig. 2 a) CA changes with the UV irradiation time on back side and front side (UV irradiated side), b) Pressure required to break through the coated fabrics (from front side for -■- water, -●- soybean oil, and -▲- hexadecane; from back side for -□- water, -О- soybean oil, and -∆- hexadecane), c) 3-D micro-CT image of the 14 hour UV irradiated fabric, d) wetting portion changes for different liquids with the increased UV irradiation time. However, once the irradiated fabric was heated at 130 °C for 10 minutes, its directional fluid-transport function was eliminated with the superamphiphobicity reappearing on both sides. The switch between the directional fluid-transport and the superamphiphobicity features was reversible and can be repeated a number of times.

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4. Conclusion The coated fabric in this study showed highly liquid-repellent property not only to water, but other liquids with lower surface tension such as cooking (surface tension is 31.5 mN/m) and hexadecane (surface tension is 27.5 mN/m). When the fabric was irradiated by a strong UV light, the directly irradiated surface became hydrophilic while the back side still maintained the superhydrophobicity or even amphiphobicity. This transformation from superamphiphobic to hydrophilic surfaces was attributed to an asymmetric wetting gradient across the thickness of the fabric. Such asymmetric superamphiphobicity/hydrophilicity can enable the fabric to have a directional fluid-transport functions not only to water, but to oils such as soybean oil and hexadecane under different UV treatment conditions: the fluid can easily transfer across the fabric in the direction from the superamphiphobic to the hydrophilic sides, but not in the opposite direction unless a sufficient external force is applied. The directional liquid-transport fabric also showed an apparent difference in the critical pressure allowing liquid to break through from the two fabric sides. More interestingly, once the irradiated fabric was heated at 130째C for 10 minutes, its directional liquidtransport function was eliminated with the superamphiphobicity reappearing on both sides. The switch between the directional liquid-transport and the superamphiphobicity features was reversible and can be repeated a number of times. The directional water transfer fabrics may find applications in various areas especially for those that involve fluid transport in both daily life and industry.

5. References [1] Sun T, Wang G, Feng L, Liu B, Ma Y, Jiang L, et al. Reversible Switching between Superhydrophilicity and Superhydrophobicity. Angewandte Chemie International Edition. 2004;43(3):357-60. [2] Feng X, Zhai J, Jiang L. The Fabrication and Switchable Superhydrophobicity of TiO2 Nanorod Films. Angewandte Chemie International Edition. 2005;44(32):5115-8. [3] Xu L, Chen W, Mulchandani A, Yan Y. Reversible Conversion of Conducting Polymer Films from Superhydrophobic to Superhydrophilic. Angewandte Chemie International Edition. 2005;44(37):6009-12. [4] Verplanck N, Coffinier Y, Thomy V, Boukherroub R. Wettability switching techniques on superhydrophobic surfaces. Nanoscale Research Letters. 2007;2(12):577-96. [5] Sinha AK, Basu M, Pradhan M, Sarkar S, Negishi Y, Pal T. Redox-Switchable Superhydrophobic Silver Composite. Langmuir. 2011;27(18):11629-35. [6] Parker AR, Lawrence CR. Water capture by a desert beetle. Nature. 2001;414(6859):33-4. [7] Zheng Y, Bai H, Huang Z, Tian X, Nie FQ, Zhao Y, et al. Directional water collection on wetted spider silk. Nature. 2010;463(7281):640-3. [8] Bai H, Tian X, Zheng Y, Ju J, Zhao Y, Jiang L. Artifi cal Spider Silk: Direction Controlled Driving of Tiny Water Drops on Bioinspired Artificial Spider Silks. Advanced Materials. 2010;22(48):5435-. [9] Daniel S, Chaudhury MK, Chen JC. Fast Drop Movements Resulting from the Phase Change on a Gradient Surface. Science. 2001;291(5504):633-6. [10] Fang G, Li W, Wang X, Qiao G. Droplet Motion on Designed Microtextured Superhydrophobic Surfaces with Tunable Wettability. Langmuir. 2008;24(20):11651-60. [11] Lai YH, Yang JT, Shieh DB. A microchip fabricated with a vapor-diffusion self-assembled-monolayer method to transport droplets across superhydrophobic to hydrophilic surfaces. Lab on a Chip. 2010;10(4):499504. [12] Tian X, Li J, Wang X. Anisotropic liquid penetration arising from a cross-sectional wettability gradient. Soft Matter. 2012;8(9):2633-7. [13] Zhou H, Wang H, Niu H, Gestos A, Lin T. Robust, Self-Healing Superamphiphobic Fabrics Prepared by Two-Step Coating of Fluoro-Containing Polymer, Fluoroalkyl Silane, and Modified Silica Nanoparticles. Advanced Functional Materials. 2012:n/a-n/a.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Sustainable Fibre Production and Textile Wet Processing for Better Tomorrow Lalit Jajpura B.P.S. Mahila Vishwavidyalaya, Sonipat-131305, Haryana, India

Abstract. Textile and apparel sector plays a pivotal role in global economy. Though it is veracity that fibre production and textile wet processing are devastating the environment by depleting the water resources and discharge of toxic chemicals. Natural fibres like cotton needs huge amount of water, fertilizers and pesticides whereas extensively used man made fibres such as viscose and polyester have their own problems in production and in dispose off. Further, textile wet processing operations such as desizing, scouring, bleaching, dyeing, printing, finishing etc., requires different types of acids, alkalis, oxidising and reducing agents, surfactants, dyes and pigments, thickeners, auxiliaries, finishing agents, etc. Most of the textile industries drain their effluent as such without required treatment. The discharged toxic chemicals are responsible heavily for land, water and air pollution. The used toxic chemicals in fibre cultivation, production and textile wet processing have great impact on environment and biodiversity. Thus there is dire need to find out eco friendly sustainable alternative processes as well as chemicals to traditional used practices. The cultivation of organic cotton and production of sustainable man made fibres such as liocell, polylactic acids fibres are great hope for greener fibre production. The application of enzymes such as amylase, lipase, pectinase, cutinase, cellulase, protease, sericinase, catalase, laccase, etc has important role in ecofriendly textile wet processing. The certain free and immobilised enzymes can also be applied to remove dyes and toxic chemicals from effluent. Beside these renewable natural materials such as natural dyes, chitosan, sericine, etc can be employed as sustainable dyeing and finishing agents. The present paper emphasises on various eco-friendly, sustainable fibre production and textile wet processing techniques which can be explored in future. Keywords: cotton, organic cotton, bast fibre, banana fibre, chitosan, sericin, dextrin, enzymes

Introduction

Definitely with the developments in technology and sciences, human being is benefited at the cost of tremendous compromises in environment and biodiversity due to the applications of synthetic non biodegradable toxic materials. The heaps of non biodegradable toxic waste synthetic materials are increasing day by day as threat for all living entities. Therefore there is utmost requirement to shift towards the biodegradable, ecofriendly sustainable textile raw materials as well as environment friendly processing. Similarly, eco-friendly textile wet processing with sustainable chemicals is required to minimize the effluent load. In foregoing section few eco-friendly fibres or textile raw materials, biopolymers, processes have been discussed in brief.

2. Sustainable fibres Cotton is a renewable natural fibre, however its cultivation requires huge amounts of water in irrigation varying from approximately 7 to 29 tons per kg of raw cotton fibres fibres [1]. Number of fresh water resources had dried up due to this reason, even the Aral Sea in central Asia has reduced to a small percentage of its original size, resulting in an almost complete loss of biodiversity in the region. Cotton is associated with various negative effects such as eutrophication, nitrate contamination, increase in soil salinity, etc due to abundant usage of water, pesticides and fertilizers. As per the study in context to India, consumption of fertilizers increased from 0.305 million in 1959-1960 tonnes to 20.34 million tonnes in 2005-06 [2]. Similarly, application of pesticides in India has also increased several hundred folds, from 154 MT in 1954 to 88,000 MT in 2000-2001. Approximately more than 54% of the total pesticides used in Indian agriculture are consumed on cotton alone, though it accounts for only 5% of the total cultivated area [3]. __________________________________________ + Corresponding author. Tel.: + 91-9996008431.

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E-mail address: lalitjajpura@yahoo.com.

Due to consequences of aforesaid toxicity people especially in cotton growing areas are suffering from cancer, mental retardation, epilepsy, etc diseases. The sustainable organic cotton, bast fibres and agro based raw materials have great scope for future as an alternative to conventional cotton and non biodegradable synthetic fibres.

2.1. Organic cotton Organic cotton is cultivated without synthetic chemicals with self relying on all available natural resources. The cultivation of organic cotton is carried out by integration of many resources and processes such as sustaining soil fertility with manure or biofertilizers, crop covering, crop rotation, strip cropping, no or less tillage, optimum water use by water harvesting, natural pesticide if required, mechanical pest and weed management, etc.

2.2. Bast, bamboo, banana and other non-conventional plant fibres Bast fibres such as sisal, jute, hemp, remie, linen, kenaf, abaca, etc are best examples of sustainable fibres as they need no or negligible pesticide and fertilizers applications than cultivation of cotton. Although, their water or dew retting processes and disposal of associated biomass are well known reasons of water pollution. Therefore, it is needed to employ novel methods such as enzymatic retting instead of conventional water/ dew retting. If these bast fibres and associated bio mass are handled properly than they can substitute cotton and other synthetic fibres significantly in favour of sustainable soil fertility with cleaner and greener environment. Banana is the worldâ&#x20AC;&#x2122;s second most important fruit crop after oil palm. It is grown in 130 countries worldwide, with having more than 71 million metric tonnes production worldwide [4]. The billion tons of banana stems are discarded without any use after the fruit harvesting. There is excellent possibility to utilise this banana stem at the full extent similar to already used abaca/ manila hemp fibre. Beside these sustainable fibres there are huge amount of other agro based byproducts produced globally. These raw materials can be used for pulp and fibre making. The agro based bio product such as corn (stover/stem/leaf), wheat (straw), rice, sorghum, barley, coir, sugarcane (bagasse fibres), pineapple, sponge gourd, etc may be boon for sustainable world if utilised efficiently. Similarly, bamboo grows naturally without applications of any fertilizers, pesticides or irrigation, with approximately 8-10 times more yield per acre than cotton. It can be used as bast fibres in ecofriendly way or converted in to the regenerated viscose form.

