ATC-13 Conference Proceedings Volume 1 by ATC-13

Volume 1

Table of Contents - Bold Content is in this Volume

Online link to: International Scientific Committee Page 3 Volume 1: Invited Speakers Page 4 Volume 1: Fashion and Clothing Science Page 5 Volume 1: High Performance Fibres and Composites Page 7 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

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 2: 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 2: 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 25 of 1108

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

Acoustic Fibre Board Screens for Office Speech Privacy Abu Shaid1, Tom Jovanovski2, Bob Stewart2, Anthony Heap2, Xiaojun Qiu3, Rajiv Padhye1 and Lijing Wang1 + 1

School of Fashion and Textiles, RMIT University, 25 Dawson Street, VIC 3056, Australia. 2 Zenith Interiors Pty Ltd 101 Tulip St, Sandringham, Vic 3191, Australia. 3 School of Electrical and Computer Engineering, RMIT University, Melbourne, Australia

Abstract. In an open plan office, an acoustic environment significantly affects the occupant’s satisfaction, performance and psychological wellbeing. The work stations or office pods in an open plan office are normally made up of partial height enclosures of acoustic screens which tend to provide a certain level of speech privacy for working individuals or corporate meeting. In general these pods consist of several acoustic screens, most of which contain fibre materials for sound attenuation and give an elegant look. In this regard, two sets of information, the performance in speech privacy and the longevity of the textile quality parameters, are two crucial tools to evaluate the effectiveness of such pod materials. Several variables affect the acoustic performance in such case, and the sound absorption and sound transmission loss are two vital acoustic parameters to gain some initial thought on speech intelligibility or speech privacy of any particular screen. These acoustic phenomena depend on the quality parameters of the covering textiles such as thickness, fineness, density, construction etc. Other textile quality parameters including the material type, fire and thermal ratings, the fastness to light and rubbing, cleanability etc. are also essential facts to consider. From the buyer’s perspective, it is very important to understand these characteristics prior to buying such products, as they greatly influence the performance in different work environment setups. The characteristics are also vital for the manufacture to develop new products or to impart new features to the existing one. However, there is lack of basic research on the quality characterization of these pods or screen materials in terms of their acoustic and textile performance. As a result not only the consumer, but also the manufacturer does not have sufficient information to critically distinguish the performance of one such product from another. This paper highlights these aspects for overall consideration through few decisive acoustic and textile characteristics of such structural pod material and their interdependency. It also introduces some commercial products, including examples from Zenith Interiors, a global company that provides innovative solutions for all corporate and commercial environments with new and innovative ways to engage their employees by creating spaces with products that are functional, appealing and forward thinking.

Keywords: acoustic, office partitioning, speech privacy, fibre board.

1. Introduction Modern open plan offices are designed with such individual workplaces where a certain degree of speech privacy is maintained for focused work or confidential meeting through acoustic screening. The main purpose of sound screening in an office is to create a comfortable acoustic environment by lowering the noise level as it is not perceived as an annoyance. Noise is the unwanted sound that is received from telephones, fax machines, printers or other office machines and most disruptively, the third party conversation. Having to listen to a neighbouring worker’s conversation is not only distracting but also a privacy concern, particularly in confidential matters. These noises (such as a phone ring) become more noticeable in a quieter room. Hence a certain level of background noise may in fact be desirable. The acoustic screens are used to absorb sound waves and lower the disruptive sound (noise) pressure level as close as possible to the background noise level (Fig. 1). If the sound pressure level of disruptive noise is P1, background sound pressure level is P2 and the required attenuation level of office screen is P, then P = P1 – P2. For example if an office compound has background noise of 40 dB and the disruptive sound pressure level is 80 dB, then it is required by the office

Corresponding author. Tel.: + 61-3-992 59414 E-mail address: lijing.wang@rmit.edu.au

Page 26 of 1108

screens and other related acoustic arrangements to lower the disruptive noise pressure level to 40 dB for a comfortable acoustic environment. The screen materials also need to provide sufficient sound transmission loss (STL) as to ensure speech privacy inside the pod. Both these two qualities â&#x20AC;&#x201C; sound absorption and transmission, depend on several types of variables including room dimension, their arrangement, screen construction etc. Finally the longevity of these pod materials in terms of light fading, rubbing damage, ease of cleaning, and fire and thermal behaviour are also needed to be considered. This paper briefly discusses these aspects of office pod material and their interdependence.

Fig. 1: Expressional diagram showing required level of sound attenuation which is expected from an office partitioning screen.

2. Sound insulation and absorption â&#x20AC;&#x201C; base for all acoustic consideration The acoustic performance is simply either insulation or absorption. The speech intelligibility of an acoustic screen largely depends on its sound absorption capability whereas the speech privacy will greatly depend on its sound insulation properties. When a sound wave falls on a surface, three phenomena take place â&#x20AC;&#x201C; reflection, absorption and transmission. A portion of the incident wave reflects back and falls on to another surface or is received by a receiver; another portion is absorbed by the surface and the rest is transmitted through the surface. In an enclosure when the sound signal is produced (Figure 2a), it spreads and hit the surrounding wall surfaces. The reflected portion bounces back and continues to fall on other surfaces until it is totally lost by absorption and transmission through multiple interactions. Both the absorbed and transmitted amounts are lost from the room. Thus the sound wave reverberates until it dies completely. The time taken for the sound signal to die away is termed as reverberation time (RT).

Page 27 of 1108

(b) Fig. 2: Schematic diagram of (a) propagation of sound wave on a surface where I = the incident sound wave, R1, … , Rn = the reflected portion of the incident wave, A = absorbed portion of the incident wave and T = the transmitted portion of the incident wave. (b) 100% sound insulation and absorption.

For high intensity sound, such as 120dB, it will take a longer time to die away than a lower intensity sound like 50 dB. Hence, to establish a reproducible parameter, a standard reverberation time RT60 has been developed which measures the time required to drop 60dB from a starting intensity. The difference of value (dB) of how much sound had carried through to other side from the source side is the measure of the sound transmission loss. It is a measure of sound insulation capacity of a material. Theoretically 100% sound insulation means there is no transmission of sound through incident surface while 100% absorption means there is no reflection from the incident surface (Figure 2b). Materials like tiles have higher reflection and lower absorption capability while a carpet has lower reflection and higher absorption capacity. The ability of a material to absorb sound can be defined by measuring the RT while the ability of sound insulation can be described by measuring the STL. Thus these two parameters – reverberation time (RT 60) and sound transmission loss are the basic key parameters to derive all other acoustic indexes like sound reduction index (Rw), noise reduction coefficient (NRC), speech intelligibility index (SII), speech privacy class (SPC) and so on.

3. Decisive facts for perfect acoustic tuning in open plan office There are two core facts to consider before deciding on an acoustic screen – firstly, the dimension of the application field and secondly, the acoustic performance required according to the need of that specific application environment. Office dimension is very important. In a large open space office, sound waves travel a long path and are refracted many times before reaching the surrounding walls for reflection. Hence it requires a balance application of sound insulation and absorption. On the other hand in a small office, sound waves frequently reflect from ceilings and walls. In this case the sound absorption capacity (lower RT value or higher NRC) of the pod material is very important while the more insulation properties (higher STL or lower SII) will worsen the situation by creating even more reflection. Hence a small office should have office pods of very good sound absorption capacity as to control the reverberation time and achieve good speech intelligibility. An open plan office is not simply a large compound with homogeneous workplaces; rather it consists of different zones with different acoustic requirements. Personal work places for management, individual work stations for focused tasks and confidential meeting rooms are the example of office zones where speech privacy is of utmost importance. In these zones, the acoustic requirement does not include to understand individual syllables. On the other hand, office zones like places for team work or general communication requires adequate speech intelligibility. Partial understanding of individual syllables has not much influence in this case. In this way, an open plan office requires a reasonably good speech intelligibility overall the whole office compound while it also requires some individual work places with good speech privacy. The speech privacy is maintained through the office pods of acoustic screen where the material has sufficiently lower speech intelligibility. These two facts create a complex scenario where low speech intelligibility is maintained within an overall good speech intelligibility surrounding. Hence it is very important to understand the different ratings which refer to speech privacy and speech intelligibility. Table 1 shows different scales of speech privacy and intelligibility. Table 1: Scale of intelligibility/privacy [1-5] AI (0 to 1) SII (0 to 1)

SPC (0 to 100)

STI (0 to 1)

Page 28 of 1108

AI = 0.0: Unintelligible. No speech can be understood AI = 1.0: Excellent intelligibility. Speech can be understood completely AI ≦ 0.05: Confidential speech privacy AI≦ 0.15: Acceptable/normal privacy for open plan office

SII = 0.0: Unintelligible. No speech can be understood

SPC = 0: No privacy. Speech can be understood completely

SII = 1.0: Excellent intelligibility. Speech can be understood completely

SPC = 100: Highest privacy. No speech can be understood

SII ≦0.1: Confidential speech privacy

SPC ≦ 70: Very little privacy

SII ≦ 0.2: Normal privacy

SPC≧ 90: Inaudible speech

STI = 0: Unintelligible. STI 1.0: Complete intelligibility STI ≦ 0.3: Unacceptable or bad intelligibility STI > 0.3 to ≦0.45: Poor intelligibility STI > 0.45 to ≦0.6: Fair intelligibility STI > 0.6 to ≦0.75: Good intelligibility STI > 0.75 to ≦1: Excellent intelligibility

Speech privacy class is the rating which shows the depth of privacy, whereas SII or AI (Articulation Index) describes the quality of comprehensible speech, i.e., the percentage of speech correctly perceived and understood. SPC is the average value of noise level perceived by the receiver where the average value is determined from the cumulative level difference (that indicates the attenuation) between the source room and the receiver position. In the ASTM standard E2638, the level difference is the average level of sound in the source room to a receiver position at 0.25m outside the meeting room. On the other hand, SII is the phenomenon that defines how clear, precise and audible/intelligible a vocal communication system is [1]. It is a more important parameter to describe the acoustic environment of an open place. Bell Laboratories started to develop techniques how to measure speech intelligibility in 1940 [2]. Primarily, Speech Intelligibility was measured in terms of AI. Nowadays, speech intelligibility can be addressed either by determining SII in American system or by various forms of STI (Speech Transmission Index) which is an equivalent European standard.

4. Textile quality parameters There are two sets of textile properties to consider for acoustic screen covering – textile properties related to acoustic performance and textile properties that determine the durability. The thickness, porosity, softness or elastic modulus and flow resistance are the key properties of the covering textile material that govern the sound absorption performance of the screen. When a sound falls on a screen surface, the acoustic energy of vibrating air molecules interact with the tiny fibres of the textile absorber and converted to the heat energy [6]. Hence the fabric which has fibres with higher surface area, such as micro fibre fabric, can offer higher flow resistance and thus is a better sound absorber [7]. Na et al. [7] showed that fabric thickness is unrelated to the sound absorption, but instead related to the fabric density. They found that bulky fabrics did not show better sound absorption but the NRC value increased when the fabric density increased up to a limit. It had been found that fabric density of about 0.14 g/cm3 gives the best sound absorption average throughout the complete range of frequencies [7]. On the other hand, in case of a porous absorber like composite, the sound penetrates into the voids and is absorbed by their frictional resistance [6, 8]. The thickness and density of the material is very important in this case. Lou et al. [9] found that in case of medium and low frequencies, increasing thickness improves the sound absorption efficiency; and in case of medium to high frequency sound, the sound absorption capacity of the composite decreased when the density increased. They argued that the increased density makes the composite more compact and results in decreasing of voids. As a result, the incident sound web reflects more and absorbs less. Office partitioning acoustic screens are usually covered with needle punched nonwoven fabric. To a limit, the thicker nonwoven covering is a better absorber. However there are few other important textile properties that contribute to the acoustic performance. It has been found that using of finer diameter yarn or increasing the level of needle punching improves the sound absorption quality [7]. Again a heat bonded nonwoven provides equal sound absorption at lower thickness than its needle punched counterpart [10]. Thus to understand the acoustic performance of a partitioning screen, it is necessary to know the facts behind its covering textile, its nature and related properties. There are few other textile properties which are not related to the acoustic performance but important to provide extra value to the product and its longevity. An acoustic screen should have a reasonable fire rating, good resistance to abrasion and good colour fastness to light fading. Again material composition has its own value. Different manufacturers of acoustic screens have different views in material composition. Zenith Interior is an Australian company that markets office furniture and acoustic screens from Allermuir, Buzzispace,

Page 29 of 1108

WovenImage etc [http://www.zenithinteriors.com.au/]. However different manufacturers have different varieties to offer. While Allermuir offer 100% pure virgin wool in their ‘Haven pod’, Buzzispace highlights that their ‘BuzziVille’ is manufactured from 100% recycled materials. Though the research [9] has identified that sound absorption does not relate whether the material is virgin or recycled, the manufacturer opens a new market segment by emphasizing the greener production. Woven Image is an Australian brand which brings its ‘Echo’ product range emphasising more on environment than other similar products [http://www.wovenimage.com/]. ‘Echo’ products are not only composed of 60% recycled PET but also have low VOC (volatile organic compounds) emission rating and also Green Tag Level A certified. The acoustic performance of the product is as good as other alternatives available in the market but ‘Echo’ products stand alone in respect of environmental superiority. In case of fire related ratings, most of the acoustic screen provides rating according to the BS EN 13501-1:2007+A1:2009 standard, which is applicable for building elements and gives results to its reaction to the fire. However manufacturer like Bene and Allermuir provides additional fire rating of their product according to BS EN 1021-1-2, smouldering cigarette and match test. Another important textile quality parameter is the fastness to abrasion damage and pilling. Almost all the screen manufacturers provide pilling rating but in different abrasion cycles. To understand the legibility of the screen against frequent everyday abrasion, it is important to know the number of abrasion cycles tested. For example, in same test standard of ISO 12947, Haven Pod of Allermuir was tested against 50000 rub cycles whereas Dock-in-bay of Bene was tested against 80000 rubbing cycles. Thus a similar abrasion rating may not necessarily express the similar performance if their abrasion cycle is not known. The light fastness of the screen is also important as it regularly exposed to natural and artificial light. Most of the acoustic screens have ratings between 5 and 7 in this regard. Lastly it is also required to know the cleanability of the screen. Some screens may clean simply by quickly blotting excess spills from the material with a damp cloth or using upholstery shampoo, whereas rubbing with shampoo may cause colour fading or pilling in other types of screens. The composition of the covering textile is vital in this respect as cleaning vary from fibre to fibre. Thus the above mentioned textile properties also play their individual role in other quality parameters than acoustic performance.

5. Conclusion Acoustic privacy and speech intelligibility in an open plan office is undoubtedly an important consideration in any corporate environment. The comfortable acoustic environment is maintained through proper selection and planning of sound absorbing materials. The paper discussed the influence of various auditory and textile parameters on the acoustic performance of office partitioning pod materials. Basic acoustic terminologies are discussed in a simpler fashion. Thus it is expected that the paper will be useful for the general and business customer to gain a preliminary understanding of the projected performance from such pod materials.

6. References [1] 3M Occupational Health & Environmental Safety Division, Is Your Emergency Communication Systems (ECS) Effective, 3M Company, 2012. [2] NTI, Introducing Speech Intelligibility, NTI Audio AG, 2015. [3] J. Bradley, B. Gover, Speech privacy criteria for closed rooms in terms of speech privacy class (SPC) values, Canadian Acoustics, 39 (2011) 3-10. [4] A.M. Amlani, J.L. Punch, T.Y. Ching, Methods and applications of the audibility index in hearing aid selection and fitting, Trends in amplification, 6 (2002) 81-129. [5] ANSI, Methods for calculation of the Speech Intelligibility Index, ANSI S3.5-1997, American National Standard, Acoustical Society of America, New York, USA, 1997. [6] T.D. Rossing, N.H. Fletcher, Principles of vibration and sound, Springer Science & Business Media, 2004. [7] Y. Na, J. Lancaster, J. Casali, G. Cho, Sound absorption coefficients of micro-fiber fabrics by reverberation room method, Textile Research Journal, 77 (2007) 330-335. [8] B.J. Smith, R.J. Peters, S. Owen, Acoustics and noise control, Addison Wesley Longman Limited, England, 1996. [9] C.-W. Lou, J.-H. Lin, K.-H. Su, Recycling polyester and polypropylene nonwoven selvages to produce functional sound absorption composites, Textile Research Journal, 75 (2005) 390-394. [10] A. Genis, E.Y. Kostyleva, L. Andrianova, V. Martem'yanov, Comparative evaluation of acoustical properties of heat-bonded and needle-punched fibrous materials prepared from polymer melts, Fibre Chemistry, 21 (1990) 479482.

Page 30 of 1108

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

Fibrous Materials and Wearable Technologies in a Nonlinear Interactive World Ron Postle Professor Emeritus and Professorial Fellow, School of Chemistry, University of New South Wales, Sydney 2052, Australia Invited Professor, ENSISA, University of Haute Alsace, Mulhouse, F68093, France

Abstract. The mechanical environments within a draped woven fabric or a biaxially stressed knitted fabric are quantitatively evaluated. The aim is to facilitate the successful integration of wearable technologies within the structural hierarchy of textile materials during manufacture and everyday wear. Textile materials have evolved over thousands of years and still form the basis of modern fashionable clothing for the essential purposes of human protection, comfort and adornment. Future commercial wearable technologies will necessarily depend on a high degree of ongoing creative interaction between the disciplines in both the textile and electronics industries.

Keywords: Textile materials, wearable technologies, soft matter, structural hierarchy, interfibre friction, mechanical environment, woven fabric drape, collapsing shear, knitted fabric formability, biaxial extension

1. Introduction When considering the future potential of wearable technologies or smart textiles capable of responding to environmental conditions, it is easy to overlook the critical importance and the essential properties of the textile material which forms the basis of our clothing. In particular, we need to concentrate on how flexible sensors, conducting yarns or threads, small lightweight power supplies capable of autonomous operation using for example solar or mechanical energy, can be incorporated into the structural hierarchy of a textile material [1]. Also it is absolutely essential that we take into account the need for wearable technologies which are integrated into our clothing to be washable and resistant to quite severe mechanical environments during textile manufacture as well as during wear of everyday clothing. Textile materials do not behave in a way that is consistent with the theories generally presented in classical engineering textbooks. We must apply the concepts of noncontinuous materials, anisotropy, large deformations and nonlinearity in order to analyse complex fibrous materials and their mechanical behaviour.

2. Fibrous Materials and Soft Matter Fibrous materials which make up our clothing are compliant when compared with traditional materials because of their inherent nature and their resultant mechanical and physical responses to external stimuli. Textile materials have the unique feature represented by a very efficiently assembled system of structural hierarchy at various scale levels. This structural hierarchy is formed only by the forces of friction from which fibrous materials derive their physical and mechanical properties, viz the polymeric molecular scale, the single fibre, the twisted yarn and the interlaced yarns forming the fabric construction. This hierarchical structure fits exactly into the definition of â&#x20AC;&#x2DC;soft matterâ&#x20AC;&#x2122; which exhibits the two features of flexibility and structural complexity. Fibrous materials therefore represent ideal structures into which we can integrate the electronic circuitry required for the development of wearable technologies. The concept of soft matter [2] has generated considerable research activity in such disciplines as physics, biology and biophysics, engineering, food science, not to mention the science of fibrous and textile materials.

Page 31 of 1108

These textile systems are formed by interfibre frictional forces only and derive their mechanical properties from the complex hierarchical structure of fibre, yarn and fabric construction (as opposed to the chemical composition of the constituent fibres). Textile materials are in fact amongst the most structurally sophisticated and hierarchical materials which we can manipulate in order to satisfy particular performance and end-use requirements including the requisite mechanical environment for successful integration of wearable technologies. We expect the textile materials to possess a unique combination of properties or more specifically we expect them to be soft, flexible, fashionable, durable, comfortable and light in weight. Conventional textile materials are not often the subject of very detailed study by material scientists. Yet the unique combination of properties possessed by fibrous or textile structures is now leading to greatly enhanced research and development activities because of their increasingly widespread use in relatively new areas such as fibre reinforced composite materials and fibre based products in medical, health and other biological fields as well as their great potential for the commercialisation of wearable technologies in the international market place [3].

3. Nonlinear Interactions in Fibrous Materials Fibrous materials are manufactured rapidly on a massive scale at very high speeds in modern textile processing and can interact over extremely high surface areas. Fine fibre surfaces are enormous in terms of area leading to very strong interactions and nonlinear behaviour between fibres. These strong fibre interactions caused by interfibre friction often lead to difficulties in analysing textile materials, for example blended twisted yarn structures or hybrid fibre reinforced composite materials [4] where in the later case fibres interact by means of a synthetic resin rather than through interfibre friction.

4. Mechanical Environment and Response of Textile Materials Some properties of textile materials take extreme values, e.g. bending and membrane shear moduli are typically several orders of magnitude smaller than the tensile moduli in the principal directions. Poisson ratios (if this is appropriate terminology) may take values of one or more. Displacements and strains may be very large by engineering standards e.g. tensile strains in excess of 100% are common for knitted fabrics. Smart textile fibres therefore may encounter radii of curvature lower than 1mm while having to endure very large tensile deformation depending on the textile construction and its location on the human body. Fabric deformation can be treated as a nonlinear material and geometric large deformation problem in continuum mechanics. By definition, an elastic textile material or flexible fabric thin shell is one for which there exists a deformation energy density which at any point in the textile material is determined completely by the local deformation (ie. the function which defines the initial and final configurations, together with many of their derivatives). In the simplest class of problems, the static equilibrium configurations of an elastic fabric are those which minimize the total deformation energy of the material. In mathematical terms, the mechanical model of a textile material can be represented using differential geometry as a collection of four tensor fields on a 2-dimensional manifold [5]. The four tensor deformation measures characterize the local finite deformations for a draped woven fabric or the formability (or conformity) of knitted fabrics. These four tensor fields represent: • fabric membrane (tensile and shear) strain; • fabric bending or the curvature of the fabric surface; • the bending of yarns within the tangent plane to the fabric surface; and • the twisting of yarns induced by deformation of the fabric (caused by fabric bending on the bias). Dynamic Drape and Shear of Woven Fabrics A particular free form fabric deformation problem is drape of woven fabrics which can be treated as an elastic fabric boundary value problem. We may need to include energy contributions due to interactions between the fabric and the fields defined throughout the space containing the fabric such as gravity or air currents.

Page 32 of 1108

The deformation energy density for woven fabrics decouples into a sum of terms representing:– the deformation energy of the warp yarns; – the deformation energy of the weft yarns; and – the large-angle collapsing (pin jointed lattice-like) shear deformation energy of the fabric. The large-angle (possibly 25 degrees under tension) shear deformation is critical for drape of woven textile materials. The steps involved in setting up the fabric free form elastic boundary value deformation model are: • Measures be defined to quantify and characterize the local finite deformation of a fabric; • An elastic deformation energy density be defined in terms of these measures including energy contributions due to interactions between the fabric and fields defined throughout the space containing the fabric eg. gravitational field when fabric drape is considered; and • The equations of equilibrium be determined using the principle of minimum total elastic deformation energy. There can be multiple valid solutions defining the mechanical response of fibrous materials under any particular set of boundary conditions, for example the dynamic drape response of a textile material forming part of an article of clothing or the drape of a flag. The mechanics of elastic fabrics are developed as a classical field theory using the calculus of variation. For this purpose, the theory of parameter invariant variational problems on a subspace of a Riemannian manifold is generalized to include problems satisfying weaker invariance conditions thus enabling the description of physical continua [5]. Formability and Biaxial Extension of Knitted Fabrics Consider the particular problem of knitted fabric 3D conformity or 3D formability. In contrast to the easy collapsing shear of woven materials, knitted fabrics have extremely high three dimensional formability as a direct result of their easy biaxial extension (often greater than 100% in at least one of the principal directions). This ability to form three-dimensional shapes enables knitted materials to be utilized for a wide variety of close fitting garments (and shaped composite material preforms). The relaxed or unstressed shape of the knitted looped structure as encountered in knitted apparel yields the characteristic very low initial tensile modulus. On the other hand, the shape of the biaxially stressed or pretensioned knitted structure yields a high tensile modulus. This latter prestressed structure determines the superior formability of knitted textile materials for the production of close fitting garments. The deformation energy density for knitted fabrics is essentially a function of the biaxial tensile properties of the knitted loop structure. Inelastic Behaviour of Textile Materials All fabrics display inelastic phenomena. If the components of the material property tensors depend on time and environmental parameters, then in principle we can also model inelastic phenomena such as viscoelasticity, hysteresis (friction), ageing, humidity and temperature effects. The static frictional forces which exist between yarns and between fibres within yarns can maintain small fabric strains in the absence of externally applied loads. Therefore, there is no unique lowest energy configuration for the fabric, but rather a family of configurations ‘close’ together. When loads are applied, these effects become manifest as hysteresis about the ‘idealised state of elastic equilibrium’ of the fabric.

5. Conclusion We are now witnessing enormous efforts directed towards the development of wearable electronic/optical technologies as smart or intelligent textiles integrated into everyday clothing capable of responding to environmental stimuli.

Page 33 of 1108

The textile or fibrous material cannot simply be regarded as an inert substrate for future successful development of wearable technologies. We need to see a high degree of creative multidisciplinary interaction between the various disciplines in both the textile and electronics industries. The basic requirements for textiles or fibrous materials to perform their functions of body protection, comfort and fashion have not changed for thousands of years and will need to be incorporated into future developments of wearable technologies. Sometimes these textile requirements may appear to be contradictory to the requirements of electronic circuits embedded within a fibre or within the structural hierarchy of the textile material itself. Wearable technologies are most likely to penetrate the markets related to the military, emergency response systems and protective clothing, health and fitness, sporting activities, medical applications and employee uniforms involving monitoring of physiological signals such as pulse rate and diabetes control. Various other commercial wearable applications can then be integrated into everyday clothing after the technologies are established and proven. In this paper, we have shown how the mechanical environments within woven or knitted clothing can be quantitatively evaluated.

6. References [1] K.Cherenack and L.vPieterson. Smart Textiles: Challenges and Opportunities. J. App Physics 112, 091301, 2012. [2] N.Pan, J.He and Z.Guo. 1st International Symposium on Soft Materials, Donghua University, Shanghai, May 2009. [3] J. McCann. Disparate Industry Connections, Textiles, The Textile Insitute, Manchester, Issue 2, 13-15, 2015. [4] N. Pan and R.Postle. The Tensile Strength of Hybrid Fibre Composites: A Probabilistic Analysis of the Hybrid Effects. Phil. Trans. Roy. Soc. Lond. Series A 354 pp. 1875-1897, 1996. [5] A.H.Norton and R.Postle. Mechanics of Complex Fabric Deformation and Drape. (50th Anniversary Conference, The Fiber Society, Princeton, U.S.A., August 1990: Polymer Symposium), J. Appl. Polymer Science, 47, 323-340, 1991.

Page 34 of 1108

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

A Novel Nonlocal Self-similarity Technique for Fabric Defect Detection Wai Keung Wong+, Jielin Jiang and Yan Cui Institute of Textiles and Clothing, The Hong Kong Polytechnic University, Hunghom, Kowloon, Hong Kong

Abstract. In apparel manufacturing process, fabric inspection is a vital step to ensure the quality of fabric before spreading, cutting and sewing of making up an apparel product. Many studies on the development of vision based automated inspection techniques, mainly including Fourier, wavelet and Gabor transform, have been reported in a recent decade. The main drawback of these approaches is that each existing detection technique is only limited to inspect a particular type of fabric pattern since each technique has its own limitation and has only been verified in controlled environment, instead of real-life apparel manufacturing environment. As apparel manufacturing plants are processing production orders with different types of fabric, color and pattern, almost all plants are still relying on workersâ&#x20AC;&#x2122; visual inspection. Owing to fatigue or boredom of workers, fabric inspection is highly prone to errors and the inspection accuracy is only about 60%-75%. Nonlocal self-similarity (NSS) is widely used in image restoration due to its effectiveness and stability, especially for image denoising. As fabric defect detection can be considered as a problem that noises in an image to be detected, this paper proposes a simple yet effective method, namely defect detection based on nonlocal self-similarity (DDNSS) technique. Experimental results prove the validity and feasibility of the proposed DDNSS algorithm on fabrics with different colors and stripe patterns. Keywords: Fabric defect detection, nonlocal self-similarity, weighted average.

1. Introduction In current apparel industry, almost all apparel manufacturing plants are still relying on workersâ&#x20AC;&#x2122; visual inspection on the moving fabric rolls loaded on the fabric inspection machine. However workers are subject to fatigue or boredom and thus unreliable and inconsistent inspection results are often generated. According to some studies, human visual inspection can only find around 60%-75% of the obviously defects [1]. In order to improve the fabric inspection accuracy and reliability, computer image recognition technology has been developed to automate the inspection process. A variety of fabric defects detection methods have been proposed in the past decades [2]-[6]. Chan et al. [2] proposed a Fourier transform based method to detect the structural defect in fabric. Kumar et al. [3] used Gabor wavelet features for automated inspection of textured materials. Mak and Tian [4] applied singular value decomposition (SVD) to defect-free image patches, extracting the left singular vectors as the basis images. Bu et al. [5] make a one-dimensional power spectral density (PSD) analysis of the fabric image by a Burg-algorithm-based Auto-Regressive spectral estimation model, and extract features capable of effectively differentiating normal textures from defective ones. In [6], the concepts of regular bands and independent components analysis (ICA) are combined for patterned fabric defect detection. Recently, Zhou et al. [7] used dictionary learning framework to address textile fabric defects detection. At present, most of the methods mentioned above can well detect the defects when the defects are obvious. However, they are not effective to detect those small and undistinguishable defects and are only limited to inspect a particular type of fabric pattern, i.e. solid colour. In other words, a detection technique can be applied to fabric with solid colour but is not feasible on fabric with stripe pattern. As nonlocal self-similarity (NSS) has been successfully applied to image denoising and fabric defects can be regarded as noise, this paper presents a NSS based method for defects detection, called defect detection based on nonlocal self-similarity (DDNSS) technique. The brief steps the proposed DDNSS technique is highlighted as below: ______________________________ + Corresponding author. Tel.: 852-27666471 E-mail address: calvin.wong@polyu.edu.hk

Page 35 of 1108

firstly, the fabric image is divided into many patches; for a given patch, the proposed method searches other several similar patches in the fabric image and uses the weighted average of these similar patches to estimate the given patch; finally, a new image will be synthesized from these estimated patches, and the defects can be located by finding the difference between the original fabric image and the reconstructed image. Experimental results prove the effectiveness of the proposed DDNSS algorithm.

2. Defect Detection Based on Nonlocal Self-similarity The nonlocal self-similarity means that for a given patch in natural image, we can find many similar patches in the same image. Efros and Leung used the NSS for the synthesis of texture images [8], which is a generalized periodicity assumption. Buades et al. first adopted this idea to denoising [9]. If a fabric image contains defects, the fabric image is similar to a natural image corrupted by random noise. Compared with natural image, image acquired from fabric is also self-similarity and thus adopting the NSS for fabric defect detection is highly feasible. The proposed method for fabric defect detection is a patch based method. The connection between a fabric image X ∈ RN and the patches extracted from X at location i is established first. Following the notation in [10], Let x i =R i X be the stretched vector of an image patch of size n × n , where R i is the matrix operator. We can obtain the least square solution of X as

X = (∑iRiT Ri ) −1 (∑iRiT x i )

(1.1)

The key steps of the proposed algorithm can be summarized as follows: For the fabric image X contains defects, it is firstly divided into many patches. Then for each patch x i , a set of similar patches to it in a certain range can be searched. A patch x i q is selected as a similar patch to x i if the Euclidean distance between them is less than a predefined threshold. Then the weighted average of first L closest patches is computed, that is,

x i' = ∑q =1 b iq x iq to predict x i . The weight b iq is set to be inversely proportional to the distance between L

patches x i and x i q , where b iq = exp(− x i − x iq

2 2

h ) ω , h is a preset scalar and ω is a normalization factor. After

each patch is handled by weighted average of their similar patches, then a new image Y can be synthesized according to Eq. (1.1). In the new reconstructed image, the free-defect pixels are similar to the pixels of original image, while the defect pixels are very different from the pixels of original image. Thus defects can be easily detected by finding the difference between the original fabric image and the reconstructed image. As the proposed method mainly uses the idea of the nonlocal self-similarity of the fabric image, the technique is called defect detection based on nonlocal self-similarity (DDNSS). Fig. 1 below is the flowchart of the proposed DDNSS.

Divide X Captured image X

Patch x1 ... Patch xi ...

L closest patches to patch xi are selected

Patch xi

Reconstruc t patch xi

Defect Location

Perform the threshold on Y-X

Synthesize Image Y

Fig 1: The flowchart of the proposed DDNSS technique

New patch xi’

Page 36 of 1108

3. Experiments Experiments were conducted to demonstrate the performance of the proposed DDNSS algorithm. There are several typical fabric defects, including line defects, knot defects and spot defects. Line defects are relatively big and easily to be detected, while knot defects and the spot defects are the most difficult defects to be detected in the apparel manufacturing process, especially under the situation with uneven illumination distribution. Thus the experiments were mainly conducted on spot defects and knots defects. Meanwhile, experiment results on spot defects will be presented to validate the robustness of the proposed DDNSS algorithm under the situation with uneven illumination distribution. All test images were captured from apparel industry and the size of each image is 500Ă&#x2014;500. In the experiments, the proposed DDNSS algorithm was run on each test image separately. The results are shown in Fig. 2 and Fig. 3. Fig. 2(a)-2(d) depict the original defect images, where Fig. 2(a) and Fig. 2(b) are spot and knot defects on the fabric with solid color respectively. Fig. 2(c) and Fig. 2(d) depict the stripe pattern fabrics with spot defects. Fig. 2(a1)-2(d1) are their respective detection results generated by the proposed DDNSS technique. Although the defects of Fig. 2(a)-Fig. 2(d) are very small and the diameter of each defect is less than 1 mm, the proposed algorithm can still detect them accurately. In the process of image acquisition, the captured image sometimes was dark due to the uneven illumination distribution. In this case, the defects are more difficult to be detected. In order to verify whether the proposed DDNSS algorithm is robust to light, Fig. 3 illustrates the results of an experiment on spot defect with uneven illumination distribution. Fig. 3 shows that the proposed algorithm can detect the defect in this case. The reason is that DDNSS adopts a local similarity-based method to handle the detection problem. It first divides the captured image into small patches and then reconstructs each patch by the weighted average of the local similar patches. Since the intensity of local illumination is much smoother than the illumination on the whole, DDNSS is robust to illumination and able to find the defects precisely even under uneven illumination distribution. In summary, all results of the experiments show that the proposed DDNSS algorithm is effective for defects extraction in fabric image.

(a)

(b)

(c)

(d)

(b1)

(c1)

(d1)

(a1) (a1)

Fig. 2: Original fabric defect images (a)-(b) solid color, (c)-(d) stripe pattern (a1)-(d1) Detection results of the proposed DDNSS technique

Page 37 of 1108

(a) Fig. 3:

(a1)

(a) Original defect image (a1) Detection result of the proposed DDNSS technique

4. Conclusion In this paper, a nonlocal self-similarity based method for fabric defect detection is presented. The experiment results show that the proposed DDNSS algorithm can accurately detect different small defects with less than 1mm on fabrics with solid color and stripe pattern under even and uneven illumination.

5. Acknowledgement The authors would like to thank the funding support from The Hong Kong Research Institute of Textiles and Apparel (Project no. ITP/037/15TP).

6. References [1] K. Schicktanz, “Automatic fault detection possibilities on nonwoven fabrics”, Melliand Textilberichte, vol. 74, pp. 294–295, 1993. [2] C.H. Chan and G. K. H. Pang, “Fabric defect detection by fourier analysis”, IEEE Transactions on Industry Applications, vol. 36, No. 5, 1267-1276, 2000. [3] A. Kumar and G. K. H. Pang, “Defect detection in textured materials using gabor filters”, IEEE Transactions on Industry Applications, vol. 38, No. 2, 425-440, 2002. [4] K. L. Mak and X. W. Tian, “Textile fabric flaw detection using singular value decomposition”, International Conference on Green Circuits and Systems, pp. 381–386, 2010. [5] H.G. Bu, X.B. Huang, J. Wang, and X. Chen, “Detection of fabric defects by auto-regressive spectral analysis and support vector data description”, Textile Research Journal, vol. 80, 2010. [6] R. K. R. Ananthavaram, O. S. Rao and M. K. Prasad, “Automatic defection detection of patterned fabric by using RB method and independent component analysis”, International Journal of Computer Applications. vol. 39, No. 18, 52-56, 2012. [7] J. Zhou, D. Semenovich, A. Sowmya and J. Wang, “Dictionary learning framework for fabric defect detection”, The Journal of the Textile Institute, vol. 105, No. 3, 223-234, 2014. [8] A. Efros and T. Leung, “Texture synthesis by non parametric sampling”, In Proc. International Conference on Computer Vision, vol. 2, pp. 1033-1038, 1999. [9] A. Buades, B. Coll, and J. M. Morel, “A review of image denoising algorithms, with a new one”, Multiscale Model. Simul, vol. 4, no.2, pp. 490-530, 2005. [10] M. Aharon, M. Elad and A.M. Bruckstein, “K-SVD: An algorithm for designing of overcomplete dictionaries for sparse representation”, IEEE Transactions on Signal Processing, vol. 54, no. 11, pp. 4311-4322, 2006.

Page 38 of 1108

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

Brief Introduction on Uyghur Traditional Headwear Gulistan Igemberdi, Xiaoming Yang Textile College of Donghua, University, Shanghai China

1. Introduction There are a variety of kinds of Doppa: taqiyah, fur cap, kerchief and homburg. In Uyghur tradition custom, headwear not only has the function of cold protection or hot protection, but only is the demand as etiquette. In the situations of social intercourse, church, family visit, friend visit, the headwear which is an important part of garment art and the respect for relatives and friends should be worn. Uyghur taqiyah can be translated as Doppa that is the traditional wear custom of Uighur people for hundreds of years and almost all like it, whether boys or girls, men or women, young or old. Doppa is not only the daily commodity but also the exquisite artwork. It has both practical and decorative art value. There are many kinds of Uyghur headwear with different local characteristics, artistic features and cultural connotations. This is closely related with the geographical environment, religion consciousness, aesthetic orientation, splendid culture and other social customs, reflecting the Uyghur artistic style and traditional heritage.

2. Historical culture origin of Doppa Uyghur ancestors came from Mobei. In 740 AD on the Mobei plain, Uyghur Khanate was established and in 840 AD disintegrated. About 100,000 people went through the Altai Mountains, into the south of the Tianshan Mountains and migrated to Hexi Corridor Turpan Depression and reached grassland and oasis surrounded by Tarim Basin which consequently was the live hood of Uyghur people and the natural environmental base of Uyghur culture. Uyghur have been lived on the Silk Road, which integrated the local Han Chinese, the Tibetan people, the Khitan and Mongol, etc. On the basis of the inheritance and development of national cultural, they learned from Chinese culture, Indian culture, Greek culture, the Islamic culture nutrition forming a unique culture. These unique cultural origins are reflected by the art of Doppa. Uyghur culture is influenced by Islam which is evidently reflected in Doppa shape. Xinjiang Islamic mosques that combined with Arab and Uyghur as one style is commonly built by forms of flattened structure or arched dome, round dome and towering minarets. In view of Doppa shape, it coincided with the construction of the mosque. If Doppa is folded by seam, the shape line is similar with dome minaret silhouette, which can’t help reminiscent of contact between them. Doppa is mostly selected with saturated bright color. With blue, green, red it obviously reflects the color view and aesthetic view of Uyghur. And this color view had its unique historical cultural origins: Turkic, the ancestors of Uyghur called "Blue Turks”; moreover Islam regards blue as heaven whose love for blue is of the religious color. Green is derived from the nomadic life that nomadic people live in the desert. Also Islam born in desert and arid areas advocate green further enhancing green reverence and love. The red is derived from their worship for fire during Shamanism, Zoroastrianism (Zoroastrian) stage, and on the other hand they are affected by color view of Han people. Meanwhile, love for red color also reflects their passionate personality. Not only the appearance of Doppa has cultural origins, lining color also makes sense. Almost all of Uyghur men’s Doppa lining is red that is the color of blood and a symbol of life and vitality. The great features of Doppa are its beautiful designs and various

Page 39 of 1108

patterns which are related to Uyghur oasis cultural background. Uighur people are known as their love for orchards and gardens. They enrich and beautify their lives with abundance of fruit and blooming flowers. The most vivid and beautiful pattern on colorful Doppa is based on the fruits and flowers, which symbolizes the Uyghur people’s love and the pursuit for a better life. From unearthed sculptures, we found there were a variety of crowns in the sixth or seventh century, classified by man or woman hats, soldier hats and night crowns and so on. Soldier hat as helmet can be closely worn on head and its front edge is down straight to guard eyebrows; felt cap as man hat that is top and curved and also there is a scarf wrapping head whose top side is flat. Women hat is bowl-shaped whose flat top is slightly arched similar with hats nowadays and also there is a scarf wrapping head and tied in the forehead that is the same with hats today. The scarf wrapping around the head and tied hair is bilateral symmetrical and top tied like dignified men’s curly and drooping ripple, also there is ripple combed or corrugated backward whose shape is different from the Peach crown that king wear, such as in HE king, Gaochang Huihe crown and so on. However HE crown is litter lower, and Gaochang crown is higher. At that time the hat was called as "Binouke" in the "Turkic Dictionary", which is now spoken as "Boke", but evolution of this name is different from the hat shape. As it can be seen from ancient sculptures, the hat is embroidered or at least has geometric patterns, but today's so-called "Boke" has neither the embroidery pattern nor cap edge(Kezaike) which is formed by eight parts. Consequently it is called "Doppa" that is not very long ago from now. There is only two or three hundred years history, which means that "Boke" has no flowers and eight parts, but "Binoukeis" may has flowers or be formed by eight parts. Therefore there is only inheritance of the name, but in fact the shape of hat has been a big change. In all kinds of Doppa, Badamu Doppa has the longest history. It is also called "Tusi" Doppa. It is embroidered with "half moon", "Star" pattern. It is said that this pattern has a tragic legend. In AD 995, Suri Tang Kesu tragfiura • Bugera from Hehan dynasty accepted Islam from the Arabian Peninsula and made it the state religion of his country. Also he made the national flag the "star and crescent Blue Flag". By AD 1176, Khitan people moved westward from the northeast destroyed Hehan dynasty and established new national flag to prohibit the use of "star and crescent Blue Flag" in order to facilitate their rule. But people were unwilling to bow to slavery fate, so the people from Yarkand, Hotan, Aksu, Kuqa and parts of Central Asia embroidered the pattern of star and crescent on black cloths, and sewn into Doppa to wear showing that they didn’t give up "star and crescent Blue Flag" and didn’t want to be slaves for foreigners. Therefore, Badam Doppa is a symbol of the indomitable spirit of the Uyghur. In the Peacock tomb ditch sites archaeologists found female wooden figurines worn peaked cap and the other 57.5 cm-long female wooden figurines whose hats were similar with Uyghur dome cap today. In addition, the terracotta warrior from Warring States period was unearthed on south bank of Gong Nance, Yili County. He wore the bowler hat whose front curled forward, which gave people a deep impression. It was little different from the hat that Behistun or Skunha wore in Darius I (BC -? 486 years ago) but they were the same type. Most scholars believe that peaked cap is one of the important criteria to determine the relics are whether the initial Cypriot artifacts or not. About the Cypriot that wore peaked cap from the north east of the Syr Darya is recorded in "history" book written by Greek historian Herodotus that "Cypriots from Scythian tribes wore towering peaked felt hat, pants, with the local bow, dagger and special money". One important feature that found in some early human cultural sites from tomb ditch of Peacock downstream, Qumul Wubao of Xinjiang and Qiemo was peaked cap that dead wore, thus many scholars believe these were the relics of Cypriots. It was indicated from archaeological material that Cypriot indeed lived in Tianshan Mountains. Although we can’t distinguish affiliation between Serbs and Uighur, it can be speculated that Uighur Doppa originated from peaked or dome cap all over the Western Regions. It was recorded in historical materials that Huige princess in Mobei period was described "gold crown like forward finger". The hats that male breadwinners wore from Bezeklik 55 caves had two styles. One was the peaked cap that was sharp at top and round at bottom. The other can be folded upward along forehead and had a shawl along back. Until Ming and Qing Dynasties "Man’s crowns were round, six or seven inches high, sharp front and back and there were six or seven inches along the length of each wing" .Woman wore small hats with several safflower, wrapped with

Page 40 of 1108

scriptures and three or four crane feathers. And they went out with colorful handkerchiefs or white clothes called "Taliji". According to these historical materials it is analyzed that Uyghur Doppa has a long history.

3. Categories and manufacture process of Doppa Uyghur Doppa is one of the most representative embroidery of the nation. According to sex, age, personality and other factors, different liner clothes are adopted to show minor difference among harmony. The forms of Doppa are various and embroidery is exquisite. It is a practical and elegant ethnic artwork. Doppaâ&#x20AC;&#x2122;s materials are selected elaborately and it has double clothes both inside and outside. Upscale Doppa uses high-grade silk and velvet material. Mid-range Doppa adopts the general silk and ornaments, while those ordinary ones use cotton. Womenâ&#x20AC;&#x2122;s Doppa is dotted with gems, agate, jade, coral, amber, fine jade and other precious ornaments. There are a number of ways to embroider Doppa: silk embroidered, cruciferous embroidered, silk knot embroidered, beaded embroidery, trellis embroidery, gold and silver plate embroidery, crochet embroidery, tie velvet embroidery, and prick, string, comprehensive embroidered dish and so on. Here introduce several the most characteristic Doppa types and manufacture process below: 1. Badam Doppa(Fig.1): The pattern is designed by deformed Badam almond added flower figures which have rich shapes. Most of them are designed by white flowers on black base that is solemn, simple and elegant, and no matter old or young Uyghur people like to wear this kind of Doppa. This pattern is embroidered with four parts and by white thread on black fabrics. On each part the Badam almond pattern downward curving is embroidered and on the hat edge there are four edge patterns, each of which is a part of arc from the Badamâ&#x20AC;&#x2122;s bigger side. Four parts have sixteen patterns. The Badam Doppa can be classified by several kinds based on regions. Each part of Qeshqer Doppa is embroidered by a white downbent Badam pattern and the edge of the hat is lower while the edge of Yarkand Doppa is higher. It is embroidered by thick white thread and the stitch is intensive. The pattern is also bigger than Qeshqer Doppa. Yarkand Doppa is texture closely thick, sharp contrast by black and white and the pattern viewed from far has good effect. The shape of net Badam and Yarkand Badam is almost the same, but the embroidery method is different. The former is embroidered by fine tread whose pattern covers other patterns to make it distinct, exquisite and suit for a closer look. Also there is "Ququer Badam" Doppa that has lower edge of hat with smaller Badam embroidered. The shape is like "Ququer" (wonton). In addition, there is a "double Badam" Doppa which is embroidered by a pair of upstanding curved Badam pattern on each part and along the edge of hat each part there are the four semicircles with a five petal flower on top of these two little Badam. Under these badam pattens there is the black or brown fabric formed by angled geometric patterns. There are four obvious and stiff angular edges on the top of Badam Doppa hat. And on the edge of Dappa there is spike-shape fringe to make capping and uncapping convenient and it can also plays a decorative role. 2. Gilem Doppa(Fig.2): By "Na yarn" stitch method, the base fabric is embroidered by white thread with rose pattern embroidered by green, pink, purple, blue and other colorful thread and the flower and leaf pattern is geometric deformation which is like the angular pattern on the Uyghur carpet, hence, it is called "Gilem Doppa" (carpet). The pattern is formed by four parts and on top of each part there is the rose flower and leaf figure. On the bottom of hat edge the pattern is formed by a part of rose figure from the top. The edge of hat is embroidered by the black velvet or silk velvet and the main color is peach red and rose red. It is fresh, gorgeous and shallower than Badam Doppa and also easy to fold. This kind of Doppa is a popular kind of Doppa in Tashkent Uzbekistan, so it is also called "Tashkent Doppa". Now "Tashkent Doppa" is generally a name for geometric grid pattern embroidery Doppa. It is very popular among Uyghur young women. 3. Menpur Doppa(Fig.3): This kind of Doppa is embroidered with four circles on the top and four oblong or circular figures on the edge of hat which is the most common Doppa for old

Page 41 of 1108

10.

or young, men or women. The shape is lower than Axun Doppa. There are angles and four parts whose background is generally black, coffee, lilac, sky blue and so on. The color of pattern is corresponding one or two kinds to contrast with background. There are Badam figures, leaf figures and petal figures. The edge of some Mempur Doppa is embroidered with flowers and it is mainly for middle-aged and elderly women. Chimen Doppa(Fig.4): It is designed by Chinese word "çął" as skeleton. The pattern of flowers interlaced with leaves is a figure that branches and trunks connect with each other or lines separate to make it a plurality of reverse triangle or diamond pattern. The shape is like Badam but the edge of hat is lower. On the top of hat, there are four thick and obvious corners which are easy to fold. The edge of hat is embroidered with black velvet. The main color of base fabric is light green or blue on which Badam branches are embroidered by white thread. The patterns are dense to fill the surface of hat like blooming flowers, so it is called "Chimen" (flowers) Doppa. It is the favor of intelligentsia because of its elegant pattern and color. Marjan Doppa(Fig.5): It is the paillette beaded Doppa. The shape is the same as Menpur Doppa, but the four angles on the top of hat are not obvious, rather round. The background of hat has many kinds of color such as brown, dark purple, black and so on. The patterns are sewed by small beads and are very plentiful. Because the figures closely centralize, the pattern is particularly distinct under the background. This kind of Doppa is suitable for young and middle-aged women to wear. Zer Doppa(Fig.6): It is also called cannetille embroidery Doppa. The flower is threedimensional and sparkles in the sunshine to make people feel luxury and dignified. The shape is the same as Marjan Doppa. The color of background is generally black, dark red and dark green. The pattern is mainly the apricot blossom shape embroidered by cannetille. Set off by dark background, the pattern appears to be gorgeous. It is mainly for old women. Altun-Qadaq Doppa(Fig.7): It is decorated with pressed, engraved sequin on the hat which is one kind of precious Doppa for rich women in old days. With the improvement of living standards "Tyrant Gold" Doppa has become popular in recent years. Turpan Doppisi(Fig.8): The characteristic is that flower figures are big and the vacancy of bottom is small with very brilliant red color. The surface is made by blue or purple pleuche. Each side is embroidered with colorful round or rectangle pattern and then is sticked with paste. Four iron wires tangled by four kraft papers (mulberry paper in ancient) are rotated into the four sewed parts inside Doppa, which makes it sharp on top and wide on bottom. Then separated them by hand and draw out four iron wires. The inside kraft paper is knitted by three or four thread and fixed to show three dimensional making it more hard. Lastly, the mold is covered and the border of hat is embroidered by black velvet. This kind of Doppa is popular in Turpan, Shanshan, Tuokexun regions. Ghulja Doppisi(Fig.9): Its pattern is slim and color is gentle. This is five-petal Doppa called as "white Xitala Doppa". Generally, the Doppa is constituted by four parts, but this kind of Doppa has one more part. It is for girls and boys. The shape is different from other Doppa. It is arched and has no angles with color of dark red, black, dark green and so on. The process is more characteristic. The choice of linen and lining and other lining to stick top and edge of hat together makes it harder. Sewing from center to two sides to make the shape shallow and round. Also by various colorful thread of strong color contrast four simple and concise rectangle or circles patterns highlight the flow of curve. The Doppa canâ&#x20AC;&#x2122;t be folded and it is popular in Ili, Tacheng, Bole and other northern regions. Kiriye Telpiki(Fig.10): It is also known as Talibaike shaped like a wine bottle or a small bowl, only 5 to 6 cm high, and its diameter is less than 10 cm, which is the world's smallest hat and has been recorded into Guinness World Records. In fact the Doppa is not used to "wear", while it is ornament of headwear. The texture of surface is black lamb skin or manmade lamb skin and the top fabric of hat is constituted of white, yellow and sky blue silk. The edge of hat is made by black pleuche and liner is white lamb skin. It is sewed by hand with process that is narrow on top and wide on bottom with black and white cotton thread. Women wear this cap on the right side of kerchief which looks like a hat near but like a flower from far. It is popular in Kiriye, Lop, Chira, Niye and other regions for middle-aged

Page 42 of 1108

and old women to wear. 11. Shapaq Doppa(Fig.11): This is also called skullcap, most of which is plain, some of which has water wave on the edge of cap. Although the shape of the Doppa is similar to Imams Doppa, it is shallower. It is constituted of four parts and has no angles. Its shape is like melon shell so it is called "Shapaq Doppa"(melon shell). The background of some cap is black with flowers embroidered. Some are white. Some have edges. Some are embroidered with multicolor flower. Hats without edge have many kinds in black, white or dark green, and some are joined by two black parts or green parts. This kind of Doppa is a normal cap for young and old men in south regions in Xinjiang in summer and some are used for liner cap in winter. 12. Tor Doppa(Fig.11): This is knitted by crochet whose shape is similar to Shapaq Doppa. But it has no parts and knitted continuously. The pattern in white is generally for middle-aged and old men in south Xinjiang in summer. 13. Selle Doppa(Fig.12): It is namely Imam Doppa. The shape is higher and shaper than normal Doppa. It is constituted of four parts without angles. Because the Doppa needs to be tangled with selle and keep constant shape, the top of it should be shaper to show the arch effect. The color of it is rich and most of background color is coffee, blue, blackish green and so on. The patterns have Badam shape or double Badam shape which are embroidered on the top of hat to make it not covered while wrapping selle.

Fig.1 Badam Doppa

Fig.3 Menpur Doppa

Fig.2 Gilem Doppa

Fig.4 Chimen Doppa

Page 43 of 1108

Fig.5 Marjan Doppa

Fig.7 Altun-qadaq Doppa

Fig.9 Ghulja Doppisi

Fig.6 Zer Doppa

Fig.8 Turpan Doppisi

Fig.10 Kiriye Doppisi

Fig.11 Shapaq Doppa & Tor Doppa Fig.12 Selle Doppa

Page 44 of 1108

Fig.13 Doppa as gift to national leaders Dengxiaoping

Fig.14 Beautiful Uyghur Doppa from Ancient time Fig.15 Uyghur Girl wearing Gilem Doppa

4. Uyghur International Doppa Festival May 5th each year is designated as the Uyghur International Doppa Festival. May 5, 2010, Xinjiang Normal University and Xinjiang Normal University hosted the first Uyghur International Doppa Festival. This festival was hosted by folk and Uyghur scholars. Every nation has its own customs and traditional festivals, as Uyghur also have their own. On this day, Uyghur people in festive costumes and Doppa dance folk dances and have parties to celebrate. We should pay attention to our customs and traditional festivals, to learn more about some relevant knowledge to broaden horizon. Let traditions and festivals continue! Protect our intangible cultural heritage! This is a great responsibility of each one of us! In development of thousands of years Uyghur gradually developed characteristic traditional costumes. In recent years, under the impact of foreign culture many Uyghur people abandon their traditional costumes. It is the most obvious that Arab costumes appear a lot. Of course it is free to wear clothes and we can't be against the right to choose costumes. However, as a Uyghur, we have responsibility and duty to inherit own culture. Various kinds of Doppa are our most remarkable characteristics. No matter men or women, once wear Doppa, the temperament from inside to outside will be changed so that men will be more handsome and powerful and women will be more graceful and charming.

5. Conclusion Uyghur Doppa as an ethnic characteristic artwork is more and more favoured by people. On

Page 45 of 1108

each great festival activity, Uyghur people embroider or buy Doppa elaborately to dress up; some also hang the Doppa on the wall indoors to increase the artistic aspiration of room decoration; sometimes, it is a precious gift to the relatives and friends or guest from afar. At annual National People's Congress, deputies of Xinjiang Uyghur hope to donate Doppa to national leaders to express their deep feelings. (Fig.13)Magnificent and colorful costumes of all peoples reflect the nation's heritage, creativity and wisdom, and this eminent national cultural tradition should be inherited and developed.

Page 46 of 1108

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

Characteristic on Color Expression of Luxury Brand’s Garments Qian Xiong, Yui Uchiyama, Hyojin Jung, Saori Kitaguchi, Tetsuya Sato Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan

Abstract: As a source of fashion all over the world, luxury fashion has a great influence on the trends of fashion world. Apparel enterprises and designers in the enterprises must not ignore the trend information given by luxury brands in the seasonal collections when they plan their merchandise for the global markets. In this study, color usage of five famous luxury brands’ garments (Louis Vuitton, Hermes, Gucci, Prada, Chanel) presented in the fashion show of Ready-to-Wear Collections 2013 were analyzed, in order to clarify the color characteristics and differences. As a result, color usage of luxury brands’ garments could be found some similarities: white, high-chroma, and high-lightness colors appear more in SS season; black, low-chroma, and low-lightness colors appear more in AW season. Meanwhile, the color expression of each brand’s garment has its own feature. Keywords: luxury brand, fashion color, garment, fashion show

1. Introduction In the fashion industry, trend information begins to flow among the related enterprises from two years ago of the season that new garments will be presented generally. There is a process that trend color is given out from color associations firstly, then yarn and fabrics makers receive and include it into their new products, after that designers of luxury brands create ready-to-wear garments containing the previous color and textile trend information as well as their creativity. Ready-to-wear garments published in the most prominent fashion weeks held in the four fashion capitals of the world will be used as references by other major or small apparel production enterprises when they are planning of products for the domestic market [1]. Although consumers rarely notice the color and fabric trends going ahead, garments exhibited in the four major fashion weeks are always investigated and incorporated for the new trends by a lot of apparel companies, and have been advertised in a variety of fashion magazines. Trend information such as colors and designs of luxury brands’ garments from the fashion collections is amplified by various routes, and subsequently recognized as "fashion" by the general public. Therefore, luxury brands could be seen as the main source of the clothing fashion trend. Concerning the luxury brand, previous researches mostly focused on brand value and marketing from commercial viewpoint, or made prediction on their garment design. However, studies done on garments color still remain in measure and analysis by a subjective way. It is also important to survey the running color trend of luxury brands garments by a quantitative way. This study focused on the color of luxury brand garments that influence the fashion of the world strongly, investigated and analyzed the color representation of readyto-wear garments presented in 2013, intended to extract their color characteristics. In our previous study [2], color characteristics of fast fashion brands had been investigated and analyzed quantitatively. The same research method was used in this study.

2. Investigations The investigated luxury brands were Louis Vuitton, Hermes, Gucci, Prada and Chanel, which were having an apparel business and with high brand value ranking in the luxury business in 2013 [3]. Colors of luxury brands’ garments were collected from images of Spring/Summer (SS) Ready-to-Wear Collection and Autumn/Winter (AW) Ready-to-Wear Collection in 2013, which were published on the website of American fashion magazine VOGUE. Three types of collection are usually presented during fashion weeks, the Ready-to-Wear Collection, the Haute couture Collection, and the Men's Collection. This study focused on Ready-to-Wear garments which are not customizable and made to standard sizes fitting most people. All the garments images of Louis Vuitton, Hermes, Gucci, Prada, Chanel were collected from their SS and AW Readyto-Wear Collections.

Page 47 of 1108

The colors of the extracted images were measured by using a color measurement software Feelimage Analyzer (Viva Computer Inc.) and quantized in terms of CIELAB values [4] and Munsell values [5]. When a garment had more than one color, the color occupying the biggest area was extracted as its representative color. However, when a representative color was not able to select because of complexity of a pattern, such garment was not used as a sample of this study. The color information was transformed through a few media such as camera and computer software analysis. It is considered that there were some color differences between real clothes and samples, however, it’s not much change on their color values. It will hardly affect to understand garment’s’ color characteristics. Table 1: The luxury brands investigated in this study Louis Vuitton

Hermes

Gucci

Prada

Chanel

Headquarter (Founded year)

France, Paris (1854)

France, Paris (1837)

Italy, Firenze (1921)

Italy, Milano (1975)

France, Paris (1909)

Designer

Marc Jacobs (Male)

Christophe Lemaire (Male)

Frida Giannini (Female)

Miuccia Prada (Female)

Karl Lagerfeld (Male)

Location of collection

Paris

Milano

Paris

Type of collection

Ready-To-Wear, Menswear

Ready-To-Wear, Couture

Table 2: The number of measured and unmeasured samples Brands

Louis Vuitton

Hermes

Gucci

Prada

Chanel

(seasons)

Collected samples

127

133

Removed samples

Measured samples

100

3. Results and discussions 3.1.Color distribution tendency of five brands As shown in Figure 1 and Figure 2, the colors of luxury brands' garments presented in SS and AW Readyto-Wear Collection in 2013, were plotted on the CIE a*b* coordinates. Colors of Louis Vuitton, Hermes, Gucci, Chanel garments presented in SS season were mainly distributed at high-chroma area that kept distance from the origin, and in AW season the plots were gathering around the origin or at low-chroma area. On the contrary, Prada was mainly consisting of low-chroma colors in the SS season, and using a lot of vivid colors in the AW season. Colors of garments presented in the collection are not only affected by the preceding color trends and fabric materials, but also affected quite by the sentiment and feeling of designers. In general, every collection of a luxury brand has a theme. Under the theme, a designer creates a series of garments to express his or her ideas. Sometimes, due to a special thought of a designer, eccentric garments come out. For example, the garments of Prada in 2013 spring and summer collection. Miuccia Prada, who is holding the post of the exclusive designer of Prada, abandoned chromatic color and used lots of achromatic color in this collection in order to express a sense of pure. The editor of magazine VOGUE said that opposite to other brands with abundant colors, the idea Prada just used monotone in summer was extremely fresh [6]. Louis Vuitton used yellow as its main color in the SS season in 2013, some green-yellow colors of highchroma area and yellow-red colors of medium low-chroma area were also used, however few blue colors. In the AW season, according to the theme of “bedtime and nightwear”, colors with a chroma value below 20 were used in quantity, at the same time blue colors were quite used. Hermes chose yellow and blue colors which were complementary colors to each other in the SS season, showing a sprightly and bouncing image. In the AW season, dark colors were dominant, a little of brown leather garments added the classic feeling. Gucci used pretty particular colors in the SS season. High-chroma colors were distributing in red, yellow, green and blue directions. There were also some achromatic colors. Red, yellow, green and blue, these four psychological primary colors gave people a fresh and bold impression by their strong contrast. Gucci's colors in the AW season were plotted on achromatic and low-chroma areas. Blue and purple colors were used as the accent colors, adding a flash point to the dark tones.

Page 48 of 1108

Prada used black and white basically as well as a few low-chroma colors in the SS season. In the AW season, in addition to low-chroma colors, there were many blue-green colors with medium-chroma and brown colors, which made more active sense than other brands in the same period. In the both of SS and AW seasons, vivid red could be seen as an accent color in the clothing color of Prada.

Figure. 1: Color distribution of five brands in SS season

Figure. 2: Color distribution of five brands in AW season

Figure. 3: Hue distribution ratio of five brands in 2013

Color distribution of Chanel was biased to blue. There were a string of blue colors from low-chroma to highchroma in the SS season, and even in the AW season when chroma was depressed there were still lots of blue colors. In addition, red colors of medium and high chroma also appeared frequently.

3.2.Hue distribution ratio of five brands The 10 hue categorization of Munsell Color System was used to describe the hue distribution ratio of five brands' clothing colors. Figure 3 shows a common characteristic of luxury brands is that concerning the achromatic color white appears more in the SS season and black appears more in the AW season. However Hermes had a high percentage of white in AW season, because it used many white and beige blouses for setting off their dark outerwear such as coat or jacket. About the chromatic colors, warm colors like red, orange and yellow were often used in the SS season. Prada presented nearly almost achromatic color of garments in the collection and both of warm and cool colors were used very little. However, colors in the AW collection were used in a good hue balance.

Page 49 of 1108

3.3.Lightness distribution of five brands Table 3 shows the lightness ratio on the color use of each brand. The lightness of colors was divided into high-lightness (Munsell V value ≥ 5) and low-lightness (Munsell V value < 5). According to these data, except Prada which presented more than half black garments in the SS season, the percentage of high-lightness colors in SS season is larger than that in AW season in a same brand, and conversely the percentage of low-lightness colors in AW season is larger than that in SS season. In particular, the tendency in Chanel was strong because the difference between the SS and AW seasons had exceeded 25%. Table 3: The percentage of high-lightness and low lightness colors Louis Vuitton SS AW

Hermes SS AW

Gucci SS AW

Prada SS AW

Chanel SS AW

High-lightness (V≥5)

49%

44%

60%

45%

39%

20%

34%

54%

26%

Low-lightness (V<5)

51%

56%

40%

55%

61%

80%

66%

46%

74%

4. Conclusions Through the investigation of garments presented in Ready-to-Wear Collections 2013, color characteristics of five luxury brands' garments were quantitatively analyzed and discussed. They were summarized as the following three points. 1. Most of the luxury brands in this study used more colors with high-chroma in the SS season, and more lowchroma colors in the AW season. However, for the strong influence given on garments design by designers, color usage of luxury brands’ garments did not follow this rule in some cases. Each brand was using colors according to its own theme. The difference of color usage among brands could be seen more clearly in the SS season than that in the AW season. 2. In general, luxury brands use a large number of achromatic color to create the sense of luxury and elegance. However, it was found that all of the five luxury brands were not using the achromatic color exactly in their 2013 collections. For instance, Chanel used the achromatic color at a high rate more than 60% in a whole year, and Gucci had a percentage of achromatic color less than 30% in the SS season. The ratio of achromatic color of each brand was different by the season. Relating to the usage of achromatic color, white appeared more in the SS season and black appeared more in the AW season. 3. There was also a common color characteristic of luxury brands' garments on lightness: color lightness was high in SS season, and lightness was low in AW season. This paper has discussed about the color characteristics of the five luxury brands’ garments just for 2013 one year. Therefore it's necessary to investigate colors of luxury brands' garments for a long period to clarity how the color trend changes on the time line. In addition, it would also be valuable to compare the luxury brand color with the fashion color in chronological order.

5. Acknowledgement This work was supported by JSPS KAKENHI Grant Number 24220012. We thank JSPS for the support.

6. References [1] KITAMURA Makoto; The Development Process of Fast Fashion : Interaction among Actors in the Fashion Industry, The Journal of Tokyo Keizai University (Business), Vol.15 No.1, 2012 [2] Qian XIONG, Hyojin JUNG, Saori KITAGUCHI, Tetsuya SATO; Color Feature of Fast Fashion Brand Outerwear on Official Online Store, International Journal of Affective Engineering, Vol.15 No.1, 2016 in press [3] Millward Brown co., 2013 BRANDZ TOP100 REPORT: http://www.millwardbrown.com/docs/defaultsource/global-brandz-downloads/global/2013_BrandZ_Top100_Report.pdf [4] Color Science Association of Japan; Handbook of Color Science, University of Tokyo Press, pp.102-103, 2011. [5] Color Science Association of Japan; Handbook of Color Science, University of Tokyo Press, pp.218-227, 2011.

Page 50 of 1108

[6] Report of PRADA 2013 Spring/Summer Ready-to-Wear Collection: http://www.vogue.co.jp/collection/brand/Prada/13ss-rtw/report [7] Magazine VOGUE Japanese official website: http://www.vogue.co.jp/collection

Page 51 of 1108

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

Conditions for laccase immobilization onto enzymatically modified woven polyamide Ji Eun Song 1, Hye Rim Kim 1, Sang Young Yeo 2, and So Hee Lee 3 1

Department of Clothing and Textiles, Sookmyung Womenâ&#x20AC;&#x2122;s University, Seoul, Korea Technical Textile & Materials R&BD Group, Korea Institute of Industrial Technology, Ansan, Kyeonggi-do 3 Research Institute of Women's Health, Sookmyung Women's University, Seoul, Korea

Abstract. In this study, laccase from Aspergillus was immobilized onto enzymatically modified woven polyamide by bromelain. The results indicated that the optimum immobilization conditions were evaluated as pH 6.0, 35% (owf) of laccase concentration, and 600 min at 4Â°C. The laccase immobilized on modified woven polyamide was shown the highest activity approximately 92% under the optimum immobilization conditions.

Keywords: Laccase, Bromelain, Immobilization, polyamide.

1. Introduction Laccase (EC 1.10.3.2) is a multi-copper-containing oxidase, which is able to catalyze a wide variety of organic and inorganic substrates. Due to the substrate specificity of laccase, it has been used widely in waste water treatment, decolorization during dyeing process [1]. However, laccase is difficult to maintain their stability in large-scale operations [1]. Immobilization enzyme on suitable supports is one of the effective methods to enhance the enzyme stability [2-3]. Woven polyamide (PA) has significant advantages as immobilization support since it is chemically inert, non-toxic, and mechanically stable [4]. Nevertheless, woven PA has been restricted for application in immobilization support due to the absence of strongly reactive groups to immobilize enzyme [4]. To overcome this problem, a partial enzymatic hydrolysis of PA surface can be performed by using protease such as bromelain. Enzyme activity is also influenced by immobilization conditions such as pH of solution, temperature and treatment time during immobilization. Thus, evaluation of optimal immobilization conditions for laccase should be controlled. Therefore, the purpose of this study is to evaluate the optimum immobilization conditions for laccase onto enzymatically modified PA.

____________________ +

Corresponding author. Tel.: + 82-10-3706-7309. E-mail address: soheelee@sm.ac.kr.

2. Experimental 2.1. Materials

Page 52 of 1108

All experiments were conducted using 100% commercial Woven PA. Commercially available laccase (EC 1.10.3.2) from Aspergillus and Bromelain (EC 3.4.22.32) from pineapple stem were used without further purification.

2.2. Methods 2.2.1 Hydrolysis of woven PA with bromelain To modify surface of woven PA by enzyme, before immobilization laccase, woven PA was hydrolyzed by 10% (owf) of bromelain at 50°C. The activity of hydrolyzed woven PA was determined by 2, 4,6-Trinitrobenzene Sulfonic Acid (TNBS, Sigma Chemicals Co., USA).

2.2.2 Determination of laccase activity Immobilization of laccase was carried out with enzymatically modified woven PA in the range of various pH (4.0-9.0), concentrations of laccase (15-100% owf), time periods (30-1440 min) at different temperatures (4-50°C). Next, the immobilized laccase mixtures were washed several times with distilled water. The activity of immobilized laccase was assayed by measuring the catalytic activity against 2, 2´azinobis-(3ethylbenzothiazoline-6-sulfonic acid) (ABTS, Sigma Chemicals Co., USA) as a substrate. The catalytic activity against ABTS was determined by measuring absorbance at 420nm with an ultraviolet visible (UVVIS) spectrophotometer (M-3000, Scinco Co. Ltd., Korea).

3. Results and discussion 3.1. Immobilization of laccase 3.1.1 Effect of immobilization pH on enzyme activity To optimize the pH condition for laccase immobilization, it was evaluated by varying the pH from 4.0 to 9.0. Fig. 1 A indicates the effects of pH conditions for immobilization laccase. The relative activity of immobilized laccase was increased gradually, and then the maximum activity was appeared at pH 6.0. By contrast, when pH values were higher than 6.0, the activity of immobilized laccase was sharply decreased following the pH changes to alkaline conditions. Therefore, the pH of 6.0 resulted in the highest activity, hence it was chosen for the optimum pH for the immobilization laccase on modified PA woven.

3.1.2 Effect of temperature on immobilization laccase Fig. 1 B indicates that the changes of relative activities of immobilized laccase on modified PA woven depending on different temperature range of 4 to 50°C. As seen in Fig.1 B, the maximum activity of immobilized laccase was found at 4°C, whereas the enzyme activity was drastically reduced with the increase

Page 53 of 1108

of temperature. The activity was reduced to approximately 20% at 40째C and was almost lost at 50째C. Therefore, the optimum temperature for immobilization laccase is found to be 4째C.

3.1.3 Effect of concentration on immobilization laccase In order to determine the optimum laccase concentration to be immobilized, the enzyme concentrations were ranged from 15 to 100% (owf). As shown in Fig. 1 C, the relative activity of immobilized laccase was increased gradually until 35 % (owf) of laccase used and then the optimum level of activity was observed at 35% (owf). However, above 35% of enzyme, the relative activities were remained constant state without any further increase. Therefore, 35% (owf) of laccase concentration was selected for the optimum concentration condition of immobilization laccase.

3.1.4 Effect of time on immobilization laccase The effect of immobilization time on the activity of immobilization laccase was studied in the range from 30 to 1440 min. As seen in Fig. 1 D, the relative activity of immobilized laccase was increased with the prolongation of immobilization time and that the maximum value of enzymatic activity was obtained at 600 min. However, when reaction time was increased over 600 min, the activity was sharply declined. Therefore, it was concluded that the desired immobilization time for laccase is 600 min, during which the relative activity was observed to be approximately 90%.

100

Relative activity(%)

80 60 40 20 0

60 40 20 0

Temperature(째C)

Page 54 of 1108

100

Relative activity(%)

80 60 40 20 0

100

60 40 20 0

Concentration(%)

200

400

600

800 1000 1200 1400 1600

Time(min.)

Fig. 1. Relative activity (%) of immobilized laccase at various conditions on enzymatically modified woven PA (A: different pH, 4°C, 10% (owf) of laccase, 600min, B: different temperature, pH 6.0, 600min, 10%(owf) of laccase, C: different concentration, pH 6.0, 600min, 4°C, and D: different time, pH 6.0, 35% (owf) of laccase, 4°C)

4. Conclusions In this study, we evaluated the optimum immobilization conditions for laccase with enzymatically modified woven PA. As results, the optimal immobilization conditions for laccase were: pH 6.0, 35% (owf) of laccase concentration at 4°C for 600min. Through this study, the optimal immobilization conditions to exhibit the highest activity are established for laccase immobilization.

Acknowledgement This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT & Future Planning (NRF-2014R1A10 05314)

References [1] H. Fang, J. Huang, L. Ding, M. Li, Z. Chen. Preparation of magnetic chitosan nanoparticles and immobilization of laccase. J Wuhan Univ Technol Mater Sci Ed, 24 (2009), pp. 42–47

[2] D.S. Jiang, S.Y. Long, J. Huang, H.Y. Xiao, J.Y. Zhou. Immobilization of Pycnoporus sanguineus laccase on magnetic chitosan microspheres. Biochem Eng J, 25 (1) (2005), pp. 15–23

[3] Lin J, Fan L, Miao R, Le X, Chen S, Zhou X. Enhancing catalytic performance of laccase via immobilization on chitosan/CeO2 microspheres. Int J Biol Macromol, 78(2015), pp. 1-8

Page 55 of 1108

[4] C. Silva, C.J. Silva, A. Zille, G.M. Guebitz, A. Cavaco-Paulo. Laccase immobilization on enzymatically functionalized polyamide 6.6 fibres. Enzyme Microb Technol, 41 (2007), pp. 867â&#x20AC;&#x201C;875

Page 56 of 1108

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

Design of Leg Compression Stockings Adaptable to Leg Size for Prophylaxis against Deep-vein Thrombosis Harumi Morooka 1 +, Riho Sakashita 1, Miyuki Nakahashi 2, Michiya Kubo 3 and Hitoshi Ojima 4 1

Kyoto Women’s University, Kyoto, Japan Toyama Industrial Technology Center, Toyama, Japan 3 Stroke Center, Saisekai Toyama Hospital, Toyama, Japan 4 Advancing Co., Ltd., Osaka, Japan 2

Abstract This study aims to obtain fundamental data for designing leg compression stockings for medical use, which are adaptable to a wide range in the length and the girth of the lower leg. We made trial leg stockings composed of a combination of hard and soft stretch portions. The regional stretch ratio of the stockings and the clothing pressure were measured with thirteen females as subjects. The results obtained were as follows. When wearing the medical stockings, the increase in the stretch ratio, in accordance with the girth of the lower leg, was approximately the same on both the anterior and posterior aspects of the calf. When wearing the trial stockings, the increase in the stretch ratio on the anterior aspects of the calf was higher than that of the posterior. The increase in the clothing pressure of the trial stockings was found to be low for a high-stretch ratio on the anterior aspects of the calf. Furthermore, it was found that each size signage of medical stockings is unlikely to fit the corresponding leg size well. It was concluded that the trial stockings are superior to the medical stockings in terms of adaptability to the leg size. Keywords: compression stocking, leg size, deep-vein thrombosis, tensile property, stretch.

1. Introduction Compression stockings are intended to encourage venous and lymph return by applying strong pressure to the legs. Compression stockings are used for both daily and medical uses. In particular, medical compression stockings used by post-operative or bedridden patients to prevent deep vein thrombosis not only apply high pressure and are very uncomfortable but are also very difficult to put on and remove [1, 2]. In this study, trial compression stockings composed of a combination of hard and soft stretch portions were created to determine design guidelines for compression stockings aimed at preventing deep vein thrombosis that can adapt to a wide range of leg sizes and are not uncomfortable because they apply high pressure. To verify their wearability, the stretch ratio on the anterior and posterior of the calf was measured for the trial compression stockings and medical compression stockings that are already available on the market. In addition, the clothing pressure on each part of the legs was measured to study the influence of stocking size and variations in clothing pressure according to the girth of the lower leg.

2. Materials 2.1.

Stocking sizes used for testing

The compression stockings now widely used by medical treatment institutions in Japan and the trial compression stockings described in this manuscript were tested. From here, the compression stockings will simply be referred to as “stockings”. The medical stocking sizes were S (for maximum calf circumferences of 23–30cm), M (for maximum calf circumferences of 30–38cm), and L (for maximum calf circumferences of 38–46cm). Three sizes of trial stockings were also used (0.8M, M, and 1.2M), which were set by modifying the loop length centered on the M size. The 0.8M dimension was considered the S size, and 1.2M was considered the L size. +

Corresponding author. Tel.: + 81-75-531-7174. E-mail address: morooka@kyoto-wu.ac.jp

Page 57 of 1108

The sizes of each type of trial stocking are shown in Table 1. The actual lengths and widths of the medical stockings were a little large for the L size, and almost no differences between the indicated sizes were observed. Slight differences were also seen in the lengths of the trial stockings, and the widths of the stockings differed only slightly.

Table 1: The actual lengths and widths of each part (thigh and ankle) of the 3 sizes of the trial stockings and of the 3 sizes of the medical stockings. Trial

Term

S（0.8M）

Length

Medical

L（1.2M）

29.3

29.7

31.7

29.3

Thigh

9.9

9.8

9.5

9.2

10.0

Anckle

9.1

9.5

6.6

6.9

Width

2.2.

Structure of the trial stockings

7.5 （Unit：cm）

Figure 1 shows the external views of the trial stockings. The trial stockings contained a combination of two different stretch portions: hard stretch and soft stretch portions. The soft stretch portion, which stretches with low resistance, was Hard always positioned on the leg in the circumferential and length (a) Soft directions to permit adaptability to a wide range of leg sizes. The hard stretch portion was positioned to be the most effective for the prevention of deep vein thrombosis. The hard stretch portion (a) was placed on the posterior (b) of the calf, which is where thrombi often occur, and was (c) designed to apply pressure to the soleal vein, which is the most prone to thrombosis. Because the Cockett perforating Front Side Back branch is important, the hard stretch portion (b) was Fig.1: Pictures of trial leg stocking composed of a combination of hard and soft stretch positioned on this branch. The hard stretch portion (c) was portions. also positioned to prevent the displacement of (a) and (b) from the part of the anterior of the calf where blood tends to accumulate. In addition, to prevent tight constriction of the ankle, we ensured that the hard stretch portion did not pass over this part of the leg.

3. Testing method 3.1.

Method of measuring the tensile properties of the stockings

Specimens were taken from the calf part of each size of medical stocking. The knitted fabric of the hard stretch portion of each size of trial stocking was sampled from the posterior of the calf, and the knitted fabric of the soft stretch portion was sampled from the anterior of the calf. A KES-FB tensile tester (Kato Tech Co. Ltd., Japan) was used to measure the stretch properties of each type of stocking. The measurement conditions were a stretching speed of 0.2mm/s, maximum load of 490N/m, or maximum stretch ratio of 180%.

3.2.

Test subjects

Thirteen women aged 20–29 years participated. The maximum calf circumferences of the test subjects were 30–38cm (average 34.3cm), which matched the applicable range of the M-sized medical stockings. The leg sizes of the test subjects were, according to the Research Institute of Human Engineering for Quality Life, almost identical to the 34.4cm maximum calf circumference of Japanese women aged 20–24 years [3].

3.3.

Measuring regional stretch ratio and clothing pressure

To measure the stretch ratio when worn, circular stamps with diameters of 2cm were printed on the anterior and posterior of the stockings corresponding to the maximum calf circumference. The stretch ratio was calculated as the difference in size before and after the stockings were worn. The test subjects underwent the test wearing a total of 6 kinds of stockings: each of the 3 sizes of the medical stockings and of the 3 sizes of the trial stockings. An air-pack type clothing pressure measurement device (AMI Co. Ltd., Japan) was used to perform measurements at four locations: the maximum circumference part of calf (anterior and posterior), perforating branch, and ankle. As indicated in the previous paragraph, the test subjects underwent the test while standing for each of 6 kinds of stockings: 3 sizes of medical stockings and 3 sizes of trial stockings.

Page 58 of 1108

4. Results and discussion Tensile properties of the stockings

Relationship between leg size and the stretch ratio of the M-sized stockings

500

Hard stretch portion

400

Soft stretch portion

Force (N/m)

400

300

M 200 100

M 300 S 200 100

100

150

Stretch ratio (%)

100

150

200

Stretch ratio (%)

Fig. 2: Tensile properties of the trial leg stockings (Course direction) 200 180 160 140 120 100 80 60 40 20 0

Trial

Stretch ratio (%)

4.2.

500

Force (N/m)

Figure 2 shows the results for the hard stretch and soft stretch portions of the trial stockings in the course direction. The stretch properties of the hard stretch portions and soft stretch portions differed greatly, with lower stretch resistance in the soft stretch portions. There was a tendency for the stretch resistance to fall in the order—L<M<S. This is thought to be a result of the control of the loop length of the knitted fabric. No differences in stretch properties were observed between sizes of the medical stockings.

Stretch ratio (%)

4.1.

200 180 160 140 120 100 80 60 40 20 0

Medical

B2 Figure 3 shows the relationship between B1 the size of the test subjects’ legs (maximum F1 circumference of the calf) and the stretch ratio F1 B1 in the M-sized medical stockings and trial 30 31 32 33 34 35 36 37 38 30 31 32 33 34 35 36 37 38 stockings. With the trial stockings, the anterior Calf circumference (cm) Calf circumference (cm) stretch differed greatly between a maximum Fig. 3: The relationships between the size of the test subjects’ legs (maximum calf circumference) and the stretch calf circumference of 30cm and 38cm, at ratio in the M-sized trial stockings and medical stockings stretch ratios of approximately 100% and 180%, respectively; the difference in the stretch ratio for the posterior stretch, which corresponds to the hard stretch portion, was small. With the medical stockings, the change in the stretch ratio accompanying an increase in the calf circumference was small for both the anterior and posterior locations. Therefore, the soft stretch portion in the anterior circumferential direction of the trial stockings stretches easily, adapting it to the calf circumference. The stretch ratio in the length direction of the legs was almost constant in both the trial stockings and medical stockings, without any dependency on the maximum calf circumference. Nevertheless, while the stretch ratio in the medical stockings was approximately 40% in both the anterior and posterior locations, the stretch ratio in the trial stockings was low, at approximately 20%. This might be due to the stretching of the medical stockings in the circumferential direction, resulting in contraction in the length direction.

4.3.

Differences in the stretch ratio according to different stocking sizes

Stretch ratio (%)

stocking sizes (mean ± standard error)

Stretch ratio (%)

The maximum calf circumferences of all of the test subjects corresponded to the M size; however, to clarify the appropriate sizes of the stockings, the stretch ratios of the trial stockings and medical stockings were measured when the same test subjects wore the S, M, and L sizes, resulting in the stretch ratios shown in Figure 4. As expected, the stretch ratio was low for the L size and higher for the S size. With the medical stockings, there were almost no differences in the stretch ratios in both the length and circumferential directions. This is likely because the tensile properties of the stockings were almost identical for the S, M, and L sizes; even if the indicated 180 180 Trial Medical size differed, the stocking sizes were almost * 150 150 identical, and it is possible that the sizes did not 120 correspond. 120 F F * 90 However, with the trial stockings, the 90 B * B stretch ratio in the anterior circumferential * 60 60 B F direction was significantly lower for the L size 30 30 than for the S size; in the posterior direction, it F B 0 was significantly lower for the L size than for 0 S M L S M L the M size, showing that the sizes corresponded. Fig. 4: Differences in the stretch ratio according to different

Page 59 of 1108

In the length direction, there was no impact of size on the stretch ratio in either the medical or trial stockings.

4.4.

Relationship between maximum calf circumference and clothing pressure Clothing pressure (hPa)

Clothing pressure (hPa)

Figure 5 shows the relationship between 35 35 Trial Medical the maximum calf circumference and clothing 30 30 F pressure of the M-sized stockings. There was 25 25 little change in the clothing pressure F 20 20 accompanying an increase in the maximum B calf circumference for either the medical 15 15 stockings or trial stockings. The soft stretch 10 10 B portion of the anterior of the trial stockings, in 5 5 particular, stretched considerably according to 30 31 32 33 34 35 36 37 38 30 31 32 33 34 35 36 37 38 Calf circumference (cm) leg size; however, because it was the soft Calf circumference (cm) Fig. 5: Relationships between the maximum calf circumference stretch portion, the tension did not increase. and clothing pressure of the M-sized stockings The clothing pressure was inversely proportional to the radius of the curvature of the leg in the circumferential direction and proportional to the tension in the course direction. The relationship between the stretch ratio and tension of the stockings was linear in the range of the stretch ratio when worn; therefore, it is assumed that the clothing pressure remained almost unchanged as a result of offsetting the radius of the curvature of the leg in the circumferential direction and the tension in the course direction of the stockings. However, it is assumed that contraction occurs in the length direction of the stockings with thick legs, and the thicker the legs, the higher the clothing pressure, albeit only slightly.

4.5.

Change in clothing pressure when wearing different sized stockings

Clothing pressure (hPa)

5. Conclusion

Clothing pressure (hPa)

Figure 6 shows the relationships between average clothing pressure and stocking size for all test subjects. With trial stockings, as the size increases from S to M and then to L, the clothing pressure significantly 35 35 decreases. With medical stockings, a significant Trial Medical difference in clothing pressure was observed in the 30 30 anterior position; however, in the posterior position, Front 25 25 no difference in clothing pressure was observed 20 20 Back with stocking size, leaving doubts concerning the Front 15 15 adaptability to different calf circumferences. The Back clothing pressure on the perforating branch and 10 10 ankle was discussed. M

Fig. 6: Differences in the clothing pressure according to different stocking sizes (mean Âą standard error)

Two kinds of compression stockings with different stocking stitch structures were created as trial compression stockings and were used to compare the stretch ratio and clothing pressure when worn with those of medical compression stockings already available on the market. With the trial stockings, which had the soft stretch portion on the anterior of the leg, the change in the stretch ratio of the stockings increased with increasing leg size, and the stretch ratio changed only slightly in the hard stretch portions on the posterior of the leg. With the medical stockings, on both the anterior and posterior of the leg, the leg size had little impact on the stretch ratio, and the stretch ratio was also low. For these reasons, we believe that the trial stockings can adapt to a wide range of leg sizes. However, at the maximum calf circumference and at the perforating branch, where strong pressure is presumed to effectively prevent thrombi, the clothing pressure of the trial stockings was lower than that of the medical stockings, indicating the need to reset the S size to the M size. In the trial stockings, where the ankles are located in the soft stretch portions, it was possible to lower the clothing pressure. In the future, the relationship between clothing pressure and prevention of deep vein thrombosis needs to be determined.

6. Acknowledgement This work was supported by Grant-in-Aid for Scientific Research 25242011.

7. References [1] Morooka, H., Nakahashi, M., Morooka, H.; Jpn. Res. Assn. Text. End-Uses, 38, 324 (1997)

Page 60 of 1108

[2] Morooka, H., Kawa, H., Morooka, H.; Jpn. Res. Assn. Text. End-Uses, 36, 389 (1994) [3] “Japanese body size data 1992-1994” Research Institute of Human Engineering for Quality Life, Osaka

Page 61 of 1108

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

Dynamic manipulation of repeat formation for engineered printing of graded garments Gavrilenko 1 + 1

School of Fashion & Textiles, RMIT University, Melbourne

Abstract. This research demonstrates a dynamic method for manipulation of repeat formation for engineered print using existing computer-aided design tools. Experimental testing of the method in comparison with traditional print matching techniques was followed by statistical analyses of the results. This has confirmed the methodâ&#x20AC;&#x2122;s validity for addressing key challenges of continuity of repeating prints at garment seams and preservation of the design intent between graded garment sizes. A dynamic template, engineered for the base size of a specific garment in Adobe Illustrator, was re-populated with various prints to generate Ready-ToPrint images. These images were graded in Adobe Photoshop. Garments for dynamic and traditional methods were simulated in 3D and rated for their performance in regards to key challenges.

Keywords: engineered print, dynamic, CAD, Ready-To-Print image, Adobe.

1. Introduction Visual appearance of a printed garment is an important consideration and innovation in this area presents opportunities for product differentiation and competitive edge (1). Around 50% of garment cost is associated with fabrics, making efficient material utilisation a priority (2). For traditionally printed fabrics, garment patterns are placed in a cutting marker as to ensure print alignment at the main seams. This practice improves the garmentâ&#x20AC;&#x2122;s visual aesthetics, but raises the fabric waste up to 30% (3). In contrast, engineered printing (EP) allows for matching of print designs whilst achieving optimised usage of substrate and colouration agent (4). The EP method was traditionally used for printing directly onto a fashion show garment with a view of adopting successful design into a continuous print for production (5). With advances in digital printing technology the method was adopted for Ready-to-Print (RTP) images, for which non-repeating print designs are engineered to fit within garment pattern shapes (6). The adoption though has been hindered by the lack of manufacturing methods for print-integrated products, necessary technical expertise of practitioners, and limited access to technology or dissatisfaction with capabilities of computer-aided design (CAD) technologies (7). To generate RTP images, manual scaling and positioning of print elements inside each garment pattern is still required in order to preserve the original design intent between garment sizes and to achieve continuity of print across seams. This iterative practice also demands high level of collaboration between creative and technical team members (8), increases the cost of product development and diminishes the EP commercial application for the mass market. Such necessary manual alterations are even more complex and timeconsuming for repeating prints. Available CAD technologies have been explored to suggest programming solutions to manual alterations. Generative software has been used to place elements of print into fabric-wide infinite non-repeating design (9). Interactive genetic algorithm has allowed the generation of designs for a rectangular carpet shape (10). Nevertheless, automatically engineering a repeating print within garment pattern shapes is still unresolved. Alternatives, such as texture mapping tools in computer animation and 3D gaming applications were also considered. However these solutions are more concerned with either mapping to regular objects or mapping of textures that do not require the precision needed in EP for complex 3D garment shapes. The introduction of random small variations in the repeat formation with dedicated software for engineering of repeating prints has been anticipated (11). Still, in the absence of dedicated solutions, this research was undertaken as part of Masters to examine existing editing tools of universal CAD Adobe software that can reduce the manual alterations required for fitting of repeating prints within garment patterns. The tools were selected for their +

Corresponding author. Tel.: + 61-412-384-211. E-mail address: olga.gavrilenko@rmit.edu.au.

Page 62 of 1108

ability to support non-destructive editing. Non-destructive editing, also known as dynamic editing, allows modification of the appearance of a graphic object without changing its underlying structure. In this study, a dynamic method for manipulation of repeat formation for EP was proposed. Ten repeating prints were engineered to fit within garment patterns of a typical dress, then RTP images were generated and graded into three garment sizes. The results were compared with traditional print matching techniques in 3D garment simulations. This allowed statistically evaluating the method’s validity for addressing key challenges of continuity of repeating printed design across garment seams and preservation of the design intent between graded sizes. The study aimed to contribute to advancement of the EP method and its adoption as a mainstream manufacturing method. This paper presents few key findings of the study.

1.1.

Research Design

This quantitative quasi-experimental confirmatory study proposed a dynamic method for fitting repeating print formation inside garment patterns. The dynamic method aimed to achieve print continuity across garment seams and was contrasted with traditional print matching techniques which can only achieve limited print alignment at the main seams. Also following the grading of the garment, the dynamic method proposed to demonstrate the preservation of the design intent between garments of different sizes by allowing the repeating print’s elements to retain position and relative proportion to overall garment proportion. The study included two independent equal allocation groups: • Dynamic group (DG), where repeating print was manipulated to fit inside the garment patterns; • Yardage group (YG), where traditional repeating print matching techniques were simulated. Ten print repeat designs were created, see Fig 1. Garment patterns for a dress in three sizes, 8, 10 and 12, were used in 3D simulations with each print design. Thus the research design allowed for the sample size of 30 cases for each group.

Fig 1: Ten print repeat designs.

A rating protocol instrument was established for evaluation of the results of 3D simulations. Definitions for rating components were formulated for two constructs of ‘print continuity across the seams of a garment’ and ‘preservation of design intent between garment sizes’, with three rating components for each construct, see Table 1. The performance achieved in 3D garment simulations was rated on the Likert-type scale, with rating values from one to five. On the scale, one meant “Excellent”, two was “Good”, three was “Satisfactory”, four was “Below satisfactory” and five was “Poor”. Table 1: Rating (R) components for two constructs Print design continuity across seams

Preservation of the design intent between sizes

Print Matching (R1) – Achieved matching of repeating print elements; assessed in nine specific locations: 01-Shoulder seam, 02-Left hand side front dart, 03-Right hand side front dart, 04-Left hand side seam above waist, 05-Right hand side seam above waist, 06-Left hand side seam below waist, 07-Right hand side seam below waist, 08-Back seam, 09-Hemline Print Flow in 3D (R2) – Achieved flow of repeating print design across seams in 3D garment; assessed for horizontal, vertical and diagonal direction of repeating print RTP Flow in 2D (R6) – Achieved flow of repeating print design across seams in generated RTP images; assessed for horizontal, vertical and diagonal direction of repeating print

Garment Registration in 3D (R3) – Achieved accuracy of print registration in 3D garment, operationalised as placement of the same print elements at the same location on garments of different sizes; assessed with front, back, left and right side views of 3D simulations Visual Proportion in 3D (R5) – Achieved visual preservation of garment proportions between sizes; assessed with front, back, left and right side views of 3D simulations RTP Registration in 2D (R7) – Achieved accuracy of print registration in generated RTP images between three sizes for the same garment pattern

Page 63 of 1108

1.2.

Experimental procedures

Models for both groups were set-up in Adobe CC, at actual size as vector graphics. Garment patterns for a dress in base size 10 were used as guides for DG and as shapes for YG. Non-destructive editing tools in Illustrator, such as Symbol, Appearance Panel, Pattern Brush and Blend, were used to set-up a template for DG. Traditional matching techniques were simulated for YG template using Pattern fill tool. Both templates were populated with a placeholder repeat, which was later replaced with print repeats via Brush and Swatches panels. RTP size 10 images then were exported as JPGs, and graded into size 8 and size 12 using Envelop Distortion tool in Photoshop. RTP images for Size 8 and 12 were also exported as JPGs. Garments were simulated in Browzwear VStitcher 3D environment on avatars sizes 8, 10, and 12, in all ten print designs, using RTP images for DG and replicating YG’s based on Illustrator JPGs. Nine camera positions were created to capture the dressed avatar and full length of the garment from front, back, left and right side, and to show shoulder seams from above. Snapshots of the dressed avatars and dresses only were recorded. RTP images and snapshots from VStitcher were sorted in Adobe Bridge by applying metadata to allow viewing them in specific combinations while they were rated, examples are demonstrated in Fig 2.

(a)

(b)

Fig 2: Examples of images viewed in specific combinations (a) In the same size dress only, and (b) dressed avatars of different sizes together from a specific camera view.

2. Results and Discussion All recorded data was screened and cleaned, and imported into SPSS v. 22. Average ratings for R1, R2, R3, R5, R6 and R7 were calculated. Descriptive analyses were performed to determine measures of central tendency and variation. Kolmogorov-Smirnov and Shapiro-Wilk tests confirmed normality for DG and YG for Print Matching (R1) and Visual Proportion in 3D (R5) for YG. The rest of ratings showed statistically significant deviations from normality, but as the sample size was high, the analysis proceeded with t-tests. Table 2: T-test for ratings, filtered to display results by Levene’s Test for Equality of Variances

Rating

Levene’s Test for Equality of Variances

t-test for Equality of Means t

Print Matching (R1) Assumed -10.589 58 Print Flow in 3D(R2) Not assumed -5.687 45.288 Garment Registration in 3D (R3) Not assumed -10.910 50.641 Visual Proportion in 3D (R5) Assumed -7.797 58 RTP Flow in 2D (R6) Assumed -11.554 58 RTP Registration in 2D (R7) Not assumed -9.152 40.253

Sig. (2Mean Std. Error tailed) Difference Difference .000 .000 .000 .000 .000 .000

-.789 -.889 -1.225 -.925 -1.278 -.633

.075 .156 .112 .119 .111 .069

95% Confidence Interval of the Lower Upper -.938 -.640 -1.204 -.574 -1.450 -.999 -1.162 -.688 -1.499 -1.056 -.773 -.493

A two-sample t-test was used to test for a significant difference between the mean scores of the ratings for DG and YG, results are shown in Table 2. The Levene’s test of homogeneity of variance was used to test the assumption of equal variance for the variables. For Print Matching (R1), the results of the two-sample t-test, assuming equal variance, found statistically significant evidence of a difference between the mean scores of the DG and YG, t(df=58)=-10.589, p<0.001, 95% CI for the difference in means [-.93801, -.63977]. The dynamic method can significantly increase accuracy of print matching and therefore improve continuity of repeating print across the seams of the garment. The differences in means of Print Matching (R1) in specific locations were also examined based on garment size category. Not much difference was observed between

Page 64 of 1108

sizes within each group. Base size 10 in DG exhibited the best performance as expected, and slightly decreased scores for sizes 12 and 8 due to errors that were added during the grading process. Statistically significant differences between mean scores of DG and YG were also found for the rest of the ratings, the results are shown in Table 2. Compared to traditional print matching techniques, the dynamic method can significantly improve print continuity across seams. Also following the grading of the garment, DG demonstrated significantly improved preservation of the design intent between garment sizes by allowing printed design elements to retain position and relative proportion to overall garment proportion. Next, the rating protocol instrument was examined for validity and reliability (12). The ratings data was analysed with Principal components analysis (PCA). Pearson correlation with the Promax oblique rotation method and Kaiser normalisation was used. KMO and Bartlett's tests confirmed suitability of the sample for PCA, with the KMO measure of sampling adequacy at .774 and the statistically significant result of Bartlett's test of sphericity, p<0.001. Six components were retained, explaining 75.81% of the total variability. Parallel Analysis results were further examined in component matrix. Component 1 had the highest number of loading on one dimension (20 loadings, 3 of them cross-loaded). Reliability of the rating protocol was confirmed by calculating Cronbachâ&#x20AC;&#x2122;s alpha (13), which indicated a high level of internal consistency of 0.927. Nonetheless, consideration will be given in future studies to dropping low loading items and reducing the dimensions of the rating protocol, or re-designing it to provide a more balanced components loading.

3. Conclusion The study has confirmed the proposed dynamic method as suitable for manipulation of a repeating print formation for EP. Non-destructive tools in Adobe CC software were used to generate a dynamic template for a specific garment in a base size, and re-populate the template with various prints. RTP images were then generated and graded into three sizes, and garments were 3D simulated both for traditional matching techniques and the dynamic method. A performance rating protocol instrument was created for the study. Achieved performance in 3D garment simulations was rated on a Likert-type scale and statistically analysed. For the dynamic method, 3D simulation of garments demonstrated improved matching of print at garment seams with significantly higher accuracy of matching compared to traditional method and therefore improved print continuity across seams. The dynamic method also allowed for the grading into three garment sizes with significantly improved preservation of the design intent between garment sizes by allowing printed design elements to retain position and relative proportion to the overall garment proportion.

4. References 1. Tyler DJ. Textile Digital Printing Technologies. Textile Progress. 2005;37(4):1-65. 2. Bond T. Computerised pattern making in garment production. In: Fairhurst C, editor. Advances in apparel production: Woodhead Publishing; 2008. 3. GerĹĄak J. Planning of clothing design, pattern making and cutting. Design of clothing manufacturing processes: Woodhead Publishing; 2013. p. 105-44. 4. Lamar TAM. Integrated digital processes for design and development of apparel. In: Hu J, editor. Computer Technology for Textiles and Apparel: Woodhead Publishing; 2011. 5. Braddock S, O'Mahony M. Techno Textiles : Revolutionary Fabrics for Fashion and Design. London: Thames & Hudson, or inventory CIM Press.; 1998. 6. Parrillo-Chapman L, editor Engineering whole garment designs. 6th Annual IFFTI Conference: Best Practices in Fashion Education, New Delhi, India; 2004. 7. Parrillo-Chapman L. Textile design engineering within the product shape [Ph.D.]. Ann Arbor: North Carolina State University; 2008. 8. Parrillo-Chapman L, Little T. Textile design engineering within the product shape. Journal of the Textile Institute. 2012;103(8):866-74. 9. Russell A. Repeatless: transforming surface pattern with generative design. Shapeshifting Conference; Auckland University of Technology 2014. 10. Zamani F, Amani-Tehran M, Latifi M. Interactive genetic algorithm-aided generation of carpet pattern. The Journal of The Textile Institute. 2009;100(6):556-64. 11. Briggs-Goode A, Russell A. Printed textile design. In: Briggs-Goode A, Townsend K, editors. Textile design: Woodhead Publishing; 2011. p. 105-28. 12. Baglin J. 9.1 Exploratory Factor Analysis RMIT2014 [cited 2014 04-10]. Available from: https://sites.google.com/a/rmit.edu.au/quantitative-research-techniques/09-advanced-statistical-topics/9-1-exploratoryfactor-analysis. 13. Field AP. Discovering statistics using SPSS : (and sex and drugs and rock 'n' roll). 3rd ed. ed. Los Angeles [i.e. Thousand Oaks, Calif.] London: SAGE Publications; 2009.

Page 65 of 1108

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

Effect of Compression Deformation of Body Surface on Back Silhouette when Wearing a Brassiere Yuhi Murasaki 1+, Miyuki Nakahashi 2 and Harumi Morooka 3 1

Graduate School of Home Economics, Kyoto Women’s University, Kyoto, Japan Human Life Technology Research Institute Toyama Industrial Technology Center, Toyama, Japan 3 Faculty of Home Economics, Kyoto Women’s University, Kyoto, Japan

Abstract This study aims to quantify the compression deformation of the back part of a body surface and to identify the factors affecting the deformation for designing brassieres with a good silhouette. We measured the compression deformation on the left side of the back. The compression deformation around the posterior axillary point (P1) and on the waistline (P8) was more significant than at the other points. The correlation between the subjects’ age and the compression deformation at P1 and P8 was analyzed. It was found that increasing age affected both the significant compression deformation and widening the individual differences. In the dorsal midline side, the compression deformation was comparatively low and correlated weakly with age. It is essential to take account of the compression deformation associated with age and physique, based on the quantitative data obtain in this study. Keywords: compression deformation, body surface, back silhouette, brassiere

1. Introduction The brassiere, a type of women’s shapewear, reduces breast vibration and provides a cosmetic effect to breasts, but may adversely affect the aesthetics of the silhouette of the wearer’s back as a result of the compression deformation of the body caused by the high pressure applied by the garment’s back panel. Clothing is generally designed based on data on body size and the tensile properties of the constituent materials, but when designing items that will be smaller than the actual body measurements, as in the case of a brassiere, it is extremely important to consider the degree of compression deformation of the body surface. Many studies of brassieres have been conducted in the past and, although much of this research has addressed functionality such as vibration resistance [1], the impact on the body [2], and comfort [3,4], hardly any work has been done on the relationship with the compression deformation of the body surface. To examine the compression properties of the human body, Morooka et al. [5] took leg measurements and showed that compression deformation increases with age, but no data on the back is available in the literature. This study set out to quantify the compression deformation on the surface of the back and reveal the factors influencing this, thus providing basic data for the pressure design of the back panels of brassieres that do not adversely affect the aesthetics.

2. Experiment method

+ Corresponding

author. E-mail address: yuhi.0420@gmail.com

Table 1: Physical characteristics of subjects. (Mean ± Standard deviation)

Page 66 of 1108

Subjects

The subjects consisted of 145 healthy females aged 20 to 70. Table 1 lists the average and standard deviation for height, weight, body fat percentage, and BMI, by age. Those subjects in their 30s and 50s were slightly taller and heavier than the national average for Japanese females of the same age, but the subjects in the other age groups had physiques that were almost identical to the national average [6].

2.2.

Measurement method

Ages

Weight

(cm)

(kg)

Body fat percentage (%)

BMI

145

156.9±6.1 52.8±8.3

25.4±5.9

21.5±2.9

158.8±4.3 51.4±6.5

23.6±4.4

20.4±2.4

30s

161.4±4.6 56.4±8.7

26.0±5.7

21.6±3.1

40s

161.4±4.7 56.7±6.1

27.1±4.9

21.7±2.1

50s

160.7±5.0 55.1±7.2

25.1±3.7

21.3±2.2

60s

153.7±5.5 52.8±9.4

26.8±6.9

22.4±3.7

70s

151.5±5.0 49.3±9.2

24.9±7.1

22.0±2.9

posterior axillary point

dorsal midline 3cm

3 11

3cm

4 12

20 5 13 21 6 14 22 7 15 23 8 16 24

waistline

28 29 30 31 32

Fig. 1: Measurement points on the left side of the back.

Compression deformation computation

Fig. 2 shows an example of the compression curves. Given that smooth curves may not be obtained due to minor vibrations of the body, smoothing was applied using quadratic curves as shown by the dotted lines in the graph. Smoothing was applied to all of the data as a very close fit could be confirmed. Furthermore, intersecting curves and curves with an extremely low quadratic regression accuracy were discarded as outliers. T0 is the sensor head travel when the detected load was 4.9mN, and T30 is the sensor head travel at the maximum load of 294mN. The value calculated by subtracting T0 from T30 is the deformation at 294mN, and is designated E30. This calculation was repeated for 196mN and 98mN, the minimum load, with the resulting values designated E20 and E 10

3. Results and discussion 3.1.

Height

20s

We used an HFT-03C portable compression tester (Kato Tech Co., Ltd., Japan) to measure the compression deformation at 32 points on the surface of each subject’s back, as shown in Fig. 1 Measurements were taken at four points from the left posterior axillary point to the midline at 3cm intervals and, similarly, at eight points down to the waistline. The sensor stroke was 20mm and the sensor head was hemispherical and 10mm in diameter. The compression speed was set to 1mm/s and the maximum compression load to 294mN. Measurements were taken with the subjects standing upright with their arms spread at a 30̊ angle. Furthermore, to minimize the vibration of the body, a body support was used.

2.3.

Number of subjects

Compression deformation by age group

E30

30 25

F (gf)

2.1.

E20

20 15

E10

10 5 0 0

T0 1

3 T30 4

T (mm)

Fig. 2: An example of the compression property of the body surface.

Page 67 of 1108

Fig. 3 shows the E30 results for the 32 measured points, plotted by age group. The left-hand side of the figure indicates the left posterior axillary side while the right-hand side indicates the midline side. For all of the age groups, the deformation was found to be high at the posterior axillary point and at the measurement points below that (P1-P3), with a large amount of variation between the ages. The difference between the 20s and 70s was around 4mm. Next, the compression deformation was found to be high for the following measurement points (in descending order): waist side (P7, P8, P15, P16), and midway between the posterior axillary point and waistline (P4-P6, P12-P14, P20-P22). For those points midway between the posterior axillary point and the waistline, large differences between the age groups could also be seen. In contrast, the deformation was low near the scapula (P9-P11, P17-P19) and at the midline side near the spine, with the differences between the age groups also being very small. posterior axillary side

dorsal midline side

E30 (mm)

measurement point

16 1

8 6

r = 0.58**

10 20 30 3140 50 60 70 80 90

Age

waistline 0 1 2 3 4 5 6 7 8 9 10

E30 (mm)

0 1 2 3 4 5 6

Fig. 4:24Relationship between32the compression deformation (E30) point (P1). 7 8 9 10 and 0 1age 2 3for 4 5all 6 7subjects 8 9 10 at 0 1the 2 3posterior 4 5 6 7 8axillary 9 10

E30 (mm)

Fig. 3: Compression deformation by age group on each measurement points of body surface. 12 ( 20s 12 30s 40s 50s 70s ) P1~P3 60s(20s,40s**) P4~P6 (20s,60s**)

3.2.

E (mm)

Fig. 4 shows the relationship (20s,40s**) (20s,60s**) (20s,40s**) 60s between the compression deformation 8 8 (20s,60s**) 40s (20s,40s*) and age for all subjects at the posterior (20s,40s**) (20s,60s**) 40s 6 6 (20s,60s*) 20s axillary point (P1), which is where the (40s,60s*) 60s (20s,40s**) measured compression deformation is 4 4 20s (20s,60s*) the highest. This shows that the 2 2 deformation significantly increases with age. On the other hand, the 0 0 0 10 20 30 0 10 20 30 deformation is between 3 and 8mm for F (gf) F (gf) subjects in their 20s, with individual differences increasing with age, while the deformation ranges widely from 4 to 16mm for those subjects in their 60s and 70s. Furthermore, a similar tendency was seen for the waist side (P8) where the deformation is high, on the order of 3 to 7mm for subjects in their 20s, with individual differences increasing with age.

Load-associated changes in compression deformation

Fig. 5 shows the relationship between the load and the average compression deformation values for the three points around the posterior axillary point (P1-P3) and the three points below that (P4-P6), where the compression deformation in the brassiere back panel area was high. For all these points, the deformation increased with the load and a tendency for greater differences between the age groups was also seen. In particular, significant differences were seen between subjects in their 20s and 40s and between subjects in their 20s and 60s, but there were hardly any significant differences between subjects in their 40s and 60s.

3.3.

Analysis of factors influencing compression deformation Fig. 5: Relationship between the force and the average compression deformation values for P1-P3 and P4-P6. (* : p<0.05, ** p<0.01)

Page 68 of 1108

To study the factors influencing the compression deformation of the back, we performed a correlation analysis using E30, the subjectsâ&#x20AC;&#x2122; ages, and body fat percentages. Fig. 6 shows the correlation coefficients for the 32 measurement points, with the graph on the left showing the relationship with age and that on the right the relationship with the body fat percentage. Apart from those areas near the scapula and the spine, the correlation with age was high, and dorsal posterior axillary point (D.M) for all locations there was a midline (P.A) tendency for the deformation to 0.58** 0.30** -0.11 0.16 0.44 0.31 0.03 0.21 increase significantly with age. -0.20 0.05 0.30 -0.14 0.53** 0.24** 0.11 0.25 This trend was particularly 0.18* 0.22* 0.34 0.23 0.54** 0.31** 0.18 0.39* noticeable for the side of the posterior axillary point. Regarding 0.31* 0.32* 0.21 0.30 0.50** 0.35** 0.39** 0.36* the relationship between E30 and 0.27* 0.35** 0.48** 0.29* 0.41** 0.14 0.28 0.28 the body fat percentage, the shaded part of the graph indicates a 0.47** 0.44** 0.36** 0.37** 0.17 0.37 0.18 0.33 tendency for E30 to increase 0.21* 0.12 0.23 0.21 0.28** 0.33** 0.24** -0.06 significantly with the body fat -0.14 -0.01 0.01 0.13 0.45** 0.39** 0.32** 0.19 percentage. For some age groups, waistline however, E30 and the body fat E30 vs Body fat percentage E30 vs Age percentage were seen to be Fig. 6: Correlation coefficients for the 32 measurement points between E30 negatively correlated. and age, body fat percentage.

4. Conclusion To obtain basic data for the pressure design of brassiere back panels that will not adversely affect the aesthetics, we set out to quantify the compression deformation on the surface of the back and reveal the factors influencing this. For every age group, the compression deformation was highest around the posterior axillary point, whereas the deformation was low near the scapula and the spine. Individual differences in the compression deformation were found to increase with age. Higher loads were accompanied by increases in the compression deformation, and also by increased differences between the age groups. The compression deformation was found to be significantly higher for the subjects in their 40s and 60s than for the subjects in their 20s. A factor analysis for the compression deformation identified a significant correlation between ages for almost every location. Regarding the relationship with the body fat percentage, a significant correlation was observed for the central flank, and it was found that the compression deformation increased with the body fat percentage. The pressure design of back panels that do not diminish the aesthetics needs to take account of the compression deformation associated with age and physique, based on the quantitative data obtained in this study.

5. Acknowledgement This work was supported by Grant-in-Aid for Scientific Research 25242011.

6. References [1] K. Okabe, T. Kurokawa, Vibration Characteristics of Breasts during Exercise with and without a Brassiere, Japan society of Home Economics,54(9), pp.731-738(2003) [2] Y. Satsumoto, H. Saito, T. Tamura, The Effect of Constructive Factor of Back Panel of Brasserie on Functional Mobility and Comfort, Descente sports science,29, pp.46-55(2008) [3] H. Morooka, R. Fukuda, H. Sasaki, H. Morooka, The Effects of the Tensile Properties of Cud-stand on Clothing Pressure and Comfort of Push-up Type Brassieres, The society of Fiber Science and Technology, Japan, 62(12), pp.287-292(2006) [4] H. Morooka, R. Fukuda, M. Nakahashi, H. Morooka, H. Sasaki, Clothing Pressure and Wear Feeling at Under-bust Part on a Part on a Push-up Type Brassiere, The society of Fiber Science and Technology, Japan, 61(2), pp.5560(2005)

Page 69 of 1108

[5] H. Morooka, M. Nakahashi, H. Morooka, Compressive Property of Legs and Clothing Pressure of Pantyhose From the View Point of Difference in Age, Journal of the Japan Research Association for textile end-uses, 38(6), pp.4452(1997) [6] Research Institute of Human Engineering for Quality Life â&#x20AC;&#x153;Japanese body size date 1992-1994â&#x20AC;?,p.81, 143 (1997).

Page 70 of 1108

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

Effect of different pigment colorants on inkjet printing performance Wang Datonga, Shaohai Fua*, a

Key Laboratory of Eco-Textile, Jiangnan University, Ministry of Education, Wuxi, Jiangsu 214122, China

Corresponding author: Shaohai Fu. TEL: +86051085912007, Email: Shaohaifu@hotmail.com

Abstract: Taking nano pigment ink, nano coated pigment ink and pigment/latex composite ink as the research object, the type of colorants which could affect the colloidal properties, the jet behavior and printing performance of ink was studied. SEM photos indicated that nano coated pigment ink better dispersed and formed different film on the surface of fiber. Particle size and Zeta potential showed that nano coated pigment ink has a better stability under different condition which was consistent with the inkjet fluency results. Representative photo sequence of ink jetting showed that different colorants has something to do with satellite formation. Nano coated pigment ink emerged better rubbing fastness and color performance which implied that this kind of ink was more suitable for textile ink jet printing.

Key words: colorants; ink-jetting performance; stability; printing performance

1. Introduction Textile inkjet printing is a technology with a remote origins which has been popular in recent years1. Ink, as an important consumable items of inkjet printing, its inkjet behavior is closely related to the printing performance. For a proper pigment ink formula, there are colorant, surfactant, polyhydric alcohols, defoamer and something else. Low viscous ink was used to jet from small nozzles. Because commercial inkjet printing machines mainly adopt piezoelectric nozzles which are less than 50 microns in diameter2. Then stable ink system was required, especially for pigmented ink systems3. Pigment dispersion is the most important factor, because all the other components just serve it to right place. Stability of the pigment dispersion is an important factor of pigment ink. Traditional pigment dispersion just depends on other components such as dispersant to improve the stability. Besides, for a good printing fastness, polymeric binder was added which affect the fluency of ink obviously4. Better fluency and fastness just like a contradiction exist in pigment inkjet printing.To solve this problem, miniemulsion polymerization was used to encapsule the pigment. Miniemulsion polymerization is a widely used methold for the preparation of polymers and has been applied to polymer encapsulation of a variety of inorganic particles5. Some researchers use this method

Page 71 of 1108

to prepare polymeric nanocapsules6. Our research group used miniemulsion polymerization to prepare nano coated pigment which had excellent dispersion stability. As the surface of pigment was coated by polymers which could anchor pigment onto fibers, fine color fastness and hand feeling were achieved. Based on these aspects, this paper took nano pigment, pigment/latex composite and nano coated pigment as the ink colorants to study the effect of pigment colorants on inkjet printing performance. The stability, proper surface tension, viscosity, inkjet performance, and printing performance are all investigated.

2. Experimental 2.1 Materials Phthalocyanine blue (C.I.P.B15:3) was purchased from Wuxi Xingguang Fine Chemical Engineering Co., Ltd, China. Tween 80, glycerol and ethylene glycol was purchased from Sinopharm Chemical Reagent Co., Ltd.S-465 was purchased from Air Products Co., Ltd, America. Surfactants EH-9, TMN-6, L-62 and defoamer FB-50 were provided by Nanjing Golden Chemical Co., Ltd.

2.2 Preparation of different inks Different kinds of nano pigments were firstly centrifuged under the conditions of 3000 r/min for 30 min, and then filtered through a 500 nm filter membrane to remove large particles. Then the pigment ink was formulated on a weight basis as given below: pigment dispersion 25 %, surfactant 1.5 %, humectant 30 %, defoaming agent FB-50 0.1 %, adding distilled water to 100 %. The above materials were mixed together, stirred for 0.5 h, and filtered through a 500 nm filter membrane.

2.3 Printing with the pigment inks PET fabric (40.0 cm Ă&#x2014; 40.0 cm, Shandong Weiqiao Pioneering Group Co., Ltd, China) was printed by a printing machine (DMP-2800, FUJIFILM Dimatix, Inc. USA). The printed fabric was dried at room temperature to remove the water, and then baked baked at 150 oC for 3 min to help the latex to form a dense film onto pigment surface.

2.4 Measurement 2.4.1 Particle size Particle size (D) and the particle distribution were determined by dynamic light scattering method (DLS) with Nano-ZS90(Malvern Instruments Co., Ltd., England) at 25 oC.

2.4.2 Stability 2.4.2.1. Freeze-thaw stability (S F ). Samples were frozen at -10 oC for 24 h, and then was thawed at 60 oC for another 24 h. This process was repeated for 3 times. The particle sizes of samples before and after freeze-thaw treatments were recorded as d 1 and d 2 . 2.4.2.2. Thermal stability (S T ).Samples were heated at 60 oC for 24 h. This process was repeated for 3 times. The particle sizes of samples before and after heated were recorded as d 1 and d 2 . 2.4.2.3 Centrifugal stability (S C ). Samples were centrifuged for 30 min at centrifugal speed of 3000 r/min. The particle sizes of samples before and after centrifuged were recorded as d 1 and d 2 .Then S F , S T and S C were calculated by Eq. (1): S = (1 â&#x2C6;&#x2019;

|đ?&#x2018;&#x2018;đ?&#x2018;&#x2018;2 â&#x2C6;&#x2019;đ?&#x2018;&#x2018;đ?&#x2018;&#x2018;1 | đ?&#x2018;&#x2018;đ?&#x2018;&#x2018;1

)Ă&#x2014;100%

(1)

2.4.3 Viscosity (Îˇ) and surface tension (Îł) The viscosity (Îˇ) was measured by Brookfield DV-Đ¨ at 25 oC with shear rate 30 s -1. The

Page 72 of 1108

surface tension (γ) was measured by Drop Shape Analysis System DSA 100.

2.4.4 Color performance The L, a, b and color strength (K/S) of printed fabric was measured by a colorimeter (Xrite8400, X-Rite Color Management Co., Ltd. USA) under the illuminant D 65 with the CIE 1964 Standard Observers.The morphology of pigment on substrates was observed by a metalloscope (XYM,Sunny Optical Technology Co, Ltd)

2.4.5 Jetting performance Jetting of the pigment inks was implemented by a Dimatix DMP-2800 inkjet printer (Fujifilm Dimatix Inc., Santa Clara, California). Jetting was carried out under constant conditions (RH 25 ± 5 % and temperature 20 ± 1oC). The diagram was showed in Scheme 1.

2.4.6 Clogging nozzle All 16 nozzles of Dimatix DMP-2800 inkjet printer were turned on to jet different pigment inks for 1h, and then record the number of clogged nozzle as B.

Scheme1.The diagram of jetting process.

3. Results and discussions 3.1 Preparation of different pigment colorants

Fig.1 Particle size distribution (a) and Zeta potential (b) of different pigment colorants

The properties of the pigment dispersion is one of the most important factors of pigment ink. Fig.1 shows particle size distribution and Zeta potential of different pigment colorants. Nano capsulated pigment had smaller particle size and narrow size distribution. This could be attributed to the coated layer which formed chemical bond onto pigment surface, and made it not easy to desorb. Then pigment particles could not gather together so that particle size was smaller and homogeneous. Nano capsulated pigment had a Zeta potential of -33.5 mv which was much higher than that of nano pigment and pigment/latex composite. This meant the electric double layer on the surface of the pigment was uniform. Within the system, greater electrostatic repulsion made the system more stable.

Page 73 of 1108

Tab.1 Physical properties of different pigment colorants Colorants

η(mPa.s)

Nano pigment

2.58

Pigment/latex composite Nano coated pigment

Stability (%) SF

8.11

16.21

12.25

7.91

3.21

8.21

10.74

8.48

6.16

3.25

8.17

3.81

1.23

5.27

Tab.1 shows the physical properties of different pigment colorants. When temperature was high, the particle random motion intensified, and the dispersant desorbed from the surface of particles more obviously. When temperature was below zero, the volume of the water molecules in the system increased due to the formation of the ice crystal which can produce certain extrusion effect on the surrounding particles, and cause the destruction of the electric double layer on the surface of the particles. The nano coated pigment showed better thermal stability than the other two which was attributed to the coated layer.Centrifugal stability was related to the viscosity of the fluid. As the viscosity of nano pigment was lower, so it showed poor centrifugal stability.

3.2 Ink-jetting performance of different pigment inks

Fig.2 Effect of surface tension on droplets formation: (a) 56.2 mN/m；(b) 39.5 mN/m; (c) 37.1 mN/m; (d) 35.1 mN/m; (e) 30.1 mN/m

Surface tension has a direct impact on the drop formation mechanism and successive drop size at a given voltage during jetting. From Fig 2, the ink-jetting performance differed a lot. As the Fig 4.(a) shows the droplet could not be ejected successfully which covered the nozzle.Fig4.(b) and Fig 4.(c) show "atomization" phenomenon appeared in the process of flight which meant droplet could not gather together completely. Stable droplets were unable to form during the process of injection which could easily form "fog point" on the fabric surface after injection . Fig 4.(d) shows: though droplet could form successfully, the filament broke into many undesired satellites. The proper reason was the surface tension was not adequate to wet the nozzle and decompose the pigment ink into fine droplets7 . Fig 4 (e) shows that satellite could catch the main droplet and keep the flight path vertically after merger. In this study, the appropriate scope of surface tension is below 35 mN/m.

Fig.3 Effect of viscosity on droplets formation: (a) 2.12 mPa.s；(b) 2.67 mPa.s; (c) 3.01 mPa.s; (d) 3.35 mPa.s; (e)5.02 mPa.s

Fig.3 shows the effect of viscosity on droplets formation. As we can see, viscosity was a key factor to restrain satellite points. As Fig. 3(a) shows, under the circumstances of fluids with low viscosity, the fluids were easily jetted by the applied voltage because viscous dissipation

Page 74 of 1108

was small enough to be ignored. However, large kinetic energy and surface tension tended to produce satellites. As Fig. 3(e) shows, increased viscosity reduced satellite points and a single droplet was achieved which meant more energy was consumed to jet the drops, then the kinetic energy for the movement of drops was reduced8. The flying velocity of the tail increased with increased fluid viscosity. So from Fig.3, we can conclude that the higher the viscosity was, the fewer the satellite points were. Tab.2 Physical properties of different pigment inks Ink

Îˇ

Îł

type

(nm)

(mPa.s)

(mN/m)

Nano pigment ink

150.5

3.51

30.1

Pigment/latex composite ink

145.0

3.82

Nano coated pigment ink

141.1

4.59

Stability (%)

7.6

5.21

3.01

3.52

29.9

7.8

3.32

3.52

4.15

30.2

8.1

2.01

1.05

3.21

Tab. 2 shows the physical properties of nano pigment ink, pigment/latex composite ink and nano coated pigment ink. As we can see, inks had a better property which maybe was related to additives. Compared with the other two inks, the nano coated pigment ink had higher stability and fewer clogging nozzle. Because the coated layer formed chemical bond onto pigment surface, and gave the fluid a higher viscosity which made it difficult to be desorbed from pigment particles, even at extremely conditions.

Fig 4. Drop formation for different pigment inksďź&#x161;(a) nano pigment ink (b) pigment/latex composite ink (c) nano coated pigment ink.

Fig 4. was the drop formation of different pigment inks. DOD drop formation typically involves: a) ejection and stretching of liquid thread, b) necking and pinch-off of liquid thread from the nozzle, c) recoil of free liquid thread, d) breakup of the free liquid thread, and e) formation of primary drop and satellites9. As can be seen from Fig 4, the difference existed at the last stage. In Fig 4(a,b),the satellite points could not catch up with the main droplet, while in Fig 4(c), satellite point combined with the main droplet. The reason maybe is the viscosity of nano coated pigment ink was higher which could restrain the formation of satellites.

3.3 Printing properties of different pigment inks Tab.3 Properties of printed textile with different pigment inks Rubbing fastness Textiles printed with

K/S

Nano pigment ink

86.48

2.73

88.49

Pigment/latex composite ink

85.81

2.89

Nano coated pigment ink

85.11

3.01

Dry

Wet

6.4138

88.37

6.7804

88.21

6.9132

3-4

Page 75 of 1108

Table 3 shows properties of printed textile with different pigment inks. Compared to the nano pigment ink, the nano coated pigment ink provided better color strength and superior colorfastness. When the nano pigment ink was printed on fibers, pigment particles were only attached to fabric via van der waals force, resulting in the poor color fastness. Pigment/latex composite ink also presented a poor fastness, because polymer just anchored itself onto the surface of fiber not the pigment particles. While for nano coated pigment ink, the coated layer played the role as a binder in the pigment ink to fix the pigment onto fabrics.

Fig.5 SEM images of PET fabrics printed with (a) Nano pigment ink (b) Pigment/latex composite ink (c) Nano coated pigment ink.

Fig.5 shows the SEM images of fabrics printed with nano pigment ink, pigment/latex composite ink and nano coated pigment ink. As we can see, all inks presented discretely dots on the firber. It was different from commercial pigment ink containing a large amount of binder which formed a thicker film and enabled pigment particles to be tightly adhered to fabric surface. It was also the reason for its excellent color fastnesses but poor softness.

Figure 6. Ink-jet performance photos of different pigment inks: (a) Nano pigment ink (b) Pigment/latex composite ink (c) Nano coated pigment ink.

Figure 6 was ink-jet performance photos of different pigment inks. As the results showed above, the different properties of pigment ink can obviously affect the jetting performance. For a pigment ink, few satellites and low viscosity are required, but the two factors are contradictory. While high viscosity can suppress satellites, the jetting fluency can be remarkably changed. As shown in Fig. 6(a) and (b), it is easy to see that scattering points are observed, and the margin of pattern is zigzag. The possible reason was the satellite points which generated during the ink-jet process. While the Fig. 6(c) shows little scattering points and a uniform margin which was related to the combination of main droplet and satellite points.

4. Conclusions Nano coated pigment showed better stability than the other two. Ultra high speed imaging system proved that nano coated pigment ink can form a single droplet during the process of ink-jet. And it also had a lower blocking rate which meant a better ink-jet fluency. In the study of printing, nano coated pigment ink still presented better color performance, rubbing fastness and uniform patterns.

Page 76 of 1108

Refferences 1.

Cahill, V., The evolution and progression of digital printing of textiles. Cambridge: Woodhead

Publishing Ltd: 2006; pp 1-15. 2.

Shin, P.; Sung, J.; Lee, M. H., Control of droplet formation for low viscosity fluid by double

waveforms applied to a piezoelectric inkjet nozzle. Microelectronics Reliability 2011, 51 (4), 797-804. 3.

Leelajariyakul, S.; Noguchi, H.; Kiatkamjornwong, S., Surface-modified and micro-encapsulated

pigmented inks for ink jet printing on textile fabrics. Progress in Organic Coatings 2008, 62 (2), 145161. 4.

Fu, Z., 13 - Pigmented ink formulation. In Digital Printing of Textiles, Ujiie, H., Ed. Woodhead

Publishing: 2006; pp 218-232. 5.

Casado, R. M.; Lovell, P. A.; Navabpour, P.; Stanford, J. L., Polymer encapsulation of surface-

modified carbon blacks using surfactant-free emulsion polymerisation. Polymer 2007, 48 (9), 2554-2563. 6.

Tiarks, F.; Landfester, K.; Antonietti, M., Preparation of polymeric nanocapsules by miniemulsion

polymerization. Langmuir 2001, 17 (3), 908-918. 7.

Park, J.-Y.; Hirata, Y.; Hamada, K., Relationship between the dye/additive interaction and inkjet ink

droplet formation. Dyes and Pigments 2012, 95 (3), 502-511. 8.

Koo, J.; Kleinstreuer, C., Viscous dissipation effects in microtubes and microchannels.

International Journal of Heat and Mass Transfer 2004, 47 (14), 3159-3169. 9.

Wu, L.; Chen, Y., Visualization study of emulsion droplet formation in a coflowing microchannel.

Chemical Engineering and Processing: Process Intensification 2014, 85, 77-85.

Page 77 of 1108

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

Effects of Acculturation on Acceptance of Cultural Apparel in the Global Fashion Consumption: A Case 2014 APEC Costume Le Xing1, Hui-e Liang 1 and Chuanlan Liu 2 1

Han Nationality Costume Culture and Non-material Culture Heritage Base, Jiangnan University, Wuxi, Jiangsu 214122, China

Textile, Apparel Design and Merchandising, College of Agriculture, Louisiana State University, Baton Rouge, LA 70830, USA

Abstract. The concept of acculturation to the global consumer culture (AGCC) was proposed and applied to understand global consumer culture and its interaction with other consumer characteristics and market behaviors. AGCC considers the range of skills, knowledge, and behaviors that consumers must acquire to acculturate to a global consumer culture(Carpenter, Moore, Alexander, & Doherty, 2013). However, how individual’s AGCC interact with cultural product acceptance has not been examined. Meanwhile, other scholars argue that national cultural effects can be determining factor in shaping consumers’ preferences for cultural products. (Chattaraman & Lennon, 2008) One of the culturally shaped behaviors is maintaining individual ethnic identity, which can be defined as the shared identity of a group of people based on a common historical background, ancestry and knowledge of identifying symbolic elements such as nationality, religious affiliation and language. One of the main approaches to keep ethnic identity is through dresses, especially cultural apparel. This study intends to explore the interaction between individual AGCC and acceptance of cultural apparel. China is one of the world’s most attractive consumer markets not only because of its vast population, but also its sustained economic growth. In addition, more Chinese stay in or immigrate to different countries joining the global consumer segments. Therefore, Chinese consumer groups were selected for empirical study.

Keywords: Fashion Consumption, Cultural Apparel, Acculturation, Consumer Acceptance

1. Introduction In an increasingly globalized economy, global consumer segments have emerged and been growing. Anecdotal and empirical evidence suggests that global consumers share homogeneous consumer culture in international markets, providing opportunities to firms using standardized marketing strategies and offering standardized merchandise assortments for domestic and nondomestic markets. Increasingly, marketing researchers and practitioners emphasis the importance of understanding the development of homogeneous global consumer culture and its implications for businesses’ competitive success in the global market environment. The concept of acculturation to the global consumer culture (AGCC) was proposed and applied to understand global consumer culture and its interaction with other consumer characteristics and market behaviour. AGCC considers the range of skills, knowledge, and behaviour that consumers must acquire to acculturate to a global consumer culture(Carpenter et al., 2013). However, how individual’s AGCC interact with cultural product acceptance has not been examined. Meanwhile, other scholars argue that national cultural effects can be determining factor in shaping consumers’ preferences for cultural products including movies, foods, and particularly fashion products (Chattaraman & Lennon, 2008). Form recent cross-cultural studies Engelen and Brettel (Engelen & Brettel, 2011) conclude that national cultural values are powerful forces that shape perceptions and behaviors, and hence consumer behavior may become more heterogeneous, making it critical to understand values of national cultures and their impact on consumer behaviour(de Mooij & Hofstede, 2002). One of the culturally shaped behaviors is maintaining individual ethnic identity. Ethnic identity can be defined as the shared identity of a group of people based on a common historical background, ancestry and knowledge of identifying symbolic elements such as nationality, religious affiliation and language. According to Deshpande et al. (Deshpande, Hoyer, & Donthu, 1986), an individual’s strength of ethnic identification signifies the individuals’ base level

Page 78 of 1108

of affiliation with an ethnic group and his or her maintenance of culture origin. One of the main approaches to keep ethnic identity is through dresses, especially cultural apparel. To this end, the specific objectives of this study were to (1) examine the difference of AGCC between groups living in home country and abroad; (2) examine the effects of AGCC on acceptance of cultural apparel of APEC leader costume.

2. Research Background Cultural apparel can be defined as apparel designed and created based on inspiration from ethnic costumes. Cultural apparel has been considered as a means of communicating the ethnic identity of an individual or group, particularly amidst other groups, by visually signaling the ethnicity of the wearer (Eicher & Sumberg, 1995). Cultural apparel has been providing energy and vitality to fashion world. Designing fashion clothing inspired by ethnic costumes turns to be a trend now. China is one of the world’s largest countries with the longest history of civilization. Previous studies have reported that Chinese styles have strong influence on modern fashion (H. D. Kim, M, 1992; Y. K. Kim, M 1991). Furthermore, traditional Chinese apparel with long history and rich cultural features, is not only profound in specifying cultural identity, but also effective in communicating values and aesthetical standard. In fashion industry, some global brands always follow or create trends through culture apparel or culture inspired dress. There are many Chinese cultural elements, which can inspire fashion designs. Meanwhile, to many global and multinational companies, China is one of the world’s most attractive consumer markets not only because of its vast population, but also its sustained economic growth and purchasing power is increasing exponentially. In addition, more Chinese stay in or immigrate to different countries joining the global consumer segments. Therefore, Chinese consumer groups were selected for empirical study. Asia-Pacific Economic Cooperation (APEC) is a forum for 21 Pacific Rim member economies that promotes free trade throughout the Asia-Pacific region. It was established in 1989 in response to the growing interdependence of Asia-Pacific economies and the advent of regional trade blocs in other parts of the world.(Elek, 1991) APEC has kept an unusual tradition for more than a decade. World leaders gather to take a “family photo” wearing the traditional dress of the hosting country. The 22nd APEC meeting was held in Beijing November 10, 2014. The leaders wore bright colored Chinese style silk outfits, Chinese culture apparel (ethnic dress/ ethnic-inspired apparel), it delighted the public, photographers, TV cameramen who had been working day and night for a week to take excruciatingly images of talking heads. APEC costume is a great concert of global culture and national identity. To an extent, APEC offers a platform for world leaders to come together to discuss major international issues, it also give the public a chance to see those same world leaders come together to wear some interesting cultural apparels, which are designed by the host country.

3. Research Rationale The theoretical framework underlying this research is the theory of reasoned behaviour. Consumers’ acceptance towards products was determined and the variables influencing consumers’ purchase intention of the product were evaluated using the theory of reasoned behaviour. (Ajzen & Fishbein, 1977; Ajzen I, 1980) The model was explicitly constructed to explain relationships between attitude and behaviour by using the variables of belief, attitude, behavioural intention, and behaviour. Though the ultimate goal is to predict and understand an individual’s behaviour, the theory focuses on the influences of relevant factors on the behavioural intention and views the intention to perform or not perform a behaviour as the immediate determinant of the action. (Yingjiao, Summers, & Belleau, 2004) Consumer acculturation is a subset of acculturation, focusing on how individuals acquire the knowledge, skills, and behaviours that are appropriate to consumer culture (Peñaloza, 1989). Acculturation level, the degree to which an individual conforms to the norms of a new culture, is multidimensional, incorporating cultural identity, cosmopolitanism, language usage, religion, and social interactions, global mass media exposure, openness to and desire to emulate global consumer culture and self-identification.(Cleveland & Laroche, 2007; Hui, 1992; Jun, 1993) We focused on two relative dimensions on AGCC, Cosmopolitanism and Self-identification. Cosmopolitanism (COS) loosely describes just about any person that moves about in the word, but beyond that and more specifically, the expression refers to a specific set of qualities held by certain individuals is a specific set of qualities held by certain individuals, including a willingness to engage with the other (i.e. different cultures) and a level of competence towards alien culture(s)’. Self-identification with global consumer

Page 79 of 1108

culture (IDT) shows individuals’ self-ascribed membership in or outright identification with a global consumer culture. COS and IDT can affect consumers’ attitude. As consumers’ attitudes toward the product will influence their purchase intention and behaviour. Consumers’ attitude toward cultural apparels is associated with the acceptance.

Fig.1: Structural model of AGCC effects on consumer attitude and acceptance

4. Data Analysis and Results An online survey was conducted. With marketing research, online surveys are currently the most commonly used survey method. More than two thirds of consumers in the United States have access to the Internet, making it a viable and powerful research tool. (Hair, Black, Babin, & Anderson,2010) Participants were recruited by emails with the URL of the online survey embedded, enabling the recipient to go directly from the e-mail to the survey page with a single click. A reminder email was sent one week after the initial invitation. An incentive of lottery prize was offered to participants. Among the total of 391 responses, 252 were completed and included into data analysis, representing a response rate of 64.45 per cent. After the elimination of invalid responses, 243 valid responses remained for inclusion in this research. Participants responded to a 19-item scale adapted from Carpenter et al. (2013) assessing two dimensions of AGCC, Cosmopolitanism (COS), and self-identification global consumer culture (IDT). Then they viewed a line of culture apparel (see Figure 2). Figure 2 shows the 22nd APEC leaders’ apparels designed by Chinese designers. Respondents can click once to turn an item or part into green if they like it.

Fig. 2: The 22nd APEC leaders’ apparel line

Page 80 of 1108

A total of 30 items were subjected to Exploratory Factor Analysis and a four-dimension factor structure with 25 items emerged with total variance explained as 74.7%. Item factor loadings ranged from .68 to .92. Cronbach’s alphas were higher than .70. Summit index variable was created for each construct. Regression analysis showed that attitudes, and two dimensions of AGCC, COS and IDT predict individuals’ acceptance of culture apparel line. MANOVA were conducted to examine the differences across two groups. No difference in attitudes toward the viewed cultural apparel line was found. However, respondents from the US showed higher acceptance rate, and AGCC than their counterparts from main land China, indicating a paradoxical phenomenon that individuals with higher degree of AGCC are more likely to purchase and consume cultural apparel. Global consumers may have strong intention to maintain their ethnic identity while embracing homogeneous global consumer culture. Global brands could also offer cultural products to their target global consumers.

5. Limitations and Future Research Although this study provides some promising insights, certain limitations in the design of the research should be recognized in order to guide future exploration of this subject. Firstly, there are some limitations to the data collection. An online survey was used to collect data from a major university at southern area of the US and eastern area of China. And it is an exploratory study, which is still need of examining more social or individual influence factors on consumers’ attitude and acceptance towards cultural apparel. Based on the present research, several recommendations for future study are suggested. Such as social events affection on consumers’ acceptance of cultural apparel like APEC or the other great events. In addition the effect of fashion leaders’ attitude toward cultural apparel are also waiting to be discovered.

6. References [1] Carpenter, J. M., Moore, M., Alexander, N., & Doherty, A. M. (2013). Consumer demographics, ethnocentrism, cultural values, and acculturation to the global consumer culture: A retail perspective. Journal of Marketing Management, 29(3/4), 271-291. doi: 10.1080/0267257X.2013.766629 [2]Chattaraman, V., & Lennon, S. J. (2008). Ethnic identity, consumption of cultural apparel, and self-perceptions of ethnic consumers. Journal of Fashion Marketing and Management: An International Journal, 12(4), 518-531. [3]Cleveland, M., & Laroche, M. (2007). Acculturaton to the global consumer culture: Scale development and research paradigm. Journal of Business Research, 60(3), 249-259. doi: 10.1016/j.jbusres.2006.11.006 [4]de Mooij, M., & Hofstede, G. (2002). Convergence and divergence in consumer behavior: implications for international retailing. Journal of Retailing, 78(1), 61-69. doi: http://dx.doi.org/10.1016/S00224359(01)00067-7 [5]Deshpande, R., Hoyer, W. D., & Donthu, N. (1986). The Intensity of Ethnic Affiliation: A Study of the Sociology of Hispanic Consumption. Journal of Consumer Research, 13(2), 214-220. doi: 10.2307/2489227 [6] Eicher, J. B., & Sumberg, B. (1995). World fashion, ethnic, and national dress. Dress and ethnicity: Change across space and time, 295-306. [7]Elek, A. (1991). ASIA PACIFIC ECONOMIC CO-OPERATION (APEC). Southeast Asian Affairs, 33-48. doi: 10.2307/27912017 [8]Engelen, A., & Brettel, M. (2011). Assessing cross-cultural marketing theory and research. Journal of Business Research, 64(5), 516-523. doi: 10.1016/j.jbusres.2010.04.008 [9]Hui, M., Kim, K, Laroche, M., & Joy, A. (1992). Acculturation as a multidimensional process: Empirical evidence and implication for consumer researchers. In C. Allen et al. (Eds). AMA Winter Educators' proceedings, 23, 466-473. [10]Jun, S., Ball, A. D.,& Gentry, J. W. (1993). Modes of consumer acculturation. Advances in Consumer Research, 20, 76-82. [11]Kim, H. D., M. (1992). Sino-Japonism in Western women's fashionable dress in Harper's Bazar,1890-1927. Clothing and Textiles Research Journal, 11(1), 24-30. [12]Kim, Y. K., M (1991). The form of Oriental dress depicted on the 20th century Western fashion(I). Journal of Korean Home Economica Association, 29(1), 12.

Page 81 of 1108

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

Evaluation and Simulation of Clothing Assembly Line Yanni Xu, Haimei Zhou, Lichuan Wang and Yan Chen + Department of Textile and Clothing Engineering, Soochow University, Suzhou, China

Abstract. This paper is aimed to pick out suitable line balancing indexes that can predict and reflect production efficiency precisely. Firstly, line balancing indexes and corresponding calculation methods were given. Secondly, clothing assembly line simulation was demonstrated, where the universal method was developed to establish clothing assembly line simulation models. Finally, six scenarios of T-shirt line were studied. Data was collected by mathematics or simulation output and analyzed with methods of normalization and correlation analysis. The experimental results showed that the smaller the line balancing indexes are, the higher production efficiency will be achieved. Abilities to evaluate clothing assembly line differ with different line balancing indexes.

Keywords: line balance, production efficiency, evaluation, simulation, clothing assembly line

1. Introduction In clothing industry chain, sewing is the most complicated and critical link[1]. Line balancing in clothing manufacturing means allocating the resources such as workers and machines to each workstation evenly, which is usually done by using various line balancing methods [2].Diverse indexes giving the description of line balance are calculated with task time in each workstation through different ways vary with different researchers under different circumstances [3]. However, it is not clear how to choose suitable indexes to evaluate clothing assembly lines before production, for the relevance among these indexes is not given. Quantity of product per unit of time and labor or machinery utilization in regard to production efficiency can be acquired by computer simulation. Arena, witness, enterprise dynamics are typical and popular software used in clothing assembly line simulation to figure out the bottleneck operation as well as resource utilizations [4,5,6],which also offers an approach to study in above indexes. This study applies Arena simulation software to a T-shirt assembly line simulation which is used to analyze relevance among line balancing indexes and relevance between line balancing indexes and production efficiency with the methods of normalization and correlation analysis. The aim of this study is to give a guidance to evaluate arrangement scenarios of clothing assembly line with suitable line balancing indexes so as to pick out the ideal scenario.

2. Clothing Assembly Line Evaluation 2.1.

Line Balancing

Clothing assembly line is balanced in three ways in view of different constrains including valid production time, the target quantity of product, labor capacity, machine capacity and the given arrangement efficiency[7]. Nonetheless, line balancing procedure is similar and demonstrated in details as follows: â&#x20AC;˘ Task and time study â&#x20AC;˘ Allocating operations to workstations â&#x20AC;˘ Workers and machines as well as facility layout

2.2.

Line balancing Indexes

All the line balancing indexes respect to task time in workstations so as to evaluate the equality of operation allocation. +

Yan Chen. Tel.: + 86-010-6715 8048. E-mail address: yanchen@suda.edu.cn.

Page 82 of 1108

Average deviation rate in task time is calculated according to the following formula which represents the proportion of the sum of deviations between task time of each workstation and the standard process cycle time in total operation time:

∑ ( Pn − SPT )

ADR= ( Pn )

(2.1)

Task time variance is calculated similarly with average deviation rate in task time: V= ( Pn )

∑ ( Pn − SPT )

(2.2)

Balance index is not commonly used. The formula is as below:

∑ ( Pt − Pn )

BI = ( Pn )

(2.3)

Arrangement efficiency is the most widely employed one in evaluation of clothing assembly line arrangement scenarios among these line balancing indexes. The relevant formula varies in alternative conditions: (Pt > SPT )  SPT Pt × 100% E (%) =  P ( N × Pt ) × 100% ( Pt ≤ SPT )

(2.4)

The two indexes balance delay and loss coefficient are also often taken into account when evaluating line balance focusing on the waste of time and calculated as the following formulas: D ( Pn ) = N × Pt − P = N × Pt − ∑Pn = ∑ ( Pt − Pn )

(2.5)

LC ( %= ) D ( N × Pt ) ×100%

(2.6)

where, ADR is the average deviation rate in task time, Pn refers to the task time in each workstation, n refers to the workstation number, SPT refers to standard task time, V is the task time variance, N refers to the number of workers, BI is the balance index, Pt refers to the maximum of task time in workstations, E is the arrangement efficiency, D is the balance delay, LC refers to the loss coefficient.

3. Clothing Assembly Line Simulation 3.1.

Production Efficiency

Quantity of product and usage ratios of labor and machines illustrate production efficiency directly which can be obtained from simulation output. The higher quantity of product is always the key point when considering the production efficiency. Quantity of product is counted according to the number of products that just left the clothing assembly line simulation model right now. In Arena, it can be achieved easily by using a counter. Resource utilization consists of labor utilization and machinery utilization which is significant to production cost. In Arena, the resource utilization standing for the proportion of busy hour in total working time is calculated by the following differential coefficient formula: T

U = ∫B ( t ) dt T

(3.1)

where, U is the resource utilization, the function B(t) accounts for whether the resource is busy or free, T refers to the total working time.

3.2.

Simulation Model Establishment

The two parts considered when establishing clothing assembly line simulation models are amount and logic. Amount simulation means the numbers and time in a clothing assembly line. The simulation of numbers consists of labor and machine numbers, arrival number and target quantity of product, while the simulation of time are composed with task time in workstations, arrival time and so on. When simulating a clothing assembly line, working time, target quantity of product are usually set with constants whereas equipment failure rate, staff absence rate and material failure rate are set with some probability distributions. Furthermore, arrival number, task time, arrival time, conveyance time, quantity of conveyance, can be set with both constants and probability distributions.

Page 83 of 1108

Logic simulation is related to the sequence of products flowing in the clothing assembly line and rules obeyed when products are waiting to be operated in a queue, e.g. in a clothing sewing line materials go and pass each workstation by sequence referring to the information shown in the production flowchart. If the workstation is vacant, the first one is operated occupying certain resources immediately, or it should wait in a queue follows the ‘first in, first out’ rule.

4. A Case Study 4.1.

Experiment Design

A general T-shirt line is selected as the research object. Six different arrangement scenarios for the T-shirt production are given by simple arrangement methods including cancel, rearrangement, combination and simplification. The simulation models of the T-shirt assembly line are set as “one piece flow”, which means pieces of a garment are conveyed together from the beginning to the end of the production. The task time is set to follow the triangular distribution to make it closer to the reality.

4.2.

Experiment Data

Data of line balancing indexes are calculated according to arrangement scenarios with formulas aforementioned in 2.1, listed in Table 1. Production efficiency data are collected from operation output of the clothing assembly line simulation models, listed in Table 2. Table 1: Line balancing indexes Scenario No. 1 2 3 4 5 6

ADR -0.087 -0.087 -0.087 -0.087 -0.087 -0.087

V 0.11 0.10 0.08 0.06 0.05 0.03

Line balancing indexes BI E 0.62 0.73 0.61 0.73 0.47 0.80 0.45 0.80 0.35 0.86 0.19 0.92

D 1.31 1.31 0.95 0.95 0.71 0.23

LC (%) 33.08 33.08 26.39 26.39 21.13 7.99

Table 2: Production efficiency indexes Scenario No. 1 2 3 4 5 6

4.3.

Production efficiency indexes Quantity of product (piece) Labor utilization (%) 723 79.88 724 85.57 796 80.31 796 83.10 854 82.86 995 91.79

Machine utilization (%) 79.88 85.57 80.31 83.10 62.14 68.84

Data Analysis

Data Analysis is divided into two parts: internal relevance among line balancing indexes and relevance between line balancing indexes and production efficiency. Data of line balancing indexes fluctuate quite differently with each other and are of different dimensions. In order to give a more directly comparison, the data are mapped in the interval from 0 to 1 with the method of normalization. The result is illustrated by curves shown in Fig. 1. In the figure, E is taken place by 1-E in that it changes opposite to other indexes and E plus LC approximately equal to 1 in view of the formula. As a result of normalization, it is found obviously that： • Most of the line balancing indexes have corresponding tendency that varies synchronously. The smaller these indexes are, the higher quantity of product is. • ADR stays steadily for single assembly line with only one product. That means ADR is not available to evaluate clothing assembly lines which have the same product. • V varies differently from others and it applies to rough description of production efficiency. • 1-E varies resembling BI while D varies resembling LC, so they can be two couples of alternative options.

Page 84 of 1108

Value after normalization

1.100

ADR V BI 1-E D LC

0.900 0.700 0.500 0.300 0.100 -0.100

Scenarios

Fig. 1: Tendency of line balancing indexes.

Result of the correlation analysis is shown in the following Table 3. What we can see from the correlation coefficients: • BI, E, D and LC can fully illustrate quantity of product but resource utilization. LC comes first and D comes next followed with BI. E lies last. • No strong link between resource utilization and line balancing is revealed. • Equipped with multi-typed machines can improve production efficiency on certain extent, nevertheless, there is possibility of lower machinery utilization in this case. Table 3: Correlation coefficients Production efficiency indexes Quantity of product Labor utilization Machinery utilization

ADR -

V -0. 927 -0. 647 0. 696

Line balancing indexes BI E D -0.985 0. 977 -0.995 -0.684 0. 645 -0.705 0.745 -0. 785 0.727

LC -1.000 -0.758 0.705

5. Conclusions Usually, the smaller the balancing indexes are, the higher production efficiency of the assembly line will be achieved. E and BI like D and LC are alternative to each other. V can only be used to distinguish clothing assembly lines with the same work content which is not like others that for example, ADR is used to evaluate different kinds of clothing assembly lines. The first index to employ must be E. BI is quite useful when difference in line balance seems to be slight. If there is a need to check idle time, the indexes D and LC can help. Full use of resources with no waste does not always benefit, sometimes it means congestion and leads to long queues accompanied with lower speed of throughput. Higher production efficiency can be achieved when the clothing assembly line is equipped with more than enough machines and without regard to high machinery utilization. [1] Khosravi, F. , Sadeghi, A.H. and Jolai, F. , “An improvement in calculation method for apparel assembly line balancing”, Indian Journal of Fiber & Textile Research, Vol. 38 No. 3, pp. 259-264, Sep 2013. [2] GÜNER, M. , YÜCEL, Ö. and ÜNAL C. , “Applicability of different line balancing methods in the production of apparel”, Textile and Apparel, Vol. 23 No. 1, pp. 77-84, Dec 2012. [3] Eryuruk, S.H. , Kalaoglu, F. and Baskak, M. , “ Assembly Line Balancing in a Clothing Company”, Fibres & Textile in Eastern Europe, Vol. 16 No. 1, pp. 93-98, Mar 2008. [4] Eryuruk, S.H. , “Clothing assembly line design using simulation and heuristic line balancing techniques”, Textile and Apparel, Vol. 22 No. 4, pp. 360-368, Sep 2012. [5] GÜNER, M. and Ünal, C. , “Line balancing in the apparel industry using simulation techniques”, Fibers & Textiles in Eastern Europe, Vol. 16 No. 2, pp. 75-782, Jun 2008. [6] Zieliński, J. and Czacherska, M. , “Optimization of the work of a assembly team by using computer simulation”, Fibers & Textiles in Eastern Europe, Vol. 12 No. 4, pp. 78-82, Dec 2004. [7] Li, Y. , “Study of sewing assembly line balancing methods”, Journal of Textile Research, Vol. 23 No. 3, pp. 5456,Mar 2002.(In Chinese)

Page 85 of 1108

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

Finite Element Modeling of Women’s Breasts for Bra Design Yu 1, Cai 1 and Chen 2 1

Institute of Textiles and Clothing, The Hong Kong Polytechnic University, Hong Kong SAR, China 2

College of Mechanical Engineering and Applied Electronics Technology, Beijing University of Technology, Beijing, China

Abstract. A well-designed bra is essential to provide the necessary support to women’s breasts by reducing the breast displacement and the force induced by free vibration during daily activities. Without adequate support, the internal breast force will stretch the skin and the ligaments that cause breast discomfort or pain. However, previous studies have seldom considered the correct material properties of the breasts in the computer models. This study aims to develop a finite element model to simulate the actual softness of women’s breasts, in the preparation for the future research on the interaction between a bra and human body. The new knowledge of the breast modelling has great importance for designing effective bras to support women’s breasts.

Keywords: one, two, three, etc.

1. Introduction Women are constantly frustrated in their attempts to find suitable bras that both fit and support them correctly and comfortably. Manufacturing customised bras to fit is currently expensive and time consuming because bra fitting is problematic. Therefore, Finite element modelling (FEM) is potentially the future technology to quantitatively optimize bra design for personalized fit in terms of comfort, support, and shaping. Previous studies and commercial software such as Lectra, Gerber, Optitex, Tukatech have simplified the problem by assuming the body to be rigid [1]. The estimated stress distribution and breast displacement was in question. Therefore, this study aims to develop a finite element model to simulate the actual softness of women’s breasts, in the preparation for the future research on the interaction between a bra and human body.

2. Objectives In this research, the specific objectives are: • to review breast material properties in terms of modulus, Poisson ratio, and density. • to define the breast boundary in the finite element model • to simulate the multi-axial deformation of breasts. It is challenging because the modulus, Poisson ratio and density of various human tissues cannot be measured accurately in vivo. There was no standard method to define the breast boundary. The accuracy of FEM of human breasts are subject to validation. Finite element modelling has been successfully used in engineering many products but has not previously been applied to bras to be worn on the breasts. The development of breast submodel requires high-resolution 3D body scans and motion analysis for estimating the breasts’ damping ratio.

3. Finite element modelling of breasts 3.1. Geometric breast model Different imaging technologies are available for extracting the 3D breast geometry. Del Palomar[2] built the breast geometric models from CT images. Ruiter et al.[3] and Unluet et al.[4] extracted the breast

Page 86 of 1108

surface from patient-specific MR images. These techniques gave an accurate representation of the breast surface, extraction of fat tissue and fibroglandular tissue regions. However, if segmented images are not required, a 3D laser scanner is usually used to capture the skin surface of a human body more conveniently.

Fig. 1 Geometric breast model

3.2. Definition of breast boundary Biomechanical breast models are commonly criticized for modeling in a too simplistic or unrealistic manner by using rather poor estimates of arbitrarily-defined breast boundaries. Maitra et al.[5] assumed the breast model as a hemispherical dome with an elliptical base which is over-simplified. Brotherston[6] defined the breast boundary, based on the positions of nipple, the medial and lateral edges of the inframammary crease and the base point. Hyun et al.[7] suggested more reference points on the breast, but it was difficult to be determined by the subject herself without professional anatomical knowledge and clear boundary reference. Yip et al.[8] defined the boundary of the breast to be a circlular line passing through highlighted skin landmarks, but it needs professional palpation to find the landmarks and ensure repeatability. Zheng et al.[9] used clearly-defined 20 reference points to define the breast boundary including 15 points around the breast root, a chest line related side point, a front axillary fold point, and 3 newly defined points It is evident from these studies that there is still no consensus as to the definition of the breast boundary.

3.3. Mesh model of breasts For modeling the behavior of soft tissues, FE models based on continuum mechanics are widely accepted as an accurate method to simulate deformation in terms of the surface and volume representation in engineering, but they are expensive in computational cost and memory usage. Lower-order elements can provide reasonable accuracy with less computational expense, but are robust for large deformation and contact problems. To discretize the breast geometry, Del Palomar[10], Stewart[11] and Eder[12] meshed the breast with linear tetrahedral elements, while Del Palomar modelled the skin with linear triangular membrane elements. Tanner[13], Schnabel[14], and Zhang[15] discretized the computational domain using quadratic tetrahedral elements. Azar[16] used linear hexahedral finite elements for simulating breast compression. Most of studies have adopted tetrahedral elements for meshing breast due to the complex geometry of the non-structural breasts.

Figure 3 Mesh model of the breast section

3.4. Material properties of human breasts Previously developed FE models of human breasts used second-hand data from the literature, or derived mechanical properties (principally elastic modulus) from in vivo ultrasonic indentation tests on a small area of breast and validated by ex vivo data. The sensitivity of a modelâ&#x20AC;&#x2122;s prediction depends on the breast boundary conditions and constitutive material parameters. Medical studies have tended to create

Page 87 of 1108

individual-specific breast models based on magnetic resonance images in prone configurations. The fatty and fibro-glandular breast tissues were all assumed to be incompressible, homogenous and isotropic, and characterized by hyper-elastic neo-Hookean equations; whereas polynomial models were used for the skin. To obtain the general biomechanical behavior of soft tissues, many researchers simply assumed the tissues to be homogeneous, and the individual tissues to be isotropic. Hyperelastic constitutive models developed for elastomers have frequently been used to study soft tissues. They are considered initially isotropic and exhibit a nonlinear instantaneous response up to large strain. Moreover for simplicity, the breast tissues were generally assumed to be incompressible materials with a Possion’s ratio of 0.5. In reality, breast tissues are viscoelastic, anisotropic, inhomogeneous. They have nonlinear force displacement characteristics. There are limited publications of the in vivo mechanical properties of human breast tissues. Krouskop[17] measured the Young’s modulus of 142 breast tissues ex vivo under various compression levels and observed the tissue nonlinear behavior, but made no attempt to characterize the nonlinear parameters. Samani [18] developed a method to measure the nonlinear elastic parameters of each breast tissue type ex vivo by studying the force-displacement response of small blocks of breast tissues undergoing an indentation experiment. According to the literature, the elastic modulus of a breast varies extensively from 0.5 kPa to 50kPa. It is difficult to measure accurate breast density in vivo, so there were various breast densities reported in previous work: 1017 kg/m3, 940kg/m3, 600kg/m3, 685-825 kg/m3, 700-720 kg/m3, 780kg/m3, 780kg/m3. However, it is known that the breast density varies in the percentage of constituent fat and tissues as age increase. Young women generally have dense breasts compared to old women. Vandeweyer & Hertens[19] directly measured the densities of the breast fat and glandular tissues of the specimen collected from breast surgeon. They found that the densities of fat and glandular tissues were 500 kg/m3, and 1060 kg/m3 respectively. Breast tissues have been modeled as isotropic, homogeneous, and incompressible with a Possion ratio set as 0.495, because v = 0.5 cannot work in the FEA software. There are several possible material model to predict the constitutive relationships of breast tissues. They can be a linear elastic model, nonlinear elastic model (exponential model) or hyperelastic model (Neo-Hookean model, Mooney–Rivlin model, Polynomial model). There was no standard breast model for such complicated soft biological tissues. For small strains, the linear material models tend to accurately characterize the hyperelastic materials. Eder[20] demonstrated that a Neo-Hookean hyper-elastic model was the most appropriate method to describe the overall mechanical behavior of the breast in FE simulation for 18 subject.

4. Conclusion In the FEM of women’s breast, the breast was commonly assumed to be isotropic, homogenous, incompressible and viscoelastic. Surprisingly, Young’s modulus of breast tissues was found in the large range of 0.5-50kPa. It is critical to build accurate FE breast sub-models by suitable material data. NeoHookean hyper-elastic model has been regarded as the appropriate method to describe the overall mechanical behavior for the breast. Tetrahedral elements have been adopted for meshing breast due to its complex and non-structural geometry. However, it is still difficult to build true breast geometric model as there is no consensus for the definition of the breast boundary.

5. Acknowledgement We would like to thank the Research Grant Council for funding this research through the project PolyU 530612

6. References [1] Ishimaru S, Isogai Y, Matsui M, Furuichi K, Nonomura C, Yokoyama A, Prediction method for clothing pressure distribution by the numerical approach: attention to deformation by the extension of knitted fabric, Textile Research Journal, 81(18):1851-1870 (2011)

Page 88 of 1108

[2] Del Palomar, A.P., et al., A finite element model to accurately predict real deformations of the breast. Medical Engineering & Physics, 2008. 30(9): p. 1089-1097. [3] Ruiter, N.V., et al., Model-based registration of X-ray mammograms and MR images of the female breast. Nuclear Science, IEEE Transactions on, 2006. 53(1): p. 204-211. [4] Unlu, M.Z., et al., Computerized method for nonrigid MR-to-PET breast-image registration. Computers in biology and medicine, 2010. 40(1): p. 37-53. [5] Brown, T.L.H., et al., A method of assessing female breast morphometry and its clinical application. British journal of plastic surgery, 1999. 52(5): p. 355-359. [6] Maitra, I.K., S. Nag, and S.K. Bandyopadhyay, A Computerized Approach towards Breast Volume Calculation. [7] Lee, H.-Y., K. Hong, and E.A. Kim, Measurement protocol of womenâ&#x20AC;&#x2122;s nude breasts using a 3D scanning technique. Applied Ergonomics, 2004. 35(4): p. 353-359. [8] Yip, J.M., et al., Accurate assessment of breast volume: a study comparing the volumetric gold standard (direct water displacement measurement of mastectomy specimen) with a 3D laser scanning technique. Annals of plastic surgery, 2012. 68(2): p. 135-141. [9] Zheng, R., W. Yu, and J. Fan, Development of a new Chinese bra sizing system based on breast anthropometric measurements. International Journal of Industrial Ergonomics, 2007. 37(8): p. 697-705. [10] Del Palomar, A.P., et al., A finite element model to accurately predict real deformations of the breast. Medical Engineering & Physics, 2008. 30(9): p. 1089-1097. [11] Stewart, M.L., L.M. Smith, and N. Hall, A numerical investigation of breast compression: a computer-aided design approach for prescribing boundary conditions. Biomedical Engineering, IEEE Transactions on, 2011. 58(10): p. 2876-2884. [12] Eder, M., et al., Comparison of different material models to simulate 3-d breast deformations using finite element analysis. Annals of biomedical engineering, 2014. 42(4): p. 843-857. [13] Tanner, C., et al. A method for the comparison of biomechanical breast models. in Mathematical Methods in Biomedical Image Analysis, 2001. MMBIA 2001. IEEE Workshop on. 2001. IEEE. [14] Schnabel, J., et al., Validation of nonrigid image registration using finite-element methods: application to breast MR images. Medical Imaging, IEEE Transactions on, 2003. 22(2): p. 238-247. [15] Zhang, O., et al. 3D finite element modeling of nonrigid breast deformation for feature registration in-ray and MR images. in Applications of Computer Vision, 2007. WACV'07. IEEE Workshop on. 2007. IEEE. [16] Azar, F.S., D.N. Metaxas, and M.D. Schnall. A finite element model of the breast for predicting mechanical deformations during biopsy procedures. in Mathematical Methods in Biomedical Image Analysis, 2000. Proceedings. IEEE Workshop on. 2000. IEEE. [17] Krouskop, T.A., et al., Elastic moduli of breast and prostate tissues under compression. Ultrasonic imaging, 1998. 20(4): p. 260-274. [18] Samani, A., J. Zubovits, and D. Plewes, Elastic moduli of normal and pathological human breast tissues: an inversion-technique-based investigation of 169 samples. Physics in medicine and biology, 2007. 52(6): p. 1565. [19] Vandeweyer, E. and D. Hertens, Quantification of glands and fat in breast tissue: an experimental determination. Annals of Anatomy-Anatomischer Anzeiger, 2002. 184(2): p. 181-184. [20] Eder, M., et al., Comparison of different material models to simulate 3-d breast deformations using finite element analysis. Annals of biomedical engineering, 2014. 42(4): p. 843-857.

Page 89 of 1108

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

Handle Durability of Reusable Cloth Diapers after Use Hiroko Yokura 1 + and Sachiko Sukigara 2 1

Faculty of Education, Shiga University, Japan 2 Kyoto Institute of Technology, Japan

Abstract. With growing environmental awareness in society, it is worthwhile to consider the hand properties of reusable woven diapers, even though their absorbency is inferior to that of disposable diapers. The aim of this study was to quantify the hand values of used dobby weave cloth diapers based on their mechanical and surface properties. We asked four mothers to use dobby weave cotton cloth diapers while they cared for their children. The sample cloth diapers were used for periods of 24 to 80 months, and these diapers went through a roughly estimated 120 to 400 wearâ&#x20AC;&#x201C;wash cycles. When the survey was finished the sample cloth diapers were collected, and their mechanical and surface properties were measured by using the KES-FB system. For the used diaper samples, the surface became smoother due to decreased surface roughness values (SMD). The extensibility at maximum tensile load (EMT) increased with use, and the bending rigidity, bending hysteresis, and shearing hysteresis decreased. Fabric thickness and weight also decreased after 400 cycles. Micrographs of the fabric surface showed that the yarns became flat and tight. These fiber assembly structures govern the decrease in surface roughness. In terms of primary hand values, calculated equation KN202-LDY showed that the Hari (anti-drape stiffness) of the used fabrics decreased and Numeri (smoothness), Sofutosa (softness) and Shinayakasa (suppleness) increased as compared with unused fabric. The cloth diapers thus became softer and seemed to have improved hand. These results suggest an advantage of using reusable cloth diapers as an alternative to disposable diapers.

Keywords: cloth diapers, dobby weave, wear trial, hand value, mechanical and surface properties

1. Introduction Nowadays, disposable diapers are very popular because of their superior absorption performance over cloth. However, they increase the level of household waste. It is important to increase consumer-awareness of the environmental impact of non-bio-degradable products such as disposable diapers. In Japan, dobby weave cotton fabrics have traditionally been used for reusable cloth diapers, and 10% of parents continue to use them as an alternative to disposable diapers [1]. One reason for this is the good hand of cloth diapers for baby skin. Given the growing environmental awareness in society, it is worthwhile to consider the hand properties of reusable woven diapers and to examine objective data after their use. Cotton cloth diapers were popular during the 1980s and 1990s, and we conducted a long-term wear trial from 1988 to 1998 to evaluate the mechanical and surface properties of used diapers. However, the data were not published. Here, we report those findings, along with new data, which together should be helpful in the design of future environmentally friendly diapers. In a previous study, we clarified the properties of disposable diapers evaluated as having good hand under both dry and wet conditions [2]. In another study, we compared the physical properties of disposable and cloth diapers [3]. In the present study, we focused on the long-term use of diapers made of dobby weave cloth and measured the related mechanical and surface properties to calculate hand values. Although this is a limited case study, the data on long-term changes in the hand values of cloth diapers should be useful.

2. Experimental 2.1.

Cloth diaper samples and wear trial

We investigated three types of cotton cloth diapers with a dobby weave (Table 1). Figure 1(A) shows micrographs of the surfaces of dobby weave fabric N2. This diaper also is worn along with a diaper cover. Specimens N1 and N2 were the cloth diaper fabrics used in the wear trial, which was conducted from 1988 to

Corresponding author. Tel.: + 81-77-537-7827. E-mail address: yokura@edu.shiga-u.ac.jp.

Page 90 of 1108

1998. These specimens were chosen because they had nearly the same weave density. Specimen N3 is a cloth diaper purchased in 2014 to compare the hand values of a more recent sample. We asked four mothers to use 30 samples each of cloth diapers N1 and N2 while caring for their children. The diapers were washed using home pulsator-type washing machines and dried under the sun. The accumulated wearing periods were 24, 40, and 80 months. The numbers of wear–wash cycles corresponding to the respective wearing periods were estimated as 120, 200, and 400 cycles per diaper. When the wear trial was finished, diapers were returned and three randomly chosen diapers were taken from each wear period. We cut out a cloth specimen with dimensions 20 × 20 cm to measure its mechanical and surface properties.

2.2.

Measurement of mechanical and surface properties

The mechanical and surface properties of these fabrics were measured by using the Kawabata Evaluation System for Fabrics under the conditions for women’s thin dresses [4]. The primary hand values of women’s dress fabrics were objectively evaluated by using conversion equations based on the mechanical and surface parameters of the fabrics [4]. The KN202-LDY conversion equations were used to obtain values for Koshi (stiffness), Numeri (smoothness), Hari (anti-drape stiffness), Fukurami (fullness), Shari (crispness), Kishimi (scroop), Sofutosa (softness), and Shinayakasa (suppleness). Table 1: Dobby weave cotton cloth diaper samples. Yarn Density (cm-1)

Yarn Count (tex)

Thickness: T0 (mm)

Weight: W (g/m2)

Remarks

1.041

112.7

Used in the wear trial

19.4

1.123

114.0

Used in the wear trial

18.0

0.970

103.8

Purchased in 2014

Sample No. N1 ■

Warp 29.53

Weft 29.53

ends 18.4

picks 19.2

●

29.53

19.2

◆

29.53

17.8

Table 2: Details of the wear trial. Sample No. F1 □ F2 △ F3 ○

Baby A B1, B2 C1,C2, D1,D2

Accumulated period of use 24 months 40 months 80 months (Total)

Numbers of cycles each diaper was used 120 cycles per diaper 200 cycles per diaper 400 cycles per diaper

Original N1 N1 N2

Fig. 1: Micrographs of cloth diaper surfaces before (A; N2) and after (B; F3) 400 wear–wash cycles. （A）

(B)

3. Results and discussion 3.1.

Changes in the mechanical and surface properties

Figure 2 shows the mechanical and surface properties of cloth diapers obtained before and after use. Characteristic values are plotted on a data chart for fabrics used in women’s garments [5], with the horizontal axis normalized by the mean value and standard deviation of each corresponding characteristic value (n = 280). The extensibility at maximum tensile load (EMT) of the used samples increased and the tensile linearity (LT) decreased after use. The bending hysteresis (2HB) and shearing hysteresis (2HG, 2HG5) of cloth diapers became smaller as compared to the unused samples, suggesting that cloth diapers may be weakened by repeated wear and washing. Diaper samples surfaces became smoother due to decreased mean deviation of the coefficient of friction (MMD) and surface roughness (SMD). The relative change of each parameter is calculated as the ratio of the value after use X to the value before use X 0 . In Figure 3, the values obtained for bending rigidity B and bending hysteresis 2HB are plotted against the number of wear–wash cycles. The relative values of B and 2HB decreased remarkably after 400 cycles.

Page 91 of 1108

Table 3 lists parameters related to the fabric structure. The weight and air resistance (R) of specimen F2-2 are slightly increased due to shrinkage caused by repeated washing. The thickness (T0) and weight of specimens F3, as well as the value of R, decreased remarkably after 400 cycles. Figure 1(B) shows micrographs of the fabric surface F3 after 400 cycles. We can see that fibers have separated, opening more space between yarns, and that the yarns become flat and tight. These fiber assembly structures govern the decrease in surface roughness and hysteresis components of fabric shear properties (2HG, 2HG5).

Fig. 2: Mechanical and surface properties of cloth diapers before and after use. The horizontal axis is normalized by the mean value (M) and standard deviation (SD) of corresponding characteristic values for fabrics (n = 280) used in women’s garments [5]. 1: warp direction; 2: weft direction. See Tables 1 and 2 for an explanation of the symbols. Unused fabrics are N1 (■) and N2 (●). Used samples at three different periods are N1→ F1 (□, 24 months), N1 → F2 (△, 40 months), and N2 →F3 (○, 80 months).

Fig. 3: Relative changes in the bending rigidity B (◇) and hysteresis 2HB (▲) of cloth diapers versus the number of wear–wash cycles.

Table 3：Structural characteristics of fabrics before and after the wear trials Sample No. N1 F2-1 F2-2 F2-3 N2 F3-1 F3-2 F3-3

Numbers of wear-wash 0 200 0 400

Thickness: T0 (mm) Mean SD 1.041 0.017 0.993* 0.013 1.063 0.025 1.042 0.016 1.123 0.061 0.987* 0.024 0.894** 0.025 0.936** 0.034

Weight: W (g/m2) Mean SD 112.7 2.00 115.1 3.87 119.8** 1.19 116.0 2.58 114.0 1.16 105.3** 1.83 95.7** 1.61 108.2** 1.41

Air Resistance: R (kPa・s/m) Mean SD 0.0439 0.0020 0.0026 0.0423 0.0025 0.0520* 0.0024 0.0453 0.0030 0.0417 0.0008 0.0434 0.0045 0.0244** 0.0026 0.0402

* The difference between N1 and F2 or N2 and F3 significant at p<0.05 level **The difference between N1 and F2 of N2 and F3 significant at p<0.01 level

Page 92 of 1108

3.2.

Changes in the primary hand values

Figure 4 shows the primary hand values of cloth diapers as calculated from their mechanical and surface properties. The grading of feeling intensity of each primary hand value is numerically expressed on a scale of 1 (weakest) to 10 (strongest) [4]. The dobby cloth diapers show large values for Sari (crispness), a feeling coming from a crisp and rough fabric surface that evokes a cool feeling [4]. Table 4 shows the primary hand vales of N2 and F3. The Hari (anti-drape stiffness) decreased after use, while Numeri (smoothness), Kishimi (scroop), Sofutosa (softness) and Shinayakasa (suppleness) increased. The cloth diapers thus became softer and seemed to have improved hand. These results suggest an advantage of using reusable cloth diapers as an alternative to disposable diapers.

Fig. 4: Primary hand values of cloth diapers before and after use. See Tables 1 and 2 for an explanation of the symbols. Unused fabrics are N1 (■), N2 (●), and N3(◆). Used samples at three different periods are N1→ F1 (□, 24 months), N1→ F2 (△, 40 months), and N2 →F3 (○, 80 months). Table 4: Primary hand values of cloth diapers N2 (before use) and F3 (after 400 cycles)

N2 F3

Koshi Mean SD 4.97 0.13 4.76 0.19

Numeri Mean SD 4.77 0.66 5.00** 0.05

Fukurami Mean SD 5.12 0.17 4.96 0.39

Hari Mean SD 5.53 0.11 4.89** 0.20

Shari Mean SD 6.68 0.06 6.74 0.37

Kishimi Mean SD 3.13 0.07 3.57** 0.07

Sofutosa Mean SD 3.97 0.03 4.14** 0.02

Shinayakasa Mean SD 3.93 0.09 4.46** 0.15

**The difference between N2 and F3significant at p<0.01 level.

4. Conclusions For the wear–wash cycled samples, the extensibility at maximum tensile load EMT increased and the tensile linearity LT decreased. The bending and shearing hysteresis of cloth diapers decreased with use. This suggests that cloth diapers are weakened by repeated wear and washing. The diaper samples became smoother due to decreased mean deviations of the coefficient of friction (MMD) and surface roughness (SMD). After 400 wear–wash cycles, the values for thickness and weight of cloth diapers decreased remarkably. We also observed fiber removal and the yarns becoming flat and tight after 400 cycles. These changes in the fiber assembly structure govern the decrease in surface roughness and hysteresis components of the mechanical properties of fabrics. In terms of primary hand values, the values for Hari (anti-drape stiffness) decreased with wear, while the values for Numeri (smoothness), Sofutosa (softness) and Shinayakasa (suppleness) increased with use. The cloth diapers thus became softer and seemed to have improved hand quality. These results suggest an advantage of using reusable cloth diapers as an alternative to disposable diapers. Acknowledgements: We express our thanks to the mothers for their cooperation in the wear trials. This work was supported by JSPS KAKENHI Grant Number 26282011.

5. References [1] [2] [3] [4] [5]

Morozumi M. et. al., Transactions of Japan Society of Kansei Engineering, 13, 347-351 (2014). Yokura H. and Niwa M., Text. Res. J., 70, 135-142 (2000). Yokura H., Proceedings of the 33rd Textile Research Symposium, 107-113 (2004). Kawabata S., “The Standardization and Analysis of Hand Evaluation”, Textile Machinery Society of Japan (1980). Inoue T. and Niwa M., J. of Cloth. Sci. Tech. , 22, 234-247 (2010).

Page 93 of 1108

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

Optimization of producing bacterial cellulose used for clothing materials Su Min Yim1, So Hee Lee2, Hye Rim Kim1  1

Department of Clothing and Textiles, Sookmyung Women’s University, Research Institute of women's health, Sookmyung Women’s University, Seoul 140-742, Korea

Abstract. This study aims to develop clothing materials using bacterial cellulose. Thus, this study investigates culture conditions to produce the fabric of bacterial cellulose. The source to produce bacterial cellulose was used tea fungus. The culture conditions of tea fungus are influenced by nitrogen sources thus their effects on production of bacterial cellulose were evaluated. The production yield from bacterial cellulose was evaluated by dry weight, thickness, and the roughness of the fabric. When the green tea was used as the nitrogen sources, the production yield was improved. K/S values of bacterial cellulose were not influenced by the nitrogen sources, however, the color of fabric by black tea became darker. Compared to other nitrogen sources, the thickness of bacterial cellulose fabrics was increased in green tea. Moreover, the even and smooth surface was obtained by the nitrogen source of green tea.

Keywords: Tea fungus, Bacterial Cellulose, Nitrogen sources, Green tea

1. Introduction Bacterial Cellulose (BC) is composed of high purity cellulose, about 90~100%, and it does not contain impurities such as lignin, hemicellulose and pectin. However, natural cellulose from plant contained those impurities, about 50~60%. Thus, in plant cellulose fabrics, desizing and scouring processes are very important to remove impurities. Compared to plant cellulose fabrics, the process for BC fabrics can minimize those processes. Moreover, fabrics can be produced from bacteria in a shorter time about 12-21 days than plant cellulose fabrics. [1] The production of BC has been studied and used only in the fields of medical and cosmetic industries because of its superior biocompatibility. [2,3] The applications of BC in those fields are used only in wet or gel forms, and the studies for the use in dry conditions have not been reported.[4] In order to use BC for clothing materials, it has to be produced as fabric forms, dried planar substrates, and maintained the shape and properties in dry conditions. Therefore, this study investigates BC production using tea fungus for development of clothing materials. The effects of nitrogen sources, such as green tea, black tea, rooibos tea and corn silk tea on the production of BC fabrics was evaluated. Nitrogen sources were optimized by measuring dry weight, thickness, surface roughness, and surface color of BC fabrics.



Corresponding author. Tel.: + 82 2-2077-7591. E-mail address: khyerim@sm.ac.kr.

Page 94 of 1108

2. Experimental 2.1.

Materials. .

To produce BC, commercial tea fungus (Get Kombucha, USA) and organic kombucha (GTs Kombucha, USA) were used without any purification. Nitrogen sources were used commercial teas: Green tea (Osulloc, Korea); Black tea (Ahmad tea, UK); Rooibos (Twinings, UK); Corn silk (Teazen, Korea).

2.2.

Experiments.

Production of BC fabrics Cultivation. BC was produced in culture medium at a liquor ratio of 5:1(medium : tea fungus) using varying nitrogen sources (green tea, black tea, rooibos tea, and corn silk tea). Culture medium was prepared as follows; each nitrogen source was dipped in distilled water at 100~105℃, for 10 min. Subsequently, add 5% (w/v) carbon sources in the medium and it was cooled down at room temperature. At 25℃ of culture medium, 5%(w/v) kombucha was added. The fermentation was performed in the medium with tea fungus at 26℃ inincubator (SI-600R, Jeio Tech Co. Korea) After fermentation, BC was washed with distilled water at 100~105℃ for 5 minutes, and then washed with distilled water. The washing process repeated with three times to remove residual on fabric surfaces.

Evaluation production yield of BC fabrics Dry weight. Dry weight was measured using the hologen moisture analyzer (HB63-P, Mettler Toledo). Sample were dried in the analyzer at 60℃until equilibrium weight.

Surface roughness and Thickness. Surface roughness and thickness were determined using the micrometer machine (Mitutoyo. Co., No.2046F) according to KS K ISO 5084[5]. Each test was performed over five times.

Color Change. Color strength (K/S) of BC fabric was evaluated using a computer color machining system (CCM, JX 777, Japan).

Page 95 of 1108

120

100

80 60 40 20 0

Relative thickness(%)

120

Relative K/S value(%)

Relative dry weight(%)

3. Results and Discussion

80 60 40 20 0

Nitrogen sources

(a)

60 40 20 0

Nitrogen sources Green tea

Black tea

Rooibos tea

Nitrogen sources Corn silk tea

(b)

(c)

Figure 1. Production yield of BC fabrics by various nitrogen sources. (a) dry weight, (b) K/S value, (c) thickness.

Figure 1 shows the production yield of BC fabrics by various nitrogen sources. Figure 1 (a) shows the relative dry weight of BC by various nitrogen sources. Nitrogen sources give nutrition to organism thus production yield of BC is influenced by them. This present study selected teas as nitrogen sources because teas contain minerals, vitamins and the other essential for nutrition. [6] The relative dry weight of BC using green tea showed the highest value compared to other teas. Since green tea contains polyphenol of catechin, the green tea restrained mutation and removed oxygen free radical damaged cell. K/S value of BC fabric was evaluated by various nitrogen sources (Figure 1 (b)). Although, it has been reported that the surface color of BC is not changed by tea sort, the color of BC by black tea was changed. Color of BC fabric became darker which represents reddish yellow thus K/S values increased because of theaflavin and thearubigin in black tea. Figure 1 (c) shows thickness and roughness of BC fabric. When black tea was used as nitrogen source, the relative thickness showed the highest; as the thickness of the fabric was increased, however, the roughness of the surface was also increased. The roughness of the surfaces decreased when the green tea and corn silk tea were used as nitrogen sources. BC fabric produced by green tea and corn silk tea had leather-like texture and smooth surface. Therefore, the nitrogen source for production of BC fabrics was determined to the green tea considering the dry weight, thickness, surface color and roughness.

4. References [1] Park, Sang-Min et al. (2010) Properties of Bacterial Cellulose Cultured in Different Carbon Sources.

Polymer Korea 34.6 522-526. [2] Embuscado, Milda E., Jay S. Marks, and James N. BeMiller. (1994) Bacterial cellulose. II. Optimization

of cellulose production by Acetobacter xylinum through response surface methodology. Food hydrocolloids 8.5 419-430 [3] Nguyen, Vu Tuan et al. (2008) Characterization of cellulose production by a Gluconacetobacter xylinus

strain from Kombucha. Current microbiology 57.5 449-453.