2.3. Regenerated fibre based on solvent spinning The regenerated man made fibres such as viscose rayon is imposing great threat to environment due to use of toxic acids, alkalis, xanthates, etc. The ecofriendly solvent spun fibre i.e. Lyocel may be explored as alternative to conventional viscose due to requirement of fewer chemicals, water and land use. The process cycle of Lyocel is eco friendly in nature as used solvent NMMO is recycled up to 99.9% as well as production time is also less.

2.4.

Biodegradable Polyester PLA Fibre

PLA has number of applications in various industries such as food, chemicals, pharmaceuticals, packaging and textile as sustainable plastic material due to biocompatible, biodegradable, non-toxic, etc favourable properties. The sustainable PLA has best suitable eco-friendly solution to non-biodegradable synthetic polymeric material. It is also ranked as best polymer on the basis of green design principle and stands at sixth position based on LCA evaluation as it needs low energy than most of the synthetic fibres [5].

3. Biopolymer The renewable, biodegradable biopolymers such as chitosan, sericine, cyclodextrine, etc are sustainable polymeric materials and employed in various applications of textile and other industries.

3.1.

Chitosan

The waste product of shells of crab, shrimp, prawn, krill, etc accumulates nearby the sea shore or sea food industries and emits foul smell if not disposed properly. These renewable biodegradable waste products are the best available sources of high nitrogen containing chitin and chitosan. Chemically, chitin (C 8 H 13 NO 5 ) n is a (1->4)â&#x20AC;&#x201C;linked 2-acetamido-2-deoxy-Î˛-D-glucan, and chitosan (C 6 H 11 NO 4 ) n is N-deacetylated derivatives of chitin. It has wide applicability in textiles such as in shrink resistance, dye exhausting, antibacterial, coagulating, chelating and anti-static agent. It is very much suitable in wound dressing, in absorbing heavy

Page 1082 of 1108

metal from effluent, etc. Although conversion of chitin to chitosan requires huge amount of toxic alkali and energy but now ecofriendly conversion is also realized by enzymatic process. In future, its production and application will increase many folds due to its ecological and environmental friendly properties.

3.2.

Sericin

Silk consists approximately 20-30% of an amorphous matrix of a water-soluble, biodegradable globular protein molecule known as sericin. In general, it is separated from silk in degumming process and discarded as such in effluent. Extraction of sericin from the degumming liquor not only decreases the load in discharged effluent of silk industries but also provides novel sustainable biopolymer having numerous profitable properties. Across the world, overall yearly cocoon production is more than 400,000 metric tons therefore large amount of sericin can be obtained as by product if extracted efficiently [6]. The polymer has valuable properties such as moisture absorption, UV resistance, cell protection, antioxidant, biocompatibility, anti-bacterial, anticoagulant wound healing, radical scavenging, anticancer, which makes it suitable for textiles and industries [7].

3.3.

Cyclodextrins (CDs)

Cyclodextrins are obtained from enzymatic hydrolysis of starch. These molecules are of a great interest for scientists due to biodegradability and of their capacity to include guest molecules in their cavities. The interior of cyclodextrin is hydrophobic and exterior is hydrophilic in nature. It can absorb number of toxic chemicals (phenols, aniline, dye residues, formaldehyde and others) from effluents. The biocompatibility and effective degradability of the low cost biopolymer make it suitable for bioremediation. In textiles, it can be used for controlled release media for drugs and flavours, dyes and auxiliaries removal from effluents, retarding agents in dyeing and finishing reactions, protection of dyes from undesired aggregation and adsorption.

4. Development in wet processing The textile wet processing from pre-treatment to finishing employs various toxic chemicals. The effects of dyes on water, ecology and associated biodiversity is tremendous as over 7 million tons of more than 10000 dyes are annually produced and out of which approximately 200,000 tons of these dyes are lost to effluents during the dyeing and finishing operations [8]. Beside dyes, various non biodegradable toxic auxiliaries and finishing agents employed in pre treatment, printing and finishing operations also pollute the environment to a great extent. Due to extreme toxicity, certain chemicals such as ortho-phthalates, halogenated compounds (AOX), azo dyes and released harmful amines, chlorobenzenes and chlorophenols, heavy metals (cadmium, lead, mercury, chromium (VI)), APEOs/NPEs, perfluorinated chemicals (PFCs), formaldehyde, etc are totally restricted [9]. Various certified agencies or certify marks such as GOTS, ISOT, Oeko-Tex 100, Fairtrade, EU ECO, etc. are really playing the crucial role by increasing the awareness amongst the customers on toxic chemicals and their hazards as well as on concerns issues discussed in earlier sections [10-11]. Load on effluent may be minimized by avoiding aforesaid toxic chemicals with use of highly exhaustive and high affinity ecofriendly degradable dyes with appropriate dyeing procedures. It is also necessary to conserve water by employing efficient processing machines working at low material to liquor ratio. Ultrasound dyeing, foam finishing, supercritical carbon dioxide, plasma technology, spray dyeing, etc are few examples which may be utilized for eco friendly wet processing. Dyes and chemicals which decompose in effluent or in environment in sustainable way must be given priority instead of mere dye fastness and cost factor. There are great possibility to replace toxic chemicals by applications of biopolymers as well as natural dyes and enzymes.

4.1.

Natural dyes

Synthetic dyes replaced the natural dyes due to mass production at low cost with good fastness, levelling and reproducibility properties. Now only about 1 % of the total textiles produced are dyed by using natural dyes [12]. But there are great scopes for numbers of natural dyes which may be obtained or extracted by product of food (pomegranate rind, onion peel off, grape skins), tree, flower waste, etc. These natural dyes are renewable and ecofreindly in nature but it is essential to choose appropriate mordant as certain heavy metals used as mordant (Cr, Cu, etc) are toxic. Natural and herbal dyes with medicinal properties with natural or ecofriendly mordants are great hope as substantive dyeing of textile materials.

4.2.

Enzymes applications

The enzymes are precious biodegradable proteineous molecules used as biocatalyst in various textile wet processing treatments as sustainable ecofriendly alternative to toxic used chemicals. Enzymes have capacity to replace various toxic chemicals in wet processing operations such as desizing, scouring, bio polishing of

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cellulosic and protein fibres, removal of scales of wool (defusing and shrink proofing), retting of bast fibres, carbonisation of wool, degumming of silk, laundering, bio bleaching, decolourisation and bio remediation of effluent treatment by employing suitable type of enzyme alone or in mixture. Although all the enzymes have their especial role in textile wet processing but laccase (E.C. 1.10.3.2) an oxidoreductase enzyme can replace various harsh chemicals such as replacement of chlorination treatment in anti-shrinking of wool and of delignification process in paper making, bio bleaching of cotton, fading of denim, discharge printing and catalyse the oxidation of various toxic aromatic compounds wonderfully. Due to its capacity in dye decolourisation or in bioremediation it has tremendous growth potential in textiles and other allied industries. The advancement in biotechnology such as RDNA, efficient extraction, mass production, immobilization, etc made possible to have enzymes with more activity, efficiency, longer shelf life, good thermal and chemical stability at low cost. It is sure that in coming future enzymes will play major role in sustainable textile production [13].

Conclusion

Nature is blessed with simple environment friendly raw material as well as numerous toxic hazardous substances. It’s up to us to choose between these two without considering the short term goals i.e. cost, efficiency, mass production, etc. Therefore, it is essential to harvest sustainable benefits of organic cotton, biopolymers, natural dyes, enzymatic operations, etc for better, greener and pollution free environment with full of biodiversity.

6. References [1] Eija, M. K., & Pertti, N. (1999) Life cycle assessment environmental profile of cotton and polyestercotton fabrics, Autex Research Journal, 1(1), 8-20. [2] Malik, R. P. S., & Sekhar, C.S.C. (2007, July) Research Study No 2007/4, Factors affecting fertilizer consumption in haryana, Delhi: Agricultural economics research centre, university of Delhi, website: http://www.du.ac.in/du/uploads/Academics/centres_institutes/Agricultural_Eco/3.2007Combined%20FACTORS%20AFFECTING%20FERTILIZER%20CONSUMPTION%20IN%20.pd f\ [3] Puri, S. N., Murthy, K. S. & Sharma, O. P. (1999) IPM for sustainable crop production, Management in Sundaram V et al, Handbook of cotton in India, Bombay: ISCI. [4] Sfiligoj, S. M., Hribernik, S., Stana, K. K., & Kreže, T., Plant fibres for textile and technical applications, Chapter 15, Advances in Agrophysical Research, Intech, 370 -398. http://dx.doi.org/10.5772/52372 [5] Tabone, M., Cregg, J., Beckman, E. & Landis, A., (2010) Sustainability metrics: life cycle assessment and green design in polymers, Environ Science and Technology, 44(21), 8264–8269. [6] Wu, J. H., Wang, Z., Xu, S.Y. (2007) Preparation and characterization of sericin powder extracted from silk industry wastewater, Food Chemistry, 103, 1255-1262. [7] Rangi, A. & Jajpura, L. (2015) The Biopolymer Sericin: Extraction and Applications. Journal of Textile Science and Engineering, 5:188. doi: 10.4172/2165-8064.1000188. [8] Ogugbue C. J. & Sawidis T. (2011), Bioremediation and detoxification of synthetic wastewater containing triarylmethane dyes by aeromonas hydrophila isolated from industrial effluent, Biotechnology Research International, DOI 10.4061/2011/967925. [9] Czarnowski, D. V. (2013, October) Sustainability Solutions for Textiles Chemical Discharge Monitoring Services (ZDHC), Bureau veritas, Website: https://www.wewear.org/assets/1/7/DirkVonCzarnowski_ENG.pdf [10] Global organic textile standards website: http://www.global-standard.org/ cited on 31st March 2015 [11] Clothing with certified responsibility website http://www.neutral.com/ on 31st March 2015 [12] Gulrajani, M. L. (1999) Present status of natural dyes. In: Book of papers of the convention on natural dyes. New Delhi: Department of Textile Technology, IIT Delhi. [13] Shukla, S. R., Jajpura, L., & Damle, A. J. (2003) Enzyme: The Biocatalyst for Textile Processes, Colourage Special issue on Textindia fair 7-9 Nov 2003, Club Melange, 41-47.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Synthesis of High-washable Azo Disperse Dyes containing a Fluorosulfonyl Group and Their Application to Cellulose Diacetate Hyunki Kim +, Hyun Jeong Kim, Hyunsang Cho and Joonseok Koh Department of Organic and Nano System Engineering, Konkuk University, Seoul 143-701, South Korea