Page 96 of 1108

[4] Malbaša, R., E. Lončar, and M. Djurić. (2008) Comparison of the products of Kombucha fermentation

on sucrose and molasses. Food chemistry 106.3 1039-1045 [5] KS K ISO 5084 (2011) Textiles－Determination of thickness of textiles and textile products. [6] Lee, Sam-Pin, and Chan-Shick Kim. (2000) Characterization of Kombucha beverages fermented with

various teas and tea fungus. Journal of Food Science and Nutrition 5.3 165-169. [7] Mayser, P. et al. (1995) The yeast spectrum of the ‘tea fungus Kombucha’. Mycoses 38.7‐8 289-295. [8] Ibrahim, N. A. et al. "J.Mater.Process.Tech., 160,99”(2005)

Page 97 of 1108

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

Relation among Three-Dimensional Shapes of Women's Trunk, Breast, and Abdomen Dong-Eun Choi 1, Kensuke Nakamura, Byung-Woo Hong 2 , Youngmi Park and Takao Kurokawa 4 1

School of Fashion and Housing Design, Kobe Shoin Women's University, Nada-ku, 657-0015, Kobe, Japan 2 Computer Science Department, Chung-Ang University, Seoul, Korea 3 Department of Clothing & Fashion, Yeungnam University, 280 Daehak-Ro, Gyeongsan ,Korea 4 Kyoto Institute of Technology, Kyoto, Japan

Abstract. A novel method of analyzing body shapes of people based on three-dimensional (3D) measurements is proposed. The method is to analyze the body shape by combining analysis results of body parts in order to avoid size and posture affecting the results. To this aim, our previous studies have analyzed the trunk, breast, and abdomen of about 500 Japanese women and extracted their shape factors by combining a body shape model and a principal component analysis. The model describes the trunk of a subject with 750 control points on a B-spline surface normalized by seventeen landmarks and enables us to treat the 3D body shape mathematically, including calculation of average shape. The extracted shape factors comprised six of the trunk, four of the breast, and four of the abdomen. An interpretation of the factors was also performed. The relation among 3D shapes of the trunk, breast, and abdomen is examined in this paper. Component scores of the 536 subjects and interpretations of the fourteen shape factors are used. A correlation matrix and a correlation diagram evaluate the relation of sixty-four pairs of shape factors between the different body parts. The average shapes of the subjects that are classified by the scores illustrate/express the difference in 3D shape of each pair of shape factors. Fifteen of the pairs with correlation coefficients (r) of more than 0.30 in absolute value are focused on and discussed. As a result, two of the pairs, reflecting breast height and degree of obesity, were found to have correlation coefficients sufficiently high (r = 0.81, â&#x2C6;&#x2019;0.53 respectively) and have similar interpretations. On the other hand, twelve of the fourteen factors have different meanings. This implies that different parts of the body have different shape factors and twelve or more parameters are necessary when treating the 3D shape in a simple way. In addition, some of the other thirteen pairs show tendencies of the 3D body shapes of the subjects. It has been confirmed that the shapes of body parts tend to change with posture, the shape of other parts, age, stature, and BMI. For instance, the level of the shoulder slope appears to affect the appearance of the breast. This paper also summarizes our series of studies on body shape analysis. Necessity, generalizability, limitation of the presented method, and application to other body parts are discussed. Keywords: three-dimensional human body shape, shape factors, abdominal shape, principal component score, correlation coefficient.

1. Introduction It is essential to extract body shape factors from a specific group of people to describe the shape of a customer in that group accurately and efficiently. The three-dimensional (3D) measurement, or scanned point cloud and anatomical landmarks, has attracted attention for this purpose in many industrial fields including apparel, ergonomics, and healthcare. However, a body shape model that can describe the 3D shape of a human body is necessary to analyze the body shape based on the 3D measurements. To solve this issue, the authors have proposed a method of body shape analysis1-3) utilizing a body shape model developed by Dr. Kurokawa and his colleagues. Our method has two steps to prevent the posture and the proportions from Dong-eun CHOI. Tel.: + 81-(0)80-5634 8493 E-mail address: g0024004@hanmail.net, g0024004@yahoo.co.jp

affecting the result as much as possible. The first step is to analyze some parts of the body separately. The trunk, the breast, and the abdomen have previously been analyzed1-3). The second step, which will be described

Page 98 of 1108

in this paper, is to analyze the whole shape by combining the results of the body analyses. The aim of this study is to analyze the relation among the 3D shapes of women's trunk, breast, and abdomen. The relation is examined based on fourteen shape factors extracted in our previous studies1-3), in which three body parts of 536 Japanese women were analyzed. 64 pairs of shape factors are evaluated by combining the component scores of the subjects and the interpretations of the factors. The analysis demonstrates that only two of the pairs have sufficiently high correlation coefficients, and similar interpretations. In other words, the shape factors of the three body parts have little relationship to each other. In addition, some of the pairs show the tendencies of the 3D shape of the subjects. The tendencies show us that the shape of some body parts change with that of other body parts, or with posture, age, stature, or degree of obesity. It is expected that the presented method and its results will be applied to the design and development process of, not only massproducts, but also mass-customized products in future markets in the various fields.

2. Difference with related studies Some researchers have analyzed the shapes of the whole body4), the breast5), 6), and the shoulder7) based on 3D measurements. There are some notable differences between our series of studies and these others: 1) A model describing the 3D shape of the body mathematically is utilized in our study. The other models only provide scanned dimensions or some feature points on the body; 2) 3D measurements of the nude figures of over 500 Japanese women have been used; 3) This is the first study that discusses body shape by combining the results of analyzing some parts of the body.

3. Summary of the shape analyses of the trunk, breast, and abdomen This study is based on the results of previous studies1-3) and summarizes our research on body shape analysis. Thus, 3D measurements, a body shape model, methods of analysis, and the results of those studies are briefly explained in this section.

3.1.

3D measurements

3D measurements of over 500 nude Japanese women were taken by laser metrology in 2000 at Wacoal Corp. VOXELAN (HEV â&#x20AC;&#x201C; 1800WHS) manufactured by Hamano Engineering Co. Ltd. was utilized. The subjects were scanned in a natural standing posture wearing only panties. 3D measurements of the trunk were extracted from the whole body data and used.

3.2.

A body shape model

The 3D measurement or point cloud does not have correspondence among different subjects. It is essential to convert it into shape data suitable for shape analysis by applying a body shape model that can describe the 3D shape of our bodies. A body shape model developed by Dr. Kurokawa and his colleagues8-10) has been utilized in our studies. The model describes the trunk shape of a woman using a B-spline surface normalized by 17 landmarks as shown in Figure 1. 1. 2. 3. 4. 5, 6. 7. 8. 9. 10. Figure. 1

Cervicale Shoulder strap Fossa jugularis Acromiale Axilla point anterior, posterior Thelion Underbust Omphalion Iliospinale anterius

17 landmarks 8-10), and crotch point (a).

Fitting the surface to a point cloud by a least square method generates 750 3D points called control points. The surface of the body can be reconstructed from the control points. A point on the reconstructed surface indicated by surface-coordinates (u, v) has a one-to-one correspondence among different bodies. The authors refer to the correspondence ensured by the landmarks as anatomical isomorphism11). The control points also have a correspondence among bodies8-10) and can be treated as a shape data.

Page 99 of 1108

The isomorphism makes it possible to evaluate the modeling error from the distance between a measurement-point and the corresponding point on the model. The mean of the modeling error per one subject is approximately 1.00mm and does not exceed 1.50mm for most women8-10). The information of the model surface is summarized into 750 control points. Therefore, we can analyze the 3D shape of people by analyzing the 3D coordinates of the control points. The details of the requirements for the body shape model were discussed in our papers 8-11). Although the Kurokawa model is limited to the trunk and has a considerable number of errors exceeding 5.00mm along the bottom of the sagging breasts, the model is the only model that describes the 3D body shape.

3.3.

Methods of shape analyses of the trunk, the breast, and the abdomen

(1) Body parts and their control points The Kurokawa model has locality, that is, the 3D shape of a body part can be analyzed using a subset of the 750 control points. In our previous studies, three parts of the bodies of about 500 Japanese women were analyzed by using the model. Firstly, the breast whose shape is important in the apparel and surgical fields was analyzed2). Secondly, the method was applied to extract shape factors of the abdomen3). Thirdly, the trunk shape could be analyzed1) by combining the method with a simple correlation analysis since the analysis variable, or the coordinates of the control points, is 2,250 and exceeds the number of the subjects. Figure 2 shows the subsets of the control points describing the trunk, the breast, and the abdomen. The right side of the body was analyzed to reduce the analysis variables by about half. The x-, y-, z-axes and the origin points O are also shown in the figure. The origin points were defined for each body part1-3) to avoid the position of the body and the length of the leg, for example, affecting the result. The trunk analysis utilizes the crotch point as the origin. The origin point of the breast and the abdomen is a point that is on the anterior median line and located at the level of the internal dividing point of the middle point of the two acromiales and that of the two iliospinale anterius at the ratio of 4:6. All the control points of the trunk, the breast, and the abdomen were normalized by the height difference between the cervical and the crotch point, an x coordinate value of the point shown in Figure 2(a), and the height difference between the fossa jugular and the crotch, respectively, to reduce the influence of the size factor, or the size of body of an individual subject1-3). u v y z

x O

(1) Trunk O

(a)

(2) Breast (3) Abdomen Figure. 2 Control-points for describing the shape of body parts1-3). (1) 18 x 23, (2) 7 x 7, (3) 11 x 9 of the control-points arranged in the u, v directions. O: Origin point for each body part. (a) A point to eliminate the size factor from the breast data.

(2) Analysis variables and subjects Analysis variables of the breast or the abdomen were generated by extracting the coordinates of the control points shown in Figure 2(2), (3) and applying the preprocessing explained in (1) to the points. Since the number of the coordinates of the trunk (18 x 23 x 3 = 1,242) exceeds that of the subjects, a simple correlation analysis was performed to reduce it to 111 so that a principal component analysis with rotation is applicable to the variables. Table 1 summarizes the conditions of the following analysis. The number of subjects differs between the trunk and the breast or the abdomen.

Page 100 of 1108

Table 1 Conditions for Principal Component Analysis (PCA) 1-3). Trunk Analysis variable Num. of subjects Rotation in PCA

Breast a)

111 560 Vari max

Abdomen

149 556 NA

297 556 NA

a) The number of coordinates of control-points describing the trunk shape was originally 18 x 23 x 3 (see Fig. 2(1)), but was reduced to 111 by correlation analysis so that PCA with a rotation is applicable to the variables1).

(3) Extraction of shape factors by principal component analysis Applying principal component analysis (PCA) to the variables of the three body parts converts the data to principal components including shape factors. Varimax rotation was employed in the analysis of the trunk to obtain meaningful components1-3). (4) Interpretation of shape factors The first six of the components trunk, the first four of the breast, and the first four of the abdomen, were interpreted as the shape factors of the three body parts. Figure 3 illustrates the contribution ratio and interpretation of each shape factor. The figure also shows the average shapes of three groups: I, II, and III into which the subjects are classified by the average ± S.D. of their component scores. The isomorphism ensures that the averaged 3D shape of people can be generated by averaging each coordinate of the control points8-10). A moiré pattern is utilized to emphasize the difference among the three groups. The interpretation of a shape factor is summarized here as "Horizontal Inclination of Trunk", or T1, for example. More details of the interpretations are explained in our previous papers1-3). The six factors of the trunk shape, labeled T1 to T6 here, mainly express body postures and the proportions. Although the body proportions could be extracted from the martin measurements inherently, the obtained factors show the variation in the 3D shape. For example, Figure 3(1) shows that increasing the score of T2 (Breast Height) also causes a change in the breast shapes. The cumulative contribution ratio of the trunk was 57.67%, which seems not enough for this kind of study. However, the 7th component was a factor of an artifact due to the lack of landmarks on the buttocks; the 8th relates to a small part of the upper abdomen. The shape factors of the breast (B1 to B4) or the abdomen (A1 to A4) are more likely to relate to "shape" as compared with those of the trunk. The objective of this study is to analyze the relation of the shapes of the three body parts by utilizing these shape factors. Principal component score

Ⅰ

Ⅱ

Ⅲ

T1 (13.32%)

T2 (11.36%)

Horizontal Inclination of Trunk

Breast Height

T3 (10.77%)

T4 (8.46%)

Shoulder Slope

Longitudinal Inclination of Trunk

T5 (7.02%)

Breast Size*1, *2

T6 (6.75%) Fatness of Trunk

(1) Trunk (Cumulative contribution 57.67%)

Page 101 of 1108

B1 (49.52%)

B2 (14.50%)

Breast Height

Circularity & Horizontal Direction of Breast

B4 (5.50%) Sagging of Breast

(2) Breast (77.14%)

A1 (48.18%)

A2 (19.93%)

Abdominal Protrusion & Waist Circumf.

Length & Round of Abdomen

A3 (9.95%) Slimness & Droop of Abdomen

A4 (4.59%) Droop of Lower Abd. & Swelling of Upper Abd.

(3) Abdomen (82.67%) Figure. 3 Principal components interpreted as shape factors of the Trunk (T), the Breast (B), and the Abdomen (A) 1-3). (Contribution ratio) and interpretation. I, II, and III are the average figures of three groups into which the subjects are classified by the average Âą S.D. of their component scores. A moirĂŠ pattern is utilized to emphasize the difference in 3D shape. *1 Shape factor whose component score is opposite to its interpretation. *2 The interpretation of T5 will be modified to "Breast Size & Thickness of Chest " in 4.4. (2)(e).

4. Analysis of the relationship among the trunk, breast, and abdominal shapes 4.1.

Outline of the analysis and research questions

The purpose of this study is to analyze the relation among the 3D shapes of the trunk, the breast, and the abdomen. The shape factors, or the principal components explained in 3-3(4), are useful for this aim, since the shape of each part of a subject is expressible by the shape factors. The correlation coefficient of the component scores should be the best way to evaluate the numerical relation of a pair of shape factors. However, when it comes to human bodies, the meaning of the factors must be considered as much as possible. Therefore, the relation analysis is performed by combining the result of a correlation analysis with the interpretation of the shape factors. There are two research questions: [1] Do the 3D shapes of the trunk, the breast, and the abdomen of the subjects have direct relationships? It is believed that there is a direct relationship between a pair of shape factors if they satisfy two conditions: (a) the correlation coefficient of the two factors is sufficiently high; and (b) their interpretations are similar. The first question concerns which and how many of the shape-factor pairs have a direct relationship. The greater the number of such pairs there is, the fewer the number of parameters that we must consider when treating the 3D body shape. [2] Are there tendencies of the 3D shapes among the three body parts? A pair of shape factors that does not satisfy conditions (a) and (b) but has a certain correlation coefficient may possibly reflect a tendency of the body shapes. The second question is about these tendencies. Relations between the body shape and age, BMI (Body Mass Index), and stature are also examined in this paper.

4.2.

Data for analysis

The component scores of the shape factors of the trunk, breast, and abdomen of 536 women are utilized. The shape factors (T1, ..., T6, B1, ..., B4, A1, ..., A4) are summarized in Figure 3. The 536 subjects are the

Page 102 of 1108

ones whose 3D measurements were used throughout the previous studies. They range in age from 19 to 63. The mean age is 37.85 years old. The principal component score of a shape factor indicates the relative level of that factor in the body shape of an individual. For instance, a woman whose (right) breast is located relatively higher than other subjects will score higher on T2. Note that the shape factors were extracted from the analysis variables normalized as explained in section 3-3(1). Thus, T2 does not directly reflect any specific y value but the relative height of the breast to the trunk. Age, BMI (Body Mass Index), and stature of the subjects are used additionally.

4.3.

Result of correlation analysis

(1) Correlation matrix Table 2 shows the correlation matrix of the shape factors of the three body parts. For the sake of ease in this paper, the expressions “r is high” or “low” refer to the magnitude of the absolute value. 64 pairs of factors among different body parts are analyzed for the purpose of this study. There are 91 pairs of shape factors in total, but it is obvious that the shape factors extracted from the same part by principal component analysis are poorly correlated. Table 2 also gives the correlation coefficient between the factors and age, BMI, and stature. Table 2 Correlation (r) matrix of shape factors, age, and BMI (N = 536). T1 T2 T3 T4 T5 T6

T1 ― − 0.01 − 0.01 − 0.01 − 0.01 − 0.01

― 0.00 0.01 − 0.01 0.00

― − 0.01 0.01 0.00

― 0.00 − 0.02

― − 0.01

―

B1 B2 B3 B4

− 0.10 0.01 − 0.03 − 0.11

0.81 0.05 0.31 − 0.15

0.28 − 0.03 − 0.58 0.39

− 0.03 0.14 0.09 0.12

− 0.12 − 0.20 0.02 0.03

− 0.01 0.05 0.27 0.31

― 0.00 0.03 − 0.01

― 0.01 − 0.01

― 0.01

―

A1 A2 A3 A4

− 0.11 0.02 0.20 0.11

− 0.18 0.66 − 0.37 0.19

0.07 0.16 − 0.17 0.05

0.64 0.17 0.23 0.02

− 0.47 − 0.01 0.36 − 0.05

0.14 − 0.36 − 0.53 − 0.05

− 0.08 0.61 − 0.53 0.23

0.50 0.24 0.02 − 0.09

0.02 0.05 − 0.08 − 0.18

0.27 − 0.02 − 0.14 − 0.07

― 0.02 − 0.02 0.00

― 0.06 0.00

― − 0.04

―

Age BMI Stature

− 0.01 − 0.08 0.13

− 0.10 − 0.24 0.04

0.04 0.03 − 0.37

− 0.06 − 0.02 − 0.08

0.09 − 0.43 0.05

0.40 0.65 − 0.22

− 0.13 − 0.04 − 0.07

0.12 0.02 − 0.02

0.15 − 0.01 0.12

0.32 0.29 − 0.33

0.07 0.32 − 0.15

− 0.18 − 0.45 0.10

− 0.19 − 0.51 0.21

− 0.04 0.01 0.02

T1 T2 T3 T4 T5 T6

Horizontal Inclination of Trunk Breast Height Shoulder Slope Longitudinal Inclination of Trunk Breast Size Fatness of Trunk

B1 B2 B3 B4

Breast Height Circularity & Horizontal Direction of Breast Swelling of Breast Sagging of Breast

A1 A2 A3 A4

Abdominal Protrusion & Waist Circumf. Length & Round of Abdomen Slimness & Droop of Abdomen Droop of Lower Abd. & Swelling of Upper Abd.

Correlation coefficient (r)

T1, ..., T6, B1, ..., B4, A1, ..., A4: Shape factors of T ．runk, B ．reast, and A ．bdomen (see Fig. 3). BMI: Body Mass Index. r(Age, BMI) = 0.13, r(Age, Stature) = − 0.20. Correlation coefficients of shape factors above 0.30 or below − 0.30 are highlighted 1.00 0.50 0.00 -0.50 -1.00 0 10 20 30 40 50 60 Rank

Figure. 4 Distribution of correlation coefficients in increasing order (N = 536). Dashed lines indicate r = ± 0.30.

(2) Pairs of shape factors to be focused on

Page 103 of 1108

Figure 4 shows the distribution of the correlation coefficients of the 64 pairs. The correlation coefficient ranged between − 0.58 and 0.81. The figure indicates that 15 pairs of shape factors with |r| > 0.30 have some meaning. Therefore, the 15 pairs highlighted in Table 2 are primarily examined in this study. Shoulder Slope Longitudinal Incl.ofTrunk Breast Height Breast Size T3 T4

T6 Fatness ofTrunk

Horiz. Incl. of Trunk T1

Droop of Lower-&

Breast Height

A4 Swelling ofUpper-Abd. A3 Slimness &Droop of Abd.

B1 Circularity & B2

Horiz. D. of Breast B3 Swelling of Breast B4 Sagging of Breast

-.60 < r ≤ -.30,

A2 Length &Round ofAbd.

Abd. Protrusion & Waist Circumf.

.30 ≤ r < .60,

.60 ≤ r

Figure. 5 Correlation diagram of the shape factors. Pairs of factors with |r| < 0.30 are not connected by any line. Some interpretations are abbreviated for space.

(3) Correlation diagram Figure 5 shows a correlation diagram constructed from the correlation matrix. In the figure, each of the small circles arranged in a large circle represents one of the shape factors. A line connects each pair of small circles with |r| > 0.30. The type of line indicates the magnitude of the correlation. The diagram helps us to easily understand the relation among the shape factors.

4.4.

Result of analysis of the relation among shape factors

The relation among the shape factors is analyzed with the research questions mentioned in 4-1. (1) Pairs of shape factors with a direct relation The correlation matrix and the correlation diagram indicate that T2-B1 and T6-A3 are the pairs that have direct relationships, as their correlation coefficients (r) are significantly high and their interpretations are similar. The correlation coefficient between T2 (Breast Height) with B1 (Breast Height) was r = 0.81, which is remarkably higher than with other pairs. The scatter plot of the component scores is shown in Figure 6. The interpretations of the two are almost the same. Figure 3 show that T2 reflects the difference in the abdominal shape of the three groups. Therefore, the two factors are not exactly the same, but have a direct relationship. Assuming that T2 and B1 are the same factor reflecting breast height, this result allows us to reduce the number of pairs to be focused on from 15 to 13. Thus, for example, although A2 is connected with both factors by segments in Figure 6, only the relation between A2 and either T2 or B1 should be discussed. This is the same for A3.

r = .81

r = -.53

Figure. 6 Correlations of T2 with B1, and T6 with A3 (N = 536) Component scores are normalized to z values in this figure.

Ⅰ

Ⅱ

Ⅲ

Ⅰ

Ⅱ

Ⅲ

Page 104 of 1108

Ⅲ

Ⅱ

T6 (Fatness of Trunk) Ⅰ

Ⅲ

Ⅱ

Ⅰ

A3 (Slimness & Droop of Abdomen) Figure. 7 Comparison of T6 with A3.

T6 (Fatness of Trunk) and A3 (Slimness & Droop of Abdomen) were correlated with r = − 0.53. Figure 6 also presents the scatter plot of the scores. Figure 7 illustrates the anterior and lateral views of T6 and A4. The average figures for A3 are arranged in reverse order, because of the inverse relationship with T6. In Figure 7, the droop of the top of the abdomen is observed in the three groups with A3 but not with T6. T6 and A4 are the top two factors that correlate with BMI. While T6 and A4 have some differences, their correlation coefficient is relatively high and the interpretations are similar. Therefore, the two factors could be treated as factors reflecting degree of obesity. (2) Pairs of shape factors reflecting the tendency of the body shape The other pairs of shape factors clearly differ in their interpretation or the correlation coefficient is not sufficient. Some of them seem to express tendencies of the body shape of the 536 women as follows. (a) Tendencies with posture Firstly, two pairs of shape factors show that subjects with different postures tend to have different body shapes in appearance. T4 (Longitudinal Inclination of Trunk) and A1 (Abdominal Protrusion & Waist Circumf.) had r = 0.64. Based on the r value and their interpretations, we can say that A1 describes the protrusion of the abdomen in principle, but that the score also varies when the appearance of the abdomen changes due to the posture. z Ⅰ

Ⅱ

Ⅲ

Ⅱ

Ⅲ

Ⅰ

T3 (Shoulder Slope) Ⅰ

Ⅲ

Ⅱ

Ⅲ

Ⅱ

Ⅰ

B3 (Swelling of Breast) Figure. 8 Comparison of T3 with B3.

The correlation coefficient of T3 (Shoulder Slope) and B3 (Swelling of Breast) was − 0.58. Figure 8 shows the average shapes of T3 and B3. As the component score of T3 increases, the shoulder is leveled and the armhole moves backward. Accordingly, the T3 of group Ⅲhas a posture with shoulders back and chest out. For reference, it should be pointed out that, while shoulder shape was not included in the breast shape analysis, the same B3-posture relationship is observed to some extent in all three groups. It seems that the score of B3 tends to increase when the shoulder lifts up the chest. Thus, the pair T3-B3 suggests that the degree of the shoulder slope affects the appearance of the breast. (b) Tendencies in relationships between parts of the body

Page 105 of 1108

Secondly, two of the pairs present tendencies in the relations between one part of the body and another. T5 (Breast Size) and A1 (Abdominal Protrusion & Waist Circumf.) had r = − 0.47. As shown in Figure 9, T5 and A1 differ on the longitudinal inclination of the trunk, but are similar in that the volume of the breast increases from Ⅲ to Ⅰ. It is natural to interpret this as showing that a subject with protruding abdomen tends to have big breasts. The correlation coefficients of the two factors with BMI (r = − 0.43, and 0.32, respectively) seem to confirm this interpretation. T2 (Breast Height) and B2 (Circularity & Horizontal Direction of Breast) were slightly correlated (r = 0.31). This would suggest that a breast located relatively high has a tendency to be small. Ⅰ

Ⅱ

Ⅲ

Ⅱ

Ⅲ

Ⅰ

T5 (Breast Size) Ⅰ

Ⅲ

Ⅱ

Ⅲ

Ⅱ

Ⅰ

\ A1 (Abdominal Protrusion & Waist Circumf.) Figure. 9 Compasion of T5 with A1.

(c) Tendencies with age, BMI, or stature Thirdly, some pairs of shape factors show tendencies of the body shape relating to age, BMI, or stature. The pair of T6 (Fatness of Trunk) and B4 (Sagging of Breast) had r = 0.31 They are the top two factors correlating with age (r = 0.40, 032), so this pair indicate that older subjects tend to be obese and also have a sagging breast. T5 (Breast Size) and A3 (Slimness & Droop of Abdomen) with r of 0.36 are correlated with BMI (r = − 0.43, and − 0.51). As mentioned in 4-4(1), A3 can be the factor reflecting degree of obesily. This pair show a tendency for the breast of an obese subject to be bigger than that of one who is slim. Ⅰ

Ⅱ

Ⅲ

Ⅱ

Ⅲ

Ⅰ

T6 (Fatness of Trunk) Ⅰ

Ⅲ

Ⅱ

Ⅲ

Ⅱ

Ⅰ

A2 (Length & Round of Abdomen) Figure. 10 Comparison of T6 with A2.

The correlation of T6 (Fatness of Trunk) and A2 (Length & Round of Abdomen) was r = − 0.36. Figure 10 shows that there are some differences between the two factors, such as relative length of the abdomen to the trunk. However, the both factors have captured the difference of waist circumference of the subjects and are correlated with BMI (r = 0.65, − 0.51). That is to say, the pair T6- A2 shows that being obese tends to result in a large circumference of the abdomen. T3 (Shoulder Slope) and B4 (Sagging of Breast) had r = 0.39. Since age was correlated with B4 but not with T3 (r = 0.32, and − 0.04, respectively), the pair seems not to relate to age. The two factors have a correlation with a stature (r = − 0.37，− 0.33). In general, it is noted that the average stature of Japanese women decreases as age increases. The stature of the 536 subjects was also negatively correlated with age (r = − 0.20). Therefore, on shape factor B4, older subjects tended to have a

Page 106 of 1108

sagging breast and be short. On T3, the shorter subjects tended to have a leveled shoulder irrespective of age. Thus, it is thought that T3 and B4 are correlated as they share a relationship with stature. Ⅰ

Ⅰ

Ⅱ

Ⅲ

Ⅰ

Ⅱ

A2 (Length & Round of Abdomen) Ⅱ

Ⅲ

Ⅰ

Ⅱ

Ⅲ

A3 (Slimness & Droop of Abdomen) Figure. 11 Comparison of the anterior and lateral views of A2 and A3.

(d) Pairs of shape factors that are difficult to interpret Rather than reflecting tendencies of body shape, two of the pairs may be artifacts that depend on the nature of the body shape analyses. Figure 6 shows that A2 (Length & Round of Abdomen) or A3 (Slimness & Droop of Abdomen) have relatively high correlations with T2 and B1. As discussed in 4-4(1), T2 and B1 would appear to be the same factor describing breast height. However, it is doubtful that A2 and A3 also relate to breast height directly. Figure 11 depicts the average figures for A2 and A3. Generally speaking, group Ⅰ has a fat figure and group Ⅲ is slim in both A2 and A3. The breast of group Ⅲ is located higher than that of groupⅠ in A2, but lower in A3. Taking T2 as an example, we can see that, while the correlation coefficient of T2 with A2 was plus (r = 0.66), that with A3 was minus (− 0.37). In other words, though T2-A3 the pair indicates that a woman whose breast is positioned relatively high would be slim, the pair suggest she would be fat. The two pairs have opposite meanings. Consequently, it is not certain whether these pairs of factors actually, reflect tendencies of the body shape. B2 (Circularity & Horizontal Direction of Breast) and A1 (Abdominal Protrusion & Waist Circumf.) had r = 0.50. B2 is only linked with A1 in Figure 5. While A1 is correlated with T4, which expresses the longitudinal inclination of the trunk as mentioned in 4-4(2)(a), the correlation of B2 with T4 is not sufficient (r = 0.14), meaning that this pair does not relate to that posture. It seems that the shape of breast relates to age, but in fact there are poor correlations between age and both B2 and A1 (r = 0.12, 0.07). The pair of B2 and A1 might reflect an unknown tendency in the relation between the shapes of the breast and the abdomen, or it may be an artifact. (e) Other notable results In addition to the pairs with |r| > 0.30, there are several other remarkable features. It may seem strange that T1 (Horizontal Inclination of Trunk) with the highest contribution to the trunk shape was not correlated with any other factors extracted from the breast and the abdominal shapes (|r| < 0.11). However, this result can be explained by the difference in size of body parts analyzed in previous studies. In the trunk shape analysis, even a slight tilt of the body results in a large swing of control points, such as those on the shoulder that are distant from the origin or the crotch point. On the other hand, the breast and the abdomen are comparatively small and the longitudinal inclination has low impact. For this reason, a shape factor reflecting longitudinal inclination did not appear among the first four factors of both parts. A4 (Droop of Lower Abd. & Swelling of Upper Abd.) has a high degree of independence from all the other variables used in this study: shape factors, age, BMI, and stature (see Table 2). Moreover, A4 is poorly correlated with the 23 fundamental body dimensions on the trunk. (More detail will be presented in a future paper). The other 13 shape factors do not have this feature. If A4 is not an artifact, this shape factor would provide us with new knowledge about our body shapes. Whereas T5 (Breast Size) and B3 (Swelling of Breast) are similar in interpretation, there was no association between them (r = 0.02). In response to these results, the authors have re-investigated their meanings. As a result of careful observation, the interpretation of T5 has been modified to "Breast Size & Thickness of Chest". T5 relates not only to the volume of the breast, but also to the thickness of the chest as shown in Figure 3(1). This is probably

Page 107 of 1108

a reason for the poor correlation of T5 with B3. It should be noted that this modification of the interpretation is consistent with the evaluation of the pair T5-A1 in (b).

5. Discussions 5.1.

On the relationship among body shapes of the trunk, breast, and abdomen The relationship is discussed in response to research questions [1] and [2]. [1] Do the 3D shapes of the trunk, the breast, and the abdomen of the subjects have direct relations? The shapes of the three body parts of the 536 women seem not to directly relate to each other. Correlations of 64 pairs of shape factors between different body parts were evaluated in 4.4.. The result showed that only two of the pairs were correlated sufficiently and had similar interpretations. They are the pairs T2-B1, relating to the breast height, and T6-A3 relating to the degree of obesily. Although it is debatable whether the factors in each of the two pairs can be the same shape factor, the appropriate answer to the first question is certain to be â&#x20AC;&#x153;NO for most casesâ&#x20AC;?. When considering T2 and B1, and T6 and A3 as the same respectively, twelve out of the fourteen shape factors are independent. This result implies that shape factors that will be extracted by the same method from other body parts, such as the shoulder, the back, and the hip, will hardly have any relation. In these cases, it requires at least twelve parameters to describe the body shapes of the 536 women precisely. This is an essential piece of information for modeling treating the body shape of a customer in a simple way. For example, when estimating the 3D shape of our bodies from martin measurements, we will need at least twelve of the measurements independent of each other. Also, it will be useful if the 3D shape of the breast can be estimated from the abdomen which is relatively easy to scan. However, the result of our study would seem to indicate that such estimation is difficult. [2] Are there tendencies of the 3D shapes among the three body parts? As described in 4.4., some pairs of shape factors show tendencies of the body shapes of the 536 women. The tendencies can be classified into three categories. Tendency of the relationship between posture and appearance of the body: The sway back posture tends to make the abdomen look bigger than it is (T4 with A1). A posture with shoulders back and chest out seems to make the breast look bigger (T3 with B3). Tendency of the relationship between the shape of a body part and that of another: Subjects with protruding abdomen tend to have big breasts (T5 with A1). The higher the relative position of a breast is, the bigger the breast tends to be (T2 with B3). The tendency of body shapes in relation to age, BMI, and stature: As age increases, the subjects tend to be obese and have a sagging breast (T6 with B4). BMI increases the volume of the breast (T5 with A3) and the waist girth (T6 with A2). Subjects who are short tends to have a leveled shoulder, are older, and have a sagging breast (T3 with B4). This is the first study showing these tendencies based on shape data that can describe the 3D shape of our bodies. In particular, the relation between the 3D shapes of the breast and the abdomen can contribute to discussions on womenâ&#x20AC;&#x2122;s body shape. As mentioned in 4.4.(d), it is not certain whether some of pairs of the shape factors reflect tendencies of the body shape or are artifacts. These are the pairs of breast height (T2) with A2 or A3, and of breast shape and abdominal shape expressed by B2 and A1 respectively. Additional research is necessary on these pairs.

5.2.

On the series of body shape analyses

The method and results of our studies are summarized. (1) Necessity of the analysis method Our idea is to analyze each part of the body separately and analyze the whole shape by combining those results. This method would not be not necessary if all the shape factors could be extracted by analyzing the whole shape all at once, or if the shape factors of the abdomen could describe those of the breast, for example. However our study has demonstrated that the most of the shape factors of the trunk, the breast, and the abdomen do not share the same meanings. Therefore, the framework of our method is suitable for the body analysis using 3D measurement.

Page 108 of 1108

(2) Generalizability and limitation 3D measurements of about 500 Japanese women were used. As mentioned above, the subjects were collected in the Kansai region. Also, there is a difference between our the measurement and the a massmeasurement that is considered standard in Japan. When comparing the mean values of fundamental dimensions including stature and the waist girth in age periods, there were maximum differences of between 1cm and 2cm even allowing for the difference in the measuring methods11). Therefore, the results of our studies cannot be extrapolated to all Japanese women directly. However, such a difference in the dimensions would not affect the shape factors and their correlations.Accordingly, the authors consider the results to reflect the body shapes of Japanese women. There are some remaining issues. Firstly, the whole of the 3D body shape of the subjects cannot be described using only the fourteen shape factors. The cumulative contribution ratios of the factors or the principal components were 57.67% to the trunk shape, 77.14% to the breast, and 82.67% to the abdomen. It is safe to say that the remaining information contains factors relating to subtle shapes such as slack of the abdomen or looseness of the breast. The reason why it is not possible to extract these factors could be attributed to the body shape analyses that treat together subjects who differ in age, household tasks or work, and lifestyle, which affect body shape. It is expected that the other shape factors could be extracted if the age range of subjects were limited, for example. The results of analyzing women as a whole presented here would also contribute to such studies. Secondly, the 536 subjects in this paper are those who were used in all the analyses of the three body parts. As mentioned in 3.3., the number of subjects differs between the trunk shape analysis and the other two. Also, the nature of the analysis differs among the three studies. Therefore, the relations among of shape factors extracted from shape data of the same subject, obtained as far as possible under the same conditions should be confirmed. (3) Application to other body parts The methods of the body shape analyses should be applicable to other parts of the body. The shapes of the shoulder, the back, the hip, and the whole body must be analyzed in future. These body parts could not be analyzed so far since the Kurokawa model is limited to the trunk shape, and landmarks necessary to describe these parts were not recorded in the measurement database. To solve this problem of the model, the authors have proposed a novel polygon model11) that can describe the whole body and the breast shape more precisely while inheriting the mathematical features of the Kurokawa model. By combining the new model with a database containing the appropriate landmarks, we would be able to analyze the other parts. The body shape of younger women and men could also be analyzed by the presented methods since they are simpler than the shape of older women in shape.

6. Conclusions The relation among the trunk, the breast, and the abdominal shapes of 536 women was examined. The fourteen shape factors extracted in a previous study were utilized. The 64 pairs of shape factors between different body parts were evaluated by correlation coefficients and their interpretations. Firstly, it has been demonstrated that most of the shape factors are independent of each other. Therefore, when analyzing body shape based on 3D measurements, it is important to examine the shapes of some body parts and then summarize those results. Our results have also indicated that the number of parameters or shape factors should be twelve or more. Such a number is essential for a study estimating the body shape of a customer accurately in a simple way. Secondly, it has been numerically confirmed that the shapes of body parts of the subjects tend to change with posture, the shape of other parts, age, stature, and BMI. These tendencies should be useful in designing garments that enhance the figure of a woman and for age-appropriate products. To design individualized products accurately and efficiently, it is essential to analyze the distribution of body shapes in the population and map an individual onto it. It is quite certain that understanding the body shape of a customer will become more and more important in future with mass-customized markets growing in the fields of apparel, ergonomics, and so on. However, it is still difficult for researchers to analyze the 3D shape of our bodies quantitatively based on 3D measurement due to the lack of a body shape model. The series of studies utilizing our model presents a strong option for analyzing body shape.

Page 109 of 1108

Acknowledgements We truly express our appreciation to the Wacoal Human Science Research Center Co., Ltd., and the subjects who participated in the measurement for providing the three-dimensional measurement data.

References [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11]

K. Nakamura, and T. Kurokawa, Int. J. Comput. Appl. T., 34, 4, 278 (2009). D.-E. Choi, K. Nakamura, and T. Kurokawa, J. Textile Eng., 52, 243 (2006). D.-E. Choi, K. Nakamura, and T. Kurokawa, Textile Sci &Eng., 48, 1, 71 (2011). Z. B. Azouz, M. Rioux, C. Shu, and R. Lepage, Visual Comput, 22, 302 (2006). H.-W. Seo, F. Cordier, and K.-G. Hong, Comput. Animat. Virt. W., 18, 141 (2007). H.-Y. Lee, and K.-G. Hong, J. Korean Soc of Cloth.& Textiles, 34, 3, 385 (2010). K. Watanabe, Proc. XXI. W. Cong. IFHE, 22, (2008). T. Kurokawa, Proc. Int. Symp. Comput.W. '90, Kobe, Japan, 210, (1990). T. Kurokawa, Keisoku to Seigyo, 35, 77 (1997). T. Kurokawa, Proc. 3rd Int. Symp. Mater. Kansei Text. Fashion, 33, (2006). K. Nakamura, Ph.D. Thesis, Kyoto Institute of Technology, Kyoto, Japan, 2012.

Page 110 of 1108

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

Research on suitability of women’s jacket for various body types KyoungOk Kim1, Miyuki Hara2, 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. To clarify the appearance stability of women’s jackets against different body shapes, we investigated the changes in appearance of a woman’s jacket for different dress forms. Changes in the appearance of a jacket worn on various bodies were examined using sensory evaluation tests. The same jacket was put on different types of dress forms and photographs were taken of the front, side and back. Paired comparison evaluation of 7 scores was carried out using these photographs. The experiment was conducted using six jackets of similar size. Five dress forms of different shapes were also used. Evaluation was carried out using the four criteria of fitability, wrinkles, silhouette and constriction in the waist for 28 points. The subjects were 10 female university students in their 20s. The jackets were divided into two types for which the appearance was either hardly or easily affected by body types. It was also found that the bust and waist size, and length from side neck point to bust point of a jacket influence its appearance as do the properties of the fabric.

Keywords: appearance, jacket, body shape, ready to wear.

1. Introduction In manufacturing ready-to-wear clothes, the suitability of a garment on various bodies is an important problem. In the clothing sizing system, the size is defined by bust, waist and hip circumferences. However, even if the wearer’s measurements match those of the size, the body shape and other measurements vary resulting in an unsuitable and unsatisfactory appearance. To make more suitable and better looking clothing, one approach is to increase clothing sizes according to body type. Many researchers have studied garment patterns taking into account body types [1-5]. Makabe and Beppu [4] investigated the Japanese body shape and divided the body type into 4 types statistically based on their 3D body measurement data. They also proposed a method of obtaining a basic pattern for an individual. These methods are effective in making custom-made clothing. However, in ready-to-wear clothes, sizes are limited and each manufacturer uses different basic patterns or slopers. Consequently, it is difficult to know the suitability of ready-to-wear clothing for an individual until it is tried on, even if the body size matches the garment size. It is also difficult to know the assumed body type for the produced garments. In contrast, it is necessary for the manufacturer to make a garment that suits various body types. If the wearer’s size and body type are close to the assumed body, the suitability should be high. However, it is difficult to predict the suitability for other wearers. A garment could be changed according to body shape especially depending on its design and dimensions. The garment with the fewest changes is considered stable. In this study, suitability was evaluated for garment appearance. We investigated the suitability of a commercial woman’s jacket for different body types and what made a garment stable.

2. Experimental Methodology To clarify the appearance stability of women’s jackets for various body types, changes in the appearance of the same jacket worn on different types of dress forms were examined using sensory evaluation tests. Photographs of the jackets were taken from the front, side and back. Paired comparison evaluation (Scheffe’s method [6], and variance of Nakaya) of seven scores was carried out using these photographs.

Page 111 of 1108

As a preliminary experiment, we collected evaluation criteria on a jacket worn by five Japanese female university students. They were considered potential purchasers. As a result, we set four evaluation criteria and 28 evaluation points as shown in Table 1. The experiment was conducted using six jackets indicating similar sizes. Five dress forms of different shapes of which bust, waist and hip sizes were the Japanese 9A size were also used. Tables 2 and 3 show the specifications of the jackets and dress forms with pictures. Evaluation was carried out using the items and parts. The subjects were 10 female university students in their 20s. They participated voluntarily in the sensory test as subjects. All subjects were not in fashion or textile major. Table 1: Evaluation item

Item Few wrinkles – many wrinkles Waist constricted – not constricted Curved line– linear line Good – poor fitting

Parts Side

Front Shoulder, bust, waist

Back shoulder, waist, hem line, sleeve

Bust, waist, sleeve

entire

Entire

Front, back

Shoulder, bust, waist, entire

Front(bust, waist, hem line), back(shoulder, waist), entire

Shoulder, waist, hem line, entire

Table 2: Jacket samples

Jacket Number

JK1

JK 2

JK 3

JK 4

JK5

JK6

Bust(cm)*

Italy 83.5

America 83.5

Spain 93

Japan 86

Japan 83.5

Japan 82.7

waist(cm)

75.5

76.5

82.5

74.9

78.5

76.5

Shoulder length (cm)

12.3

13.3

10.2

11.5

Hip(cm)*

91.5

Photo

Brand country

*Bust: measured horizontally through the bottom of the arm scythe except for the open part between the lapels. *Hip: circumference at 18 cm below the waist Table 3: Dress forms

Dummy Number

JB1

EB1

JBL1

EBL1

JB2

Manufacturing country Bust(cm) Waist(cm)

Japan 85.8 63.0

France 86.2 67.5

Japan 87.9 66.1

France 89.7 67.0

Japan 86.3 60.5

Hip(cm)

91.0

91.3

89.6

88.2

Length from side neck point to bust point(cm)

23.0

26.5

24.5

26.5

23.5

Photo

Page 112 of 1108

3. Results and Discussion As a result of the paired comparisons, the differences were tested for each criterion between each pair of dress forms with a 5% significant level. Percentages for the evaluation criteria on the parts which showed significant differences between the dress forms for an entire garment and in three directions are shown in Figure 1. In all of the jackets, significant differences were shown between the dress forms for some evaluation criteria. Thus, it was established that the appearances of the jackets were affected by body shapes. Jackets were divided into two groups according to the percentages. JK1, 2 and 5 showed relatively large percentages and JK 3, 4 and 6 showed relatively small percentages. Thus it was also found that the effects were different depending on the jackets. Jackets returning a small percentage meant high stability to differences in body shape. JK4 showed the smallest percentage so it was the most stable. JK4 on the dress forms is shown in Figure 2. The bust size of JK4 was large so wrinkles on the bust area were small. Moreover, it was evaluated that the waist was constricted because the jacket waist was narrow. The fabric handling was harder than the other jackets and the jacket seemed to be manufactured to retain its three dimensional shape. Even on the flat table, the three dimensional shapes were clearly maintained. JK3 also had a large bust size but it was unable to retain its three dimensional shape and showed many wrinkles. In particular, the differences were obvious on the shoulder. Thus, it was thought that for these reasons a stable jacket was created. In contrast, JK5 showed the greatest percentages which meant the least stability. JK5 on the dress forms is shown in Figure 3. The evaluation of JK5 worn on JBL1, which had a large bust size and short length from the side neck point (SNP) to the bust point (BP), was different when on EBL1 which had a large bust size and was long from SNP to BP. Thus, the stability on difference in length from SNP to BP was considered to be one factor in the jacketâ&#x20AC;&#x2122;s appearance stability. In addition, the fabric handling of JK5 was relatively soft, and the shape of the jacket easily changed to the shape of the body. Consequently, the jackets were divided into whether the appearance was hardly or easily affected by the body shapes. It was found that bust and waist size, and the length from SNP to BP of the jacket have an effect on its stability. In addition, the fabric properties also have an effect on stability. Percentage of evaluation items for significant difference between the bodies(%)

Enire

Front

Side

Back

50 45

40 35 30 25 20 15 10 5 0 JK1

JK2

JK3

JK4

JK5

JK6

Jaket name

Fig. 1: Percentage of evaluation criteria for significant differences between dress forms (%).

(a) JB1

(b) EB1

(e) JB2

Page 113 of 1108

(a) JB1

(b) EB1

(e) JB2

4. Conclusions To clarify the appearance stability of women’s jackets for different body shapes, the changes in appearance of a woman’s tailored jacket on different dress forms were investigated. It was found that there were two groups of jackets for which the appearance was hardly or easily affected by the body shapes. A highly stable jacket showed waist constriction caused by bust and waist size, with less wrinkles and a good three dimensional shape. Conversely, a less stable jacket was affected by the length from SNP to BP of the jacket. Design and construction retaining the three dimensional shape are an important factor for maintaining stability. In addition, the fabric properties also have a large effect on the stability. Investigating these effects related to jacket stability will be the focus of our future study.

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

5. References [1] Haruko MAKABE, Human factor for clothing, Japan Publication service, 2 edition, 2011 [2] Michiko MIYOSHI, The Dress Making, Bunka Women’s University, Tokyo, Japan, 2002. [3] Miyuki BEPPU and Haruko MAKABE, The construction of the basic system for the clothing pattern design. (Part. 2) The indispensable measurement items of the lower body, The Japanese Journal of Ergonomics, 34(1), pp.17-27, 1998. [4] Haruko MAKABE and Miyuki BEPPU, The construction of the basic system for the clothing pattern design.(Part.3)Relation between the difference of body figure and clothing pattern-The upper body-, The Japanese Journal of Ergonomics, 35(1), pp.17-24, 1999. [5] Miyuki BEPPU and Haruko AKABE, The construction of the basic system for the clothing pattern design. (Part 4) Relation between the difference of body figure and clothing pattern-The lower body (Basic skirt pattern)-, The Japanese Journal of Ergonomics, 35(4), pp.241-251, 1999. [6] Scheffe, H., “An analysis of variance for paired comparisons”, Jour. Am. Stat. Ass., 47, pp.381-400, 1952.

Page 114 of 1108

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

Scenario in BRICS Region and Textile Potential Arvind Sinha National President Textile Association (India)

1. Information on BRICS Countries In the past few decades, some large economies such as Brazil, Russia, India, China and South Africa (BRICS) have acquired a vital role in the world economy as producers of goods and services, receivers of capital, and as potential consumer markets. The BRICS economies have been identified as some of the fastest growing countries and the engines of the global recovery process, which underscores the changed role of these economies. Even in the G-20 countries forum, BRICS are playing a formidable role in shaping macroeconomic policy after the recent financial crisis. At present, these five countries encompass over 40 percent of total global GDP in terms of PPP. If one compares the GDP in PPP terms, four economies figure among the top ten, with China, India, Russia, Brazil, and South Africa in 2nd, 4th, 6th and 26th places, respectively.

1.1 Economic Growth It is widely perceived that over the next few decades the growth generated by the largest developing countries, particularly the BRICS, could become a much more significant force in the world economy. Among the BRICS, India and Brazil are relatively more domestic demand-driven economies. As a group, they witnessed faster economic recovery from the 2008 financial crisis than advanced and other emerging market economies. Although they have strong external linkages, they have nonetheless undergone significant rebalancing of their economies towards their domestic sectors in the post-crisis period. The four original BRIC countries are expected to represent 47 per cent of global GDP by 2050, which would dramatically change the list of the worldâ&#x20AC;&#x2122;s 10 largest economies. The inherent strength of the BRICS emanates from strong domestic demand-based economies in the case of India and Brazil and the significant outward linkages of China and Russia. South Africa benefits from its large resource base proximity to untapped growth potential of the African continent.

1.2 The BRICS Report The salient features of the BRICS economies are their large geographical dimensions and size of population. It is widely perceived that all the BRICS markets have great potential for establishing the most stabilizing of forces, that is, a prosperous middle class.

2. Textile Industry in BRICS Countries We can comfortably say that BRICS Countries is providing textiles of all types to 7 billion people of the world. Everybody wherever they are, using some textiles products manufactured by BRICS Countries. China and India are very big. They contribute almost 50% of Global Textile Figures. Following figures are indicated:

China India Global

274 billion 40 billion 773 billion

Page 115 of 1108

Hence talking about India and China will take days and I am sure everybody present here knows about textile volumes and scales in India and China hence, I will discuss textile business in Brazil, Russia and South Africa.

2.1 BRAZIL Textile Figures • • • • •

In terms of international Commerce, the participation is very slow. In world exports, Brasil ranks 26st and imports 34th (for textiles). Last three years, the excessive valorization of the national coin caused new outbreak of growth of the imports and stagnation of the Brazilian exports of textile products and apparel. In the last 16 years, more than USD 10.5 billion were invested only in textile machines. The textile production worldwide grew 97% for the last ten years, international trade in textile and clothing grew by 175%, if we consider only the clothing, and the growth was even greater, 220% over the same period. (United States of America Commerce Department Figures). Brazil ranking among the eight largest world producers of yarns, fabric and knitwear, and ranks seven in the production of apparel, behind only China, India, USA, Mexico, Turkey and South Korea.

2.2 South Africa’s textile industry Since 1994, over US$1-billion has been spent on upgrading and modernizing South Africa’s textile, clothing and footwear industry, making it efficient and ready to compete internationally. South African market demand increasingly reflects the sophistication of developed markets, and the local textile and clothing industry has grown accordingly to offer the full range of services, from natural and synthetic fibre production to non-wovens, spinning, weaving, tufting, knitting, dyeing and finishing. With technological developments, local textile production has evolved into a capital-intensive industry producing synthetic fibres in increasing proportions.

2.3 Achievements Although the industry is still relatively small, it boasts some impressive results in world markets. Local yarn manufacturer Sans Fibres supplies 80% of the sewing thread used in the world’s apparel sewing operations. Local fabric mill Gelvenor Textiles supplies more than 50% of the world’s demand for parachute fabrics. Local suit manufacturer House of Monatic has delivered its one millionth suit to the UK market.

2.2 Market access Several factors make the prospect of investing in SA’s textiles, clothing and footwear market attractive. Most significant, perhaps, is the fact that South Africa has trade agreements with the European Union and the Unites States whereby the country enjoys a 17.5% duty advantage. In the case of the US, textile exports have increased by 62% since the advent of the Africa Growth and Opportunity Act. Friends, as leading economies are getting into recession other economies, which were not noticeable till few years ago are expanding and attained a very significant status. Thus, there is a need in today’s time to explore possibilities apart from America and Europe, which are facing their own problems.

Page 116 of 1108

2.3 Russian Textile Industry Теxtiles and clothing have been very old and tradition industry in Russia. Textile Industry in Russia has been developing successfully for many years and Russia have been a large importer of basic textiles from all over the world. India has been a very huge supplier to Russian market during communist time billions of meters of textiles for generally used for public supply from India. Even today, India continues to be major supplier to Russian market. Textile industry is an important sector of the Russian economy. Main textile regions are situated in the Central, Northwestern and Southern Federal Districts. The enterprises of the branch are producing a wide range of textile products. Those are fabrics, home textiles, knitted products, medical and geotextiles, workwear and protective wear, nonwovens and other goods.

2.4 Asian vs. Domestic While fashion industry experts expect Russian manufacturers to compete with imports from Southeast Asian counties, Russian brands could consider these countries as manufacturing partners. Although the Russian government supports expanding domestic manufacturing capacity and improving production efficiency, conditions are still difficult for domestic players. There are 653 large and medium enterprises and about 4,000 small companies in Russia engaged in the garments and textile industry, according to government statistics. The industry has been on a slow but steady path of revival since the crisis of 2009. According to (Russian Union of Entrepreneurs of Textile and Light Industry), domestic manufacturers benefit from Russia's Light Industry Development Strategy, which provides state support for textile and garments manufacturers, including modernization of technological base and enhancing their competitiveness, among other measures. Last year, the Russian government restricted using imported textiles for manufacturing of military uniforms and few other products. Russian manufacturers now big advantage that government support which is to manufacturers of Defense textiles and industrial uniforms. BTK Group, one of Russia’s largest producers of men’s apparel and uniforms, has a $1.5 billion contract with the Russian Ministry of Defense for army uniform manufacturing, and has been recently included in the list of 199 enterprises approved by the anti-crisis Commission of the Government of the Russian Federation. BTK Group spokesperson believes that in the current economic environment, Russia can compete with Southeast Asian counties in terms of salaries in the garment sector. “The wages there have been increasing by 20 percent yearly since 2006. At the same time, the high level of local manufacturers’ dependence on imported raw materials and machinery remains a major challenge. Local manufacturers benefited from exchange rates fluctuations that made their prices extremely competitive, the lack of variety of materials and technologies, when compared to what Southeast Asian countries can offer, remains the main problem for Russian manufacturers. The ruble’s sharp drop against the dollar last year and the following period of recession and uncertainty caused many Russian brands to revise their manufacturing strategy. “Many companies prefer not taking any risks in binding themselves by external contracts implying payment in dollars because they could not predict the final price of the products since the manufacturing cycle is at least 6 months long, sometimes more.” More Russian brands now opt for combined production. They purchase fabrics and accessories abroad and sew in Russia where the cost of sewing is cheaper. Since consumers value not only cheap prices, but also overall impression and quality of the apparel, factors like modern materials and new processing technologies become important.

Page 117 of 1108

2.5 Trade and currency To promote trade in local currencies, the BRICS countries signed the Master Agreement on Extending Credit Facility in Local Currency and the Multilateral Letter of Credit Confirmation Facility Agreement to replace the United States dollar as the main unit of trade between them. The trade ministers also said that tightening intraBRICS trade would help as an antidote to the European sovereign debt crisis. The trade ministers also called for collective action to fight the European and United States economic downturns. The world has to stop accumulating risks. There is a need to work closer.

2.6 Formation of BRICS Bank A new USD 100 billion bank floated by BRICS nations, including India, as an alternative to the World Bank and IMF to boost infrastructure funding in the emerging economies and offer them tailor-made services was launched here on Tuesday. This is now known as New Development Bank recently opened in Shanghai and Mr. K.V. Kamath a very well known and successful Banker from India is the 1st President. BRICS New Development Bank (NDB) has opened for operations in Shanghai, and will seek to deploy its $50 billion initial capital to fund infrastructure and sustainable development projects. Combining their strength BRICS will perform very well and strength of all the member countries combine together will bring lot of positive results in todayâ&#x20AC;&#x2122;s time.

Arvind Sinha : Tel. +91-9820062612

Email : lionasinha@gmail.com

The Textile Association (India)

Page 118 of 1108

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

Seam Pucker Evaluation of Fused Fabric Composites Based on Subjective Method Anahita Shokoohi1, Ezzatollah Haghighat1, Saeed Shaikhzadeh Najar1 +, Seyed Mohammad Etrati1 1

Textile Engineering Department, Amirkabir University of Technology, Tehran 15875-4413, Iran + saeed@aut.ac.ir

Abstract. Seam pucker is an undesirable wrinkle surface along the stitch line, which happens after sewing and adversely affects the appearance and performance of final products. The aim of this research is to assess seam pucker using subjective method and to investigate the influence of interlining type and sewing parameters on the seam pucker of fused fabric composites. Objective evaluation of seam pucker was accomplished in the previous study. The interlining weight, needle size, sewing machine speed, and stitch length were chosen as variable parameters. The other parameters were kept constant. The statistical analysis results show that seam pucker of fused fabrics is significantly influenced by mentioned parameters. Moreover, it clarifies the interaction effects of the parameters on the seam pucker are significant. The weight of interlining has the greatest influence on seam pucker followed by needle size, stitch length and sewing speed. It is found that the values of seam pucker decrease with interlining weight, stitch length and increase by needle size. Changes of seam pucker with stitch length obtained by subjective method were different from objective measuring (percent of differences in thickness). According to the different definition of the two methods, subjective method was chosen as more accurate way for assessing seam pucker of fused fabric composites, since both length and altitude of the waves forming pucker is being considered in this method.

Keywords: seam pucker, interlining, needle size, sewing machine speed, stitch length, fused fabric Composites.

1. Introduction Seam pucker is the distortion in the surface of sewn material which appears as a swollen effect along the stitch line [1]. Among the various defects in sewing process, seam pucker inspection is considered as one of the most important facets affecting quality of the garment [2]. Seam pucker occurs due to several conditions including yarn displacement (structural jamming of fabric yarns), tension puckering (excessive thread tension and recovery), machine puckering (uneven ply feeding), and shrinkage (where seam components have differential shrinkage) [3]. In order to evaluate the seam pucker, American Association of Textiles Chemists and Colorists (AATCC) have produced a set of photographic standards and various objective methods have been developed as well [4]. Several researches have been accomplished investigating influence of sewing machine parameters, mechanical properties of sewing threads, physical and mechanical properties of fabric [58] and developing methods for measuring, modelling or minimizing seam pucker [9-13]. In this study, seam pucker of fused fabrics is investigated using subjective method. The effects of sewing parameters and interlining weight on seam pucker are studied as well.

2. Materials and Methods In this research, a woven cotton/polyester fabric, usually used in shirts, and three different interlinings were used for evaluation of seam pucker composites. Each interlining was fused to the fabric at its determined optimum condition (including temperature, pressure, and time), which were obtained by accomplishing tests. The characteristics of the fabric and interlinings are given in Table 1. A stitch line were formed at the middle of the fused samples using different sewing conditions including three needle sizes, 10, 12, and 14 (American sizing system), three sewing machine speeds, 1000, 2000, and 3000 (rpm), and three stitch lengths, 2, 3 and, 4 (mm). Thus, 81 different conditions were obtained each of which necessitates three test samples. Therefore, 243 test samples were prepared for the purpose of this research. Seam pucker of fused fabric composite samples were evaluated using subjective method. Subjective

Page 119 of 1108

evaluation was carried out in accordance with ISIRI 9527 in which three samples are hung under standard lighting, graded by three judges in comparison with a set of photographic standards produced by AATCC. The average grade obtained from evaluating three samples and three judges was calculated as seam pucker grade. Grade 5 depicts the best pucker appearance (no pucker) and grade 1 represents the worst pucker look. The results were statistically analyzed for the purpose of discovering relationships between seam pucker, and above-mentioned factors. Individual effects of parameters and their interactions were analyzed using Multiple ANOVA test. One way ANOVA and multiple comparisons tests (Tukey test) were also applied with the aim of finding the influence of each parameter on seam pucker. Table 1: The characteristics of the fabrics and interlinings Sample

Fabric

Interlining A

Interlining B

Interlining C

Composition

Cotton/ PE

100% PE

100% Cotton

Construction

Woven (plain)

Nonwoven

Woven

Weight (g/m )

147.2

175.6

Thickness (mm)

0.27

0.24

0.27

0.31

Density (cm-1)

Warp

57.6

Weft

41.4

* PE: Polyester

3. Results and Discussions The statistical analysis of results is given in Table 2. With confidence level of 95%, the alpha would be 0.05 and comparison between P-Values (Values of Sig in Table 2) and alpha shows that the interlining weight, needle size, sewing speed, and stitch length have meaningful influence on the seam pucker. Mean Square is obtained by proportion of Sum of Squares to df (Degree of Freedom). F is calculated by ratio of Mean Squares between groups to Mean Square within groups (Error in the table). The more the value of F, the more distinct the averages of groups are. In other words, the parameter which has the most value of F is the most influential factor. Therefore, seam pucker is mostly influenced by interlining weight followed by needle size, stitch length and sewing speed and most of the interaction effects on seam pucker are significant as well. Table 2: The effects of interlining weight, needle size, stitch length, sewing speed and their interactions on seam pucker Source

Type III Sum of

Mean Square

Sig.

21.934

.000

Squares Corrected Model

182.936a

2.287

Intercept

2644.730

Interlining Weight

97.057

48.529

465.491

.000

Needle

30.731

15.365

147.386

.000

Speed

1.548

.774

7.425

.001

Stitch Length

27.359

13.679

131.215

.000

Interlining Weight * Needle

.721

.180

1.728

.146

Interlining Weight * Speed

1.121

.280

2.689

.033

Interlining Weight * Stitch Length

1.763

.441

4.228

.003

Needle * Speed

1.349

.337

3.235

.014

Needle * Stitch Length

.863

.216

2.070

.087

Speed * Stitch Length

3.297

.824

7.906

.000

Interlining Weight * Needle * Speed

1.891

.236

2.268

.025

Interlining Weight * Needle * Stitch Length

3.035

.379

3.639

.001

Interlining Weight * Speed * Stitch Length

2.791

.349

3.346

.001

Needle * Speed * Stitch Length

4.604

.576

5.521

.000

Interlining Weight * Needle * Speed * Stitch Length

4.806

.300

2.881

.000

25368.531 .000

Page 120 of 1108

Error

16.889

162

Total

2844.556

243

Corrected Total

199.825

242

.104

3.1. Interlining Weight Statistical analyses show that seam pucker decreases with increase of interlining weight. Light weight interlinings show less resistance whilst needle penetrates the structure. This yields a growth in yarn displacement leading to a more structural jamming. As it is shown in Figure 1, seam pucker grade which has an adverse relation with seam pucker, increase with interlining weight.

Figure 1: Seam pucker grade of fused fabric composites against interlining weight for different needle sizes (in three sewing machine speeds used)

3.2. Needle size Seam pucker reduces as needle size increases. Figure 2 shows the changes of seam pucker grade against needle size. Penetration of needle result in structural jamming of fabric yarns. More jamming occurs with larger needle sizes, leading to a greater extent of seam pucker. Hence, choosing the finest needle size (considering the fabric thickness) provides a better appearance along the stitch line.

Page 121 of 1108

Figure 2: Seam pucker grade of fused fabric composites against needle size for different interlining weights (in three sewing machine speeds used)

3.3. Stitch length The results show that seam pucker decreases with increase of stitch length. When stitch length rises, the number of joining points between layers and sewing yarn reduces, and as a result the number of waves which are formed along the stitch line diminishes as well. However, in the previous study, while seam pucker was calculated by percent of thickness, different result was achieved. Percent of thickness is referred to the difference between thicknesses before and after sewing under a constant compressive load reporting in percent. Comparing the two different results, the subjective method is seen to be more accurate, since individuals consider both wavelength and amplitude as they evaluate the samples. But percent of thickness is merely affected by amplitude which weakens its precision.

3.4. Sewing machine speed A certain pattern for seam pucker with changes of sewing speed is not found. As mentioned in the previous study, the investigation of the single effect of sewing machine speed on seam pucker was difficult, since it was observed that stitch length lessens at higher speeds. When sewing machine speed grows, material sewn cannot be fed enough due to fast needle penetrations and this causes a reduction in stitch length.

3.5. Results of multiple comparison tests In this section, the result for one parameter is mentioned, for instance. Changes of interlining weight have a significant effect on seam pucker grade, since the weights are classified in more than one group in all the cases except one. Interlinings A (74 g/m2) and C (175.6 g/m2) are in one group in most cases, which means under several conditions, using either of them lead to same results regarding appearance of seam pucker.

4. Conclusion In this research, seam pucker of a woven fabric fused with interlinings is assessed using subjective method. The impacts of interlining weight, needle size, sewing machine speed, and stitch length on the seam pucker grade (which has an inverse relationship with the extent of seam pucker) are studied. The statistical analysis of results clarifies that seam pucker is affected most by interlining weight, followed by needle size, stitch length and sewing speed. Seam pucker reduces with increase of interlining weight and stitch length, while it rises with needle size. It is observed that changes of seam pucker with stitch length obtained using this method is dissimilar to objective method involving percent of thickness.

5. Reference [1] Rajkishore Nayak, Rajiv Padhye, Debi Prased Gon. Sewing performance of stretch deni. Journal of Textile and Apparel, Technology and Management. 2010. 6. [2] Shigeru Inui, Atsuo Shibuya. Objective evaluation of seam pucker. International Journal of Clothing Science and Technology. 1992. 4(5): 24-33. [3] Minimizing seam puckering. Technical Bulltein. http://www.amefird.com. [4] K.L Mak, Wel Li. Objective evaluation of seam pucker on textiles by using self organizing map. IAENG International Journal of Computer Science. 2008. 35: 1. [5] Milda Juciene, Vaida Dobilaite. Seam pucker indicators and their dependence upon the parameters of a sewing machine. International Journal of Clothing Science and Technology. 2008. 20(4): 231-239. [6] Vaida Dobilaite, Milda Juciene. The influence of mechanical properties of sewing threads on seam pucker. International Journal of Clothing Science and Technology. 2006. 18(5): 335-345.

Page 122 of 1108

[7] B. K Behera, S Chand. Sewability of denim. International Journal of Clothing Science and Technology. 1997. 9(2): 128-140. [8] S. Inui, T. Yamanka. Seam pucker simulation. International Journal of Clothing Science and Technology. 1998. 10(2): 128-142. [9] Jin Lian Hu, Liang Ma. Modelling multi-layer seam puckering. Textile Research Journal. 2006. 76(9): 665-673. [10] Chang Kyu Park, Tae Jin Kang. Objective evaluation of seam pucker using artificial intelligence part II: method of evaluating seam pucker. Textile Research Journal. 1999. 69(11): 835-845. [11] Chang Kyu Park, Joo Young Ha. A process for optimizing sewing conditions to minimize seam pucker using the Taguchi method. Textile Research Journal. 2005. 75(3): 245-252. [12] Le Nguyen Thi, Trung Ngo Chi, Cao Trinh Van. Seam pucker prediction based on fabric structure and mechanical properties using fuzzy system. 7th International Conference TEXSCI. 2010. [13] Binjie Xin, George Baciu, Jinlian Hu. Image-based evaluation of seam puckering appearance. Journal of Electronic Imaging. 2008. 17(4).

Page 122i of 1108

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

Study on the Model of Feature Points of the Bust Curve Gao Peipei, Xing Xiaoyu, Shang Xiaomei Soochow University

Abstract. To study the trajectory of feature points of bust curve, this paper chose 230 adult men aged from 18 to 22 as research subjects, collecting the data of height, bust, waist and hip, and made correlation analysis. The main body index could be gained by comparing significant difference value, and then the type classification was obtained by the use of cluster analysis. Select the feature points of bust curves and established the regression equation model of feature pointsâ&#x20AC;&#x2122; coordinate of experimental samples, and randomly selected experimental sample to verify the established mathematical model. Regression model established in the experiment was verified whether it applied to anyone of the tested samples through Independent-Sample Test analysis. The paper studied the model of feature points of bust curve and it helped acquire detailed size and parametric design of human bust and provided verification path for automatic measurement data in the perspective of graph.

Keywords: type classification, cluster analysis, regression equation model, model verification

1. Introduction Changes in the human body shape are divided into two directions of length and girth. The girth direction determines the section curves changes of each characteristic part [1]. The paper studied the sectional profile of bust in the girth direction and established the diversification models of feature points coordinates of the bust, which had a certain practical significance for human body type classification and acquisition of the bust detailed size[2].

2. Experimental Sample and Data 2.1. Experimental sample The paper studied 240 young men aged 18-22 year-old in school, experimental methods adopted manual measurement, and experimental tools were soft ruler, setsquare, ruler and record board. The experimental subjects wore tight pants in the average temperature of 24-26 degree celsius and the average humidity of 50% -60% indoors.

2.2. Experimental data Each experimental subject was measured three times and the average value of three measured data obtained as the experimental data. The experiment obtained 240 sets of the measured data wherein the value of height, bust, waist and hip were selected, filtered and eliminated. A total of 220 sets of experimental data were finally reserved.

Page 122ii of 1108

3. Classification of Human Body Type 3.1. Extract the human body type index Firstly, correlation analysis and significant analysis was made between height, bust, waist, hip and each body index, including the ratio of bust and height(B/H), the difference between bust and waist(B-W), the ratio of bust and waist(B/W), the difference between hip and waist(H-W), the ratio of hip and waist(H/W), the difference between hip and bust(H-B), the ratio of hip and bust(H/B)[3]. Wherein the Sig. value of B/H and H/W was closest to 0.000, and the Sig. value of the other human body index was bigger than that above. And then the two human body index of B/H and H/W and height, bust, waist and hip were chose to classify the human body shape. Table 1: Significant Test of Each Human Shape Body Index Kind

Sig.

Part

B/H

B-W

B/W

H-W

H/W

H-B

H/ B

Height

0.020

0.133

0.603

0.000

0.081

0.044

0.127

Bust

0.000

0.730

0.000

Waist

0.000

0.970

0.091

Hip

0.000

0.579

0.000

0.071

3.2. Cluster analysis of the human body type Select B/H, H/W, height, bust, waist and hip for cluster analysis based on the Sig. value of each human body index and height, bust, waist and hip. As the number of experimental observed sample was too large, K- means clustering analysis was chosen. The sample took 2 class aggregation, where the sample size of class 1 was 66 and the sample size of class 2 was 154 of the final sample cluster center as shown in table 2. Circumference value of class 1 sample was relatively larger, so class 1 sample was classified as the wide and heavy, the class 2 sample as the thin and narrow. Table 2: Final Sample Cluster Cluster

Height

Bust

Waist

Hip

B/H

H/W

172.70

92.90

82.38

99.36

0.54

1.21

171.26

82.27

70..48

88.93

0.48

1.26

4. Establish Mathematical Model of the Bust Feature Points When the bust size was divided, file difference was defined as 4cm. So the difference interval was divided into 4, 4, 4, 4+1, wherein 4+1 was the result of individual samples. When class group was selected, the individual sample data could be eliminated, which would not affect data analysis. Class 1 and class 2 sample ware respectively divided into 4 ascending groups based on the above 4, 4, 4, 4 + 1. Class 1 sample was divided into A1, A2, A3, A4 and class 2 sample was divided into B1, B2, B3, B4. Specific groups were as follows in table 3 below. Randomly select the data of a person from each group of A1-A4 and B1-B4 as a model sample m for establishing a aggression model and the sample size was eight.

Page 122iii of 1108

Table 3: Interval Division of Class 1 and Class 2 Class 1

Class 2

Group

Interval(cm)

87-91

91-95

95-99

99-104

75-79

79-83

83-87

87-92

Number

4.1. Select the bust curve feature points The paper selected the highest point of the convex back bust curve named the point a and the center point of the back bust curve named the point b as the feature points[4].

4.2. Establish regression model of feature points

Fig. 1: Regression Equation of point a

Fig. 2: Residuals Distribution of Regression Equation

Establish the coordinate system of the feature points where chest width line was along the x-axis direction, the chest thick line was along the y-axis direction, and the intersected point of the chest width line and the chest thick line was the original point. The bust curve is substantially symmetrical about the chest thick line. Select the sample m, obtain the coordinates of the point a and b, and establish each regression model. Observe the scatter gram of the coordinates (x, y) of the point a and b respectively and it could be found that y and x showed a significant linear relationship, which indicated that y and x should establish a linear regression model. In the formula y = a + bx +μ, y is the independent variable; a is an intercept of the model; b is a parameter to be estimated; x is the explanatory variable;μ is a random error. The linear regression equation and the residuals distribution of the point a was as shown in Figure 1 and Figure 2. In Table 4, model 1 was the regression model of the point a, and model 2 was the regression model of the point b.

4.3. Analysis of feature points regression model Table 4: Coefficients of the Regression Model of Point a and b Model

Unstandardized

Standardized

95% Confidence

Coefficients

Interval for B

Std.

Beta

Sig.

Error 1 （constant） x 2 （constant） x

-.144

.536

1.176

.076

-.441

.571

2.406

.162

.988 .987

Lower

Upper

Bound

-.268

.798

-1.456

1.168

15.462

.000

.990

1.362

-.771

.470

-1.838

.957

14.869

.000

2.010

2.802

Page 122iv of 1108

The estimated value of unstandardized coefficients B in model 1 was 1.176; the significance level Sig. was 0.000 which was smaller than 0.05 and indicated the regression equation was significant. Therefore, the regression equation of point a was as follow: y = 1.176*x-0.144. Similarly, the regression equation of the point b was observed from model 2 : y = 2.406*x-0.441, and the value of standardized regression coefficient was 0.987. The variance analysis and significance test of the regression equation in model 1 and model 2 indicated that the equation was significant and valid.

5. Model Verification 5.1. Data acquisition of model verification sample Select one in each interval of A1-A4 and B1-B4 randomly as the verification sample n, different from m, and the sample size was 8. The observed value of the experimental sample n was coordinate groups (x, y), and y’ was the estimated value of y when y was substituted into the regression model.

5.2. Analysis of verification results The experimental data of the point a and b was at the 95% confidence interval difference for independent sample test. From the independent test results of point a, it can be seen: t=0.062; df=14; the average value difference of the two sets of data, y and y’, was 0.1625; the standard error was 0.26133. The two-tailed significance level of difference, Sig.=0.951>0.05, indicated that y and y’ of the point a had no significant difference. Similarly, the two-tailed significance level of difference, Sig.=0.810> 0.05, explained that y and y’ of the point b had no significant difference. The regression model established by the sample m also applied to the validation sample n randomly selected in the experimental subjects by analysis of independent sample test results.

6. Conclusion The paper made classified the human body shape of the experimental subjects and then studied the regression model of the highest point a of the convex back bust curve and the center point b of the back bust curve of the experimental sample m and the verification sample n. The sample m and n were gained by interval division of the bust data and made independent sample test analysis of the sample m and n. The paper studied the model of feature points of bust curve and it provided some reference path for verification of the automatic scanning data and detailed size and parametric design of human bust[5,6].

7. References [1] Wang Weiping, Li Juan, Zhang Wenbin. Applications of garment size designation for men [J]International Textile Leader, 2006,11:74-76. [2] Dai Hung, Yang Lin. A research on the somatotype application in the apparel size standard [J] Knitting Industry, 2006,11: 19-21 + 71. [3] Zou Ping, Wu Shigang, Lu Xin, Che Lu. Establishment of fit jacket basic type for young women with big breasts [J] Journal of Textile Research, 2014,09: 120-126. [4] Gu Lin, Zhang Xin. Three-dimensional parameter mannequin oriented measurements of the characteristic data on female chest[J]Journal of Xi’an University of Engineering Science and Technology, 2007,05:580-584. [5] Yuwei Meng, P.Y. Mok,Xiaogang Jin. Interactive virtual try-on clothing design systems Original Research Article [J] Computer-Aided Design, 2010,42(4):310-321. [6] Zou Ping. Influence relationship between clothing structure designing math model positions in stepwise regression [J] Journal of Textile Research, 2007,02: 95-99.

Page 123 of 1108

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

Sustainability Challenges in Fashion Business Philip KW Yeung and Kit KY Li 1

Clothing Industry Training Authority, Hong Kong

Abstract. Sustainability is the most current and major global issue faced by everyone who is dealing with fashion business. The proper way to tackle such an important issue is by means of the 'bottom-triple line' approach that include environment, social and economic aspects. Pressure groups and consumers have increasing call for brands to provide environmental friendly, socially acceptable and yet affordable products. This paper describes contemporary qualitative and quantitative measures adopted by various global stake holders including brands, manufacturers, non-government and related organisations, in meeting the ever changing demand of consumers. The newly developed carbon footprint and water footprint measuring models are presented to demonstrate the active participation and readiness of the local fashion industry in working towards sustainability.

Keywords: sustainability, fashion supply chain, carbon and water footprint.

1. Meaning of Sustainability and Sustainable Development There are many ways to address the term ‘sustainability’ and ecologists have led the discussion to the ‘limits of growth’ [1]. The term was also used to describe an economy ‘in equilibrium with basic ecological support systems’ [2]. In a more systematic approach, the term was employed to describe the ability of an ecosystem to maintain ecological processes, functions, biodiversity and productivity into the future [3]. Developed through decades of transformation, ‘sustainability’ has become a multifaceted term that transcends disciplinary boundaries across our institutions. As the concept of ‘sustainable development’ is highly complex, it plays a very special role and has always been a heavily value-laden term. One of the most frequently cited definition is by the Brundtland Report of the World Commission on Environment and Development [4] as the kind of ‘development that meets the needs of the present without compromising the needs of future generations’. Another definition by The Johannesburg Declaration on Sustainable Development is the ‘interdependence and mutually reinforcing pillars of sustainable development encompasses economic development, social development and environmental protection –– at local, national, regional and global levels’ [5]. More broadly, sustainable development policies encompass three general policy areas: economic, environmental, and social (Figure 1). Only at a point where all three areas merge is real sustainable action being taken [6].

Fig. 1: Scheme of Sustainable Development: three interdependent and mutually reinforcing pillars of sustainable development [6]

Page 124 of 1108

Although sustainable development remains an irreducibly holistic concept that requires integration along its supply chain, the fashion industry can still be depicted as â&#x20AC;&#x2DC;satisfying the present needs for fashion but without compromising the ability of future generations to meet their own fashion needsâ&#x20AC;&#x2122;. During the last few decades, stakeholders in the global fashion supply chain had strived to prove themselves being authentically sustainable-minded, but only few significant achievements have been accomplished.

2. Contemporary Issues on Sustainability of Fashion Supply Chain 2.1.

Environmental aspects

The major development in the aspect of environmental issues started with the publication of Dirty Laundry by Greenpeace in 2011 [7]. This was followed by a number of publications targeted on the effect of chemicals on environmental and safety aspects during the manufacturing of fashion products. As a result, a group of major apparel and footwear brands and retailers made a shared commitment to help lead the industry towards zero discharge of hazardous chemicals (ZDHC) by 2020. ZDHC Group was then formed aiming to work on the industry guideline, standard and even audit protocol for chemical issues [8]. At the same time, The Institute of Public and Environmental affair (IPE) operates a blacklist platform for monitoring Chinese manufacturers who violate environmental regulations. IPE, a pollution-focused organization, is mostly working with the Chinese government to increase the transparency of wastewater quality or other pollutants discharge by the local manufacturers/factories. It also works with Greenpeace to provide a platform for supporting Detox champion [9].

2.2.

Social aspects

In the last few years, we have noted some prominent cases that have raised concern for the social environment for workers of garment production; cases such as the tragedies in Bangladesh with regard to factory fire and building collapse causing many fatalities; hundreds of workers fainted each year in Cambodia and many young workers died suddenly at night during sleep in Southern China. In order to improve on the situation, different initiatives have been taken by the authorities. One example is the establishment of the Alliance for Bangladesh Worker Safety and the Accord on Fire and Building Safety and these associations have issued their first annual reports, provided an update on the work carried out on improving safety and working conditions in the country to date [11]. Actually, all Bangladesh factories have now been audited and conversations have started with brands on how to spread out the scope covering other Asian countries. Another example is the Business Social Compliance Initiatives [12]. BSCI is a leading business-driven initiative supporting retailers, importers and brands to improve working conditions in supplying factories and farms worldwide. Its vision is a world of free trade and sustainable global supply chains, and it works to tackle these challenges by offering one common Code of Conduct and one single Implementation System that enables all companies sourcing all types of products from all geographies to collectively address the complex labour issues of their supply chain. To ease the implementation of the BSCI Code of Conduct, it develops a broad range of tools and activities to audit, train, share information and influence key actors towards improving labour conditions in the supply chain of participating companies.

3. Initiatives taken by fashion business players As the public awareness in both the environmental and social aspects has grown rapidly, fashion brands are faced with the increasing demand from their consumers to improve. Many brands have taken their own sustainability strategies for managing its supply chain but the most promising initiative is the recent establishment of the Sustainable Apparel Coalition (SAC) in the United States [13]. One of its key outcomes by 2020 of SAC is for all fashion product lifecycles to have achieved transparency with companies and people at every step of design, production and distribution take full accountability for environmental and social impacts. The Coalitionâ&#x20AC;&#x2122;s main focus is on building the Higg Index, a standardized supply chain measurement tool for all industry participants to understand the environmental and social and labour impacts of making and selling their products and services.

Page 125 of 1108

With regard to the production stage within the fashion supply chain, it depends very much on the size of the business among the manufacturers. Small and Medium Enterprises in general lack the expertise and knowledge to fully implement measures to satisfy the various sustainability requirements. Mind-set is another hindrance as these companies still focus on financial aspects in preference to environmental and social issues. However, with increasing pressure from brands and the market, there is no option for them but to adopt and put effort into self-monitoring of their environmental and social performances.

4. Initiatives taken by Clothing Industry Training Authority Hong Kong Clothing Industry Training Authority was established with the main objective to enhance the overall competitiveness of the local industry. As such, it has taken a number of initiatives to promote and encourage the active participation of companies to face the future challenge of this important issue. One of the many initiatives is the development of carbon footprint and water footprint measuring models. The main objective to develop an activity-based carbon footprint model is to understand the carbon emission status-quo of the manufacturing processes of fashion apparel products, so that carbon reduction opportunities can be identified for the development of low carbon competitive advantages. In this model, manufacturing processes are dissected into activity-based carbon footprint constituting modules, followed by model, gather, analyse and disclose the activity-based carbon footprints of the apparel products. The gathered carbon footprints of products will be effectively consolidated in form of an industrial specific database. A customized computer program is adopted to analyse and report the carbon footprints so that significant carbon reduction opportunities can be identified for the development of low carbon competitive advantages. Using a similar approach, the activity-based water-footprint model is currently under development which aims to assess and to analyse water-footprint of each manufacturing process of the textile industry. This model can formulate specific and measurable targets with respect to water-footprint reduction, with special attention to areas where problems of water usage and pollution are most critical. Based on the findings, actual improvements will be demonstrated and can lead to an enhanced competitive advantage. In this model, the manufacturing processes of textile dyeing, printing and finishing are dissected into activity-based waterfootprint constituting modules, then measure, gather, analyse and disclose the activity-based water-footprints of the final products. In endeavour to collect accurate data, this project will set up a water-footprint data collection and monitoring system throughout the pilot factories. The innovative and practical approach of both models, together with the comprehensive database and customized computer program will allow maximal flexibility and cost effectiveness in carbon and water footprint disclosure that fits the characteristics and demand of the current trend of fashion business.

5. References [1] D. Meadows, D.L. Meadows, J. Randers, and W. Behrens, The Limits to Growth, New York: Universe Books, (1971). [2] R. Stivers, The Sustainable Society: Ethics and Economic Growth, Westminster Press, Philadelphia (1976). [3] REO Information Center, Definitions Râ&#x20AC;&#x201C;S, (2003). http://www.reo.gov/general/definitions_r-s.htm#S, [4] Report of the World Commission on Environment and Development, General Assembly Resolution 42/187, United Nations, 11 December 1987. [5] Johannesburg Declaration on Sustainable Development, Division for Sustainable Development, Department of Economic and Social Affairs, United Nations, (2002) http://www.un.org/esa/sustdev/documents/WSSD_POI_PD/English/POI_PD.htm. [6] D. Hershgal, M. Denner, A. Harush, and R. Bitan, Intelâ&#x20AC;&#x2122;s First Designed and Built Green Building, Intel Technology Journal, 12(1), (2008). [7] Dirty Laundry, Green Peace Publications, (2011) http://www.greenpeace.org/international/en/publications/reports/Dirty-Laundry/

Page 126 of 1108

[8] http://www.roadmaptozero.com/ [9] http://www.ipe.org.cn/default.aspx [10] http://fashionrevolution.org/ [11] http://www.bangladeshworkersafety.org/ and http://bangladeshaccord.org/ [12] http://www.bsci-intl.org/ [13] http://apparelcoalition.org/

Page 127 of 1108

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

The application of Nvshu pattern in the modern women’s apparel design Hui’e Liang 1 , 1

ZhongJie Wang 1

Han Nationality Costume Culture and Non-material Culture Heritage Base, School of Textiles & Clothing, Jiangnan University, wuxi, China

Abstract. With the progress of globalization and the cultural fusion between different areas and nationalities, diversification is typical of global culture and aesthetic appreciation. Regional, ethnic and highly distinctive garments have drawn unprecedented attention and are being used as a fashion for textile clothing design. Nvshu is the only surviving female writing system in the world. Its design originated from weaving patterns, with unique regional characteristics. The application of Nvshu pattern, as an ethnic element, to the design of modern women’s dress not only highlights the uniqueness of these garments, but also will serve as new reference to the introduction of cultural products to the design of textile clothing.

Keywords: Nvshu pattern, fashion , women’s apparel design

1. Introduction With the progress of globalization and the cultural fusion between different areas and nationalities, diversification is typical of global culture and aesthetic appreciation.[1] Regional, ethnic and highly distinctive garments have drawn unprecedented attention and are being used as a fashion for textile clothing design. [2] Nvshu is the only female character still in use in the world.[3] Meanwhile, Nvshu patterns originated from textile patterns[4], therefore application of Nvshu patterns to modern women’s fashion design as a national element not only increases the uniqueness of women’s clothes with women’s patterns, but also provides new reference basis for the design of cultural products in textiles and apparels.

2. The characteristics of Nvshu pattern Nvshu is the only female character still in use in the world. Prevalent in Jiangyong County, Hunan, China, it was created by local women and circulated among local women, it was usually written on fans, handkerchiefs and paper, while some were woven or embroidered on ribbons and fabrics. Nushu pattern is a kind of female characters combined with decorative patterns of decorative needlework pattern. And the modeling based on female characters, in the form of plane geometry, is decorated with patterned natural form, in accordance with the composition •

Hui’e Liang. Tel.: + 86-510-15861420606. E-mail address: 274413194@qq.com

Page 128 of 1108

rule and artistic treatment technique, presents a unique Needle Arts features.[5]As is shown in Table 1，Nushu patterns respectively from the insole fabric, scraps of paper, ribbon and Babao bed blanket. In Nushu pattern element selection with birds, insects, fish and folk propitious patterns. Pictorial form is divided into separate patterns, suit patterns, two continuous pattern and square continuous pattern. Nushu features female characters as the main element of the pattern, combined with flower and plant elements, constitutes a flat, decorative, conformal mapping features. Table 1. Nvshu pattern’s feature

Nvshu pattern

Pictorial form Source of pattern

separate pattern insole fabric

suit pattern scraps of paper

Two continuous

Square continuous

pattern

ribbon

Babao bed blanket

3. The application of Nvshu pattern in the apparel design Nvshu patterns are composed in the features of planarization, decorativeness, and framework fitting-in, thus providing reference and development space for design and application of such patterns in modern dresses. This paper, on the basis of shape, color and texture in accordance with original structure of Nvshu patterns, analyzes how to design and apply the patterns in modern dresses by means of three-dimensional and planar presentations.

3.1. The planar application of Nvshu pattern The application of Nvshu pattern plane is the main object for female characters, through combinations of design elements, arrangement, mixing, with the line as the main decoration, is a kind of graphic design through the overlap, accumulation, bending. As is shown in Table 2, in Nvshu pattern "tian(田)", for example, one character is extracted from the fabric, Join the design elements such as wheat, or leaves, constitute a "tian(田)" character of main frame by lapping, stacking and bending line, form a suitable pattern, design a Nvshu pattern "tian(田)" with diamond frame and geometrical characteristics. The Nvshu "tian(田)" has an explanation of origin of farming fields, so choose national style color of red pottery, green and other color combination in the performance of color, creates a full of retro colors collocation. Table 2. Nvshu pattern "tian(田)" design Nvshu pattern

Extract

Add design

Nvshu pattern

（design

characters

elements

（design after－

（design after －

sketch）

colored ）

before）

In terms of the design application of modern women’s clothes, the application method of pattern planarization could be divided into integrated application and local application of

Page 129 of 1108

patterns. As is shown in Table 3, the integrated application focuses on the interlaced organization, color reversing and size change of the designed patterns of nvshu. The local application of patterns focuses on showing the patterns in women’s clothes in the form of embroidery or printing. At the same time, the application of pattern planarization can combine the color lump matching and the change of wrinkle technique to further enrich the application of nvshu patterns in the planarization of the design for women’s clothes. Table 3. The planar application of Nvshu pattern (For example of integrated application)

3.2.

The ways of paterrn

Pattern design

Style design

Apparel effect

application

interlaced organization

color reversing

size change

The three-dimensional application of Nvshu patterns The three-dimensional application of Nvshu patterns mainly targets the Nvshu characters. Based on plane patterns, the base for the pattern structure is built. Through the integrated application and local application of the design have been adopted to design the point, line and surface texture shaping of elements to carry out the three-dimensional designs of patterns. As is shown in Table 4, taking the pattern of “fan(凡)” as an example, we can extract the major character from the fabric. According to the major framework of the character, we can use the space cotton as materials to serve as the base of the three-dimensional pattern so that the pattern can take up the three-dimensional space of length, width and height and is three-dimensional visually. Table 4. The structure of Nvshu pattern "fan(凡)" Nvshu pattern

Extract nvshu characters

The structure of pattern

In terms of the design application of modern women’s clothes, based on the three-dimensional

Page 130 of 1108

framework, we can adopt the integrated application and local application for the threedimensional pattern of “fan(凡)” of Nvshu. Through the combination application and filling of the point, line and surface elements among the textures so that the pattern’s three-dimensional effects could be enhanced based on the original height.

Table The three-

The ways of

The structure of

paterrn application

pattern

Style design

Apparel effect

integrated application

local application

dimensional application of Nvshu patterns

4. Conclusion As a kind of national element, Nvshu pattern deserves a better application and exploration in modern apparel design. The pattern not only boasts highly decorative beauty in form, but also embodies rich national culture in content. With nvshu pattern as the object, we make use of the division between the plane design and the three-dimensional design. By means of the

Page 131 of 1108

overall and partial application, we intend to intensify its pattern change and visual effects in women's clothing design. Such pattern design has broken through people's limited and onesided understanding for traditional costume design, blazing a new trail for the nvshu pattern design.

5. References [1] Guo Yiyi. Study on Integrated Design Methods of National Elements and Fashion Design [D]. Beijing Institute of Fashion Technology, 2015 [2] Tang Haiyang. Study on Application Methods of National Elements in Innovative Fashion Design [D]. Shanghai University of Engineering Science, 2014 [3] Lun Yumin. Thirty Years of Study on Nvshu in China [J]. Journal of Hubei Institute for Nationalities (Philosophy and Social Sciences Edition). 2012 (06) [4] Gong Zhebing. Female Characters and Female Society [M]. Xinjiang People’s Press 2008 [5] Zhou Feizhan. Forms and Artistic Characteristics of Nvshu Patterns [J]. Beauty and Age (in Chinese). 2010(07) [6] Zhao Liming. “Nvshu and Nvshu Culture” [M]. Beijing: Xinhua Press, 1995.

Page 132 of 1108

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

Virtual Draping by Mapping and Manipulation Shigeru Inui 1, Yosuke Horiba 2, Yuko Mesuda 3 and Mariko Inui 4 1

International Cluster for Cutting Edge Research Institute for Fiber Engineering, Shinshu University, 3-15-1 Tokita, Ueda, Nagano, 386-8567, Japanâ&#x20AC;¨ 2 Faculty of Textile Science and Technology, Shinshu University, 3-15-1 Tokita, Ueda, Nagano, 386-8567, Japan 3 Nagano National College of Technology, 716 Tokuma, Nagano Nagano, 381-0041, Japan 4 Kacho Collage, 3-456 Hayashishita-cho, Kyoto, Kyoto, 605-0062, Japan

Abstract. The objective of this study is to virtualize draping and we would like to make consumers to get clothes to fit their bodies more easily. In our study, the shapes of clothing patterns are obtained by applying planar cloth model to the surface of three-dimensional dummy or body surface as draping in the real world. The virtualized draping system consists of cloth model, dummy or body model and hand or finger model. We are aiming at combining a technique is to map cloth model on the surface of the dummy model to make patterns and a technique is to handle virtual cloth model to adjust patterns on the dummy model for this system. Natural shaped patterns of simple structured skirt can be obtained by the mapping method. And the cloth model can be touched and picked by the hand model. It is expected to construct the system to combine those methods.

Keywords: virtual draping, cloth model, virtual hand, simulation.

1. Introduction The objective of this study is to virtualize draping and we would like to make consumers to get clothes to fit their bodies more easily. As consumers usually buy mass-produced clothes, the clothes do not always fit their body even if they buy clothes fit to their body size. On the other hand, some clothes are ordered and made by draping for each person. A problem of order made is that it takes much time and cost. Our goal is to decrease the time and costs of draping dramatically by virtualizing the processes of draping. The studies to make clothing pattern in a computer have been conducted. In some studies, threedimensional surface shape of dummy or human body was measured. The three-dimensional surface shape was deformed to the shape of clothes. The shapes of clothing patterns were obtained from planar development of the three-dimensional surface shape. In the study of Wibowo et al. [1], they utilized an instrument to trace the surface of a dummy in the real world to make clothing patterns. Contour curves and style curves were utilized for making clothing patterns in the study of Wang et al. [2]. Huang et al. [3] utilized wireframe model for body shape which is deformed to make clothing patterns. Au et al. [4] made clothing pattern from planes and boundaries of clothing. Meng et al. [5] attached and sew clothing patterns on a body model to obtain threedimensional shape of clothing. Takatera et al [6,7] developed the surface shape of dummy or human body and obtain patterns. In our study, the shapes of clothing patterns are obtained not from the planar development of the shape of dummy, but from applying planar cloth model to the surface of three-dimensional dummy or body surface as draping in the real world.

2. System Architecture We are aiming at combining two techniques for this system. One technique is to map cloth model on the surface of the dummy model to make patterns. Other technique is to handle virtual cloth model to adjust patterns on the dummy model.

2.1.

Mapping Technique for Draping

In the virtual world, it is more efficient to map cloth model on the surface of the dummy model. All the processes of draping are done by hand in the real world. For example, cloth is applied on the front centerline

Page 133 of 1108

of a dummy by hand. In the virtual world, it is more efficient to map cloth model on the front centerline of a dummy than to apply cloth on the line and to fix by movement of virtual fingers. To make a clothing pattern, cloth model is mapped on the front centerline or warp line on the surface of dummy model. To make a skirt pattern, the lattice points in the same height in planar cloth model are mapped to a cross section of a dummy model from left to right. Mapping is done to take the distance between two neighboring lattice points on the planar cloth model on the surface of dummy model in order. In the case of skirt, darts have to be taken because the boundary length of cross section of the dummy model becomes shorter above hipline. In the mapping method, the position and the depth of darts have to be given as numerical values before mapping. As the cloth model is geometrically mapped on the surface of the dummy model, the cloth model is deformed more than necessary in this state. Then mechanical calculation is conducted, and the natural shape of the cloth model can be obtained. Three-dimensional shape of the cloth model is obtained by cutting unnecessary part of the cloth model such as overwrapping part at darts or outside part of pattern. After that, the three-dimensional shape is developed to a plane and pattern shape is obtained.

Fig. 1a: Planar Cloth Model. Fig. 1b: Mapped Cloth Model Fig. 1c: Cut Unnecessary Part. Fig. 1d: Skirt Pattern

2.2.

Cloth handling technique

A technique to handle the virtual cloth model is necessary for the virtual draping system. In the mapping technique, the position and the depth of darts are assigned as numerical values before mapping. When some adjustments are required for the darts, the processes have to be iterated. To obtain proper darts shape, some tries and errors may be necessary. It is more efficient to adjust the darts by cloth manipulation of the hand model. To this purpose, the cloth model, the hand model and the dummy model should be combined.

2.2.1. Cloth Model The cloth model is lattice-structured and it is planar in the initial state. Cloth is modeled as mass-spring model, and masses are arranged at lattice points and springs are arranged between neighboring lattice points. When position of a mass is changed, forces act on the springs connected to the mass according to the expansion or contraction of the springs. The resultant force of the springs connected to a mass act on the mass. The time evolution of the masses can be calculated to solve the motion equation with the resultant force. Leap-frog method is utilized as numerical integration method for the motion equation. Though leap-frog method is not always stable because it is an explicit method, this method is used for fast calculation because lattice points of the cloth model have to be calculated in real time.

2.2.2. Dummy Model Three-dimensional dummy or human surface model is a static model. Three-dimensional surface shape of a dummy was measured by an instrument (BOXELAN) for a dummy model. A vertical center axis of the dummy model can be determined to average the values of the coordinates of the point cloud obtained by the measurement projected on a horizontal plane. Horizontal cross sections are made in increments of a certain distance along the vertical centerline of the dummy. Each horizontal cross section consists of distances from the center axis to the cross section in increments of a certain angle.

2.2.3. Hand or Finger Model For virtual draping, it is necessary to handle virtual cloth model by the motion of hand or fingers in the real world. â&#x20AC;&#x153;LeapMotionâ&#x20AC;? is utilized as a sensor for this purpose. The motion of hand and fingers is detected by the sensor and the information of the motion is transferred to a computer. The virtual hand model consists of joints and tips of fingers, and the virtual hand model can be moved just as the same motion in the real world by giving the detected coordinates of the real joints of a hand to the virtual joints.

2.2.4. Interaction

Page 134 of 1108

Interaction has to be determined between the cloth model and the hand model, and between the cloth model and dummy model to avoid penetration. At the lattice points of the cloth model and the points of finger joint or tip, existence of a sphere is supposed. The radius of the sphere is the distance to detect collision. All those points are sorted along one of the axis of three-dimension, and collisions are checked to avoid duplicates. In case of collision, penetration is avoided to act a force to repulsive direction. Therefor, self collisions of the cloth model are checked at the same time. Collisions are also checked between the cloth model and the dummy model. For this purpose, distance function is calculated for the dummy model. A three-dimensional lattice containing the dummy model is set, and the distance from each lattice point is calculated. The distance function is calculated once before the dynamic mechanical calculation begins, as the dummy model remains stationary while the calculation. The value of the distance function at the three-dimensional lattice point nearest to the node of the cloth model is utilized as the distance from the node of the cloth model to the dummy model for simplicity. As only a reference of an array is needed instead of calculation of a distance, collision detection between the cloth model and the dummy model can be processed very fast.

3. Results and Future Works As described earlier, the combination of the geometrical mapping method and the cloth handling by manmachine interface provides more efficient system. With the mapping method, natural shaped patterns of simple structured skirt can be obtained. On the other hand, the cloth model can be touched and picked by the hand model. It is expected to construct the system to combine those methods. The figure 2 shows that the cloth model is mapped in the condition that the odd part of the cloth model over the hipline is floating on the surface of the dummy model.

Fig. 2: Hand Model Touches and Picks the Cloth Model on Dummy Model.

It is planned to take darts from the floating part of the cloth model by the hand model. The interaction between the hand model and the dummy model has not yet installed at the moment. When the cloth model is manipulated by the hand model on the surface of the dummy model, usability is not so good because the hand model may penetrate into the dummy model. To solve the problem, it is necessary to make some kind of devise for man-machine interface.

4. Acknowledgment This work is partly supported by Grants-in-Aid for Scientific Research (No. 24220012, 26350069) from the Ministry of Education, Science, Sports and Culture and Grants for Excellent Graduate Schools, MEXT, Japan.

5. References [1] Wibowo A, Sakamoto D, Mitani J, Igarashi T. DressUp: A 3D Interface for Clothing Design with a Physical Mannequin. Proceedings of The 6th International Conference on tangible, embedded and embodied interaction (TEI 2012) 2012:99-102.

Page 135 of 1108

[2] Wang J, Lu GD, Li WL, Chen L, Sakaguti Y. Interactive 3D garment design with constrained contour curves and style curves. COMPUTER-AIDED DESIGN 2009;9:614-625.  [3] Huang HQ, Mok PY, Kwok YL, Au JS. Block pattern generation: From parameterizing human bodies to fit feature-aligned and flattenable 3D garments. COMPUTERS IN INDUSTRY 2012;63:680-691. [4] Au, CK, Ma YS. Garment pattern definition, development and application with associative feature approach. COMPUTERS IN INDUSTRY 2010;61:524-531. [5] Meng Y, Mok PY, Jin X. Computer aided clothing pattern design with 3D editing and pattern alteration. Computer-Aided Design 2012;44:721-734. [6] Cho Y, Takatera M, Tsuchiya K, Inui S, Park H, Shimizu Y. Computerized pattern making focus on fitting to 3D human body shapes. International Journal of Clothing Science and Technology. 2010;22;16-24.  [7] Takatera M, Kim K. Improvement of Individualized Pattern Making Using Surface Flattening Technique. Journal of Fiber Bioengineering and Informatics. 2013;6:4;467-480.

Page 136 of 1108

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

A Study on the Thermal Properties of Polyhydroxyamide Derivatives Chae Won Park, Ho Jin Yun, Chan Sol Kang, Min Jung Paik, Sun Hong Kim, and Doo Hyun Baik + Department of Advanced Organic Materials and Textile system Engineering, Chungnam National University, Korea +

dhbaik@cnu.ac.kr

Abstract. We have synthesized a PHA copolymer via low-temperature solution polymerization of 3,3’dihydroxybenzidine (DHB) with isophthaloyl chloride (IPC) and terephthaloyl chloride (TPC) in N,Ndimethylacetamide (DMAc), and then hydroxyl group of PHA copolymer have been substituted by trifluoroacetic anhydride or heptafluorobutyric anhydride. Such a PHA copolymer and its derivatives have investigated chemical structure and thermal properties. Chemical structures of PHA copolymer and its derivatives and their PBOs obtained from PHA by heat-treatment were identified by FT-IR. TGA results rexvealed that the PHA copolymer derivatives have low cyclization temperature and similar thermal stability compared to PBOs.

Keywords: Polybenzoxazoles, Polyhydroxyamides, substituents, thermal cyclization temperature.

1. Introduction Polybenzoxalzoles (PBOs) are representative high performance polymer with excellent thermal stability and mechanical properties. However, PBOs are difficult to be processed due to their high glass transition temperature (T g ) and low solubility in organic solvent except for strong acid. To improve these disadvantages, polyhydroxyamides (PHAs) can be used for precursor polymer to PBO[1]. PHAs can be converted into PBOs by thermal cyclization with release of water above 350℃. This high cyclization temperature is troubled with energy consumption in the aspects of manufacturing process. In this study, we have prepared PHA copolymer derivatives that changed hydroxyl group to OCOCF 3 or OCOCF 2 CF 2 CF 3 groups in order to decrease cyclization temperature[2]. And then we have investigated chemical structure and thermal properties of PHA copolymer and its derivatives.

2. Experimental 2.1.

Materials

3,3’-dihydroxybenzidine (DHB, 99.0%) was purchased from Wakayama Seika Co.. Terephthaloyl chloride (TPC, 99.0%), isophthaloyl chloride (IPC, 99.0 %), anhydrous N,N-dimethyl acetamide (DMAc, 99.8 %), lithium chloride (LiCl, 99.0 %), trifluoroacetic anhydride(TFA, 99.0%), and Heptafluorobutyric anhydride(HFBA, 99.0%) were purchased from Sigma-Aldrich Co,. Also, 4-pyrrolidinopyridine(PLP, 98.0%) were purchased from Tokoyo Chemical Co..

2.2.

Synthesis

A PHA copolymer was synthesized using low-temperature solution polycondensation. The DHB was dissolved in DMAc/LiCl solvent system. And then TPC/IPC (80/20) were added into the DHB solution. This solution was stirred using a mechanical stirrer under nitrogen atmosphere in low temperature (0 °C) for an hour and then at room temperature for 24 hours. The reaction mixture was poured into distilled water and repeatedly washed, and finally dried in a vacuum oven at 80 °C for 24 hours. And then PHA copolymer +

Corresponding author. Tel.: + 82-042-821-6618. E-mail address: dhbaik@cnu.ac.kr.

Page 137 of 1108

derivatives were prepared by adding TFA or HFBA into PHA copolymers solution using syringe. The synthetic route is shown in Scheme 1 and the sample codes is listed in Table 1.

Scheme 1. Synthesis of PHA copolymer and its derivatives. Table 1. Sample codes of PHA copolymer and its derivatives Sample code PHA s-PHA-1 s-PHA-2

2.3.

Monomer DHB

TPC

IPC

100

Chemical compound for substitution

After heat treatment

TFA HFBA

PBO s-PBO-1 s-PBO-2

Characterization

Chemical structures of synthesized PHA copolymer and its derivatives were identified by FT-IR (Nicolet iS50, Thermo Fisher). Their thermal properties were also investigated using TGA (Q50, TA Instrument). TGA was performed under nitrogen atmosphere at a heating rate of 20â&#x201E;&#x192;/min.

3. Results and Discussion Figure 1 shows FT-IR spectra of PHA copolymer and its derivatives. All the samples showed typical PHA structure bands at 3412 cm-1, 3400-3000 cm-1, 1647 cm-1, and 1408 cm-1 corresponding to N-H stretching, OH stretching, amide C=O stretching, and aromatic N-H bending, respectively. To identify the effects of substitution in PHA copolymers, it was confirmed that three characteristic bands of C-O-C ester, C-F stretching in CF 3, and C-F stretching in CF 2 appeared at 1735 cm-1, 1228 cm-1 and 1162 cm-1, respectively.

Figure 1. FT-IR spectra of PHA copolymer and PHA derivatives.

Page 138 of 1108

Figure 2 displays TGA and DTG curves of PHA copolymer and its derivatives. There showed typical twostep weight losses during heating. The first weight loss was due to the thermal cyclization of PHA copolymer and its derivatives and the second one was owing to the thermal decomposition of PBO copolymers. As shown in figure 2(b), thermal cyclization temperature shifted to lower temperature range with an introduction of substituents. Also, thermal cyclization temperature was decreased with increasing length of substituents. On the other hand, thermal decomposition temperature did not almost change.

Figure 2. TGA (a) and DTG (b) curves of PHA copolymer and PHA derivatives.

Figure 3 exhibits FT-IR spectra of PHA copolymer and its derivatives after heat treatment. It was observed that, characteristic bands corresponding to PHA and substituent structures are disappeared . And then, characteristic bands of the oxazole ring appeared at 1621 cm-1, 1457 cm-1, 1262 cm-1, and 1049 cm-1 corresponding to Ar-C=N stretching, C=N bending, Ar-O-C mixed stretching, and Ar-C-O stretching, respectively. It means that PHA copolymer and its derivatives are completely converted into PBO structures.

Figure 3. FT-IR spectra of PBO copolymers.

4. Conclusions We have synthesized a PHA copolymer via low-temperature solution polymerization. And then we have successfully prepared PHA copolymer derivatives by adding chemical compound for substitution into PHA copolymers solution using syringe. As a results, FT-IR spectra identified that the characteristic bands of PHA copolymer and its derivatives revealed distinctly. After the heat treatment, it was confirmed that characteristic bands of PHA and substituent structures disappeared, while characteristic bands of PBO appeared. When substituent was introduced to side chain of PHA copolymer, thermal cyclization temperature was decreased about 20 째C. In addition, thermal cyclization temperature was decreased about 30 째C with increasing length of substituent. In contrast, thermal decomposition temperature did not almost change. It was found that the introduction of substituents in side chain of PHA copolymers has an influence on the thermal cyclization temperature of PHA copolymers.

References [1] k. Takashi, and N. Royji, J Polym Sci, 1964, 2(6), 655-659. [2] D. H. Baik, H. Y. Kim, and S. W. Kantor, Fiber Polym, 2002, 3, 91-96.

Page 139 of 1108

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

Analyzing the tensile behavior of woven-fabric reinforced composites using fiber orientation theorem F Hasanalizade 1, H Dabiriyan 2 and Ali A A Jeddi 3 Textile Engineering Department, Amirkabir University of Technology, Tehran, Iran

Abstract. Mechanical behavior of woven fabric reinforced composites is almost studied using fiber orientation theorem so that the woven fabric are considered as two orthogonal UD composite. Whereas the structure of woven is differ from constituent yarns due to yarn crimp in interlacing points. In the present study, the difference between tensile behavior of woven fabric reinforced composites and two orthogonal UD composite is investigated. For this purpose, multilayered composites were made of E-glass plain woven fabric using hand lay â&#x20AC;&#x201C; up method. Tensile characteristics of the prepared composite were measured by means of INSTRON 5566. The results showed a significant difference between theoretical and experimental values.

Keywords: woven fabric composites, lay-up orientation, tensile behaviour 1. Introduction Today application of textile composites has been developed because of specific properties such as high strength to weight ratio, resistance and impact properties. In study of mechanical behavior of woven textile composites, each layer of fabric is assumed as two UD orthogonal layer. Therefore total mechanical behavior of composite follow combination of mechanical behavior of yarns as reinforcement [1-5]. Kumar et.al [4] researched the effect of angle ply orientation of composites on tensile properties of them, they considered latter assumptions and reported that the highest tensile strength is in đ?&#x;&#x17D;đ?&#x;&#x17D;Â° . In this research difference between theoretical results and experimental values considered because of difference nature between yarn and fabric. For this purpose tensile behavior of multilayer composites evaluated according to classical layers theory with orthotropic assumption.

2. Mechanical behavior of multilayer composites Relation between stress and strain of every layer of a multilayer composite in material direction follows Equation (1): đ??¸đ??¸1 â&#x17D;Ą đ?&#x153;&#x17D;đ?&#x153;&#x17D;1 â&#x17D;˘1 â&#x2C6;&#x2019; đ?&#x153;&#x2C6;đ?&#x153;&#x2C6;12 đ?&#x153;&#x2C6;đ?&#x153;&#x2C6;21 ďż˝ đ?&#x153;&#x17D;đ?&#x153;&#x17D;2 ďż˝ = â&#x17D;˘ đ?&#x153;&#x2C6;đ?&#x153;&#x2C6;12 đ??¸đ??¸2 đ?&#x153;?đ?&#x153;?12 â&#x17D;˘1 â&#x2C6;&#x2019; đ?&#x153;&#x2C6;đ?&#x153;&#x2C6;12 đ?&#x153;&#x2C6;đ?&#x153;&#x2C6;21 â&#x17D;Ł 0

đ?&#x153;&#x2C6;đ?&#x153;&#x2C6;12 đ??¸đ??¸2 1 â&#x2C6;&#x2019; đ?&#x153;&#x2C6;đ?&#x153;&#x2C6;12 đ?&#x153;&#x2C6;đ?&#x153;&#x2C6;21 đ??¸đ??¸2 1 â&#x2C6;&#x2019; đ?&#x153;&#x2C6;đ?&#x153;&#x2C6;12 đ?&#x153;&#x2C6;đ?&#x153;&#x2C6;21 0

0 â&#x17D;¤ đ?&#x153;&#x20AC;đ?&#x153;&#x20AC; â&#x17D;Ľ 1 đ?&#x153;&#x20AC;đ?&#x153;&#x20AC; ďż˝ 2ďż˝ 0 â&#x17D;Ľ đ?&#x203A;žđ?&#x203A;ž â&#x17D;Ľ 12 đ??şđ??ş12 â&#x17D;Ś

(1)

Where đ??&#x2C6;đ??&#x2C6;, đ??&#x2030;đ??&#x2030;, đ?&#x153;şđ?&#x153;ş, đ?&#x153;¸đ?&#x153;¸, đ??&#x201A;đ??&#x201A;, E and G are tensile stress, tensile strain, shear strain, Poissonâ&#x20AC;&#x2122;s ratio, elasticity modulus and shear modulus respectively. Subscripts 1 and 2 indicate to main direction of material. Itâ&#x20AC;&#x2122;s necessary to know thatđ?&#x2018;Źđ?&#x2018;Źđ?&#x;?đ?&#x;? , đ?&#x2018;Źđ?&#x2018;Źđ?&#x;?đ?&#x;? , đ??&#x201A;đ??&#x201A;đ?&#x;?đ?&#x;?đ?&#x;?đ?&#x;? , đ??&#x201A;đ??&#x201A;đ?&#x;?đ?&#x;?đ?&#x;?đ?&#x;? and đ?&#x2018;Žđ?&#x2018;Žđ?&#x;?đ?&#x;?đ?&#x;?đ?&#x;? relate to composite and calculate by rule of mixtures (Equations (2)-(5)). đ??¸đ??¸1 = đ??¸đ??¸đ?&#x2018;&#x161;đ?&#x2018;&#x161; đ?&#x2018;&#x2030;đ?&#x2018;&#x2030;đ?&#x2018;&#x161;đ?&#x2018;&#x161; + đ??¸đ??¸1đ?&#x2018;&#x201C;đ?&#x2018;&#x201C; đ?&#x2018;&#x2030;đ?&#x2018;&#x2030;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C; đ??¸đ??¸2 = đ??¸đ??¸đ?&#x2018;&#x161;đ?&#x2018;&#x161; đ?&#x2018;&#x2030;đ?&#x2018;&#x2030;đ?&#x2018;&#x161;đ?&#x2018;&#x161; + đ??¸đ??¸2đ?&#x2018;&#x201C;đ?&#x2018;&#x201C; đ?&#x2018;&#x2030;đ?&#x2018;&#x2030;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C; đ?&#x153;?đ?&#x153;?12 = đ?&#x153;?đ?&#x153;?21 = đ?&#x153;?đ?&#x153;?đ?&#x2018;&#x161;đ?&#x2018;&#x161; đ?&#x2018;&#x2030;đ?&#x2018;&#x2030;đ?&#x2018;&#x161;đ?&#x2018;&#x161; + đ?&#x153;?đ?&#x153;?đ?&#x2018;&#x201C;đ?&#x2018;&#x201C; đ?&#x2018;&#x2030;đ?&#x2018;&#x2030;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C; đ??şđ??şđ?&#x2018;&#x161;đ?&#x2018;&#x161; đ??şđ??şđ?&#x2018;&#x201C;đ?&#x2018;&#x201C; đ??şđ??ş12 = đ??şđ??şđ?&#x2018;&#x201C;đ?&#x2018;&#x201C; đ?&#x2018;&#x2030;đ?&#x2018;&#x2030;đ?&#x2018;&#x161;đ?&#x2018;&#x161; + đ??şđ??şđ?&#x2018;&#x161;đ?&#x2018;&#x161; đ?&#x2018;&#x2030;đ?&#x2018;&#x2030;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;

(2) (3) (4) (5)

Page 140 of 1108

That V is volume fraction and subscripts m and f indicate to matrix and fiber/ fabric, respectively. In order to translation of coordinate system in x-y direction Equation (6) has been used: đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;11 đ?&#x153;&#x17D;đ?&#x153;&#x17D;đ?&#x2018;Ľđ?&#x2018;Ľ ďż˝ đ?&#x153;&#x17D;đ?&#x153;&#x17D;đ?&#x2018;Śđ?&#x2018;Ś ďż˝ = ďż˝đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;21 đ?&#x153;?đ?&#x153;?đ?&#x2018;Ľđ?&#x2018;Ľđ?&#x2018;Ľđ?&#x2018;Ľ đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;61

đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;12

đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;22 đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;62

đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;16

đ?&#x153;&#x20AC;đ?&#x153;&#x20AC;đ?&#x2018;Ľđ?&#x2018;Ľ đ?&#x153;&#x20AC;đ?&#x153;&#x20AC; đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;26 ďż˝ ďż˝ đ?&#x2018;Śđ?&#x2018;Ś ďż˝ đ?&#x203A;žđ?&#x203A;žđ?&#x2018;Ľđ?&#x2018;Ľđ?&#x2018;Ľđ?&#x2018;Ľ đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;66

(6)

đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;11 = đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;11 đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;? 4 đ?&#x153;&#x192;đ?&#x153;&#x192; + 2(đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;12 + 2đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;16 )đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; 2 đ?&#x153;&#x192;đ?&#x153;&#x192; đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;? 2 đ?&#x153;&#x192;đ?&#x153;&#x192; + đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;22 đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; 4 đ?&#x153;&#x192;đ?&#x153;&#x192; đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;12 = (đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;11 + đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;22 â&#x2C6;&#x2019; 4đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;66 )đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; 2 đ?&#x153;&#x192;đ?&#x153;&#x192; đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;? 2 đ?&#x153;&#x192;đ?&#x153;&#x192; + đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;12 (đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;? 4 đ?&#x153;&#x192;đ?&#x153;&#x192; + đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; 4 đ?&#x153;&#x192;đ?&#x153;&#x192;) đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;22 = đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;11 đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; 4 đ?&#x153;&#x192;đ?&#x153;&#x192; + 2(đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;11 + 2đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;66 )đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; 2 đ?&#x153;&#x192;đ?&#x153;&#x192; đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;? 2 đ?&#x153;&#x192;đ?&#x153;&#x192; + đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;22 đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;? 4 đ?&#x153;&#x192;đ?&#x153;&#x192; đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;61 = (đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;11 â&#x2C6;&#x2019; đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;22 â&#x2C6;&#x2019; 2đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;66 )đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;? 3 đ?&#x153;&#x192;đ?&#x153;&#x192; + (đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;12 â&#x2C6;&#x2019; đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;22 + 2đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;66 )đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; 3 đ?&#x153;&#x192;đ?&#x153;&#x192;đ?&#x153;&#x192;đ?&#x153;&#x192;đ?&#x153;&#x192;đ?&#x153;&#x192;đ?&#x153;&#x192;đ?&#x153;&#x192;đ?&#x153;&#x192;đ?&#x153;&#x192; đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;62 = (đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;11 â&#x2C6;&#x2019; đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;22 â&#x2C6;&#x2019; 2đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;66 )đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; 3 đ?&#x153;&#x192;đ?&#x153;&#x192; đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;? + (đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;11 â&#x2C6;&#x2019; đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;22 + 2đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;66 )đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;? 3 đ?&#x153;&#x192;đ?&#x153;&#x192; đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;62 = (đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;11 + đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;22 â&#x2C6;&#x2019; 2đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;12 â&#x2C6;&#x2019; 2đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;66 )đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; 2 đ?&#x153;&#x192;đ?&#x153;&#x192;đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;? 2 đ?&#x153;&#x192;đ?&#x153;&#x192; + đ?&#x2018;&#x201E;đ?&#x2018;&#x201E;66 (đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; 4 đ?&#x153;&#x192;đ?&#x153;&#x192; + đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;? 4 đ?&#x153;&#x192;đ?&#x153;&#x192;)

(7) (8) (9) (10) (11) (12)

Where đ?&#x153;˝đ?&#x153;˝ is angel orientation.

If the composite contents N- layers and distance of each layer from internal layer is assumed đ?&#x2019; đ?&#x2019; đ?&#x2019;&#x152;đ?&#x2019;&#x152; , stiffness properties of composite evaluated by Equation (13): đ??´đ??´đ?&#x2018;&#x2013;đ?&#x2018;&#x2013;đ?&#x2018;&#x2013;đ?&#x2018;&#x2013; đ?&#x2018; đ?&#x2018; đ?&#x2018;&#x2013;đ?&#x2018;&#x2013; ďż˝đ?&#x2018;&#x20AC;đ?&#x2018;&#x20AC; ďż˝ = ďż˝ đ??ľđ??ľđ?&#x2018;&#x2013;đ?&#x2018;&#x2013;đ?&#x2018;&#x2013;đ?&#x2018;&#x2013; đ?&#x2018;&#x2014;đ?&#x2018;&#x2014;

đ??ľđ??ľđ?&#x2018;&#x2013;đ?&#x2018;&#x2013;đ?&#x2018;&#x2013;đ?&#x2018;&#x2013; đ?&#x153;&#x20AC;đ?&#x153;&#x20AC;đ?&#x2018;&#x2013;đ?&#x2018;&#x2013; ďż˝ďż˝ ďż˝ đ??ˇđ??ˇđ?&#x2018;&#x2013;đ?&#x2018;&#x2013;đ?&#x2018;&#x2013;đ?&#x2018;&#x2013; đ?&#x2018;&#x2DC;đ?&#x2018;&#x2DC;đ?&#x2018;&#x2014;đ?&#x2018;&#x2014;

(13)

That đ?&#x2018;ľđ?&#x2018;ľđ?&#x2019;&#x160;đ?&#x2019;&#x160; and đ?&#x2018;´đ?&#x2018;´đ?&#x2019;&#x2039;đ?&#x2019;&#x2039; show in-plane and flexural loads applied to width respectively. đ?&#x153;şđ?&#x153;şđ?&#x2019;&#x160;đ?&#x2019;&#x160; and đ?&#x2019;&#x152;đ?&#x2019;&#x152;đ?&#x2019;&#x2039;đ?&#x2019;&#x2039; are in-plane and flexural strains respectively and đ?&#x2018;¨đ?&#x2018;¨đ?&#x2019;&#x160;đ?&#x2019;&#x160;đ?&#x2019;&#x160;đ?&#x2019;&#x160; , đ?&#x2018;Šđ?&#x2018;Šđ?&#x2019;&#x160;đ?&#x2019;&#x160;đ?&#x2019;&#x160;đ?&#x2019;&#x160; , đ?&#x2018;Ťđ?&#x2018;Ťđ?&#x2019;&#x160;đ?&#x2019;&#x160;đ?&#x2019;&#x160;đ?&#x2019;&#x160; are extensional stiffness matrix, coupling stiffness matrix and bending stiffness matrix respectively.

3. Material and Methods

4-layer composite samples made up in 3 angle orientation with woven E-glass fabric and epoxy resin by hand lay-up method (Figure (1)). Table (1) presents details of samples data. Samples S4, S5 and S6 produced with rotating S1, S2 and S3 in đ?&#x;&#x2014;đ?&#x;&#x2014;đ?&#x;&#x2014;đ?&#x;&#x2014;Â° respectively; so the volume fraction is same in both samples with or without rotating.

Figure 1. 4-layer composite samples preparation Table 1. Detail of sample preparation No. S1 S2 S3 S4 S5 S6

Angle ply orientation (0,90,90,0)2 (0,90,+45,-45,-45,+45,90,0) (+45,-45,0,90,90,0,-45,+45) (90,0,0,90)2 (90,0,-45,+45,+45,-45,0,90) (-45,+45,90,0,0,90,+45,-45)

Resin volume fraction 0.48 0.45 0.43 0.48 0.45 0.43

Fabric volume fraction 0.52 0.55 0.57 0.52 0.55 0.57

Page 141 of 1108

3 samples from each group were cut in 25×150 mm and stretched according to ASTM- D3039 standard. The thickness of samples is 2 mm. Table (2) shows results of tensile test of 4-layer composites. The reported modulus of samples indicate initial modulus.

No. S1 S2 S3 S4 S5 S6

Table 2. Results of tensile test of 4-layer composites E (MPa) σ (MPa) ε (%) 24.49 1.74 1761 24.49 1.91 1887 24.49 1.94 1826 24.49 2.09 1451 24.49 1.75 1951 24.49 1.15 2466

Every samples had been stretched by same strain because strain assumed benchmark for compare the experimental and theoretical results. Also for theoretical stiffness evaluation of composite, tensile properties of yarn and fabric was observed as composite reinforcement. Technical information of each of them present in tables 3 and 4 separately. Table3. Technical data and tensile test results of yarns Maximum Length Strain load (mm) (%) (N) 250 80 1.076 250 80 1.064

Count (tex) warp weft

314 309

Modulus (gf/tex)

Stress (gf/tex)

2628 2707

25.98 26.40

The plain woven fabric had 0.32 mm thickness, 5 (end/pick) per centimeter density and (365 g/mm2) weighted. The tensile measurement of this sample brought in table (4).

Maximum load (N) warp weft

3000 2487

Table 4. results of tensile test of fabric Modulus in 0.5Strain 1% strain (%) (MPa) 4.42 2215 4.58 2570

Modulud in 1.52% strain (MPa) 6614 5889

Stress (MPa) 234.4 194.36

Each biaxial layer is assumed equal to two uniaxial layer, this means yarns is the composite reinforcement and in theoretical calculation, mechanical behavior of yarn shall be use [6]. Figure (2) shows comparative results between experience and theory. 2.5

strain (%)

2 1.5 1

0.5 0

Theoretical strain (%)

1.44

2.04

2.13

1.44

2.04

2.13

Experimental strain (%)

1.74

1.91

1.94

2.09

1.75

1.15

Theoretical strain (%)

Experimental strain (%)

Figure 2. Result comparison between theoretical and experimental

Page 142 of 1108

4. Result and discussion As can be seen in Figure (2), for samples S1 and S4 experimental strain is more than theoretical strain because of yarn decrimping which is ignored in theoretical analysis. This subject disguise in theoretical evaluations because in tensile behavior analysis of multilayer composites, when the yarns assumed as reinforcement, effect of weaving on the yarn structure such as elastic terms is not considered. In the other word difference between yarn in the fabric structure and when singly roles as a reinforcement, why so crimp factor shall be considered. Also we can claim that when we use the fabric parameter, our analysis will be more accurate. Unlike S1 and S4, theoretical results for samples S2, S3, S5 and S6 is more than experimental. This samples produced with diagonal angle and except crimp factor, other effective variables on the tensile behavior exist for example shearing stress. Analyzing these samples need more detailed studies. Difference between S1, S2, S3 and S4, S5, S6 that rotated those, is the sequence of layers, and for this samples the angle of layer not be changed, in this condition we can claim that sequence of the layer in addition to angle orientation is important for tensile behavior of composites.

References [1] T. Hussain, Z. Ali Malik and A. Tanwari, "Prediction of Tensile Strength of Polyester/Cotton Blended Woven Fabrics," Indian Journal of Fiber & Textile Research, vol. 35, pp. 243-249, 2010 [2] Z. Alimalik, A. Tanwari and H. Rehman sheikh, "Influence of Plain and Twill (3/1) Weave Designs on the Tensile Strength of PC Blended Fabrics'', Mehran University Research Journal of Engineering & Technology, vol. 30, 2011. [3] W. Jianhua and N. Pan, "Grab and Strip Tensile Strengths for Woven Fabrics," Textile Research Journal,vol. 73, 2005. [4] K. Kumar, P. Reddy and D. Shankar, "Effect of Angle Ply Orientation On Tensile Properties Of Bi Directional Woven Fabric Glass Epoxy Composite Laminate," International Journal of Computational Engineering Research, vol. 03, no. 10, 2013. [5] D. Roylance, Laminated Composite Plates, Cambridge, 2000. [6] Heral, Grosberg and Backer, Structural Mechanics of Fibers, Yarns and Fabrics,Johns Wiley & Sons, London, 1969.

Page 143 of 1108

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

Biodegradable composites from natural bamboo fibres Erwan Castanet 1 +, Rangam Rajkhowa 1, Jin Zhang1, Bernard Rolfe 2 and Kevin Magniez 1 1

Institute for Frontier Materials, Deakin University, Geelong, 3220 Victoria, Australia 2 School of Engineering, Deakin University, Geelong, 3220 Victoria, Australia

Abstract. We investigated the chemical composition of natural bamboo fibre using GB5889-86 standard and micro-fibril angle by SAXS. The tensile properties of single bamboo fibre were investigated by FAVIMAT fibre tester and compared to single flax and hemp fibres. Natural bamboo fibres, were used to reinforce a Polylactic-acid (PLA) matrix to produce 100% biodegradable composite targeting automobile applications such as indoor panel or dash board. To manufacture the bio-composites, fibres were blended with PLA fibres at 50/50 wt% ratio and carded into homogeneous web, followed by needle punching to a non-woven mat. Multiple layers (x12) of such mats were hot-compression moulded to produce the composites. The paper also compare the tensile properties of the bamboo fibre composites with a flax/PLA and hemp/PLA bio-composite. Keywords: Bamboo fibre, Biodegradable polymer, Bio-composites.

1. Introduction The European Union has a target to reuse and recycle at least 95% in mass of end of life vehicles (ELV) by 2015 [1]. Currently, in Australia, more than 500,000 cars annually become categorised as ELV, of which 75% by weight are recycled (ferrous materials), leaving 25% of the material (foam, seats, glasses, rubbers, plastics and composites) sent to landfill [2]. These non-recycled materials often take hundreds of years to degrade [3]. In light of the stringent up-coming environmental regulations for the automotive industry, the environmental impact of cars from production to end of life as well as their recyclability are a major consideration for car manufacturers [1, 4]. The recyclability and footprint of automotive materials must be improved to match new regulations set by governments worldwide [1, 5]. The automotive industry is slowly trying to come up with sustainable materials and processes [6, 7]. Sustainable materials such as natural fibre composites have been used in the automotive industry for over a decade because they display many advantages (specific mechanical properties) for non-structural automotive applications (indoor panels, dashboard). Additionally, using natural fibres in automotive production contributes to a weight reduction of 10-30% compared to glass fibres, resulting in a lower fuel consumption [4, 8]. In this project we are examining the advantage of bamboo fibre to produce composites. The bamboo fibres used in this project are natural, not regenerated, and commercially available. To produce 100% bio-degradable composites for automotive applications, we have used Polylactic acid (PLA) bio-polymer instead of currently used non-bio-degradable petroleum derived polymers resins such as epoxy or polyurethane as matrices[9]. A common challenge of a natural fibre composite is the poor interfacial adhesion which limits their applications. This happen because the fibres are hydrophilic whereas the matrices are hydrophobic resulting in poor interactions and hence less satisfactory mechanical properties. This project therefore aims at improving interfacing properties by some novel approaches.

Corresponding author. E-mail address: ecastane@deakin.edu.au.

Page 144 of 1108

2. Experimental details Bamboo fibres were supplied by an ISO9001 certified company, Suzhou Shenboo Textile Co., Ltd in China [10]. The elementary fibres were extracted by using a combination of steaming, mechanic and enzymatic degumming process (Fig. 1). The fineness of the supplied fibres is between 5 and 8.3dtex with an average value of 6dtex. The properties of the bamboo fibres were compared to flax fibres (Linum usitatissimum) sourced from Durafibre Inc and hemp fibres (Cannabis sativa) sourced from Ecofibre Industries (Australia). Natural fibres were cleaned at 60°C for 20 min with a solution of sodium hydroxide (NaOH; 2g/L) and a detergent (Clariant Imerol; 1g/L) and then dried at 70°C in a vacuum oven. PLA fibres were supplied by Fibre Innovation Technology Inc. in the USA. PLA fibres are hollow fibres (15% void) with a fineness of 9 dtex per filament and a crimp of 5cpi. Fibres and composites samples were conditioned for at least 48h at 20°C ± 2 °C and 65% ± 2% relative humidity prior to processing and characterisation.

2.1.

Fig. 1: Bamboo fibres sleeves

Fibre characterization

The density of each natural fibre (bamboo, flax and hemp) was analysed by a pycnometer Ultrapyc 1200e from Quantachrom (USA). For the measurement of each fibre, three samples of 2g of dry fibres were run 30 times each at 23°C to obtain an average density. The chemical composition of natural bamboo fibres was determined using the GB 5889-86 standard which is a common standard used for chemical characterization of ligno-cellulosic fibres. The standard involves a series of chemical digestion aimed at selectively removing specific components present in the fibre. The micro-fibril angle of bamboo fibre was determined on the SAXS/WAXS beam line at the Australian Synchrotron (Victoria, Australia). Single bamboo fibres were mounted one by one on a support and perpendicular to the beam. The beam size was set at 250 x 130 µm, the wavelength was chosen at 0.619921 Å and the camera was positioned at 0.958 m from the sample. The azimuthal signal was extracted using the software FIT2D after correction of the beam centre position, pixel and frame size. The tensile properties (tensile strength and Young’ modulus) of bamboo fibres were measured on a Favimat from Textechno (Germany). All the tests were run with 30 mm gauge length, 2 mm/min testing speed and a pre-load of 1.5cN/Tex.

2.2.

Fibre processing and production of non-woven fabrics

First of all (Fig. 2: stage 1), each type of natural fibres and PLA fibres were blended at 50/50 wt% ratio and carded, “Mesdan” lab carding machine, into homogeneous non-woven webs which were subsequently consolidated by a needle punch, Fiber Locker, James Hunter, USA. The web was needle punched as a multilayer web (12 layers), 20 punch/ cm2 on a both side to provide the webs with mechanical cohesion. Then the bio-composites were fabricated by hot-compression moulding (Fig. 2: Stage 2) at optimized time (20min), pressure (4.5t) and temperature (185°C).

2.3.

Composites characterization

Tensile strength and Young’s modulus were determined in accordance with ASTM D638-10 standard with a type IV specimen and loading speed of 2 mm/min using the Instron 30kN universal tensile tester. Fig. 2: Manufacturing process of Bio-composites

Page 145 of 1108

3. Result and Discussion The density of the fibres measured on the pycnometer was found to be ≈1.48 g/cm3 ± 0.05% for bamboo, 1.28 g/cm3 ± 0.05% for flax and 1.42 g/cm3 ± 0.05% for hemp fibres. These results lie within the average of most of the ligno-cellulosic fibres that have a density of ≈1.5 g/cm3 [11]. Aforementioned, the chemical composition of bamboo fibres was determined using a chemical digestion method. It was found that bamboo fibres contain a high amount of cellulose (~75%) as well as ~10% lignin, ~8% hemicellulose then fat & wax, water soluble content and pectin (~ 6%). The results are consistent with reports from Wang Yueping et al. [12]. Fig. 3: a) Azimuthal signal; b) Image from SAXS of single The micro-fibrils grow with a certain angle to bamboo fibre the fibre axis and provide strength to the fibre. The micro-fibril angle was calculated from the azimuthal signal obtained from the SAXS scan (Fig. 3a). By fitting the azimuthal signal extracted from the image (Fig. 3b) of several bamboo fibres, the average microfibril angle was calculated as 6.65° ± 0.42°. This value seats among the values reported by literature for bamboo flax and hemp fibres which all display a small micro-fibril angle [13]. The tensile properties of the natural fibres were compared in Table 1 after the load-extension curves were translated into stress-strain curves using the mean average diameter previously measured. Table 1: Tensile properties of bamboo, hemp and flax fibres. Natural Fibre

Tensile strength (MPa)

Young’s Modulus (GPa)

Bamboo

435 ± 171

34.5 ± 8.4

Flax

419 ± 188

29.32 ± 8.9

Hemp

408 ± 200

25.93 ± 8.5

The tensile properties of all tested fibres (i.e. bamboo, flax and hemp) are comparable but also similar to what has been reported in literature [14, 15]. This is also consistent with the previous work published by Bledzki et al. who established clear relationships between high cellulose content of fibres coupled with low micro-fibril angle (<10°) providing the fibre with high tensile modulus [16].

The tensile properties of bio-composites correlate well to the tensile properties of the natural fibres (Fig. 4). The Young modulus of the composites was found to be highest for the bamboo fibre. Furthermore, the tensile strength of bamboo composite was much higher compared to flax and hemp fibre based composites. It is interesting to note that difference in tenacity and modulus of bamboo composites was much higher compared to their difference in fibre tenacity and modulus indicating a better interaction of fibre matrix adhesion in case of bamboo compared to flax and hemp.

4. Conclusion This work examined the fibre and composite properties of bamboo fibre reinforced composites, which displays superior performance over conventional natural fibre composites with flax or hemp as reinforcement.

Page 146 of 1108

5. Acknowledgements The author would like to acknowledge Dr Kevin Magniez, Dr Rangam Rajkhowa, Dr Jin Zhang, Ass/Prof Bernard Rolfe and Prof Xungai Wang for their support and advice. Dr Ludovic Dumee is thanked for his assistance with access of the Australian Synchrotron. The financial support from AutoCRC is acknowledged.

Figure 4: Tensile properties of Bio-composites

6. References 1. 2.

3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13.

14. 15.

16.

PARLIAMENT, E., DIRECTIVE 2005/64/EC OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL of 26 October 2005 2005, Official Journal of the European Communities L 310/10: Strasbourg, France. RACV. Vehicle Recycling. 2010 18/072014]; Available from: http://www.racv.com.au/wps/wcm/connect/racv/Internet/Primary/my+car/advice+_+information/motorin g+_+the+environment/reduce+your+emissions+and+fuel+costs/vehicle+recycling. Satyanarayana, K.G., G.G.C. Arizaga, and F. Wypych, Biodegradable composites based on lignocellulosic fibers—an overview. Progress in Polymer Science, 2009. 34(9): p. 982-1021. Bledzki, A.K., O. Faruk, and V.E. Sperber, Cars from Bio-Fibres. Macromolecular Materials and Engineering, 2006. 291(5): p. 449-457. Jody, B.J., et al., End-of-life vehicle recycling : state of the art of resource recovery from shredder residue. 2011. p. Medium: ED. John, M.J. and S. Thomas, Biofibres and biocomposites. Carbohydrate Polymers, 2008. 71(3): p. 343-364. Suddell, B.C. Industrial Fibres: Recent and Current Developments. in Symposium on Natural Fibres. Joshi, S.V., et al., Are natural fiber composites environmentally superior to glass fiber reinforced composites? Composites Part A: Applied Science and Manufacturing, 2004. 35(3): p. 371-376. Faruk, O., et al., Biocomposites reinforced with natural fibers: 2000–2010. Progress in Polymer Science, 2012. 37(11): p. 1552-1596. Co., S.T. New Green Natural and Eco-friendly Product—Natural Original Bamboo Fiber. 2014 [cited 2014 25/11/2014]; Available from: http://www.kongfi.com/new.htm. Zini, E. and M. Scandola, Green composites: An overview. Polymer Composites, 2011. 32(12): p. 1905-1915. Yueping, W., et al., Structures of Natural Bamboo Fiber for Textiles. Textile Research Journal, 2009. Mussig, J., et al., Testing Method for Measuring Physical and Mechanical Fibre Properties, in Industrial Application of Natural Fibres: Structure, Properties and Technical Applications, J. Mussig, Editor. 2010, John Wiley & Sons, Ltd. p. 269-310. Ku, H., et al., A review on the tensile properties of natural fiber reinforced polymer composites. Composites Part B: Engineering, 2011. 42(4): p. 856-873. Osorio, L., et al., Morphological aspects and mechanical properties of single bamboo fibres and flexural characterization of bamboo/epoxy composites. Journal of Reinforced Plastics and Composites, 2011: p. 0731684410397683. Bledzki, A.K. and J. Gassan, Composites reinforced with cellulose based fibres. Progress in Polymer Science, 1999. 24(2): p. 221-274.

Page 147 of 1108

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

Biosynthesis of bacterial cellulose/carboxylic multi-walled carbon nanotubes for enzymatic biofuel cells application Pengfei Lv, Qingqing Wang, Guohui Li, Qufu Wei (School of Textile and Clothing, Jiangnan University, Wu Xi 214122 China)

Abstract: Bacterial cellulose (BC), which was synthesized by acetobacter xylinum, was a natural and low-cost biopolymer. A fuel cell application was studied by biosynthesis of BC/carboxylic multi-walled carbon nanotubes (cMWCNTs) in agitated culture. The biocathode and bioanode were prepared by injection of glucose oxidase (GOD) and laccase (Lac) with glutaraldehvde (GA) crosslinking into BC/c-MWCNTs respectively. An enzyme biological fuel cell (EBFC) composed of a bioanode and biocathode was developed and tested. Biosynthesis of BC/c-MWCNTs composite was characterized by digital photos, scanning electron microscope (SEM) and Fourier Transform Infrared (FTIR). The results revealed the inclusion of c-MWCNTs into the BC. The BC/c-MWCNTs/Lac was characterized by cyclic voltammetry (CV). An EBFC was characterized by linear sweep voltammetry (LSV). The results showed EBFC exhibited excellent performance. The cell also exhibited acceptable stability over 30 days collected. Preliminary tests on double cell indicated that renewable BC has great potential in EBFCs field. Preliminary tests on double cell indicated that renewable BC has great potential in EBFCs field. Keywords: Bacterial Cellulose; Laccase; Glucose Oxidase; Enzyme Biological Fuel Cell

1 Introduction Nowadays, enzymatic biofuel cells (EBFCs) as the new green energy devices have drawn much attention because they are capable of harvesting electricity from renewable and abundantly available biofuels using enzymes as the catalysts for oxidation of biofuels (most commonly, glucose) and reduction of oxidizers (most commonly, oxygen)[1,2]. They are essentially product without any harmful intermediates and side products. Most EBFCs cathodes involve the four-electron reduction of O 2 to water[3]. O 2 +4H++4e2H 2 O (1) Due to the active centers of the enzymes are usually buried inside the protein matrics, it is crucial important for improving EBFC performance by solving the problem of the poor electron transfer to the electrode[4]. Various types of carbon nanotubes (CNTs) have therefore been explored as the conducting nanowires to facilitate electron transfer from the catalytic centers of enzymes to electrode because they are chemically inert with excellent conductivity, electro-chemical stability, and molecular dimension that enables intimate interaction with the enzymes[5,6]. The unique properties of CNTs make them extremely attractive for electrochemical applications, protein electrochemistry, electrochemical sensors, and especially for biosensors or biofuel cells[7]. In the bioelectronics filed, CNTs have been used as supports for enzyme immobilization to enable direct electron transfer, because of their large specific surface area and good conductivity[8]. Bacterial cellulose (BC), which is usually synthesized by acetobacter xylinum, is a natural and low-cost biopolymer[9]. BC has demonstrated unique properties including high ultrafine porosity, 3D network structure, high crystallinity, water absorbance, mechanical properties and biocompatibility, which make it a very useful biomaterial in many different fields such as in paper, food and electronic industries. Furthermore, the hydroxyl groups on its backbone can provide BC with a high hydrophilicity, which is crucial for the operation of polymer electrolyte membrane fuel cells[10]. In this work, biosynthesis of BC/carboxylic multi-walled carbon nanotubes(c-MWCNTs) in agitated culture were used as both bioanode and biocathode in EBFCs (Fig 1a) . The biocathode and bioanode were prepared by BC/c-MWCNTs which were injected with laccase (Lac) and glucose oxidase (GOD) by

+ Corresponding author. Tel.: 13771106262 E-mail address: qfwei@jiangnan.edu.cn.

Page 148 of 1108

glutaraldehvde (GA) crosslinking , respectively. The performance of the membrane electrode assemblies (MEAs) in EBFCs was studied.

Fig.1: Illustration of (a) the EBFC equipped with 3D BC/c-MWCNTs hybrid electrodes (not to scale) and (b) the Lac and GOD immobilized on BC/c-MWCNTs by GA crosslinking.

2 Experimental 2.1 Materials The industrial laccase powder (3 U/mg); The industrial glucose oxidase (800 U/mg); The c-MWCNTs (OD,<8 nm; Length, 0.5-2 ฮผm; Purity, >95%)

2.2 Preparation of BC/c-MWCNTs/Lac and BC/c-MWCNTs/GOD First, c-MWCNTs were dispersed in culture media. These culture media were sterilized at 120 ยบC in autoclave for 2 h by autoclaving and poured into Erlenmeyer flasks. The bacterium was cultured on Hestrin and Schramm (HS)( 5% (w/v) glucose, 1.6% (w/v) bacto-peptone, 0.2% (w/v) citric acid, 0.2% (w/v) disodium hydrogen phosphate, 0.3% (w/v) potassium dihydrogen phosphate, 0.03% (w/v) magnesium sulphate medium by staticing incubation. Then cells pre-cultured in a test tube containing a small cellulose pellicle on the surface of the medium were inoculated into a 100 mL Erlenmeyer flask containing 10 ml of the HS medium (in the presence of final 0.01 w/v% c-MWCNTs in HS medium). The flasks were incubated on a rotary shaker operating at rotational speed of 100 rpm, for 7 days at 30 ยบC. The synthesized cellulose was separated from the medium by filtration and were dipped into 1% sodium hydroxide solution for 2 h at 80 ยบC in order to eliminate the cells and medium embedded in the cellulose material, then rinsed 3 times to pH 7 in deionized water. Then the biocathode and bioanode were prepared that BC/(c-MWCNTs) were injected with 40 mg mL-1 laccase (Lac) and 20 mg mL-1 glucose oxidase (GOD) by 1.5% (v/v) GA in 0.1 M acetic acid/sodium acetate buffer (pH= 5.5) solution, as shown Fig 1b.

3 Results and discussion 3.1. Structural analysis

Page 149 of 1108

Fig. 2: (a) FESEM images of pure bacterial cellulose synthesized in shaking culture system; (b)Digital Photos of c-MWCNTsdispersed HS medium a shaking culture system at 30 ºC for 7 days (100 rpm).

The SEM image in Fig 2a shows the ultrafine nanofiber structure of BC membrane. The fibers looked very fine and the fiber diameters varied from 30 nm to about 100 nm. It is clearly observed the membrane possessed high porous 3D structure, as shown in Figure 3a. BC membrane contained interconnecting pores, which was in good agreement with the report in the literature[11]. It’s ultrafine network structure and large specific surface area provided a good tunnel for O 2 transmission. The digital image in Fig 3b shows the, BC/c-MWCNTs samples in water. The image reveals that c-MWCNTs were tightly wrapped in BC pellicle.

3.2 FTIR analysis

Fig. 3: FTIR spectra of (a) BC, (b) c-MWCNTs,(c) Biosynthesis of BC/c-MWCNTs

Fig 3 shows the FT-IR spectra of the pure BC, c-MWCNTs and BC/ c-MWCNTs. The band at 3465 cm-1 for c-MWCNTs was attributed to the presence of hydroxyl groups(-OH)[12]. The absorption band at 1659 cm-1 for cMWCNTs was assigned to the presence of carboxyl functional groups (C=O), which was in agreement with references[13]. The absorption band at 2973 cm-1 for BC were attributed to the presence of C-H stretching vibrations, which was in good agreement with the characteristic bands of BC reported in the literature[14]. The main difference in the spectra of BC and BC/c-MWCNTs was found in the region of 3465 cm−1. In the region of 3465 cm-1 the peak for BC/c-MWCNTs composite membranes enhanced. It revealed that BC and c-MWCNTs had only physical interaction.

3.3 Electrochemical behavior of the Lac/BC/c-MWCNTs electrode

Fig. 4: (a)Cyclic voltammograms of BC/c-MWCNTs/Lac electrode in a 0.1 M acetic acid/sodium acetate buffer solution (pH 5.5) at scan rates of (I) the bare 3-D BC/c-MWCNTs electrode. (II) 50, (III) 150, (IV) 250, (V) 350mV/s. (b) The inset is a plot of the oxidation and reduction peak currents against the scan rate.

As shown Fig 4a, it indicates that the CVs of the BC/c-MWCNTs/Lac electrode were exist of obvious redox peaks from laccase redox transition, whereas a pair of prominent redox peaks (at 0.74 V and 0.11 V, respectively) can be observed, which was attributed to the redox reaction of the Lac immobilized on the cMWCNTs. This showed the good coupling between the enzymes and 3D BC/c-MWCNTs substrate. The redox

Page 150 of 1108

of Lac on the electrode was a reversible and surface-confined process, as evidenced by the linear scaling between redox currents and scan rate as shown Fig 4b. In comparison, the bare 3D BC/c-MWCNTs electrode shows no catalytic action to O2.

3.4 Performance of the biofuel cell

Fig. 5: (a) The maximum open circuit voltage of the EBFCs; (b) The open circuit voltage from the EBFCs over 30 days; (c) The power density curve of glucose/O 2 biofuel cell obtained by LSV in 0.1 m, pH 5.5, HAc/NaAc buffer containing 50 mM glucose. Data were collected at 10 mV.sâ&#x2C6;&#x2019;1.

The EBFCs were fabricated with a 3D BC/c-MWCNTs/Lac cathode and 3D BC/c-MWCNTs/GOD anode by GA crosslinking. As demonstrated in Fig 5a, the open circuit voltage of the EBFC was approximate 0.64 V. Based on the open circuit voltages over 30 days collected, a 51 % drop of open circuit voltage was observed, indicating relative stability. To evaluate the electrochemical performance as an enzymatic biofuel cell operating with glucose, linear sweep voltammetry (LSV) was used. As shown in Fig 5c, the change of power density showed first increased and then decreased with the increasing of open circuit voltage and the open-circuit voltage was about 0.62 V in consistent with the biggest open circuit voltage in Fig 5a. The maximum current density was 0.29 mA/cm3 and the maximum power density was 32.98 ÂľW/cm3.

4 Conclusions For the first time, Lac and GOD immobilized on biosynthesis of BC/c-MWCNTs was used in EBFCs. The nanotopographic surface of c-MWCNTs networks ensured snug anchoring of enzyme molecules by GA crosslinging. EBFCs were fabricated with a BC/c-MWCNTs/Lac cathode and BC/c-MWCNTs/GOD anode. BC, elaborate threedimensional structure, controllable porosity as well as designable shape may make provides the possibility in biofuel cell application.

References: [1] M.J. Cooney, V. Svoboda, C. Lau, G. Martin, S.D. Minteer, Energ Environ Sci 1 (2008) 320. [2] X.Y. Yang, G. Tian, N. Jiang, B.L. Su, Energ Environ Sci 5 (2012) 5540. [3] S. Tsujimura, Y. Kamitaka, K. Kano, Fuel Cells 7 (2007) 463. [4] K.P. Prasad, Y. Chen, P. Chen, ACS Appl Mater Interfaces 6 (2014) 3387. [5] S.D. Minteer, P. Atanassov, H.R. Luckarift, G.R. Johnson, Mater Today 15 (2012) 166. [6] W. Feng, P.J. Ji, Biotechnol Adv 29 (2011) 889. [7] K.P. Gong, Y.M. Yan, M.N. Zhang, L. Su, S.X. Xiong, L.Q. Mao, Anal Sci 21 (2005) 1383. [8] C.E. Zhao, Y. Wang, F.J. Shi, J.R. Zhang, J.J. Zhu, Chem Commun 49 (2013) 6668. [9] D. Klemm, D. Schumann, U. Udhardt, S. Marsch, Prog Polym Sci 26 (2001) 1561. [10] Y. Wan, K.A.M. Creber, B. Peppley, V.T. Bui, J Membrane Sci 280 (2006) 666. [11] F.G. Torres, S. Commeaux, O.P. Troncoso, Journal of functional biomaterials 3 (2012) 864. [12] Z.Y. Yan, S.Y. Chen, H.P. Wang, B.A. Wang, J.M. Jiang, Carbohyd Polym 74 (2008) 659.

Page 151 of 1108

[13] B. Zhao, H. Hu, A.P. Yu, D. Perea, R.C. Haddon, J Am Chem Soc 127 (2005) 8197. [14] C.R. Rambo, D.O.S. Recouvreux, C.A. Carminatti, A.K. Pitlovanciv, R.V. Antonio, L.M. Porto, Mat Sci Eng C-Bio S 28 (2008) 549.

Page 152 of 1108

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

Characterization of Polyimide/Poly(VDF-co-HFP) Composite Membrane Prepared by Electrospinning Il Jae Lee, Chan Sol Kang, and Doo Hyun Baik* Department of Advanced Organic Materials & Textile System Engineering, Chungnam National University, Korea *dhbaik@cnu.ac.kr

Abstract. Commonly electrospun nanowebs have high porosity, specific surface area, and wettability. In addition, polyimide (PI), one of the materials of lithium ion battery separators, has good thermal stabilities and chemical resistance. Accordingly, PI nanowebs are suitable for lithium ion battery separators. Although PI nanowebs have many advantages, they have low tensile strength because of their physical structures. PI nanowebs thus need to increase interaction between nano fibers. In this study, to improve tensile strength of PI nanowebs, composite nanowebs were prepared through thermal calendaring process using both PI nanowebs and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-co-HFP) nanowebs. To confirm effect of thermal calendaring process, PI/PVDF-co-HFP nanowebs were measured by mechanical properties using UTM. In addition, PI/PVDF-co-HFP nanowebs were examined by field-emission scanning electron microscope (FESEM). It was found that PVDF-co-HFP fibers presented enhanced bonding point and the binding between PI nanowebs and PVDF-co-HFP nanowebs.

Keywords: Polyimide, Poly(vinylidene fluoride-co-hexafluoropropylene), Electro spinning, Thermal calendering.

1. Introduction Lithium ion battery separators are a porous membrane placed between anode and cathode. Separators are permeable to ion, simultaneously they are preventing short circuit of the electrodes. Electrospun nanowebs have extensively investigated for lithium ion battery separators because of their high porosity, specific surface area, and wettability. In addition, polyimide (PI), one of the materials of lithium ion battery separators, has excellent thermal stabilities and chemical resistance. Accordingly, PI nanowebs are suitable for lithium ion battery separators. However, the PI nanowebs have low tensile strength because of their physical structures. PI nanowebs thus need to increase interaction between nanofibers. In this study, to improve tensile strength of PI nanowebs, composite nanowebs were prepared through thermal calendaring process using PI nanowebs and Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-co-HFP) nanowebs.

2. Experimentals 2.1.

Electro spinning process

15 wt% Poly(amic acid) (PAA) solution was prepared by dissolving the polymer in N, NDimethylacetamide (DMAc) and 24 wt% PVDF-co-HFP solution was obtained by dissolving the polymer in mixture solvent of acetone and DMAc with mechanical stirring at room temperature for 24 h. Solutions were conducted electrospun at the applied voltage of 25 kV, and tip to collector distance of 15cm.

2.2.

Heat treatment and Calendaring process

Page 153 of 1108

For preparing PI nanowebs, PAA nanowebs were heat-treated, and this route is described in Scheme 1. Imidization of PAA nanowebs were performed under nitrogen flow environment at 350 ℃ for 1 h. In addition, PI nanowebs were treated with hot drawing process under tension at 400 ℃ for 30 min. PI nanowebs and PVDF-co-HFP nanowebs overlapped each other. The layered nanowebs were post-treated on thermal calender at the 135 ℃, pressure of 0.8 MPa.

Scheme 1 : Imidization from PAA to PI

2.3.

Characterization

Melting temperature of composite nanowebs was investigated by Differential scanning calorimetry (DSC, TA Instrument, Q100, USA). Morphology of composite nanowebs was observed using a field emission scanning electron microscopy (FE-SEM, JEOl, JSM-7000F, Japan). Mechanical properties of composite nanoweb were confirmed by Instron® (Instron®, Instron 4467, USA).

3. Results and Discussion

Endo

Figure 1 shows DSC heating thermograms of PI and PVDF-co-HFP nanowebs. In Figure 1, PI shows straight line without any peak, otherwise PVDF-co-HFP display a endothermic peak at around 160℃, with the 160℃ representing the melting temperature of PVDF-co-HFP nanowebs. Consequently thermal calendering temperature set under 160℃.

(a) PI (b) P(VDF-co-HFP) 100

120

140

160

180

200

Temperature (oC)

Fig. 1 : DSC heating thermograms of PI and PVDF-co-HFP nanowebs. Figure 2 shows surface of PVDF-co-HFP nanowebs compare with thermal calendaring before and after. In Figure 2a, surface of PVDF-co-HFP nanoweb shows common nanofibers structure, otherwise Figure 2b shows bonding point between PVDF-co-HFP nanofibers after thermal calendaring process. For this reason, composite nanowebs increase interaction between PI nanowebs and PVDF-co-HFP nanowebs.

Page 154 of 1108

Fig. 2 : Surface of PVDF-co-HFP nanowebs; (a) before thermal calendering, (b) after thermal calendering Figure 3 shows strain-strength curve of nanowebs and these results are summarized in Table 1. After thermal calendaring, PI/PVDF-co-HFP nanoweb shows higher tensile strength of 11.4 MPa compared to 9.1 MPa of PI nanoweb. In addition elongation of PI/PVDF-co-HFP nanoweb increases from 260% to 331%. It comes from bonding of PI and PVDF-co-HFP nanofibers, which served to improve the mechanical property of composite membrane.

Fig. 3 : Stress-strain curves of PI, PVDF-co-HFP and PI/PVDF-co-HFP nanowebs Table 1: Mechanical properties of nanowebs PI/PVDF-co-HFP

PVDF-co-HFP

Tensile strength (MPa)

11.4

9.1

5.6

Elongation (%)

331

260

4. Conclusions In this study, we could observe variation of PI/PVDF-co-HFP nanowebs by thermal calendaring process. The DSC results showed that melting temperature of PVDF-co-HFP. FE-SEM results observed bonding points in composite nanowebs, these were made by thermal calendaring process. Also the bonding poionts enhaced interaction between PI and PVDF-co-HFP nanofibers. Tensile strength of PI/PVDF-co-HFP nanowebs increased compared with untreated nanowebs, this results supplement disadvantages of PI nanowebs.

5. References [1] J. E Lee, C. L. Lee, K. S. Park and I. D. Kim, J. Power Sources, 2014, 248, 1211-1217. [2] W Chen, Y Liu, Y Ma, J Liu and X Liu, Mater. Lett., 2014, 133, 67~70.

Page 155 of 1108

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

Chemical Resistance of Polyphenylene Sulfide Needle Non-woven Fabric Wenjun Dou Wuhan Textile University

Abstract: The basic idea of this paper is to simulate use of the environment of high temperature filter material and study chemical resistance of needle-punched nonwoven fabric made from polyphenylene sulfide (PPS). An orthogonal test was designed to investigate the interaction effect of various factors, namely concentration of hydrochloric acid and sodium hydroxide, treatment time and treatment temperature, on the needle-punched nonwoven fabric. The concentration of hydrochloric acid and sodium hydroxide and treatment time were found to have important effects on mechanical property under the condition of 0.1 significant level. While needle-punched nonwoven fabric made from PPS was still keeping its excellent breaking strength, only less than the 10% drop under the condition of 24 hours in 12 mol/L hydrochloric acid at 80â&#x201E;&#x192;. The same loss was found under the condition of 24 hours in 14.5 mol/L sodium hydroxide 80â&#x201E;&#x192;.Another factor having significant effect on mechanical property of the fabric was the oxidation of reagents. It was found that the loss of breaking strength of PPS needle-punched nonwoven fabric was more than 35%.

Keyword: needle non-woven material; filter non-woven material; polyphenylene sulfide; mechanical properties; orthogonal test

1. Introduction A major role of nonwoven fabric in air filtration is to control air pollution, especially in high temperature filtration. The main high temperature filter material is to choose the organic material to suit the high temperature environment, including polyphenylene sulfide (PPS), aramid, polytetrafluoroethylene (PTFE) and polyimide (P84) [1]. The non-woven materials is made by spun-lace, needle-punched and other molding techniques with certain finishing methods, working in high-temperature dust-laden gas filtration such as chemical, petroleum, metallurgy, cement, waste incineration and other industrial production. A great number of studies have reported on filtration performance of fiber masses [2]. However, every little work has reported on service life of the high temperature material. In actual use process, flue gas composition is relatively complex, there are SO 2 , SO3 , NO x and other alkaline tiny solid particles [3]. These industrial waste course a lot loss to the filter material [4]. In order to simulate use of the environment of high temperature filter material and study chemical resistance of needle-punched nonwoven fabric made from polyphenylene sulfide (PPS).An orthogonal test

Page 156 of 1108

was designed to investigate the interaction effect of various factors, namely concentration of hydrochloric acid and sodium hydroxide, treatment time and treatment temperature, on the needle-punched nonwoven fabric. It provides a new reference for PPS high temperature filter material more effective.

1.1 Experimental 1.2 Materials The PPS needle-punched non-woven fabric samples were prepared using production line machineries in industry and the fibres having average fineness of 2.2 dtex and length of 51 mm were used for the present study; Sodium hydroxide (NaOH, A. R.); hydrochloric acid(HCL,A.R.)

1.3 Preparation of PPS needle-punched non-woven fabric samples Opening

Carding

Lapping

Pre-needling

Needling

2.3 Methods One of the most common methods of experimental design is to vary the selected parameters to be studied one at a time, keeping all the other parameters constant. This type of study is quite useful in understanding the effect of the varied selected parameters, but this technique has a major drawback. In this type of study, the trend of response was observed [5]; while varying the selected parameters at a fixed level of other parameters, the effect may not be same at other levels of fixed parameters [6]. If the experiments are carried out on a multivariable approach, then it is quite possible to study the individual and interactive effects of the chosen variables [7]. To study the effect of the concentration of the alkali or the acid, temperature and treatment time on the fabric properties, experiments were designed as factorial design for three variables. For acid and alkali can’t coexist, therefore 2 three-variable factorial design were needed. In the actual use, not too strong the concentrations of alkaline gas near the factories, simulating physical environment, the concentration of the alkali should not be too strong, so choose a lower concentration of 1.35 mol / L and 2.8 mol / L. But in order to reflect the corrosion of alkali on the material, a group larger concentration close to saturation lye at a concentration of 14.5 mol / L is needed. A different length of time to reflect the influence of time on the material is needed, namely 3 hours, 12 hours and 24 hours. Actual use, exhausted gas from powder plant is generally about 80 ℃,close to the glass transition temperature of PPS, so temperature is chosen as 80 ℃ or so. The alkaline resistance three-variable factorial design, and the actual values of the three variables corresponding to coded levels are given in Tables 1 and 2, respectively. Table 1 the alkali resistance factor levels coding table factors level

A the concentration /（mol/L）

B temperature/（℃）

C treatment time /（h）

14.5

2.8

1.35

Table 2 the alkali resistance orthogonal experiment scheme

Page 157 of 1108

factors The experiment number A the concentration /（mol/L）

B temperature/（℃）

C treatment time /（h）

Considering the strong acidic gas from plant, a set of concentration close to the saturated concentration of hydrochloric acid larger 12 mol/L is needed. The choice of time and temperature are consistent with alkali resistance test. The acid resistance three-variable factorial design, and the actual values of the three variables corresponding to coded levels are given in Tables 3 and 4, respectively.

Table 3 the alkali resistance factor levels coding table factors level

A the concentration /（mol/L）

B temperature/（℃）

C treatment time /（h）

14.5

2.8

1.35

Table 4 the acid resistance orthogonal experiment scheme factors The experiment number A the concentration /（mol/L）

B temperature/（℃）

C treatment time /（h）

2. Results and discussion 2.1 Alkali resistance test results analysis Figure 1 and figure 2 show the SEM image of untreated PPS needle-punched nonwoven samples. Figure 3 and figure 4 show the SEM image of PPS needle-punched nonwoven samples in

Page 158 of 1108

a sodium hydroxide concentration of 14.4 mol / L, treatment temperature 80 ℃, the processing time for the 24 h.

Figure 1 SEM image (× 8000) of untreated samples

Figure 3 SEM image (× 8000) of alkali treatment samples

Figure 2 SEM image (× 1000) of untreated samples

Figure 4 SEM image (× 1000) of alkali treatment samples

Comparing Figure 1 and Figure 3, it can be seen PPS fiber surface becomes rough, and the precipitate gathered at the surface of the fiber, the fiber has a slight injury through the alkali treatment. Comparing Figure 2, Figure 4, it can be seen, the contact between the fibers reduce and there is no significant change on the fiber diameter. Table 5 Untreated PPS needle-punched nonwoven samples Elongation at break / (%)

Breaking strength /(N)

The areal density /( g/m2)

Thickness /(mm)

22.5

1150

530.5

3.2

The calculated values are shown in table 6 in accordance with table 2 and table 3. Table 6 orthogonal experiment results The experiment number

Elongation at break / (%)

Breaking strength /(N)

The areal density /( g/m2)

Thickness /(mm)

21.5

1123

533.1

3.16

22.1

995

540.1

3.69

22.3

924

549.6

3.46

22.2

960

547.5

3.32

23.1

1046

547.4

3.62

22.1

1058

562.3

3.48

22.1

942

556.8

3.61

Page 159 of 1108

23.0

1076

547.9

3.72

21.8

960

568.1

3.58

Sorting data for analysis of variance, the total sum of squares of variation is decomposed into experimental error caused by the error sum of squares as well as the level of various factors (including the interactions between factors) causing the sum of squares of factors. Comparing the two, so as to determine the impact of various factors on test index of significance, cannot make up for poor analysis to estimate the shortcoming of test error. PPS needle on the mechanical properties of the nonwoven material analysis of variance results are shown in Table 7. * Indicates a degree of influence on indicators of the factors in the significant level a = 0.1 condition it is significant, in which a = 0.1, F (2,2) = 9.

Table 7 Analysis of variance Sources of variance

Bias squares

variance

Deviation from the

Significance

mean of sum of squares A

19609.67

9804.84

3.3

7070.33

3535.17

1.2

258751

129375.66

14.5

Error e

5303.67

2952.34

The sum

290735.67

From Table 7, it can be found at significant levels 0.1, the processing time has a significant impact on breaking strength of PPS needle nonwoven. Concentration and processing temperature process had no significant influence. Which deals with the influence of concentration on the material mechanics performance slightly larger than the processing temperature. As can be seen from Table 6, PPS needle nonwovens areal density and thickness increases with treatment time. Comparing Figure.1 and 3 the fiber surface precipitation accumulates, increasing the quality of the fiber and areal density and thickness of the PPS needle nonwoven samples. PPS needle nonwovens samples’ breaking strength decreases with time. This is due to in the alkali environment, the temperature reached 80 ℃, which is close to PPS glass transition temperature where polymer chain gradually begins to move. Ever tiny change of the amorphous part of the polymer from the frozen state to thawed state will affect the structures of materials. Comparing Figure 2, Figure 4, it can be seen that the contact between the fibers decrease, resulting in the decreasing of the entanglement and the friction between the fibers and finally the decreasing mechanical properties of PPS needle-punched nonwoven samples. However, it’s the benzene ring structure that makes the molecular structure of the PPS fiber is more stable. In alkali environment, it’s mainly the volatilization of small molecules, the macromolecular chain structure is stable. Moreover, due to the high degree of crystallinity, sodium hydroxide solution is difficult to enter crystallization area of fiber molecules. So sodium hydroxide can’t cause damage to the PPS fiber molecules. After the alkali treatment, the breaking strength of PPS

Page 160 of 1108

needle-punched nonwoven samples was still able to reach about 90% of the maximum, PPS needle nonwoven materials have great alkali resistance.

2.2 Acid resistance test results analysis Figure 5 and figure 6 show the SEM image of PPS needle-punched nonwoven samples in a hydrochloric acid concentration of 12 mol / L, treatment temperature 80 â&#x201E;&#x192;, the processing time for the 24 h.

Figure 5 SEM image (Ă&#x2014; 8000) of acid-treated samples

Figure 6 SEM image (Ă&#x2014; 1000) of acid-treated samples

Comparing figure 5 with figure 1, it can be seen that there is significant damage to the fiber surface, but no significant change in fiber diameter, comparing figure 6 with figure 2, it can be seen that the spacing between fibers becomes large, reducing the contact between the fibers. The mechanical properties of PPS needle-punched nonwovens acid resistance test and analysis of variance, the results shown in Table 8. Table 8 The results of orthogonal experiment The experiment number

Elongation at break / (%)

Breaking strength /(N)

The areal density /( g/m2)

Thickness /(mm)

20.0

900

544.3

3.12

22.0

875

541.8

3.41

21.5

859

542.0

3.48

21.9

1012

554.5

3.28

21.5

1053

551.3

3.50

22.4

1095

545.6

3.59

22.1

942

556.8

3.61

20.0

900

544.3

3.12

22.0

875

541.8

3.41

** idicates a degree of influence on indicators of the factors in the significant level a = 0.1 condition it is significant, in which a = 0.1, F (2,2) = 9. Table 9 Analysis of variance Sources of variance

Bias squares

variance

Deviation from the

Significance

mean of sum of squares A

46230.67

23115.36

374.85

1455

727.5

11.80

Page 161 of 1108

5876.67

2938.34

Error e

123.33

61.66

53685.67

The sum

47.65

From Table 9, it can be found at significant levels 0.1, the concentrations of hydrochloric acid has a very significant impact on breaking strength of PPS needle nonwoven samples. Then is the processing time, the temperature has the least impact on breaking strength of PPS needle nonwoven samples, but has a certain impact. As can be seen from Table 8, PPS needle nonwovens areal density and thickness increases with increasing concentration of hydrochloric acid. Comparing figure 2 and figure 6 the fiber surface precipitation accumulates, increasing the quality of the fiber and areal density and thickness of the PPS needle nonwoven samples. There are precipitation accumulation and obvious damage on the fiber surface, which means the fibre is corrupted by hydrochloric acid corrosion and generate new material adhesion on the fiber surface. Therefore, the areal density and thickness of the PPS needle-punched nonwovens increase with the increasing of the concentration of hydrochloric acid. PPS needle-punched nonwovens samples’ breaking strength decreases with the increasing concentration of hydrochloric acid. Comparing figure 1and figure 5, it can be seen that the interval between the fibers becomes larger, contact between the fibre becomes less. Under the corruption of hydrochloric acid, the contact and friction between the fibers reduce, resulting PPS needling-punched nonwovens samples’ breaking strength with increasing concentration of hydrochloric acid decreases. In hydrochloric acid solution, while the fiber surface has obvious damage, but material can still keep more than 75% of the highest breaking strength in concentrated hydrochloric acid. This is because the presence of benzene ring structure of PPS fiber molecular formula, whose benzene ring of PI bond energy is high, 619 KJ/mol, not easy to break. This is the reason why the PPS fiber has excellent chemical resistance to avoid to be corrupted. However, benzene and sulfur molecules linked together, bond energy is relatively lower, 271 KJ / mol, the benzene ring meta position is opened easily by oxidants causing chemical reaction, which will destroy the molecular structure of the PPS fiber. However concentrated hydrochloric acid is not the oxidizer. It’s the oxygen in an acid environment that oxides the benzene ring meta position leading to the destruction of the material and mechanical properties, rather than the corrosion of the hydrogen ion directly. Namely PPS needle-punched nonwoven material has good acid resistance.

3. Conclusions Needle-punched nonwoven fabric made from PPS still kept its excellent breaking strength, only less than the 10% drop under the condition of 24 hours in 12 mol/L hydrochloric acid at 80℃. The same loss was found under the condition of 24 hours in 14.5 mol/L sodium hydroxide 80℃. PPS needle-punched nonwoven material has excellent chemical resistance. In the alkali resistance test, the effect of treatment time on breaking strength of PPS Needle-punched nonwoven samples is remarkable. In acid resistance test, concentration of hydrochloric acid has a significant impact on breaking strength of PPS Needle-punched nonwoven samples.

Page 162 of 1108

4. Reference [1] Wang C,Lin H,cen Y Y. Study on the preparation of steady-state chitosan nanoparticle as silk-fabric finishing agent [J]. Advanced Material Research. 2011.175: 745-749. [2] Honghong Yi，Jiming Hao，Lei Duan．Fine particle and trace element emissions from an anthracite coalfired power plant equipped with a bag-house in China[J]．Fuel，2007，11：2050-2057． [3] Fuping Qian，Hmgang Wang．Retracted：Study of the filtration performance of a plain wave fabric filter using response surface methodology[J].Journal of Hazardous Materials，2010，176(1-3)：559-568． [4] Rajesh D. Anandjiwala, Lydia Boguslavsky. Development of Needle-punched nonwoven fabrics from flax fibers for air filtration applications[J].Textile Research Journal，2008，78(7)：614-624. [5] G. E. P. Box, D. W. Behnken. Some new three level designs for the study of quantitative variables [J]. Technometrics, 1960, 2(4):455-475. [6] V. K. Kothari& A. Das. The Compressional Behaviour of Spunbonded Nonwoven Fabrics [J]. Journal of the Textile Institute, 1993, 84(1):16-30. [7] Filter media endure tough conditions，Membrane Technology, 2005.11:25-36.

Page 163 of 1108

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

Cost-efficient and flexible production of high quality fabrics for composite applications Klingele, Josef Lindauer DORNIER GmbH

Abstract: The use of innovative reinforcement materials is a key aspect of future lightweight designs. Woven textiles typically offer good overall properties and can be adjusted to the specific needs by a multitude of production parameters. Therefore, in a variety of applications woven structures are used as reinforcement of fiber reinforced plastics (FRP) with thermoset matrices. With increasing relevance of FRP with thermoplastic matrices, innovative materials and production processes are currently emerging. This leads to new requirements for all players along the value chain for this promising class of lightweight materials. Typically, repeatability and capability of all production processes from the roving to the composite part are of greatest relevance. As for woven fabrics, both the position of the fibers within the textile structure and the interlocking of the fibers is determined precisely during the weaving process. The weaving pattern, and therefore the path of the fiber can be defined in the controller of the weaving machine. In fact, Jacquard looms in the early 18th century can be described as the first completely digitalized production machines in history – with punched cards storing the digital information about the warp yarn movements. With recent developments in drive and control technology, this machine type is becoming powerful enough to tackle todays challenges in composite manufacturing. Being an established manufacturer of weaving machines for reinforcement structures such as carbon fiber woven fabrics, Lindauer DORNIER is now enforcing its commitment regarding composite production technologies. With DORNIER Composite Systems®, the company is providing a family of machines for the manufacturing of FRP. This includes the production technology for unidirectional (UD) tapes and the processing of such tapes by means of tape weaving technology. In this presentation, both the targets and the technological approaches regarding these technologies is described. Also, the innovative use of Jacquard weaving for the production of complexly shaped 3D-parts is presented. It is shown that the combination of different members of the DORNIER Composite Systems® machine family allows for the cost efficient and flexible production of high quality composites materials. Keywords: Tape Production, Tape Weaving, 3D-Weaving, Tape Fabric, Spreading, Thermoplastic composite

1. Motivation 1.1.

Woven fabrics for composite applications

For the production of continuous fiber reinforced composites, a large variety of materials and process routes is currently used. The selection of suitable manufacturing routes is typically done based on certain boundary conditions which include: • Mechanical, physical and chemical composite properties • Production volume, cycle times and available production technology • Accepted manufacturing/material costs and necessary certifications and documentation At the moment, woven fabrics are among the most widely used textile structures for high performance carbon fiber reinforced plastics (CFRP). This includes both applications with thermoset matrix (e.g. woven prepreg) and thermoplastic matrix (e.g. woven organo sheets). The reasons for the use of woven textiles are manifold. As for dry woven fabrics, both drapeability and permeability of the structures is advantageous. For thermoset prepregs, woven structures have been used for many years, resulting in good availability of certified

Page 164 of 1108

materials, robust production technology and knowledge of the material properties. However, there are certain challenges regarding the properties and production technology for reinforcement woven fabrics.

1.2.

Challenge 1: Low grammage with heavy tow

Typically, the price of carbon fiber (per kg) decreases significantly with an increasing filament count. In terms of material cost, it is therefore favourable to process carbon fiber materials with high filament counts such as heavy tow material (i.e. >24.000 individual filaments, 24k). At the same time, grammages (i.e. fiber areal weight) are often needed to meet the material property requirements. However, fabrics with low grammages typically require low filament counts of the carbon fiber roving. As shown in Fig. 1, grammages below 150 g/m² are typically manufactured using 1k or 3k carbon fiber (CF) rovings [1],[2],[3]. As for 24k rovings, grammages of in the area of 800 g/m² are typical for unspreaded fabrics. By means of processing the woven fabric with PrimeTex® proprietary spreading technology, grammages of 330 g/m² for 24k roving material are possible. Yet, current weaving technology is not suitable for the production of high quality fabrics with low grammages (<150 g/m²) using heavy tow material (>24 k). To achieve such textile structures, weaving of spreaded unidirectional (UD) fiber tapes is a promising approach. However, both the availability of technologies for production and weaving of such tapes is limited.

grammage [g/m²]

12k

24k

900 800 700 600 500 400 300 200 100 0

Fig. 1: Typical grammages of commercially available woven carbon fabrics [1],[2],[3].

1.3.

Challenge 2: Production and processing of unidirectional fiber tapes

To cut down cycle times and reduce costs in composite production, thermoplastic matrix materials have very interesting properties. But because of the high viscosity of thermoplastic materials even in molten state, infiltration processes as for thermoset matrices are not suitable for thermoplastic matrix processing. Thermoplastic fiber tapes combine reinforcement fibers and matrix material at meso-scale (i.e. roving-level) and are a suitable intermediate product for various process routes. Two exemplary process routes for the production of composite parts with both thermoplastic and thermoset matrix material by means of UD tapes are shown in Fig. 2. The use of woven tape fabrics has a great potential for composite production. This is because weaving allows for reliable and automated production processes, exact fiber orientation, low undulation, no additional binder yarn and high productivity. However, conventional weaving machines are not able to process UD tapes. This is due to the fact that many parts (i.e. rapier system, presentation device…) of the weaving machine are not designed to process wide tapes of more than 10 mm width.

1.4.

Challenge 3: Realization of complex fiber architectures

The material properties of CFRP are greatly influenced by the fiber orientation within the matrix. To improve the out of plane properties, the introduction of fibers in z-direction can be favourable. The design of 3D-fiber architectures is widely described by researchers. Also, there are some very promising industrial applications of 3D-woven structures in aerospace industry [4]. Yet, the production of such complex 3D-fiber architectures remains challenging regarding productivity and flexibility.

Page 165 of 1108

Tape production

Forming

Tape weaving

Hotforming

Roving

Tape

Binder

Preform

Composite Part

Thermoset Infusion (RTM…)

Fig. 2: Exemplary process routes for the production of composite parts by means of tape fabrics.

1.5.

Development targets and approach

As described above, there are many challenges regarding the cost-efficient and flexible production of high quality fabrics for composite applications. To fully exploit the technical and economical potential of these structures, the following targets can be identified: • Production of spreaded fiber tapes for both thermoset and thermoplastic matrix systems • Weaving of unidirectional fiber tapes • Production of complex 3D-fiber architectures In the following, three machine concepts are presented which are suitable to tackle these challenges. The technologies are described and evaluated regarding efficiency, flexibility and product quality.

2. Production Technology 2.1.

Tape Production

For the production of spreaded fiber tapes, all production parameters must be set according to the desired product properties i.e. the application. In order to allow for such flexible production, a highly modular machine concept was developed by DORNIER. In fact, the entire machine is set up according to DORNIER Toolbox for Tape Production - a tool for modular machine development. In the following two favourable process routes as shown in Fig. 2 and an accordingly designed lab-scale tape production machine is described.

100 µm

20 µm

Fig. 3: DORNIER lab line for tape production (left) and microscopy image of dry carbon fiber spreaded tape (right)

As for thermoplastic tapes, the rovings is first spread by means of a proprietary spreading technology. The spreaded fibers are then pre-fixated with a matrix compatible binder material in a dip-coating process with an

Page 166 of 1108

aqueous suspension. After heating and drying, the pre-fixated fibers are impregnated with the thermoplastic matrix material by means of an innovative flat die. Here, the molten polymer which is fed from an extruder through heated pipes, is pressed into the fiber material. For cutting the tape, different cutting technologies are available. For the production of “dry” tape material, the spreaded tape is pre-fixated with a resin-compatible (i.e. epoxy) binder material. This is also done by means of an aqueous suspension with binder particles. After heating and drying, the tape is directly wound. If necessary, the tape can be cut online or offline to the desired tape width. While the commercially available tape production line features a working width of 600 mm, a laboratory line for the production of 70 mm wide dry and thermoplastic tapes is shown in Fig. 3 (left). The lab line is available at DORNIER in Germany and is used for both internal research projects and customer trials. A microscopy image of a spreaded carbon fiber roving with Co-PA binder material is shown in Fig. 3 (right).

2.2.

Tape Weaving

Compared to weaving of conventional technical textiles, the weaving of UD fiber tape material requires specific solutions for many machine components. This includes • Feeding the tape into the weaving machine • Gripping the tape with the rapier • Beat up of the tape with the reed • Realizing a suitable shed geometry In the following, an innovative machine concept is described which allows for the weaving of UD tape material. The machine is shown in Fig. 4 (left). It features a zero twist feeder working in yo-yo principle for constant tension in the weft tape. Two weft material bobbins can be used simultaneously to achieve continuous fabric production. The presentation of the weft tape is realized by means of a complex cinematic with individual servo-motors. The rapier head is adapted to grip up to 25 mm wide tape. Since a conventional beatup with a reed would damage the weft tape, a novel displacement motion was developed. Here, the fabric is moved backwards to securely grasp the inserted weft tape. The machine can be used to produce fiber tape fabrics at speeds of up to 50 picks/min. The resulting tape fabrics can be hot-formed into complex shapes as shown in Fig. 4 (right).

50 mm [DORNIER / CrossLink Faserverbundtechnik]

Fig. 4: DORNIER Tape weaving machine (left) and hot formed carbon fiber tape fabric (left)

2.3.

3D-Weaving

For the production of reinforcement structures with three-dimensional fiber architecture, 3D-weaving is a very promising technology. A novel weaving machine was developed by DORNIER which allows for the efficient production of such 3D-fabrics from a wide range of fiber materials. Here, the reinforcement fibers are taken up from a creel and are then woven in complex patterns using Jacquard technology. The rapier is run in “free flight mode” i.e. without a raceboard. Therefore, the entire weft insertion can be realized without contact between rapier head and warp threads which leads to reduced filamentation of the warp material. Furthermore, the UNIVAL® Jacquard machine can be used to realize complex and favourable shed geometries to run the machine at high production speeds. The weaving machine at DORNIER composite facilities is shown in Fig. 5. It is currently used for both internal research project and customer trials.

Page 167 of 1108

Fig. 5: DORNIER 3D-weaving machine at DORNIER Composite Systems® laboratory facilities.

3. Summary To tackle today’s challenges in composite manufacturing, tape production, tape weaving and 3D-weaving are suitable means. Being an established machine manufacturer for the composite industry, Lindauer DORNIER GmbH has developed three novel machine types under the brand DORNIER Composite Systems®. For the production of both thermoplastic and “dry” unidirectional fiber tapes, a highly modular tape production line allows for high quality spreading, pre-fixation, impregnation and slitting of the tape. While a laboratory line with a working width of 70 mm is available for trials, the commercial line is running at 600 mm working width. For the production of tape fabrics, an innovative tape weaving machine is available. Tapes of up to 25 mm width can be converted into tape fabrics which feature low undulation, low grammage and good drapeability. To realize complex three-dimensional reinforcement structures, an innovative 3D-weaving machine was developed and is available at DORNIER Composite Systems® laboratory facilities. With this machine technology, multilayer structures and complex geometries can be manufactured at high production rates.

4. References [1] SGL Technologies GmbH: SIGRATEX® Textile Materialien aus Carbon-, Glas- und Aramidfasern http://www.sglgroup.com/cms/_common/downloads/products/product-groups/cm/textileproducts/High_Performance_Textiles_d.pdf (access 08/2015) [2] Hexcel Corporation: Selector Guide Industry http://www.hexcel.com/Resources/SelectorGuides/Industrial_SelectorGuide.pdf (access 08/2015) [3] Toho Tenax Co. Ltd.: Properties of TENAX® Woven fabric http://www.tohotenax.com/tenax/en/products/pdf/w_property.pdf (access 08/2015) [4] Ginger Gardiner: Albany Engineered Composites - Weaving the Future in 3-D, High-Performance Composites http://www.compositesworld.com/articles/albany-engineered-composites-weaving-the-future-in-3-d (access 08/2015)

Page 168 of 1108

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

Crystallization Kinetics and Structural Features of Polyarylate/ Nylon6 Island-in-the-sea Fibers Used for Thermoplastic Composites Jinho Park 1, Sung Chan Lim 1, Jong Sung Won 1, Seung Goo Lee 1, Wan Gyu Hahm 2, Jong Kyoo Park 3 and Young Gyu Jeong 1 + 1

Department of Advanced Organic Materials and Textile System Engineering, Chungnam National University, Daejeon 34134, Republic of Korea 2 Korea Institute of Industrial Technology, Cheonan 31056, Republic of Korea 3 Agency for Defense Development, Daejeon 34188, Republic of Korea

Abstract. The mechanical properties of thermoplastic composites fabricated from a series of prepregs, which were composed of uniaxially aligned polyarylate(PAR)/nylon6 island-in-the-sea fibers, have been recently found to be strongly dependent on melt-compression conditions such as temperature, pressure, and time. In order to understand the structure-process-property relationship of the thermoplastic composites, we have investigated the isothermal crystallization kinetics and associated morphological features of the PAR/nylon6 fibers by using differential scanning calorimetry and polarized optical microscopy, respectively. From the isothermal crystallization kinetics analysis of the PAR/nylon6 fibers by using the Avrami relationship, it was found that the nylon6 matrix in the fibers exhibited highly enhanced crystallization rates, compared to the neat nylon6, and that the heterogeneous nucleation and following low-dimensional crystal growth of the nylon6 matrix was dominated by the presence of PAR components in the fibers. This transcrystalline structural feature of the nylon6 matrix on the surface of PAR fiber components was also identified by POM images.

Keywords: polyarylate, nylon6, island-in-the-sea fiber, isothermal crystallization, transcrystallization.

1. Introduction Polyarylates (PAR) as wholly aromatic polyesters are a family of high-performance engineering polymers noted for their high mechanical strength/toughness, chemical resistance, and impact absorption. Due to these well-combined excellent properties, PAR has been employed in various applications such as automotive parts, electronic devices, sports goods, etc. Since PAR can be melt-spun into superfibers with high strength, low moisture absorption, and superior abrasion resistance, PAR fibers have been employed for making ropes, fishing nets, sheathing, protective gloves/shoes, and many other products. Nylon6 also has high strength and melting point of ~220 째C. Owing to these properties, nylon6 is used in various categories such as textile fibers, engineering plastics, automotive industry, etc. Recently we have manufactured a series of PAR fiber-reinforced thermoplastic composites by melt-compressing of uniaxially aligned PAR/nylon6 island-in-the-sea fibers, which were obtained by a conjugate melt-spinning process, and have investigated their structures and mechanical properties as functions of melt-compression variables such as temperature, pressure, and time. The mechanical properties of thermoplastic composites manufactured from uniaxially aligned PAR/nylon6 islandin-the-sea fibers were found to be strongly influenced by the melt-compression conditions. It is thus conjected that the mechanical properties of PAR/nylon6-based thermoplastic composites are highly influenced by the interfacial adhesion between PAR fibers and nylon6 matrix [1]. In the present study, in order to understand the structure-processing- property relationship of the PAR fiber-reinforced thermoplastic composites, we have investigated the crystallization kinetics and associated morphological features of the PAR/nylon6 island-inthe-sea fibers by using differential scanning calorimetry and polarized optical microscopy, respectively.