Abstract. High-washable azo disperse dyes containing a fluorosulfonyl group and applicated to cellulose diacetate. Analyzed dyeing and fastness properties compared with conventional 4-aminoazobenzene dyes containing a nitro group. Found out proper hydrophobicity condition in dyeing of cellulose diacetate. Azo disperse dyes containing a fluorosulfonyl group are showed excellent wash fastness properties due to the outstanding wash-off properties compared with conventional azo disperse dyes. Keywords: disperse dye, cellulose diacetate, phthalimide, color fastness

1. Introduction Acetate fibres belong to the class of man-made cellulosic fibres and are manufactured by treating cellulose in the form of pure wood pulp or, less frequently, cotton linters, with a mixture of glacial acetic acid and acetic anhydride at low temperature in the presence of an activation catalyst such as sulphuric acid, perchloric acid, zinc chloride or similar salts. Cellulose diacetate, once widely known by its producer’s company name, Celanese, can be written and drawn in a similar manner to cellulose, except that between 77-80% of the hydroxyl groups have been acetylated by reaction with acetic acid, to give cellulose acetate esters. The demand for environmentally friendly dyes of high wet fastness on fabrics is increasing. As a result of current trends towards the increased use of finishing treatments and stringent wash fastness test criteria, previously satisfactory colorants are no longer suitable. In disperse dyeing of polyesters, dye remaining on the surface of the fabric can be cleared by a reduction clearing treatment (for 20 to 30 min at 70–80 °C in an aqueous bath containing 2.0 g/l sodium hydroxide and 2.0 g/l sodium dithionite) and this improves the fastness of the dyeing and also improves its brightness of shade. However, in case of disperse dyeing of cellulose diacetate, when reduction-clearing is carried out, the acetyl groups in cellulose acetate fibers may be alkalihydrolyzed, giving loss of their characteristic properties. Therefore, the dyed acetate fabrics are usually aftertreated with soaping agent at a relatively low temperature for the better wet fastness although it is not satisfactory enough to meet the customers’ demands. R4

R4 1

R O O S F

R N R7

N N R5 R2

O O S O-

R6 N R7

N N R5 2

Water-insoluble Water-soluble Affinity for Acetate High-Washability Scheme 1: Alkali-hydrolysis of an azo disperse dye containing a fluorosulfonyl group.

Corresponding author. Tel.: + 82-2-450-3512. E-mail address: s.mamunkabir@yahoo.com.

Page 1085 of 1108

In the present study, the azo disperse dyes containing a fluorosulfonyl group were synthesized (Table 1) and their dyeing and colorfastness properties on cellulose acetate fabrics were investigated. In particular, conventional 4-aminoazobenzene dyes containing a nitro group in the 4′-position were synthesized in order to compare their colorfastness properties on cellulose acetate with those of the azo disperse dyes containing a fluorosulfonyl group. The aim of this research was the investigation of the properties of alkali-clearable azo disperse dyes containing a fluorsulfonyl group with respect to their synthesis, alkali-hydrolysis kinetics and application cellulose diacetate fiber.

2. Experimental 2.1.

Materials

The chemicals used in the synthesis of a disperse dye and its intermediates were of laboratory-reagent grade. REAX 85A(Westvaco Corp.) and Dywell (DYWELL INC.) were used as dispersing agents for milling of the synthesized dye.

2.2.

Dye synthesis

Azo disperse dyes containing a fluorsulfonyl group were synthesized by fluorination, nitration and hydrolysis followed by coupling reaction. Dye dispersions were prepared in water. The dispersing agent (REAX 85A and Dywell), and the dye (1.0% owf concentration) were milled with glass beads for 1 week in 100 ml of water buffered at pH 4.0–4.5.

O Cl

O S

KF H2O / p-dioxane O F

O S O

HCl / EtOH

O S O

NH2

Scheme 1: Dye intermediates synthesis.

O F S O

NH2

NaNO2/HCl 0~5°C

0~5C0

O F S O

N2+

N N

Y N Z

C2H5 N C2H4OH

Scheme 2: Dye synthesis.

2.3.

Dyeing

Page 1086 of 1108

The reflectance and CIE LAB values of the dyed samples were measured using a spectrophotometer (Xrite 8000 Series, standard light D65, 10° standard observer, specular component included) interfaced with a personal computer. The color strength (f k ) is the sum of the weighed K/S values in the visible region, given by [3]:

fk =

700

∑ ( K / S )λ ( x

10 ,λ

λ = 400

+ y10,λ + z10,λ ) (2.1)

where X 10 , Y 10 and Z 10 are color matching functions for the 10° standard observer at each wavelength (ISO 7724/1-1984).

2.4.

Color fastness test

In order to evaluate the color fastness properties of the cellulose acetate fabrics, the dyed fabric was aftertreated with soaping agent followed by heat-setting at 150 °C for 45 seconds in a laboratory tenter (Texdryer, Daelim Starlet Co. Ltd.). Color fastness was determined according to the respective international standards: fastness to washing (ISO 105-C06 A2S), fastness to perspiration (ISO 105-E04), fastness to rubbing (ISO 105-X12), fastness to sublimation (ISO 105-P01) and fastness to light (ISO 105-B02). Change in shade and staining of adjacent multifiber (Multifiber DW, adjacent fabric, BS EN ISO 105-F10) were assessed using grey scales.

3. Results and Discussion 3.1.

Dyeing properties

Figure 1 illustrates the relative color strength (fk) of dyed cellulose diacetate fabrics depending on the amounts of dye applied (%owf). Conventional 4-aminoazobenzene dyes containing a nitro group and fluorosulfonyl based disperse dyes exhibited Similarly. The most hydrophobic dyes (Dye1) showed the lowest color yield probably due to the relatively lower hydrophobicity of cellulose diacetate fibers compared with polyester. Diacetate fabrics need proper condition of hydrophobicity in dyeing. 300

250

200

300

150

100

150

100

F-Dye 1 F-Dye 2 F-Dye 3

N-Dye 1 N-Dye 2 N-Dye 3

0 0

% o.w.f dye applied

Figure 1. Build-up properties of gluorosulfonyl based azo disperse dyes(F-Dyes) and 4aminoazobenzene disperse dyes (N-Dyes) Color Fastness properties N-alkyl phthalimide-based disperse dyes showed higher wash fastness on cellulose acetate fabrics compared with 4-aminoazobenzene disperse dyes.

3.2 Fastness properties Azo disperse dyes containing a fluorosulfonyl group showed better wash fastness on cellulose acetate fabrics compared with 4-aminoazobenzene disperse dyes (Tables 2)

Page 1087 of 1108

Table 2. Wash fastness of cellulose diacetate fabric dyed with fluorosulfonyl-based dyes Staining Dyes Change Wool Acryl PET Nylon Cotton Acetate F-Dye1

3-4

4-5

F-Dye2

4-5

F-Dye3

4-5

N-Dye1

4-5

3-4

2-3

4-5

N-Dye2

4-5

2-3

3-4

N-Dye3

3-4

4-5

3-4

2-3

1-2

4. Conclusions Synthesis high-washable azo disperse dyes containing a fluorosulfonyl group and application to cellulose diacetate compared with conventional 4-aminoazobenzene dyes containing a nitro group in the property of dyeing and fastness. Dye properties are exhibited similarly in the both case of dyes. In case of fastness properties Azo disperse dyes containing a fluorosulfonyl group showed better wash fastness on cellulose acetate fabrics compared with 4-aminoazobenzene disperse dyes. This result is probably attributed to the excellent washoff properties resulting from the easy clearability.

5. Acknowledgement This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2009-0066635)

6. References [1] E. R. Trotman, Dyeing and Chemical Technology of Textile Fibres (New York, USA: John Wiley & Son, 1984) [2] J-H. Choi, S-H. Hong, E-J. Lee and A.D. Towns, Color. Technol., 116 (2000) 273. [3] S M Burkinshaw, Chemical Principles of Synthetic Fibre Dyeing (Glasgow: Chapman and Hall, 1995) 68. [4] J. S. Koh and J. P. Kim, J.S.D.C., 114 (1998) 121. [5] A. G. Green and K. H. Saunders, J. Soc Dyers and Colourists, 40, 138 (1924). [6] J. S. Koh, J. P. Kim, "Synthesis of phthalimide based alkali-clearable azo disperse dyes and analysis of their alkalihydrolysis mechanism", Dyes and Pigments, 37(3), 265-272, 1998 [7] J. S. Koh, J. P. Kim, "Application of phthalimide based alkali-clearable azo disperse dyes onto polyester and polyester/cotton blends", Journal of Society of Dyers and Colourists, 114(4), 121-124, 1998

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Synthesis of N-alkylphthalimide-based High-washable Azo Disperse Dye and Their Application to Cellulose Diacetate Hyun Jeong Kim +, Hyunki Kim, Hyunsang Cho and Joonseok Koh Department of Organic and Nano System Engineering, Konkuk University, Seoul 143-701, South Korea

Abstract. N-alkylphthalimide-based easily high-washable azo disperse dyes were synthesized and their dyeing and fastness properties on cellulose diacetate fabrics were investigated. N-alkyl phthalimide-based disperse dyes showed relatively lower build-up properties than that of 4-aminoazobenzene disperse dyes, probably due to their lower substantivity towards cellulose diacetate fiber. However, phthalimide-based azo disperse dyes showed excellent wash fastness properties due to the outstanding wash-off properties compared with conventional azo disperse dyes.