Corresponding author. Tel.: + 82-42-821-6617. E-mail address: ygjeong@cnu.ac.kr.

Page 169 of 1108

2. Experimental 2.1.

Materials

Neat PAR fiber, nylon6 chips (BRT 1011, Hyosung), and PAR/nylon6 island-in-the-sea fibers were obtained from Korea Institute of Industrial Technology (KITECH). The PAR/nylon6 island-in-the-sea fibers were manufactured by a conjugate melt-spinning process at a variety of rates of 1000, 1500, and 2000 m/min.

2.2.

Characterization

The thermal transition characteristics and isothermal crystallization behavior of PAR/nylon6 fibers were characterized by using a differential scanning calorimeter (DSC 1, Mattler-Toledo). The crystalline structural features of PAR/nylon6 fibers obtained at different cooling rates were identified by using a polarized optical microscope (S38, Bimience) equipped with a temperature-controllable hot state.

3. Results and Discussion 3.1.

Isothermal Crystallization

The isothermal crystallization experiments of PAR/nylon6 fibers were carried out at different isothermal crystallization temperatures (T c ) of 185-205 °C. As a result, the changes of heat flow with time at different isothermal crystallization temperatures were obtained, as shown in Fig. 1. It was found that the crystallization rates of the PAR/nylon6 fiber were much faster than those of neat nylon6 at a same isothermal crystallization temperatures, which might be owing to the nucleation effect of PAR components during the meltcrystallization of nylon6 matrix in the fibers.

Fig. 1: Time-dependent heat flow curves of (a) PAR/nylon6 island-in-the-sea fiber (b) nylon6 chips during isothermal melt-crystallization at different temperatures of 185, 190, 195, 200 and 205 °C.

To analyse the isothermal crystallization kinetics of PAR/nylon6 fibers and neat nylon6, the following Avrami equation was adopted [2]

1 − θ= exp(− Kt n )

(0.1)

where θ is the crystallinity fraction of crystallisable polymer at time t, n is the Avrami exponent on the nature of nucleation and growth geometry of the crystals, and K is the temperature-dependent crystallization rate constant. In the case of the DSC experiment, θ is evaluated as the ratio of the area under the exothermic curve between the onset crystallization time and the crystallization time t to the whole area under the exothermic curve from the onset crystallization time to the end crystallization time. The half-life crystallization time, t 0.5 , is the time required to attain 50% of the final crystallinity of the samples and it is an important parameter for the discussion of crystallization kinetics. The parameters n and K were obtained by fitting isothermal crystallization data with the following modified relationship of the Avrami equation.

log K + n log t = log[− ln(1 − θ )]

(1.2)

Fig. 2 demonstrates the plots of relative crystallinity against crystallization time and associated Avrami plots for PAR/nylon6 and neat nylon6. All the crystallization kinetics parameter for the isothermal crystallization at various crystallization temperatures are summarized in Table 1. For a given crystallization temperature, the t 0.5 values of the PAR/nylon6 fibers are lower than those of neat nylon6. In addition, the higher K values of

Page 170 of 1108

the PAR/nylon6 fiber are attained, compared with the neat nylon6. It indicates that the isothermal crystallization of the nylon6 component in the PAR/nylon6 fiber is faster than that of the neat nylon6, since the PAR component serves as a nucleating agent for the crystallization of nylon6 component in the fibers. On the other hand, the n values of the PAR/nylon6 fiber are lower than those of the neat nylon6 at a given crystallization temperature. It suggests that spherulitic growth of nylon6 crystals is restricted by the presence of PAR components dispersed in the fiber, although the PAR components serve as nucleating agents for the nylon6 crystals.

Fig. 2: The Avrami plots of (a) PAR/nylon6 fiber and (b) neat nylon6, and the changes of relative crystallinity with crystallization time of (c) PAR/nylon6 fiber and (d) neat nylon6. Table 1: Isothermal crystallization kinetics parameters of PAR/nylon6 and neat nylon6 powder. Sample

PAR/nylon6 fiber (1500 m/min)

Neat nylon6

3.2.

T c (°C)

K (sec-n)

t 0.5 (sec)

185 190 195 200 205 185 190 195 200 205

1.6 1.9 2.3 2.5 2.7 2.8 3.1 2.7 2.6 2.5

1.56×10-2 2.90×10-3 1.37×10-4 3.77×10-6 2.01×10-8 2.97×10-6 1.24×10-7 1.42×10-7 2.91×10-8 8.02×10-9

10 17 39 116 556 80 146 276 679 1308

Morphological Features

Fig. 3 shows the POM images of the PAR/nylon6 crystallized at slow and fast cooling rates. For the fiber crystalized at a slow cooling rate, well-developed transcrystalline features of nylon6 around a single PAR fiber were observed (Fig. 3a). On the other hand, the transcrystallization of nylon6 on the surface of PAR fiber was

Page 171 of 1108

restricted, when the sample was prepared at a fast cooling rate (Fig. 3b). Overall, it is reasonable to contend that the crystallization of nylon6 matrix in the PAR/nylon6 fiber was dominated by the spherulitic growth with heterogeneous nucleation by the existence of PAR.

Fig. 3: POM images of transcrystallization between polyarylate fiber and nylon 6 matrix at slow cooling (a) and fast cooling (b).

4. Conclusions In this study, the isothermal crystallization kinetics and associated crystalline features of the PAR/nylon6 island-in-the-sea fibers were investigated by taking account the Avrami relationship and transcrystallization behavior. The overall crystallization rates of the nylon6 component in the fibers were found to be much faster than those of the neat nylon6. The POM images confirmed that the crystallization of nylon6 as the matrix component took place dominantly via the spherulitic growth with heterogeneous nucleation at the surfaces of PAR components in the fibers. It is thus believed that the mechanical properties of PAR/nylon6 fiber-based thermoplastic composites, which are dependent on the melt-compression temperatures, could be influenced by the transcrystallization behavior of nylon6 matrix on the surfaces of PAR components in the island-in-the-sea fibers.

5. References [1] Felix, J. M., and Gatenholm, P., J. Mater. Sci., 1994, 29(11), 3043-3049. [2] Avrami, M., J. Chem. Phys., 1939, 7(12), 1103-1112.

Page 172 of 1108

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

Development of Composite Technical Filament for Smart Applications Ali Afzal 1 , 2 +, Nabyl Khenoussi 2, Sheraz Ahmad 1, Jean Yves Drean 2 and Niaz Ahmad Akhtar 3 1

National Textile University, Pakistan Université de Haute-Alsace, France 3 University of Engineering & Technology Taxila, Pakistan 2

Abstract. The aim of this study is to develop a specialized oval shaped core sheath technical filament for smart applications. The developed specialized composite filaments finds its application in electromagnetic shielding, electrical signal transmission, electrical heating pads and microelectronics etc. In this study copper wire was used as a core filament having a diameter of 50μm while virgin polyester resin was used as the polymer matrix. The modified conventional lab scale melt extrusion machine was used for this study. The round shaped spinneret was chosen for extrusion of composite filament. The oval shaped composite filament having core at the edge of composite filament, at distance of 20-25μm from surface was developed. The major to minor diameter ratio was 1.5 with minor diameter of 450μm. The developed filament can be used for effective heat generation, signal transmission and microelectronics in moist conditions without any short circuiting. Keywords: Composite filament, Copper wire, Heating, Polyester, Technical filament.

1. Introduction Composite technical filaments are multifunctional filaments which can be used as smart materials in functional textiles. These filaments have considerable importance in smart and functional textiles. Electrically conductive textiles are one of the basic areas of smart textile. Conductive textiles are the upcoming high tech field of textiles in regards of performance, application and uses. This area finds its application in fields such as electromagnetic shielding, antistatic, microelectronics, heat generation and textile sensors etc. Textiles products during their life cycle required washing and cleaning as well as also exposed to water in different ways such as in form of perspiration, rain fall and accidental wetting etc. Owing to conductive yarns present in the textile structure, water content short circuited the conductive yarns resulting in damaging of their required characteristics and therefore limiting their use and shortening of their life cycle. In a study, Alagirusamy et. al. [1] worked on insulation coating of conductive yarns. They coated polypropylene fibres with the help of friction spinning on the single and plied structure of silver coated polyamide yarns followed by melting of coated fibres to convert into a uniform coated sheet and observed the insulation obtained thereafter in presence of water as well as their impact on tenacity and flexural rigidity of the conductive yarn. In another study, Afzal et. al. [2] and Khoffi et. al. [3-5] developed a composite fiber having core of copper filament with sheath of polyester using melt spinning technique. The developed filament can be used for signal transmission in fabric structures. Kechiche et. al. [6] developed a coaxial composite fiber using poly(vinyledene fluoride-trifluoroethylene) and copper filament. The developed fiber can be used as sensor and can be incorporated in textile material for online data acquisition. Sato et. al. [7] developed a composite

Corresponding author. Tel.: + 92-322-4075 177. E-mail address: aliafzalch89@gmail.com.

Page 173 of 1108

sheath/core fiber having metal in the core with sheath of lead zirconate titrate (PZT). They used this fiber as sensor for the detection of resonance vibrations. Sancak et. al. [8] used copper and stainless steel wire to fabricate cotton coated composite yarns for electromagnetic shielding applications. Bedeloglu et. al. [9] investigated the mechanical and electrical properties of composite metallic core cotton yarn. Rajendrakumar and Thilagavathi [10] also used core sheath yarn of copper cotton composite for electromagnetic shielding purpose. Same like, Liu and Wang [11] used stainless steel cotton blend with different linear densities to develop blended electromagnetic shielding fabric. Ortlek et. al. [12] manufactured a composite yarn made of stainless steel core with cotton as sheath. The present paper deals with development of a moisture insulated filament used for efficient heating application in textile structures. This textile structure developed with such a filament should be washable resultantly increases the product life cycle.

2. Materials and Methods The conductive core of the composite filament was composed of copper monofilament produced by Goodfellow with 99.9% purity having diameter of 50±5µm. The technical data of the copper monofilament is shown in Table 1. The virgin polyethylene terephthalate polymer was used as resin matrix in shape of pallets for the development of the composite filament. The rheological properties of the polyester are shown in Table 2. Table 1: Technical specifications of copper monofilament Attribute Temper Form Diameter Purity Density at 20°C Melting point Boiling point Tensile strength Thermal conductivity from 0°C to 100°C Specific heat at 25°C

Value As drawn 50±5µm 99.9% 8.96g cm-3 1083°C 2567°C 224MPa 401W K-1 m-1 385J K-1 Kg-1

Table 2: Rheological properties of polymer

PET

Intrinsic viscosity [dL/g]

Content of COOH [mol/t]

Color value (b)

Melting point [°C]

0.675

4.0

260

Page 174 of 1108

Fig. 1: Melt spinning machine.

The lab scale melt extrusion machine marketed by FilaTech GmbH was used for the development of composite filaments (Figure 1). It comprised of spinneret head, winding section and control section which controls the whole process. The machine is designed for the manufacturing of monofilaments with various controlling parameters including the extrusion speed at range from 0.1 mm/min to 20 mm/min, oven temperature selected up to 350Â°C and winding speed can be varied up to 200 rev/min. The piston extrusion mechanism made it possible to use hollow piston for the passage and delivery of copper monofilament through it. The single hole conventional round shaped spinneret having internal diameter of 1mm was used as shown in Figure 2.

Fig. 2: Spinneret shape.

3. Results and discussion The obtained results revealed that copper core was located at the extreme edge of the composite filament with edge to core distance of 22Âą2Âľm at one side of major axis of oval shaped filament as shown in Figure 3.

Page 175 of 1108

Fig. 3: Cross sectional shape of composite technical filament.

The polymer covered the conductive core completely at extreme location of oval shape. This structure would be used to transfer heat through the moisture resistant cladding by the conductive core of composite filament in textile structure. The layer of the moisture resistant polymer was so small at one edge that it heat can be passed easily through it for the development of heating pad in textile material.

4. Conclusion A new structural design of composite filament was developed for specialized application areas. The oval shaped polyester composite filament with conductive copper monofilament as core was developed using melt extrusion process. The developed composite filament have core at edge of oval structure of the filament. The thin layer of polymer at one side of the conductive core made it possible to transmit heat through it and can be easily and effectively used in electrical heating pads in textile structures in moist conditions. Furthermore, the developed composite filament can also find its application in signal transmission and microelectronics in textile structures.

5. References [1] [2]

[3] [4] [5] [6] [7] [8]

[9]

[10] [11] [12]

R. Alagirusamy, et al., "Coating of conductive yarns for electro-textile applications," Journal of The Textile Institute, pp. 1-8, 2012. A. Afzal, et al., "Influence of drawing parameter on the development of composite polymeric technical filaments," presented at the 3rd International Conference on value addition and innovation in textiles, Faisalabad, Pakistan, 2015. F. Khoffi, et al., "Mechanical behavior of polyethylene terephthalate/copper composite filament," Physics Procedia, vol. 21, pp. 240-245, 2011. M. B. Kechiche, et al., "Mechanical characterization of composite Polyethylene Terephtalate / Copper filaments," presented at the Fiber Society Conference, Saint Gall, Switzerland, 2012. M. B. Kechiche, et al., "The development and characterization of conductive composite filaments," presented at the AUTEX International Conference, Mulhouse, France, 2011. M. B. Kechiche, et al., "Development of piezoelectric coaxial filament sensors P(VDF-TrFE)/copper for textile structure instrumentation," Sensors and Actuators A: Physical, vol. 204, pp. 122-130, 2013. H. Sato, et al., "Metal Core Piezoelectric Complex Fiber and Application for Smart System," presented at the MRS Proceedings, 2005. E. Sancak, et al., "An investigation of electromagnetic shielding effectiveness of knitting fabrics with different metal wire," presented at the 2nd International Conference on Value Addition & Innovation in Textiles, Faisalabad, Pakistan, 2013. A. Bedeloglu, et al., "Bending and tensile properties of cotton/metal wire complex yarns produced for electromagnetic shielding and conductivity applications," Journal of The Textile Institute, vol. 103, pp. 13041311, December 1 2012. K. Rajendrakumar and G. Thilagavathi, "A study on the effect of construction parameters of metallic wire/core spun yarn based knitted fabrics on electromagnetic shielding," Journal of Industrial Textiles, March 21 2012. Z. Liu and X. Wang, "Relation between shielding effectiveness and tightness of electromagnetic shielding fabric," Journal of Industrial Textiles, February 11 2013. H. G. Ortlek, et al., "Determination of electromagnetic shielding performance of hybrid yarn knitted fabrics with anechoic chamber method," Textile Research Journal, vol. 83, pp. 90-99, January 1 2013.

Page 176 of 1108

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

Development of hydrophilic polyamide and its applications on functional textiles Wei Hung Chen, Wei Hsiang Lin, Wei Peng Lin, Ko Feng Chen, Ta Ko, and Ta Chung An Department of Raw Materials and Yarns, Taiwan Textile Research Institute (TTRI), Taiwan

Abstract. In the work, we designed and synthesized a modified polyamide which features high moisture regain and moisture desorption ability, a highly hydrophilic nylon. The modified polyamide was copolymerized by caprolactam, adipic acid and polyesteramide via copolymerization. With spinning process, we made this copolymer into nylon fiber, and use this fiber to make fabrics. △MR is a reasonable indicator for the feeling of comfortableness of worn clothes, and the moisture absorbing ability △MRa and moisture releasing ability △MRd of these fabrics are 4.6% and 4.3%, higher than regular nylon. (The △MRa and △MRd is 2.2% and 2.0%) The result demonstrate the clothes made by this modified fiber, would provide a better comfortableness to the wearer. The other important feature of this hydrophilic nylon fiber, is it could provide the cool feeling function for fabrics, The heat transferring ability of fabrics were testing by FTTS-FA-019, and the Q-Max value of fabric made with this fiber is 0.21 W/cm2, much better than original nylon.(Q-Max=0.14 W/cm2). These test result demonstrate the hydrophilic polyamide was a suitable material for functional fiber and applied on cool feeling textile products. Keywords: polyamide, nylon fiber, copolymerization.

1. Introduction A polyamide is a macromolecule with repeating units linked by amide bonds. [1] Polyamide can convert to nylon fibers through melt-spinning process. Nylon is a man-made fiber wildly used in textiles due to their high durability and strength. Although nylon had better water absorbs ability than PET, the most popular man made fiber in the world, but it absorbs less moisture than nature fibers. It makes the skin feel sticky and uncomfortable under certain circumstances. [2] In some works, the water uptake ability of nylon fabrics had been improved by surfaced modification using plasmas. [3] In others, vinyl oracrylic monomer has been grafted onto the nylon to enhance its water absorption. [4] Many polymers including polyurethanes, polyester, polyimide, and polyamide was cooperated with poly(ethylene oxide) (PEO) to improve their moisture regain.[5] PEO provides flexible segments and hydrophilic moieties, which enable the nylon/PEO fiber to perform like a natural fiber,[6] However, investigations of the basic properties of nylon/PEO copolymer and fiber, including their thermal properties and physical properties, are very few.

2. Experimental In this study, a series of PEO-copolymerized polyamide with various poly(ethylene oxide) diamine (PEODA) content were synthesized. Figure 1~3 describes the chemical reaction that then occurred. All of the prepared copolymers were tested to determine their molar mass was examined by performing basic analyses such as relative viscosity (RV) and amino-end group analysis. The thermal properties were investigated by differential scanning calorimetry (DSC). More investigations of the fibers, examining the moisture regain was carried following fabric formation. The fiber strength, elongation, moisture regain and desorbs ability were tested by regular methods. The maximum heat flux, Qmax, which indicated a material warm/cooling feeling was also measured.

Page 177 of 1108

Fig. 1: Synthesis of PA6/PEO copolymer

Fig. 2: Synthesis of PA610/PEO copolymer

Fig. 3: Synthesis of PA11/PEO copolymer

2.1.

Materials

Caprolactam (CPL, >99.9%) was purchased from DSM. PEODA (>99%) was obtained from Huntsman, and its molar mass was about 2000 and 900, the product name is ELASTAMINE速 RE-2000 and ELASTAMINE速 RE-900 respectively. Adipic acid (>99.9%) was supplied by BASF. HMDA (Technical grade, 70% and remainder water 30%) and 11-Aminoundecanoic acid were provided by Aldrich. The sebacic acid(>99.9%) was purchased from DuPont.

2.2.

Polymerization

The hydrolytic polymerization in a batch was used to obtain the nylon and its copolymers. The hydrolysis and addition reactions took place at the first stage where the pressure was maintained and water was held. The second step, a poly-condensation stage, carried on when the reactor was switched to a vacuum condition to suck the water out. The reactor was purged by nitrogen several times before heating to ensure that it contained no residual oxygen. Scheme 1~3 describes the chemical reaction that then occurred. The molar mass was accelerated under the vacuum condition, and the desired molar mass was reached after 2~3 h. The molten copolymer was then cooled and pelletized. Table 1~2 presents all of the constituents of the copolymers.

Page 178 of 1108

Table 1: Formulation of Prepared Nylon 6 Copolymers Symbol PA6-1 PA6-2 PA6-3 PA6-4 PA6-5 PA6-6 PA6-7 PA6-8 PA6-9 PA6-10

CPL (g) 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000

RE-2000 (g) 18.4 37.6 57.6 78.6 100.6 0 0 0 0 0

RE-900 (g) 0 0 0 0 0 79.1 101.4 124.8 149.5 175.5

AA (g) 1.3 2.7 4.2 5.7 7.3 12.8 16.4 20.2 24.3 28.7

Table 2: Formulation of Prepared Nylon 6.10 and Nylon 11 Copolymers Symbol PA610-1 PA610-2 PA610-3 PA610-4

SA (g) 500 500 500 500

HMDA (g) 284 283 276 275

RE-2000 (g) 48 66 83 200

Symbol PA11 PA11-1 PA11-2 PA11-3

N11m* (g) 1000 1000 1000 1000

RE-2000 (g) AA (g) 0 0 78.4 6.5 173.3 12.7 228.7 19.0 * N11m: 11-Aminoundecanoic acid

3. Results and Discussion 3.1.

Polymerization

The yield was maintained about 60–70%. The weight loss was mainly from the extraction and pelletization. The pellets produced herein had a diameter, length, and width of 2.3 mm, 2.5 mm, and 2.3 mm, respectively. All pellets were dried to less than 0.1 wt % (water content). The relative viscosity (RV), amino-end group analysis and melting temperature of prepared copolymers were listed in Table 3~4. Table 3: Characterization of Prepared Nylon 6 Copolymers Symbol

Tm(℃)

N-terminal(μeq/g)

PA6-1 PA6-2 PA6-3 PA6-4 PA6-5 PA6-6 PA6-7 PA6-8 PA6-9 PA6-10

2.5 2.2 1.9 1.8 1.8 1.6 1.6 1.6 1.4 1.4

221.5 221.3 213.3 221.4 220.8 218.9 217.0 216.0 215.1 214.4

49 58 52 49 45 56 41 42 27 31

Table 4: Characterization of Prepared Nylon 6.10 and Nylon 11 Copolymers Symbol

Tm(℃)

N-terminal(μeq/g)

PA610-1 PA610-2 PA610-3 PA610-4

2.1 2.1 1.9 1.7

222 223 223 221

37 77 11 86

Symbol

Tm(℃)

PA11 PA11-1 PA11-2 PA11-3

1.5 1.3 1.3 1.2

190.7 187.6 180.8 181.9

Page 179 of 1108

3.2.

Fibers and Fabrics

The characterization result of fibers and fabrics made of prepared nylon copolymers were listed in Table 5. The specification of the FDY filaments was 70 den/48 f. The draw ratio was adjusted within the range 1.8~2.0 between the first and second godet. The spinning speed was set to around 3200 m/min, and the temperature was set 270℃. The pressure of interlace was maintained about 1.5 kg/cm2. The parameters, including draw ratio, spin speed and throughput were then slightly adjusted according to each the characteristics of each polymer during the spinning process. The test results of moisture regains demonstrate the △MRa and △MRd value of nylon fiber could enhanced by PEO attached. △MR is a reasonable indicator for the feeling of comfortableness of worn clothes, and the moisture absorbing ability △MRa and moisture releasing ability △MRd of these fabrics are 4.6% and 4.3%, higher than regular nylon. (The △MRa and △MRd is 2.2% and 2.0%) The same test result were shown in PA6.10/PEO copolymer and PA11/PEO copolymer. The △MRa and △MRd of regular PA6.10 fabrics are 0.6% and 0.3%, and raised to 2.9% and 2.7% after modification. The △MRa and △MRd of regular PA6.10 fabrics are 0.4% and 0.01%, and raised to 3.62% and 1.87% after modification. Table 5: Characterization of fibers and fabrics made of prepared Nylon Copolymers Symbol

Strength (gf/d)

PA0 PA6-4 PA610-0 PA610-4 PA11-0 PA11-4

3.7 3.5 4.1 3.2 4.5 4.1

Elongation (%) 43.4 42.5 33.2 58.6 37.1 39.8

△MRa(%) 2.2 4.6 0.6 2.9 0.4 3.62

△MRd(%)

Qmax (W/cm2)

2.0 4.3 0.3 2.7 0.01 1.87

0.14 0.21 0.12 0.16 -

Index of warm/cool feeling, Q-Max The Q-Max value (W/cm2) indicates the instantaneous warm/cool feeling when the skin touches the fabric. A higher Q-Max indicates a more rapid transfer of heat from the body to the fabric. People feel cool when they touch the fabric. The identification of this characteristic has opened a new field of ‘‘cool fiber’’ application. The Q-Max value was tested by FTTS-FA-019, and the test results were also listed in Table 5. The Q-Max value of fabric made by PA6/PEO fiber is 0.21 W/cm2, much better than original nylon6. (Q-Max=0.14 W/cm2). The same test result was shown in PA6.10/PEO fabrics. The Q-Max of regular PA6.10 fabrics is 0.12 W/cm2, and raised to 0.16 W/cm2 after PEO modification. These test result demonstrate the hydrophilic polyamides were suitable materials for functional fiber and applied on cool feeling textile products.

4. References [1] Palmer, R. J. 2001. Polyamides, Plastics. Encyclopedia of Polymer Science and Technology. [2] Rwei,S.P.*, Tseng,Y.C., “Synthesis and Characterization of Polyethylene Oxide & Nylon-6 Copolymer in a Fiber Form”, Journal of Applied Polymer Science, Vol. 126, E206–E217, Nov. 2012 [3] Yan-Chun, L.; Yan, X.; Da-Nian, L. Appl Surf Sci 2006, 252, 2960. [4] Chahira, M.; Stephane, M.; Sadok, R. Appl Surf Sci 2007, 253, 5521. [5] Anne, J.; Robert, C.; Pierre, L. Prog Polym Sci 2002, 27, 1803. [6] Lofquist, R. A.; Saunders, T. T. Y.; Twilley, I. C. Textile Res J 1985, 55, 325.

Page 180 of 1108

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

Effect of Cross-sectional Configuration on Fiber Formation Behavior in the Vicinity of Spinning Nozzle in Bicomponent Melt Spinning Process Y. Chen, W. Takarada, T. Kikutani + Department of Organic and Polymeric Materials, Graduate School of Science and Engineering, Tokyo Institute of Technologyďź&#x152; 2-12-1, O-okayama, Meguro-ku, Tokyo 152-8552, Japan

Abstract. To investigate the fundamental melt spinning behavior of the islands in the sea (S/I) fibers, bicomponent melt spinning of polystyrene (PS) and polypropylene (PP) with the composition of 1:1 was performed using a spinning die for the preparation of S/I fibers with 1519 islands in the fiber cross-section. The sheath-core (S/C) fibers and blend fibers of the same composition were also prepared for comparison. By comparing the configurations of sheath-core and 1519 islands-in-the-sea type spinning die, the cross-sectional reduction ratio of polymer flow for the sheath-core type spinneret is 16:1, whereas that for the islands-in-the-sea type spinneret is 3200:1. In this research, particular attention was paid to the swelling behavior of polymer flow at the die exit. It was found that the swelling effect was much larger for the S/I spin-line in comparison with that for the S/C spin-line. With the increase of the extrusion temperature, the swelling effect tended to be decreased. On the other hand, the swelling effect of blend spinning was larger than S/I and S/C spin-lines and increased with the extrusion temperature. The peak position of swelling shifted to downstream, i.e. the distance from the die surface to the position of maximum spin-line diameter increased in the order of S/C<S/I<blend. When the S/C and S/I components were exchanged from PS/PP to PP/PS, the swelling behavior of S/C spin-line decreased whereas that of S/I spin-line did not show any significant change. These results suggested that the swelling effect in the S/C and S/I spinning is governed by the viscoelastic effect whereas that in the blend spinning is caused mainly by the interfacial tension between the two components.

Keywords: nanofibers; melt spinning; swelling effect; interfacial tension

1. Introduction In recent years, nanofibers are recognized as an exciting new class of material for various applications. One of the well-known methods for the production of nanofibers is electrospinning, however it can be said that the utilization of the preparation of islands-in-the-sea type bicomponent fibers (S/I fibers) for the production of nanofibers has an advantage of higher controllability of the diameter and mechanical properties of nanofibers [1]. In this technique, the sea component is dissolved into solvent after the formation of the S/I fibers. To investigate the fundamental melt spinning behavior of the S/I fibers, high-speed bicomponent melt spinning of polystyrene and polypropylene has been performed in this study for the preparation of S/I fibers with 1519 islands. In comparison with the sheath-core bicomponent fibers and the blend fibers of the same composition, there can be various factors which affect the fiber formation behavior. Those are: (1) effect of flow history in the spinning die on the swelling effect and structure development behavior, (2) effect of the interfacial tension on the swelling effect and thinning behavior, and (3) effect of the development of temperature distribution in fiber cross-section on cooling and solidification behavior of each component. In this research, particular attention was paid for the fiber formation behavior in the vicinity of spinning nozzle. When a molten polymer is extruded through a capillary, the wall pressure at the exit is not zero but somewhat above the atmospheric pressure, which causes the phenomenon of post-extrusion swell or the Barus effect [2]. Origin of the Barus effect can be discussed from two perspectives. One is the elastic fluid flow, and the other is the first normal stress difference [3, 4]. The effect of elastic fluid flow is governed by the reduction ratio of +

Takeshi Kikutani Tel: +81-3-5734-2468 Corresponding author. Tel.: + 86-010-xxxx xxxx. E-mail: kikutani.t.aa@m.titech.ac.jp E-mail address: xxxxxx.

Page 181 of 1108

the cross-sectional area of polymer flow in the die, while the effect of first normal stress difference originates from the shear flow in the capillary. In addition to the viscoelastic flow behavior of polymer melt, effect of the interfacial tension at the interface of two molten polymers also can be the origin of the swelling effect [5].

2. Experimental In this experiment, we compared the effect of the configurations of sheath-core and 1519 islands-in-the-sea type spinneret on the fiber formation behavior. The schematic of the configurations of both type spinnerets are shown in Fig.1. The molten polymers passed through the paths in a) and c), and then flowed into the same size nozzle of 1 mm diameter in b) and d). The reduction ratio of the cross-sectional area from the position of the confluence of two polymer flows to the die exit for the sheath-core type spinneret is 16:1, whereas that for the 1519 islands-in-the-sea type spinneret is 3200:1. It can be said that the reduction ratio of cross-sectional area in S/I was much larger than that in S/C.

c) a) b)

Fig. 1 The schematic of spinneret configurations: sheath-core: a) and b), sea-islands: c) and d). The materials used in this research were polystyrene (PS) and polypropylene (PP) with MFR of 18 and 20, respectively. Melt spinning of sheath-core (S/C) and islands-in-the-sea (S/I) bicomponent fibers as well as blend fibers were carried out. Throughput rates of both PP and PS components were set at 2.5 g/min for S/C, S/I and blend fibers. Extrusion temperatures of 230, 250, 270 and 290â&#x201E;&#x192; were adopted. A high speed camera was used for studying the swelling effect of S/C, S/I, and blend spin-lines.

Fig. 2 Schematic diagram for in-situ observation of spin-line at die exit in bicomponent melt spinning process.

Page 182 of 1108

3. Results and Discussion The photographs of free-fall PP/PS = S/I, S/C and blend spin-lines at four different extrusion temperatures are shown in Fig.3. Diameter profiles of the spin-line analyzed from these photographs for the extrusion temperature of 230 °C are shown in Fig.4. If the S/I spinning is compared with the S/C spinning, diameter increase for the S/I spin-line caused by the swelling effect was much larger than that for the S/C spin-line. This is considered to be due to the difference in the reduction ratio of the cross-sectional area in the die. On the other hand, the peak position of swelling was close to the spinneret for the S/C and S/I spin-lines, whereas the spin-line diameter continuously increased to the downstream in the case of blend spinning as shown in Fig.4. This tendency can be seen clearly by comparing the S/C bicomponent fibers with blend fibers because both spin-lines were extruded from the same S/C spinneret. It was found that the blend spinning exhibited another peculiar behavior. With the increase of extrusion temperature, the swelling effect tended to decrease for the S/C and S/I spin-lines. Oppositely, the swelling effect of blend spin-line increased with the increase of temperature. 250 °C 230°C

290 °C 270 °C

250 °C 230 °C

290 °C 270 °C

2mm

250 °C 230°C

290 °C 270 °C

2mm

S/I

S/C

Blend

Fig. 3 Photographs of free-fall S/I, S/C and blend spin-lines of PP/PS near the spinneret at different extrusion temperatures. For the spinning of blend fibers, S/C type spinneret was used.

Radius (mm)

S/I Blend (S/C spinning die)

S/C 0.5

230℃

0 0

Distance from spinneret (cm) Fig.4 Comparison of spin-line diameter profiles near the die exit for PP/PS bicomponent melt spinning of S/I, S/C and blend at extrusion temperature 230 °C.

Page 183 of 1108

For clarifying the influence of various factors for the swelling behavior, swelling index (S.I., the ratio of maximum swelling diameter versus spinneret diameter) of single component and bicomponent spin-lines were calculated and summarized in Fig.5. The S.I. for blend spinning could not be determined because the appearance of maximum diameter at positions far away from the spinneret. In the single component spinning, S.I. for the S/I spinneret was larger than that for the S/C spinneret because of larger reduction ratio of the crosssectional area. The S.I. for PS was larger than that for PP especially at low spinning temperatures. This is presumably caused by higher melt viscosity and its activation energy of PS than PP. If position of polymer in the fiber cross-section was exchanged from S/C or S/I = PS/PP to PP/PS, S.I. for the S/C spin-line became significantly smaller, whereas no significant change was observed in the S/I spin-line. From these results, it can be said that the swelling behavior of bicomponent spin-line was mainly governed by the PS component. On the other hand, larger swelling of blend fibers occurring at downstream was considered to be caused by the effect of interfacial tension. During the flow in the capillary, there can be an elongation of dispersed phase, which causes the increase in interfacial area between two polymers. For the reduction of generated excess energy, the elongated phase tends to retract and causes the swelling of the flow. It seems that the swelling caused by interfacial tension tends to appear in downstream in comparison with the swelling caused by the viscoelastic effect. a) 2 PS (S/I) spinneret

1.8

PP (S/I) spinneret

1.6 1.4

PS (S/C) spinneret

1.2

PP (S/C) spinneret

Swelling index

1.8

PS/PP = S/I PP/PS = S/I

1.6 PS/PP = S/C

1.4 1.2

PP/PS = S/C

1 210 230 250 270 290 310

210 230 250 270 290 310

Temperature (℃)

Fig.5 Swelling index of free-fall spin-lines at various extrusion temperatures. a) Single component spinning of PP and PS with S/C and S/I spinnerets, b) Bicomponent spinning of S/C and S/I fibers of PP/PS and PS/PP.

4. Conclusions Effect of flow history in the spinning die, i.e. sheath-core spinneret and sea-islands spinneret and polymer combination on the swelling effect was investigated. If S/I spinning is compared with S/C spinning, swelling effect was more significant in S/I spinneret, and the swelling effect of both S/I and S/C spinnings decreased with increase of temperature. These results can be explained from the view point of larger viscoelastic effect. Oppositely, the swelling effect of blend spinning increased with the increase of temperature. The swelling of spin-line continued to the downstream in the order of S/C<S/I<blend. It was concluded that the swelling behaviors of bicomponent spin-lines of S/C and S/I spinnings were governed by PS component, whereas the swelling behavior of blend spin-line was affected by interfacial tension.

References [1] M. Kamiyama, T. Soeda, S. Nagajima and K. Tanaka, Polymer Journal, 44 (10), 987–994 (2012) [2] Y.Hori and S.Okubo, Journal of Rheology, 24 (1). 39-53 (1980) [3] M. Sekikuti, Kobunshi Kagaku, 26, 295, 721-727 (1969) [4] K. Funatsu, and Y. Mori, Kobunshi Kagaku, 29, 329, 638-642 (1972) [5] L. Levitt, and C.W. Macosko, J. Rheol. 41(3), 671-685 (1997)

Page 184 of 1108

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

Effect of Processing Conditions on Reflectance Characteristics of PA6/PET Blend Fibers for Artificial Hair Masatoshi Seki1 +, Fumitaka Sugawara1, Senkichi Yagi1, TerumiTakaya1, and Takeshi Kikutani2 1

R & D Division, Aderans Co., Ltd. 13-4, Araki-cho, Shinjuku-ku, Tokyo 160-0007, Japan 2 Department of Organic and Polymeric Materials, Graduate School of Science and Engineering, Tokyo Institute of Technology, 2-12-1, O-okayama, Meguro-ku, Tokyo 152-8552, Japan

Abstract. Control of surface characteristics is one of the important subjects for the development of synthetic fibers for artificial hair. Various technologies including formation of spherulites on fiber surface by controlling cooling conditions in the melt spinning process, erosion of fiber surface by sand-blasting, extraction of blended soluble components after the formation of fibers etc. have been applied for the production of fibers with surface roughness. Recently, we have reported that the fibers with surface roughness can be produced by extruding a blend of polyamide 6 (PA6) and poly(ethylene terephthalate) (PET) with PET as a minor component at a temperature lower than the melting temperature of PET. Mechanism for the development of surface roughness has been analyzed from the view point of the crystallization of PET component in fiber processing. In this research, with the aim of controlling the appearance of fibers for artificial hair, PA6/PET blend fibers were prepared under various fiber processing conditions by varying extrusion temperature, blend ratio, drawing conditions etc. The optical characteristics of the prepared fibers were evaluated by taking SEM photographs of the fiber surface and by measuring the surface reflectance characteristics. It was confirmed that the PA6/PET blend fibers with its reflectance versus reflecting angle characteristics almost identical to the human hair can be produced under an optimized processing conditions.

Keywords: artificial hair; surface roughness; polymer blend; melt spinning; polyamide

1. Introduction Polyamides and polyesters are generally used for preparing artificial hair for wigs of daily use. Fibers of these polymers produced through ordinary fiber processing technologies have round shape with smooth surface in principle. Accordingly those fibers exhibit shiny look, which is totally different from the appearance of human hair with cuticles on its surface. Therefore, introduction of roughness to the surface of fibers is one of the most important research subjects for the development of synthetic fibers for artificial hair. For the incorporation of roughness on fiber surface, various technologies have been developed. Those are: 1) Drawing of fibers after dissolving and scouring its surface by inorganic acid [1], 2) Extraction of soluble component after preparing fibers of polyamide 6 blended with alkali-soluble co-polyester containing inorganic particles [2 - 4], 3) Erosion of fiber surface by sand-blasting [5, 6], and 4) Enhancement of the formation of spherulites in the melt spinning of polyamide fibers by passing the spin-line through a water bath of elevated temperature [7,8]. Polyamide 6 fibers generally have good texture and resilience as an artificial hair. More recently, with the aim of further improving the characteristics of polyamide 6, polyester was blended with polyamide 6 to +

Corresponding author. E-mail address: masatoshi.seki@aderans.com

Page 185 of 1108

enhance rigidity and shape memory characteristics. In the course of this research, it was found that the fibers with surface roughness can be obtained under particular extrusion conditions [9 - 11], and the reflectance characteristics of these fibers was investigated [12]. In addition, utilizing a co-rotating twin-screw extruder, factors governing the roughness development was investigated [13, 14]. In this research, from a view point of commercial scale production of blend fibers utilizing a single screw extruder, optimum conditions for producing artificial hair with undistinguishable light-reflecting characteristics in comparison with natural human hair was explored.

2. Experimental Schematic diagram of apparatus for fiber production is shown in Fig.1. Melt spinning was carried out using a single screw extruder equipped with a gear pump, spinning head and nozzles. Diameter and L/D of the screw were 25 mm and 28, respectively. The spinning head had fifteen nozzles of 0.5 mm diameter and L/D 4. Filaments extruded from the nozzles were quenched in a water bath of 40 °C set at 0.2 m below the nozzles, and subsequently drawn and annealed using four drawing units (R1 – R4) and three non-contact heating units of 2 m long. Winding of the filaments was conducted at winding speed of 120 m/min after applying 5.0 % relaxation.

① ②

③ ④ ⑥

① ④ ⑦

⑤

Hopper Head and nozzle Drawing oven

② ⑤ ⑧

⑦

⑥

⑦

R2 Single screw extruder Water quenching-bath Annealing roll unit

⑥

⑦

⑧

⑨

③ Gear pump ⑥ Pinch roll unit ⑨ Winder

Fig1 Equipment for melt spinning, drawing and annealing processes.

Materials used in this research were polyamide 6 (PA6, NOVAMID 1020, Mw 25000, Royal DSM. N.V), PA6 mixed with pigment (Master batch, MB), poly(ethylene terephthalate) (PET, BR3067, IV 0.617, Toyobo Co., Ltd.) and aromatic-aliphatic polyamide (Nylon-MXD6, S-6001, Mitsubishi Gas Chemical Co., Inc.) Surface characteristics of the prepared fibers was investigated using a scanning electron microscope (SEM, S-3500N, Hitachi High-Technologies Corp.). Light reflecting characteristics of the fibers was measured using a goniophoto meter (GP-5, Murakami Color Research Lab.) with the incident angles of 30 and 45 degrees.

3. Results and Discussion SEM photographs of the fibers prepared under various processing conditions are summarized in Fig. 2. It can be seen that the degree of roughness was enhanced with the increase of PET composition, decrease of extrusion temperature and decrease of draw ratio. Roughness on the fiber surface was elongated after the drawing. Optical characteristics of selected fibers measured using a gonio-photometer with the incident angles of 30 and 45 degrees are shown in Fig. 3. There was a few degrees shift of the peak position of reflected light intensity for the human hair because of the slightly inclined surface of cuticles with respect to the fiber axis. Sharp intensity distribution was observed for the fibers of smooth surface produced with the conditions of lower PET composition and higher extrusion temperature, whereas the fibers with higher PET composition, lower extrusion temperature and lower draw ratio exhibited much wider intensity distribution. To evaluate the similarity of light reflecting characteristics between the produced artificial hair and the

Page 186 of 1108

human hair, degree of deviation was estimated using the following equation: n

X = ∑ {I (θ ) − I * (θ − θ 0 )} / n 2

i =1

where I(θ) and I*(θ) are the scattering light intensity distributions for artificial hair and human hair, θ is the scattering angle, and θ 0 is the peak shift for human hair. Range of data for the calculation was set to be ± 15° from the peak position. Here, 1/X can be defined as a “similarity index” of light reflecting characteristics.

5 ｗｔ％

20 ｗｔ％

10 ｗｔ％

5 ｗｔ％

10 ｗｔ％

20 ｗｔ％

230 °C

240 °C

250 °C

×4.0

×4.5

×5.0

230 °C

240 °C

250 °C e)

×4.0

×4.5

×5.0 f)

PA6/PET/MXD6

PA6/PET

Fig. 2. SEM photographs of fibers of PA6/PET blend and PA6/PET/MXD6 blend prepared under various processing conditions. Standard conditions were: PET composition 20 wt%, MXD6 composition 10 wt%, extrusion temperature 230 °C and draw ratio 4.0. Effects of PET composition [a) and d)], extrusion temperature [b) and e)] and draw ratio [c) and f)] are shown. 100

Intensity

5%-x5.0-DN250

20%-x4.0-DN230

20%-x4.0-DN240

Intensity

100

Human Hair

5%10%-x5.0-DN250

20%10%-x4.0-DN230

20%10%-x4.0-DN240

20 0

0 0

100 60

20%-x4.0-DN230

20%-x4.0-DN240

20 0 0

Scattering Angle (deg)

Intensity

5%-x5.0-DN250

100

Human Hair

Scattering Angle (deg)

Intensity

Human Hair

5%10%-x5.0-DN250

20%10%-x4.0-DN235

20%10%-x4.0-DN240

20 0 0

Scattering Angle (deg)

Fig.3 Reflected-light intensity distributions measured using a gonio-photometer for human hair and artificial hairs of PA6/PET [a) and b)] and PA6/PET/MXD6 [c) and d)] prepared under various fiber processing conditions.

Page 187 of 1108

The analyzed results are summarized in Fig.4. In general, the similarity index was low at the extrusion temperature of 250 °C and decreased with the increase of draw ratio. PA6/PET fibers exhibited better similarity index than PA6/PET/MXD6 fibers.

1/X

IA30

0.060

DN230 DN240 DN250

0.040

0.080

0.020

DN230 DN240 DN250

0.040 0.020

0.000 4

Draw Ratio

0.080

0.000

5.5

3.5

DN230

0.040

DN250

0.020

IA45

0.060

DN240

4.5

Draw Ratio

0.080

IA45

0.060

4.5

1/X

3.5

1/X

IA30

0.060

1/X

0.080

5.5

DN230 DN240 DN250

0.040 0.020

0.000

3.5

4.5

Draw Ratio

5.5

0.000 3.5

4.5

Draw Ratio

5.5

Fig.4 “Similarity index” of light reflecting characteristics for artificial hairs of PA6/PET [a) and b)] and PA6/PET/MXD6 [c) and d)] prepared with PET composition of 20 wt% . Data for incident angles of 30 and 45 degrees are shown.

4. Conclusions Fibers with surface roughness could be prepared using a single-screw extruder adopting an appropriate fiber processing conditions. In the range of processing conditions investigated in this experiment, fibers prepared under the conditions of PET composition 20 wt%, nozzle temperature 230 or 240 °C, and draw ratio 4.0 exhibited the optical characteristics most similar to the human hair.

References 1. 2. 3. 4. 5. 6. 7. 8. 9. 10.

Jap. Pat. No. 579096 Jap. Pat. No. 2059712 Jap. Pat. No. 3134421 Jap. Pat. (Open Laid) No. 2007-303014 Jap. Pat. No. 3427224 Jap. Pat. No. 3858152 Jap. Pat. (Open Laid) No. S62-156308 Jap. Pat. (Open Laid) No. S62-156309 Xu, X.-S, Shirakashi, Y., Ishibashi, J., Takarada, W. and Kikutani,T., Seikei-Kakou ’09, 221 (2009) Xu, X.-S, Shirakashi, Y., Ishibashi, J., Takarada, W. and Kikutani,T., Proceedings of Asian Textile Conference (ATC-10),CD-R (2009) 11. Shirakashi, Y., Asakura, O., Ito, S., Ishibashi, J., Xu, X., Takarada, W., and Kikutani, T., Seikei-Kakou, 23 (6) 358-364 (2011) 12. Shirakashi, Y., Asakura, O., Ito, S., Ishibashi, J., Xu, X., Takarada, W., and Kikutani, T., Proceed. PPS2010 Istanbul Regional Meeting, CD-ROM (2010) 13. Xu, X., Shirakashi, Y., Ishibashi, J., Takarada, W. and Kikutani, T., Text. Res. J., 83(19) 2042-2050 (2013)

Page 188 of 1108

14. Xu, X., Shirakashi, Y., Ishibashi, J., Takarada, W. and Kikutani, T., Text. Res. J., 82(13) 1382-1389 (2012)

Page 189 of 1108

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

Effects of bonding system on the interfacial adhesion between polyketone fiber and EPDM rubber Da Young Jin 1, Jong Sung Won 1, Do Un Park 1, Hyun Jae Lee 1, and Seung Goo Lee 1 ď&#x20AC;Ť 1

Department of Advanced Organic Materials & Textile System Engineering, Chungnam National University, Gung-dong, Yuseong-gu, Daejeon, 305-764, South Korea

Abstract. When using fibers in combination with rubber, good adhesion is essential especially for high safety products such as MRG (Mechanical Rubber Goods). The adhesion between untreated fibers and rubber is always low, because there is a significant difference in modulus and polarity between the reinforcing fibers and the rubber matrix. The adhesion between the interface of fiber and rubber is achieved by coating the surface of fiber with resorcinol-formaldehyde-latex (RFL) adhesive solution. The adhesion strength between fiber-RFL-rubber, depends on several factors such as component of RFL and process condition (temperature, time, pressure) etc. In this study, a dry bonding system comprising of resorcinol, hexamethylene tetramine and hydrated silica was suggested to achieve improved bonding between the fiber and the matrix. So, it is able to improve interfacial strength of fiber/rubber composites by using modified RFL after added resorcinol, hexamethylene tetramine and hydrated silica in RFL. In addition, the effect of coupling agent on the interfacial adhesion of polyketone fiber/EPDM rubber was analyzed and discussed with fiber pull-out test. Adhesion strength of polyketone fiber/EPDM rubber was evaluated according to the content of each component in the bonding system.

Keywords: Polyketone fiber, EPDM rubber, Composite, Surface treatment

1. Introduction Rubber composites are widely used in many industrial applications such as tires, belts, hoses and packing. Although the rubber used in the tire and other rubber industries has good mechanical properties, reinforcing fiber is required to improve strength and dynamic properties of rubber. Therefore, the adhesion between rubber matrix and reinforcing fiber is a key factor which determines the mechanical properties of the rubber composite. The role of adhesion can be to impart desirable properties, improve durability and maintain the shape of the composite material. Many adhesion systems have been developed to give desirable properties of rubber composites [1]. One of the most widely used techniques for accomplishing fiber-matrix adhesion is the use of a three component dry bonding system consisting of hexamethylene tetramine, resorcinol and hydrated silica, popularly known as HRH dry bonding system. Several authors have studied the effect of dry system in a variety of short fiber-rubber composites. Newly developed polyketone fiber is available by copolymerization of carbon monoxide and unsaturated hydrocarbon monomer, ethylene. Hence, the cost of its raw material is very cheap and the spinning process is environmental-friendly. Also, it has the additional benefits of similar tenacity and modulus compared to the para-aramid fiber, and has higher breaking elongation and good adhesion property with a rubber matrix. Therefore, it is expected to apply it to the reinforcement of mechanical rubber goods (MRG) such as tires, hoses and protective gloves [2-3]. In this study, a dry bonding system comprising of hexamethylene tetramine- resorcinol-hydrated silica (HRH) was suggested to achieve improved bonding between the fiber and the matrix. So, it is able to improve interface strength of fiber/rubber composites by using modified RFL after added resorcinol, hexamethylene tetramine and hydrated silica in RFL. In addition, ď&#x20AC;Ť

Corresponding author. Tel.: + 82-42-821-6616. E-mail address: lsgoo@cnu.ac.kr.

Page 190 of 1108

the effect of coupling agent on the interfacial adhesion of polyketone fiber/EPDM rubber was analyzed and discussed with H-test. Adhesion strength of polyketone fiber/EPDM rubber was evaluated according to the content of each component in the bonding system.

2. Experimental 2.1 Materials 2.1.1 Rubber compound Composition of the EPDM compound used in this study is given in Table 1. Same formulation was used in all experiments. Materials were weighed and mixed in an internal mixer and rolled in a roll mill. Finally, they were changed to a sheet with thickness of 6 mm. Table 1 : Composition of rubber compound Component

Weight (g)

EPDM

100

Carbon black

Paraffinic oil

Sulfur

1.2

CBS

2.1.2 Fiber The molecular structure of the polyketone fiber is shown in Figure 1. In this study, polyketone fiber was supplied from â&#x20AC;&#x153;Hâ&#x20AC;? company in Korea.

Fig. 1 Chemical structure of the polyketone fiber

2.1.3 Cord preparation Polyketone cord was prepared through the two-for-one twisting by using the polyketone fiber supplied. Twist Per Meter (TPM) of the polyketone cord was fixed at 550 TPM in this study.

2.2 Surface treatment Polyketone cords were washed with acetone by using ultrasonic agitation for 1 hour. Then, they were washed with distilled water repeatedly. After purifying the polyketone cord, their surfaces were treated with a primer consisted with HRH. Typical formulation of the HRH is given in Table 2.

Page 191 of 1108

Table 2 : Typical formulation of the adhesive (Unit: g) Primer → RFL Primer → HRH RF solution RF solution Resorcinol 16 Resorcinol Formaldehyde 7 Formaldehyde Water 200 Water Maturation: 25°C, 4h 223 Maturation: 25°C, 4h Final dip solution Final dip solution RF solution 223 RF solution SBR Latex 160 Hexamethylene tetramine SBR + VP (5:5) Latex Hydrated silica SBR + VP (2:8) Latex Water Water 120 Maturation: 25°C, 12h Maturation: 25°C, 12h 503

16 7 200 223 223 16 8 120 367

2.3 Thermal properties Using a TGA (TA Instrument), changes in thermal stability of the HRH treated polyketone cords were analysed. In measurements, heating rate was 10℃/min from 25℃ to 450℃ under nitrogen atmosphere.

2.4 Morphological properties Surface morphologies of the treated polyketone cords were observed with a scanning electron microscope (SEM, S4700, HITACHI). Additionally, atomic force microscopy (AFM, Bioscope, Digital Instruments Inc) was utilized to measure the three dimensional images of polyketone cords and root mean square (RMS) roughness data, which were obtained by analyzing topographical images.

2.5 Surface characterization A fourier transform infrared spectrophotometer (FT-IR, Bruker Optic GmbH, ALPHA-P) equipped with an attenuated total reflectance (ATR) accessory was used to examine the surface composition of the polyketone cord. The spectra were recorded in the transmission mode in the range of 4000-500 cm-1. FTIR spectra were measured at a spectral resolution of 4 cm-1, and the spectra were obtained with an accumulation of 128 scans for a high signal-to-noise ratio.

2.6 Interfacial adhesion tests The interfacial adhesion properties were measured with the H-test method according to the ASTM D4776. To prepare the H-test samples, rubber sheets were placed in the channels of a stainless steel die. Then, the surface treated cord was embedded in rubber sheets. Samples were vulcanized at 160°C, for 20min. at pressure of 10MPa. Then the products were cut into H-shape samples. Test was performed by using an Instron 4467 tester under room temperature and the cross-head speed was fixed at 125mm/min. Adhesion strength was calculated from the maximum load.

3. Results and Discussion 3.1 Thermal properties The thermal stability of the RFL and HRH are shown in Figure 2. Obviously, the thermal stability was improved with hydrated silica addition.

Adhesion strength (Kgf)

7 6 5 4 3 2 1 0

Fig. 1 : TGA curves according to hydrated silica addition.

Untreated

RFL treated

HRH treated

Fig. 2 : H-test results according to primer dips.

Page 192 of 1108

3.2 Interfacial adhesion strength A total of 2 primer dips were investigated with different composition as giver in Table 2. Figure 2 shows H-test results according to RFL and HRH dip of the polyketone cord. The highest adhesion force was obtained at the HRH dip containing the Hexamethylene tetramine and hydrated silica.

3.3 Interfacial adhesion strength ATR analysis of the HRH-treated-polyketone cord in Figure 3 confirms the presence of hexamethylent tetramine (1100~1400 cm-1) group.

Fig. 3 : ATR spectra of HRH treated the polyketon cord

3.4 Morphological observation Figure 4 and 5 shows the surface morphology of polyketone cord according to primer treatment. The HRH treated the polyketon cord shows a morphological view of the primer diffusion into the cord surface compared with the raw the polyketone cord. As increase of adhesion strength, it was confirmed that the more the EPDM rubber found at surface of the polyketone cord.

(a) (b) (c) Fig. 4 : SEM micrographs of the surface of the polyketone cord according to primer treatment: (a) Raw, (b) RFL treated, (c) HRH treated

(a) (b) (c) Fig. 5 : AFM images of the surface of the polyketone cord according to primer treatment: (a) Raw, (b) RFL treated, (c) HRH treated

4. Conclusions In this study, surface of the polyketone cord was coated by primers in order to improve the interfacial strength with a rubber. The surface chemical composition and morphological properties of the polyketone cord were changed by the primer treatment. With the experimental results, adhesion strength increased by RFL and HRH dip treatment. The highest adhesion strength of the polyketone cord was obtained with a condition of HRH dip. ATR analysis showed that there are active zones on HRH that react with functional groups on cord and rubber. Consequently, the interfacial adhesion properties between the polyketone cord and rubber increased largely with the primer treatment.

5. References [1] K.H. Chung, W.B. Im and T.H. Yoon, Polymer International, 53, 344 (2004). [2] M. Jamshidi, F.A. Taromi and N. Mohammadi, Iranian Polymer Journal, 14, 229 (2005). [3] S.F. Halim, S.N. Lawandy, and M.A. Nour, Polymer composites, 9, 34, (2013).

Acknowledgement

â&#x20AC;&#x153;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 & Energy, Republic of Koreaâ&#x20AC;?

Page 193 of 1108

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

Evaluating Acoustic and Climatic Ageing Properties of Natural Fiber Based Nonwovens for Automotive Applications Asis Patnaik 1, 2 + 1

CSIR Materials Science and Manufacturing, Polymers and Composites Competence Area, Nonwovens and Composites Group, P.O. Box 1124, Port Elizabeth 6000, South Africa 2

Department of Textile Science, Faculty of Science, Nelson Mandela Metropolitan University, Port Elizabeth 6031, South Africa

Abstract. Weight reduction in the material components plays a significant role in cost savings particularly in automotive applications. The overall fuel efficiency of a vehicle increases with the reduction in the component weight. Nonwovens are widely used for sound absorption (acoustic) applications in automotive industries. This paper reports a study on the development of natural fiber nonwovens with better acoustic properties at a lower areal density and thickness in comparison to existing commercial samples, particularly for under floor sound absorption applications. Acoustic properties of six different types of needle-punched nonwovens were studied. Four different types of nonwovens were prepared by combining polyester (PET) fibers with waste animal fibers (WF), which were blends wool and cashmere waste. Blends of PET and WF were prepared in 50/50 proportion. The first sample was prepared as a single layer blend of PET and WF. The second sample was prepared from the previous blend, but in a double layer structure, of which one side was PET and other side was WF. The third sample was prepared in a double layer of polyester microfibers (PETM) and WF and the fourth sample constitute of blends of PET/WF on one side and PETM/WF on the other, forming a double layer. The performance properties of above four and two commercial under floor samples were evaluated. These properties were acoustic, pore size, fire and climatic ageing cycles. All the developed samples showed better performance properties as compared to the commercial samples. Two layered PETM/WF showed the best properties among the developed samples, with sound absorption acoustic coefficient (Îą) of 0.59 as compared to the commercial sample (areal density 1000 g/m2 and thickness 10.12 mm), which showed Îą value of 0.39 in the frequency range of 50â&#x20AC;&#x201C;5700 Hz. Marginal decrease in the properties of the developed and commercial samples were observed after climatic ageing. The result showed that it was possible to design alternative materials with better acoustic properties in the overall frequency range at a lower areal density and thickness.

Keywords: acoustic, nonwovens, pore size, climatic ageing

1. Introduction There is an increasing demand for light-weight materials for automotive applications in the current global trend of green/recycled products. Approximately 40 m2 of fibrous materials are used in a car production in various forms, of which 50% are nonwoven fabrics [1]. Nonwovens are used for sound/noise control or acoustic applications in the form of floor carpets, dashboard, roof and top covering, rear covers, door lining, head liners, etc [2-3]. Noise control can be achieved in the form of an acoustic absorber or barrier. It is a well-known fact that increasing weight and thickness of the absorber material improves the acoustic properties [2-3]. The challenge is to develop acoustic materials with better performance properties at a lower areal density and thickness as compared to the existing products, which opens up a new avenue for better/alternative materials. With the recent upsurge in the use of natural and recyclable materials in the automotive industries, there is plenty of scope for developing nonwoven based acoustic materials from sustainable resources. A number of research papers on the acoustic properties of nonwovens are published by considering various fiber parameters, fabric parameters and nonwoven processing parameters [2-3]. Cheng and Jiang [2] reported the improvement in acoustic properties of layered nonwovens. Layered nonwoven composites were prepared by combining activated carbon surface layer with the needle-punched base layers of cotton, ramie and polypropylene. Thilagavathi et al. [3] studied the acoustic properties of natural fiber +

Corresponding author. Tel.: + 27-041-508 3267. E-mail addresses: apatnaik@csir.co.za; asispatnaik@gmail.com

Page 194 of 1108

nonwovens made from bamboo, banana and jute fibers blended with polypropylene fibers in 50:50 blends for automotive interior applications. Authors reported that acoustic properties decreased at a higher frequency. The short wool fibers that are obtained by shearing the sheep’s hair and the short cashmere fibers obtained from goats are not suitable for apparel/clothing purpose; and therefore generally discarded as a waste material. These non-standard fibers are known as waste animal fibers (WF). Such waste fibers are plenty available in South Africa that does not add any value to the farmers. The prices of such WF are less than $0.3 US dollar/Kg [4]. In terms of environmental profile of materials, wool fiber based materials consume lowest amount of energy during material usage and at disposal stage than any other existing natural materials [5]. Since the quantities of WF are not enough to meet the alternative material demand, it needs to be combined with another material to develop value based products like acoustic materials. Polyester (PET) fibers and polyester microfibers (PETM) obtained from plastic bottles are in turn mixed with WF fibers in order to meet the supplydemand cycle. WF are known for their susceptibility to higher moisture content, fungus and moth problems, and poor fire resistance as per automotive requirements. These issues are covered in the next section. The objective of this study was to develop natural fiber nonwovens with better acoustic properties at a lower areal density and thickness in comparison to existing commercial samples, particularly for under floor sound absorption applications. Four different types of needle-punched nonwovens were prepared and their performances were evaluated and compared with two commercial under floor carpets. Furthermore, climatic behaviors of the materials were also evaluated.

2. Materials and Methods 2.1.

Nonwoven mat preparation

For preparing the nonwoven mat, individual fibers (waste wool, cashmere, PET, PETM) were first opened on a bale opener. Then, the fiber web was cross-lapped on a cross lapper and needle-punched on a needlepunching machine to bond the fibrous web. Specifications of the fibers used were, PET- linear density 6.7 dtex, staple length 32 mm, siliconized; PETM- linear density 0.9 dtex, staple length 38 mm, siliconized; coring wool- fiber diameter 20.7 µm, staple length 22 mm; dorper wool- fiber diameter 28.6 µm, staple length 38 mm, cashmere waste- fiber diameter 20.9 µm, staple length 50 mm. Since material requirements for automotive industries are stringent in terms of fire properties, WF, PET and PETM fibers were sprayed with a low level of fire retardant (15% by weight, comprising a mixture of di-ammonimum phosphate and sodium tetraborate) to impart fire retardancy properties. This treatment also assists in eliminating fungus and moth problems associated with the waste animal fibers. Furthermore, 3% silicon (by weight) was sprayed on the WF in order to improve their moisture resistance. For example, preparing PET/WF mix type sample (Table 1), fibers were opened and then blended together before carding. Similarly for preparing PET/WF, single layer mats of WF and PET were prepared which were, further punched together with PET on the top side and WF at the bottom side of the mat. The third sample was prepared from a double layer of PETM and WF. The fourth sample comprised of blends of PET/WF on one side and PETM/WF on the other side. These layers were produced first and then punched together as a double layer. Commercial reference samples consist of mixture of polyester and recycled shoddy fibers, which are currently used as acoustic carpets by majority of the local automotive manufacturers. Specifications of the samples are listed in Table 1. The areal densities of the experimental nonwoven samples were maintained at 850 g/m2 in comparison to the reference commercial samples (areal densities 1000 g/m2 and 1200 g/m2, respectively). The rationale behind this was to achieve better acoustic properties at lower areal density and thickness than the reference samples.

2.2.

Acoustic properties

Normal incidence acoustic coefficient (α) was measured according to ASTM E 1050-10 standard test method for impedance and absorption of acoustic materials using a tube, two microphones and a digital frequency analyzer [6]. The LMS acoustic testing instrument was used for this purpose [7]. The frequency range used for the measurement was 50–5700 Hz. This frequency range can be divided into 3 different classes, low (50–1000 Hz), medium (1000–2000 Hz) and high (2000–5700 Hz) frequency ranges.

2.3.

Pore Size and its distribution

The capillary flow porometer (Porous Materials Inc., model CFP-1100-AEXCC) employing a principle based on the liquid extrusion porometry technique was used to characterize the pore structure of nonwovens [8-9].

2.4.

Thickness and areal density

Page 195 of 1108

The thicknesses of the nonwovens were measured according to the European Disposables and Nonwoven Association (EDANA) standard, WSP 120.6 (05) [10]. The areal densities of the nonwovens were measured according to ASTM D 3776 by using an electronic balance [11].

2.5.

Tensile and fire properties

The tensile properties were measured on an Instron tensile tester according to ASTM D 5034 [12]. Fabric strip test was used to report the tensile properties in both machine and cross directions. The fire property was tested as per ISO 3795 standard [13], where the material should not glow after the fire extinguishes.

2.6.

Climatic ageing cycles

It was measured according to the automotive material standard D47 1309 /D, by using the cycle D in the Binder climatic chamber [14]. Two cycles were uses, Cycle 1 for 17 hours at 85ºC and 95% relative humidity (RH). It was immediately followed by Cycle 2 for 7 hours at 100ºC and 0% RH. At the end of the above two cycles, the samples were left in the climatic chamber for 24 hours maintained at 23±2 ºC and 50±5% RH.

3. Results and Discussion The physical and performance properties of various samples are shown in Table 1. The developed samples showed better acoustic properties as compared to the commercial sample 1 in comparable areal density range. Two layered PETM/WF showed the best properties among the developed samples, with sound absorption acoustic coefficient (α) of 0.59 as compared to the commercial sample1 (areal density 1000 g/m2 and thickness 10.12 mm), which showed α value of 0.39 in the frequency range of 50–5700 Hz. A combination of fine (micro) and coarse (macro) structures helps in absorbing the sound waves passing through it. The two-layer structure resulted in the conversion of the kinetic energy of the incident sound wave into low level of heat energy as it passed from one layer to other layers, thereby dampening the effect of the propagating sound wave and thereby resulting in good acoustic properties. Furthermore, the thickness of the developed samples was lower than commercial sample 1. The mean pore size (average) of most of the developed samples were lower than that of the commercial samples, which further assisted in dampening the air borne sound wave. Sound absorption coefficients (α) in various frequency ranges are shown in Table 2. As expected, α value increases in high frequency range (2000-5700 Hz) as it was easier to dampen these sound waves. There was no change in the acoustic properties of the developed samples after climatic testing (Table 3). The silicon spraying prevents the moisture absorption by the samples, thereby, maintaining the acoustic value. Marginal decrease in the breaking strength of the developed and commercial samples was observed after climatic testing, and was found to be non-significant. All samples were non-combustible after fire testing. Table 1: Physical and performance properties of various samples Sample type

Blend (%)

Number of layers

Thickness (mm)

Areal density (g/m2)

Sound absorption coefficient (α) 50-5700 Hz

Average Pore size (µm)

Fire property

PET/WF (mix type)

50/50 mix

9.45

850

0.45

78.448

Noncombustible

PET/WF

50/50

9.63

850

0.52

65.448

Noncombustible

PETM/WF

50/50

11.15

850

0.59

60.359

Noncombustible

(PET/WF)/ (PETM/WF)

50/50

10.67

850

0.57

61.982

Noncombustible

Commercial 1

Shoddy mix

10.12

1000

0.39

75.797

NonCombustible

Commercial 2

Shoddy mix

12.23

1200

0.45

69.522

NonCombustible

Table 2: Sound absorption coefficients (α) in various frequency ranges Sample type

50-1000 Hz

1000-2000 Hz

2000-5700 Hz

50-5700 Hz

PET/WF (mix type)

0.10

0.21

0.58

0.45

Page 196 of 1108

PET/WF

0.10

0.28

0.63

0.52

PETM/WF

0.13

0.40

0.79

0.59

(PET/WF)/ (PETM/WF)

0.12

0.36

0.74

0.57

Commercial 1

0.06

0.15

0.51

0.39

Commercial 2

0.10

0.30

0.60

0.45

Table 3: Properties of the samples before and after climatic cycles Sample type

Sound absorption coefficient (α) 50-5700 Hz, Before After

Maximum breaking force (N) in cross direction Before After

Areal density (g/m2) Before

After

PET/WF (mix type)

0.45

0.44

230

225

850

PET/WF

0.52

238

230

850

PETM/WF

0.59

0.57

232

228

850

(PET/WF)/ (PETM/WF)

0.57

225

220

850

Commercial 1

0.39

0.38

245

241

1000

Commercial 2

0.45

0.43

263

258

1200

4. Conclusion Alterative acoustic materials were developed by blending and layering waste animal fibers with PET and PETM fibers. Better acoustic properties were observed for the developed samples in the overall frequency range (50-5700 Hz) as compared to the commercial samples. Two layered PETM/WF showed the best sound absorption coefficient (α) of 0.59 among the developed samples as compared to the commercial sample having α value of 0.39 in the overall frequency range (50-5700 Hz). It was possible to design alternative materials with better acoustic properties at a lower areal density and thickness. Marginal decrease in the breaking strength of the developed and commercial samples was observed after climatic testing, whereas there were no changes in the acoustic properties. All samples have adequate fire resistance.

5. References [1] www.edana.org, EDANA automotive nonwovens news, May 2013. [2] Chen Y and Jiang N, Text. Res. J., 77 (2007) 785. [3] Thilagavathi G, Pradeep E, Kannaian T and Sasikala L, J. Ind. Text., 39 (2010) 267. [4] www.capewools.co.za [5] Shen L and Patel M K, J. Polym. Env., 16 (2008) 154. [6] ASTM: E1050, (ASTM, West Conshohocken, PA), 2010. [7] LMS Acoustic Testing Instrument, Instruction Manual, LMS International, Leuven, 2011. [8] Jena A and Gupta K, Int. Nonwovens J., 12 (2003) 45. [9] Capillary Flow Porometer, Instruction Manual, Porous Materials Inc., Ithaca, New York, 2005. [10] EDANA: WSP 120.6 (05) (EDANA, Brussels, Belgium), 2005. [11] ASTM: D3776, (ASTM, West Conshohocken, PA), 1997. [12] ASTM: D5034, (ASTM, West Conshohocken, PA), 2013. [13] ISO: 3795, 2013. [14] Automotive material standard D47 1309 /D.

Page 197 of 1108

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

Fabrication and Characterization of Flexible Polyaniline-Decorated Fiber Nanocomposite Mats for Supercapacitors Danyun Lei,2 Tae Hoon Ko,1 Ji-young Park,1 Yong Sik Chung,1 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 *E-mail: kbsuhk@jbnu.ac.kr

Abstract. Carbon nanofiber (CF) mats are potential materials for supercapacitors due to their unique properties such as high surface area, electrical conductivity, and chemical stability. Among the conductive materials, polyaniline (PANi) is preferred for the preparation of flexible transparent electrodes due to its ease of synthesis, high conductivity, and environmental stability. In our work, we prepared two kinds of Flexible Polyaniline-Decorated Fiber Nanocomposite Mats. One is carbon fiber (CF)-polyaniline (PANi) nanocomposite via an in situ polymerization technique. At first, carbon fiber mats prepared from new precursors, poly(acrylonitrile-co-crotonic acid) and poly(acrylonitrileco-itaconic acid-co-crotonic acid) copolymers, were evaluated as substrates for supercapacitors. The flexible carbonized precursors were further used as the substrate for in situ polymerization of aniline. The electrochemical performances of PANi/CF nanohybrids were characterized by cyclic voltammetry and galvanostatic charge-discharge tests. The PANi/CFs exhibited a maximum specific capacitance of 113 F/g. The other is PANi nanowire/nylon nanofiber reinforced cellulose acetate thin film. At first, the nylon was electrospun to produce the nanofibers followed by infiltration with cellulose acetate to get highly transparent substrate. Then PANi nanowires were grown uniformly on the transparent substrate by an in situ polymerization technique. The resulting thin films showed transparency from 39% to 82% and sheet resistivity between 188 and 8700 立/sq depending on the aniline monomer concentration. In addition, the transparent electrode exhibited outstanding toughness during bending cycles. Further, the transparent electrode showed excellent capacitive performance with specific capacitance of 402 F/g.

Keywords: Nanofiber mats, supercapacitor, polyaniline, fiber nanocomposites.

1. Introdution Supercapacitors or electrochemical capacitors are promising alternatives to meet the demands for the energy storage systems [1, 2]. The preference for the supercapacitors over conventional energy storage systems are owing to their relatively high power capability and energy density of the supercapacitors. Supercapacitors based on carbon materials and conductive polymers have attracted much attention due to their unique properties such as high accessible surface area, ease of synthesis, good stability in ambient conditions, and higher conductivity. Blending of carbon nanomaterials such as CNT [3], graphene, carbon fibers, and porous carbon materials with PANi offered highperformance and low-cost alternative energy storage systems that can replace conventional rechargeable batteries. In our work, we prepared two kinds of flexible polyaniline-decorated fiber nanocomposite mats. One is carbon fiber (CF)-polyaniline (PANi) nanocomposite via an in situ polymerization technique. At first, carbon fiber mats prepared from new precursors, poly(acrylonitrile-co-crotonic acid) and poly(acrylonitrile-co-itaconic acid-co-crotonic acid) copolymers, were evaluated as substrates for supercapacitors. The flexible carbonized precursors were further used as the substrate for in situ polymerization of aniline. The electrochemical performances of PANi/CF nanohybrids were

Page 198 of 1108

characterized by cyclic voltammetry and galvanostatic charge-discharge tests. The PANi/CFs exhibited a maximum specific capacitance of 113 F/g. The other is PANi nanowire/nylon nanofiber reinforced cellulose acetate thin film. At first, the nylon was electrospun to produce the nanofibers followed by infiltration with cellulose acetate to get highly transparent substrate. Then PANi nanowires were grown uniformly on the transparent substrate by an in situ polymerization technique. The resulting thin films showed transparency from 39% to 82% and sheet resistivity between 188 and 8700 ÎŠ/sq depending on the aniline monomer concentration. In addition, the transparent electrode exhibited outstanding toughness during bending cycles. Further, the transparent electrode showed excellent capacitive performance with specific capacitance of 402 F/g. The synthesized materials were evaluated as supercapacitors and the results are discussed in the following sections.

2. Experimental Preparation of PANi /CFs Nanohybrids Electrodes The precursors of carbon fiber (CF) mats, poly(AN-IA), poly(AN-CA), poly(AN-IA-CA) were prepared according to our previous paper [4]. At first, 1.140 mL aniline and 1.890 g of ammonium persulfate were dissolved separately in each 25 mL of 0.5 M HCl solution. The solutions were mixed and stirred for approximately 3 min. Then the CF mat (ca. 2 cm x 2 cm) prepared using Poly(AN-IA) was immersed in the solution and kept at 4 oC. After 2 h of incubation, the nanofiber mat was washed with deionized water followed by re-doping in 1.0 M HCl for 30 min to get PANi/CF nanocomposite. Similarly, the CF mats prepared from PANi/poly(AN-CA), PANi/poly(AN-IA-CA) were also similarly treated to obtain PANi/CF nanocomposites. The CF mats obtained from poly(AN-IA), poly(AN-CA), and poly(AN-IA-CA) were indicated by CF1, CF2, CF3, respectively. Correspondingly, the PANi nanocomposites prepared were indicated by PANi/CF1, PANi/CF2, and PANi/CF3. Preparation of PANi nanowires/PA/CA thin film transparent electrode At first, a 6.0 wt% solution of nylon-6 (PA-6, Mw = 104.83 kDa, Aldrich) was prepared using formic acid and electrospun at 9 kV at a tip-to-collector distance of 15 cm at 20 oC and at relative humidity of 30â&#x20AC;&#x201C;40%. The electrospinning was performed for 5 min and the PA-6 electrospun non-woven fibers (PA-ESNW) were collected on aluminium foil and then dried at 25 oC in vacuum for 24 h. Secondly, the PA-ESNW was infiltrated with cellulose acetate (CA). CA (M n = 50 kDa, Aldrich) was dissolved in dimethylformamide at the concentration of 10.0 wt%. The PA-ESNW mat on aluminium foil was coated with CA solution and kept for drying at room temperature for 1 h followed by drying at 25 oC under vacuum for 24 h. Then the film (PA/CA fibrous thin film) was peeled off from the aluminium foil and stored at room temperature until further use. Finally, PANi nanowires were grown on PA/CA fibrous thin film mat via in situ polymerization technique. In a typical procedure, aniline was first dissolved in 25 mL of 0.5 M HCl solution. Then ammonium persulfate (APS) was dissolved in 25 mL of 0.5 M HCl. Then these solutions were mixed and stirred vigorously for 3 min followed by immersing a piece of PA/CA fibrous thin film (ca. 2 cm * 2 cm) in the solution. After keeping the substrate for 2 h in the solution, it was rinsed with de-ionized water (DIW) and dried at room temperature to obtain the PANi nanowires-coated PA/CA (PANi/PA/CA) fibrous thin films. Then the PANi/PA/CA fibrous thin film was soaked in 1.0 M HCl for 30 min, then rinsed with DIW and dried at 25 oC in vacuum for 4 h. The concentrations of aniline were varied at 25, 50, 100, 200, and 400 mM. Accordingly, the concentrations of APS also varied at 8.3, 16.6, 33.2, 66.4, and 132.8 mM.

3. Results And Discussion

Page 199 of 1108

The surface morphologies of PA/CA fibrous thin film (Fig. 1a) showed the complete infiltration of cellulose acetate into the voids of nylon nanofibers with preserving its fibrous structure. The microstructure of the PANi/PA/CA electrode was observed by FE-SEM. Fig. 1b shows the thin film electrode morphology having highly homogeneous PANi nanowires. More detailed images were presented in Figs. 1c and 1d, and further revealed that the average diameters of the PANi nanowires were about 50 nm.

Figure 1 (a) SEM image of precursor PA/CA fibrous thin film. (b)–(d) FE-SEM images of in situ polymerized PANi nanowires on PA/CA thin film electrode prepared using 2000 mM of aniline monomer.

The cyclic voltammograms (CV) of the electrodes at different scan rates exhibited two pairs of redox peaks with respect to charge-discharge behavior and pseudocapacitance property of PANi (Fig. 2a). The electrochemical impedance spectroscopy of PANi /CFs was exhibited in Fig. 2b. In the high frequency range, the semicircle indicates charge transfer resistance R ct , the diameter of semicircle of the PANi/CF1 is smaller than that of others.

Figure 2 (a) Representative cyclic voltammograms of PANi/CF prepared using poly(AN-IA) precursor and (b) electrochemical impedance spectroscopy of the PANi/CFs prepared using different precursors.

Transmittance and sheet resistance were directly proportional to each other. An electrode with about 81% of transparency with sheet resistivity of 8700 Ω/sq was achieved using 25 mM of aniline. Among the PANi/PA/CA thin films, the electrode prepared using 2000 mM of aniline exhibited as low as 188 Ω /sq, which is corresponding to 5.32 mS/cm. The capacitance of the fabricated

Page 200 of 1108

supercapacitor decreased in the first 400 cycles followed by a slight increase between 400 and 500 cycles. Subsequently the capacitance was in decreasing mode between 500 and 700 cycles and then a very slight decrease was observed for cycles 700â&#x20AC;&#x201C;1000. About 61% of the capacitance was retained by the flexible PANi nanowire/PA/CA transparent electrode after 1000 cycles, indicating good capacitance retention of the electrode.

Fig. 3. Specific capacitance, transparence and capacitive retention of PANi nanowires/PA/CA flexible transparent electrode.

4. Conclusion We have successfully fabricated flexible PANi/CFs hybrid electrodes and PANi nanowires/PA/CA flexible transparent electrodes. It is noteworthy that the in situ polymerization technique for growth PANi on substrate is a simple, cost-effective, time-efficient, and promising candidate for applications such as supercapacitors, fuel cells, electronic displays and other optoelectronic displays.

5. References [1] Simon P, Gogotsi Y. Materials for electrochemical capacitors. Nat Mater 2008;7:845-54. [2] Devarayan K, Lei D, Kim HY, Kim BS. Flexible transparent electrode based on PANi nanowire/nylon nanofiber reinforced cellulose acetate thin film as supercapacitor. Chem Eng J 2015;273;603-9. [3] Mariano LC, Salvatierra RV, Caga CE, Koehler M, Zarbin AJG, Roman LS. Electrical properties of selfassembled films of polyaniline/carbon nanotubes composites. J Phy Chem C 2014;118:24811-8. [4] Lei D, Devarayan K, Seo MK, Kim YG, Kim BS. Flexible polyaniline-decorated carbon fiber nanocomposite mats as supercapacitors. Mater Lett 2015;154;173-6.

Page 201 of 1108

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

Fabrication of core-shell conducting fibers and their characteristics Jaeho Kim1, Youbin Kwon1, Ho Sung Yang1, Sarang Park1 and Woong-Ryeol Yu1 + 1

Department of Materials Science and Engineering and Research Institute of Advanced Materials (RIAM), Seoul National University, Gwanak-ro, Gwanak-gu, Seoul, 151-744, Korea

Abstract. Due to their versatile application to wearable electronics, flexible core-shell fibers with conducting core and polymer insulating shell have attracted much attention. The core-shell fibers exhibit good mechanical properties and stable electron transport due to multi-layered structure, suggesting their potential as a perfect building block for smart apparel as they could naturally be integrated into textiles during weaving processes. In the previous studies, highcost and complicate processes such as evaporation deposition or variable coating methods were used to manufacture core-shell conducting fibers. In this study, we investigate whether such core-shell fibers could be manufactured by using a wet spinning. For simplification, polyacrylonitrile (PAN) containing nanocarbons and styrene-co-acrylonitrile (SAN) are used as core and shell materials, respectively. Two major concerns in the process development are nozzle geometry and coagulation bath. By simulating the fluid behavior of spinning dopes within the nozzle, the desirable nozzle structure was designed. Additionally, in order to achieve proper mechanical properties of core-shell conducting fibers, optimal coagulation condition was studied. Keywords: wet spinning, core-shell fiber, conducting fibers

1. Introduction Fibers with core-sheath, hollow, or porous structures have many potential applications in microfluidics, photonics, and energy storage. Especially, conductive core-insulating shell fibers can mainly be exploited in the future electric devices due to its particular structure, i.e., the conducting core is covered by insulating layer, enabling to transport electrons without any loss of electrons. There have been many studies about nano scaled core-shell fibers. Despite of its large surface area, we found that nano fibers as the basic building block for the wearable devices draw some limitations, such as the processability and the device operational inefficiency. Although electrospinning provides a simple and highly versatile method for the fabrication of core-shell nanofibers [1], these electrospun nanofibers are too small and randomly aligned. Therefore, in this study, we tried to fabricate micron-sized core-shell fibers via wet spinning. To design a proper nozzle for core-shell spinning, numerical simulation was carried out [2], demonstrating that a core-cut nozzle is the most advantageous in electrospinning system because the stable core flow is formed by the shear flow of the shell fluid; hence no need extruded core pipe in the nozzle, and the core-cut geometry induces less polarized bound charges which can generate jet instability. In the current study, we examined whether such core-cut nozzle is effective in the wet spinning. We also explored a suitable coagulation for core-shell wet spinning system. In this study, we used CNT and graphene as a conducting material of the core. To introduce the conductivity with those materials, their dispersion in the solution is important, thereby establishing conducting path of the core. However, because of the difficulty of the CNT and graphene dispersion in the organic solvent due to their inhomogeneous or aggregation property [3, 4], few studies has been published [5]. Since Shigeta and Kamiya et al. reported that CNTs can be dispersed in organic solvent by polymers with ethylene chains as dispersion agents, we adopted dimethylformamide (DMF) and PAN as the organic solvent and dispersion agent, respectively.

2. Experimental 2.1 Numerical simulation for designing core-shell nozzle system +

Corresponding author. Tel.: + 82-2-880-9096 E-mail address: woongryu@snu.ac.kr

Page 202 of 1108

The fluid behaviour in the wet spinning nozzle system was simulated using the Multiphysics® software from COMSOL, Inc. The Navier–Stokes equation was coupled with the level-set method, which has been widely used to trace the evolution of interfaces [6]. Two fluids having different density and dynamic viscosity were assumed to be styrene-co-acrylonitrile (SAN) and polyacrylonitrile (PAN). SAN and PAN solutions were set to 2.24 and 3.61 Pa∙s respectively, and their density were 1.12 and 1.08 g∙cm-3. The surface tension coefficient was assumed to be 45mN/m. Liquids were assumed to be Newtonian and incompressible fluids for convenience. To simulate the application of core-cut nozzle into wet-spinning system, Navier-Stokes (1.1) and the Level Set physics [2] were used to describe the motion of the core and shell fluids and their interfaces.

 ∂u  + u ⋅∇u  + ∇p = ∇ ⋅ ( µ (∇u + (∇u )T ) ) + ρ g + Fst  ∂t  ∇ ⋅u =0

ρ

(1.1)

   ∂φ ∇φ   + u ⋅∇= + ∇ ⋅∇ φ γ  ∇ ⋅  −φ (1 − φ ) ε φ    ∂t ∇φ      Here, ρ , u , p, µ and g denote the density, velocity, pressure, dynamic viscosity and gravitational acceleration, respectively. F st , the surface tension force, is computed as follows:

( (

) )

Fst = ∇ ⋅ σ I − ( nnT ) δ

(1.2)

Here σ is the surface tension coefficient, I is the identity matrix, n is the interface normal and δ indicate a Dirac delta function that represents nonzero values at the interface between two fluids. Since the interface moves with the fluid velocity, u, the density and viscosity of the solution also need to be redefined across the µ φµcore + (1 − φ ) µ shell moving interface: = ρ φρcore + (1 − φ ) ρ shell and = The interface is kept by ε and γ . ε is the parameter controlling interface thickness and the reinitialization parameter, γ , is the maximum magnitude occurring in the flow. By manipulating these two parameters, we can control the interface thickness. All the parameters are referred from COMSOL library card.

Fig 1. (a) Photograph and (b) schematic diagram of the core-shell wet-spinning apparatus

2.2 Fabrication of the core-shell fibers PAN (Mw = 200,000 g·mol−1, Poly Science) was used as the shell layer and SAN (28.5 mol% AN, Mw = 120,000 g·mol−1, Sigma-Aldrich) was used as the core. 12wt% of PAN and 30 wt% of SAN were dissolved in N, N-dimethylformamide (DMF; purity 99.5%, Daejung Chemical). For preparing SAN core- PAN shell fiber, SAN colored by red ink was transferred to an injection syringe connected to a core of spinneret. PAN was transferred to an outer channel syringe connected to a 1/16 inch Teflon hose bridging to the spinning nozzle (Fig. 1). The extruded gel-like core-shell shaped solution was immersed into the coagulation bath. The

Page 203 of 1108

typical extruded flow rates of solutions for core and shell were set at 3 and 15 ml/hr. respectively. The three different coagulation conditions were prepared with DMF/water (7:3, 6:4, 5:5 v/v) solutions.

2.3 Preparation of conducting core-insulating shell solution CNT (Carbon Nano-material Technology Co. Ltd), graphene nanoplatelets with 5 micron-average particle diameters (XG science) and GO (CRESIN), obtained from the modified Hummers method were used a conducting material. PAN was used as dispersion agent of CNT and graphene. The mixture of 0.5 wt% of each CNT/GO and CNT/graphene nanoplatelets were dissolved in DMF (purity 99.5%, Daejung Chemical), then PAN solution, ranging from 0 to 2 wt%, was added to the suspensions and ultra-sonicated for 24h. The 12 wt% of PAN solution for the shell was consistently used.

3. Results and discussion

Fig. 2: (a) Schematic diagram of core-cut nozzle and transient behavior of the core fluid within the nozzle at (b) 0, (c) 0.1 (d) 0.3s after application of the pumping pressure. The red and blue region represents the SAN and PAN fluids.

The core-cut nozzle we adopted for making the core-shell fibers was practically simulated (Fig. 2). Since the simulation software was limited to a two phase flow model, the SAN was located in the core and the surrounding environment outside the nozzle, while the PAN was placed in the shell. The schematic diagram of the core-cut nozzle is shown in Fig. 2(a). The transient behavior of the core fluid within the nozzle chamber was shown in Fig. 2(b)-(c). As the core fluid envelope grows until its’ critical size, determined by the surface tension between two fluids, then the shear flow from the shell fluid thins the core fluids. The stable fluidic interface of the core-shell was observed in the Fig.2 (d) since the yellow line represents the interface. This behavior enables us to utilize core-cut nozzle in wet spinning system. By using this characteristic of the corecut nozzle, we will research that as the thinning length is longer, the core thereby acquires the better alignment within the nozzle chamber. Thus, the enhanced electrical conductivity of the core could be achieved by the extended nozzle chamber in axial direction.

Fig.3: SEM image of the (a) cross-sectional view of SAN-core/PAN-shell wet spun fiber (a), 0.5wt% of CNT/Graphene-core/ PAN-shell (b) and the micro view of CNT/graphene conducting core (c). Scale bars, 100 µ m (a), 30 µ m (b) and 1 µ m (c)

The products from the core-cut nozzle were shown in Fig. 3. The SEM images demonstrated that the corecut nozzle is also applicable to the fabrication of the core-shell fiber via wet spinning. Despite the fact that no external force (e.g. electric force) was applied other than the pumping pressure, the core-shell shape appeared.

Page 204 of 1108

This experimental observation agrees with the simulation result. The mechanical property changing with the various coagulation condition will be measured. The conductivity of the conducting core-insulating shell fibers and the insulative single fiber were measured as we prepared CNT/graphene mixture with PAN as a dispersion agent (as shown in Table.1). The core-shell fiber showed two times higher than the PAN single fiber in terms of resistance. Since the black colored conducting core was obviously observed (Fig. 3 (b) and (c)), we assumed that the conducting path in the core was formed. However, the conductivity of the both fibers were in the range of typical insulating materials. This low conductivity was caused by the relatively higher PAN composition to the each CNT and graphene, in which the conducting path was impeded by the insulating property of PAN. This result let us explore a proper formula of core solution. To increase conductivity, the PAN composition will be minimized while some other conducting material will be adopted. Note that the CNT/GO mixture as the other core solution was unable to be spun because GOs in the solution were insufficiently dispersed and they agglomerated in the neck of the nozzle. Additionally, the drawing effect in the wet spinning processing will be addressed since we expect that the drawing process would not only help the conducting material to be aligned in the core but also increase the flexural strength. Table 1: Conductivity of wet spun core-shell fibers and single fiber

* Sample 1 and 2 were core solutions with 0.5wt% of CNT and graphene, and 1 and 2 wt% of PAN solution were added respectively, and 12 wt% of PAN dissolved in DMF was used as shell layer. Sample 3 was single fiber fabricated with only 12wt% of PAN solution.

4. Summary We demonstrated that the core-cut nozzle, mostly used in electrospinning, can also be utilized in wetspinning system. This finding will open the opportunity in the fabrication of conducting core-shell fiber because the absence of the core exit pipe enables the conducting material to be aligned by the shear flow from the shell fluid in the nozzle. By doing so, a uniform conducting path in the core can be achieved. We will introduce the basic processing parameters that enhance the mechanical property and conductivity of core-shell wet spun fibers.

5. References [1] McCann, Jesse T., Dan Li, and Younan Xia. "Electrospinning of nanofibers with core-sheath, hollow, or porous structures." Journal of Materials Chemistry 15.7 (2005): 735-738. [2] Lee, Byoung-Sun, et al. "New Electrospinning Nozzle to Reduce Jet Instability and Its Application to Manufacture of Multi-layered Nanofibers." Scientific reports 4 (2014). [3] Shigeta, Masahiro, et al. "Dispersion of carbon nanotubes in organic solvent by commercial polymers with ethylene chains: Experimental and theoretical studies." Japanese Journal of Applied Physics 54.3 (2015): 035101. [4] Yang, Qing-sheng, et al. "The effective properties and local aggregation effect of CNT/SMP composites." Composites Part B: Engineering 43.1 (2012): 33-38. [5] Kou, Liang, et al. "Coaxial wet-spun yarn supercapacitors for high-energy density and safe wearable electronics." Nature communications 5 (2014). [6] Sethian, James Albert. Level set methods and fast marching methods: evolving interfaces in computational geometry, fluid mechanics, computer vision, and materials science. Vol. 3. Cambridge university press, 1999.

Page 205 of 1108

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

Fabrication of Superionic Conductive Nanofiber Young Ah Kang 1 +, Kyoung Hou Kim 2 and Yang Hun Lee 1 1

Department of Organic Material and Polymer Engineering, Dong-A University, Busan 604-714, Korea. 2 Faculty of Textile Science and Technology, Shinshu University, Nagano 386-8567, Japan.

Abstract. Superionic conductive organic-inorganic nanofiber can be fabricated by electrospinning of polyamide 6 (PA6) complex with iodide and by treatment of silver nitrate (AgNO 3 ) in order to approach a well-dispersed AgI nanoparticle in PA6 fiber structure. To apply a spinning solution for electrospinning, we prepared an iodophor compound solution with PA6 polymer and potassium iodide (KI), which was directly related to the nature of iodine interaction with the PA6 polymer, and fabricated successfully the complex membrane by the electrospinning process. The nanofibers composing of the membranes varied from about 30 to 300 nm in diameter with changing content of PA6, and the fiber diameters decreased remarkably for low content of PA6. With increasing content of KI, the as-spun complex nanofibers seemed to be stiffened. WAXD measurement of the as-spun complex nanofibers showed that crystal diffractions of PA6 as well as KI crystal increased comparing with nanofibers with only PA6. Keywords: superionic conductivity, silver iodide, polyamide 6, nanofiber, electrospinning.

1. Introduction Ionic conduction is a major premise for many applications of electrochemical devices, such as sensors and batteries. Silver ion conductors have been studied as battery electrolytes because silver iodide (AgI) shows extremely high ionic conductivity due to a partially molten Ag sublattice only above 147˚C when Ag+ ions becomes mobile and contribute to fast ion conduction, as called a solid superionic conductor [1-3]. The crystal structure of AgI is temperature dependent. Below 147˚C, β-AgI and γ-AgI exist, and above 147˚C stable αAgI develops. The level of ionic conductivity of α-AgI is extremely high and comparable to those of liquid electrolytes (about 1 S/cm). To obtain the superionic conductive high-temperature structure of α-AgI near room temperature, particle size was reduced to nano-level by several researchers, about 10-11 nm, and the high-temperature structure, α-AgI survived near room temperature [2, 3]. It may be caused by the quantum size effect, where the electronic properties of solids are altered with great reductions in particle size. Several researchers studied nanocomposite materials with AgI nanoparticle dispersed in matrices [2, 4], but β-AgI or γ-AgI of low ionic conductivity were formed in the composites. Therefore, in this study, we tried to fabricate a hybrid composite nanofiber with well-dispersed AgI nanoparticles, by electrospinning of iodophor compound solution with polyamide 6 (PA6) polymer and potassium iodide (KI) and then by treatment of silver nitrate (AgNO 3 ) aqueous solution. Fine structures of obtained nanofibers were characterized by scanning electric microscopy (SEM) and wide-angle X-ray diffraction (WAXD) measurements.

2. Experimental 2.1. +

Materials

Corresponding author. Tel.: + 82-51-200-7544. E-mail address: yakang@dau.ac.kr.

Page 206 of 1108

Poly(caprolactam) pellets (M w =35,000, [η]=4.1, Polysciences, Inc.) was used as a polymer to prepare the electrospinning dope. As solvents, formic acid and water were used, and their properties were presented in Table 1. KI was purchased from Junsei chemical Co. Ltd. All chemicals were used without further purification. Table 1: Solvent properties

2.2.

Solvent

Chemical Formula

Molecular Mass (g/mol)

Boiling Point (°C)

Density (g/ml)

Dielectric Constant

Formic acid water

HCOOH HOH

46.0 18.0

100.8 100

1.220 1

57.9 78.2

Preparation of nanofibers

For the preparation of spinning solution, PA6 was dissolved in formic acid to make a solution with a concentration of 10~20 wt%, which was stirred at room temperature until homogenous solution was produced. KI was also dissolved in formic acid with stirring at room temperature with concentrations of 5, 10, and 15 wt% . Spinning dopes were then prepared by mixing the both solutions. The electrospinning was carried out using a syringe and a 20 gauge needle with an applied voltage of 19 kV. The complex membranes were collected as a mat form on a grounded copper plate. The distance between needle tip and the grounded plate was 20 cm. The schematics diagram was presented in Fig. 1.

Fig. 1: Schematics of electrospinning apparatus.

2.3.

Measurements

The morphology of electrospun nanofibers was observed with magnified to 2,000 and 35,000 times using SEM (SEM, Hitachi S3500N). Based on the SEM images, the average fiber diameter could be determined. An X-ray generator (Rigaku, D/max-Ⅲ-A) with CuK α beam was used to obtain the WAXD intensity profile of the as-spun nanofibers.

3. Results and Discussion Fig. 2 presented SEM images of the electrospun membranes prepared with selected contents of PA6 and KI. The as-spun membranes were composed of nanofibers of which diameters ranged approximately from 30 to 300 nm. The prepared nanofibers showed smooth surfaces as well as well-controlled diameter. The fiber diameters decreased remarkably for complex membranes with 10 wt% content of PA6 (the bottom line for (a)) comparing with 20 wt% content (the top line for (a)). An original PA6 nanofiber membrane without KI content was inaccessible steadily. On the other hand, for 20 wt% content of PA6, the complex nanofibers seemed to be stiffened with increasing KI content. For images magnified to 35,000 times, nanofibers with 10 wt% content of PA6 were welded flatly one another, while nanofibers with 20 wt% content of PA6 nanofibers maintained separated fiber shapes.

Page 207 of 1108

(a)

(b) Fig. 2: SEM images of as-spun nanofibers: (a) ×2,000 and (b) ×35,000.

Fig. 3 showed WAXD intensity profiles of the as-spun fibers by electrospinning. For the nanofiber membrane with only PA6 (20:0), a sharp peak at about 2θ=21.9° (d=0.404 nm) in broad diffraction was observed. The peak intensity increased for complex nanofibers, and it may correspond to (200) diffraction of γ-crystal. For complex nanofibers, the strongest diffraction peak at about 2θ=25.3° (d=0.351 nm) appeared, which is probably due to KI crystal [5]. A diffraction peak appearing at near 2θ=36° is also presumably related to the α-crystal of PA6 [6]. Another peaks at around 2θ=42.5 and 44.5° were observed for complex nanofibers with 20 wt% content of PA6. Therefore, PA6 crystals seemed to be developed at room temperature after electrospinning. It may be caused by the fact that mobility of PA6 chains could increase because iodide ions were coordinated to amide groups of PA6. Accordingly, it can be explained that iodide ions was coordinated well to PA6 chain and PA6 molecules being free from iodide ion could be ordered.

Page 208 of 1108

Fig. 3: WAXD intensity profiles of as-spun nanofibers.

4. References [1] Saijo, H., Iwasaki, M., Tanaka, T., and Matsubara, T. Photogr. Sci. Eng. 1982, 26, 92. [2] Fujimori, Y., Gotoh, Y., Kawaguchi, A., Ohkoshi, Y., and Nagura, M. J. Appl. Polym. Sci. 2008, 108, 2814. [3] Makiura, R., Yonemura, T., Yamada, T., Yamaguchi, M., Ikeda, R., Kitagawa, H., Kato, K., and Takata, M. Nature Materials 2009, 8, 476. [4] Wang, Y., Ye, C., Wang, G., Zhang, L., Appl. Phys. Lett. 2003, 82, 4253. [5] Jeong, W.Y., Kang, Y.A., Lee, Y.H. J. Polym. App. Sci. 2004, 94, 1062. [6] Murthy, N.S., Szollosi, A.B., Sibilia, J.P. J. Polym. Sci. Polym. Phys. Ed. 1985, 23, 2364.

5. Acknowledgement This research was supported by the Ministry of Education, Science and Technology of Korea, from the Scientist in Local Universities support program (Grant No. NRF-2015R1D1A3A01020764) supervised by the NRF (National Research Foundation of Korea).

Page 209 of 1108

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

Fiber-Reinforced Rigid Polyurethane Foam Composite Boards: Manufacturing and Property Evaluations Yu-Chun Chuang 1, Chen-Hung Huang 2, Ting-Ting Li 3, 4, Ching-Wen Lou 5 and Jia-Horng Lin 1, 6, 7 + 1

Laboratory of Fiber Application and Manufacturing, Department of Fiber and Composite Materials, Feng Chia University, Taichung City 40724, Taiwan. 2 Department of Aerospace and Systems Engineering, Feng Chia University, Taichung City 40724, Taiwan. 3 School of Textiles, Tianjin Polytechnic University, Tianjin 300387, China. 4 Tianjin and Education Ministry Key Laboratory of Advanced Textile Composite Materials, Tianjin Polytechnic University, Tianjin 300387, China. 5 Institute of Biomedical Engineering and Materials Science, Central Taiwan University of Science and Technology, Taichung City 40601, Taiwan. 6 School of Chinese Medicine, China Medical University, Taichung City 40402, Taiwan. 7 Department of Fashion Design, Asia University, Taichung City 41354, Taiwan.

Abstract. Studies on protective or functional composites have been immensely developed, and such composites can be classified by their functions in terms of sound absorption, thermal resistance, mechanical impact, and puncture resistance. It has thus become a trend to develop function composites that are favorable to diverse environmental conditions, according to their required applications. This study proposes using carbon fiber (CF) and glass fiber (GF) as reinforcing fibers, which are then added to a polyurethane (PU) foam solvent. The PU foam then undergoes foaming and curing, in order to create multi-functional fiber-reinforced rigid PU foam composite boards. Mechanical property evaluations are performed on the resulting composite boards in order to determine their puncture resistance and impact resistance. The test results indicate that the composite boards have a sound absorption coefficient of 0.8 at a medium frequency, a thermal conductivity below 0.2 W/mK, and good mechanical properties. An amount of 5wt% reinforcing fiber can strengthen the puncture resistance and impact resistance of the composite boards, without undermining their sound absorption.

Keywords: polyurethane (PU) foam, fiber-reinforced, puncture resistance, impact resistance.

1. Introduction Polyurethane (PU) is a polymer of structural unit that contains urethane groups and isocyanate groups, and is a production of the foaming of isocyanate and polyol [1]. PU foam has a honeycomb form, and is insulating to electricity, heat, and sound. In addition, it is also lightweight, and has a high specific strength and ease of processing. These advantageous attributes allow PU foam to be commonly used [1-3]. PU foam is commonly used in packaging materials for furniture and in transportation, as well as used in industrial and construction materials, in noise protection fields [4-6] and thermal insulation fields [7, 8]. There is a great deal of composite materials, the majority of which is composed of polymers with fibers being their reinforcement. Therefore, the properties of composites are highly dependent on the properties and components of fibers. Based on their raw material and morphology, fibers can be divided into many types. The commonly used types include glass fibers, carbon fibers, and Kevlar fibers [9, 10], which have high hardness, high strength, high modulus, and chemical resistance, and thus are used in transportation equipment, aerospace applications, military applications, and shells of products. In this study, different densities of PU foam are used with the reinforcement of 5 wt% carbon fibers (CF) and glass fibers (GF). The incorporation of fibers is expected to change the nucleation structure of PU and strengthens the mechanical properties of PU foam composite boards. The compression, +

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

Page 210 of 1108

impact resistance, and puncture resistance of fiber-reinforced rigid PU foam composite boards are then evaluated in order to examine their mechanical properties.

2. Sample Preparation and Measurement 2.1. Materials PU foam solvent, provided by Zhong-Xing Chemical, Taiwan, is composed of polyol foaming agent and Isocyanate (MDI) hardener. The two reinforcing fibers are HTS 40 carbon fibers (Toray Ind. Inc., Japan) and glass fiber (Taiwan Glass Ind. Corp., Taiwan), which have 7 Îźm diameter, 6.2 mm length and 13Âľm diameter, 3.2 mm length, respectively.

2.2. Sample Preparation PU foam is fabricated by blends of polyol and MDI. The sample thickness is changed as 20 mm. PU foams are made into various foaming densities of 60, 70 and 80 kg/m3. The reinforcing fibers are carbon fibers (CF) and glass fibers (GF). The addition content of fibers is 5 wt%. For the foaming process, reinforcing fibers are uniformly blended first with polyol and then with MDI hardener, and finally are injected into a sealed metal mould for a 120-min curing to fabricate rigid fiber-reinforced PU foam composite boards. The volume of PU foam is fixed by the mould, and the type and content of reinforcing fibers are changed.

2.3. Measurement Compression As specified in ASTM D1621-10, standard test method for compressive properties of rigid cellular plastics, the samples are cut into 50 mm Ă&#x2014; 50 mmĂ&#x2014; 20 mm. The testing speed is 2 mm/min. The sample is compressed with a 25 % thickness of the samples. The test results are then used to compute the compressive modulus by incorporating the equation as follows (1.1). Ec=WH/AD (1.1) where Ec = modulus of elasticity in compression, Pa (psi); W = compression load, N (lbf); H = initial specimen height, m (in.); A = initial horizontal cross-sectional Farea, m2 (in.2); and D = deformation, m (in.).

Drop-Weight Impact Resistance This impact resistance test is conducted according to ASTM D4168-95 (2008) E1. The impactor is dropped on surface of 100 mm Ă&#x2014;100 mm sized samples. The residual impact force is used to characterize the cushion property of composite foam board. The original impact load is set as 10000 N. The residual impact load is given by the sensor set under the test sample. The test results are then used to compute the absorption of impact load by incorporating the equation as follows (1.2). đ??żđ??ż

đ??żđ??żđ?&#x2018;&#x17D;đ?&#x2018;&#x17D; = ďż˝đ??żđ??żđ?&#x2018;&#x153;đ?&#x2018;&#x153; ďż˝ Ă&#x2014; 100%â&#x20AC;Śâ&#x20AC;Śâ&#x20AC;Śâ&#x20AC;Śâ&#x20AC;Śâ&#x20AC;Śâ&#x20AC;Śâ&#x20AC;Śâ&#x20AC;Śâ&#x20AC;Śâ&#x20AC;Śâ&#x20AC;Śâ&#x20AC;Śâ&#x20AC;Śâ&#x20AC;Śâ&#x20AC;Śâ&#x20AC;Ś..(1.2) đ?&#x2018;&#x;đ?&#x2018;&#x;

Where đ??żđ??żđ?&#x2018;&#x17D;đ?&#x2018;&#x17D; = the absorption of impact load, %; đ??żđ??żđ?&#x2018;&#x153;đ?&#x2018;&#x153; = The original impact load, N; The residual impact load, N.

Static Puncture Resistance

Puncture resistance test is performed by using an Instron 5566 universal testing machine (Instron, U.S.) according to ASTM F1342-05. 4.5 mm diameter probes are attached on the cross head and then penetrated through 100 mm Ă&#x2014; 100 mm samples at a speed of 508 mm/min. The sample is compressed to 15mm thickness (25 % compression). Finally, static puncture resistance with corresponding displacement are recorded to characterize the puncture resistance property.

3. Results and Discussion 3.1. Compression of PU Foam The compression and modulus results of PU foam are indicated in Table 1. The PU foams have a thickness of 2 cm, and the compression range is 25 % of the thickness of the PU foam. The compression increases as a result of a PU foam density of 70 kg/m3. Because PU foam is managed by a sealed mould, a greater density causes the molecular chain extension and a higher cross-linking level during the reaction of PU foam. The pores thus have a higher rigidness, and thereby increase the compressive strength. However, a density of 80 kg/m3 causes the compression to decrease. When PU foam has pores with a higher rigidness, its toughness

Page 211 of 1108

decreases. The pore walls are subjected to breakage, and then collapse. As a result, PU foam with a density of 80 kg/m3 has a lower compression and modulus. The optimal compression occurs when the PU foam has a density of 70 kg/m3. Table 1. Compression resistance of PU foam in relation to different PU densities

D60 D70 D80

Density (kg/m3) 60 70 80

Compression (N) 472.2±47.04 539.4±47.07 399.9±48.40

Modulus (MPa) 7.55 8.63 6.40

3.2. Impact Resistance of PU Foam The impact resistance of PU foam is indicated in Figure 1. The PU foam with a thickness of 2cm have an impact resistance that increases when the PU density increases from 60 to 80 kg/m3. When the test results and impact load of 1000N are calculated for the absorption rate of impact load, all samples have an impact load absorption between 97-98 %. In other words, the three density parameters of 60, 70, and 80 kg/m3 are not in relation to the impact resistance of PU foam under a 10000N impact load. The PU foam distributes and dissipates the load caused by an externally applied force via the extrusion and collapse of its pores. Therefore, regardless of the density, the PU foam are instantly damaged and compressed by a high impact load. According to the test results that incorporates a 10000N impact load, the PU foam with a density of 60, 70, and 80 kg/m3 can absorb an impact load of 9700~9850 N, attaining an absorption rate of impact load between 97 % and 98 %.

Fig. 1: Absorption rate of impact load of PU foam in relation to different PU densities.

3.3. Static Puncture Resistance of PU Foam The static puncture resistance of PU foam is indicated in Figure 2. The static puncture resistance of PU foam is proportional to their density. This result is ascribed to an increase in the rigidness of the pores as a result of molecular chain extension and a high cross-linking level during the reaction process of PU foam. The static puncture resistance of PU foams stems from the resistance of their surface against the probe. A highly rigid PU foam thus has a high static puncture resistance. In particular, an optimal static puncture resistance of 48.9 N is present when PU foam are composed of a density of 80 kg/m3.

Fig. 2: Static puncture resistance of PU foams as related to PU densities.

3.4. Effects of Reinforcing Fibers on Mechanical Properties of Fiber-Reinforced PU Foam Composite Boards

Page 212 of 1108

According to the test results in 3.1, 3.2, and 3.3, the PU of 60 kg/m3 density is used to make the composite boards. 5wt% of carbon fibers or glass fibers are used as reinforcement that are added to PU foams. The mechanical properties of the fiber-reinforced PU foam composite boards are indicated in Table 2. The test results show that the incorporation of fibers positively improves the compression and puncture resistance of the composite boards. The composite boards also have a desired absorption rate of puncture load according to the drop-weight impact test. This result is due to the fact that the incorporation of fibers results in a higher rigidness of the structure, as well as increases a greater nucleation amount to the interior pores of the PU foam composite boards. A large amount of pores cause more friction when the probe damages and then penetrates the composite boards, and thereby provides the composite boards with a higher puncture resistance. Specifically, PU foam composite boards containing glass fibers have optimal mechanical properties. Glass fibers are composed of SiO 2 that have powerful hydrogen bonding force between it and the polarity group of PU molecular chain, which provides the composite boards with a higher rigidness. As a result, PU foam composite boards that are reinforced with 5 wt% glass fibers have an optimal compression of 585.4 N, an optimal impact resistance of 9788.9 N, and puncture resistance of 38.1N. Table 2. Mechanical properties of PU foam composite boards in relation to reinforcing fibers.

D60 CF-5% GF-5%

Density

Compression

(kg/m3) 60 60 60

(N) 458.6 522.2 585.4

Absorption of Impact Load (N) 9773.4 9794.5 9788.9

Puncture Resistance (N) 33.1 36.5 38.1

4. Conclusions This study examines the mechanical properties of PU foams that are composed of different PU densities, and also examines the influences of different reinforcing fibers on the impact strength, impact resistance, and puncture resistance of the PU foam composite boards. The test results indicate that the PU foam with a density of 70 kg/m3 have an optimal compression of 539.4 N, an optimal impact resistance of 9840.5 N, and an optimal puncture resistance of 46.1 N. In addition, the incorporation of glass fibers provides the PU foam composite boards with a higher rigidness, which is exemplified by the yields of an optimal compression strength (585.4 N), an optimal impact resistance (9788.9 N), and an optimal puncture resistance (38.1 N).

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-035-019-CC3.

6. References [1]

A. Demharter, Cryogenics, 38, 113-117 (1998).

[2]

D. Klempner, Hanser Munich, (1991).

[3]

G. Harikrishnan, S.N. Singh, E. Kiesel and C.W. Macosko, Polymer, 51, 3349-3353 (2010).

[4]

T.C. Hung, J.S. Huang, Y.W. Wang and K.Y.Lin, Constr. Build. Mater, 50, 328-334 (2014).

[5]

J.H. Lin , C.M. Lin, C.C. Huang, C.C. Lin, C.T. Hsieh and Y.C.Liao, J Compos Mater, 45(13), 1355-1362 (2011).

[6]

R. Verdejo, R. St채mpfli, M. Alvarez-Lainez, S. Mourad, M.A. Rodriguez-Perez, P.A. Br체hwiler and M. Shaffer, Compos Sci Technol, 69, 1564-1569 (2009).

[7]

C.H. Huang, J.H. Lin and Y.C. Chuang, J Ind Text, 0(00), 1-14(2013).

[8]

T.T. Li, Y.C. Chuang, C.H. Huang, C.W. Lou and J.H. Lin, Fiber Polym, 16(3), 691-698(2015).

[9]

L. Shen, F.Q. Wang, H. Yang and Q.R. Meng, Polym Test, 30,442-448 (2011).

[10] M. Wen, X. Sun, L. Su, J. Shen, J. Li and S. Guo, Polymer,53,1602-1610 (2012).

Page 213 of 1108

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

Growth of zinc oxide nanorodes with respect to surface condition of carbon fiber and post annealing Seung A Song 1, Soo Jin Ham 1 and Seong Su Kim 1 + 1

Department of Organic Materials and Fiber Engineering, Chonbuk National University, 567 Baekje-daero, Deokjin-gu, Jeonju-si, Jeollabuk-do, Republic of Korea.

Abstract. Many researchers have studied about methods to enhance the interfacial adhesion between fiber and matrix by using the surface treatment. However, most surface treatment such as acid treatment and plasma treatment have shown degradation of mechanical properties of carbon fibers. Accordingly, whiskers of carbon nanotubes and metal oxide nanorods (NRs) have been introduced to enhance the interfacial properties of composites through interpenetrating networks or mechanical interlocking. It can be grown at the solution of low temperature without degradation of mechanical properties from thermal or catalyst. However it takes a long time to grow ZnO NRs by using conventional hydrothermal method. In this work, the electrodeposition and microwave was used to attach the ZnO seed on the carbon fiber and the microwave was applied to grow the ZnO NRs for a short time. Single filament test was performed to investigate the mechanical properties of the carbon fiber before and after the ZnO NRs growth and and surface free energy of ZnO NRs grown carbon fiber was estimated from result of contact angle measurement. Micro-droplet test was performed to investigate the interfacial shear strength (IFSS) between the carbon fibers and polypropylene (PP) matrix. Scanning electron microscopy (SEM) is used to confirm the impregnation state of PP matrix and fracture mode after IFSS test.

Keywords: Zinc oxide nanorods (ZnO NRs), Interfacial shear strength (IFSS), Micro-droplet test, Electrodeposition, Microwave.

1. Introduction Carbon fiber reinforced polymers (CFRPs) have outstanding properties such as high specific strength and stiffness, light weight, high thermal stability, high thermal conductivity and corrosion resistance, which have led to numerous advanced applications in areas of high technology [1, 2]. As our knowledge of CFRPs, one of the most important factors in properties of fiber reinforced composite is the quality of the interface between the reinforcement and matrix. A strong fiber and matrix may not necessarily result in strong composite because the polymer matrixes exhibit poor interfacial adhesion with carbon fibers (CF) because of their low surface energy and chemically inert surface [2]. Many prominent researchers have investigated methods to enhance the interfacial adhesion between fiber and matrix. Chemical treatment, fiber coating surface treatment and functionalizing treatment have shown promising results for improvement of interface shear strength, however, the mechanical properties of fiber are significantly degraded after the treatments [1,2]. Therefore, recently carbon nanotubes, silicon carbide nanowire and whiskers have been used to enhance the interfacial properties of composites. These methods increased the interfacial strength by interlocking without decreasing mechanical properties of fibers [3]. However, the conventional methods require the high growth temperature and catalysts for growth of the nanowires or nanorods. The high growth temperature may degrade the fiber strength and significantly reduce the compositeâ&#x20AC;&#x2122;s in-plane properties Therefore, methods for ZnO synthesis at low temperature was introduced by using the hydrothermal method. The hydrothermal method can be carried out at a low temperature around 60-90Â°C [4]. However, this method is not adequate for the mass-production because it takes long time to grow the ZnO NRs. In this work, the ZnO NRs were grown on the carbon fiber under low temperature without degrading the mechanical properties of the fibers. Plasma treatment was applied to the carbon fibers before the NRs growth to increase the interfacial strength between the fibers and ZnO seed layer by functionalizing the carboxylic +

Corresponding author. Tel.: + 82-063-270-2336. E-mail address: sskim@jbnu.ac.kr.

Page 214 of 1108

acid group on the fiber surface. X-ray photoelectron spectroscopy (XPS) was performed to investigate the effect of plasma treatment. Scanning electron microscopy (SEM) is used to confirm the ZnO NRs growth morphology on the carbon fiber surface. To investigate the interfacial strength between ZnO NRs and carbon fibers, micro-droplet tests were performed.

2. Materials and experimental 2.1. ZnO seed coating process on the carbon fiber Functional group like carboxylic acid can increase the interaction between the carbon fibers and the ZnO seed layer. Ar/O 2 mixture plasma treatment was performed to enhance the oxygen fraction on the carbon fiber surface. The Ar and O 2 gas flow rate are 30 and 60 sccm respectively and 400 W power is applied for 10 minutes.

2.2. ZnO NRs growth on the carbon fiber Fig. 1 shows the preparation process and experimental process for the growth of ZnO NRs. The formation of ZnO seed on the carbon fiber is carried out by dissolving 0.0125M zinc acetate dihydrate (Zn(CH3COO)2∙2H2O, Sigma Aldrich Co. LLC., USA) in ethanol at 50°C using magnetic stirrer. The solution is diluted with additional solvent to a concentration of 0.0014 M. And then, the solution was cooled to room temperature. A NaOH (Samchun chemical Co. LTD., Korea) is dissolved in ethanol solution at 60°C to make the 0.02 M NaOH solution and after cooling is diluted to a concentration of 0.0057 M. The two solutions are continuously stirred at 50°C for 30 min by a volume ratio of 18:7 [4]. The carbon fibers were dipped into the seeding solution and then annealed at 150°C for 10minutes to enhance adhesion between the carbon fibers and the ZnO seed. ZnO seed coated carbon fiber was rinsed in deionized (DI) water to remove the residual seed on the carbon fiber. The ZnO seed coated carbon fibers were soaked into the ZnO growth solution. The ZnO NRs growth solution was fabricated by dissolving the 0.025 M zinc nitrate hydrate (Zn(NO 3 ) 2 ∙6H 2 O, Sigma Aldrich Co. LLC., USA) with hexamethylenetetramine (HMTA) of 0.025 M (C6H12N4, Sigma Aldrich Co. LLC., USA) in DI water at 70°C. The growth process was performed in a sealed container with the solution temperature maintained at 90°C for 4 hours in the oven. And then ZnO NRs coated carbon fiber rinsed several times in DI water to finish the reaction and rinsed carbon fiber was dried at 60°C for 30 minutes in atmosphere.

3. Characterization We installed a 5 N load cell and a micro-vise in the tester. The gap between a pair of micro-vise tips was about 20 µm considering the meniscus size of the droplet whose embedded lengths ranged from 80 to 130 μm. The center of a single fiber was positioned at the center of the gap between vise tips by an incremental adjustment in the XYZ direction. After adjusting the specimens to the micro-vise jaw, the upper jig of the universal testing machine was moved with a displacement rate of 0.1 mm/min. More than 10 specimens for each sample were tested and averaged to get the IFSS.

4. Result and discussion Ar/O 2 mixture gas plasma assisted the formation of C-O and O-C=O bonds because Ar/O 2 mixture gas has high concentration of active oxygen compared with pure O 2 plasma [5]. That oxygen peak was increased on plasma treated carbon fiber (PCF) as shown in Figure 2 (c). The hydroxyl group (C-O(H)), and carboxyl group (COO(H)) were detected on the plasma treated carbon fiber surface. Some of the carbonyl group (C=O) were also detected as shown in Fig. 2. These results are attributed to the formation of functional group on the carbon fiber surface by the plasma treatment. SEM micrograph of hydrothermally grown ZnO NRs on the carbon fiber surface is illustrated in Figure 3 (a). The ZnO NRs on the sized carbon fiber surface was randomly attached because ZnO seed layer was not properly formed on the sized carbon fiber. In the case of DCF and PCF, the ZnO NRs are aligned radially on the carbon fiber surface while maintaining an almost uniform length and distribution in Figure 3 (b) and (c). Fig. 4 shows the micro-droplet test results. From the results, ZnO NRs grown carbon fiber has higher interfacial shear strength compared with specimens without ZnO NRs due to the mechanical interlocking effect. The plasma treated carbon fiber has low interfacial shear strength because plasma treatment formed the groove

Page 215 of 1108

on the surface of carbon fiber. And polypropylene cannot impregnated into the groove of carbon fiber due to their high molten viscosity. Carbon fiber Carbon fiber Solution 1

Solution 1

Zinc acetate dehydrate (0.0014M) aqueous solution was mixed with NaOH (0.0057M) aqueous solution at 50째C (Volume ratio 18:7)

Carbon fiber was soaked in the ZnO seed solution

Carbon fiber was annealed in the ZnO seed solution at 150째C for 10min (2 times)

ZnO seed coated carbon fiber

Teflon film

Solution 2

Solution 2 Zinc nitrate hexahydrate (0.025M) was mixed with hexamethylenetetramine (HMTA; 0.025M)

ZnO seed coated carbon fiber was annealed in solution2 at 90째C for 4h

Carbon fiber was rinsed using deionized (DI) water and dried at 100째C

Fig. 1: ZnO NRs growth process on the carbon fiber surface using the hydrothermal method. (b)

(a)

C-C C-C

C-O C=C

C=C COOH

C-OH

C=C

Fig. 2: C1s XPS spectra with respect to surface condition of carbon fiber; (a) epoxy sized carbon fiber, (b) neat carbon fiber, (c) plasma treated carbon fiber. (c)

(b)

(a)

(d)

(e)

Page 216 of 1108

Interfacial shear strength (MPa)

Fig. 3: SEM topographies of the ZnO NRs grown carbon fiber surface; (a) ZnO NRs on the sized carbon fiber using the hydrothermal method, (b) ZnO NRs on the neat carbon fiber using the hydrothermal method, (c) ZnO NRs on the plasma treated carbon fiber using the hydrothermal method, (d) ZnO NRs on the neat carbon fiber using the microwave, (e) ZnO NRs on the neat carbon fiber using the electrodeposition method. 8

4.82

4.96 6

4.53

3.34

5.30 3.46

4 1.41 2 0

Fig. 4: Micro-droplet test result with respect to surface condition of the carbon fiber.

5. Conclusion In this work, ZnO NRs were grown on the carbon fiber surface using microwave and electrodeposition method to improve the interfacial shear strength between carbon fiber and matrix. Based on the experiments, the following results were obtained; (1) Ar/O 2 mixture gas plasma assisted the formation of C-O and O-C=O bonds. (2) The ZnO NRs on the sized carbon fiber surface was randomly attached because ZnO seed layer was not properly formed on the sized carbon fiber. In the case of DCF and PCF, the ZnO NRs are aligned radially on the carbon fiber surface while maintaining an almost uniform length and distribution (3) ZnO NRs grown carbon fiber has higher interfacial shear strength compared with specimens without ZnO NRs due to the mechanical interlocking effect. (4) The plasma treated carbon fiber has low interfacial shear strength because plasma treatment formed the groove on the surface of carbon fiber. And polypropylene cannot impregnated into the groove of carbon fiber due to their high molten viscosity.

6. Acknowledgements This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning(2011-0010156); it was also supported in part by the Korea Institute for Advancement of Technology (A000600052); and it was also supported by Kolon Industry.

7. References [1] Wong KH, Mohammed DS, Pickering SJ, Brooks R. Effect of coupling agents on reinforcing potential of recycled carbon fibre for polypropylene composite. Composite science technology 2012;72(7):835-844. [2] Fuad MYA, Ismail Z, Ishak ZAM, Omar AKM. Application of ricehuskash as fillers in polypropylene: Effect of titanate, zirconate and silane coupling agents. European polymer journal 1995;31(9):885-893. [3] Drzal LT, Rich MJ, Lloyd PF. Adhesion of Graphite Fibers to Epoxy Matrices: I. The Role of Fiber Surface Treatment. The journal of adhesion 1983;16(1):1 -30. [4] Lin BY, Ehlert G, Sodano HA. Increased interface strength in carbon fiber composites through a ZnO nanowire interphase. Advanced functional materials 2009; 19:5654-2660. [5] Chen C, Liang B, Ogino A, Wang X, Nagatsu M. Oxygen functionalization of multiwall nanotubes by microwaveexcited surface-wave plasma treatment. The journal of physical chemistry C 2009;113:7659-7665.

Page 217 of 1108

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

Heat and Moisture Transfer Properties of Natural Silkworm Cocoons Xing Jin 1, Jin Zhang 1 and Xungai Wang 1 2 + 1

Australian Future Fibres Research & Innovation Centre, Institute for Frontier Materials, Deakin University, Geelong, Australia 2 School of Textile Science and Engineering, Wuhan Textile University, Wuhan, China

Abstract. Many species of insect larvae can construct cocoons to protect themselves against potential hazards such as predation and extreme weather conditions, while supporting their metabolic activity. The silkworm cocoons, as typical examples of them, have been investigated widely in recent years. In the present investigation, the heat and moisture transfer properties of both domestic Bombyx mori (B. mori) and wild Antheraea pernyi (A. pernyi) silkworm cocoons have been studied. The knowledge from this natural protective system contributes to developing advanced materials and structures with superior protection performance. The temperature of cocoon exterior and interior under warm and cold conditions was monitored for investigating their thermal insulation function. In the platinum series of temperature and humidity standard chamber (ESPEC), the moisture transfer characteristics of A. pernyi and B. mori silkworm cocoons have been studied. The wild A. pernyi cocoon shows significant thermal buffer against environmental temperature changes. On the other hand, the domestic B. mori cocoon has shorter temperature lag when the surrounding conditions are changed. For moisture transfer characteristics, the wild A. pernyi cocoon reveals a higher moisture resistance than that of B. mori cocoon. The higher thermal and moisture resistance of A. pernyi cocoon is mainly caused by the cubic mineral crystals in the outer section, low porosity and high tortuosity. The characteristics of A. pernyi cocoon can promote the survival chance of the A. pernyi pupa under extreme weather conditions. Compared with A. pernyi cocoon, B. mori cocoon has a higher porosity and lower tortuosity, which cannot affect the air and moisture transfer through the cocoon wall, leading to lower thermal and moisture resistance. Therefore the breathability of B. mori cocoon is excellent and can assist with maintaining comfort conditions inside.

Keywords: Silkworm cocoon, Biological structure, Thermal property, Moisture transfer

1. Introduction A perennial problem in the development of protective clothing is the difficulty in realizing both protection and comfort for the wearer. Clothing with good protection, against extreme weather conditions, is usually heavy and bulky, with poor breathability, hence uncomfortable to wear. Evolved over many millions of yearsâ&#x20AC;&#x2122; natural selection, the thin and lightweight wild silkworm cocoon shell provides multiple protective functions against environmental and physical hazards, promoting the survival chance of moth pupae resides inside. By comparison, the domestic silkworm cocoon shell promotes the living condition of the pupa in the indoor environment. A silkworm cocoon is made of silk fibres that are spun around the silkworm pupa when it is undergoing transformation. It is a light porous multilayer structure, constructed from continuous twin silk filaments (fibroin) bonded by silk gum (sericin). From the composite materials point of view, a silkworm cocoon can be considered as a porous matrix of sericin reinforced by randomly oriented continuous silk fibroin. Pores with different sizes are located between the silk filaments and they can be either interconnected or disconnected. As +

Corresponding author. Tel.: +61 3 52272894 E-mail address: xwang@deakin.edu.au

Page 218 of 1108

the silk spinning continues towards the center, the silk filaments become finer and stronger, as a result of the increased crystallinity and molecular orientation of silk polymer. In contrast to the domestic B. mori cocoon, the structure of the Chinese tussah silkworm A. pernyi cocoon is more compact. Cubic mineral crystals are present on the outer surface of the A. pernyi cocoon, while there are no crystals in B. mori cocoon [1]. These crystals have been identified as calcium oxalates, which show unique functionality such as preferential gating of CO 2 transfer [2]. As a typical porous composition, silkworm cocoons have been investigated on mechanical and physical properties by a number of researchers due to its functional support of the pupa during metamorphosis [3, 4]. The knowledge from this natural protective system gives insight into the development of advanced protection materials and structures. However, limited research has been conducted on the different thermal and moisture transfer functions from varying silkworm cocoons. In this work, both domestic B. mori and wild A. pernyi silkworm cocoons were tested in the oven, fridge and humidity chamber to investigate their thermal and moisture transfer functions.

2. Materials and methods 2.1. Materials Two silk cocoon varieties, the wild A. pernyi and the domestic B. mori, were used. The wild A. pernyi cocoons were of Chinese origin and the domestic B. mori cocoons were obtained from the Physics laboratory of National University of Singapore.

2.2. Methods 2.2.1. Temperature monitoring A. pernyi and B. mori silkworm cocoons were tested in the oven (Binder) and fridge (Thermo scientific) to investigate their heat transfer properties. The oven temperature was set as 50 째C to simulate the warm condition; the fridge temperature was set as 4 째C to simulate the cold condition. The temperature was measured inside of A. pernyi and B. mori cocoons (about 10 mm away from the outer surface) at the same time using two needle-type temperature probes (from ICT SFM, a sap flow meter produced by ICT international Pty. Ltd.). Each temperature probe is 1.3 mm in diameter and 35 mm in length, with two sensors located 15 mm apart (one of the sensors is 7 mm distant from the needle tip). The temperature probe was placed into the cocoon through the proximal end from which the moth usually escapes and the data was recorded every second. The silkworm cocoons were translocated from ambient environment to an oven or a fridge, after the cocoon interior temperature reached the setting values, the silkworm cocoons were moved back to the ambient environment. Under the same environmental condition, the silkworm cocoons were tested three times and the standard deviations were indicated in the graphs as error bars. 2.2.2. Relative humidity monitoring and simulation A. pernyi and B. mori silkworm cocoon walls were tested in the platinum series of temperature and humidity standard chamber (ESPEC, Model 306-421, HUDSONVILLE, MICHIGAN, USA), in which the relative humidity measurements were conducted. The relative humidity inside and outside the cocoons were measured by the sensors SHT71 combined with the evaluation kit EK-H4 (The sensors and the evaluation kit EK-H4 are produced by Sensirion AG). The experiments were conducted in a silent surrounding condition (the air velocity in the surrounding was controlled to be less than 0.3 m/s). During the testing, the temperature in the chamber was controlled to be 20 째C. After the samples were placed in the chamber, the relative humidity increased from a lower relative humidity value (about 50%); after the relative humidity became higher than 90%, it was kept for a period of time, and then decreased back to a low relative humidity value (about 60%). 2D A. pernyi and B. mori cocoon models were built to simulate the moisture transfer process through the cocoon walls. The geometries of the cocoon walls in the models were constructed based on the cross section of the natural cocoons. For simulation, the following assumptions were introduced: (1) The cocoon walls are homogeneous in terms of fibre arrangement and material properties; (2) The fluid is composed of dry air and water vapour; (3) No shrinking, expansion or movement of the cocoon

Page 219 of 1108

structure occurs during moisture transfer; (4) The fluid channels are much larger than the mean free path of the fluid molecules thus the continuum hypothesis holds.

3. Results and discussion 3.1. Thermal insulation of cocoons Both the domestic B. mori and wild A. pernyi cocoons were tested in the oven or fridge. Fig. 1 shows the temperature profiles of locations inside the B. mori cocoon and the A. pernyi cocoon. In the beginning of the heat transfer process, when the temperature difference between surrounding and cocoon interior temperature was high, the temperature changing rate inside the B. mori cocoon was higher than that inside the A. pernyi cocoon. As a result, the A. pernyi cocoon showed relatively slower changing rates and therefore more significant thermal buffer than the domestic B. mori cocoon. With the progress of the heat transfer process, the inner temperature difference between two cocoons decreased after reaching a maximum value. When the cocoons were shifted to the ambient surrounding from the oven or fridge, the cocoon interior temperature changed in a reverse direction, the temperature changing rate inside the B. mori cocoon was still higher than that inside the A. pernyi cocoon, showing a higher thermal resistance of A. pernyi cocoon.

Fig. 1: Temperature profiles for locations both inside the A. pernyi cocoon and the B. mori cocoon. (a) in the oven; (b) in the fridge

The porosity of B. mori cocoon is higher than A. pernyi cocoon, leading more air can be stored in the B. mori cocoon. If the air was silent, the B. mori cocoon should have a higher thermal resistance. But the opposite result was observed from the experiment. Therefore, natural convection in the cocoon wall was unavoidable in the heat transfer process, caused by the temperature difference between the interior and exterior of the cocoon. In the A. pernyi cocoon, the organization of silk fibres is more compact and the gap among the fibres is much smaller and arranged with high tortuosity [5]. This kind of structure can weaken the convection and therefore reduce the heat transfer by convection, resulting in reduced heat flux through the cocoon wall. It also explains why the temperature difference between the A. pernyi cocoon interior and B. mori cocoon interior was larger at the initial stage and decreased later. At the initial heat transfer stage, the temperature between the surrounding and the cocoon interior was larger so the natural convection was more drastic. The fibre structure of the A. pernyi cocoon wall assisted with reducing natural convection effectively. With the heat transfer time, the temperature difference between surrounding and interior became smaller, especially for the B. mori cocoon, the insulation function of the A. pernyi cocoon wall was not as obvious and the temperature difference between the A. pernyi cocoon and B. mori cocoon interior decreased.

3.2. Moisture transfer through cocoons A. pernyi and B. mori silkworm cocoons were tested in the humidity chamber. Fig. 2 shows the relative humidity profiles of locations inside and outside the A. pernyi and B. mori cocoons. Under the same condition, a lower relative humidity gradient occurred inside the A. pernyi cocoon, indicating its higher moisture resistance. Computational fluid dynamics (CFD) models were built to simulate the moisture transfer process through the cocoon walls. From the models, the micro-flow field within the cocoon walls were

Page 220 of 1108

investigated. The pressure difference between the outer and inner surfaces of the cocoon walls is shown in Fig. 3. The pressure difference was caused by the kinetic energy loss of the moisture flow through the cocoon wall. High pressure difference indicates the high moisture transfer resistance. In Fig. 3, the positive pressure difference signifies the moisture transfer from outer to inner surface of the cocoon wall. The negative pressure difference, however, indicates the moisture transfer in the opposite direction. Compared with B. mori cocoon wall, the pressure difference through the A. pernyi cocoon wall is higher in both directions, showing the higher moisture transfer resistance of the A. pernyi cocoon wall.

Fig. 2: Relative humidity profiles for locations inside and outside the A. pernyi and B. mori cocoons.

Porosity and tortuosity of the cocoon can influence the moisture transfer process through it. Porosity is a measure of void volume fraction over the total volume in a porous material, which is proportional to the moisture transmission rate. Tortuosity expresses the path of the water vapour transferred in the cocoon wall being tortuous. The resistance of the substance diffused in the porous media with a higher tortuosity can be also increased. Due to the high porosity and low tortuosity, B. mori cocoon exhibits a lower moisture resistance. The structure of A. pernyi cocoon wall is more compact, which lead to lower porosity and higher tortuosity, causing a higher moisture resistance. This ability of A. pernyi cocoon can prevent the room inside the cocoon from over wetting and further decrease the heat loss under cold conditions.

Fig. 3: Pressure difference through the A. pernyi and B. mori cocoon walls.

4. Reference [1] Zhang, J., Rajkhowa, R., Li, J., Liu, X., and Wang, X., Silkworm cocoon as natural material and structure for thermal insulation. Mater. Des., 2013. 49:842-849. [2] Roy, M., Meena, S., Kusurkar, T., Singh, S., Sethy, N., Bhargava, K., Sarkar, S., and Das, M., Carbondioxide Gating in Silk Cocoon. Biointerphases, 2012. 7:1-11. [3] Jin, X., Zhang, J., Gao, W., Li, J., and Wang, X., Cocoon of the silkworm Antheraea pernyi as an example of a thermally insulating biological interface. Biointerphases, 2014. 9:1-11. [4] Zhang, J., Kaur, J., Rajkhowa, R., Li, J., Liu, X., and Wang, X., Mechanical properties and structure of silkworm cocoons: A comparative study of Bombyx mori, Antheraea assamensis, Antheraea pernyi and Antheraea mylitta silkworm cocoons. Mat Sci Eng C-Mater, 2013. 33:3206-3213. [5] Horrocks, N.P.C., Vollrath, F., and Dicko, C., The silkmoth cocoon as humidity trap and waterproof barrier. Comp Biochem Phys A, 2013. 164:645-652.

Page 221 of 1108

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

High spatial resolution confocal Raman mapping: New frontiers in carbon fibre research Andrea L Woodhead 1, 2 +, Bronwyn L Fox 2 and Jeffrey S Church 1 1

CSIRO Manufacturing Flagship,PO Box 21, Belmont, VIC 3216, Australia Institute for Frontier Materials, Deakin University, Waurn Ponds, Geelong, Victoria 3216, Australia

Abstract. Carbon fibre and its composites are rapidly becoming the material of choice in a wide range of applications due to their unique properties. To realise the full potential of carbon fibre, a better understanding of its structure and the correlation to its properties is required. Raman spectroscopy can provide detailed chemical and structural information about carbon fibres, including the relative amounts of graphitic, disordered and amorphous carbon present. In this paper we probe the structure of the pitch based carbon fibre surface and its cross-section. The fibre structure is dominated by low level sp2 order with micron scale pockets of highly ordered graphitic carbon near the surface. The results clearly demonstrate the power of confocal Raman mapping in developing a better understanding of the carbon fibre structure. Keywords: carbon fibre, confocal Raman spectroscopy mapping, chemical and structural information

1. Introduction There is an increasing demand for the use of carbon fibres (CF) and carbon fibre composites in a broad range of applications, including aerospace, military, engineering, automotive, and sporting uses, due to their lightweight, high strength, high modulus, high heat tolerance and chemical resistant properties [1]. With the increasing demand comes the need to better understand the correlations between manufacturing parameters and the final characteristics of the carbon fibre. Many techniques, including X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, scanning tunnelling microscopy (STM) and surface energy analysis have been used to gain an understanding of the CF structure and surface [2, 3]. These methods have shortcomings in that they either provide no chemical information or the information is at a low spatial resolution. Recent developments in Raman spectroscopy, including confocal and area mapping capabilities, provide the potential to obtain highly spatially resolved (sub-micron) chemical and structural information about CF surfaces. In this work we investigate the capability of confocal Raman spectral mapping and a number of visualisation techniques to provide detailed information regarding the structure of P25 pitch based carbon fibres. P25 CF was chosen as we previously found marked variations in the fibre surface structure including zones of highly graphitic material [2]. Mapping the fibre along the longitudinal surface as well as cross section will give insight into the distribution of graphitic zones along the surface of the fibre as well as throughout the fibre.

2. Experimental 2.1 Materials Low modulus pitch based Thornel P25 (Cytec) carbon fibres were used for in this study. For longitudinal maps, single fibres were mounted on glass microscope slides using adhesive tape at both ends to ensure the +

Andrea Woodhead. Tel.: +61-3-52464000 E-mail address: andrea.woodhead@csiro.au

Page 222 of 1108

fibres were taut, but not under tension. For the cross sectional maps, a bundle of fibres was threaded through heat shrink tubing which was then shrunk and the end cut to expose the carbon fibre cross sections.

2.2 Confocal Raman spectroscopy maps Raman spectral maps of longitudinal sections were obtained using an inVia confocal microscope system (Renishaw, Gloucestershire, UK) equipped with a Streamline charge coupled device (CCD) camera. The excitation of 514 nm from an argon ion laser through a ×50 (0.75 na) objective gave an incident laser power of 4.5 mW at the sample as measured using an Ophir Nova power meter. The fibres were orientated parallel to the polarisation of the laser with the aid of a rotating stage. Raman spectral maps were collected in highly confocal mode over an area approximately 56.5 × 2 .5 μm with 0.5 μm steps between data points, giving a total of 565 data points per map. Each spectrum was a single static accumulation with a 10 s exposure time over the range of approximately 842 - 2087 cm−1. Maps of fibre cross sections were collected using the standard CCD camera and a ×100 (0.85 na) objective which gave a laser power of 3.44 mW at the sample surface. The circular maps were collected in highly confocal mode over the area of the cross section (diameter ~9 µm) with 0.5 μm steps between data points, the total number of data points per map varied based on fibre diameter. Each spectrum was a co-addition of two static accumulations with a 10 s exposure time over the range approximately 1175 - 1770 cm-1. The Raman shifts were calibrated using the 520 cm−1 line of a silicon wafer. The spectral resolution was ∼1 cm−1. D/G ratios were calculated from the intensities of the D (~1354 cm−1) and G (~1576 cm−1) bands and false colour maps created using WiRE software version 4.2 (Renishaw, Gloucestershire, UK). All Raman maps were translated onto the same colour scale through the use of a look-up table.

3. Results 3.1 Longitudinal Mapping The Raman spectra shown in Figure 1 were obtained from the surface of a P25 fibre. They are typical for that expected from CF.

Fig. 1: Range of Raman spectra obtained from the longitudinal surface of a P25 fibre showing G band variation.

The dominant features of spectra from carbon based materials are the so-called disordered induced (D) and graphitic (G) bands that are due to the stretching vibrations of the C-C bonds [4]. These bands are associated with the presence of sp2 (trigonal-planar) hybridised carbon atoms. The D band is a breathing mode of A 1g symmetry. In perfect graphite this mode is forbidden but becomes active in the presence of disorder [5]. The G band arises from the in-plane bond stretching motion of pairs of sp2 hybridised carbon atoms and has E 2g symmetry [5]. The presence of amorphous carbon, whilst not a clearly defined band, is detectable as a broad underlying feature between the D and G bands[4]. The D’ band, which often appears as a shoulder on the high energy side of the G band, is also part of the first order CF spectrum, and is attributed to disordered graphitic structure [4].

Page 223 of 1108

As evident from Figure 1, large variations in the amount of graphitic material present were observed in the spectra obtained across the mapped area. While the D band was consistently observed at 1354 cm-1, the sharp G band is observed in varying degrees across the mapped region. For PAN based carbon fibre, it is generally accepted that the D’ feature is a weaker band seen as a shoulder on the side of the G band. Whilst this appears to be the case in the pitch based fibre spectra that exhibit an intense graphitic band, as the intensity of the G band reduces the dominance of the D’ band (~1612 cm-1) on this region of the spectra becomes evident (lowest trace of Figure 1). The G band frequency appears to shift to lower frequency (1579-1574 cm-1) with increasing relative band intensity. These changes can be attributed to increased bond disorder and decreased graphitic crystallite size, respectively [5]. A map of the D/G intensity ratio, shown in Figure 2 (left) enables visualization of the distribution of ordered graphitic material at a sub-micron resolution. Distinct regions of such graphitic structure on the order of a micron can be visualized in the dark blue/purple regions of the map. The spectra from these zones are consistent with that shown as the top trace in Figure 1. Representation of the data as a histogram (Figure 2, right) reveals a multi-modal distribution of the D/G values. It clearly illustrates the spread of D/G values across the mapped area, in this case showing the majority of the area has low levels of graphitic order. 1.20

10 1.03

D/G 10 μm

Frequency

0.92

6 4

0.80

0.15

1.11

0.70

0.2

0.4

0.6

0.8

1.2

D/G ratio

Fig. 2: False colour D/G map (left) and histogram of D/G values (right). The map colours match those of the corresponding spectra shown in Fig. 1.

3.2 Cross section Mapping The spectra obtained from a typical fibre cross section exhibited similar variations to that observed in spectra from the longitudinal map. The lowest trace of Figure 3 suggests that the intensity of the D’ (~1612 cm-1) is slightly higher than that of the D band (1354 cm-1). This is in contrast to the observations in the longitudinal map. This is possibly due to the structural orientation of the sample relative to the polarised laser.

Fig. 3: Range of Raman spectra from a P25 cross section.

Page 224 of 1108

Several different cross sections from the same CF tow were mapped. The number of graphitic regions detected in any given cross section varied from none to a few. In all cases the graphitic zones appeared to be located towards the edge of the cross section. An example of D/G intensity ratio map obtained from a P25 cross section is shown as Figure 4. The majority of the D/G values fall into the range 0.84 - 0.94 (shown in green) and are indicative of a structure similar to that represented by the lower trace of Figure 3 where little of no graphitic structure is evident in the spectra. The two blue/purple zones, approximately 1 x 2 µm in size, at the bottom of the cross section represent regions of higher graphitic material as indicated by the reduced D/G values (less than 0.7). Comparison of the of the longitudinal and cross section map histograms (right panels of Figures 2 and 4) reveals that the cross section has a much tighter, largely uni-modal distribution. This suggests that there is significantly less variation in structure across the diameter of the fibre than on the surface.

0.90

Frequency

40 30 20 10 0

0.2

0.4

0.6

0.8

1.2

D/G ratio Fig. 4: False colour D/G map (left) and histogram of D/G values (right). The map colours match those of the corresponding spectra shown in Fig. 3.

Pitch fibres such as P25 have only undergone low level graphitization. STM results suggest that the fibre surface consists of domains of relatively large turbostratic crystallites elongated parallel to the fibre axis in a sheet-like structure [3]. Graphitic and microporous regions are randomly distributed amongst the turbostratic crystallites. This is consistent with the Raman maps which revealed predominant regions of low level order along with small domains of highly ordered graphitic content.

4. Conclusions This work has demonstrated the potential for confocal Raman mapping to provide detailed chemical and structural information through the detection of micron-scale highly graphitic pockets at the near surface of pitch-based carbon fibres. By combining a number of visualisation techniques a more detailed model of the fibre structure can be obtained with the potential to correlate with specific manufacturing parameters and fibre properties.

5. References [1]

Morgan P. Carbon Fibers and their Composites. Boca Raton: Taylor & Francis; 2005.

[2]

Huson MG, Church JS, Kafi AA, Woodhead AL, Khoo J, Kiran MSRN, et al. Heterogeneity of carbon fibre. Carbon. 2014;68(0):240-9.

[3]

Hoffman WP, Hurley WC, Liu PM, Owens TW. The surface topography of non-shear treated pitch and PAN carbon fibers as viewed by the STM. Journal of Materials Research. 1991;6(08):1685-94.

[4]

Cuesta A, Dhamelincourt P, Laureyns J, Martínez-Alonso A, Tascón JMD. Raman microprobe studies on carbon materials. Carbon. 1994;32(8):1523-32.

[5]

Ferrari AC, Robertson J. Interpretation of Raman spectra of disordered and amorphous carbon. Physical Review B. 2000;61(20):14095.

Page 225 of 1108

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

High-speed Melt Spinning Behaviors of Flame-retardant PET Fibers Containing Antibacterial Deodorant Function Chae-Hwa Kim, Wan-Gyu Hahm, Tae-Hee Kim * Technical Textile & Materials Group, Korea Institute of Industrial Technology, Ansan, Korea *thkim75@kitech.re.kr

Abstract. High functional flame resistant textiles have been developed due to rising global safety regulations. Polyethylene Terephthalate (PET) fibers is one of the versatile synthetic fibers widely used, and the market for flame retardant PET fibers has shown a steady increase. Besides the flame-retardant property, interior textiles especially used for transport vehicles such as ships and aircraft need to have antibacterial, deodorant, and oil repellent properties due to the inconvenience of cleaning. In this study, we focused on the preparation and characterization of flame retardant (FR) PET filament fibers containing antibacterial and deodorant properties. FR PET filament fibers were prepared by melt spinning process using phosphoric acid-based FR PET, antibacterial masterbatch chip and deodorant masterbatch chip. To investigate the potential use of multifunctional FR PET, characteristic structure and properties of obtained FR-PET asâ&#x20AC;&#x201C;spun fibers were studied through differential scanning calorimetry (DSC), birefringence measurements, and tensile test. Antibacterial and deodorant function was also tested.

Keywords: polyphosphoric acid, flame retardant, multifunctional FR PET, poly(ethylene terephthalate), antibacterial, deodorant, spinning, fibers

1. Introduction Flame retardant textile usually refers to textiles or textile based materials that inhibit or resist the ignition and flame propagation. There has been a constant need of developing high functional flame retardant textiles for transport vehicles because of safety issues. Commercial flame retardants can be typically divided into three different classes such as minerals, halogen compounds, and phosphrous compounds [1]. Halogenated flame retardants have been reported to be toxic, and in response to concerns about the potential impact on human health, phosphrous compounds have been focused as one of new substitutive flame retardants for halogenated flame retardants and its market has been drastically increasing. Poly(ethylene terephthalate) (PET) is one of the versatile synthetic fibers widely used to manufacture clothes, home textiles and industrial materials [2]. The market for flame retardant PET fibers has shown a steady increase due to rising global safety standards. Besides the flame-retardant property, interior textiles especially used for transport vehicles such as ships and aircrafts need to have antibacterial, deodorant, and oil repellent properties due to the inconvenience of cleaning. In this study, flame retardant (FR) PET filament fibers containing antibacterial and deodorant properties were prepared by high-speed melt spinning at various spinning conditions. The melt spinning behaviors and the structural properties of obtained multifunctional FR PET as-spun fibers were systemically investigated. Antibacterial function was also tested.

2. Experimental 2.1.

Materials

Page 226 of 1108

Poly(ethylene terephthalate) containing phosphoric acid-based flame retardant (FR-PET, I.V. (intrinsic viscosity) 0.721 dl/g) prepared through in-situ polymerization method, antibacterial and deodorant masterbatches (M/B) were supplied by Huvis Co. Ltd..

2.2.

Spinning Conditions

All the polymer chips were blended in various conditions (Table 1), and dried under vacuum at 140℃ for 12hrs before spinning. The polymers were melted using a single screw extruder and extruded from a spinneret with 36 holes (hole diameter: 0.25 mm, Y type) by gear pump. Total throughput rate and spinning temperature were controlled to 40g/min and 275℃, respectively. High-speed melt spinning for FR-PET(A) and multifunctional FR PET(B), (C) was conducted from 1 up to 4 km/min using high-speed take-up winder (Fig. 1). Table 1. Sample preparation Sample Code A B C

Material flame retardant (FR) PET FR PET + antibacterial M/B(1.5wt%) + deodorant M/B(2.5wt%) FR PET + antibacterial M/B (3wt%) + deodorant M/B (2.5wt%) Gear Pump PET

Nozzle

Extruder

Quenching Chamber

High-Speed Winder (1 ~ 4 km/min)

Figure 1. Schematics of high-speed melt spinning process used in this study

2.3.

Analyses

Structural evolution of as-spun fibers obtained at various spinning velocities were analysed by measurements of birefringence, differential scanning calorimetry (DSC), and tensile properties. Antibacterial activity was quantitatively evaluated against Staphylococcus aureus and Klebsiella pneumonia according to ASTM E 2149:2010.

3. Results and Discussion FR-PET and multifunctional FR-PET containing antibacterial and deodorant properties could be spun up to the spinning velocity of 4km/min, and showed similar spinnability in high-speed spinning process. Fig. 2 shows DSC thermograms of FR-PET and multifunctional FR PET(B, C) as-spun fibers obtained at various spinning velocities. A, B and C as-spun fibers showed similar glass transition temperature (Tg) at around 76℃, and position of Tg didn’t shift by change of spinning velocity. Crystallization peak (Tc) of FRPET as-spun fibers obtained at low spinning velocity of 1 km/min appeared at 135℃, and the peak position shifted toward lower temperature with decrease of peak area as spinning velocity continued to increase. Crystallization peak of FR-PET as-spun fibers obtained at 4 km/min nearly disappeared on the DSC

Page 227 of 1108

thermogram. Tc peak of multifunctional FR-PET as-spun fibers obtained at 1km/min appeared at 130â&#x201E;&#x192;, and showed similar shift of peak position and decrease of peak area as spinning velocity increased. These results indicated that the molecular orientation of PET as-spun fibers increased with spinning velocity and then straininduced crystallization started to occur from 4 km/min [3].

Figure 2. DSC thermogram of FR-PET and multifunctional FR-PET(B, C) as-spun fibers obtained at various spinning velocities.

As shown in Table 2, birefringence of multifuctional FR-PET (B) as-spun fibers increased with spinning velocity, and maximum birefringence value reached around 83.2 at the spinning velocity of 4 km/min. Multifunctional FR-PET (C) fibers with higher amount of antibacterial showed similar curve as multifunctional FR-PET (B), but slightly lower value around 79.9 at the spinning velocity of 4 km/min. A maximum birefringence value of FR-PET as-spun fibers at the spinning velocity of 4 km/min was around 90.66, and relatively higher than that of (B),(C) fibers. The S-S curves of (A),(B) and (C) as-spun fibers, obtained at spinning velocity of between 1 and 4 km/min, showed that mechanical properties such as tensile strength increase with spinning velocity. The tensile strength of FR-PET showed the tendency to decrease with addition of antibacterial. The maximum tensile strength values of (A), (B) and (C) as-spun fibers were 2.83, 2.6, and 2.33 g/d, respectively, at the spinning velocity of 4 km/min, corresponding with the results of DSC and birefringence.

Table 2. Tensile property and birefringence of FR-PET Sample A

Spinning speed (km/min)

Tenacity (g/den)

Elongation (%)

Birefringence (Î&#x201D;n*10^3)

1 2 3 4 1 2 3 4 1 2 3 4

1.19 1.77 2.3 2.83 0.93 1.38 1.95 2.6 0.95 1.36 1.96 2.33

433.25 260.15 161.43 105.04 394.75 228.53 146.91 97.21 423.01 226.57 151.35 78.85

24.25 57.99 86.65 90.66 25.43 29.28 75.94 83.24 7.37 37.73 79.46 79.9

As shown in Table. 3, multifunctional FR-PET (B) and (C) showed 99.9% reduction of the test microorganism (S. aureus and K. pneumonia) within 1hr.

Page 228 of 1108

Table 3 . Antimicrobial test of multifunctional FR PET Antibacterial test (ASTM E 2149:2010) Test Strain 1 initial (Staphylococcus 1hr aureus) rate Test Strain 2 initial (Klebsiella 1 hr pneumoniae) rate

Blank

1.7×10⁵ 1.3×10⁵ 2.0×10⁵ 1.2×10⁵ -

1.7×10⁵ <10 99.9 2.0×10⁵ <10 99.9

4. Conclusion The multifunctional phosphoric acid-based flame-retardant PET filament fibers containing antibacterial and deodorant properties could be successfully developed by using high-speed melt spinning process. Multifunctional FR-PET with antibacterial and deodorant showed similar spinnability as FR-PET at high speed spinning velocity, while the degree of molecular orientation and tensile showed relatively lower tendency than those of FR-PET as-spun fibers. On the other hand, multifunctional FR-PET showed excellent antimicrobial property.

5. References [1] S.V. Levchik, and E.D. Weil, A review of recent progress in phosphorus-based flame retardants, Journal of Fire Sciences, 2006, 24:345-364. [2]

H.T. Deo, N.K. Patel, and B. K. Patel, Eco-friendly Flame retardant PET fibers through P-N Synergism, Journal of Enigneered Fibers and Fabrics, 3(4), 2008, 23-38.

[3] W. G. Hahm, H. Ito, and T. Kikutani, Analysis of necking deformation behavior in high-speed in-line drawing process of PET by on-line diameter and velocity measurements, International Polymer Processing, 2006, 21: 536-543.

6. Acknowledgement This work was supported by Industrial Source Technology Development Program (No.10040067) funded by the Ministry of Trade, Industry and Energy (MOTIE, Korea).

Page 229 of 1108

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

Hybridization of Preforms for Textile Composites Mankodi Hireni R1 1

Associate Professor, Principal Investigator (MRP GUJCOST), Department of Textile, The M.S University of Baroda, Kalabhavan, Vadodara 390001. M: +919376222724, dr.mankodi@gmail.com

Abstract. Textile preforms have growing market in structural applications. The Carbon, aramid and glass fibers are inherently superior to conventional textile fibers in terms of mechanical properties and other characteristics. However, each material has its inherent advantages and disadvantages and it is usually recommended to hybridize them to fully benefit of their high performance in practical applications to many products. This paper is concerned with a commingling process for hybridization of glass as reinforcement filament with polypropylene thermoplastic filament as matrix. A commingling machine has been developed for hybridizations of yarn. The various glass/pp hybrid yarns with different percentage combinations of polypropylene have been produce to get homogenous mix of two dissimilar materials. The commingling behavior of glass filament distribution and proportion play important role in deciding laminates properties even arrangement of yarns, type of material, and structures of performs. The hybrid preforms developed with different material combinations.

Keywords: Thermoplastic, Preform, Laminates,Hybrid yarn,Hybridization, Glass.

1. Introduction Hybridization mean combination of two fibers this concept is widely explore for textile composite. The hybridization has been done at yarn manufacturing or fabric forming stage. The hybrid yarns are tailor made yarn manufactured using matrix forming fiber and reinforced fiber has the potential to achieve good composite properties. The different method has been developed to produce hybrid yarns. In this project commingling machine has been developed to produce hybrid yarns with different polypropylene proportion. The final properties of thermoplastic composite depend on homogenous distribution of matrix fiber and reinforced fiber in yarn structure [1], [2]. Further it reported that non-uniform distribution of fiber in final laminates lead insufficient impregnation. Hence the commingling behavior of glass fiber filament distribution and proportion play important role in deciding laminates properties even arrangement of yarns, type of material, structure of preforms and preform properties gives different combination of preforms for thermoplastic composite[1].This paper describe the manufacturing process of commingled yarn and preforms with different combination has been prepared and effect of change in glass content in Glass /PP yarn on hybrid yarn has been discussed and checked for its homogeneous glass distribution and the optimized combination has been taken for further studies. The hybrid preforms produced on handloom and characteristic has been check for laminate [4], [7].

2. Material and Methodology 2.1. Manufacturing of Hybrid Yarn The commingling machine has been fabricated for producing glass/pp combination. The machine provided with two positive feeding zones to control overfeeds and tension of individual yarn. The passage has been kept as straight as possible to avoid bending of glass filament to avoid breakage. The ceramic jet has been fabricated for glass. The glass filament of 150 tex, 300 tex and PP of 94 tex stand were taken for study and the Glass % varied by liner density and PP% by varied number of stand change during process. The lower amount of over feed has been given to polypropylene. The very high pressure gives glass filament break but also need high pressure for proper opening. Hence by trial error method three level of air pressure 5, 6, 7 bar has been selected for producing yarn without glass filament breakage. ___________________ Dr Hireni Mankodi.Tel.: + 91-9376222724

Page 230 of 1108

dr.mankodi@gmail.com

The three level of processing speed 50, 75 and 100 m/min has been taken for study. To investigate the effect of change in polypropylene content the sample has been prepared at 6 bar with 1% overfeed and 50 m/min take up speed. The hybrid yarns prepared were checked for commingling properties the analyses of results are given in next section [3], [5].

2.2. Manufacturing of Performs The different combination of Glass, PP, Carbon and hybrid yarn has been prepared for studies. It was decided to use hand loom for producing samples and after initial trail, the selected sample will be prepared on commercial loom. It was observed to maintain uniformity of weaving parameter is difficult for hand loom so tried to minimize it [8]. On handloom the different type of heald wire and reed has been selected as per yarn diameter. The different 6 sample has been prepared as shown in Table 1. Table 1: Tensile Properties of Hybrid Preforms with different combination Sample

Warp

Weft

GSM

Thickness in mm

End/ Inch

Pick/ Inch

Tensile strength MPa Warp Weft

% Strain

Warp

Weft

254

0.50

52.66

43.54

36.79

1.84

406

0.72

33.93

27.16

38.26

2.61

10G+10C

228

0.46

75.70

31.18

35.24

2.60

PP/4G/ 4C PP/4G/ 4C PP/4G/ 4C

20H+10C

350

0.73

55.78

52.17

38.38

1.61

330

0.57

46.77

63.64

33.15

2.13

10B/10H

326

0.69

46.09

40.01

35.53

2.66

P5 P6

PP: Polypropylene, G: Glass, C: Carbon, H: Hybrid yarn, B: Basalt

2.3. Measurement Technique In order to study the qualitative and quantitative effect commingling hybrid yarns, various samples of hybrid yarns have been made from glass/polypropylene filaments have been tested using standard method. The tensile testing machine used for finding tenacity and extension at break. The mingling characteristics have been evaluated in terms of nip frequency using needle insertion method, nip stability by acarâ&#x20AC;&#x2122;s method and nip regularity using microscope studies. The preforms were tested using standard method on instron tensile tester.

3. Result and Discussion The Fig.1 shows the Tensile and extension value of hybrid yarn. The Sample H1 with100% glass and H6 with 100% PP content shows the parent yarn with commingling effect. The hybrid sample tensile value ranging between these samples. The samples H4 (40% PP) and H5 (60% PP) have higher tenacity and extension value that due to higher percentage of PP content. The H2 (20% PP) and H3 (25%) have high tenacity but low extension due to high percentage of Glass.

3.1. Effect of Change in Polypropylene Constant on Properties of Hybrid Yarn

The commingling characteristics of hybrid yarn as shown in Fig 2. It is observed that 100% polypropylene interlaced yarn give poor interlacing properties and 100% glass give unstable yarn. The hybrid yarns gives better commingling characteristics compared to 100% polypropylene or glass mingled yarn. The specimen H3 with 25% PP content give high nip frequency with good nip stability compared to other hybrid yarns that may be due to PP filaments commingled properly with glass give better commingled behavior and also give homogenous mix. The specimen H4 and H5 give almost similar characteristics.

Page 231 of 1108

Fig.1: Tensile Properties of Hybrid Yarns Sample with Different Polypropylene Content 25

Nip frequancy (nips/meter)

22.2

Commingling properties

Nip stability (cycles)

17.8 15.2

16.7

Nip regularity (cm) 12.2

12.1

12.5

10 6.5

4.2 2.5

2.3

2.1

1.8

1.5

1.2

0 H1

Hybrid yarn

Fig.2: Commingling Properties of Hybrid Yarns with Different Polypropylene Content

The SEM analysis of hybrid yarn at different Polypropylene content has been investigated. It has been found that H3 and H5 give better mixing compared other yarn as shown in Fig 3 that may be due to may result due to proper opening of glass and PP in processing stage and give good commingling behavior. Hence, to study the effect of processing parameter glass: polypropylene content 75:25 is investigated further.

H3(25% of PP)

H5 (60% of PP)

Fig.3: Homogeneity of hybrid yarns at different Glass: Polypropylene content

3.2 Performance of Preform at Different Combination The hybrid preforms has been prepared using hybrid yarns and combination with high performance material like Glass, Carbon, Basalt with self adhesive material PP (which melt under heat).This preforms have been prepared for thermoset as well as thermoplastic laminate (. The 6 sample prepared with different combination as given in Table 2. The sample P1, P2, P3 prepared using PP in warp with almost similar ends and picks density and in P4, P5, P6 the 4 Glass and 4 Carbon stand introduce at equal interval in PP warp. The different weft with reinforced material has been used.

Page 232 of 1108

The P1 and P3 show higher strength both in warp and weft direction compare to P2 due to PP content in hybrid yarns. The PP content resulting high extension of performs but this PP filament will melt during final process and give self adhesion between layers and glass, carbon and basalt gives reinforcement. Hence in preform number of epi and ppi need to take as per final property requirements of laminate. Even P5 with basalt give better strength then P1 with glass. Hence new basalt material gives better reinforcement then glass. The glass and carbon also increase the strength of preforms significantly. The possible combination has been prepared. The Basalt and Glass with and without hybrid yarn has been taken for commercial production and further investigation.

4. Conclusion The behavior of Glass/PP hybrid yarn studied with different processing parameter and process optimized. The influence of air pressure, overfeed, Take up speed and % polypropylene content in hybrid yarn on commingling characteristics has been investigated. The studies show that the commingling characteristics of hybrid yarn have been greatly influenced by air pressure and % of matrix forming fiber. The hybrid yarn with different Glass/Polypropylene content viz. 75:25 give better commingling properties. The hybrid yarns with Glass/Polypropylene content of 75:25 and 40:60 give homogenous mixing of matrix and reinforced filament within hybrid yarn. The Preform structured with self adhesive matrix fiber greatly influence mechanical properties of laminate. The hybridization done of preforms using different combination of reinforced fiber with polypropylene matrix. The preform with Glass and Carbon give higher strength. Minimum two layers in perpendicular direction need take to study the laminate properties. % PP can be decided at yarn stage or preform stage by selecting epi, ppi and pattern. Thus hybridization process uses to improve quality of final laminates.

5. Acknowledgment The author greatfully acknowledge the Member Secreatory of Gujarat Council of Science and Technology for providing financial support for this project. Also thanks to weaving and testing lab staff of Textile Engineering Department for helping during sample making and testing.

6. References [1] Hireni Mankodi, Pravin Patel; “Study the effect of commingling parameters on glass / polypropylene [2]

[3]

[4]

[5] [6]

[7]

[8]

hybrid yarns properties”, Autex research journal, vol. 9, no3, September 2009. Dr Hireni Mankodi, Dr Pravin Patel; “Effect of Nozzle Design and Processing Parameter on Characteristics of Glass/Polypropylene Hybrid Yarns”,S.R. Verma Int. Journal of Engineering Research and Applications”, Vol. 4, Issue 12( Part 6), December 2014, pp.144-149. Hireni Mankodi, Pravin Patel;”New Advance Manufacturing Technique for Textile Based Thermoplastic Composites”, Proceedings of an International Conference ‘Processing and Fabrication of Advanced Materials XIX’, Pp 1153-1161, January 2010. Hireni Mankodi;” Multiaxial Multiply Structures For Textile Composites”, Proceedings of an International Conference ‘Processing and Fabrication of Advanced Materials XIX’, Pp 1145-1152, January 2010. Hireni Mankodi, Pravin Patel “Hybrid Yarn for Textile Flexible” composite International Conference Technical Textile: A Innovative Approach, UMIST, Manchester, April 2006. Hireni Mankodi, Pravin Patel;“Hybrid Yarns For Thermoplastic Composites: A scope of Technical Textile Application” World conference (83rd TIWC) on Quality Textile for Quality Life, organized by The Textile Institute and Donghua University, shanghai, China, 23rd-27th May (2004). Hireni Mankodi, D J Chudasama “Effect of Non-Crimp Fabric Structure on Mechanical Properties of Laminates” 17th International Conference on Textile Composite Material and Processes, NY, waste publication, June 2015 Ali Hasan Mahmood, Rong Hung Gong;” Use of fabric and Composite made from Airjet Textured coreand-effect glass yarn for improved properties of Textile Composites” NED University Journal of Research-Structural Mechanics, Vol XI,No 3,2014

Page 233 of 1108

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

Improvement of flexural properties of FRP by filament cover method Ryo Sakurada 1, Fangtao Ruan2 and Limin Bao2+ 1

Functional Machinery and Mechanics Course, Graduate School of Science and Technology, Shinshu University, Ueda, Nagano, Japan. 2 Faculty of Textile Science and Technology, Shinshu University, Ueda, Nagano, Japan.

Abstract: The flexural property and failure pattern of unidirectional carbon fiber, which are covered by PBO fiber, reinforced epoxy matrix composites has been investigated. In this study, Three-point bending test was conducted to test the flexural property of FRP. When the CFRP specimens under bending, there are two different forces distributing on the upside and underside of specimens, compression force and tension force. Due to carbon fiberâ&#x20AC;&#x2122;s excellent tensile property, there is hardly appearing tensile failure. On the contrary, compression failure, in the compressive buckling manner, is very common because of carbon fiberâ&#x20AC;&#x2122;s weak compression property. A PBO fiber filament-covering method is proposed to improve the buckling critical load of unidirectional carbon fiber reinforced plastic. Three-point bending testâ&#x20AC;&#x2122;s result shows that the filamentcovering method has a positive effect on the flexural strength and modulus of CFRP. The failure pattern was observed by SEM. Keywords: CFRP, Flexural properties, Improvement, Filament cover.

1. Introduction Fiber reinforced composite materials consist of high strength and high modulus fibers embedded in or bounded to a matrix with distinct interfaces between them. Fiber reinforced polymer (FRP) composites have found widespread use in various fields such as aerospace and sports, automotive field, etc[1]. A defect of FRP is their compressive strength generally being lower compared to the tensile strength, Since FRP materials have directional dependent properties, the directional dependence coming from the strength and stiffness of the reinforced fiber along with the fiber direction. It is much softer and weaker in directions perpendicular to the stiff and strong direction for unidirectional FRP [1]. At the same time, when the FRP under bending load, the load is applied the unidirectional FRP deflects such that the underside of the test specimen will be under tension whilst the upper side will be subjected to compression stress is present. Compression side is destroyed in a smaller stress than the tensile side, strength of FRP is not sufficiently exhibited. With the above description, it is critical for high flexural property of FRP to improve compression performance of the side of applied bend force. In this study, a novel manner, named filament covering, is proposed to improve the flexural properties of unidirectional fiber reinforced plastic based on improving the compressive buckling critical load of FRP. The schematic diagram of fiber bundle was covered with filament was shown on Fig.1.

Fig. 1: The schematic diagram of fiber bundle was covered with filament

Corresponding author. Tel: + 86-0268-21-5423 E-mail address: baolimin@shinshu-u.ac.jp

Page 234 of 1108

In our previous study, the filament covering method was proved effective for unidirectional compressive performance of unidirectional ultrahigh molecular weight polyethylene fiber reinforced epoxy resin[2].The impetus for this study comes from the above buckling failure theory and ultimate buckling loading formula(1). From the formula, the critical wavelength l has a great influence on the ultimate buckling loading Pcr, the shorter fiber waviness may improve the Pcr when the fibers under compression. Thus improve the critical buckling stress of longitudinal compressive unidirectional FRP. Pcr =

λπ 2 EI l2

(1)

In this formula, λ is the fiber’s waviness, l is the critical wavelength, E is flexural modulus, I is moment of inertia and EI is the flexural rigidity.Based on the theory and experience, in this study, it is aimed to improve the flexural property of unidirectional carbon fiber reinforced plastic.

2. Experimental 2.1 Materials and Specimen Preparation The carbon fiber (T300B-1000) was choose for the reinforced fiber, which manufactured by Toray Company, Japan. The cover filament used in this study was a kind of PBO fiber, ZYLON, which was manufactured by Toyobo Co., Ltd., and it consists of rigid rod chain molecules of poly (p-phenylene-2, 6benzobisoxazole). It has high tensile strength and a high modulus. The covered carbon fiber bundles with a PBO fiber filament were prepared using a custom winding machine, and the schematic diagram was shown on Fig.1. The covered UHMWPE bundle was converted into a fiber sheet using the winding method. A thermosetting epoxy resin (XNR6815) was obtained from Nagase ChemteX Corporation and was used as the matrix for the CFRP. A hardener (XNH6815) was also purchased from Nagase ChemteX Corporation. The epoxy resin and the hardener were 100 and 27 parts by weight. The FRP specimens used for the tests were fabricated by the VARTM (vacuum assisted resin transfer molding) process. A unidirectional CFRP(CFRP) and CCF/CFRP(Covered Carbon Fiber/ Carbon Fiber Reinforced Plastics) were thus prepared. It shows a schematic image of CCF/CFRP laminate in Fig.2. It was intended to verify the effect of the covering filament on the compressive side of a CFRP. So, the CCF/CFRP contains two parts, on the compressive, there was PBO filament covered carbon fiber bundle sheet lamina, and on other side, it was normal unidirectional carbon fiber lamina. The thickness of each specimens for testing was approximate 2 mm.

Fig. 2: Schematic of CCF/CFRP laminate structure.

2.2 Determination of Flexural Properties and Fracture Cross-sectional Observation Flexural test was performed by three point bend test according to JISK7074. The width of the bend specimens was 15 mm and length of 100 mm. Compressive tests of the FRP composites were conducted by Auto Graph (AG-20KND) with a load cell manufacture by Shimadzu Corporation, Japan.These specimens were loaded at a cross-head speed of 1 mm/min. Values of bend modulus E, were calculated at a loading condition of 0.1% strain with a minimum of six specimens being tested, the failure mode of specimen was determined through an electron microscope (KEYENCE) and scanning electron microscopy(JSM-6010LA， JOEL).

3. Results and discussion The three-point bending test measured CFRP and CCF/ CFRP bending strength and the bending elastic modulus are shown in Fig.3. Form the histogram compare, the average bend strength of CCF/CFRP has increased about 34% than that of CFRP. At the same time, the bend elastic modulus has slight increase in spite of there was relatively large deviation for result of CFRP.

Page 235 of 1108

Fig. 3: Bend strength and modulus of CFRP and CCF/CFRP. An example of the image of damaged side portion of specimens after three-point bend test shown in Fig. 4 and Fig.5. It was revealed that CFRP and the CCF/ CFRP are both failure at the compression side, which were indicated by red lines, while the tensile side almost has no damage, that is contributed to high tensile strength and modulus of carbon. From fig.4, there was de-lamination occurs between the plies of the laminate at middle layer and tensile layer, one of the reasons is the strength transverse to the carbon fiber is low, so the unidirectional is very susceptible to splitting. For CCF/CFRP, the de-lamination phenomenon was not obvious than the CFRP, especially for the compression side. The join of PBO fiber changed the bend failure mode of CFRP. That may also be a reason for the increase of bend properties for CCF/CFRP. For both specimens, the failure mainly occurred at the compression side, failure mode was primarily macro-buckling. In order to further investigate the relationship of failure mechanism and bend properties, the SEM observation were conducted.

Fig. 4: Image of band failure side CFRP

Fig.5: Image of band failure side CCF/CFRP SEM images of CFRP and CCF/CFRP is shown in Fig.6 and Fig.7. As shown in Fig.6, CFRP is damaged causing the buckling independent carbon fiber by one by one on the compression side. In contrast, for CCF/ CFRP, several fiber buckling in the whole the compression side by a bundle has occurred because it is covered. CFRP and CCF/ CFRP were able to observe the difference in the fracture mechanism. Both CCF/ CFRP and CFRP caused buckling at compression side, the compression side of the buckling stress exerted on fiber bundles, while CFRP that buckled on alone fiber. That may be a reason for the improved bend properties.

Page 236 of 1108

Moreover, the shorter critical wavelength made the buckling stress increases. From the foregoing, it was confirmed the usefulness of the improvement of CFRP of bending properties by covering filament method.

Fig. 5: Scanning electron microscope images of CFRP.

Fig. 6: Scanning electron microscope images of CCF/CFRP.

4. Conclusions A filament covering is proposed to improve the flexural properties of a unidirectional CFRP. PBO fiber filament were employed as the cover filament. A unidirectional carbon fiber reinforced epoxy resin (CFRP), and PBO filament covered Carbon Fiber/ Carbon Fiber reinforced epoxy resin were prepared by VARTM method. Using JIS K7074 three-point bend testing standards, bend strength and modulus for the prepared specimens were obtained. And their fracture surface were examined by optical microscopy and scanning electron microscopy. It increases the buckling stress of the fiber bundle in using the covering filament method, which was contributed to the improvement of the CFRP of bending strength. It has been seen as both the damage of CFRP and the CCF/CFRP buckling failure, but their mechanisms of buckling were different. For the CCF/CFRP, since the cover filament restricted the critical wavelength, caused the increase of ultimate buckling loading.

5. Acknowledgments This study has received the assistance of independent administrative institution Japan Society for the Promotion of Scientific Research Grant Program (B) (26289005) and JSPS KAKENHI Grant number 15H01789.

References [1] Sudarisman, I.J.Davies, H.Hamad, Compressive failure of unidirectional hybrid fibre reinforced epoxy composites containing carbon and silicon carbide fibres. Composite Part A 38, 1070-1074(2007). [2] Ruan F, Bao L, Improved longitudinal compression performance of a unidirectional Fiber reinforced plastic with a filament covering, Polymer Composites. Polymer Composite, (under review).

Page 237 of 1108

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

Mechanical and open hole tensile properties of self-reinforced recycling PET composites Chang Mou Wu1*, Wen You Lai1, Po Chung Lin1, Jieng-Chiang Chen2 1

Department of Materials Science and Engineering, National Taiwan University of Science and Technology, Taipei 10607, R.O.C. 2 Graduate Institute of Materials Science and Technology, Vanung University, Chungli, Taiwan, ROC

Abstract. Self-reinforced recycling poly (ethylene terephthalate) (srrPET) composites composed of double covered uncommingled yarn (DCUY) were hot pressed using a film stacking technique. The influence of specimen width-to-hole diameter (W/D) ratios on open hole tensile was evaluated. The experimental results show that the srrPETs exhibit superior mechanical properties (uniaxial tensile, flexural and izod impact) similar to that of srPETs. The open hole tensile (OHT) stress–strain (S-S) curves showed a bilinear elasticductile behavior. Significant yielding and post-yield strain hardening were observed, which are indicative of ductility of the srrPET composites. The tensile load-displacement curves of open hole samples follow the curve path of undrilled sample and show earlier failure with hole size increasing. The srrPET composites have extremely high yield strength retention up to 142% and high breaking strength retention up to 81%. The results prove that srrPET composites exhibit notch insensitivity and superior tough behavior.

Keywords: A. Recycling; B. Plastic deformation; C. Stress concentrations; Open hole tensile

1. Introduction PET flakes are used as the raw material for a range of products that would otherwise be made of polyester [1]. There is a growing interest to either improve the methods for recycling and reusing existing materials, or develop new and intrinsically more suitable composites [1]. The idea for developing new srPCs by using rPET fibers is thus initiated. The main challenge when producing a srPC material is combining fiber and matrix into one composite [2]. Using commingled yarns is one of the more promising methods for applying the rPET fibers in srrPET composites. The cowrap spinning commingled methods have been applied to developing srPETs successfully [3]. The tensile strength of notched composites is one of the important factors for composite structural design. A number of authors have studied the effect of hole on the mechanical properties of composite structures.[4, 5] Despite the recent increased attention to srPCs, there has been virtually no work on notch sensitivity of srPETs. In order to elucidate the effect of stress concentration on the tensile strength of srPET composites, specimens with open circular holes and different ratios of D/W were tested in tension. Failure modes, damage initiation and progression of notched srrPETs are also characterized and discussed.

2. Experimental 2.1. Materials In this study, high tenacity recycled PET multifilaments (rPET), consists of 111 tex multifilament bundles with tenacity of 55.9±2.2 cN/tex and strain of 20.6±0.8 % (Fig. 1), was used as reinforcement. Every multifilament bundle consists of 192 filaments. The copolymerized PET yarn (mPET), consists of 35.6 tex multifilament bundles with tenacity of 18.0±1.1 cN/tex and elongation of 36.1±1.2 % (Fig. 1), was used as matrix. Every multifilament bundle consists of 96 filaments. The DSC thermograms of the rPET and mPET yarn were shown in the Fig. 2. Two major melting peaks were found in 238 ℃ and 262 ℃ for the rPET yarns. By contrast, the melting temperature of mPET yarns is 226 ℃.

2.2. Sample preparation The srrPET sample preparation follows the same method in our previous articles [3]. The main spinning parameters are number of turns (694 T/M), machine rotation Speed (5500 r.p.m.) and machine output (7.93

Page 238 of 1108

m/min). The DCUY was used as a feed material to produce the 2/2 basket-woven fabric. The cowrap spinning yarns (which served as warp and weft yarns) were then woven on a rapier weave machine. The density of wrap and weft is 13.4 bundles/cm and 11.8 bundles /cm respectively. The srrPET composites were fabricated with mass-production scale hot pressing system (FC-650TON, Long Chang, Taiwan). The srrPETs sample size was fabricated in 1 m2. The srrPET composites were prepared by stacking five layers of fabric at 238 oC for 1 minute under the pressure of 12 MPa. The fiber volume fractions and void content of srrPET composites are 55 % and 1 %, respectively.

Fig. 1. The tensile stress- strain curves of the rPET and mPET yarns

Fig. 2. Thermograms of the rPET and mPET yarns

2.3. Mechanical tests Tensile, flexural and izod impact test of srrPET composites were carried out by ASTM D3039, D790, and D256 standard, respectively. OHT test of composites were performed by universal testing machine (MTS 810, MTS Systems Corporation, Mpls. MN) with a load cell with a capacity of 100kN at room moisture according to the ASTM D5766 standard. The dimension of specimens is 250 mm × 25 mm × 2 mm. The circular holes were prepared through the center of the specimen using a modified hollow-cylindrical steel drilling bits. Circular holes with three different diameters, namely 4, 6 and 8 mm, which were equivalent to W/D ratios of 6, 4 and 3 were studied for the open hole tensile test. The testing crosshead speed is 5 mm/min. The experimental OHT strength is calculated by the following equation:

σ OHT =

Pmax (W − D ) × t

(1) where σOHT is the ultimate OHT strength, Pmax is the maximum load, W is the specimen width, D is the hole diameter and t is the specimen thickness.

3. Results and discussions 3.1. Mechanical properties of the srrPET composites The mechanical properties, including tensile strength, tensile modulus, tensile elongation, yield strength, and postyield modulus are summarized in Table 1. The tensile stress–strain curve shows a bilinear elasticductile behavior similar to the srPETs have reported in our previous studies [3]. Significant yielding and post-yield strain hardening were observed, which are indicative of the reinforcing effect and structural integrity of the srrPET composites. The tensile and yield strength of srrPETs is 121.3 and 41 MPa, respectively, which was respectively 33% and 84% higher than the values obtained at srPETs (Table 1). The improvement may attribute to partly fusing of the srrPET at the consolidation temperature and thus facilitate the compatibility between rPET and mPET fibers. In addition, lower void content of srrPETs caused by different manufacturing setup may be another reason. Sample

Table 1. The mechanical properties for the srrPET composites of undrilled specimen Tensile Tensile Yield Postyield Flexural Flexural Strength Modulus Strength Modulus Strength Modulus (MPa) (GPa) (MPa) (MPa) (MPa) (GPa)

Impact energy (J/m)

srrPETs

121.3 ± 1.8

3.4 ± 0.1

41.0 ± 1.3

323 ± 5

82.0 ± 0.8

2.8 ± 0.3

1103 ± 64

srPETs [3]

91.1 ± 9.0

3.2± 0.2

22.3 ± 0.9

292 ± 30

77.9 ± 5.2

3.7 ± 0.2

710 ± 49

Table 1 shows the flexural and impact properties of the srrPET composites. No significant different in the failure mode and flexural stress-strain curves between the srrPETs and srPET underwent flexural and impact test. The flexural strength and modulus of srrPET composites are 82 MPa and 2.8 GPa, respectively.

Page 239 of 1108

Lower flexural modulus in srrPETs was attributed to lower tenacity of the rPET and mPET fiber compare to the high tenacity PET fibers used in srPET. The flexural results demonstrate a ductile character of srrPET composites. The izod impact results (Table 1) show high impact energy absorption (1103 J/m) when compared to the srPETs (710 J/m). Unlike the broke apart failure in srPETs [3], the impacted srrPET composites did not break apart due to the use of low tenacity (tough) rPET and mPET fibers. Due to plastic hinge effect, additional energy would be necessary to break the srPET composite sample. The real impact energy would be greater than the measured value.

3.2. Open hole tensile (OHT) properties of the srrPET composites The typical OHT load-displacement curves of srrPET composites with different W/D ratio are shown in Fig. 3. A bilinear elastic-ductile behavior was found in the OHT srrPET composites. The loaddisplacement curves of open hole samples followed the curve path of undrilled sample and showed earlier failure with hole size increasing. The responses of different hole size cases and undrilled samples are qualitatively the same in essence before yielding. The results demonstrate structural integrity and notch insensitivity of srrPET composites. This unique OHT behavior have never reported and found in fiber composites. The typical OHT stress-stain curves of srrPET composites are shown in Fig. 4 and the OHT properties such as strength, strain, modulus, yield strength and post-yield modulus at different W/D ratio are summarized. The OHT modulus, yield strength and post-yield modulus increased with hole size increasing. The stiffening phenomenon is because the reduction of cross section area in open hole samples with the same yield loading. The presence of yielding in the vicinity of the hole allows greater plastic deformation that reduces the stress concentration, so the plastic deformation rather than crack growth occurred with load increasing prior to rapid and unstable catastrophically fracture were found. The tensile strength of undrilled sample is 121.3 MPa and the open hole samples are in the range of 90-98 MPa. The OHT strain decreased with hole size increasing, from 24.4% (undrilled sample) to 7.9% (W/D = 3). The OHT strength results did not follow the trend that OHT strength decreased with W/D decreasing. The unusual results were attributed to the increased of yield stress and compensated for the decreased caused by strain reduction. For larger hole size (8 mm), necking was observed clearly before catastrophically failure. The hole shape changed from circle to ellipse. The local strain at hole edge was calculated according to the longitudinal deformation of the hole. A dramatic difference between the OHT strain to the strain at hole edge was found. A local strain of 60% was obtained when the OHT strain at 7.4%, with 8 times increase. A local strain of 33% was obtained after sample catastrophically failure, which reveals permanent local deformation in the OHT sample. It is clear evidence to prove the stress concentration in srrPET composites. The reasons for srrPET to endure so high local deformation may be attributed to: (1) good interface bonding between fiber and matrix and resulted in load transfer effectively, prevent the crack initiation and propagation. (2) plastic yielding around the hole and resulted in the stress concentration reduction.