Keywords: disperse dye, cellulose diacetate, phthalimide, color fastness

1. Introduction Cellulose acetates are esters of cellulose in which a large fraction or even all the hydroxyl groups have been esterified using acetic anhydride. The two major types of cellulose acetate have about 55 and 62% of combined acetic acid. These values correspond to cellulose with degree of substitution of 2.48 and 3.00, respectively. The latter is called cellulose triacetate, and the former is called cellulose diacetate. Cellulose diacetate can be written and drawn in a similar manner to cellulose, except that between 77-80% of the hydroxyl groups have been acetylated by reaction with acetic acid, to give cellulose acetate esters. Acetate fibers belong to the class of man-made cellulosic fibers and are manufactured by treating cellulose in the form of pure wood pulp or, less frequently, cotton linters, with a mixture of glacial acetic acid and acetic anhydride at low temperature in the presence of an activation catalyst such as sulfuric acid, perchloric acid, zinc chloride or similar salts Cellulose diacetate fibers are resistant to dilute solutions of acids but are sensitive to alkaline solution, which cause hydrolysis of the acetate ester to hydroxyl groups, especially at high temperatures. Cellulose diacetate fibers can be dyed only with disperse dyes due to their hydrophobic properties. In disperse dyeing of polyester fiber, reduction clearing is performed for the improvement of wet fastness of the dyed material. However, in case of disperse dyeing of cellulose diacetate, when reduction-clearing is carried out, the acetyl groups in cellulose acetate fibers are hydrolyzed, giving loss of their characteristic properties. Therefore, instead of reduction clearing, the dyed acetate fabrics are usually after-treated with soaping agent at a relatively low temperature for preserving their unique characteristics. In the present study, N-alkylphthalimide-based high-washable azo disperse dyes were synthesized and their dyeing and fastness properties on cellulose acetate fabrics were investigated. In particular, conventional 4-amino-azobenzene dyes containing a nitro group in the 4?-position were synthesized in order to compare their fastness properties on cellulose acetate fabrics with those of the N-alkyl phthalimide-based azo disperse dyes.

Corresponding author. Tel.: + 82-2-450-3512. E-mail address: bona111491@naver.com.

Page 1089 of 1108

2. Experimental 2.1.

Materials

2.2.

Dye synthesis

N-alkyl phthalimide-based azo disperse dyes were synthesized by nitration, alkylation and amination followed by azo coupling reaction with diethylaniline (Schemes 1 and 2). Dye dispersions were prepared in water. The dispersing agent (REAX 85A and Dywell), and the dye (1.0% owf concentration) were milled with glass beads for 1 week in 100 ml of water buffered at pH 4.0â&#x20AC;&#x201C;4.5.

Scheme 1: Dye intermediates synthesis.

Scheme 2: Dye synthesis. Table 1. The synthesized dyes in the present study

P-Dye Dye No. Dye1 Dye2 Dye3

N-Dye X H H H

Y C2H5 C2H5 C 2 H 4 OH

Z C2H5 C 2 H 4 OH C 2 H 4 OH

Page 1090 of 1108

Dye4 Dye5 Dye6

2.3.

CH 3 CH 3 CH 3

C2H5 C2H5 C 2 H 4 OH

C2H5 C 2 H 4 OH C 2 H 4 OH

Dyeing

Cellulose acetate fabrics were dyed in a laboratory infrared (IR) dyeing machine (DL-6000; Daelim Starlet Co., Korea) at a liquor ratio of 20:1. A 40-ml dyebath was prepared with formulated dye and a dispersing agent. The cellulose acetate fabric (2.0 g) was dyed in the dyebath for 60 min at 130oC and washed with soaping agent. The reflectance and CIE LAB values of the dyed samples were measured using a spectrophotometer (Xrite 8000 Series, standard light D65, 10° standard observer, specular component included) interfaced with a personal computer. The color strength (f k ) is the sum of the weighed K/S values in the visible region, given by [3]:

fk =

700

∑ ( K / S )λ ( x

10 ,λ

λ = 400

+ y10,λ + z10,λ ) (2.1)

where X 10 , Y 10 and Z 10 are color matching functions for the 10° standard observer at each wavelength (ISO 7724/1-1984).

2.4.

Color fastness test

3. Results and Discussion 3.1.

Dyeing properties

Build-up properties of N-alkylphthalimide based azo disperse dyes and 4-aminoazobenzene disperse dyes were investigated. Conventional 4-aminoazobenzene dyes containing a nitro group exhibited higher color yield at saturation points compared with N-alkyl phthalimide-based disperse dyes. Thus, in the dyeing of cellulose diacetate fiber, the substantivity of nitro derivatives which contain a p-nitro group in the diazo component was shown to be higher than that of N-alkylphthalimide based azo disperse dyes. The most hydrophobic dyes showed the lowest color yield probably due to the relatively lower hydrophobicity of cellulose diacetate fibers compared with polyester.

3.2.

Color Fastness properties

N-alkyl phthalimide-based disperse dyes showed higher wash fastness on cellulose acetate fabrics compared with 4-aminoazobenzene disperse dyes.

4. Conclusions The dyeing and fastness properties of N-alkylphthalimide-based azo disperse dyes and 4-aminoazobenzene disperse dyes containing a nitro group on cellulose diacetate have been investigated and compared. Nalkylphthalimide-based disperse dyes showed relatively lower build-up properties than that of 4aminoazobenzene disperse dyes, probably due to their lower substantivity towards cellulose diacetate fiber. However, the fastness properties of N-alkyl phthalimide-based azo disperse dyes were excellent. This result is probably attributed to the excellent wash-off properties resulting from the easy clearability imparted by the ring opening and ionization of N-alkyl phthalimide ring structure.

Page 1091 of 1108

5. Acknowledgement This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2009-0066635)

Page 1092 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Synthesis of Nanofibrillar Para-aramid Aerogel through Supercritical Drying Kazumasa Hirogaki1 +, Lei Du1, 2, Isao Tabata3, and Teruo Hori4 1

Frontier Fiber Technology and Science Course, Graduate School of Engineering, University of Fukui, 3-91, Bunkyo, Fukui-shi, Fukui 910-8507, Japan 2 School of Fashion Design & Engineering, Zhejiang Sci-Tech University, Hangzhou (310018), China 3 Technical Division, University of Fukui, 3-9-1, Bunkyo, Fukui-shi, Fukui 910-8507, Japan 4 Headquarters for Innovative Society-Academia Cooperation, University of Fukui, 3-9-1, Bunkyo, Fukuishi, Fukui 910-8507, Japan

Abstract. Para-aramid fiber used as the precursor was dissolved in the solution of dimethyl sulfoxide / tetrabutylammonium fluoride, then regenerated in a poor solvent and dried by the supercritical CO 2 to obtain an aerogel. The acetone was the appropriate solvent for regenerating. It was found that the wet gel in the solvent of methanol, ethanol or water induced large shrinkage and opaque appearance, while the sample in the acetone had less shrinkage in size and kept transparent. In our investigation, the most suitable condition of temperature was 80 Â°C and the pressure was 10 MPa. The depressurization time was 3 hours with setting the releasing rate (Î&#x201D;p / MPa) as 0.01. Under this condition, the volume of the gel was remained as 43.5 % after drying. It reveals that it is effective in preserving the nanoporous structure to keep the process of depressurization staying away from the critical temperature and using the smaller density change at the critical pressure of CO 2 . The aerogel was characterized by the density measurement, the scanning electron microscope observation, and the nitrogen adsorption method. The aerogel, which was prepared in the optimal condition, has regular bundles of molecular chains with the width about 20 nm. The bundles of molecular chains cross-linked each other and formed the 3D-network structure. In this structure, there are lots of nanopores with the average pore size of 11.4 nm, and with the modal pore size of 0.77 nm. Besides, the nanopores were open-pores cross-linked each other. The aerogel has large specific surface area of 510 m2/g and density is as low as 0.083 g/cm3 (up to 94.3% of porosity). It also exhibited yellow translucent appearance. On the basis of these results, the aramid aerogel fiber with the diameter of about 100 Âľm was also prepared by the optimal drying condition. The aerogel fiber was flexible and bended without deformation or breaking of the fiber. Keywords: Aerogel, para-aramid, supercritical carbon dioxide, nanofibrillar structure, nanoporus structure.

1. Introduction Aerogels are lightweight for their only containing about 1-15% solid material with their outstanding surface area and high porosity. They have been expected to be widely used as thermal or sound insulations, particle filters, particle trappers and adsorbents. However, most of the aerogels share with the same shortage, which are described as their poor mechanical property. Nowadays two of the most sophisticated aerogels are cellulose-based aerogel and silica aerogel. Those aerogels also have some insurmountable shortages such as inflammability and fragile. Therefore it is essential to find the new material to overcome the shortages. We investigated to use the para-aramid fiber as the precursor of the aerogel. The para-aramid fiber is widely used as protective materials since it has high modulus, strong strength and the flame retardance. It was dissolved in the solution of tetrabutylammonium fluoride (TBAF) / dimethyl sulfoxide (DMSO). Then it was regenerated, aged and dried by several conditions to find the best solvent to regenerate the aramid wet gel [1]. We tried to find the optimal method to dry the aerogel and present the relation between the quality of the aramid aerogel

Corresponding author. Tel.: + 81-776-28 8631. E-mail address: hirogaki@u-fukui.ac.jp.