Fig. 3. The OHT load-displacement curves of srrPET composites with different W/D

Fig. 4. The OHT stress-strain curves of srrPET composites with different W/D

The strength retentions of srrPETs were 81%, 74% and 80% with W/D ratio decreasing, respectively. The strength retentions did not follow the trend that strength retentions decreased with W/D decreasing. As mentioned above, the unusual results were attributed to the increased of yield stress and compensated for the decreased caused by strain reduction. In addition, bilinear elastic-ductile behavior with significant yielding was observed in srrPET composites. In practical structural design, yield strength shall be considered. Those results were never discussed in the opening literatures since yielding is rare in OHT test of composites. The yielding strength retentions of srrPET are 118%, 127% and 142%, respectively, with W/D ratio decreasing.

Page 240 of 1108

It is attributed to the superior ductile nature of the srrPETs, which induces plastic yielding near the hole and reduces the stress concentration effect. The results are strong evidence showing the notch insensitivity of srrPET composites. Many studies have proved less strength retention or high notch sensitivity for the carbon fiber reinforced thermoplastic or thermoset composites. The thermoset composites yielded the lowest strength retention (about 40% to 52%), follow by thermoplastic composites (about 43% to 81%). Some natural fiber reinforced thermoplastic composites exhibited high strength retention (about 70% to 97%). Based on the above surveying results, we can conclude that srrPETs was relatively ductile and insensitive to the notch. The highest stress occurring near the hole was mitigated by the nonlinear yielding behavior of srrPETs, especially for samples with W/D ratio of 6. The strength retentions of srrPET compsoites proved it belongs to highly tough materials and shows behavior of notch sensitivity.

3.3. Failure mechanism The OHT failures of srrPET specimens with different W/D ratio are shown in Fig. 5, underwent breakapart failures. The specimens with different hole sizes exhibited similar failure modes before the catastrophically failure. Fractography results involved in breakage and fiber pullout of warp tows, splitting fracture of weft yarns, and resin fracture. No delamination was observed in all srrPET composites with or without hole. The absence of interlaminar delamination is associated with crack growth resistance in delamination, preventing the interplay crack from extending. This resistance may be ascribed to the good interfacial bonding and non-planar interply structure of woven plies. Fig. 6 illustrated the failure modes and mechanism of the OHT srrPET composites. Failure appear within fiber bundles and in the interlace points where the weft fibers undulate over warp fibers at the hole rim (Fig 6, (2)). It results in the splitting of the initially perpendicular weft and warp fibers bundles. The presence of yielding in the vicinity of the hole allows greater plastic deformation that reduces the stress concentration, so the plastic deformation rather than crack growth occurred with load increasing prior to rapid and unstable catastrophically fracture was found. It is obvious that the yield deformation initiated at the hole edge and grew in size with the increasing load up to the final fracture. The failure starts at the location of the highest yield deformation, and grows perpendicular to the loading direction along the weft tows towards the edge of specimen.

Fig. 5. Optical images showing the final failure of OHT srrPET composites with different W/D ratio

Fig. 6 Failure modes of the OHT srrPET composites

4. Conclusion The srrPET composites was investigated and analyzed by performing uniaxial tensile, flexural, izod impact and open hole tensile tests. A bilinear elastic-ductile behavior was found in the OHT srrPET composites. The presence of yielding in the vicinity of the hole allows greater plastic deformation that reduces the stress concentration, so the plastic deformation rather than crack growth occurred with load increasing prior to rapid and unstable catastrophically fracture was found. The tensile strength of undrilled sample is 121.3 MPa and the open hole samples are in the range of 90-98 MPa. The OHT strain decreased with hole size increasing, from 24.4% (undrilled sample) to 7.9% (W/D = 3). The srrPET composites have extremely high yield strength retention up to 142% and high breaking strength retention up to 81%. The results reveal its superior ductile behavior and insensitive to the notch.

5. References [1] Merrington A. In: Kutz M, editor. Applied Plastics Engineering Handbook, Oxford: William Andrew Publishing; 2011. p. 177-192. [2] Karger-Kocsis J, Bรกrรกny T. Composites Science and Technology. 2014;92(0):77-94. [3] Wu CM, Lin PC, Tsai CT. Polymer Composites. Published online: 30 APR 2015, DOI: 10.1002/pc.23531.

Page 241 of 1108

[4] Thoppul SD, Finegan J, Gibson RF. Composites Science and Technology. 2009;69(3â&#x20AC;&#x201C;4):301-329. [5] Gobi Kannan T, Wu CM, Cheng KB. Composites Part B: Engineering. 2014;57(0):80-85.

Page 242 of 1108

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

Mechanical Properties of Poly(lactic acid)/Hemp Hurd Biocomposites using Glycidyl Methacrylate Khan 1 + , Wang 1 and Wang 1 1

University of Southern Queensland, QLD-4350, Australia

Abstract. Natural fibre reinforced Polylactide (PLA) composites are a 100% biobased material with a promising mechanical properties profile. The main problem of biocomposites is the incompatibility between hydrophilic natural fibers and hydrophobic thermoplastics, which results in the weak adhesion at the two-phase interface and leads to the poor mechanical and physical properties. Here, PLA and Hemp hurd (HH) have been melt compounded by lab-scale extruder with glycidyl methacrylate (GMA) as a compatibilizing agent. The properties of composites were analyzed as a function of the HH amount. Fourier transform infrared spectroscopy results demonstrate that GMA was successfully grafted onto the molecular chain of PLA. Enhancement of interfacial adhesion between the PLA and HH was improved with GMA and confirmed by scanning electron microscopy. Thus, mechanical properties were greatly improved in GMA gratfted PLA/HH composites. All experimental results indicated that this GMA grafted PLA/HH composites could find applications as packing materials, disposable goods, electronics materials for cost-saving and environment benefits.

Keywords: Biocomposite, Injection Moulding, Mechanical Properties.

1. Introduction Poly(lactic acid) (PLA) is recognized as the most promising biodegradable polymers for industrial plastic applications because of its high mechanical properties and good processability [1]. To fabricate biodegradable composites by combining PLA with plant-derived fibers for instance flax, hemp, kenaf and bamboo fibers is becoming a promising research direction in recent years [2]. Hemp hurd (HH), a lignocellulosic waste material, is obtained from the hemp stem after the bast has been removed for textile materials and application is mostly limited to animal bedding and construction sector [3]. Therefore, HH can be a good choice as a renewable filler of PLA for its low price and easy availability. The incompatibility between hydrophilic natural fibers and hydrophobic thermoplastics results in the weak adhesion at the two-phase interface and leads to the poor mechanical and physical properties [4]. Typically, surface modification of cellulose [5] or addition of compatibilizers such as isocyanates [6] and maleated PLA [7] are the common practices to enhance the interfacial compatibility between PLA and cellulosic fillers. Glycidyl methacrylate (GMA) is a well-known bifunctional monomer, which consists of acrylic and epoxy groups. The epoxy group of GMA can react with many other groups, such as hydroxyl and carboxyl groups, whereas acrylic groups show the capability of free-radical grafting of GMA onto the polymer chain [7]. The GMA-grafted copolymer is a potential compatibilizing agent for reducing the interfacial tension in polymer blends or a coupling agent in polymer-based composites. In this work, the reactive grafting of GMA onto PLA was achieved in the process of HH-filled PLA biocomposite blending extrusion to improve the interfacial adhesion in PLA/HH biocomposites. The mechanical properties of biocomposites were investigated.

2. Experimental Commercial PLA (4032D) was purchased from NatureWorks LLC., (Minnetonka, MN) and hemp hurd powder (mean particle size 40 Âľm) was obtained from Ecofibre Industries Operations Pty Ltd, Australia. GMA and tert-butyl perbenzoa (TBPB) were obtained from Aladdin Chemistry Co., Ltd. (Shanghai, China) and used without further purification. +

Corresponding author. Tel.: + 61-07-4631 1336. E-mail address: belasahmed.khan@usq.edu.au.

Page 243 of 1108

PLA and HH were firstly vacuum-dried at 85°C for 12h. And then pure PLA, PLA/HH and PLA/GMA/TBPB/HH were melt-blended by lab-scale conical twin screw extruder (Ruiming Plastics Machinery, Wuhan, China) with rotational speed 40rpm at 175°C for 5min. All of the materials were sequentially injected into standard test bars via a miniature injection machine (SZ-15, Wuhan, China). The injection pressure, injection temperature and time were set at 3MPa, 200°C and 30s, respectively, and the mould temperature was controlled at 40°C. Fourier transform infrared (FT-IR) spectra of PLA or GMA-g-PLA samples prepared with KBr were recorded by one spectrophotometer (Nicolet FTIR6700) with a resolution of 4cm-1 and 32 scans in the range 4000-400cm-1. The morphology of the blends was recorded by a scanning electron microscope (SEM, Hitachi TM-1000). The resulting flexural fractured surfaces were sputtered with gold prior to examination. An Instron 5567 was used for the tensile test following the GB/T 1040.1-2006. The impact test was performed according to ISO179-1: 98 with a mechanical impact tester (XJ-50Z, Chengde Dahua Testing Machine Co. Ltd., Chengde, China). A 5.5J pendulum was used to determine the Charpy impact strength of the bar samples (80 × 10 × 4mm). The flexural properties of the biocomposites were measured on an Instron 5567 at a crosshead speed of 10mm/min. All the values reported in this paper were the average of at least five replicated tests.

3. Results & Discussion 3.1. Characterization of GMA grafted PLA FTIR spectra of neat PLA, neat GMA and GMA/PLA are presented in Fig. 1. In the neat PLA, the carbonyl stretching vibration is observed at 1757cm-1. In GMA, the stretching vibrations of the carbon-carbon double bond are observed at 1637cm-1 and 944cm-1. In the GMA grafted PLA, the chemical environment of the carbonyl group in GMA and PLA changes, showing a shift of the PLA stretching vibration peak of the carbonyl group to the range of 1744cm-1 to 1760cm-1. The stretching vibrations of carbon-carbon double bond of GMA are also invisible in the infrared spectra of GMA-g-PLA. The results indicate that GMA was successfully grafted onto the molecular chain of PLA.

Fig. 1. Infrared spectra of pure PLA, GMA, and graft copolymer prepared using TBPB.

Compared with PLA, GMA-g-PLA has a new peak at 908cm-1, which corresponds to GMA’s characteristic peak (the asymmetric stretching vibration) of the epoxy group. This also indicates that GMA was successfully grafted onto the molecular chain of PLA. The free radical of GMA was grafted onto the polymer chain through the acrylic acid groups of GMA [7]. The GMA-g-PLA. As a compatibilizer, the epoxy group can react with the hydroxyl group on the surface of Ag-HH.

3.2. Measurements of mechanical properties The average tensile strength and Young’s modulus of the HH/PLA composites are shown in Fig. 2. The elastic modulus increased with an increase in HH weight fraction in the composites, while tensile strength decreased. The reduction in strength in the composites is attributed to an embrittlement caused by the filler acting as discontinuities that restrict polymer chain movement, and hence a lower elongation upon a mechanical energy input [8]. Furthermore, inadequate fiber wetting also leads to an incompatible fiber-matrix interface. Such flaws and imperfections can induce fracture in highly crystalline polymers [8]. Compared to continuous fibers, HH lacks sufficient length to trigger toughening mechanisms that impede brittle fracture. However, the tensile strength was significantly improved in comparison to the non-compatibilized composite when GMA was grafted to modify the PLA. Without GMA grafting, the tensile strength reduced from 65 MPa to 50 MPa with 10 wt. % and 20 wt. % of HH addition with retention rate of 77% compared to neat PLA.

Page 244 of 1108

However, with 1 wt. % GMA grafting, the tensile strength improved to 61 MPa, at a retention rate of 94% compared to neat PLA. GMA grafting clearly enhanced interfacial adhesion between PLA and HH. Nevertheless, the addition of more than 20% HH caused a decrease in tensile strength. Crystallization of the PLA matrix enhanced stiffness and brittleness of the neat PLA and composites, which was reflected in increased modulus and in diminished strength respectively. However, GMA improved the interfacial adhesion and contributed for higher strength of composites. HH inclusion exhibited a stronger effect on the modulus in the PLA matrix. This can be attributed to the nucleation capability of HH in PLA crystallization [5].

Fig. 2. Mechanical properties of PLA/HH composites as a function of HH content.

The average notched impact strength of the HH/PLA composites is shown in Fig. 2. The notched impact strength decreased with increasing HH content. For instance, the impact strength of PLA dropped from 2.99 kJ/m2 to 2.57 kJ/m2, when filled with 10 wt. %HH. The reduction in impact strength of PLA by incorporation of natural fibers is consistent with existing literature [9]. This decrease is because of insufficient interaction between PLA matrix and HH, which cause the fibers to become sites of stress concentration, inducing microspaces between the HH and PLA matrix. The resultant micro-cracks upon impact energy incidence induce crack propagation easily and therefore decrease the impact strength of the composites. The impact testing results showed the impact strength of the HH/PLA composite improved upon the use of GMA as a compatibilizer. With the addition of GMA at the 10 wt. % HH, the average impact strength was 3.1 kJ/m2, which was higher than the neat PLA (2.99 kJ/m2). The impact strength data demonstrated that the addition of GMA possesses the potential of improving physical and mechanical properties of HH/PLA composites. These results are consistent with the SEM fractography analysis shown in Fig. 3. The average flexural strength and flexural modulus of the HH/PLA composites as a function of fiber content are presented in Fig 2. It can be seen that the flexural strength decreased with increased fiber content. For instance, flexural strength of PLA was decreased from 103 MPa to 82 MPa with a 10 wt. % of HH. This decrease is attributed to the inability of the HH with irregularly shaped to support stresses transferred from the PLA matrix and inadequate interfacial bonding, which is the resultant of voids created at the HH/PLA interface, and causing a weak structure [10]. In contrast to flexural strength, Fig. 2 shows that flexural modulus of the composites increased as the fiber content increased. With the addition of 20 wt. % HH, the flexural modulus of PLA was increased from 3.8 GPa to 4.1 GPa. The inclusion of HH (elastic particulate) to a (plastic) PLA [11] causes restricts chain movement and hence shows a higher stiffness in comparison to the neat polymer, which can show a relatively higher deformation at an equivalent stress. As can also be seen in Fig. 2, GMA grafting caused an increase in the flexural strength and flexural modulus of the composites. The higher flexural strength and flexural modulus of the composite with GMA compared to the composite without GMA can be attributed to the increase in interfacial adhesion between HH and PLA as reported [7]. The PLA/GMA/HH composite with 10 wt. % HH showed the highest flexural strength of 95.6 MPa. Overall, the inclusion of HH alone to the PLA caused an increase in the elastic/flexural modulus and a decrease in strength of the HH/PLA composite in comparison to the neat polymer. The grafting of GMA to the HH/PLA system caused increases in the interfacial compatibility and thereby the strength of the biocomposite blends. Hence, the addition of GMA was deemed highly beneficial for achieving a balance of mechanical and thermo-physical properties. In Fig. 3, SEM micrographs also show the comparison of the fracture surfaces of HH/PLA and HH/GMAg-PLA biocomposites, specifically the interfacial behavior upon fracture. Evidence of voids, fiber fracture, and pullout were observed in the SEM images of the composite without GMA (Fig. 3a), and these artifacts can be attributed to the absence of effective interfacial adhesion and thereby a reduction in tensile, flexural, and impact strength. However, lesser and shorter fiber pullouts were observed when the composites were compatibilized with GMA (Fig 3b), also appear to be coated with PLA. These observations suggest good adhesion between

Page 245 of 1108

the HH and PLA matrix in the composites with the GMA. This improved adhesion is the reason why the tensile and flexural strength was improved to composite with GMA.

Fig. 3. SEM of fracture surface of a) PLA/HH (80/20), b) PLA/GMA/TBPB/HH (78.5/1/0.5/20) composites.

4. Conclusion Public consciousness on climate change and resource depletion may cause an increasing demand for sustainable products based on renewable resources. In the near future, fully biodegradable biocomposites are bound to appear in many more commercial products. In this study, biomass waste HH was investigated as a filler to reduce the cost of PLA however preserving the biodegradability, and GMA was added as an interfacial compatibilizer. The effect of GMA grafted PLA on the mechanical properties and interfacial adhesion of the PLA/HH bio-composites was confirmed to be highly beneficial. The PLA/HH composites compatibilized by the GMA can be one of the good candidates in potential applications, such as packing materials, disposable goods and electronics materials.

5. References [1] Lee, B.-H., et al., Bio-composites of kenaf fibers in polylactide: Role of improved interfacial adhesion in the carding process. Composites Science and Technology, 2009. 69(15): p. 2573-2579. [2] Zini, E., et al., Biodegradable Polyesters Reinforced with Surface-Modified Vegetable Fibers. Macromolecular bioscience, 2004. 4(3): p. 286-295. [3] Karus, M. and D. Vogt, European hemp industry: Cultivation, processing and product lines. Euphytica, 2004. 140(1-2): p. 7-12. [4] Xie, Y., et al., Silane coupling agents used for natural fiber/polymer composites: A review. Composites Part A: Applied Science and Manufacturing, 2010. 41(7): p. 806-819. [5] Faruk, O., et al., Biocomposites reinforced with natural fibers: 2000â&#x20AC;&#x201C;2010. Progress in polymer science, 2012. 37(11): p. 1552-1596. [6] Chen, F., et al., Performance enhancement of poly (lactic acid) and sugar beet pulp composites by improving interfacial adhesion and penetration. Industrial & engineering chemistry research, 2008. 47(22): p. 8667-8675. [7] Xu, T., Z. Tang, and J. Zhu, Synthesis of polylactide-graft-glycidyl methacrylate graft copolymer and its application as a coupling agent in polylactide/bamboo flour biocomposites. Journal of Applied Polymer Science, 2012. 125(S2): p. E622-E627. [8] Wu, J., et al., Effect of fiber pretreatment condition on the interfacial strength and mechanical properties of wood fiber/PP composites. Journal of Applied Polymer Science, 2000. 76(7): p. 1000-1010. [9] Serizawa, S., K. Inoue, and M. Iji, Kenaf-fiber-reinforced poly(lactic acid) used for electronic products. Journal of Applied Polymer Science, 2006. 100(1): p. 618-624. [10] Ismail, H., J. Nizam, and H.A. Khalil, The effect of a compatibilizer on the mechanical properties and mass swell of white rice husk ash filled natural rubber/linear low density polyethylene blends. Polymer Testing, 2001. 20(2): p. 125-133. [11] Sawpan, M.A., K.L. Pickering, and A. Fernyhough, Effect of various chemical treatments on the fibre structure and tensile properties of industrial hemp fibres. Composites Part A: Applied Science and Manufacturing, 2011. 42(8): p. 888-895.

Page 246 of 1108

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

Mechanical properties of woven juteâ&#x20AC;&#x201C;carbon fiber cloth hybridreinforced epoxy composite Zhili Zhong 1, Manyi Li 2 and Zhendong Liao 1 + 1 2

School of textile,Tianjin polytechnic university,Tianjin300387,China School of textile,Tianjin polytechnic university,Tianjin300387,China

Abstract A new fiber reinforced composite materials was prepared with the hessian on the surface, four layers of carbon fiber cloth (carbon fiber unidirection) and a layer of jute fabric was used as strengthen body, E51 epoxy resin was used as matrix. Composites were prepared by using hand lay-up technique. The Orthogonal test was conducted with three factors of A(Content of T31 curing agent), B ( content of Polyamide203#), C (content of methyl silicone oil ). Tests were conducted on INSTRON Material Test System at room temperature using automatic data acquisition software, and impact testing machine (Dynatup9250HV type) was used to test the samples in shock resistance. After orthogonal test and a serious analysis, the optimal parameters can be created by adhesive resin solution containing 25% curing agent, 10% deforming agent and 0.3% polyamide203#.

Keywords: Bending strength, Carbon fibers cloth, Composite materials, Jute fabric, Orthogonal test, Tensile strength

1. Introduction

Hybrid fiber reinforced plastics, "HFRP" for short, is composed of two or more fibers and matrix composite. According to the different mix ways of constituent materials, the composites can be divided into sandwich mixed type, interlaminar hybrid type, Layer in mixed type[1]. Many scholars attache great attention to HFRP both at home and abroad, and in-depth study on it[2-3]. It is called hybrid effect that the calculation results of some HFRP's performance deviates from the law of mixing phenomenon[4]. HFRP has structured design, good construction technology, good economic benefit etc., and having hybrid effect in breaking elongation, strength, energy, and functional characteristics. Carbon fiber with carbon content over 90%, is the use of organic fiber strand as raw material, under the condition of high temperature (temperature above 1000 â&#x201E;&#x192;), Carbon obtained with co fiber is a kind of inorganic polymer fiber, its microstructure are similar with graphite, but it is threedimensional chaotic layer structure between the layers of carbon atoms, and carbon atoms are arranged in a level of irregular features[5]. Today, carbon fiber and carbon fiber products is in rapid development stage, in the field of composite materials, carbon fiber composite material has occupied a large proportion. Jute fiber as a kind of natural fiber, in addition to the green, biodegradable and renewable fast, and many other advantages, fiber mechanical performance is excellent, the specific strength and Specific modulus of jute fiber is close to E - glass fiberâ&#x20AC;&#x2122;s, jute fiber is a kind of ideal natural fiber reinforced material[6]. Scholars around the world has made systematic research on the jute fiber composites . The purpose of this project is to develop plant fiber and high performance fiber reinforced composites, which have performance advantages of both jute fiber reinforced epoxy resin composites and carbon fiber reinforced epoxy resin composites. And because of the jute fiber and wood with the same components, good affinity, hence the finished products could be used to enhance timber structure, which will have a unique advantage.

2. Materials and Methods 2.1. +

Raw materials

Corresponding author. Tel.: + 86-13821315952. E-mail address: limanyi1123@163.com.

Page 247 of 1108

Carbon fiber (unidirectional cloths) are produced by Heng Shen co., LTD, Jiangsu. The gram weight of jute fiber (woven) is 250 g/m2. The specifications of E - 51 epoxy resin, provided by the tianjin JinNing sanhe chemical co., as shown in table 1. In order to be able to make the liquid resin adhesive can be cured under the atmospheric pressure, curing agent T31 was selected. 203 # low molecular weight polyamide resin used for toughening agent during the curing reaction of epoxy resin, provided by the tianjin JinNing sanhe chemical co., LTD.Methylsilicone oil is used as defoamer, provided by the Tianjin Yingda Rare Chemical Reagents Factory. Release agent provided by the Tianjin Loctite Chemical Supermarket Chain, is liquid, less irritating smell. Table 1:The main parameters of the E - 51 epoxy resin

Viscosity value The average epoxy (Pa·s) value (mol/100g) ≤2.5

2.2.

0.51

Organochlorine content (mol/100g)

Inorganic chlorine content (mol/100g)

≤0.02

≤0.001

Volatile Density(20 content(%) m3) ≤2

℃

0.98

Composite fabrication

According to the size of the design, the carbon fiber fabric and jute fabric is cut into 360 mm × 160 mm by using the method of manual. Then jute fabric is placed in the outermost layer, the inner layer is carbon fiber fabric with four layers, and carbon fibre cloth was laying into 0/90/0/90. Finally, the epoxy resin was applied to make composites samples. The diagram of composite sample without demould as shown in figure 1.

Fig. 1: Schematic diagram of making composite materials sample: 1-the pressure plate, 2-tin foil, 3-release agent, 4resin adhesive, 5-jute fabric, 6-carbon fiber cloth, 7-baseplate

According to the design of orthogonal table, three factors influencing the performances of composite materials, the dosage of T31 curing agent(A), the dosage of Polyamide203#(B), the dosage of methyl silicone oil(C) - are designed to different combination plan. Test were made into 9 products with different combination.

2.3.Testing Tensile properties test was carried out using Universal Instron power tester according to GB1447-2005 standard. The composite specimen was cut into 250mm×25mm×3mm. At the rate of loading, 5mm/min was used for testing. Universal Instron power tester was also used for testing bending properties according to GB1449-2005 standard. The composite specimen was cut into 80mm×15mm×3mm. At the rate of loading, 2mm/min was used for testing. Sample was placed on the instrument, the instrument have a 30 mm span. Shock resistance of the composite specimen was carried out using material impact testing machine according to ASTM D7136 / D7136M standard. The composite specimen was cut into 90mm×9mm×3mm. The quality of the drop weight is 7.2 Kg. Placing the specimen in the middle of the two pieces of steel plate, and the diameter of round hole of steel plates is 75 mm.

3. Results and Discussion 4

The L9 (3 ) Orthogonal test was designed, which is including 9 experimental combination plans. The test results for bending modulus of elasticity, bending strength, tensile strength, and maximum impact load are shown in table 2.

Page 248 of 1108

Table 2: The L9 (3 ) Orthogonal test used for study and the test results Combination schemes Test results The dosage of T31 curing agent(A)

The dosage of Polyamid e203#(B)

The dosage of methyl silicone oil(C)

20%

0.1%

20%

Bending modulus of elasticity(M Pa)

Bending strength( MPa)

Tensile strength (MPa)

Maximu m impact load (MPa)

1714.8

212.0

192.7

1.6

0.3%

1818.2

222.3

192.7

1.6

10%

0.5%

1786.5

221.6

204.2

1.7

25%

0.3%

1992.0

236.2

204.2

1.7

25%

0.5%

1972.2

235.8

213.0

1.7

25%

10%

0.1%

1965.4

230.9

225.9

1.9

30%

0.5%

1642.1

199.6

215.4

1.8

30%

0.1%

1640.6

196.3

219.4

1.8

30%

10%

0.3%

1665.8

206.2

231.3

1.9

Numbers

The bending modulus of elasticity was evaluated with Variance analysis. As seen in Table, we get much:the critical value were: F0.005(2, 2)=199.0, F0.01(2, 2)=99.01, F0.10(2, 2)=9. After a serious calculation, we can achieve that FA ≥ F0.01, indicating that factor A has significant influence on test results; However, factor B and factor C have no significant influence on the test results.For factor A (the dosage of T31 curing agent) , when the dosage of T31 curing agent is 25% (A2), the bending modulus of the sample is the highest. The bending strength was evaluated with Variance analysis. Because of the sum of square of deviations of factor C is smaller than error term, it is merged into error term. As seen in Table, we get much: the critical value were: F0.005(2, 4)=26.28, F0.01(2, 4)=18.00, F0.05(2, 4)=6.94, F0.10(2, 4)=4.32. After a serious calculation, we can achieve that FA≥F0.005. Factor A has highly significant influence to the result of the experiment, Factors B and C was not significant factors. For factor A (the dosage of T31 curing agent), when the dosage of T31 curing agent reached 25% (A2), the highest bending strength of samples is achieved. Also, the tensile strength was evaluated with Variance analysis. Because of the sum of square of deviations of factor C is smaller than error term, it is merged into error term. As shown in Table, we get much: the critical value were: F0.005(2, 4)=26.28, F0.01(2, 4)=18.00, F0.05(2, 4)=6.94, F0.10(2, 4)=4.32. After a serious calculation, we can achieve that FA≥F0.005 and FB≥F0.01. Therefore, factor A has highly significant effect, factor B has significant effect, and factor C has no significant effect. When the dosage of T31 curing agent reached 30% (A3), and the dosage of Polyamide203#(B3) reached 10%, the highest tensile strength of specimens is achieved. The Maximum impact load was evaluated with Variance analysis.As shown in Table, we get much: the critical value were: F0.005(2, 2)=199.0, F0.01(2, 2)=99.01, F0.10(2,2)=9. After a serious calculation, we can achieve that FA≥F0.01 and FB≥F0.1, so we can get that factor A and factor B has significant effect on test results, and factor C has no significant effect on test results. When the dosage of T31 curing agent reached 30% (A3), and the dosage of Polyamide203#(B3) reached 10%, the highest maximum impact load of specimens is achieved. Through the above analysis results, for the four test indicators, the effects of factors C are not significant

Page 249 of 1108

on the experimental results. However,with the serious calculation, we can find that, when the dosage of methyl silicone oil reached 0.3%(C2), the performance of the four test indicators are the best.

4. Conclusion In the three point bending test, when the dosage of T31 curing agent is 25%, namely A2, the bending strength and bending modulus is optimal, the dosage of Polyamide203#(B) and dosage of methyl silicone oil(C) was not significant effects on the bending strength of carbon fiber composites. In the tensile test, the effect of dosage of T31 curing agent(A) and dosage of Polyamide203#(B) on the tensile strength of composite materials is very significant, the best combination is A3B3. But it no significant differences to the impact on the tensile strength when the dosage of T31 curing agent is 25%(A2) and 30%(A3), so we choose the combination A2B3. In the drop weight impact test, when the dosage of T31 curing agent is 30% (A3), and the dosage of Polyamide203# is 10%(B3), the Maximum impact load of specimens is the highest. Also when the dosage of T31 curing agent is 25% (A2), the Maximum impact load of specimens is the higher, not much difference. So we choose the combination A2B3. In conclusion, the mechanical properties of fiber reinforced epoxy resin composite materials was effected by the fluid of resin adhesive. After orthogonal test and a serious analysis, the best treating parameters were 25% T31 curing agent, 10% Polyamide203# and 0.3% methyl silicone oil.

5. Reference [1] W.Shi, Z.Zhang, J.Li..Journal Beijing uni. aero.astr.,11(4): 53-55(1996). [2] W.Li, H.Cao. Thermosetting Resin, 24(5): 39-43(2009). [3] N K Naik, R Ramasimha, H Arya, etc. Composi., 32(7): 565-574(2001). [4] H.Song, Z.Zhang. Journal Beijing uni. aero.astr., 1989. [5] Mi.Xu. Shanghai: Donghua univ., 2011. [6] L.Liu, R.Wang. Tech. Textiles, 2: 37-40(2004).

Page 250 of 1108

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

Modeling of Tensile Mechanics of 3D Woven Orthogonal Composites Ashwini Kumar Dash and B.K.Behera Department of Textile Technology, Indian Institute of Technology Delhi, India

Abstract. The tensile mechanics of 3D orthogonal structure based composites are studied mathematically using appropriate rule of mixture. Finite element simulation is also carried out to examine the load deformation behaviour of structural composites using thick multilayer solid structures up to 6 layers of woven construction produced on a customised special weaving machine. Tensile mechanics of these load bearing composite materials are investigated to facilitate commercial production of new structures. Model results obtained from mathematical modeling and finite element analysis are compared with experimental values to authenticate the modelling methodologies. Keywords: Glass Fibres,3D orthogonal woven fabric,Tensile Properties, Finite Element Analysis

Introduction

Textile composites are considered to be light weight strong materials having favourable mechanical properties and various attractive reinforcing materials with low fabrication cost and easy handling.Various combinations of different parameters like fibre architecture, fibre properties, matrix properties are possible as the material properties are anisotropic and inhomogeneous in nature. It is almost impractical to investigate experimentally the mechanical properties of textile structural composites and their dependence on the major architectural parameters because of their complexity in geometry and spatial organisation as well as nature of adhesion between reinforcement and matrix. Hence it is desirable to develop adequate modelling approaches which are generally considered to be the cost effective alternatives to gain preliminary understanding of behaviour of the complicated architecture composites and the effects of various construction parameters. An understanding of failure strength of textile composites is expected to accelerate the design of improved structures.Thick multilayer single unit of 3D fabrics have distinct advantages like better delamination resistance and damage tolerance during composite application, higher tensile strain-to-failure values and higher interlaminar fracture toughness properties compared to laminated structures of same thickness. Few researchers [1-3] worked on tensile properties of 3D woven fabrics where they showed superior strength over traditional 2D laminates. A significant study relating to the unique microstructural features and failure mechanisms of 3D woven composites to their tensile properties have been outlined by Cox et al.[4-7]. In this paper, the analytical and finite element analysis (FEA) modelling approaches are employed to the tensile property of glass fibre based 3D woven orthogonal structure reinforced composites (GFRC) upto six stuffer layers. The modelling are done using Solidworks looking to the actual geometry of the fabric, which translates the topology into actual placement of the yarns in space and calculates the dimensions of the yarns. The model is than imported to Ansys 14 workbench to calculate the deformation resistance of the composites that is in tension, based on the geometrical model of the composite and mechanical behavior of the constituent yarns and resins. The important aspect of this finite element simulation is that the yarn volume is meshed correctly, and cross sections of the yarns are considered from the geometrical modelling of 3D structures.[8]

Materials and Methods

2.1.

Constituent materials

Page 251 of 1108

Orthogonal 3D fabrics are made using E-Glass on a customized weaving machine. The fabric consisted of 2, 4 and 6 warp layers woven with 1200 tex tows (stuffer direction) and accordingly 3, 5 and 7 layers of filler tows are used respectively. The linear densities of the filler tows are 600 and 300 tex .The outer layer fillers are comprised of 600 tex where as the inner layer fillers are comprised of 300 tex of glass tows in order to increase stability to the structure. These layers are bound together with 300 tex glass tows as binder. The weaving is carefully controlled to minimize the amount of fibre waviness in the warp and weft tows, although this could not be totally avoided. The weaving machine has the arrangement of multiple beams for stuffer yarns. Arrangements are made for linear take up of the fabric as well as cramming motion is incorporated so as to lay weft yarns one above the other as per the requirement. Binder yarn is passed from a separate beam.

2.2.

Fabric design

The binder path in the structure travelled through the entire thickness of the fabric as illustrated in the Fig. 1. The stuffer yarns that indicate number of layers are represented by horizontal lines.

2 layers

4 layers

6 layers

Fig. 1: Orthogonal unit structures of 2, 4 and 6 layers of stuffer tows. Ideally the binder yarn should pass vertically through the platform but it is found that friction caused by tension on the binders during weaving process tended to straighten the binders [8] .Thus the binder path tended towards a sinusoidal profile, which resulted in the warp yarn becoming collimated and creating resin rich channels running parallel to the warp yarns.

2.3.

Construction parameter of the fabric design

The tow linear density,fabric sett,weaversâ&#x20AC;&#x2122; parameters are summerised in Table1. Table 1.Construction parameter of the fabric where S stands for stuffer and B stands for binder. Weaving Layers Tow linear density in tex for stuffer Tow linear density in tex for filler Tow linear density in tex for binder Reed count

2 1200

4 1200

6 1200

600 and 300 for upper and inner layers respectively 300

Page 252 of 1108

Denting order

S 1 S 2 B 1 /S 1 S 2 B 2

EPM stuffer EPM filler EPM binder Fabric width (metres)

196 394 196 0.381

2.4.

S1S2S3S4B1/ S1S2S3S4B2 196 394 196 0.381

S1S2S3S4S5S6B1/ S1S2S3S4S5S6B2 196 394 196 0.381

The fibre volume fraction of the 3D fabric

Table 2 summerises fibre volume fraction data for all fabrics.The overall fibre volume fraction as well as each constituent fibre volume fraction is calculated using the formula obtained from the geometrical modeling of 3D solid structures [8] Table 2. Fibre volume fraction of the fabric Fabrics

2 layer stuffer

Specimen Thickness mm) 1.85

4 layer stuffer

2.31

0.3048

0.5877

0.2924

0.1198

6 layer stuffer

4.55

0.2911

0.6695

0.2220

0.1084

(in

Total fibre volume fraction

Fraction by volume of all fibres lying in Stuffers (f s )

Fillers (f f )

Binders (f b )

0.3354

0.4301

0.4279

0.1418

Table 3 shows the thickness and fibre volume fraction of all composites. Table 3.Actual fibre volume fraction of the composite

2.5.

Composites

Specimen thickness in mm

2 layer stuffer 4 layer stuffer 6 layer stuffer

1.10 2.20 2.38

Actual fibre volume fraction in percentage 47 48 55

Methods

2.5.1. Composite sample fabrication The woven preforms are consolidated by compression moulding machine in a closed mould using epoxy LY556 resin. The panels are compacted to a fibre volume fraction of approximately 50%. The following parameters are maintained. Curing time = 900 secs, Breathing Pressure = 6 bar, Curing Pressure = 12 bar, Curing temperature = 1200C, Hardener to epoxy ratio = 1:10

2.5.2. Tensile load analysis by experimental method Tensile testing is performed with Instron 5582 using 50 KN load-cell according to ASTM: D3039. The sample size is 250 mm x 25 mm, gauge length 150 mm, cross head speed 2 mm/min. Ten observations are taken for each sample.

2.5.3. Finite elements analysis using ANSYS

Page 253 of 1108

Models are prepared using Solidworks 2014 which is a parasolid-based solid modeler, and utilizes a parametric feature based approach to create models and assemblies. Then these models are imported to ANSYS 14 workbench for simulation. ANSYS is a general purpose finite element modeling package for numerically solving a wide variety of mechanical problems.

2.5.4. Mathematical analysis Reasonable estimates of Youngâ&#x20AC;&#x2122;s modulus in the loading direction (stuffers) are found by rule of mixture and inverse rule of mixture. [9]

Results and Discussion

3.1.

Load extension curves of different layers of 3D orthogonal fabric

The load extension curves of different layered composites are determined experimentally and compared in Figure 2. The bar diagrams of the multilayered structural composites for maximum tensile strength are shown in Figure 3. 25000

Maximum tensile strength

15000

2 Stuffer

10000

4 Stuffer

5000

6 Stuffer

0 -5

Stress (MPa)

Load in N

20000

3.2.

20000 10000 0 2 Stuffer

4 Stuffer

6 Stuffer

Different layers

Elongation in mm

Fig. 2: Load-elonagtion curve of 2, 4 and 6 layers of 3D composite

30000

Fig. 3: Maximum tensile strength of 2, 4 and 6 layers of 3D composites

Finite element analysis in ANSYS

Due to application of force, deformation occurred in the unit cell and reaction force generated on the displaced face are recorded. The total deformation before and after simulation for the composites are shown in figure 4(a), 4(b) and 4(c) respectively.

(a) Two stuffer layer orthogonal composites before and after simulation

Page 254 of 1108

(b) Four stuffer layer orthogonal composites before and after simulation

3.3.

Calculation of the modulus of the composites

The following assumptions are considered in order to calculate modulus of the composite in the stuffer direction. Let V = Volume fraction constituted by all fibres f s = The fraction of all fibres that lie in stuffer A s = Area fraction occupied by stuffers on a section normal to the load axis Than the axial modulus by the stuffer can be given as fs.V

Es=

E f + (1-

fs.V As

) E m (1.1)

where E f = Axial modulus of the fibres E m = Modulus of the resin which is assumed to be isotropic. The remaining resins and fibres i.e. those in the fillers and binders may be considered to form an effective medium whose modulus E' s may be approximated in the direction parallel to the stuffers by E' s = [

(1−fs).V 1

+ 1-

1−As Ef

(1−fs).V 1 1−As

)

]-1

(1.2)

Now the young’s modulus E x for the entire composite in the direction of stuffers is approximately E x = A s E s + (1-A s ) E' s (1.3) For Glass/Epoxy composites the dominant term in E x is thus f s VE f which is independent of A s .This has practical significance because the cross section of stuffers and indeed all tows are often heavily distorted and variable. It is difficult to measure. Hence E x can be measured by knowing f s, V and E f V = It is measured by acid digestion f s = Weaver’s specification E f = Standard value of the modulus of a particular fibre. The stress σ s in the fibres in the aligned tows (stuffers) is approximately related as

Page 255 of 1108

σs = σa Ex σ a = Applied Stress

(1.4)

As per the equation-III , the young’s modulus E x for the entire composite in the direction of stuffers is approximately E x = A s E s + (1-A s ) E' s (1.5) By expansion as well as by taking the assumptions as illustrated in the same section, the above equation becomes E x = [f s VE f + (1-f s V) E m ] + [(1-f s ) V/E f + (1-f s ) V/E m ] (1.6) The Young’s modulus of E-glass fibre = 67.170 GPa The Young’s modulus of matrix = 3.800 GPa Then using the above values E x becomes 4.832 GPa for 2S, 13.746 GPa for 4S and 19.14 GPa for 6S respectively.

3.4.

Comparison of experimental with predicted results

3.4.1. Comparison of load-elongation curves The experimental and FEM predicted load extension curves for the 2,4 and 6 layered composites are shown in Figure 5 to 7.The values of R2 are well within the limit.

Load-Elongation curve of a R2=0.87441 four stuffer composite

10000 0 0

Extension in mm Experimental

Load in N

Load-Elongation curve of a six composite R2stuffer = 0.87421 50000 0 2

Extension in mm Experimental

20000 0 0

Predicted

Fig. 7: Comparison of experimental with predicted (FEM) load extension curves of 6 stuffer composite

Extension in mm Experimental

Predicted

Fig. 5: Comparison of experimental with predicted (FEM) load extension curves of 2 stuffer composite

Load in N

Load-Elongation curve of a two stuffer composite R2= 0.83221

Predicted

Fig. 6: Comparison of experimental with predicted (FEM) load extension curves of 4 stuffer composite

Page 256 of 1108

3.4.2. Comparison of modulus The experimental and mathematically predicted modulus values of different fabric layered composite are shown in Figure 8.

Modulus in GPa

Comparison of modulus 50 0 2 Stuffer

4 Stuffer

6 Stuffer

Different stuffer layers Experimental

Mathematical

Fig. 8: Comparison of modulus of different layers obtained from experimental with predicted (Mathematical) analysis

The predicted values are 30-40% higher than the experimentally measured values for the composites These discrepancies are consistent with rough estimates of the effects of the stuffer waviness .Waviness leads to lower effective moduli because the reaction of a wavy tow to an aligned is not merely to extend but also to shear. Some further reductions can be expected from irregularities in stuffer geometry that are difficult to quantify.

References

[1] Chou S, Chen H-C, Chen H-E. Effect of weave structure on mechanical fracture behaviour of threedimensional carbon fiber fabric reinforced epoxy resin composites. Comp Sci Tech 1992;45:23. [2] Chou S, Chen H-C, Wu C-C. BMI resin composites reinforced with 3D carbon-fibre fabrics. Comp Sci Tech 1992;43:117. [3] Guess TR, Reedy ED. Comparison of interlocked fabric and laminated fabric Kevlar 49/epoxy composites. J Comp Tech Res 1985;7:136 [4] Cox BN, Carter WC, Fleck NA. A binary model of textile composites. I Formulation. Acta Metall Mater 1994; 42:3463. [5]

Cox BN, Dadkhah MS. The macroscopic elasticity of 3D woven composites. J Comp Mat 1995;29:785.

[6] Cox B. Failure models for textile composites. NASA CR4686. Langley Research Center, Hampton (Virginia, USA), August 1995. [7]

Cox BN, Dadkhah MS, Morris WL. On the tensile failure of 3D woven composites. Comp 1996;27A:447.

[8] Dash B.P.Modeling and characterisation of 3D woven solid structures and their composites,PhD Thesis,October 2013,IIT Delhi. [9] Lee B, Herszberg I, Bannister MK, Curiskis JI. The effect of weft binder path length on the architecture of multi-layer woven carbon preforms. Proc ICCM-11, 14â&#x20AC;&#x201C;18 July 1997, pp. V260â&#x20AC;&#x201C;V269. [10] Callusa P.J., Mouritza A.P., Bannisterb M.K., Leongb K.H. Tensile properties and failure mechanisms of 3D woven GRP composites.Composites:Part A 30 (1999)1277-1287.

Page 257 of 1108

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

Modification of chemically Stable Polymeric Materials 61. Improvement in the Adhesive Property of Polymeric and FRP Materials Hitoshi Kanazawa, Aya Inada* and Takuto Tanaka Department of Industrial Systems, Faculty of Symbiotic Systems Science, Fukushima University, 1 Kanayagawa, Fukushima, 960-1296, Japan

Abstract. Chemically stable polymeric materials such as polypropylene, polyethylene, PET were modified by new combination methods. The modified materials gave the improvement of adhesion, water-based paint coating or ink-jet printing. We further improved this technique, and the adhesion property of poly(methyl pentene), silicone resin, polycarbonate silicone resins, fluorocarbon resins and engineering plastics, polymer composites for cars and aircrafts were improved. The modified materials gave a high durability as compared with a plasma treatment and the other methods.

Keywords: surface modification, adhesive property, polypropylene, GFRP, CFRP, ink-jet printing

1. Introduction Polyolefins such as polypropylene (PP), polyethylene (PE) and poly(methyl pentene) (PMP), etc. have both high tensile strength and resistance to chemical reagents. However, these materials cannot be bonded to each other or other materials with usual adhesives. Many techniques were carried out to modify the surface property of polyolefins [1,2]. However, durable modifications for polyolefin materials were not obtained. For instance, when PE or PP materials are treated by a plasma or a corona discharge treatments, the improved properties are lost with time. Thus, the modified materials have to be used quickly. In addition, the discharge treatments are not effective for some polymeric materials. We tried to combine two or three methods, and found that the combination of some modification techniques was effective for the modification of chemically stable polymeric materials [3,4]. This method is named as “Kana methods”. We studied the improvement of the adhesion property of polycarbonate (PC), silicone resin (SIR), fluorocarbon resin and several engineering plastics, and polymer composites (GFRP and CFRP) for cars and aircrafts, furthermore. In addition, the water based paint coating and inkjet printing with water-based ink on polymeric materials were also investigated.

2. Experimental 2.1 Materials Polymeric materials (forms: film, sheets, fabrics, fibers, boards, rods and tubes) were used after washing with methanol. Commercial chemical reagents and hydrophilic reagents were used after a simple purification.

2.2 Adhesives Adhesives poly(vinylpyrrolidone) (PVP), starch, woodwork bonds, PVAC-water mixture (Konishi Co.), cyanoacrylate adhesive (CA; Aron alpha: Toa Gosei Kagaku Co.), epoxy resin adhesive (Quick 5 ; mixture of epoxy resin and polythiol, a product of Konishi Co. Ltd.), a CA-primer set (PPX of Cemedine Co. Ltd. ; primer : organic amine 1% and heptane 99%), etc. were used. Film-type epoxy resin adhesive (3M AF163-2) are used for the adhesion of CFRP boards for aircrafts.

2.3 Modification Polymeric materials were activated by chemical oxidations or energy irradiations. The activated polymeric materials were treated with chemical reagents in the presence of catalysts or initiators. These techniques were named as “KANA1-3 methods”.

Corresponding author. Tel.: + 81-24-548-8184.

Page 258 of 1108

E-mail addressďź&#x161;kana@sss.fukushima-u.ac.jp

2.4 Adhesion strength and analysis Adhesives such as polyvinylpyrrolidone (PVP) glue, starch glue, polyvinylacetate (PVAC)-polyvinyl alcohol (PVA) mixture, polycyanoacrylate (PCA), epoxy resin bonds were used to examine the adhesive property of modified polymeric materials. Adhesion shear strength of a polymeric material bonded to other materials was measured by a tensile tester, Shimadzu AGS-H5KN. IR spectra were observed by a Shimadzu IRPrestige-21 equipped with a Smiths DuraSampl IR II (ATR accessory). XPS of materials were observed by a Ulvack-Phi, PHI 5000 VersaProbe II.

3. Results and Discussion 3.1 Mechanism Polymeric materials are oxidized in the activation process. The extent of oxidation could be estimated by FTIR. IR spectra of untreated PP and treated PP oxidized in the activation process were obtained by ATR method. The treated PP gives an adsorption peak of carbonyl groups at around 1710 cm-1. It was important to make the activation process only on the surface area of materials in order to avoid the degradation. When thick PP films were treated, the degradation could be negligible. The other polymeric materials were treated similarly to PP. The oxidation mechanism of PP was studied well by several researchers [5-6]. The mechanism of the modification of polymeric materials is considered as follows. Several oxidized structures such as carbonyl groups, perhydroxyl groups and hydroxyl groups are formed on PP materials in the activation process. When a chemical reagent, RX is mixed with the oxidized materials, these functional groups can react with RX and the materials are modified. The mechanism is given in Scheme 1.

Scheme 1 Mechanism

3.2 Improvement of adhesive property

Page 259 of 1108

3.2.1 Comparison of the adhesion of modified materials with usual adhesives and that of unmodified materials with a primer-adhesive set (TPX) Unmodified PP boards were adhered to Al boards using a primer-CA adhesive set, PPX. On the other hand, PP boards modified by the KANA method were adhered to Al boards using only CA adhesive. In the adhesion test of unmodified PP boards to Al boards, an adhesion with CA gave 0.01 MPa, that with PPX, 1.69 MPa. On the other hand, the adhered specimen was broken at 3.02 MPa in the adhesion of PP boards modified by the KANA method. The KANA method increased the adhesive force more than the primer-adhesive set. The specimen used in the test is shown in Figure 1.

Fig. 1 A specimen of modified PP board adhered to Al board used in the adhesion shear strength test.

3.2.2 Improvement in adhesive property of CFRP (epoxy resin) CFRP (epoxy resin) boards for car and aircraft use are adhered to each other using epoxy resin adhesive. But, the CFRP boards modified by the KANA method gave the adhesion strength higher than unmodified ones. Table 1 gives the adhesion tensile shear strength test of the epoxy-resin CFRP boards adhered with an epoxy adhesive, 3M- AF163-2; the results of unmodified-unmodified CFRP boards, plasma-treated–plasma-treated CFRP boards, Peelply–Peelply treated CFRP boards, and KANA modified-Kana modified CFRP boards are shown. The largest shear strengh was obtained in the adhesion of KANA-modified boards. Figure 2 gives the appearance of specimens. The adhesion property of plasma treated or Peelply treated CFRP boards is known to be decreased with time. On the other hand, KANA treated CFRP boards could be adhered to each other even at a month after the treatment. The adhesion property of plasma treated or Peelply treated CFRP boards is known to be decreased with time. On the other hand, KANA treated CFRP boards could be adhered to each other even Table 1 Adhesion shear strength test of CFRP (epoxy resin) boards adhered using at a month epoxy adhesive and failure styles after the specimen Shear strength (MPa) Ratio(Mod/Un) Failure style treatment. unmodified-unmd. 25.4 1.00 Interface plasma-plasma Peelply-Peelply

35.2 35.0

1.40 1.38

Cohesion Cohesion

KANA–KANA

51.3

2.02

Cohesion+material

Page 260 of 1108

Fig. 2 Specimen after the adhesion shear strength test; unmodified CFRP-unmodified CFRP adhesion (upper) and KANA modified- CFRP- KANA modified CFRP (under).

3.3 XPS analysis of PP films Unmodified and modified PP films were analyzed by XPS. Table 2 gives functional groups observed by XPS. It is remarkable the the amount of C-O bonds was increased by the present modification. This suggests the formation of C-OH groups. Table 2 Functional groups observed by XPS functional group contents (%) specimen C-C, C-H C-O C=O O=C-O unmodified 100 0 0 0 plasma treated 81.6 8.2 3.58 6.58 Kana treated 74.9 17.3 3.23 4.53

O/C ratio 0.02 0.22 0.30

3.4 Improvement in water-based paint coating Polymeric materials such as PP, PE, UHMPE, silicone resin, polycarbonate, and fluorine resin, etc. and GFRP or CFRP boards modified by the present method could be coated with water-base paint. Figure 3 gives water-based paint coating on unmodified GFRP (PP resin) board and modified one. A full- Fig.3 Water-based paint coating on unmodified mark, 100/100 was obtained in the cross-cut test of GFRP (PP) board and modified one the coating of modified GFRP. On the other hand, unmodified GFRP board was not coated with water-based paint.

3.5 Inkjet printing Modified PP, PET, PC and silicone resin sheets were printed by an ink-jet printer using water-based ink. Figure 4 shows modified and printed PP sheets.

4. Conclusion

Fig.4 Modified PP film printed by an ink-jet printer using a water-based resin ink.

The present modification methods (KANA 1-3) were effective for the durable improvement in the adhesion property of chemically stable polymeric materials. The technique is applicable for many kinds of materials such as new medical devices, printings, machine devices and battery separators. Especially, the adhesion property of polymer composite materials was improved well, and the obtained property was not changed even after five years. This property is expected for the weight saving of cars and aircrafts, etc.

Page 261 of 1108

5. References [1] Young, R.H. Sr., et. al., United State Patent, No.5432000 (1995). [2] Kinoshita, M., Japanese Patent Application, No.09012752 (1997). [3] Kanazawa, H., USA Patents No.7294673 and No. 6830782B2, [4] Kanazawa, H., Japanese Patent No.4229421, etc. [5] Kawamatsu, T.，Polymer (Kobunshi)，8, 643 (1959). [6] Matsui, T. And Yamaona, A. Nihon Kagaku-kai Shi, 732(1992).

Page 262 of 1108

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

Morphlogy and Thermal Property of Neoprene Textiles Coated with CNF/polymer Composites Hyelim Kim1 and Sunhee Lee 2 + 1

Dept. Fashion and Textiles, Dong-A University, Busan, 604-714, Korea 2 Dept. Fashion Design , Dong-A University, Busan, 604-714, Korea

Abstract. The main objective of this study has been to development of improved functional textiles for marine leisure clothing. Neoprene fabrics were coated with carbon nanofibers(CNFs)/Poly(vinylidene fluoride-cohexafluoropropylene)(PVDF-HFP) composite solution via electrospinning. CNF/PVDF-HFP composite solution were prepared by 0~16 wt% CNF into 15 wt% PVDF-HFP solutions. Electrospinning was carried out at from 15 to 24kV. Characterization of neoprene textiles coated with CNF/PVDF composite with various applied voltages was investigated as follows. Morphology of resultant samples was examined using FE-SEM. It was confirmed the surface and crosssection of nanoweb on the neoprene rubber The thermal storage of resultant samples was analyzed using a Thermal imaging camera (FLIR system). Increasing CNF contents, the surface temperature of nanoweb coated neoprene rubber was increasing. The tensile property test was measured using Universal Testing Machine. In the case of applied voltage at 15kV, as increasing CNF contents, the value of elongation of nanoweb coated neoprene rubber is tend to decreasing and load of those is increasing.

Keywords: neoprene, carbonnanofiber composite, nanoweb, morphology, thermal property

1.1. 2. Introduction 2.1. Neoprene, a type of synthetic rubber made from polychloroprene, is used as an elastomeric fiber or a supported elastic film. It is found in protective gloves and clothing, wetsuits, anticorrosive seals and membranes, and coating for wiring. The main objective of this study has been to development of improved functional textiles for marine leisure clothing[1]. Electrospinning is widely accepted as a simple and versatile technique for the fabrication of micron and nanometer-scaled coatings. It has been reported that the polymer molecular chains within electrospun fibers are oriented in the fiber axis. Carbon Nano Fibers (below CNF) have taken high attention due to their unique mechanical, electrical and thermal properties. With embedding, aligning and uniform distribution of CNF in electrospun nanofibers, it is able to transfer these properties to high ordered structures[2]. In this study, PVDF-HFP nanofibers web, +

Corresponding author. Tel.: + 82-51-200-7329. E-mail address: shlee014@dau.ac.kr

Page 263 of 1108

containing CNFs were produced successfully by electrospinning process. First, CNFs with various contents were dispersed in acetone using ultrasonic and then PVDF-HFP chip at different concentrations were added to the dispersions and mixed by mechanical mixer to reach a homogenous electrospinning solution dope. Finally, a neoprene rubber under optimized processing conditions were electrospun. The CNF/PVDF-HFP nanoweb coated neoprene rubber were characterized with SEM, thermal property and mechanical property.

3. Experimental 2.1. Materials Neoprene fabrics were coated with carbon nano fibers (CNFs)/poly(vinylidene fluoride-cohexafluoropropylene)(PVDF-HFP)(Solef 21508, Solvay Co. Ltd.) composite solution via electrospinning. CNF/PVDF-HFP composite solution were prepared by 0, 2, 4, 8, 16 wt% CNF into 15 wt% PVDF-HFP solutions.

2.2. Nanoweb coating conditions The electrospinning apparatus for nano coating include a plastic syringe, a 21 gauge stainless steel needle, a microinfysion pump, a high-voltage power supply(Chungpa Co. Ltd), and an aluminum foil as the collector. Applied voltage was carried out at 15, 18, 21, and 24kV. CNFs-PVDF-HFP solution was drawn horizontally from the needle tip by the electrostatic force, which was formed between the tip and the collector by high voltage. The ejection rate of the solution was set at 15ml/h, and the distance between the tip and the collector was 8cm. The electrospun nanofibers deposited on the neoprene fabrics collector in the form of a web after the evaporation of the acetone.

2.3 Characterizations The morphology was measured by FE-SEM (JSM-6700F, Jeol, Japan). To find out samples coated by CNF content and applied voltage were taken at ×100 and ×10,000. Thermal storage characteristics of samples were measured by Thermal imaging camera (FLIR SYSTEMS. Co., Ltd). Each sample was heated for 10 minutes at 37℃. And then after 20 seconds at room temperature, using a thermal imaging camera to measure the surface temperature of the sample. And each sample were measured three times. The mechanical property test was measured using Universal Testing Machine. Using 5 samples were tested and each sample size was 25×75×3mm. The clamp distance of the tensile property tester was set to 25mm. Samples were held between the clamp and load was gripping samples to strainghten the position to the zero point of the graph. The constantspeed extension to the speed of 50mm/min were recorded strength-strain curve for each sample.

4. Results and Discussion

4.1. Morphology of CNF/PVDF-HFP nanoweb coated neoprene rubber Fig. 1 presents the SEM image of CNF/PVDF-HFP nanoweb coated neoprene rubber with applied voltage at 15kV and various CNF contents. It was confirmed the surface and crosssection of nanoweb on the neoprene rubber. Increasing CNF contents, the surface was shown irregular web and grey color.

Page 264 of 1108

Fig. 1 : SEM image of CNF/PVDF-HFP nanoweb coated neoprene rubber with various CNF at 15kV.

3.2 Thermal storage property of CNF/PVDF-HFP nanoweb coated neoprene rubber Fig. 2 shows the thermal storage property of CNF/PVDF-HFP nanoweb coated neoprene rubber with applied voltages at 15kV and various CNF contents. Increasing CNF contents, the surface temperature of nanoweb coated neoprene rubber was increasing. 38 un-coated 15kV

Temprature(ยกร )

36 34 32 30 28 26 -4

-2

10 12 14 16 18

Concentration of CNF (wt%)

Fig. 2: Thermal storage property of nanoweb coated neoprene rubber with various CNF contents at 15kV.

4.2. Mechanical property of CNF/PVDF-HFP nanoweb coated neoprene rubber Table 1 shows the mechanical property of nanoweb coated neoprene rubber with various CNF contents and applied voltages at 15kV. Load and elongation of uncoated neoprene rubber were present 3.33N and 336.01%. In the case of applied voltage at 15kV, as increasing CNF contents, the value of elongation of nanoweb coated neoprene rubber is tend to decreasing and load of those is increasing.

Page 265 of 1108

Table 1 Mechanical property of nanoweb coated neoprene rubber with various CNF contents and applied voltages CNF contents (wt%) Applied Voltage (kV)

load (N)

elonga tion (%)

uncoated

3.33

336.01

3.20

18 21 24

load (N)

elonga tion (%)

load (N)

elonga tion (%)

load (N)

elonga tion (%)

load (N)

elonga tion (%)

255.01

3.50

299.33

2.97

290.91

3.23

285.53

3.53

350.21

3.57

335.44

3.20

298.15

3.27

248.19

3.13

300.53

3.23

332.35

3.83 3.57

349.36 320.08

3.27 3.17

316.24 262.51

3.10 3.03

262.55 268.08

2.93 3.07

275.13 285.84

3.47 3.23

400.33 366.34

5. Acknowledgements This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (No.NRF2014R1A1A2057445).

References

[1] Lee et al, Analysis of thermal insulation and material specific areas in marine immersion suits, Conferences of J. Korean Soc. Cloth. Ind. , 2015

Page 266 of 1108

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

pH- / Temperature-responsive Materials Prepared from β-Amino Acid Ester Carrying Polymerizable Group Yasuhiro Kohsaka 1*, Yusuke Matsumoto 2 and Tatsuki Kitayama 2 1

Faculty of Textile Science and Technology, Shinshu University (3-15-1 Tokida, Ueda, Nagano 386-8567, Japan, e-mail: kohsaka@shinshu-u.ac.jp, Tel: +81-268-21-5488) 2 Department of Chemistry, Graduate School of Engineering Science, Osaka University (1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan)

Abstract. α-(Aminomethyl)acrylates, i.e. β-amino acid esters carrying polymerizable vinylidene groups, were radically polymerized, where the generated polymers were found to undergo ester-amide exchange reaction with the pendant amino groups in the generated polymers, resulting acrylamide bearing copolymer. Nevertheless, the amidation ratios were up to 15% and linear soluble polymers were obtained under the optimized conditions. Among the obtained polymers, the ethyl ester exhibited pH- / temperatureresponsiveness in dilute acidic aqueous solution; for example, it was insoluble in 1 M HCl solution above the cloud point, which was tunable by pH and counter anions. Keywords: Stimuli-responsive polymer material, poly(amino acid derivatives), radical polymerization, polymer reaction

1. Introduction Polypeptide, a natural polycondensation product of α-amino acid, is one of the fundamental materials for textile science and technology. On the other hand, artificial polymers of α-amino acids and their derivatives composed of carbon-chain backbone has been a hot topic in synthetic polymer chemistry. (Meth)acrylamide[1] and vinyl ester[2] of natural α-amino acid are typical examples, which affords carbohydrate backbone bearing pendant α-amino acid residues, by radical polymerization. In these cases, however, the amino or carboxyl groups of α-amino acids are consumed for connecting them to the backbone. In contrast, poly(dehydroalanine) (PDA) has α-amino acid (alanine) structure in its main chain, retaining the reactivity of the amino and carboxyl groups. According to molecular simulation, PDA is expected to have more flexible backbone than polypeptide due to the carbon-chain backbone, allowing variety of stable conformations with support of hydrogen bonding between the amino and carboxyl pendants.[3]Although the synthesis of PDA has been attempted since 1959,[4] however, the successful example had not been reported until very recently.[5] The difficulty of the synthesis of PDA is attributed to the instability of the corresponding monomer, dehydroalanine (Scheme 1), which undergoes tautomerization to an imine. That is, the synthesis of PDA directly from dehydroalanine is almost impossible and requires laborious protection-deprotection protocols. [5] NH CH3 C C O OH

NH2 CH2 C C O OH

NH2 CH2 C n C O OH PDA

Scheme 1. Poly(dehydroalanine) (PDA) and the corresponding vinyl monomer.

Recently, we have been interested in the polymerization chemistry of α-functionalized acrylates,[6]-[8] in which the α-substituents are bound to the vinylidene group so that it strongly affects the reactivity and polymerization behavior as compared to the cases of ester functionalized (meth)acrylates. For example, the anionic copolymerization of α-arylacrylate with methyl methacrylate (MMA) resulted in the formation of an alternating copolymer, which exhibited different fluorescence from the homopolymer.[8] On the extension of this line, we newly designed a series of amino-functionalized monomers, α-(aminomethyl)acrylates (M1-M4,

Page 267 of 1108

see Scheme 2). From another point of view, the monomers can be regarded as β-amino acid esters carrying polymerizable vinylidene group. Since the β-methylene group functioned as a spacer between the amino group and the C=C double bond, the monomer does not undergo the tautomerization that dehydroalanine does, and can be isolated as a stable compound. In fact, a derivative of the monomer is found in the metabolic product of some sponges in Red Sea[9] and Hawaii. [10] In this report, we describe the synthesis and polymerization of M1-M4 and the stimuli-responsiveness of the obtained polymers of M1 and M2 in aqueous media.[11]

2. Results and Discussion 2.1. Syntheses of β-amino acid esters

Holm et al. reported the preparation of M1 via amination of ethyl α-(bromomethyl)acrylate with liquid ammonia.[12] For the purpose of large-scale synthesis for polymerization, this procedure was slightly modified here; ethyl α-(chloromethyl)acrylate was treated with aqueous ammonia solution to afford M1 in 91% yield. In a similar way, M2-M4 were prepared. Notably, the amino group may have scare nucleophilicity, because the protection of the amino group with di-tert-butyl dicarbonate (Boc 2 O) in the presence of base catalyst did not proceed. Since the IR absorption of the carbonyl group of M1 in 1 wt% CHCl 3 ) was observed at 1718 cm−1, 7 cm−1 smaller than that of MMA (1725 cm−1), suggesting an intramolecular hydrogen bonding between the amino proton and the carbonyl group. Presumably, the hydrogen bonding may suppress the nucleophilicity of the primary amino group. Generally speaking, (meth)acrylate carrying a primary amino group tends to be converted to an amide through the S N 2 reaction by the primary amine. In fact, 2-aminoethyl methacrylate is commercially available only in its ammonium salt form. In contrast, M1-M4 was found enough stable to be stored in refrigerator for more than a half year without any stabilizer, probably due to the low nucleophilicity of the primary amine.

2.2. Radical polymerization

Radical polymerization of M1 was conducted at 60 °C in 1,4-dioxane with 2,2’-azoisobutyronitrile (AIBN) (Table 1, Run 1).[11] Fig. 1B shows the 1H NMR spectrum of the obtained polymer, P1., Beside the broad signals assignable to the expected monomeric units, the olefinic signals, the vinylidene proton signals, which exhibited 1H-1H COSY correlation with the N-CH 2 signal (z). In order to assign these unexpected signals, NH2 z CH 2

NH2 x H z CH2 C C yH C O OR M1 (R = Me) M2 (R = Et) M3 (R = iPr) M4 (R = Bu)

AIBN CH2

NH2 CH2 C n C O OR

CH2 C C O NH2 NH z CH z CH 2 2 CH2 C n CH2 C x x C O C O OR OR

CH2 SH

cat. Et3N

CH2

NH2 CH2 C CH2 C O OR

NH2 CH2 C H C O NH CH2 C n C O OR

P1 (R = Me) P2 (R = Et) P3 (R = iPr) P4 (R = Bu)

Scheme 2. Radical polymerization of M.

Run 1 1 2 3 4f

Table 1. Radical polymerization of M1-M4 with AIBN (5 mol%) at 60 °C for 12 h. Monomer Solvent Conversionb /% Mnc Mw / Mnc e 1,4-dioxane 77 (2200) (2.54)e M1 Toluene -f -f -f M1 Toluene 85 3450 2.08 M2 Toluene 84 6110 4.89 M3 Toluene 80 5290 2.69 M4

Ad /% (9)e -f 11 12 18

[M] 0 = 1.0 M. b Determined by 1H NMR (400 MHz, CDCl 3 , 30 °C). c Determined by SEC (THF, 40 °C, PMMA standards). d Content of amidated units. e Soluble fraction. f Not measured due to the poor solubility. a

Page 268 of 1108

Fig. 1. 1H NMR spectra of A: M1, B: P1 and C: the product of thiol-ene reaction of P1 with benzyl mercaptan (400 MHz, CDCl 3 , 55 °C). D: IR spectra of P1. Labels x-z correspond to those in Scheme 1. •: CHCl 3 , *: 1,4-dioxane.

Michael addition-type thiol-ene reaction, which was known as a click reaction and thus effective to detect the α,β-unsaturated carbonyl compounds, was employed with benzyl mercaptan in the presence of Et 3 N as a base catalyst (Scheme 2). After the reaction, the olefinic proton signals completely disappeared, confirming the olefinic grourp should be in the carbonyl conjugated structure. Moreover, IR spectrum of P1 showed carbonyl absorption of amide group at 1688 cm−1 as a small shoulder of that of ester (1728 cm−1). These spectral evidences suggest that the ester-amide exchange reaction between the ester group of the monomer and the amino group of the polymer occurred during the polymerization to afford acrylamide-type pendant structure (Scheme 2). As described previously, the monomers do not undergo ester-amide exchange reaction, meaning that the amino group of M1 has lower nucleophilicitythan that of the polymer. On the other hand, the ester group of M1 has higher electrophilicity than the polymer owing to the α,β-unsaturated structure. Consequently, the amino pendant of the polymer might undergo the ester-amide exchange reaction with the monomer. From the intensities of olefinic proton signals [Int.(olefin), 6.5-5.0 ppm] and aliphatic signals [Int.(aliphatic), 5.00.5 ppm] in 1H NMR spectrum, the content of amidated units (A) could be roughly estimated as 9% according to the following equation; (1) The polymerization of other monomers (M2-M4) afforded similar results. All the resulting polymers except P1 prepared in toluene (Run 2) were soluble in common organic solvents such as CHCl 3 and THF.

2.3. Stimuli-responsiveness of the obtained polymer in aqueous media P1 was insoluble in neutral water but soluble in 1 M HCl aq due to the hydrophilic ammonium pendants. In addition to a similar pH-responsiveness, P2 exhibited temperature-responsiveness (Fig. 2); in 1 M HCl aq, P2 was soluble at 10 °C, but the solution became cloudy around 25 °C and completely non-transparent at 40 °C.[11] In order to investigate this pH-/temperature-responsiveness, 1 M HCl solution of P2 (20 mg / 5.0 mL) was titrated with 1 M NaOH aq., and the change of transparency was visually inspected at each pH. Fig. 3 shows the plots of pH and cloud points (T c ). Apparently, could points are dependent on pH of aqueous media. In this phase diagram, P2 was soluble and insoluble in the areas above and below the dot line, respectively. Notably, the soluble regime became smaller in HBr aq than in HCl aq. Moreover, P2 was entirely insoluble in HI aq. The results indicate that the solubility of P2 are dependent on the counter anions as well as pH and temperature. P3 and P4 were insoluble in aqueous media even under acidic conditions, due to the larger hydrophobic ester substituents. In other words, a good balance of hydrophilic (ammonium/amino groups) and hydrophobic

Page 269 of 1108

(ester substituents) groups are required to gain pH-/temperature-responsiveness. In addition, as poly(2aminoethyl methacrylate), the isomer of P2, does not exhibit pH-/temperature-responsiveness and is soluble in water even under neutral and basic conditions, the hydrophilic and hydrophobic groups should be located in the different pendant groups. Thus, it can be concluded that the dual stimuli-responsiveness are characteristic properties of the polyacrylates possessing β-amino acid ester unit across the backbone.

Fig. 2. Temperature-responsiveness of P2 in 1 M HCl aq.

Fig. 3. Plots of T c of P2 in various aqueous media.

3. Conclusion In the radical polymerization of β-amino acid esters, M1-M4, were found to lead the following amidation between the amino pendants on the resulting polymers and ester group in the monomers. Nevertheless, the ratio of amidated units was ca. 10% and crosslinking by polymerization of the acrylamide pendants could be avoided in the optimized conditions, affording the linear polymers with good solubility. Among them, P1 and P2 changed the solubility in aqueous media according to the pH; in particular, P2 exhibited temperature responsiveness, of which T c was tunable with pH and the counter anions. Recently, stimuli-responsive materials attract textile scientists’ interest for the application to artificial actuators and intelligent clothes. We believe that the materials provide a new potentiality for smart fabrics.

4. Acknowledgements This work was supported by JSPS KAKENHI Grant Number 26810069. This study was supported by a grant from the Ogasawara Foundation for the Promotion of Science & Engineering in 2012 (Y.K). The authors would like to thank Nippon Shokubai Co. Ltd. for providing methyl and ethyl α-(hydroxymethyl)acrylates.

5. References [1] M. Casolaro, Macromolecules, 1995, 28, 2351. [2] G. B. Thomas, C. E. Lipscomb, M. K. Mahanthappa, Polym. Chem., 2012, 3, 741. [3] P. Fábián, V. S. Chauhan, S. Prongor, Biochem. Biophys. Acta, 1994, 1208, 89. [4] S. Sakakibara, Bull. Chem. Soc. Jpn., 1959, 33, 814. [5] U. Günther, J. V.Sigolaeva, D. V. Pergushov, F. H. Schacher, Macromol. Chem. Phys., 2013, 214, 2202. [6] a) Y. Kohsaka, T. Kurata, T. Kitayama, Polym. Chem., 2013, 4, 5043. b) Y. Kohsaka, T. Kurata, K. Yamamoto, S. Ishihara, T. Kitayama, Polym. Chem., 2015, 6, 1078. c) Y. Kohsaka, K. Yamamoto, T. Kitayama, Polym. Chem., 2015, 6, 3601. [7] Y. Kohsaka, K. Suzawa, T. Kitayama, Macromol. Symp., 2015, 350, 86. [8] Y. Kohsaka, E. Yamaguchi, T. Kitayama, J. Polym. Sci. Part A: Polym. Chem., 2014, 52, 2806. [9] Y. Kashman, L. Fishelson and I. Ne'eman, Tetrahedron, 1973, 29, 3655. [10] M. B. Yunker and P. J. Scheuer, Tetrahedron Lett., 1978, 19, 4651. [11] Y. Kohsaka, Y. Matsumoto, T. Kitayama, Polym. Chem. 2015, 6, 5026. [12] A. Holm and P. J. Sceuer, Tetrahedron Lett., 1980, 21, 1125.

Page 270 of 1108

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

Pitch-based Carbon Fiber Prepared by Melt Spinning Using Screw Type Extruder Tae Hwan Lim 1, So Hee Lee 2 and Sang Young Yeo 1 + 1

Technical Textile and Materials R&D Group, Korea Institute of Industrial Technology, 143 Hanggaul-ro, Sangnok-gu, Ansan-si, Gyeonggi-do, 15588, Korea 2 Research Institute of Women Health, Sookmyung Women`s University, Cheongpa-ro 47-gil 100, Youngsan-gu, Seoul, 140-732, Korea

Abstract. Mesophase and isotropic pitch based carbon fiber is prepared by melt spinning process using screw type extruder. Carbon fiber, especially, pitch based carbon fiber is of considerable interest for future transportation and portable electronic device because of its low weight and high electrical properties. However, carbon fibers produced from pitch are considered too expensive, low yield, and difficult procesability. Here screw type extruder is introduced and it enables to continuous and easy melt spinning process that is difficult to conventional batch type extruder. Isotropic and mesophase pitch based carbon fiber have been prepared by both batch type and screw type extruder to compare mechanical and electrical properties. Scanning electron microscopy images and mechanical test results verify that there are little difference in the various properties of the CFs obtained screw type extruder without melt spinning process duration. Whereas the process using batch type extruder shows poor melt spinnability when the processing time is accumulated and the mechanical strength of CF is dropped winding 1h after. These approaches can produce large amount, easy and uniform quality of CF for the applications needed strong, light, and high electrical and thermal properties.

Keywords: Pitch, Carbon fiber, Extruder, Melt spinning.

1. Introduction Carbon fiber is attractive material because of its light weight, high modulus and tensile strength, and excellent thermal and electrical conductivities, therefore, it could be used in variety of specialized applications such as aerospace, automative, sports goods, and electrical devices. In general, carbon fiber is classified into three types according to the precursor: polyacrilonitrile (PAN), rayon, and pitch. Particularly, carbon fiber made from pitch is spotlighted recently substituted for PAN based carbon fiber because the pitch is low cost and recreated material, the yield from pitch to carbon fiber is high, and the modulus, thermal and electrical conductivities of pitch based carbon fiber are higher than that of other material based carbon fiber. Pitch based carbon fiber is divided into isotropic and mesophase by pitch precursor. Isotropic carbon fiber is utilize to modest performance carbon fiber or activated carbon fiber after the activation process. Mesophase carbon fiber, which shows liquid crystal behavior, exhibits high performance in the respect of tensile modulus and electrical property. Pitch based carbon fiber is prepared by melt spinning process [1,2]. It is general that the spinning barrel is designed to batch type to block the contact with oxygen gas. It is one of major factors for successful melt spinning. Oxygen makes the pitch to cokes by oxidation, therefore, the oxygen-purged system is adapted through nitrogen gas injection. The injection gas acts not only fill the barrel but give the pressure to pitch for spinning with the piston pressure. However, It is not an ideal concept because it is discontinuous process. The capacity of barrel is limited and decisively, it provides pitch fibers having different heat history according to the melt spinning time. Here continuous process is suggested using screw type extruder in this study that is normally adapted polymer fabrication system to overcome these disadvantages. Pitch, in common with polymer pellet, is fed into hopper purging with nitrogen gas, and the screw moves pitch from hopper to nozzle with nitrogen gas injection pressure. The spinning temperature and screw speed is the other major factors to get the optimum softening pitch fiber for elongation and winding. This system can produce pitch fiber applied

Corresponding author. Tel.: + 82-31-8040-6068. E-mail address: miracle@kitech.re.kr

Page 271 of 1108

identical heat capacity through melt spinning process, therefore, it would be expected that it shows benefits to get carbon fiber having uniform quality, continuous process and mass production. This present work concentrates on the researches of the difference of the regularity following melting time, mechanical strength, and crystallinity between the carbon fiber fabricated by batch type extruder and screw type one.

2. Experimental 2.1.

Materials and Devices

Different types of pitch, isotropic pitch (AS280, Anshan Sinocarb Fibers Co., Ltd.) and mesophase pitch (MP290) were purchased and purged with N 2 gas to prevent from oxidation. To predict the thermal and physical behaviors of pitches, various analyses were performed using softening point (SP) determination system (DP90, Mettler Toledo, Switzerland). Optimum spinning temperature and residence time were selected using isothermal mode and gravimetric force by standard ball (ASTM D3461). Following the analysis, the softening points of AS280 and MP290 are confirmed by 284oC and 293oC, respectively. Two types of extruder were used for fabricating carbon fiber as-spun. One is batch type extruder that is generally used to make glass (ceramic) fiber. The stainless steel laboratory scale apparatus with capacity for 20g of pitches are used to extrude the precursors. N 2 gas acts as not only prevents oxidation but extrudes of pitches. N 2 pressure and winder speed have been controlled in order to evaluate their effect over the diameters of the pitch fibers. The other, twin screw type extruder (BA-11, Bautek, Korea) is introduced to fabricate the pitch fiber. In general, single screw type extruder is used to make fiber from bulky shape. The molten material moves to the end of barrel according to screw rotation and pulls out in the shape of the fiber through the nozzle by pressure. The fiber prepared by single screw type extruder had good mechanical properties having little pores because it is formed by pressure. However, this screw type is unsuitable to carry the powder material. For helping the carrying problem although it is not an ideal type to fabricate fiber shape, twin screw type extruder system is applied to fabricate the continuous pitch fiber. The scheme and photograph image are shown in Fig. 1.

Fig. 1: Scheme and images of extruder type melt spinning system

Page 272 of 1108

2.2.

Fiber preparation

2.3.

Characteristics

Pitch fiber fabricated by batch type extruder (bPF) is pushed out through a mono-hole spinneret of Ф0.5 mm of diameter. Under 50 μm diameter MP290_bPF and AS280_bPF are obtained the condition of above 50oC of softening point, 1.0 bar nitrogen pressure, and over 400 mpm. Isothermal time before spinning is controlled to confirm the effect of mechanical properties according to heat treatment time. The fiber fabricated by screw type extruder (sPF) is prepared by 10-hole spinneret (L/D=5) of Ф0.7 mm of diameter. The diameter of sPF is regulated through the screw and gear pump rpm, winder speed and free drop length. The PFs are oxidatively stabilized near SP for 12h in air in the extended state. The stabilized fibers are carbonized at 1000oC for 1h holding in N 2 air. The abbreviations of stabilized and carbonized fibers are regulated to StabF and CF.

Observations of the diameter and cross section images of the carbon fiber are carried out field emission scanning electron microscope (FE-SEM, SU8000, Hitachi, Japan). X-ray diffractometer (XRD) and RAMAN spectroscopy are used to compare the crystallinity of carbonized fiber (CF). The mechanical properties of CF are determined with automatic linear density and tensile tester for single fibres (FAVIMAT, Textechno H. Stein GmbH & Co. KG, Germany).

3. Results and discussions High performance and uniform CFs are obtained by screw type extruder system and its cross section images are shown in Fig. 2. We also obtained various AS280_bCFs and MP290_bCFs according to aging time at spinning temperature to compare mechanical and other properties with those of sCFs. The information of melt spinning, oxidation and carbonization temperature are supplied by thermogravimetric analysis (TGA) profiles in oxygen and nitrogen atmosphere.

Fig. 2: Cross-section images of AS280_sCF (left) and MP290_sCF (right). The mechanical properties of various bCFs the melt-spun winded within 1h are verified slightly higher than those of sCFs. However, the elongation and strength properties and spinability are drastically dropped over 1h aging pitch at melt-spinnable temperature. It is announced that excessive heat induced the decomposition and producing coking material interrupting well-spinnability [3]. Whereas the sCFs obtained after 0h, 1h, 3h, 5h, and 7h have nearly similar mechanical properties because it is possible to distribute same heat and pressure of molten pitches. Therefore, it is judged that the screw type extruder is suitable for adapting continuous process acquiring uniform CF. Though sCF takes advantages of this fact, it is difficult to reveal the optimum properties because it could not have sufficient time to remove low molecular weight pitch and impurities. It is regarded as the overcome problems in order to commercialize high functional carbon fiber industry.

4. References [1] Y Korai, SH Hong, and I Mochida, Development of longitudinal mesoscopic textures in mesophase pitch-based carbon fibers though heat treatment. Carbon 37 (1999) 203-211. [2] AH Wazir and L Kakakhel, Preparation and characterization of pitch-based carbon fibers. New Carbon Materials 24 (2009) 83-88. [3] BJ Kim, Y Eom, O Kato, J Miyawaki, BC Kim, I Mochida, and SH Yoon, Preparation of carbon fibers with excellent mechanical properties from isotropic pitches. Carbon 77 (2014) 747-755.

Page 273 of 1108

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

Preparation and Characteristics of Carbon Nanotube/Carbon Fiber Composite Paper Wan Jin Kim, Wan Jin Kim Hyun Myung Kwon and Yong Sik Chung + Department of Organic Materials & Fiber Engineering, Chonbuk National University, Jeonju 561-756, Korea

Abstract. Carbon nanotube paper (CNTP) has considerable potential in multi-functional nano-composites for electrical and thermal applications. In this study, we confirmed the manufacturing possibilities of the CNTP by coagulation and dispersion. Multi-walled carbon nanotube (MWCNT)/carbon fiber (CF) composite paper for the enhanced electrical properties was prepared using a homogeneous precipitation method in accordance with the ratio of MWCNT and CF. SEM observations showed that most of the MWCNTs were deposited directly on the outside surface of the CF. The mechanical properties of MWCNT/CF papers showed higher tensile strength than pure MWCNT paper, which was increased with increasing content of CF. Also, the electric conductivity of the MWCNT/CF papers was increased with increasing the content of CF except papers of pitch based CF. In addition, the results of the mechanical and electrical analysis in accordance with the types and contents of the CF indicated that the PAN-based MWCNT/CF paper showed a better performance than Pitchbased CF. Keywords: Carbon fiber, Carbon nanotube, Composite paper, Homogeneous precipitation method, Coagulation, Dispersion

1. Introduction In the past two decades, nanotechnology (NT) and nano-oriented materials, especially carbon nanotube (CNT) has aroused a major interest among engineers and scientists, owing to its unique and remarkable mechanical and electrical properties, such as high stiffness, strength, conductivity. There are four types of CNTs, single-walled carbon nanotube (SWCNT) and double-walled carbon nanotube (DWCNT) and multiwalled carbon nanotube (MWCNT) and rope carbon nanotube (RCNT). CNTs composites with polymers and ceramic materials have been investigated by many researchers due to the excellent performances of CNTs [1,2]. But the solubility and the dispersion of MWCNTs limited its applications in the process of making hybrid materials. To overcome these problems, several approaches were suggested by some works, such as surfactant mixing, chemical oxidation, and polymer wrapping [3,4]. Particularly, polymer wrapping by using polyelectrolytes was an efficient approach to disperse MWCNTs well in solutions. Polyelectrolytes have been intensively investigated as dispersants for ceramic processing for decades. The interesting feature of polyelectrolyte dispersants is that it maintains the stability of slurries by electrostatic and steric forces. These electrostatically stabilized ceramic slurries showed enhanced stabilities compared to pure electric double layer stabilized ceramic slurries [5]. Poly(acrylic acid) (PAA) has been widely used as polyelectrolyte dispersant for ceramic processing, such as, paint, adhesive, and paper industry[6-8]. Carbon nanotube paper (CNTP) has typical paper morphologies such as enormous aggregation, thin and wide sheet. However, it has thinner thickness and higher surface area than typical paper because of the high aspect ratio (length/diameter) of nano-sized CNTs. CNTP also has good properties, such as higher electrical and thermal conductivity. Therefore, CNTP has been evaluated as one of the most promising materials in making the multifunctional nanocomposites for structural, electrical, and thermal applications.

Corresponding author. Tel.: + 82-010-7247-2350 E-mail address: psdcolor@jbnu.ac.kr

Page 274 of 1108

In current study, it was confirmed that CNTP was fabricated by homogeneous precipitation method with binder and dispersant. In order to enhance the structural, mechanical, electrical and thermal properties, CNT/carbon fiber (CF) composite paper was fabricated in accordance with the ratio of MWCNT and CF. Finally, we confirmed the optimum conditions for fabricating the MWCNT/CF papers through the measurements of structural, mechanical, electrical and thermal properties.

2. Experimental CNTs (Multi-wall type, Jeio Korea Co., Ltd), PAN-based CF (6mm chopped fiber, Toray), and Pitch based CF (6mm chopped fiber, Kureha) were dispersed in water with different CF contents range from 0 wt.% to 80 wt.%. CNT and CNT/CF slurries were agitated in colloid mill (Fig. 1a) at 2000 rpm of rotor speed, and then 1 wt.% of PAA was added into slurry as dispersant. Using a uniformly dispersed CNT and CNT/CF slurries, CNT and CNT/CF papers were fabricated by paper making machine (Fig. 1b). The properties of CNTs, which used in CNT and CNT/CF papers were listed in Table 1. The fabricated CNT and CNT/CF papers were pressed at 130 ℃ with a pressure of 0.03 MPa for 3 min, in order to remove water in paper and enhance bonding strength between CNTs and CF.

Fig. 1: schematics of colloid mill (a) and paper making machine (b).

The morphologies of CNT and CNT/CF papers were explored using a field emission scanning electron microscope (SU-70, Hitachi, Japan). The pore size distribution of the obtained papers was characterized by capillary flow porosimetry (porous material Inc. PMI).The mechanical and electrical properties such as tensile strength and conductivity were measured by universal testing system (INSTRON 5560) and four point probe method (FPP-HS8, Dasol Eng.), respectively. Table 1: Properties of carbon nanotube (CNT) Type

Diameter (nm)

Length (µm)

Purity (%)

Bulk density (g/cm3)

BET (m2/g)

Multi-wall

8∼10

300∼500

0.01

450∼650

3. Result and Discussion The surface structure of pure CNT paper with and without dispersant were observed by field emission scanning electron microscopy (FE-SEM), as shown in Fig. 2. In the pure CNT paper without dispersant (Fig. 2a), CNTs were dispersed unevenly and entangled each other. However, pure CNT paper with dispersant (Fig. 2b) showed a homogeneous pore structure due to the effects of dispersant. Pore size distribution of CNT papers with and without dispersant was determined by capillary flow porosimetry, it can be seen that the pore size of CNT paper without dispersant (Fig. 3a) is between 0∼8 ㎛ (90%) and 30∼40 ㎛ (10%), however, the pore size of CNT paper with dispersant (Fig. 3b) is less than 5 ㎛ (100%). These differences between papers with and without dispersant are expected to affect mechanical and electrical properties of papers. Fig. 4 shows the tensile strengths of CNT papers with and without dispersant. The tensile strength of CNT paper with dispersant had been improved two times compared with that of CNT paper without dispersant. The results indicated that the CNTs in the paper with dispersant showed more homogeneous dispersion and stronger bonding strength than the paper without dispersant.

Page 275 of 1108

Fig. 2: FE-SEM images of pure CNT papers surface; (a) without dispersant, (b) with dispersant.

Fig. 3: Pore size distributions of pure CNT papers; (a) without dispersant, (b) with dispersant.

Fig. 4: Effect of the tensile strength with presence or absence of dispersant in pure CNT paper.

Fig. 5, Fig. 6 and Fig. 7 show the porosity, tensile strength and electric conductivity change of CNT/CF papers with different CNT/CF ratio from 100/0 to 20/80, respectively. With the increase of CF content, the porosity of CNT/CF papers decreased gradually, but in the case of CNT/CF(PAN) paper, its porosity increased again at the ratio of 20/80 (Fig. 5). As seen in Fig. 6, tensile strength of CNT/CF(PAN) papers at the ratio of 95/5 was lower than that of pure CNT paper, however, samples of more than 90/10 ratio were higher. Moreover, the tensile strength of all CNT/CF(pitch) papers were lower than that of pure CNT paper. In the result of electric conductivity, conductivity values of CNT/CF(PAN) and CNT/CF(pitch) papers at the ratio of 95/5 were almost the same (Fig. 6). However, while conductivity values of CNT/CF(PAN) papers were constantly increased, the conductivity of CNT/CF(pitch) papers were decreased from the ratio of 90/10 to 20/80.

Page 276 of 1108

Fig. 5: Porosity changes of CNT/CF paper according to CNT/CF ratio.

Fig. 6: Tensile strength changes of CNT/CF paper according to CNT/CF ratio.

Fig. 7: Electric conductivity changes of CNT/CF paper according to CNT/CF ratio.

4. References [1] M.S.P. Shaffer, A.H. Windle, Adv. Mater. 11 (1999) 937. [2] J. Sun, L. Gao, W. Li, Chem. Mater. 14 (2002) 5169. [3] K.F. Fu, Y.P. Sun, J. Nanosci. Nanotechnol. 3 (2003) 351. [4] Y.P. Sun, K.F. Fu, Y. Lin, W.J. Huang, Acc. Chem. Res. 35 (2002) 1096. [5] Y.Q. Liu, L. Gao, J.K. Guo, Colloid Surf. A 174 (2000) 349. [6] K. Tabata, H. Abe, Y. Doi, Biomacromolecules 1 (2000) 157. [7] K. Tabata, K. Kasuya, H. Abe, K. Masuda, Y. Doi, Appl. Environ. Microbiol. 65 (1999) 4268. [8] K. Tabata, M. Kajiyama, T. Hiraishi, H. Abe, I. Yamato, Y. Doi, Biomacromolecules 2 (2001) 1155.

Page 277 of 1108

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

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

Abstract. Recently, the applications of carbon fiber reinforced plastics (CFRPs) composite are much broader than before when it comes to the industries of automobile, ship, aerospace and war military because of its lightness, and high mechanical properties. Thermosetting plastics like epoxy are frequently used as binding matrix of CFRPs due to their high hardness, wetting characteristics and low viscosity. However, thermosetting plastics with excellent properties cannot be melted and remolded. Due to this reason, a thermosetting plastic waste causes serious environmental problems with the production of fiber reinforced plastic composites. Thus, many studies have focused on the carbon fiber reinforced thermoplastics (CFRTPs) composite and recycled carbon fiber (RCF). In this study, RCF was prepared from CFRPs using a pyrolysis method for separated resin, and degree of decomposition for epoxy resin was sufficiently confirmed from analysis of thermal gravimetric analysis (TGA) and scanning electron microscope (SEM). The cutting and grinding methods of RCF was used to prepare the carbon fiber composite sheet (CFCS). CFCS was manufactured by applying recycle carbon fibers and various thermoplastic fibers and compared the morphologies of surface and cross-section, mechanical properties, and crystallization enthalpy of CFCS at the different cooling conditions.

Keywords: Carbon fiber, Recycled carbon fiber, Composite sheet, Carbon fiber reinforced thermoplastic composite, Sheet molding compound.

1. Introduction Carbon fiber consists of a few or numerous filaments which diameter is 5-15 Îźm. When carbon fiber is mainly used as composite material reinforcement, it performs a role bearing external loads with matrix. In this case, matrix plays the role of binder between fibers used as reinforcement in carbon fiber reinforced plastics (CFRPs) composite and thermosetting plastics have been used usually as the matrix [1-4]. Thermosetting plastics like epoxy are frequently used as binding matrix of CFRPs due to its properties such as hardness, wetting characteristics and low viscosity. However, thermosetting plastics with excellent properties cannot be melted and remolded. For this reason, a thermosetting plastic waste cause serious environmental problems with the production of fiber reinforced plastic composites [4]. Thermoplastics are environment-friendly material as there is the possibility of separation from carbon fiber and remolding process can be applied through simple heat treatment. In addition, various ways such as treatments with acid, organic solvent and supercritical fluid are suggested as recycling plan of waste carbon fiber. However, carbon fiber separated from carbon fiber reinforced thermoplastics (CFRTPs) composite is discarded or utilized as low-grade filler, because its length and type are so various and expensive for treatment process. In this research, an optimal treatment condition is suggested for recycling of carbon fiber from CFRPs composites through pyrolysis method. Recycled carbon fiber composite sheet (RCFCS) is also fabricated by mixture of RCF and thermoplastic fiber. And in the fabrication process, effects of each condition on the physical and chemical properties of RCFCS is compared and analyzed.