Page 1093 of 1108

and drying condition [1]. And we also tried to create the flexible aramid aerogel fiber based on the results of the investigation.

2. Experimental section 2.1.

Preparation for the solution

The appropriate amount of TBAF and DMSO were mixed to obtain solution with a weight ratio of 1:11 of TBAF / DMSO. To remove the water from the solution, we added the excess amount of CaH 2 . We stirred the solution at 25 °C higher than the melting point of DMSO for 48 hours and kept in standing for 24 hours to accelerate the reaction of CaH 2 with water. At last the solution was centrifuged replications by the centrifuge machine.

2.2.

Preparation for the wet gel

The para-aramid fiber was washed by deionized water and ethanol. Then it was put in the drying oven for 3 hours at 120 °C. After that the dried fiber with content of 1.0 wt% was put in the solution of TBAF / DMSO during heating and stirring (80 °C, 250 rad / min). The procedure to dissolve the para-aramid fiber took 60 minutes. The hot solution was poured into the desired form by mold and cooled down to the room temperature. The samples were regenerated to get a wet gel in several kinds of solvent, which were ethanol, water, methanol, and acetone for 24 hours, respectively. Then the solvent exchanging step was repeated three times and each replication took more than 24 hours.

2.3.

Drying methods

The samples were dried in the supercritical CO 2 to remove solvent. The samples were placed with the dishes into the high pressure vessel. The vessel was closed and heated to the drying temperature. The liquid CO 2 from a storage tank was pressurized to set pressure and then the CO 2 was introduced into the vessel. After that, the condition set was kept for 4 hours. The final step the pressure was released to atmospheric pressure by the Back-Pressure Regulator. There were seven kinds of conditions of supercritical CO 2 drying as shown in Table 1. And the △P/MPa 0.01 was set as the releasing rate under all the conditions. Table 1: Conditions of supercritical CO 2 drying and properties of aramid aerogel.

Shrinkage Density Pressure Depressurizatio Specific surface Modal pore (MPa) n time (h) size (nm) (%) (g/cm3) area (m2/g) 1 20 3 57.7 0.088 430 0.77 2 10 → 20a 3 57.7 0.096 460 0.77 3 10 3 56.5 0.083 510 0.77 4 20 6 71.9 0.157 390 0.67 5 20 1 58.4 0.135 210 0.72 6 10 3 94.7 0.871 7 20 3 94.5 0.692 a The sample was dried at 40°C for 4 hours and then the temperature was risen to 80 °C for releasing CO 2 . No.

2.4.

Temperature (°C) 80 40 → 80a 80 80 80 40 40

Average pore size (nm) 11.6 11.7 11.4 11.8 11.6 -

Analytical methods

The density of the samples was depended on their geometric volumes and their mass. The specific surface area was examined by the BET method and pore size distribution was determined by the H-K method [2] with the nitrogen adsorption. The microstructure was observed with a thermal field emission scanning electron microscope.

3. Results and discussion 3.1.

Effects of solvent for substitution

Four kinds of solvents were used to regenerate the wet gel. It was found that the wet gel in the solvent of methanol, ethanol or water induced large shrinkage and opaque appearance, while the sample in the acetone had less shrinkage in size and kept transparent as shown in Fig. 1. This means that the acetone can remove the fluorine effectively with no change in shape and transparency of the sample. The reason might be that the acetone has the highest similarity with the para-aramid fiber in terms of the solubility parameter, which is 20.25 (J/cm3)1/2 and 23 (J/cm3)1/2, respectively [3]. The solubility parameter of ethanol is 26.39 (J/cm3)1/2 and the methanol is 29.73 (J/cm3)1/2 [4]. In other words, the acetone has more affinity with aramid fiber than other solvents. It can prevent from aggregating molecular chains.

Page 1094 of 1108

(c)

Fig. 1: Photographs of the wet gels: (a) solution before regeneration, (b) the wet gel substitution in the acetone, (c) the aerogel prepared by the condition of No. 3 in Table 1 with the thickness 0.5 mm.

3.2.

Drying condition

The properties of the aerogels in different drying conditions are provided in the Table 1. The gels dried by the condition of NO. 6, and dried by the condition NO. 3 as described in the Table 1 are presented in the Fig. 2 respectively. It is quite different from each other, the gel dried by the condition of NO. 6 shrank greatly. According to the Table 1, the final results were highly related to the temperature, pressure, and the time of depressurization. In fact, it can be concluded that the critical point and the density of CO 2 can significantly affect the drying of the samples. As displayed in Fig. 3, it can be easily found that the density change of scCO 2 around the critical pressure is more gradually at 80 째C than at 40 째C. Rapid density change will result in destruction of the nanoporous structure. When we compare the characters of the sample dried by the condition of the NO. 2 and the NO. 3, we have found another evidence showing that the temperature of depressurization will affect the result and it looks like that the drying temperature has no large influence. The other impact on the character of the aramid aerogels is the density of CO 2 which is decided by the temperature and pressure. The lower density will exchange the acetone slowly that contributes to keep the nanopores. This was demonstrated by the sample dried in the condition of the NO. 3, which is considered as the most appropriate condition. We can see it clearly the sample is transparent and it is an attractive result.

CO2 density / g/cm3

1.0 No. 6

0.8

40 oC, 40 oC, 80 oC, 80 oC,

10 MPa 20 MPa 10 MPa 20 MPa

0.6 No. 1

0.4 No. 7

0.2 No. 3

0 0

Fig. 2: Photographs of the dried gel: (a) the aerogel dying in the condition of No. 3, (b) the aerogel dying in the condition of No. 6 in Table 1.

80 120 Time / min

160

200

Fig. 3: Density behavior of CO 2 calculated by compressive factor: (1) the condition of NO. 1, (2) NO. 3, (3) NO. 6, (4) NO. 7 in Table 1.

The depressurization time also has a large influence in the quality of the aerogel. The most appropriate depressurization time is 3 hours since 1 hour is too rapidly to depressurize, while 6 hours is so long that may make the sample being exposed at high temperature. The samples depressurized with 1 hour or 6 hours changed to less transparent and shrink more compared to the one depressurized with 3 hours, as shown in Table 1 No. 1 , 4, and 5.

Page 1095 of 1108

The sample dried in the condition of the NO. 3 with the average pore size of 11.4 nm and the modal pore size of 0.77 nm were obtained from the BET method. We think there are also many small pores on the surface of the bundles of molecular chains that we could not observe clearly by the SEM in Fig 4. The sample has large specific surface area of 510 m2/g and very low density of 0.083 g/cm3. On the basis of the density of paraaramid fiber (1.44g/cm3) and the density of air (0.00129 g/cm3), the air volume within it should be up to 94.3 %. From the SEM observations of sample dried in the condition of the NO. 3, we can find the rod-like shape of regenerated aramid fiber, as shown in Fig. 4a. With the clear observation, there are regular bundles of molecular chains and these bundles are cross-linked with each other, leading to the formation of hierarchical and the corresponding nanoporous structure as shown in Fig. 4b. This is also the reason for the large specific surface area in the BET measurement. And then the width of the bundles ca.20 nm observed from Fig. 4c.

Fig. 4: SEM micrographs of the aerogel dying in the condition of No. 3 in Table 1.

3.3.

Preparation of aerogel fiber

In order to overcome fragile of the traditional aerogel, the para-aramid aerogel fiber with the diameter about 100 µm was prepared by the optimal drying condition of No. 3 in Table 1. The obtained aerogel fiber has translucent appearance and it was constructed from nonofibrillar network of molecular chain bundles similar to the bulk aerogel as shown in Fig. 5. We could bend the aerogel fiber freely without deformation or breaking of the gel.

100 µm

100 nm

Fig. 5: Photograph (left) and SEM micrograph (right) of the aerogel fiber prepared by the condition of No.3 in Table 1.

4. Conclusion The new highly nanoporous aerogel was prepared from para-aramid fiber dissolved in solution of DMSO / TBAF. The acetone is proved as the most appropriate solvent for regenerating and exchanging. The most suitable condition of temperature is 80 °C and the pressure is 10 MPa. The drying time is 4 hours and the depressurization time is 3 hours with setting the releasing rate (△p/MPa) as 0.01. The obtained aerogel has high cross-linked structure consisting of nanometer-sized regular bundle of molecular chains. It also reveals that it is effective in preserving the nanoporous structure to keep the process of depressurization using the smaller density change at the critical pressure of CO 2 . The specific surface area of as-prepared aerogel is well over 510 m2/g. Under this condition, the volume of the wet gel will be remained as 43.5 %. The aramid aerogel fiber with the diameter of ca.100 µm was prepared by the optimal drying condition. It is flexible aerogel to overcome fragile of the traditional aerogel. We assume that such a new kind of aerogel with high performances can be used in many fields.

5. References [1] L. Du, I. Tabata, K. Hirogaki, Sen’i Gakkaishi, 70, 197 (2014).

Page 1096 of 1108

[2] G. Horvรกth, K. Kawazoe, J. Chem. Japan, 16, 470 (1983). [3] A. F. M. Barton, Chem. Rev., 75, 731(1975). [4] R. Marr, T. Gamse, Chem. Eng. Proc., 39, 19 (2000).

Page 1097 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Synthesis of novel cationic gemini surfactants having benzene dicarboxylic ester structures in the spacer group and the solubilization of non-ionic dyes in their micellar solutions Yuichi Hirata, Misato Sakakibara and Kunihiro Hamada Shinshu University,3-15-1,Tokida,Ueda,Nagano,386-8567,Japan.Tel0268-21-5411,Fax 0268-21-5319, email yhirata@shinshu-u.ac.jp

Abstract. Novel gemini surfactants having benzene dicarboxylic ester structures in the spacer group were synthesized by quaternization reaction of intermediates of three position isomers which possessed two chloroethyl ester groups with different substituent positions such as ortho- and meta-, para- positions. And for comparison, DC-6-12 Cl which the number of carbon number of hydrophobic group is same and spacer group had alkyl group was used. The micellization parameters such as critical micelle concentration (CMC) and, degree of counterion dissociation were determined for the synthesized surfactants by the fit of the experimental raw data to a simple nonlinear function obtained by direct integration of a Boltzmann type sigmoidal function. The solubilization power of non-ionic dye such as 1,4-diaminoanthraquinone in the micellar solutions of the position isomers of gemini surfactants was evaluated. The CMC of these surfactants depended on the substituent position of ester group on the benzene dicarboxylic unit in the spacer group. The order of the CMC was as follows: oetho isomer < meta isomer < DC-6-12Cl <para isomer. The solubilization power of 1,4-diaminoanthraquinone in the micellar solutions of the position isomers of gemini surfactants showed para isomer < DC-6-12Cl < meta isomer < ortho isomer. The chemical structure of the spacer group of isomer gemini surfactants affected the micellar properties and solublization of the non-ionic dyes.

Keywords: gemini surfactant, solubilization, non-ionic dye

1. Introduction Disperse dyes are used for dyeing polyester, acetate, and polyamide fibres. The disperse dyes are hardly soluble in water. Therefore, dispersing agent (surfactant) was used as auxiliary agent. The dimeric surfactants called as gemini surfactant exhibit a 10 times lower critical micelle concentration (CMC) than that of conventional surfactants such as dodecyl trimethyl ammonium chloride (DTAC). The lower CMC are favoured for the solubilisation of disperse dyes in micelle aqueous solutions. The chemical structure of the spacer group in a gemini surfactant affects the solubilisation of the disperse dyes as well as the micellar properties. In this study, three isomers of cationic gemini surfactants having benzene dicarboxylic ester structure in the spacer group. These isomers possessed two ethyl ester groups with different substituent positions such as ortho- and meta-, para- positions. The effect of substituent positions on the micelle properties and the solublization of a disperse dye such as 1,4-diaminoanthraquinone (1,4-DAA) in their micelles was investigated compared with a gemini surfactant having an alkyl type spacer, called as DC-6-12 Cl.

2. Experiment Fig.1 shows the chemical structure of the synthesized gemini surfactants. Intermediate was synthesized by reacting benzene dicarboxylic acid chloride which have the three different positions of the substituent groups with chloroethanol, and quaternization using a tertiary amine N, N-dimethyl-n-dodecylamine. 1,4DAA was purchased from Tokyo Kasei Co. Ltd. and used without further purification. Fig.2 shows the chemical structure of 1,4-DAA. The micellization parameters such as critical micelle concentration (CMC) and degree of counterion dissociation were determined using the conductance meter for the synthesized surfactants by the fit of the experimental raw data to a simple nonlinear function obtained by direct integration of a Boltzmann type sigmoidal function[1].

Page 1098 of 1108

 1  e ( x  x0 x )   F ( x)  F (0)  A1 x  x( A2  A1 ) ln   x0 x   1 e 

(1.1)

(x : the surfactant concentration, A1：The slope of the approximate line of the low-concentration side, A2 ： The slope of the approximate line of high-concentration side, Δx：transition width of conductivity, x0： CMC / mol dm-3 ) For solubilisation experiments, the surfactant solution was prepared in a suitable concentration range around the critical micelle concentration (CMC). After the addition of the excess dye in the surfactant solutions, by using a water bath incubator, and the mixture was shaken for 3 days at 25 ±0.2℃. Excess dyes were removed by glass fibre filter paper .The dye concentration of the filtrate was determined by UV/VIS spectrometer with a calibration curve.

3. Results and discussion Fig.3 shows the CMC value of the synthesized gemini surfactants. The value of CMC increased in order of o-EO-12 < m-EO-12 < DC-6-12Cl < p-EO-12. With respect to a series of gemini surfactant having a spacer group of alkyl chains, it was reported that the CMC of the surfactants increased with the length of the spacer group. The difference of substituent position on the benzene ring affected the length of two charged quaternary ammonium groups at the head part of the surfactant. The solubilisation power of the surfactants was shown in Fig.4. The solubilisation power increased in order of p-EO-12< DC-6-12Cl< m-EO-12< o-EO12. It was found that the solubilisation power became larger with decrease in the value of CMC. It suggests that the dye molecules are solubilized near the spacer group of the surfactant rather than the core of micelles consisting of alkyl chain.

4. Conclusions The different substituent positions of benzene dicarboxylic ester structures in the spacer group affected the micelle properties and the solubilization of disperse dye in their micelles. Solubilization becomes larger with decrease in the value of CMC. CMC value and Solubilization ability were controllable by the position of a benzene dicarboxylic acid ester connection chain of the gemini surfactant isomers.

5. References [1] P. Carpena et al., Langmuir, 18, 6054−6058 (2002).

Fig. 1: Chemical structure of gemini surfactants used in this study.

Page 1099 of 1108

Fig. 2: Chemical structure of gemini surfactants used in this study. 22 20 18 16 14 12 10

Fig. 3: Critical micellar concentration of surfactant at 25â&#x201E;&#x192;.

Fig. 4: Solubilization power of surfactants at 25â&#x201E;&#x192;.

Page 1100 of 1108

The 13th Asian Textile Conference Geelong, Australia, November 3 - 6, 2015

Ultrasonic Dyeing of Cotton with Natural Dye Extracted from Marigold Flower Awais Khatri, Sadam Hussain, Ameer Ali, Urooj Baig and Pashmina Khan Department of Textile Engineering, Mehran University of Engineering and Technology, Jamshoro â&#x20AC;&#x201C; 76060 Sindh Pakistan

Abstract. Increasing worldwide interest towards natural and sustainable products has driven the textile processing industry to use dyes and chemicals obtained directly from natural resources. Also, textile processors and researchers have been exploring the emerging technologies such as using ultrasonic energy, plasma, supercritical carbon dioxide, microwave and electrochemical methods for processing. In the same context, this work was undertaken to develop a method for dyeing of cotton fabric with natural dye extracted from marigold flower petals using ultrasonic energy. The aqueous extraction of natural dye from marigold flower petals was optimized for temperature and time. The resulting extract was used to further optimize its dyeing conditions on cotton fabric by ultrasonic and conventional exhaust dyeing methods. The effect of pre-mordanting with alum was also studied. Generally, all dyed samples were built with either yellow, golden yellow or tan colours (depending on varying dyeing parameters and conditions). It was found that the optimum aqueous extraction can produce strong colour yields with K/S value up to 5. Whereas, ultrasonic dyeing produced better colour yields comparing to conventional exhaust dyeing method. The colourfastness testing of optimum dyed fabric samples was also carried out for rubbing, washing and light exposure. The overall colourfastness of the dyed samples was acceptable except washing fastness of the sample dyed by conventional exhaust method without mordanting. However, washing fastness was considerably improved with pre-mordanting and further improved by ultrasonic dyeing method. Further, the rubbing and light fastness results were very good in case of premordanting and ultrasonic dyeing method.

Keywords: Ultrasonic, Dyeing, Cotton, Natural dye, Marigold

1. Introduction Due to global shift of industrial practices towards sustainable processing and products, use of natural colorants has obtained a great attention. And, most of the natural colorants are non-toxic, non-carcinogenic and biodegradable. However, the biggest challenge for dyeing textile materials with natural dyes is reproducibility in presence of highly reproducible synthetic dyes. Therefore, textile processors and researchers have been exploring a variety of natural colorants and using them by various techniques and emerging technologies [1-2], for having a comparably reproducible natural dyeing processes. Natural colours extracted from marigold flower, scientifically known as tagetes species, have been used as one of the potential source of the yellow and brown natural dye for textile materials [3-6]. Use of ultrasonic energy to expedite the textile wet processes is one of the emerging technologies for reducing energy consumption and wastewater pollution. A number of successful works have been reported on ultrasonic-assisted dyeing of textile materials [7-11]. An industrial scale success on reactive dyeing of cotton using ultrasonic energy has also been reported [12]. Ultrasonic-assisted dyeing of textile material with natural dyes have shown an additional advantage of reducing energy consumption and reducing more wastewater pollution [13-18]. Marigold plants are widely cultivated in Pakistan, and hence, are indigenous source of marigold flowers. Moreover, marigold flower extracts have not been used for ultrasonic-assisted dyeing of textile materials yet. Therefore, this work was undertaken to study the ultrasonic-assisted dyeing of cotton fabric with natural dye extracted from marigold flower. The dye extraction process was optimised. Optimised extracts were used for exhaust and ultrasonic dyeings of cotton fabric, and processes were optimised. The dyed fabric samples were tested for colour yield and colourfastness.

Page 1101 of 1108

1. Material and methods 2.1. Material A mill scoured and bleached cotton woven fabric (150 g/m2) was obtained from Gul Ahmed Textile Mills Ltd. Karachi Pakistan. Fresh marigold flowers were purchased from local market in Hyderabad Pakistan. The flower petals were taken off and mixed homogenously for extraction. Fresh marigold flowers were purchased from local market. The sodium chloride was analytical and alum was commercial grades. Deionised water was used for all experiments.

2.2. Processes 2.2.1. Dye extraction Homogenous mixture of flower petals were heated in water (petals-to-water ratio of 1:10) at varying temperatures (60 – 120 oC) for varying time (30 – 105 min). For optimising extraction temperature and time, ready-to-dye fabric samples were treated in the extract with the conditions: extract-to-fabric ratio of 15:1, 50 g/L sodium chloride, temperature of 70 oC for 30 min. The treated samples were tested for colour yield (K/S value), the highest value was noted for the optimum extraction conditions.

2.2.2. Exhaust dyeing Fabric samples were dyed in the extract with extract-to-fabric ratio of 15:1 on an H.T. dyeing machine (Rapid Labortex H-120, Taiwan). The dyeing process was started at 40 oC followed by addition of sodium chloride (30 – 90 g/L) after 10 min. The process was continued for 15 min, then temperature was raised to 45 – 105 oC (dyeing temperature) and continued for 30 – 105 min (dyeing time). Finally dyeing solution was drained and samples were rinsed thoroughly with running tap water.

2.2.3. Ultrasonic dyeing Fabric samples were dyed in the extract with extract-to-fabric ratio of 15:1 on an ultrasonic bath (Getidy KDC-200B, China). The rest of the process steps same as those for exhaust dyeing except the fixation temperature that was constant (80 oC).

2.2.4. Mordanting To study the effect of mordanting before dyeing (at optimum conditions), fabric samples were treated with 1 – 5 % (on mass of fibre) of the alum at 60 oC for 60 min. The solution-to-fabric ratio was 15:1.

2.3. Testing

4 K/S

K/S

Colour yield (K/S value at maximum absorption peak) of all dyed samples and CIE L* a* b* values of the samples subjected to pre-mordanting were measured on an Xrite Spectrophotometer CE7000. The optimum dyed samples were tested for colourfastness to mercury light (BS 1006: 1990 UK-TN), rubbing (ISO-105: X12), and washing (ISO-105: CO2).

0 60

105

Extraction temperature (oC)

120

45 60 75 105 Extraction time (minutes)

Page 1102 of 1108

Fig. 1: Effect of extraction temperature and time on colour yield of the dyed fabric.

2. Results and discussion 3.1. Optimization of extraction temperature and time Figure 1 shows the effect of extraction temperature and time on colour yield (K/S) values of the fabric samples dyed as per dyeing method for dye extraction mentioned in the section 2. Optimisation of temperature was carried out at constant time (45 min) followed by optimisation of the time at optimum temperature (90 oC). The results show that colour yield was increased with increasing extraction temperature and time up to a maximum level (i.e. 90 oC and 60 min) then decreased with further increase. That may be because more temperature and time over-cooked the extracted colour resulting in colour decomposition [19].

3.2. Exhaust and ultrasonic dyeings 3.2.1. Effect of dyeing temperature and time Results of the effect of exhaust dyeing temperature on colour yield of the fabric dyed for constant time (60 min) is shown in Figure 2. The results show that the colour yield increased up to 75 oC then decreased with increasing temperature. The increase in colour yield can directly be attributed to the increase in dye exhaustion with increasing temperature. However, the decrease in the colour yield at higher dyeing temperatures may be attributed to dyebath stability and colour decomposition [19]. 6 5 K/S

4 3 2 1 0 45

Dyeing temperature

105

(oC)

Fig. 2: Effect of exhaust dyeing temperature on colour yield of the dyed fabric. Figure 3 shows the effect of dyeing time on colour yield of the fabrics dyed at constant temperature (75 oC for exhaust dyeing and 80 oC for ultrasonic dyeing). The optimum dyeing time for exhaust dyeing was 60 min and that for ultrasonic dyeing was 45 min. Moreover, ultrasonic dyeings produced considerably higher colour yields comparing to those obtained by exhaust dyeings. The higher colour yield obtained in lesser dyeing time may be attributed to the increased dye mobility due to continuous formation of cavitation in the ultrasonic bath [7].

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Exhaust dyeing Ultrasonic dyeing

K/S

4 3 2 1 0 30

105

Dyeing time (min) Fig. 3: Effect of exhaust and ultrasonic dyeing time on colour yield of dyed fabric in comparison

3.2.2. Effect of sodium chloride concentration Sodium chloride was used as an electrolyte for promoting dye exhaustion during dyeing. In Figure 4, colour yield values increase with increasing sodium chloride concentration up to 70 g/L then decrease for both exhaust and ultrasonic dyeings. However, at optimum values exhaust dyeing had slightly better effect of the concentration. This may be due to higher molecular mobility in the ultrasonic bath. 6 5

Exhaust dyeing Ultrasonic dyeing

K/S

4 3 2 1 0 30

Sodium chloride concentration (g/L) Fig. 4: Effect of sodium chloride concentration on colour yield of fabrics dyed by exhaust and ultrasonic dyeing methods

3.2.3. Effect of mordanting CIE L* a* b* values were preferred for this experiment because colour of the dyed fabric can change by mordanting depending on the type and concentration of mordant. Effect of alum (mordant) concentration on colourimetric values of the fabrics dyed by exhaust and ultrasonic dyeings is given in Table 1. The results show that colour depth was increased with increasing alum concentration up to 4 %. After that there was a slight decrease in the depth. The hue values (CIE a* and b*) changed slightly with changing alum concentration, however, the overall hue was yellowish brown. The CIE a* values were very close to the central axis therefore had a greyish red effect whereas CIE b* values show dull yellow effect, thus the overall hue appeared yellowish brown. Table 1: Effect of alum concentration on CIE colour coordinates CIE Color Coordinates Alum concentration

Exhaust dyeing

Ultrasonic dyeing

Page 1104 of 1108

70.13

3.22

13.07

68.01

3.13

13.01

69.82

3.09

12.61

68.70

3.00

12.76

68.69

2.80

12.46

67.83

2.75

12.31

68.63

3.22

11.93

63.16

3.13

11.21

63.78

3.28

10.21

63.00

3.30

10.93

64.13

3.30

9.23

67.43

3.91

10.82

(%, on mass of fibre)

3.3. Colourfastness results The colourfastness results given in Table 2 show that the overall colourfastness of the dyed samples was acceptable except washing fastness (change in colour) of the sample dyed by exhaust method without mordanting. However, washing fastness was considerably improved with pre-mordanting by 2 units and further improved by ultrasonic dyeing method by 0.5 unit. The wet rubbing of dyed samples was moderate axcept pre-mordanted sample dyed by ultrasonic method. The dry rubbing was generally good. Further, the lightfastness results were also generally good. The pre-mordanted samples dyed by ultrasonic method had very good overall colourfastness. Table 2: Colourfastness results of samples dyed with optimum conditions Rubbing fastness (Grey scale rating)

Washing fastness (Grey scale rating)

Dry

Wet

Colour change

Staining on cotton

Exhaust dyeing without mordanting

1/2

2/3

Exhaust dyeing with mordanting

3/4

4/5

Ultrasonic dyeing without mordanting

4/5

2/3

Ultrasonic dyeing with mordanting

4/5

Dyeing method

Light fastness (Blue wool reference scale)

3. Conclusions The dyeing of cotton fabrics can successfully be done with Marigold flower extracts. However, mordanting is required to achieve acceptable colourfastness results. The ultrasonic dyeing method can be employed to further improve the colour yields and colourfastness results. Moreover, energy required to heat-up the dyebath can be saved in case of ultrasonic dyeings due to a fact that ultrasonic bath heats-up by itself due to cavitation [7].

4. References [1] M. Shahid, Shahid-ul-Islam, F. Mohammad, ‘Recent advancement in natural dye applications: a review’, Journal of Cleaner Production, 53 (2013) 310-331. [2] M. Banchero, ‘Supercritical fluid dyeing of synthetic and natural textiles – a review’, Coloration Technology, 129 (2012) 2-17. [3] D. Jothi, ‘Extraction of natural dyes from african marigold flower (tagetes ereectal) for textile coloration’, AUTEX Research Journal, 8 (2008) 49-53. [4] M. Montazer, M. Parvinzadeh, ‘Dyeing of wool with marigold and its properties’, Fibers and Polymers, 8 (2007) 181-185. [5] P. S. Vankar, ‘Chemistry of natural dyes’, Resonance, October (2000) 73-80.

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[6] M. R. Katti, R. Kaur, N. Shrihari, ‘Dyeing of silk with mixture of natural dyes’, Colourage, 43 (1996) 37-39. [7] S. A. Larik, A. Khatri, S. Ali, S. H. Kim, ‘Batchwise dyeing of bamboo cellulose fabric with reactive dye using ultrasonic energy’, Ultrasonics Sonochemistry, 24 (2015) 178–183. [8] C. Udrescu, F. Ferrero, M. Periolatto, ‘Ultrasound-assisted dyeing of cellulose acetate’, Ultrasonics Sonochemistry, 21 (2014) 1477–1481. [9] Z. Khatri, M. H. Memon, A. Khatri, A. Tanwari, ‘Cold pad-batch dyeing method for cotton fabric dyeing with reactive dyes using ultrasonic energy’, Ultrasonics. Sonochemistry, 18 (2011) 1301-1307. [10] M. M. Kamel, H. M. Helmy, H. M. Mashaly, H. H. Kafafy, ‘Ultrasonic assisted dyeing: dyeing of acrylic fabrics C.I. Astrazon Basic Red 5BL 200%’, Ultrasonics Sonochemistry, 17 (2010) 92-97. [11] M. M. Kamel, R. M. El-Shishtawy, H. L. Hanna, N. S. E. Ahmed, ‘Ultrasonic-assisted dyeing: I. Nylon dyeability with reactive dyes’, Polymer International, 52 (2003) 373-380. [12] K. A. Thakore, ‘Ultrasound Treatment in Exhaust and Pad-Batch Dyeing’, AATCC Review, July-August (2011) 66-74. [13] A. Guesmi, N. Ladhari, F. Sakli, ‘Ultrasonic preparation of cationic cotton and its application in ultrasonic natural dyeing’, Ultrasonics Sonochemistry, 20 (2013) 571–579. [14] M. M. Kamel, M. M. El Zawahry, N. S. E. Ahmed, F. Abdelghaffar, ‘Ultrasonic dyeing of cationized cotton fabric with natural dye. Part 1: Cationization of cotton using Solfix E’, Ultrasonics Sonochemistry, 16 (2009) 243-249. [15] M. M. Kamel, H. M. Helmy, N.S. El-Hawary, ‘Some studies on dyeing properties of cotton fabrics with crocus sativus (saffron) (flowers) using an ultrasonic method’, AUTEX Research Journal, 9 (2009) 29-35. [16] M. M. Kamel, R. M. El-Shishtawy, B. M. Youssef, H. Mashaly, ‘Ultrasonic assisted dyeing. IV. Dyeing of cationised cotton with lac natural dye’, Dyes and Pigments, 73 (2007) 279-284. [17] P. S. Vankar, R. Shanker, J. Srivastava, ‘Ultrasonic dyeing of cotton fabric with aqueous extract of Eclipta alba’, Dyes and Pigments, 72 (2007) 33-37. [18] M. M. Kamel, R. M. El-Shishtawy, B. M. Yussef, H. Mashaly, ‘Ultrasonic assisted dyeing: III. Dyeing of wool with lac as a natural dye’, Dyes and Pigments, 65 (2005) 103–110. [19] Shaukat Ali, Tanveer Hussain, Rakhshanda Nawaz, ‘Optimization of alkaline extraction of natural dye from Henna leaves and its dyeing on cotton by exhaust method’, Journal of Cleaner Production, 17 (2009) 61–66.

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The 13th Asian Textile Conference Geelong, Australia, November 3 - 6,2015

Wool and Hair Dyeing by Using Saccharides and Amino Acids I. Dyeing Conditions and Dyeability YASUNAGA, Hidekazu + and OSAKI, Hiroshi Kyoto Institute of Technology, Department of Fibre Science and Engineering

Abstract. It was tried to invent a novel fibre and hair dyeing technique using saccharides and amino acids. Wool textiles are dyed yellowish brown and dark brown in D-xylose and glycine solution through the reaction initiated by heating. The dyeability is increased with an increase in the concentration of amino acid, dyeing time and dyeing temperature. The human hair is dyed yellowish brown and brown by the technique under the optimum condition found in the dyeing of wool textile. The D-xylose is indispensable for the technique, and wool and hair are dyed deeper by the addition of glycine. The colour fastness to washing for hair dyed by the technique was found to be high.

Keywords: Wool, Hair, Dyeing, Saccharide, Amino Acid.

1. Introduction The human hair dyeing by using oxidation dyes is most frequently employed throughout the world today and the number of the people dyeing their hair is increasing. However, the hair dyeing by using oxidation dyes carries potential health risks. Some of the major components and produced byproducts of oxidation hair dyes work as strong allergens, and sensitisation symptoms and severe dermatitis are caused for some people following their use. On the other hand, a massive amount of waste fluid given by the fibre dyeing and hair dyeing is discarded in sewer systems and plenty of energy is needed to treat it for environmental protection. The largest amount of waste fluid is produced by the fibre and dyeing industry in the world. However, it is not easy to reduce the waste fluid. Therefore, a novel dyeing technique should be invented, which is safer and eco-friendly. Under such the situation, the authors have studied hair dyeing by using biobased materials (obtained from natural materials) to invent safer hair dyeing techniques [1 - 5]. In the study, the dyeing of wool textiles and hair by using a saccharide, D-xylose, and an amino acid, glycine, was examined. The dyeing is set off by heating the reaction solution, and wool textiles and hair are immersed into the solution. The dyeability of the technique was estimated by colour measurements.

2. Experimental D-xylose (Nacalai tesque) was dissolved in distilled water with or without glycine (Nacalai). Wool textile samples (Shikisensha) were immersed into the solution (liquor raito: 1 : 62.5) at 30-70 째C for 0.5-4.0 h. The treated wool textiles were washed twice in distilled water at 30 째C for 10 min and air-dried. The colour of dyed wool samples were measured by a spectrocolourimeter (Konica Minolta CM-2600d) and the resulting colour was expressed in L*a*b* standard colourimetric system (CIE 1976). The L* is the lightness index. The a* and b* are the chromaticity coordinates, a* shows red - green degree and b* shows yellow - blue degree. On the other hand, the sample white hair (Beaulax) was immersed into the prepared aqueous solution containing D-xylose with or without glycine (liquor ratio: 1 : 62.5) at 70 째C for 4.0 h. The treated hair was washed twice in distilled water at 30 째C for 20 min and air-dried. The colour of hair samples was measured by the same way as the wool textiles. The hair dyed with the D-xylose and glycine was washed repeatedly with sodium dodecyloxy polyoxyethylene sulfate solution and rinsed out with distilled water for colour +

Corresponding author. E-mail address: yasunaga@kit.ac.jp.

Page 1107 of 1108

fastness test. The colour of washed hair was measured after every washing and the procedures were repeated 30 times.

3. Results and Discussion

Table 1 L*, a* and b* values of wool textile samples dyed

The wool tetiles are dyed brown with Dwith 2.0 M of D-xylose and glycine under the conditions xylose. The resulting colour becomes deeper, changing glycine concentration (cG), dyeing time (t) or when they are dyed with D-xylose in temperature (T). Sample c G / M t / h T / ºC L* a* b* combination with glycine. The colour values in L*a*b* standard colourimetric system for wool Initial 91.7 -1.10 12.7 samples dyed with changing glycine wool concentration (c G ), dyeing time (t) or 1 0 4.0 70 70.7 4.30 23.8 temperature (T ) are summerised in Table 1. The 2 1.0 4.0 70 59.7 15.1 35.6 brown colour of the textile is deepened and 3 2.0 4.0 70 51.7 15.9 35.2 darkened with the increase in the glycine 4 3.0 4.0 70 46.6 16.6 34.2 concentration (sample No. 1-5), dyeing time 5 4.0 4.0 70 46.9 17.1 34.8 (sample No. 6-9 & 5) and dyeing temperature (sample No. 10-13 & 5) as shown in Table 1. It 6 4.0 0.5 70 81.6 4.98 28.4 was shown from the results that the wool is dyed 7 4.0 1.0 70 68.9 11.9 32.2 deep brown by using D-xylose and glycine. The 8 4.0 2.0 70 57.9 14.4 33.4 mechanism of colourant formation can be based 9 4.0 3.0 70 48.9 17.3 35.1 on Maillard reactions [6], [7]. The colourants 10 4.0 4.0 30 91.5 -1.10 12.4 formed, which work as the dyestuff may be the melanoidine compounds. 11 4.0 4.0 40 91.2 -1.30 14.7 Human hair was subsequently treated with 12 4.0 4.0 50 84.4 3.30 29.6 D-xylose and glycine under the proper conditions 13 4.0 4.0 60 63.3 14.3 33.2 (as the sample No. 5 etc. in Table 1), which were found in the dyeing experiments of wool textiles. The hair is dyed yellowish brown with D-xylose or dark brown with D-xylose and glycine. The obtained L*, a* and b* values of dyed hair are summarised in Table 2. The L* and a* of hair dyed with DTable 2 L*, a* and b* of initial hair (a), hair dyed with 2.0 xylose and glycine are lower and higher, M of D-xylose (b), hair dyed with 2.0 M of D-xylose and respectively, than those of hair dyed only with D4.0 M of glycine (c). t : 4.0 h, T : 70 °C. xylose as shown in Table 2. The results show that human hair can also be dyed brown by using D-xylose and the colour is deepened by the addition of glycine. Sample L* a* b* The colour fastness to washing for hair dyed by the technique should be higher preferably for (a) 70.7 4.30 23.8 practical use. Therefore, the colour fastness to (b) 62.7 8.60 35.4 washing for hair dyed by using D-xylose and glycine was estimated. Figure 1 shows the (c) 41.7 20.9 36.5 change in colour difference (ΔE*) between the freshly-dyed and washed hair as a function of the number of washing (n). ΔE* is calculated by ∆E* = {(L* n - L* 0 )2 + (a* n - a* 0 )2 + (b* n - b* 0 )2}1/2, where L* 0 , a* 0 , b* 0 are L*, a*, b* of hair samples just after dyed, respectively, and L* n , a* n , b* n are those of n-times-washed ones. The changes in ΔE* of hair dyed by a commercial oxidation dye (using Kao Blaunē and dyed at 30 °C) is also shown in Figure 1 for comparison. The ΔE* for oxidation hair dye increases largely with n. On the other hand, ΔE* of hair dyed by the novel technique of this study increases slightly at initial washings and changes scarcely for n > 3. It can be said that the colour fastness to washing of hair dyed by the technique is high enough. It was also found that other amino acids such as β-alanine, L-glutamic acid monosodium salt, L-serine, Larginine and so on are available for the dyeing technique.

Page 1108 of 1108

4. References

[2] Matsubara, T., Wataoka, I., Urakawa, H. and Yasunaga, H., International Journal of Cosmetic Science, 35, 362-367 (2013). DOI: http://dx.doi.org/10.1111/ics.12051

14 12 10

∆E*

[1] Yasunaga, H., Takahashi, A., Ito, K., Ueda, M. and Urakawa, H., Journal of Cosmetics, Dermatological Sciences and Applications, 2, 158-163 (2012). DOI: http://dx.doi.org/10.4236/jcdsa. 2012.23031

6 4 2 0

[3] Matsubara, T., Wataoka, I., Urakawa, H. and Yasunaga, H., Sen’i Gakkaishi, 70, 19-22 (2014). DOI: http://dx.doi.org/10.2015/fiber.70.19 [4] Matsubara, T., Wataoka, I., Urakawa, H. and Yasunaga, H., Advances in Chemical Engineering and Science, 4(3), 292-299 (2014). DOI: http://dx.doi.org/10.4236/aces.2014.43032

n / times Figure 1 Change in ΔE* between the colour of freshly-dyed and washed hair, which were dyed by an oxidation hair dye (■) or D-xylose and glycine (●), against the number of washing (n).

[5] Matsubara, T., Taniguchi, S., Morimoto, S., Yano, A., Hara, A., Wataoka, I., Urakawa, H. and Yasunaga, H., Journal of Cosmetics, Dermatological Sciences and Applications, 5, 94-106 (2015). DOI: 10.4236/jcdsa.2015.52012 [6] Maillard, L. C., Ann. chim. Sér., 9(5), 258-317 (1916). [7] Hodge, J. E., Agricultural and Food Chemistry, 1(15), 928-943 (1953).