Corresponding author. Tel.: + 82-010-7247-2350 E-mail address: psdcolor@jbnu.ac.kr

Page 278 of 1108

2. Materials and Experimental 2.1. Recycled carbon fiber (RCF) preparation RCF was obtained from CFRP (USN150 SK chemical, Korea) which is reinforced by one-way carbon fibers. Before pyrolysis, CFRP was cut by Cutter mill (Hankook crusher Co., Ltd.), and due to selection of optimal pyrolysis temperature, Thermogravimetric analyzer(TGA, Q50, TA Instruments) was utilized by applying the heating rate of 10 ℃/min at temperature of 400 ℃, 600 ℃ and 800 ℃. Pieces of CFRP were pyrolyzed at temperature of 400 ℃, 600 ℃ and 800 ℃ using a horizontal high temperature furnace (Jeon Heating Industrial Co., Ltd). Surface morphology of pyrolyzed CFRP was observed by scanning electron microscope (SEM, SU-70, HITACHI), Prepared RCF which removed resin from CFRP was cut by cutter (HC, Ham-cut) at 4000 rpm for uniform length.

2.2. Recycled carbon fiber composite sheet (RCFCS) fabrication RCFCS was fabricated by RCF prepared in 2.1. with PET(Polyethylene terephthalate, Huvis, Korea), PE/PP (Polyethylene/Polypropylene, Huvis, Korea) as thermoplastic fibers binder. Properties of thermoplastic fibers are listed in Table 1. RCF and thermoplastic fibers were dispersed in 3000 ml of water with different ratio. RCF/thermoplastic fiber slurries were agitated at 400 rpm of rotation speed, and then 100 ml of PAA(Poly(acrylic) acid. 0.5 wt.% in water) was added into slurries as dispersant. Using uniformly dispersed slurries, RCFCS were fabricated by paper making machine. Fabricated RCFCS was dehydrated by vacuum pump and then dried at 80 ℃ for 3 h. Hot-pressing process was performed for improvement of bonding strength with melting of thermoplastic fibers at 150 ℃ at 5 MPa for 3 min. And then RCFCS was cooled for variations of crystallinity according to different cooling methods. Temperature of hot-pressing and cooling method of RCFCS are showed in Fig. 1. The morphologies of RCFCS are explored using a SEM and the mechanical properties are measured by universal testing machine (UTM, INSTRON 5560). Thermal analysis measurement was performed for crystallinity characterization according to different cooling methods using a TGA. Table 1: Properties of thermoplastic fibers. Fineness (Denier)

Length (mm)

Melting point

Working temperature

(℃)

6 2

32 38

100/250 130/170

150 150

LM-PET PE/PP

Fig. 1: Change of hot-pressing and cooling temperature of RCFCS as a function of time.

3. Result and Discussion 3.1. Recycled carbon fiber (RCF) The thermal decomposition behavior of CFRP was analyzed by heating rate of 10 ℃/min at temperature of 400 ℃, 600 ℃ and 800 ℃ respectively. As seen in Fig. 2, weight loss of CFRP was appeared to 55 %, 70 % and 72% at 400℃, 600℃ and 800℃, respectively. As the results of TGA analysis, epoxy resin was existed in CFRP at 400 ℃ and decomposed completely at more than 600 ℃. Therefore, the optimal pyrolysis temperature

Page 279 of 1108

was

determined

600

℃

for

separation

the

epoxy

from

CFRP

CFRP pyrolyzed at 400 ℃, 600 ℃, 800 ℃ using the high-temperature furnace was observed through SEM (Fig. 3). Untreated CFRP showed that epoxy resin was coated on the surface of the carbon fiber (Fig. 3 a) and CFRP treated at 400 ℃ showed that residual amount of epoxy resin was partially present (Fig. 3 b). However, in the Fig 3 c and Fig 3 d, CFRPs treated at 600 ℃ and 800 ℃ indicated that surface of carbon fibers was oxidized partially and had rough appearance because of relative high pyrolysis temperature. But, epoxy resin deposited was completely removed on the carbon fiber.

Fig. 2: TGA analysis of RCF according to temperature condition.

Fig. 3: Surface observations of RCF according to pyrolysis temperature; (a) untreated, (b) 400 ℃, (c) 600 ℃, (d) 800 ℃.

3.2. Recycled carbon fiber composite sheet (RCFCS) RCFCS was fabricated by mixture of RCF and thermoplastic fiber using a paper making machine, and then hot-pressing was performed. Fabricated RCFCS was observed cross-section and surface through SEM. Fig. 4 shows SEM image on surface and cross section obtained from RCFCS according to CF-PET content ratio and cooling conditions. With increase of PET binder content, it was distributed uniformly in surface of RCFCS and the shape of surface could be seen smoother. Binding points between carbon fibers were increased with increase in PET binder content, and binder was penetrated uniformly into internal RCFCS. In addition, thickness of RCFCS fabricated in a slow cooling condition was thinner than that of natural cooling condition because pressure applied to the composite sheet was maintained until the binder was completely solidified. In the RCFCS fabricated by PE/PP binder, appearance and thickness of RCFCS were appeared tendency similar to those of RCFCS used by PET binder which is described above. Consequently, the amount of binder and cooling conditions affected the morphology and physical property of RCFCS. It is indicated that crystallinity of binder solidified in slow cooling condition is higher than that of natural cooling condition. In general, the cooling rate is known to affect the crystallinity of the molten polymer resin in the process of solidification. When the cooling rate is lowered rapidly from the melting point, crystalline polymer resin is presented in amorphous state at room temperature. However if the cooling rate is lowered slowly, the polymer resin is produced in crystal with heat at crystallization temperature (T c ). At this time, the crystallization temperature and degree of crystallinity can be determined by DSC measurement. Fig. 5 shows DSC analysis of RCFCS fabricated with PE/PP binder. Degree of crystallinity and crystallization temperature of PE/PP binder was calculated from area and temperature of exothermic peak appeared in Fig. 5. From these results of calculation, it was confirmed that degree of crystallinity of PE/PP binder was lower in the natural cooling condition than in slow cooling condition.

Page 280 of 1108

Fig. 4: SEM of surface and cross section obtained from RCFCS according to CF-PET content ratio and cooling conditions; (a) natural, (b) slow.

Fig. 5: DSC analysis of RCFCS (PE/PP) according to content ratio and cooling condition; (a) natural, (b) slow.

4. Conclusion In this paper, RCF was prepared after the epoxy resin was separated from carbon fiber composite using a pyrolysis method. Prepared RCF was used for fabrication of composite sheet with PET and PE/PP thermoplastic fiber as binder, and then cooling process of RCFCS was performed through the different temperature. From the TGA and SEM measurements, it was confirmed that epoxy resin was completely decomposed at more than 600 ℃ by pyrolysis method. Binding points of RCFCS were increased with increase in content of binder, which was penetrated uniformly into internal composite sheet. In addition, thickness of RCFCS fabricated in a slow cooling condition was thinner than that of natural cooling condition because pressure applied to the RCFCS was maintained until the binder was completely solidified. Increase of binder content led to higher tensile strength of RCFCS, which fabricated with PET binder had the highest tensile strength. In the slow cooling condition, crystallinity of binder was improved as result of sufficient crystal growth which has to have higher tensile strength.

5. References [1] Kim, Y.A., “Carbon Fiber Composite.” Physics & High Technology, Vol. 12, No. 3, 2003, pp. 31-35. [2] Schwartz, M.M., Composite Materials Handbook, McGraw Hill Higher Education, 1983. [3] Rosato, D., Designing with Plastics and Composites: A Handbook, Springer, 1991.

Page 281 of 1108

[4] Gauthier, M.M., Engineered Materials Handbook, Asm International Handbook Committee, 1995.

Page 282 of 1108

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

Preparation and Characterization of Aramid Copolymer Fibers Including Ester and Cyano Groups Eun Ji Jang, Hwa Hyun Cha, Moon Jin Yeo, Min Woo Nam, Chan Sol Kang, and Doo Hyun Baik* 1

Department of Advanced Organic Materials & Textile System Engineering, Chungnam National University, Korea *dhbaik@cnu.ac.kr

Abstract. A series of F-M3/CYPPD copolymers containing ester and cyano groups were synthesized by lowtemperature solution polycondensation of 2-cyano-1,4-phenylenediamine (CYPPD) and F-M3 (a fluorinecontaining ester type new diamine monomer) with terephthaloyl chloride (TPC) in N,N-dimethylacetamide (DMAc). And then, F-M3/CYPPD fibers were prepared by dry-jet wet spinning from isotropic solution involving DMAc with lithium chloride (LiCl). Chemical structure of the synthesized F-M3/CYPPD copolymers was investigated by FT-IR spectroscopy and mechanical properties of F-M3/CYPPD fibers were characterized by universal testing machine. Tensile test results showed that tensile strength and initial modulus of F-M3/CYPPD fibers were enhanced after the heat-treatment.

Keywords: aromatic polyamide, cyano group, ester group, solubility, mechanical property

1. Introduction Aromatic polyamides (Aramids) have been used in various fields as fiber materials having excellent thermal stability and chemical resistance as well as tensile mechanical properties. However, aramids are only soluble in strong acids, because they have rigid structure and strong hydrogen bond between amide groups. The use of strong acid as spinning solvent leads to reduction of mechanical properties, a toxic environment, and difficulty in handling the manufacturing process[1]. For practical uses, studies on solubility of aramids in organic solvents have been required. Incorporation of pendent groups or flexible linkages into the backbone is a typical approach to improve solubility and processability while maintaining the high thermal stability of aramids[2]. In this study, we synthesized a series of F-M3/CYPPD copolymer containing ester and cyano groups and prepared their fibers using organic solvent as spinning solvent. Then, chemical structure and solubility of F-M3/CYPPD copolymers and mechanical properties of F-M3/CYPPD fibers were systematically investigated.

2. Experimental 2.1. Synthesis Aramid copolymers with various diamine contents were synthesized by low temperature polycondensation method. CYPPD and F-M3 were dissolved in DMAc/LiCl solvent system using a mechanical stirrer and the solution was cooled to 0-5 â&#x201E;&#x192; in an ice bath. Then, TPC flakes were added with vigorous stirring, which leads to a rapid increase of the viscosity and finally solidification of the reaction product in a few minutes. Synthesized F-M3/CYPPD copolymers were finely grinded using blender and washed in distilled water in order to eliminate by-product. The sample identification and synthetic condition are shown in table 1.

Page 283 of 1108

Table 1. Sample identification of F-M3/CYPPD copolymers

FCN100 FCN80 FCN60 FCN40 FCN20 FCN0

Solvent

F-M3/CYPPD ratio

Polymer Conc.

DMAc/LiCl

100/0 80/20 60/40 40/60 20/80 0/100

10wt%

Optical anisotropy

Phase

Solid

2.2. Spinning & heat treatment Spinning dope was prepared by dissolving F-M3/CYPPD copolymers in DMAc with the aid of LiCl. Isotropic spinning dope was extruded through a spinneret into a coagulation bath (water) and the air gap between spinneret and coagulation bath was kept as 3 mm. F-M3/CYPPD fibers were collected on bobbins, washed in distilled water, and dried at 80 ℃ for 24 hours. Then, they were heat-treated under tension (3.0 kgf) in nitrogen atmosphere at 300 ℃ for 15 min.

2.3. Characterization Chemical structure of synthesized F-M3/CYPPD copolymers was identified by FT-IR and solubility test was conducted using various organic/inorganic solvents (solvent 10 ml, LiCl 0.4 g, polymer concentration 6wt%) at 50 ℃ for 24 hours. Mechanical properties of F-M3/CYPPD copolymer fibers were characterized by tensile tester at 30 mm/min. Intrinsic viscosity of each sample was confirmed by Ubbelohde viscometer.

3. Results and Discussion Figure 1 exhibits the FT-IR spectra of F-M3/CYPPD copolymers. All the samples showed typical bands at 3280 cm-1, 1653 cm-1, and 1404 cm-1 corresponding to amide N-H stretching, amide C=O stretching, and amide C-N stretching, respectively. Also, it was found that C≡N stretching and ester C=O stretching bands were identified around 2225 cm-1 and 1734 cm-1.

Transmittance (a.u.)

FCN100 FCN80 FCN60 FCN40 FCN20 1734 cm-1

FCN0

3280 cm-1

2225 cm-1

1653 cm-1 1492 cm-1 1404 cm-1

4000

3500

3000

2500

2000

1500

1000

500

-1

Wavenumbers (cm ) Figure 1. FT-IR spectra of F-M3/CYPPD copolymers. The solubility results of the F-M3/CYPPD copolymers are listed in Table 2. As shown in Table 2, the FM3/CYPPD copolymers were partially soluble in DMAc, NMP, and DMSO with LiCl, while the solubility of F-M3/CYPPD copolymers were slightly enhanced in DMAc and NMP as compared with DMSO When the FM3 content was above 60%. Also, the F-M3 CYPPD copolymers were insoluble in THF and Chloroform. It

Page 284 of 1108

was thought that the improvement of solubility was caused by reduction hydrogen bonding force and chain packing efficiency between main chains, Table 2. Solubility of F-M3/CYPPD copolymers FCN100 FCN80 FCN60 FCN40 FCN20 FCN0

H 2 SO 4

DMAc

NMP

DMSO

THF

Chloroform

** ** ** ** ** **

** ** ** -* -* -*

-* -* -* -* -* -*

** : soluble, -* : partially soluble, - : insoluble Figure 2 indicates stress-strain curve of F-M3/CYPPD fibers and their heat-treated ones. For the FCN0, 20, and 40 with less solubility in DMAc, it is difficult to make their spinning dope. So, when F-M3 content was above 60%, F-M3/CYPPD fibers were manufactured. In case of as-spun fibers, it was observed that they showed good mechanical properties with tensile strength of 418.1-454.1 MPa and initial modulus of 9.2-12.6 GPa, which enhanced with increasing CYPPD contetnt. After the heat-treatment, both tensile strength and initial modulus of all the fibers were much higher than those of as-spun fibers. It is thought that significant improvement in mechanical properties is caused by increase of crystal size and orientation along the fiber axis. Tensile properties of F-M3/CYPPD fibers are summarized in Table 3.

Figure 2. Stress-strain curve of F-M3/CYPPD fibers. Table 3. Mechanical properties of F-M3/CYPPD fibers FCN100 FCN80 FCN60 h-FCN100 h-FCN80 h-FCN60

Tensile strength (MPa)

Initial modulus (GPa)

Strain (%)

418.1 ± 22.65 427.6 ± 41.14 454.1 ± 31.45 489.8 ± 42.20 553.9 ± 43.39 865.3 ± 38.04

9.2 ± 0.74 11.0 ± 0.81 12.6 ± 0.91 18.8 ± 1.52 29.0 ± 2.24 46.1 ± 2.53

47.3 ± 4.26 28.4 ± 6.55 23.0 ± 2.81 3.7 ± 0.67 2.2 ± 0.37 1.7 ± 0.28

Page 285 of 1108

4. Conclusions We successfully synthesized F-M3/CYPPD copolymers with different diamine contents via lowtemperature solution polycondentation and prepared F-M3/CYPPD fibers by using dry-jet wet-spinning. Solubility results confirmed that F-M3/CYPPD copolymers with F-M3 content over 60% could be dissolved in DMAc and NMP with LiCl. F-M3/CYPPD fibers have good mechanical properties such as tensile strength and initial modulus, which were enhanced through heat-treatment. It was found that the introduction of F-M3 could affect the solubility in organic solvents and mechanical properties. Thus, if the condition of heattreatment would be properly established in order to enhance mechanical properties, F-M3/CYPPD fibers could be considered as promising high performance fiber materials.

5. References [1] M. J. Yeo, N. D. Gu, E. J. Jang, C. S. Kang, Y. G. Jeong, and D. H. Baik, Text Sci Eng, 2014, 51(3), 134-139. [2] J. I. Kim, D. S. Ryu, and E. S. Park, Polymer, 1988, 12(6), 531-539.

Page 286 of 1108

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

Preparation and Characterization of High Temperature Carbon/Silica Composite by Sol-gel Process Sung Chan Lim 1, Ji Eun Lee 1, Jong Sung Won 1, Chi Hong Joo 2, Seung Goo Lee 1 + 1

Chungnam National University, Daejeon, South Korea 2

Nexcoms Co. Ltd., Daejeon, South Korea

Abstract. Because of high mass specific properties and high heat resistance, the carbon/silica composites have been developed for insulation of aerospace and military applications. In this study, the carbon/silica composites were prepared by the sol-gel process to improve thermal properties without gas emission. The carbon/silica composites were manufactured by using carbon fiber preforms and impregnation process of silicate sol. The silica was synthesized by hydrolysis and condensation of tetraethoxysilane (TEOS) using isopropyl alcohol (IPA) as a solvent and dimethyl formamide (DMF) as an additive. The thermal properties of the composite were investigated to find an optimum process condition under various content of solvent and additive. The structural and surface morphologies were also investigated by using a scanning electron microscope (SEM) and a micro-CT.

Keywords: Sol-gel, Carbon/silica composite, Carbon fiber, silica matrix, Impregnation process, CMC

1. Introduction Non-oxide ceramic matrix composites (CMCs) consist of a SiC(silicone carbide) based matrix reinforced with either carbon or SiC fibers. CMCs have the potential for being used as structural materials at temperatures up to 1500℃, in different fields including gas turbines, nuclear reactors, airplane and propellant of rockets. CMC are processed according to ⑴ the gas phase route(CVI:chemical vapour infiltration), ⑵ the liquid phase routes either form polymers(PIP : polymer impregnation and pyrolysis), or molten elements reacting with ceramic charges in the preforms or with the atmosphere(RMI : reactive melt infiltration), ⑶ the ceramic route(SI-HP : slurry impregnation and hot processing), and ⑷some hybrid processes. In CMC process, the CVI process yields well controlled composition and microstructure and can be employed in different step of CMC manufacturing. But, the CVI process has a high cost of production of CMC and is relatively slow process. Comparatively, the PIP process is a low temperature process, however, it has a long process time since PIP sequences are necessary to achieve an acceptable densification. The composite from PIP process reveals a significant residual porosity and implies considerable handling. MI process or RMI process in the impregnation process is reactive a porous fiber preform when preform first consolidated with a carbon deposit. And preform is impregnated with liquid silicon which climbs by capillary forces in the pore network. When silicon is reacted with the consolidation carbon to yield, a composite has a SiC+Si matrix and almost no open residual porosity. So, these have an excellent hermeticity with respect to gas and liquid fluids as well as a high thermal conductivity. In ceramic composites, manufacturing costs are mainly affected by the processing time and fiber costs. Therefore, the low cost of CMC process required the development of short time and costeffective processes. A sol-gel process can give a solution for this problem. A sol-gel reaction is progressed by short time (Fig. 1). So, the impregnated process the using a sol-gel method has short process of composite manufacturing.[1-6] In this paper, sol-gel process was studied to develop a fully dense matrix and to develop of short time and convenient process. Sol-gel process was used by impregnation process. The manufacturing process of CMC composite consist in ⑴ the fiber preform putting in the molds, ⑵ a silica sol impregnate into the fiber preform, ⑶ a silica Sol is converted into a gel, ⑷ a gel is concerted the ceramic by the sintering process. In this study, +

Corresponding author. Tel.: + 82-10-3404 6150. E-mail address: lsgoo@cnu.ac.kr.

Page 287 of 1108

the silica was synthesized by tetraethoxysilane (TEOS) using isopropyl alcohol (IPA) as a solvent and Dimethylformamide (DMF) as an additive. A pH of Sol is controlled by hydrogen chloride (HCl). The IPA gave the change of concentration in order to the change of gel time. The thermal properties of the composite were investigated to find an optimum process condition in a various content of solvent and additive. The structural and morphology of composite were investigated to find an optimum process condition by using a scanning electron microscope (SEM) and a Micro-CT.[4-8]

Fig 1. Sol-gel reaction and application method

2. Experimental 2.1. Materials In this paper, the TEOS(SIGMA-ALDRICH, 86578) was used as a dispersoid and the IPA in concentration of 99.5%(DAEJUNG CHEMICAL) was used as a solvent. As a DCCA(Drying control chemical additives), DMF was used in concentration of 99.8%(DAEJUNG CHEMICAL). HCl in concentration 99.5% was used to shorten the processing time as a catalyst(DAEJUNG CHEMICAL). The IPA and DMF have a variation of concentration to set an optimum process condition(Table 1). To fabricate a composite, carbon fiber preform is prepared by needle punching the multi-layer fabric. Table 1: Composition of silica sol Sample name

(molar ratio)

0.0

IPA

H2O

0.0

S n

TEO Compositio

HCl DMF

ID1

ID2

ID3

ID4

ID5

0.05

0.0

2.2. Analysis The morphology and microstructure of composite is analysed by using an electron microscope (SEM, JSM-7000, JEOL) and a micro-CT. The thermal property is investigated to find an optimum process condition of composite by using a themogravimetric analyser(TGA, Metter-Toledo). The analysis condition of TGA is

Page 288 of 1108

0℃~1200℃. The dynamic properties are investigated by using a dynamic mechanical analyser (DMA, TA DMAQ800). The analysis condition of DMA is 0℃~600℃, heating rate of 3℃, frequency of 1 Hz and dual cantilever in ASTM D4065.

3. Results and discussion In this paper, the manufacturing process of CMC is investigated by Sol-gel method. The gel time of sol show the Fig.2 in the change of IPA concentration and DMF condition. High IPA concentration has a long gelation time. In the manufacturing process of composite, a long gel time revealed a long process time. And a short gel time cause insufficiency impregnation time of sol into preform. So, the CMC process need the proper gel time.[6]

Fig. 2 Gel time in the change of IPA concentration and DMF condition

In TGA analysis, the CMC of proper gel time has the lowest ratio of weight in 0℃~1200℃. The proper gel time reveal the low porosity and hence excellent matrix density. The SEM and Micro-CT analysis prove the excellent matrix density. The Micro-CT photograph showed the Figure 3. In Figure 3, the sol is well impregnated in carbon preform.

Page 289 of 1108

Fig 3. Micro-CT photograph of CMC composite made by sol-gel process

The short gel time gives the high porosity and reveals the crack of silica matrix. This crack causes the composite defect and the low strength. In DMA analysis, the short gel time resulted in the low storage modulus. This result is due to the high porosity and crack. The long gel time cause the high costs of CMC process. Therefore, the proper gel time for an optimum condition of CMC process would be very important. [1] Jérôme Magnant, Laurence Maillé, René Pailler, Jean-Christophe Ichard, Alain Guette, Francis Rebillat, Eric Philippe, “Carbon fiber/reaction-bonded carbide matrix for composite materials-Manufacture and characterization ”, Journal of the European Ceramic Society, Vol 32(16), p4497-4505, 2012 [2] J. Magnan, R. Pailler, Y. Le Petitcorps, L. Maillé, A. Guette, J. Marthe, E. Philippe, “Fiber-reinforced ceramic matrix composites processed by a hybrid technique based on chemical vapor infiltration, slurry impregnation and spark plasma sintering”, Journal of the European Ceramic Society, Vol 33(1), p181-190, 2013 [3] L. Maillé∗, S. Le Ber, M.A. Dourges, R. Pailler, A. Guette, J. Roger, “Manufacturing of ceramic matrix composite using a hybrid process combining TiSi2 active filler infiltration and preceramic impregnation and pyrolysis”, Journal of the European Ceramic Society, Vol 34(2), p189-195, 2014 [4] Yongdong Xu, Yani Zhang, Laifei Cheng, Litong Zhang, Jianjun Lou, Junzhan Zhang, “Preparation and friction behavior of carbon fiber reinforced silicon carbide matrix composites”, Ceramics International, Vol 33(3), p439445, 2007 [5] Lok P. Singh, Sriman K. Bhattacharyya, Rahul Kumar, Geetika Mishra, Usha Sharma, Garima Singh, Saurabh Ahalawat, “Sol-Gel processing of silica nanoparticles and their applications”, Advances in Colloid and Interface Science, Vol 214, p17-37, 2014 [6] Dae Hyun Kim, Ki Chang Song, Jae Shik Chung, Bum Suk Lee, “Preparation of Hard Coating Solutions using Colloidal Silica and Glycidoxypropyl Preparation of Hard Coating Solutions using Colloidal Silica and Glycidoxypropyl”, Korean Chemical Engineering Research, Vol 45(5), p442-447, 2007 [7] Jae Jun Lee, Young Woong Kim, Woon-Jo Cho, In Tae Kim, Hae-June Je, Jae-Gwan Park, “Preparation of Silica Films by Sol-gel Process”, Journal of the Korean Ceramic Society, Vol 36(9), p893-900, 1999 [8] Byung-hoon Kim, Kyu-seog Hwang, “Deposition Technique of Thin Film by the Sol-gel Process”, Journal of the Korean Ceramic Society, Vol 6(4), p275-279, 1991

Page 290 of 1108

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

Preparation and properties of polyetherimide(PEI)-MWCNT conductive composite fibers A-Rong Kim,1 YoungAh Kang,1 Jong S. Park 2 * 1

Department of Organic Material and Polymer Engineering, Dong-A University, Busan 49315, Korea Department of Organic Material Science and Engineering, Pusan National University, Busan 46241, Korea. E-mail: jongpark@pusan.ac.kr

Abstract: We have prepared multi-walled carbon nanotube (MWCNT) embedded, using polyetherimide (PEI) as a polymer matrix, conductive composite (denoted as PEI-MWCNT) fibers. Uniform dispersion in dimethylacetamide was achieved after functionalizing MWCNT with quadruple hydrogen bonding sites, and conductive composite fibers were produced via electrospinning process. PEI-MWCNT fibers, containing the content of MWCNT up to 3 wt%, were prepared, and properties of resulting fibers were analyzed in terms of fiber diameter and electrical conductivity. Scanning electron microscope (SEM) image revealed highly porous fiber structures, in which MWCNTs maintained fine dispersion inside a PEI matrix. Increasing MWCNT contents resulted in a decrease in the average fiber diameter, and the electrical conductivity was improved even in the presence of small amounts of functionalized MWCNT.

Keywords: polyetherimide, multi-walled carbon nanotube, quadruple hydrogen bonding, conductive composite fibers, electrospinning

1. Introduction Polyetherimide (PEI), due to high glass transition temperature, exhibits excellent strength and elastic modulus even at an elevated temperature [1,2]. In addition, PEI emits no harmful gas when burnt and thus finds useful applications for flame retardancy. Other peculiar properties include stable electrical properties in wide frequency and temperature domains and superior resistance against ultraviolet rays. In spite of these numerous attractive features, not so many reports have been made concerning PEI-based composite fibers. In this study, we have presented the preparation of PEI- multi-walled carbon nanotubes (MWCNTs) composite fibers, composed of PEI as polymer matrix and MWCNT as a conducting nanofiller, by way of electrospinning process. In order to ensure the uniformity and dispersibility of MWCNTs inside a PEI matrix, functionalization of MWCNTs with quadruple hydrogen bonding sites was employed [3]. The prepared fiber structures were investigated in terms of morphology, diameter and electrical conductivity, depending on the content of the nanofiller, and their surface morphologies were characterized using scanning electron microscope (SEM). A thermalgravimetric analyzer (TGA) was used to examine the thermal stability of the resulting fibers.

2. Experimental 2.1. Materials

PEI (ULTEM 1000 grade) was obtained from Sabic Co, and MWCNTs were provided from JEIO Co (Seoul, Korea). All chemicals used in the experiment, including sulfuric acid, nitric acid, N,Ndimethylformamide (DMF), 2-amino-4-hydroxy-6-methyl-pyrimidine (AHMP), and toluene 2, 4-diisocyanate (TDI), were purchased from Aldrich (Seoul, Korea). N,N-dimethylacetamide (DMAc) was provided from Junsei Chemicals (Japan), and used as received.

2.2. Preparation of PEI-MWCNT spinning solution

Page 291 of 1108

MWCNTs were functionalized with quadruple hydrogen bonding sites following a previous report [3], by which numerous AHMPs was introduced on the surface of MWCNT. As a polymer matrix, 20 wt% PEI solution was first prepared by sonicating PEI polymer (1.17 g) in DMAc solvent (5 ml) for 10 hours. After that, 1, 2, and 3 wt% of functionalized MWCNTs were added to polymer solutions, and the PEI/MWCNT mixture was mechanically stirred at 50 oC for 1 hours in a closed glass vial. The solutions were cooled to room temperature before electrospinning.

2.3. Fabrication of composite fibers via electrospinning

The prepared PEI/MWCNT solutions were transferred into the injection syringe (gauge 24) and allowed to stand for some time to remove any trapped air inside the solution. The polymer solution was pumped through a syringe needle at the rated of 7 m/s. Fiber web was collected on the aluminum foil for an hour. The distance between the tip of the syringe and the collector was fixed at 10 cm, and the applied voltages were 17 kV. The spun composite fibers were dried in a convection oven at 80oC for 12 hours in order to completely remove residual solvent.

2.4. Property characterization

The surface morphology and diameter of prepared PEI-MWCNT fibers were investigated by SEM (JSM6700F, JEOL, USA). Their electrical properties of fiber web was analysed by 4-point-probe (M4P302 Systems, Keithley Instuments Inc., USA). TGA thermograms were measured using TGA (TGA Q500, TA Instruments, USA) at a heating rate of 10 oC/min from 25 to 800 oC.

3. Result and discussion 3.1. Morphology of electrospun PEI-MWCNT fibers

Surface morphology of electrospun PEI-MWCNT fibers was evaluated by SEM (Fig. 1). At first sight, it was noticed that all fibers have very minimal amount of small bead formation. PEI fibers without the addition of MWCNT showed a surface structure consisting of relatively dense porous texture. In case of composite fibers after adding MWCNTs, these pores became coalesced along with fiber axis, thus its surface appearance was visually less uniform compared to the pristine PEI. Most interestingly, fibers in the presence of MWCNT looked smaller in diameter, which is the opposite to previous findings [4,5].

Fig. 1. SEM images of electrospun PEI-MWCNT composite fibers containing different amount of functionalized MWCNTs: (a) 0 wt%, (b) 1 wt%, (c) 2 wt%, and (d) 3 wt%. The insets present the maginified images of corresponding samples.

Page 292 of 1108

The average fiber diameter with MWCNT concentrations of 0, 1, 2 and 3% were calculated to be 2.28, 1.44, 0.72 and 0.49 m, respectively (Fig. 2). Indeed, increasing MWCNT contents resulted in a decrease in the average fiber diameter. This could be the result of better de-bundling and dispersion of MWCNT inside the fibers, which may be attributed to strong interfacial interaction between the polymer matrix and the nanotubes.

Fig. 2. The diameter distribution of electrospun PEI-MWCNT composite fibers, containing different content of functionalized MWCNTs.

3.2. Electric conductivity of PEI-MWCNT fibers

Fig. 3 shows the conductivity measurements with respect to MWCNT contents. It was found that PEI itself exhibited insulating character, but, in the presence of MWCNT, conductivities of electrospun fibers gradually increased with increasing amount of MWCNT, showing an average value of up to 10-1 S/cm. These results indicate that MWCNTs efficiently forms electrically conductive pathways in a PEI matrix as a consequence of free electronâ&#x20AC;&#x2122;s hopping [6,7].

Fig. 3. Electrical conductivities of electrospun PEI-MWCNT composite fibers, containing different content of functionalized MWCNTs.

3.3. Thermal behavior of PEI-MWCNT fibers

The thermogravimetric analysis (TGA) curves are shown in Fig. 4. In case of pristine PEI nanofibers, the first major weight loss occurs at ~445 oC, which is consistent with the degradation pattern of PEI. For the electrospun PEI-MWCNT composite fibers, the major weight loss of ~45% occurs at a slightly higher temperature of 480 oC, which corresponds to the thermal decomposition of the polymer backbone [8,9]. The weight loss at ~200 oC is attributed to the destruction of the functionalized nanotube skeleton.

Page 293 of 1108

Fig. 4. TGA analyses, under an air atmosphere, of electrospun PEI-MWCNT composite fibers, containing different content of functionalized MWCNTs.

4. Conclusion Here in this article, we have demonstrated the preparation of multi-walled carbon nanotube (MWCNT) embedded, using polyetherimide (PEI) as a polymer matrix, composite fibers by way of electrospinning process. Morphological and electrical properties of PEI-MWCNT composite fibers were analysed using various characterization techniques. SEM measurements showed highly porous surfaces, with MWCNTs uniformly dispersed in a PEI matrix. Increasing MWCNT contents resulted in a decrease in the average fiber diameter. In addition, electrical conductivity was improved even with small amounts of functionalized MWCNT.

5. References [1] I. Echeverria, P. C. Su, S. L. Simon, D. J. Plazek, J. Polym. Sci. Part B: Polym. Phys. 1995, 33, 2457-2468. [2] S.T. Amancio-Filho, J. Roeder, S. P. Nunes, J.F. dos Santos, F. Beckmann, Polym. Degrad. Stabil. 2008, 93, 15291538. [3] J. T. Han, B. H. Jeong, S. H. Seo, K. C. Roh, S. Kim, S. Choi, J. S. Woo, H. Y. Kim, J. I. Jang, D. C. Shin, S. Jeong, H. J. Jeong, S. Y. Jeong, G. W. Lee, Nat. Commun. 2013, 4, No. 2491. [4] A. Laforgue, L. Robitaille, Macromolecules 2010, 43, 4194-4200. [5] C. Q. Yin, J. Dong, Z. T. Li, Z. X. Zhang, Q. H. Zhang, Compos. Part B-Eng. 2014, 58, 430-437. [6] J. H. Zhu, H. B. Gu, Z. P. Luo, N. Haldolaarachige, D. P. Young, S. Y. Wei, Z. H. Guo, Langmuir. 2012, 28, 1024610255. [7] R. Bhatia, C. S. S. Sangeeth, V. Prasad, R. Menon, Physica B. 2011, 406, 1727-1732. [8] S. Kumar, T. Rath, R. N. Mahaling, C. S. Reddy, C. K. Das, K. N. Pandey, R. B. Srivastava, S. B. Yadaw, Mat. Sci. Eng. B-Solid. 2007, 141, 61-70. [9] S. A. Hashemifard, A. F. Ismail, T. Matsuura, Chem. Eng. J. 2011, 170, 316-325.

Page 294 of 1108

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

Preparation and Thermal Properties of Polybenzoxazole Precursors Containing Sulfone Group Min Jung Paik, Sun Hong Kim, Chan Sol Kang, Chae Won Park, and Doo Hyun Baik Department of Advanced Organic Materials and Textile System Engineering, Chungnam National University, Daejeon, Korea *

dhbaik@cnu.ac.kr

Abstract. PHA and its copolymers were synthesized by low-temperature solution polymerization of 3,3’dihydroxybenzidine (DHB), bis(3-amino-4-hydroxyphenyl)sulfone (BAHS), and isophthaloyl chloride (IPC) in 1-methyl-2-pyrrolidone (NMP) with aid of lithium chloride (LiCl). Chemical structures of PHA and its copolymers were identified by using fourier transform infrared spectroscopy (FT-IR). Solubility of PHA and its copolymers was evaluated in a series of organic solvents. Thermal properties such as cyclization behavior and decomposition behavior were investigated using differential scanning calorimetry (DSC) and thermogravimetric analyzer (TGA), respectively.

Keywords: polybenzoxazole precursors, polyhydroxyamide copolymers, sulfone group, thermal properties, cyclization temperature

1. Introduction Polybenzoxazoles (PBOs), a well known flame retardant polymer, have superior thermo-oxidative stability, chemical resistance, and good mechanical properties. However, PBOs are dissolved only in strong acid such as sulfuric acid, phosphoric acid, and they are not dissolved in organic solvents due to their inert rigid structure[1]. To overcome the poor solubility of PBOs, many researchers have studied on the polyhydroxyamides (PHAs) as possible precursors to PBOs. However, since PHAs convert to PBOs through cyclization above 350 ℃, there is a disadvantage in terms of energy consumption[2]. On the other hand, incorporation of sulfone groups along the backbone of polymers generally increases the solubility and decreases thermal cyclization temperature[3]. In this study, we synthesized PHA and its copolymers with different DHB/BAHS mole ratios and investigated the relationship between chemical structures and thermal properties of them.

2. Experiments 2.1.

Materials

3,3’-dihydroxybenzidine (DHB, 99.0 %) was purchased from Tokyo Chemical Ind. (Japan). Terephthaloyl chloride (TPC, 99.0 %), isophthaloyl chloride (IPC, 99.0 %), anhydrous N,N-dimethyl acetamide (DMAc, 99.8 %), and lithium chloride (LiCl, 99.0 %) were purchased from Sigma-Aldrich Co. (USA), respectively. N-methyl-2-pyrrolidinone (NMP, 99.5 %), N,N-dimethylformamide (DMF, 99.8 %), dimethyl sulfoxide (DMSO, 99.5 %), tetrahydrofuran (THF, 99.8 %), and sulfuric acid (H2SO4, 95.0 %) were purchased from Samchun Chemical Co. (Republic of Korea).

2.2. Synthesis PHA and its copolymers were synthesized by low-temperature condensation polymerization method. DHB and BAHS were dissolved in NMP/LiCl solvent system using a mechanical overhead stirrer and IPC flakes were added into the DHB solution. The solution was stirred under nitrogen atmosphere at low temperature (0~5 ℃) in ice bath for an hour. This reactive solution continued to be stirred at room temperature for 23 hours.

Page 295 of 1108

The mixture was poured into distilled water and washed for 24 hours and then, dried in a vacuum oven at 100 ℃ for 24 hours. The synthetic route is shown in Scheme 1 and Table 1 listed synthesizing profile, sample code, and intrinsic viscosity of PHA and its copolymers.

Scheme 1. Synthesis for the PHA copolymers and their conversion to PBO copolymers. Table 1. Synthesis of PHA and its copolymers

Sample code

DHB/BAHS

S-0 (m-PHA)

100/0

S-50

50/50

IPC

Solvent/metal salt system

I.V. 1) 1.5 0.7

100

NMP/LiCl (3 %)

S-60

40/60

S-70

30/70

0.65 0.58

S-80

20/80

0.55

S-90

10/90

0.51

S-100

0/100

0.48

Intrinsic viscosity ( 30 ℃, H2SO4)

2.3. Characterization Chemical structures of PHA and its copolymers were identified by FT-IR and their thermal properties were investigated by TGA and DSC. Intrinsic viscosity of PHA and its copolymers were measured by Ubbelohde viscometer (30 ℃, H2SO4).

3. Results and Discussion Figure 1 shows FT-IR spectra of PHA and its copolymers. All the samples showed typical IR bands at 3412 cm-1, 3000~3400 cm-1, 1647 cm-1 and 1511 cm-1 corresponding to N-H stretching, O-H stretching, amide C=O stretching and N-H bending, respectively. It was observed that PHA and its copolymers were synthesized perfectly.

Page 296 of 1108

Figure 1. FT-IR spectra of PHA and its copolymers. Table 2 presents the solubility results of PHA and its copolymers in various solvents. S-0 (m-PHA) was dissolved in organic solvents with metal salt, while PHA copolymers was easily dissolved in organic solvents without metal salt. It is believed that the improvement in solubility of PHA copolymers with sulfone group is caused by the reduction of the chain packing efficiency in the main chain. Table 2. The solubility test results of PHA and its copolymers Sample

DMAc

DMF

NMP

DMSO

THF

H2SO4

S-0 S-50 S-60 S-70 S-80 S-90 S-100

* ** ** ** ** ** **

** ** ** ** ** ** **

**: soluble, *: soluble with LiCl, -: insoluble Figure 2 presents TGA analysis and derivative TGA curves of PHA and its copolymers. There showed a two-step weight loss during heating. The first weight loss was due to thermal cyclization of PHA copolymers and second one was owing to the thermal decomposition of PBO copolymers. It was observed that thermal cyclization and decomposition temperatures shifted lower temperature range with increasing BAHS content.

Figure 2. TGA thermograms and derivative TGA of PHA and its copolymers.

Page 297 of 1108

Figure 3 displays DSC heating thermograms of PHA and its copolymers. It was noticed that the thermal cyclization temperatures of PHA copolymers entirely were decreased with increasing the BAHS content. It is believed that the lower thermal cyclization temperature is due to bulky pendant sulfone groups along the main chain. Also, this result is consistent with the solubility results in Table 2.

Figure 3. DSC thermograms of PHA and its copolymers

3. Conclusion In this study, PHA and its copolymers with different DHB/BAHS mole ratios were synthesized by low-temperature solution polycondensation in NMP/LiCl solvent system. FT-IR spectra identified that the characteristic bands of PHA and its copolymers. The solubility results confirmed that all the PHA copolymers were dissolved in organic solvents used without the aid of LiCl. TGA and DSC results revealed that thermal cyclization and decomposition temperatures of PHA and its copolymers were decreased with increasing BAHS content. Also, S-70 was thought to be a good candidate for a precursor polymer of PBO due to good solubility and lower thermal cyclization temperature. It was concluded that thermal cyclization temperature of PHA copolymers can be controlled by changing BAHS content.

4. References [1] T. MIYAZAKI and M. HASEGAWA, High Perform. Polym., 2007, 19, 243-269 [2] Hsiao S.H. and Huang P.C., Macromol. Chem. Phys., 1997, 198, 4001-4009 [3] S.ZULFIQAR and M.I.SARWAR, High Perform. Polym., 2009, 21, 3-15

Page 298 of 1108

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

Preparation of Helical Crystals of Poly(ester-imide) by Crystallization during Polymerization - Influence of Oligomer Structure on Helical Morphology Takuya Ohnishi 1, Tetsuya Uchida 2, Shinichi Yamazaki 1 and Kunio Kimura 1 1 2

Graduate School of Environmental and Life Science, Okayama University Graduate School of Natural Science and Technology, Okayama University

Abstract. Poly(ester-imide) helical crystals were obtained via the crystallization during polymerization of N-(4carboxyphenyl)-4-acetoxyphthalimide in aromatic solvent. In the case of the polymerization of 4-acetoxyphthalic anhydride and 4-aminobenzoic acid, fibrillar and ribbon-like crystals of poly(ester-imide) were formed, but they did not exhibit helical morphology even though the structure of the obtained poly(ester-imide) was the same. The difference in the structure of the precipitated oligomer significantly influenced the helical morphology, especially composing of the imide ring or precursor amide linkage.

Keywords: Poly(ester-imide), Helical morphology, Oligomer structure, Crystallization during polymerization.

1. Introduction Aromatic poly(ester-imide)s are high-performance polymers combining many remarkable properties. [1] Morphology of polymers with molecular orientation is of great importance to create materials having essential properties, and the ideal morphology must be a one-dimensional structure such as a needle and a fiber. When the polymerization of N-(4-carboxyphenyl)-4-acetoxyphthalimide (CAP) was carried out in aromatic solvent, poly(ester-imide) helical crystals were obtained via the crystallization during polymerization. [2] The helical crystal of rigid polymers has not been prepared so far. The crystals prepared at 280oC are averagely 243 nm in width and 3.60 m in length. Molecular chains aligned along the long axis of the helical crystals. The helical pitch increased with the polymerization temperature from 321 nm to 1.29 m. Although the true nature of the helical morphology has not been clarified, the bent-core structure of the precipitated oligomers might be one of the possibilities of the helical morphology via the phase chirality. In this study, the polymerization of 4-acetoxyphthalic anhydride (APA) and 4aminobenzoic acid (AmBA) was examined as shown in Scheme 1 in order to clarify the influence of the oligomer structure on the formation of the helical morphology.



Corresponding author. Tel.: + 81-86-251-8902. E-mail address: polykim@okayama-u.ac.jp.

Page 299 of 1108

Scheme 1 Synthesis of poly(ester-imide)

2. Experimental APA and AmBA were synthesized and used as monomers. Dibenzyltoluene mixture (DBT) was used as solvent. DBT (10 mL) and APA were placed into a cylindrical vessel equipped gas inlet and outlet tubes and a thermometer, and then heated up to desired temperature with stirring under nitrogen atmosphere. AmBA was added to the solution with stirring, and then heated up to polymerization temperature without stirring. After the polymerization, the crystals were collected by vacuum filtration at the polymerization temperature to avoid the precipitation of oligomers during cooling, washed with n-hexane and acetone, and then dried at 50oC under vacuum for 12 h. Oligomers dissolved in the solution were collected by pouring the filtrate into n-hexane.

3. Results and discussion 3. 1. Model reaction

Scheme 2 Model reaction of APA and AmBA In this polymerization, amic acid which was a precursor structure of imide ring was formed at the initial stage of the polymerization, and then the polymerization occurred with elimination of acetic acid between carboxyl group and acetoxy group to form the ester linkage. In order to optimize the condition for the formation of amic acid, the model reaction was first carried out at a concentration of 2.0% in DBT as shown in Scheme 2. APA and DBT were placed into a cylindrical vessel and the solution was heated. Then AmBA was added at 150 - 220oC. The reaction time was changed from 1h to 3h. After the reaction, the products were collected by pouring the solution into n-hexane and filtrating. However, the products were precipitated in the solution during the reaction at 150oC and then the products were collected by filtrating. The chemical structure of all precipitates was analyzed by FT-IR and the amide C=O stretching band appeared at 1657 cm-1, indicating the formation of amide linkage. However, the carboxylic anhydride C=O stretching band appeared at 1842 and 1780 cm-1 at more than 180oC. It was found that AmBA was sublimated at more than 180oC. The stoichiometric balance between APA and AmBA was not maintained because of the sublimation of AmBA, and then unreacted APA was remained in the solution. From these results, the reaction temperature was determined at 150oC. AmBA was also used as a monomer of polybenzamide [3] and it might self-condense depending on the reaction condition. Then AmBA was reacted at 150oC for 3h. It was found by the analysis of the products with FT-IR and 1H-NMR that the self-condensation did not occur under these conditions. Based on these results, the reaction was carried out at 150oC and a concentration of 2.0% for 3h to form the amic acid.

3. 2. Polymerization Table 1 Results of polymerization of APA and AmBA Run Polymerization Polymer b) DI (%) No. Temperature (oC) Yield (%) 1

280

10.7

69.7

300

14.8

65.6

330

10.4

65.0

Morphology c)

RE RE, Rod RE, Rod, Ribbon, SP e)

4 350 22.6 59.9 Rod, SP a) Polymerizations were carried out at a conc. of 2.0% for 5h in DBT. b) Degree of imidization c) RE stands for rods with enation-like crystals on the surface. d) SP

Page 300 of 1108

stands for spheres with needle-like crystals on the surface. e) SP stands for spheres with plate-like crystals on the surface.

The polymerization was carried out at 150oC and a concentration of 2.0% for 3h in DBT and then heated up to 280 - 350oC. The polymerization temperature was changed from 280oC to 350oC. The polymerization was stopped after 2h. The results of polymerization are presented in Table 1. Precipitates were obtained with the yields of 10 - 23%. Although precipitates prepared at 280, 300 and 330oC were fiber-like crystals having enation-like crystals on the surface as shown in Fig. 1 (a), rod-like crystals were formed at 300, 330 and 350oC as shown in Fig. 1 (b). At 350oC, the width of rod-like crystals became larger than that prepared at 280oC as shown in Fig. 1 (c). A small amount of ribbon-like crystals were formed as shown in Fig. 1 (d) at 330oC. Helical ribbons prepared from CAP were not formed at all in the polymerization of APA and AmBA. The chemical structure was analyzed by FT-IR. The imide C=O stretching band appeared at 1744 cm-1. The imide C-N stretching band also appeared at 1370 cm-1 and the bands characterized as the end group such as carboxylic acid group at ca. 3100-2200 and 1688 cm-1 were not visualize in the spectrum of the precipitates. However, the amide C=O stretching band appeared at 1670 cm-1 and precipitates were not completely imidization. The degree of imidization was 60-70%. From these results, they were high molecular weight polymers comprised of ester-imide moiety and amide moiety.

Fig. 1 Morphology of polymer precipitates prepared at (a) 280oC, (b, d) 330oC and (c) 350oC

Page 301 of 1108

WAXS diffraction of all precipitates was measured and the WAXS diffraction peaks were different from that of helical ribbons prepared from CAP as shown in Fig. 2. In the polymerization of APA and AmBA, the imidization reaction occurred simultaneously with the polymerization. And then the molecular weight and the molecular chain structure of oligomers precipitated during polymerization were changed because the reaction rate of imidization was different from the rate of polymerization depending on the temperature and concentration of polymerization. In this polymerization, amic acid which was a precursor structure of imide ring was contained in precipitated oligomers and the molecular chain structure was disordered. Therefore, helical morphology was not formed at all. Even though the true nature of the helical morphology remained unclear, it was speculated that the uniformity of oligomer structure is important for the formation of helical morphology.

Fig. 2 WAXS intensity profiles of polymer precipitates prepared from (a) CAP and from APA and AmBA at (b) 280oC, (c) 300oC, (d) 330oC and (e) 350oC

4. Conclusion In the polymerization of APA and AmBA via the formation of precursor, fibrillar and ribbon-like crystals of poly(ester-imide) were formed, but they did not exhibit helical morphology at all. The difference of oligomer structure significantly influenced the helical morphology, especially composing of the imide ring or precursor amide linkage.

5. References [1] H. R. Kricheldorf, S. A. Thomsen, J. Polym. Sci.,1991, 29, 1751. [2] T. Ohnishi, M. Nakagawa, T. Uchida, S. Yamazaki, K. Kimura, Proceedings of The 11th Asia Textile Conference, 2011, 151. [3] K. Kobashi, K. Kobayashi, H. Yasuda, K. Arimachi, T. Uchida, K. Wakabayashi, S. Yamazaki, K. Kimura, Macromolecules, 2009, 42, 6128

Page 302 of 1108

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

Preparation of rigid polymer nanofiber by using crystallized from dilute solution and its application Tetsuya Uchida +, Masashi Furukawa and Haruka Dodo Graduate School of Natural Science and Technology, Okayama University,3-1-1 Tsushima-naka Kita-ku, Okayama 700-8530, Japan

Abstract. Poly(p-phenylene benzobisoxazole) (PBO) has excellent thermal stability and mechanical properties because of its rod-like rigid structure. Preparing nanofibers of PBO using ordinary methods (e.g. electrospinning) is difficult because PBO is not soluble in organic solvents. In this work, PBO nanofiber with an average diameter of approximately 50 nm was prepared by using rapid cooling crystallization from dilute solution in sulfuric acid. In addition, PBO nanofiber mat was prepared. Resultant PBO nanofiber mat has very excellent properties (e.g. thermal stability, mechanical properties, low linear thermal expansion coefficient).

Keywords: rigid polymer, nanofiber, composite, crystallization

1. Introduction Poly(p-phenylene benzobisoxazole) (PBO) (Fig. 1) is a rigid polymer in which the molecular chains are unable to fold. PBO fibers have excellent physical properties, including high strength, a high elastic modulus, and high thermal stability [1-5].

Fig.1 Structure of Poly(p-phenylene benzobisoxazole) (PBO) However, nanofibers with diameters of less than 100 nm and aspect ratios higher than 100 have attracted attention recently because of potential applications in many areas, including high efficiency filters, organic electronics, electromagnetic shield materials, compact batteries, and high-performance polymer composite [610]. Methods for the preparation of nanofibers include conjugated melt spinning, melt-blowing, and electro spinning, with the lattermost being the most versatile. However, these methods require not only specialized equipment but also high voltages. Furthermore, using conventional nanofiber preparation methods for a rigid polymer such as PBO is difficult because it is insoluble in organic solvents, and soluble only in concentrated sulfuric acid and other similar acids. We previously reported that single crystals with different forms can be produced by crystallizing PBO from dilute solutions in concentrated sulfuric acid [11]. Here, we have used this result to develop new method for preparing PBO nanofibers. The properties of a PBO nanofiber mat prepared using the obtained PBO nanofibers were also investigated.

2. Experimental Preparation of PBO Nanofibers

Corresponding author. Tel.: + 81-862518103 E-mail address: tuchida@cc.okayama-u.ac.jp

Page 303 of 1108

PBO with an intrinsic viscosity of 10.7 dl/g and a weight-average molecular weight of 16,600 was used [12]. Sulfuric acid and PBO was added to an eggplant flask and heated to 120 °C to dissolve the PBO. Subsequently, PBO nanofibers were prepared by rapidly cooling the solution to 0 °C. The obtained nanofibers were then rinsed. Preparation of the PBO Nanofiber Mat PBO nanofibers dispersed in water were precipitated via filtration under reduced pressure. The PBO nanofiber mat was prepared by performing decompression pressing of the PBO nanofiber precipitate via a vacuum heating press.

3. Results and Discussion The diameter and length of the obtained PBO nanofibers (Fig. 2) were 53 ± 22 nm and 6.7 ± 1.1 µm, respectively. Electron diffraction images revealed that the molecular chains of the PBO were oriented in the longitudinal direction of the nanofibers, and that the nanofibers were highly crystalline.

Fig.2 TEM of PBO nanofibers and a selected area electron diffraction image of the circled area. In addition, the specific surface area of the PBO nanofibers was 88.4 g/m2, which is a large specific surface area. From these results, it was concluded that a method for the preparation of high crystallinity PBO nanofibers was developed that required neither high voltage nor special equipment. A PBO nanofiber mat was then prepared using the obtained PBO nanofibers (Fig. 3). Because PBO fibers exhibit excellent properties, including high strength, high elasticity, and high heat stability [1-3] as described above, the PBO nanofiber mat was also expected to exhibit excellent properties. In particular, since the thermal diffusivity of PBO fiber is high [4, 5], it is expected that the thermal diffusivity of the PBO nanofiber mat is also high. The apparent density of the prepared PBO nanofiber mat was 1.10 g/cm3. The porosity calculated using a PBO fiber density of 1.54 g/cm3 [13] was found to be 29 %. In addition, the PBO nanofiber mat was determined to have a high specific surface area of 42.6 g/m2, and numerous meso pores were observed in its structure.

1cm Fig.3 Photo of the PBO nanofiber mat. The elastic modulus, yield strength, rupture strength, and rupture elongation of the PBO nanofiber mat were 1.48 ± 0.14 GPa, 54.1 ± 5.7 MPa, 54.1 ± 5 MPa, and 6.3 ± 1.0 %, respectively. These results indicate that the prepared PBO nanofiber mat had excellent mechanical properties and also retained a high level of porosity.

Page 304 of 1108

In addition, PBO nanofibers were clearly observed both on the surface and in the cross-sectional SEM images of the tensile fracture surface of the PBO nanofiber mat (Fig. 4).

Fig.4 SEM images of the a) surface and b) tensile fracture surface of the PBO nanofiber mat.

Weight[%]

The data obtained for the thermogravimetric analysis of the PBO nanofiber mat are shown in Fig. 5. The 5% and 10% weight loss temperatures for the PBO nanofiber mat were 610 °C and 650 °C, respectively, which confirmed that the mat possessed high thermal stability. Furthermore, the results of the viscoelastic modulus analysis revealed that the elastic modulus of the PBO nanofiber mat remained stable at temperatures up to 400 ℃. Finally, the PBO nanofiber mat was found to exhibit a high thermal diffusivity of 5.36 ± 0.38 × 10−6 m2/s in the in-plane direction and 0.29 ± 0.04 × 10−6 m2/s in the thickness direction, indicating a large difference in the thermal diffusivity depending on the measurement direction. Based on the results described above, it was concluded that the PBO nanofiber mat exhibited excellent properties. 100 90 80 70 60 50 40 30 20 10 0 0 100 200 300 400 500 600 700 800 9001000

Temperature[°C] Fig.5 Thermogravimetric analysis results for the PBO nanofiber mat.

Table 1 Properties of the PBO nanofiber mat. Physical property Density 1.10 ± 0.07 g/cm3

Page 305 of 1108

Porosity Elastic modulus Thermal resistance: 5% weight loss 10% weight loss Specific surface area Thermal diffusivity: In-plane direction Thickness direction

28.7% ± 4.2 % 1.48 ± 0.14 GPa 610 °C 650 °C 42.6 g/m2 5.36 ± 0.38×10−6 m2/s 0.29 ± 0.04×10−6 m2/s

4. Conclusions We have developed a method for the preparation of PBO nanofibers with molecular chains crystallized in a highly oriented manner via the crystallization (self-assembly) of the rigid polymer without the need for the use of a high voltage or special equipment. In addition, a PBO nanofiber mat were simply prepared using filtration and a vacuum heating press. The PBO nanofiber mat prepared from the PBO nanofibers exhibited excellent mechanical properties, high thermal stability, and high porosity. Notably, the thermal diffusivity was found to be anisotropic, with the value in the in-plane direction of the film greater than that in the thickness direction.

5. References [1] J. F. Wolfe, et.al., Macromolecules, 14, 915 (1981). [2] E. W. Choe, et.al., Macromolecules, 14, 920 (1981). [3] S. J. Krause, et.al., Polymer, 29, 1354 (1988). [4] H. Fujishiro, et.al., Jpn. J. Appl. Phys., 36, 5633 (1997) . [5] X. Wang, et.al., Macromolecules, 46, 4937 (2013). [6] M. Nogi, et.al., Adv. Mater., 21, 1595 (2009). [7] G. Duan, et.al., Nanomaterials, 2010, 1 (2010). [8] M. Nogi, H. Yano, Adv. Mater., 20, 1849 (2008). [9] C. Huang, et.al., Adv. Mater., 18, 671 (2006). [10] T. Fukumaru, et.al., Macromolecules, 45, 4247 (2012). [11] K. Shimamura, T. Uchida, M. Suzuki and C. Zhang, SEN’I GAKKAISHI, 54, 374 (1998). [12] G. C. Berry, et.al., Polym. Prep., 20, 42 (1979). [13] D. C. Martin and E.L.Thomas, Macromolecules, 24, 2450 (1991). [14] T. Uchida, M. Furukawa, J. Photopolymer Science and Tech., 27, 177-180 (2014)

Page 306 of 1108

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

Preparation of Well-Defined Polyacrylonitrile Fiber-Forming Polymer via New Controlled Radical Polymerization Techniques Xiaohui Liu +, Bowen Cheng School of Materials Science and Engineering, Tianjin Key Laboratory of Fiber Modification and Functional Fiber, Tianjin Polytechnic University, Tianjin 300160, China

Abstract. Poly(acrylonitrile) is an important polymer, especially for preparing the precursor of carbon fibers, due to its excellent physical and chemical properties, such as high rigidity and strength, and good chemical resistance. Generally, the key to high-performance carbon fibers is to prepare high-quality PAN precursors with high molecular weight (MW) and well-controlled architecture. Commercially available PAN with high MW is usually synthesized by conventional radical polymerization of acrylonitrile. However, this method cannot control molecular weight and molecular weight distribution. We developed varied novel stable and facile ATRP mediating systems to produce the catalyst in situ at ambient conditions. Importantly, the processes involve very fast activation and deactivation steps and negligible bimolecular termination at low polymerization temperature as well as ppm level metal concentrations. Therefore, this work provides a profound comprehension for successful synthesis of well-defined high-molecular-weight PANs via new living/controlled polymerization methods. That is, Zn(0)/ppm concentrations of CuBr 2 (10-50 ppm) was firstly used to catalyze radical polymerization of acrylonitrile at ambient temperature. The polymerization displayed typical living radical polymerization characteristics, as evidenced by pseudo first-order kinetics of polymerization, linear increase of number-average molecular weight, and low polydispersity index value.

Keywords: acrylonitrile, ambient temperature, ppm concentration.

1. Introduction The controlled/living radical polymerization (CRP) of acrylonitrile (AN) is challenging to control owing to its high reactivity and the poor solubility of polyacrylonitrile (PAN). However, PAN is an important polymer, especially for preparing the precursor of carbon fibers, which motivates us to synthesize PAN in a controlled fashion. In this regard, more efforts should be concentrated on the preparation of PAN of higher molecular weights via novel CRP technique. Atom transfer radical polymerization (ATRP) is an important technique to provide well control over molecular dimension and polymer structure.1,2 To date, two promising techniques are activators regenerated by electron transfer (ARGET) ATRP and initiators for continuous activator regeneration (ICAR) ATRP as they can allow for a substantial reduction in the amount of metal catalyst required (usually ca. 10-100 ppm versus 1000-10000 ppm for normal ATRP).3 Similarly, ARGET ATRP employs an excess of an appropriate reducing agent (e.g., ascorbic acid) to continuously in situ reduce oxidatively stable deactivator compound (Cu(II)X 2 ) to the activator complex (Cu(I)X), whereas ICAR employs an organic radical initiator (AIBN). Consequently, they have been successfully accessed to a wide range of monomers using ppm levels of catalyst, particularly some challenging monomers, such as acrylonitrile (AN). Matyjaszewskiâ&#x20AC;&#x2122;s and Chenâ&#x20AC;&#x2122;s groups successively reported controlled synthesis of polyacrylonitrile (PAN) via 25-75 ppm concentrations of copper or iron-mediated ARGET ATRP with tin(II) 2-ethylhexanoate, glucose, and ascorbic acid as reducing agents.4 More recently, our group also first utilized ICAR ATRP to yield well-defined PAN with a low concentration of copper catalyst (50 ppm).5,6 In general, these cases were carried out under relatively high temperature, which means the enhancement of possible undesirable side reactions and energy consumption. Thus it is very important to explore the ambient temperature living radical polymerization (LRP) with ppm levels of catalyst to produce well-defined PAN.

Corresponding author. Tel.: + 86-022-8395 5055. E-mail address: xiaohuilau@163.com.

Page 307 of 1108

Inspired by this issue, we noted the recently reported LRP catalyzed by a combination of copper(II) and zero-valent metals including zinc wire, magnesium ribbon, and iron wire. Originally, the systematic studies on the reactions between some pure metals and organic halides were carried out by Ostu’s and Bamford’s groups early in the 1960s.7 Ostu and Matyjaszewski respectively attempted to realize “living” radical polymerization using the different combinations of metals with organic halides.8 Unfortunately, most polymerization reactions were loss of control. In the meantime, Percec et al. successfully employed Cu(0) complexes to mediate LRP of various vinyl monomers.9 Subsequently, they reported the first Cu(0)-catalyzed room temperature living radical polymerization of VC in aqueous media and revealed that the polymerization probably proceeded by a competition between single electron transfer and degenerative chain transfer mechanisms (SET-DTLRP). In 2006, an important strategy coining as SET LRP, Cu(0)-mediated LRP, was developed by Percec and his coworkers.10 Especially interesting is that SET-LRP can be carried out at ambient temperature because it undergoes an outer-sphere SET process that has a very low activation energy. Electrochemically, the reaction of CuBr 2 and metallic powder is apt to generate Cu(0) in situ through a facile redox process (Cu(II) + 2e- → Cu(0), ΔE = 0.337 V). The utility of Zn(0) as reductant to produce Ni(0) catalyst that was highly efficient for mediating homo- and cross-coupling reactions, borylation reactions and polymerizations reactions based on these organic reactions were reported by Percec and his coworkers.11 Furthermore, Gerard’s and Canturk’s groups also demonstrated the potential by using zinc powder as a special reducing agent.12 The present work reports the facile ambient temperature LRP of AN using the combination of ppm concentrations of CuBr 2 and Zn(0). Living/controlled nature was confirmed by Gel permeation chromatography (GPC) and 1H NMR analyses as well as chain extension reaction.

2. Results and discussions 2.1.

Zn(0)/ppm concentrations of CuBr 2 mediated-LRP of AN at Ambient Temperature

As noted previously, various nitrogen-based ligands, including N,N,N′,N′,N′pentamethyldiethylenetriamine (PMDETA), tris[2-(dimethylamino)-ethyl] amine (Me 6 TREN), and bpy, have been successfully employed for copper-mediated LRP of AN. The choice of an appropriate ligand significantly affected Zn(0)-ppm concentrations of Cu(II) mediated-radical polymerization of AN at ambient temperature. Firstly, higher reactivity ligands (Me 6 TREN, and PMDETA) are not recommended as they can reduced Cu(II) to Cu(I) species efficiently. On the other hand, some ligands, particularly PMDETA, are potential for coordinating with cyano group in AN rather than copper center, thus leading to low activation/deactivation rate and bad control of the AN polymerization. In contrast, a typical LRP ligand for AN monomer, bpy, was generally inert to these activities. Therefore, bpy was utilized as the ligand for the current work. Preliminary experiments also show that a large excess of bpy (Figure 1) and Zn(0) (Figure 2) to CuBr 2 provided an ideal rate of polymerization. Therefore to guarantee a high active catalytic system, the polymerizations were conducted with a CuBr 2 /bpy molar ratio of 0.01:0.6 and a CuBr 2 /Zn(0) molar ratio of 0.01:0.2. In addition, EBiB was chosen as the initiator due to higher reactivity. The representative results of AN polymerization using CuBr 2 /Zn(0) as the catalyst in various solvents at 25 °C are summarized in Table 1. 100

[bpy]0/[CuBr2]0 = 60:1

Conversion (%)

80 60 40 20 0

90 120 150 180 210 240 270 300

[bpy]0/[CuBr2]0 (mole/mole)

Fig. 1: Dependence of monomer conversion on [bpy] 0 /[CuBr 2 ] 0 for Zn(0)/ppm concentrations of copper(II)-mediated living radical polymerization of AN in EC. Reaction conditions: [AN] 0 /[EBiB] 0 /[Zn(0)] 0 /[CuBr 2 ] 0 = 200:1:0.2:0.01, AN/EC = 1:1 (v/v), [AN] 0 = 7.60 M, T = 25 °C, reaction time = 16 h.

Page 308 of 1108

100

Conversion (%)

80 60 40 20 0

[Zn(0)]0/[CuBr2]0 (mole/mole)

Fig. 2: Dependence of monomer conversion on [Zn(0)] 0 /[CuBr 2 ] 0 for Zn(0)/ppm concentrations of copper(II)-mediated living radical polymerization of AN in EC. Reaction conditions: [AN] 0 /[EBiB] 0 /[bpy] 0 /[CuBr 2 ] 0 = 200:1:0.6:0.01, AN/EC = 1:1 (v/v), [AN] 0 = 7.60 M, T = 25 째C, reaction time = 16 h.

Clearly, the poor solvent for PAN, NMP, achieved a very low monomer conversion after 16 h (3.64%, entry 1 in Table 1). Contrarily, the good solvents for PAN, DMF, DMSO, and EC, could reach higher monomer conversions after the same duration, especially DMSO (65.71% conversion, entry 3) and EC (78.04% conversion, entry 4). Importantly, only EC provided the lowest PDI value (PDI = 1.16, entry 4), while DMSO, DMF, and NMP provided relatively higher PDI values (PDI >1.30, entries 1-3). Thus the results strongly indicate that EC as a solvent for the AN polymerization mediated by Zn(0)/ppm concentrations of Cu(II) at ambient temperature can produce a higher rate of polymerization and low PDI value. This is in line with the copper-mediated LRP of AN reported previously. Table 1: Effect of varied solvent on LRP of AN.a Conv. M n,th M n,GPC Entry Solvent (%) (Da) (Da) PDI 1 NMP 3.64 581 14690 1.37 2 DMF 27.80 3145 8500 1.37 3 DMSO 65.71 7168 25330 1.33 4 EC 78 04 8476 19200 1 16 a [AN] 0 /[EBiB] 0 /[Zn(0)] 0 /[bpy] 0 /[CuBr 2 ] 0 = 200:1:0.2:0.6:0.1, AN/solvent = 1:1 (v/v), [AN] 0 = 7.60 mol/L, [Cu] 0 = 50 ppm, T = 25 째C, reaction time = 16 h.

2.2.

Effect of copper concentration

For copper-based LRP, the ratio of Cu(I) to Cu(II) determines the rate of polymerization, while absolute Cu(II) concentration influences the PDI value considerably. Therefore it is necessary to determine the minimal amount of CuBr 2 required for a well-controlled polymerization of AN. The dependence of the polymerization on catalyst concentration was analyzed by varying the CuBr 2 loading when the ratio of [AN] 0 /[EBiB] 0 /[Zn(0)] 0 /[bpy] 0 remained a constant value (Table 2). Clearly, the rate of polymerization decreased with a decrease of the concentration of copper (50-2.5 ppm). Lowering the amount of CuBr 2 to 2.5 ppm yielded no polymer, indicating that there was not enough Cu to initiate the polymerization and maintain the equilibrium. Meanwhile, the differences between the measured molecular weight values and the theoretical ones progressively enlarged, accompanied by the corresponding increase of PDI values from 1.16 to 1.53. Notwithstanding, it is worth pointing out that the polymerization was well controlled in terms of PDI values even though the CuBr 2 loading decreased to 10 ppm (PDI = 1.27, entry 3).

Entry 1 2 3 4 5 a

Table 2: Effect of catalyst concentration on LRP of AN.a [AN] 0 /[EBiB] 0 /[Zn(0)] 0 / [Cu] 0 Time Conv. [bpy] 0 /[CuBr 2 ] 0 (ppm) (h) (%) 200:1:0.2:0.6:0.01 50 16 78.04 200:1:0.2:0.6:0.005 25 16 53.43 200:1:0.2:0.6:0.002 10 46 40.81 200:1:0.2:0.6:0.001 5 46 28.81 200:1:0.2:0.6:0.0005 2.5 46 trace

AN/EC = 1:1 (v/v), [AN] 0 = 7.60 M, T = 25 째C.

M n,th (Da) 8476 5865 4526 3252

M n,GPC (Da) 19200 25920 39430 57340

PDI 1.16 1.25 1.27 1.53

Page 309 of 1108

3. Conclusions The CRP reactions of AN catalyzed with Zn(0)/ppm concentrations of CuBr 2 (10-50 ppm) have been successfully conducted. The inexpensive, facile, and easily conducting catalytic system proved to be a good candidate to control AN polymerization at ambient temperature, as evidenced by pseudo first-order kinetics of polymerization, linear increase of number-average molecular weight, and low PDI value. The dependences of the polymerization on varied experimental parameters, such as solvent, copper concentration, and initiator concentration, were investigated in detail. EC is superior in many respects to NMP, DMF, and DMSO in terms of rate of polymerization as well as control of molecular weight and PDI. The increase of the copper concentration from 2.5 to 50 ppm leads to a higher rate of polymerization and a better control over the polymerization reaction.

4. References [1] Ouchi, M; Terashima, T; Sawamoto, M. Chem. Rev. 2009, 109, 4963-5050. [2] Siegwart, D.J.; Oh, J.K., Matyjaszewski, K. Prog. Polym. Sci. 2012, 37, 18-37. [3] Jakubowski, W.; Matyjaszewski, K. Angew. Chem. Int. Ed. 2006, 45, 4482-4486. [4] Dong, H.C.; Tang, W.; Matyjaszewski, K. Macromolecules 2007, 40, 2974-2977. [5] Liu, X.H.; Wang, J.; Yang, J.S.; An, S.L.; Ren, Y.L.; Yu, Y.H.; Chen, P. J. Polym. Sci. Part A: Polym. Chem. 2012, 50, 1933-1940. [6]

Liu, X.H.; Wang, J.; Zhang, F.J.; An, S.L.; Ren, Y.L.; Yu, Y.H.; Chen, P.; Xie, S. J. Polym. Sci. Part A: Polym. Chem. 2012, 50, 4358-4364.

[7]

Ostu, T.; Yamaguchi, M.; Takemura, Y.; Kusuki, Y. Aoki, S.; J. Polym. Sci. Polym. Lett. 1967, 5, 697-701.

[8] Matyjaszewski, K.; Gaynor, S.G.; Coca, S. U.S. Patent 6, 512, 060 B1, 2003. [9] Percec, V.; Barboiu, B.; van der Sluis, M. Macromolecules 1998, 31, 4053-4056. [10] Percec, V.; Guliashvili, T.; Ladislaw, J. S.; Wistrand, A.; Stjerndahl, A.; Sienkowska, M. J.; Monteiro, M. J.; Sahoo, S. J. Am. Chem. Soc. 2006, 128, 14156-14165. [11] Grob, M.C.; Feiring, A.E.; Auman, B.C.; Percec, V.; Zhao, M.; Hill, D.H. Macromolecules 1996, 29, 7284-7293; [12] Gerard, P. PCT Int. Appl. WO 2009/007792 A1, 2009.

Page 310 of 1108

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

Properties of Cellulose Regenerated Fibers Spun from Ionic Liquid Solutions Jiaping Zhang 1, Keita Tominaga 1 and Yasuo Gotoh 1, 2 1

Faculty of Textile Science and Technology, Shinshu University, Nagano 386-8657, Japan 2 Institute for Fiber Engineering, Shinshu University, Nagano 386-8657, Japan

Abstract. High performance cellulose regenerated fibers were prepared from the solutions of 1-butyl-3methylimidazolium chloride (BMIMCl) via dry-wet spinning method. The effect of draft ratio on the properties of the fibers was investigated by wide angle X-ray diffraction. When the molecular weight and concentration of cellulose solutions were high, the draft ratio of spinning was increased, and consequently the regenerated fibers with high tensile strength over 1 GPa could be obtained. Moreover, the comparison with Lyocell fibers spun from the NMMO solutions was conducted, and consequently knot and loop strengths and anti-fibrillation properties of the fibers spun from BMIMCl solutions were superior to those for Lyocell fibers, which was extrapolated to due to the difference in the amorphous regions.

Keywords: Cellulose, Regenerated Fiber, Ionic Liquid, Lyocell, High Strength.

1. Introduction Biopolymers from renewable resources have drawn great attention as alternative for petroleum due to the increasing environmental pollution and the exhaustion of oil resources. Cellulose is the most abundant biopolymer on the earth and is widely used in commercial materials for its attractive properties such as renewability, biodegradability, thermal and chemical stability [1]. However the processing of cellulose is difficult because cellulose consists of rigid glucose polymer chains which also can form intra- and intermolecular hydrogen bonded structures. In 2002, Rogers et al. firstly reported the solubility of natural cellulose in a series of ionic liquids [2]. Ionic liquids (ILs) particularly refer to salts with a melting point below 100 °C. They offer various advantages such as low toxicity, chemical and thermal stability, near non-volatility, recyclability [3]. In addition, the properties of ILs can be manipulated according to the requirements by changing the structure of cations or anions, thus termed the “designer solvents” [4]. Therefore, ionic liquids are promising as efficient cellulose solvents. In this study, cellulose regenerated fibers with high performance were obtained via dry-wet spinning method using 1-Butyl-3-methylimidazolium chloride (BMIMCl) as solvent. We investigated rheological properties of cellulose/BMIMCl solutions on dependence of molecular weight and polymer concentration. Mechanical properties and crystal structures of cellulose/BMIMCl regenerated fibers were also characterized. In addition, the comparison with Lyocell fibers spun from NMMO solutions was conducted on fibrillation behaviors.

2. Experimentals Dissolving pulp with a [η] of 300 ml/g and 425 ml/g (measured according to JIS P 8215:1998) was used in this study. BMIMCl was purchased from Aldrich. The cellulose pulp was pulverized and dried in an oven at 100 °C for 4 h to remove moisture before use. Typically, a 10wt% cellulose/BMIMCl solution was prepared by successively adding 10 g cellulose, 90 g heated BMIMCl and 0.05 g propyl gallate into a stainless steel vessel. The mixture firstly swelled in an oven at 60 °C for 30 min. It was subsequently stirred in a kneader at 90 °C for another 1 h to obtain a homogeneous cellulose/BMIMCl solution. The dissolved state of solution was checked with a polarized optical microscope. The fibers were prepared by dry-wet spinning process. The spinning solutions heated at 100 °C were extruded into a water coagulation bath kept at 15 °C after passing through a 15 cm-long air gap from nozzle. And a nozzle with diameter of 0.27 mm and length of 12 mm was applied. The filaments were wound onto a

Page 311 of 1108

take-up rollers at a fixed winding speed while changing the feed speed in order to vary draft ratio. After spinning, the fibers were soaked in water overnight and dried at room temperature for 12 h.

3. Results and Discussion Rheology is a fundamental property to evaluate spinning solutions. Fig. 1 shows the steady-shear and oscillation rheological properties of two samples before spinning. As can be seen from Fig. 1(a), the zero-shear-rate viscosity of 12wt% cellulose ([η] = 425 ml/g) solution is higher than that of 10wt% cellulose ([η] = 300 ml/g) solution. Moreover, the viscoelastic properties can be obtained from Fig. 1 (b). We find that the crossover frequency of storage modulus (G') and loss modulus (G") curves becomes lower (that is, relaxation time becomes longer) with the increase of molecular weight and polymer concentration. High strength fibers with the strength over 1 GPa were successfully prepared from a 12wt% cellulose ([η] = 425 ml/g)/BMIMCl solution. In the range of our research, the spinning solution having longer relaxation time enables to achieve higher draft ratio in the spinning and to make higher strength fibers. As an example, an X-ray fiber photograph of a high strength fiber is shown in Fig.2. Both the crystalline and crystallite orientation are sufficiently high. In order to compare to properties of our fibers, Lyocell was also prepared from the NMMO spinning solution under the same spinning conditions. Tensile strength and modulus were almost same for each fiber, while knot strength and loop strength were remarkably higher than those of Lyocell fibers. Fibrillation behavior of the fibers was also different. The fibers spun from BMIMCl solutions didn’t appear visible fibrillation on surface. The tendency of fibrillation of fibers spun from NMMO solutions was possibly due to the weaker phase between micro- or macrofibrils, which may strongly related to the results of knot strength and loop strength.

Fig. 1 Rheological properties of cellulose/BMIMCl solutions at 100 °C. Upper: Shear rate dependence of shear viscosity η. Lower: Frequency dependence of storage modulus G' and loss modulus G".

4. Conclusions Cellulose regenerated fibers with tensile strength over 1 GPa were prepared successfully from BMIMCl solutions via dry-wet spinning method. With the increase of molecular weight and concentration, higher draft ratio and tensile strength could be achieved. In addition, knot and loop strengths and anti-fibrillation property of the fibers spun from BMIMCl solutions were remarkably superior to those of Lyocell.

5. References [1] M. Jiang, M. Zhao, Z. Zhou, et al. Industrial Crops and Products, 2011, 33, 734-738. [2] R. P. Swatloski, S. K. Spear, J. D. Holbrey, R. D. Rogers. J. Am. Chem. Soc, 2002, 124, 4974-4975. [3] M. Soheilmoghaddam, P. Pasbakhsh, M. U. Wahit, et al. Polymer, 2014, 55, 3130-3138. [4] L. Liu, M. Ju, W. Li, et al. Carbohydr. Polym, 2013, 98, 412-420.

Fig. 2 X-ray fiber photographs of regenerated cellulose fibers spun from 12wt% BMIMCl solution ([η]=425 mL/g) at draft ratio of 77.7. fc represents the degree of crystallite orientation.

Page 312 of 1108

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

Property Evaluations of Composite Films made of Polyvinyl Alcohol and Graphene Nano-Sheets by Using the Solution Mixing Method Zheng-Ian Lin 1, Ching-Wen Lou 2, Chien-Lin Huang 3, Chih-Kuang Chen 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 Institute of Biomedical Engineering and Materials Science, Central Taiwan University of Science and Technology, Taichung City 40601, Taiwan, R.O.C 3 Department of Fiber and Composite Materials, Feng Chia University, Taichung City 40724, 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. This study aims to prepare the conductive composite films with a light weight, ease of processing, and electromagnetic interference shielding effectiveness (EMI SE). Therefore, this study uses the solution mixing method to produce the polyvinyl alcohol (PVA)/graphene nano-sheets (GNs) composite films. The tensile property, thermal behaviors, electric conductivity, EMI SE of the composite films are tested in order to determine the influence of GNs. The test results show that 0.25 wt% of GNs provides the PVA/GNs composite films with an optimal tensile strength, as well as improves their glass transition temperature (T g ), melting temperature (T m ), and crystallization temperature (T c ). In addition, the electrical conductivity and EMI SE of PVA/GNs are also proportional to the content of GNs, and they reach 7Ă&#x2014;10-7 S/cm and -18.79 dB, respectively. This study has approved that the solution mixing method is an easy and effective method to produce lightweight and EMI SE composite films.

Keywords: Polyvinyl alcohol (PVA), graphene nano-sheets (GNs), composite film, the solution mixing method, and electromagnetic interference shielding effectiveness (EMI SE)

1. Introduction Graphene has recently been used to improve the mechanical properties and electrical conductivity of polymers, due to having outstanding mechanical properties, a structure featuring a high aspect ratio, as well as electrical conductivity [1, 2]. Composites that are made out of polymer and graphene thus have good electrical conductivity, and as such can be used in sensors, capacitors, nanocomposites, and EMI shielding materials. Graphene-based composites have mechanical properties and electrical conductivity that depend on the dispersion and compatibility of graphene in the matrices. However, it is difficult for graphene to disperse in polymer matrices, due to its low compatibility to polar polymers, as well as their van der Waals interactions. In order to compensate for these two disadvantages, functionalized graphene is used, such as graphene oxide (GO). GO is featured as being hydrophilic and thus can be dispersed in polar solutions [3, 4]. Liang et al. prepared PVA/GO composites by administering a water solution processing method. The test results showed that GO had a good dispersion in PVA matrices, and was thus favorable for an effective load transfer that simultaneously promoted mechanical properties. Incorporating 0.7 wt% GO provided PVA/GO composites with a 76 % greater tensile strength and 62% greater tensile modulus [5]. Zhao et al. used sodium +

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

Page 313 of 1108

dodecylbenzenesulfonate (SDBS) to disperse the aqueous dispersion, in order to form PVA/graphene composites. The test results showed that 1.8 vol% graphene increased the tensile strength by 150 %, and increased the modulus by ten times [6]. Moradi et al. used the electrochemical method to wrap graphene sheets (GSs) in order to prepare a stable suspension, after which GSs were dispersed in PVA by using the liquid blending method. The test results showed that the tensile strength and modulus of PVA/GSs composites increases as a result of a low amount of GSs [7]. In sum, graphene that has hydrophilic functional groups can be dispersed in a water soluble polymer matrix. Therefore, this study uses GNs that are composed of oxygen-containing functional groups, as well as the solution mixing method for the preparation of PVA/GNs composite films. Finally, the tensile strength, thermal behaviors, electrical conductivity and EMI SE of the PVA/GNs composite films are tested in order to determine the influences of GNs.

2. Experimental 2.1.

Materials

Polyvinyl alcohol (PVA, Feng Xiang Materials Company Limited. Taiwan, R.O.C.) is modified by a plasticizer and thus has a melting point of 154.9 oC. Graphene nano-sheets (GNs, P-ML20, Enerage Inc. Taiwan, R.O.C.) have an oxygen content of 2.5 %, and a thickness of 50-100 nm.

2.2.

Methods

10 wt% of PVA is stirred while being heated for 6 hours in deionized water, in order to form a PVA solution. 0, 0.25, 0.5, 1, 1.5, or 2 wt% of GNs is then added to the PVA solution for the heating and stirring for 6 hours. The PVA/GNs mixtures are processed with dispersion in an ultrasonic bath for 1 hour. The mixtures with a specified volume of 20 mL are then casted in a glass dish, and then dried at 60 oC for 12 hours, in order to have the PVA/GNs composite films that have a thickness of 0.2 mm.

2.3.

Characterizations

Tensile test is performed by using an Instron 5566 universal tester (Instron, US) at a crosshead speed of 50 mm/min. The test samples have a size of 50 mm × 10 mm × 0.2 mm. There are a total of five samples. 810 mg fragments of PVA/GNs composites are sealed in an aluminum sample pans that are placed in a DSC (Q20, TA Instruments, U.S.). The samples are first heated from 40 oC to 200 oC at an isothermal heating rate of 10 oC /min, followed by being kept at this temperature for 5 minutes in order to delete the thermal history. Next, samples are cooled inversely (from 200 oC to 40 oC), and heated and then cooled again with the same temperature range and the same isothermal increments. The heating and cooling curves for the second cycle are recorded. The electrical conductivity of the samples is measured by using a four-pin probe (Keith Link Technology Co., Ltd., Taiwan, R.O.C.), as specified in ASTM D4496-13. When samples exhibit an electrical conductivity that is below 10-7 S/cm, their electrical conductivity is measured via a high resistance meter (RT100, OHM-STAT, Static Solutions Inc., US). EMI SE is performed by using an EMI shielding analyzer (EInstrument Tech Ltd., Taiwan, R.O.C.), as specified in ASTM D4935-10. Samples measuring 100 × 100 × 0.2 mm are placed in a coaxial transmission clamps (EM-2107A Electro-Metrics, Inc., US) and measured by a spectrum analyzer (Advantest R-3132, Burgeon Instrument Co., Ltd., Taiwan, R.O.C.) that is equipped with electromagnetic waves generator. The scan range falls between 300 kHz and 3 GHz.

3. Results and Discussion 3.1.

Tensile Strength of PVA/GNs Composite Films

Figure 1 indicates the tensile strength of PVA/GNs composite films. The tensile strength of pure PVA matrices is 15.81 MPa, while it is 39.0 MPa when 0.25 wt% of GNs is added to the matrices. However, the tensile strength of the PVA/GNs composites starts declining when the GNs content exceeds 0.25 wt%. GNs are nano fillers with a high specific surface area, and their amount exceeding 0.25 wt% causes them to succumb to Van der Waals forces, which in turn results in their agglomeration in the PVA matrices. The agglomerations form a stress concentrator that hampers the tensile strength of PVA/GNs composite films, the result of which confirms that of the study by Liao et al [8].

Page 314 of 1108

Fig. 1: Tensile strength of PVA/GN composite films.

3.2.

Thermal Behaviors of PVA/GNs Composite Films

Figure 2 indicates the thermal behaviors of PVA/GNs composite films. The glass transition temperature (T g ) of PVA increases as a result of the increasing GNsâ&#x20AC;&#x2122; amount, as indicated in Figure 2 (a). When PVA is dissolved in water, its molecular chains are simultaneously distributed in the solution. The GNs used in this study possess oxygen containing groups that can form hydrogen-bonding with the hydroxyl groups of PVA molecular chains. Therefore, a decrease in the mobility of PVA molecular chains results in an increase in the T g of PVA. PVA that is used in this study is modified by a plasticizer, and its melting temperature (T m ) is 154.9 oC, which is lower than that of the commercially available PVA, as indicated in Figure 2 (b). The Tm of PVA is proportional to the content of GNs. There is good compatibility between GNs and PVA, and this protects the crystalline region from damages and subsequently increases the T m of PVA. The crystallization temperature (T c ) of PVA increases as a result of increasing GNsâ&#x20AC;&#x2122; amount, as indicated in Figure 2 (c) GNs serve as a nucleating agent, and are conducive to the crystallization of PVA. This is a common result for polymer composites, because fillers are added as crystal nucleus that induces polymers to crystalize, and thus promotes the T c of the polymer[9].

Fig. 2: Thermal behaviors of PVA/GNs composite films in terms of: a) glass transition temperature; b) melting temperature; and c) crystallization temperature.

Page 315 of 1108

3.3.

Electrical Conductivity and EMI SE of PVA/GNs Composite Films

Figure 3 illustrates the electrical properties of PVA/GNs composite films. The electrical conductivity of PVA is 12×10-12 S/cm as indicated in Figure 3 (a), which indicates that PVA is an insulator. The incorporation of 0.25 wt% of GNs results in a significant increase in electrical conductivity, which is 7×10-7 S/cm. No occurrence of significant increases in the electrical conductivity of PVA/GNs can be observed with a GNs’ content above 0.25 wt%. GNs is an excellent conductive filler. Namely, the combination of GNs generates remarkable increases in the electrical conductivity of PVA/GNs composite films. When the specified amount of GNs (i.e., 0.25 wt%) forms a conductive network, any increases of GNs fail in augmenting the electrical conductivity. PVA/GNs composite films that are composed of less than 0.5 wt% of GNs barely possess EMI SE, as indicated in Figure 3 (b). The optimal EMI SE of -18.79 dB occurs when the composites are composed of 2 wt% GNs. The majority of GNs constructs a consecutive electrically conductive network. This in turn makes the PVA/GNs composites electrically conductive, and destroys the electromagnetic waves and engenders the EMI SE.

Fig. 3: Electrical properties of a) electrical conductivity and b) EMI SE of PVA/GNs composite films.

4. Conclusions This study disperses GNs that have oxygen-containing functional groups in PVA matrices, and successfully creates PVA/GNs composite films with good tensile and electrical properties. An incorporation of 0.25 wt% GNs results in a 146 % greater tensile strength of PVA/GNs, in comparison to that of pure PVA. The thermal behaviors results indicate that the conjunction of GNs benefits the Tm and Tc of PVA, and at the same time the electrical conductivity and EMI SE of PVA/GNs composite films. This study shows that GNs that have oxygen-containing functional groups are well compatible to and interactive with PVA. As a result, the diverse properties of PVA/GNs composite films are strengthened accordingly.

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. References [1] J. R. Potts, D. R. Dreyer, C. W. Bielawski, and R. S. Ruoff, Polymer, 52, 5 (2011). [2] T. Kuilla, S. Bhadra, D. Yao, N. H. Kim, S. Bose, and J. H. Lee, Progress in Polymer Science, 35, 1350 (2010). [3] H. K. F. Cheng, N. G. Sahoo, Y. P. Tan, Y. Pan, H. Bao, L. Li, S. H. Chan, and J. Zhao, ACS Applied Materials & Interfaces, 4, 2387 (2012). [4] A. Guimont, E. Beyou, P. Alcouffe, P. Cassagnau, A. Serghei, G. Martin, and P. Sonntag, Polymer, 55, 22 (2014). [5] J. Liang, Y. Huang, L. Zhang, Y. Wang, Y. Ma, T. Guo, and Y. Chen, Advanced Functional Materials, 19, 2297 (2009). [6] X. Zhao, Q. Zhang, D. Chen, and P. Lu, Macromolecules, 43, 2357 (2010). [7] M. Moradi, J. A. Mohandesi, and D. F. Haghshenas, Polymer, 60, 207 (2015). [8] W.-H. Liao, S.-Y. Yang, J.-Y. Wang, H.-W. Tien, S.-T. Hsiao, Y.-S. Wang, S.-M. Li, C.-C. M. Ma, and Y.-F. Wu, ACS Applied Materials & Interfaces, 5, 869 (2013). [9]

P. Song, Z. Cao, Y. Cai, L. Zhao, Z. Fang, and S. Fu, Polymer, 52, 4001 (2011).

Page 316 of 1108

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

PVA-Gel with Colossal Dielectric Constant Deflects Laser Beam Toshihiro Hirai 1 +, Hiromu Sato 2 and Chizuru Sakaguchi 1 1

Fiber Innovation Incubator, Shinshu University 3-15-1 Tokida, Ueda-shi 386-8567, Japan

toshihirohirai@me.com, tohirai@shinshu-u.ac.jp

Abstract. PVA swollen with DMSO has been known to be an excellent dielectric gel actuator. Applying dc field could induce swift and huge strain. The deformations are contraction, bending, and crawling. The deformation was resulted from the solvent migration in the gel matrix. The migration has been explained by iondrag. The dielectric solvent has been known migrated by ion-jet of charged DMSO solvent emerged on cathode under the dc electric field application. The ion-jet is occluded in PVA matrix. PVA matrix disturbs or retards discharging on cathode. The accumulated charge causes tacking or stickiness to cathode, and results in the contractile deformation of the gel. Thus caused space-charge distribution is asymmetric. The asymmetric space charge distribution leads to the bending and crawling deformation. In the case of plasticized PVC, extreme asymmetric space charge distribution was observed that caused â&#x20AC;&#x153;amoeba-like pseudopodialâ&#x20AC;? deformation. In comparison with the case of PVC gel, if the reason of its excellent performance can be attributed to its cooperativity-induced colossal dielectric constant [1] in the low frequency range, PVA gel with DMSO will be better also, since PVA-DMSO gel can possess colossal dielectric nature. Because of the colossal dielectric constant, PVC gel have been revealed to possess very large Kerr effect and could have deflect light by applying dc electric field. In this presentation, we investigated what kind of electro-optical function can be observed on PVAgel. We found huge Pockets effect on PVA gel instead of Kerr effect. We would like to propose a concept of electrooptical gel from conventional textile polymers.

Keywords: poly(vinyl alcohol), poly(vinyl chloride), dimethyl sulphoxide, plasticizer, light deflection, actuator, electro-optical function, colossal dielectric electrorheology

constant, electroactive dielectric

materials,

1. Introduction Conventional polymers widely used in textile industries are fairly easily crystallized and provide enough strength as fibers and textiles. Most of these polymers are dielectric materials with low dielectric constant, and are known as electrically inactive. Some vinylidene polymers are exception, although the dialectic constants are still not very high compared to those of the ferroelectric inorganic materials. Therefore, the application of these conventional textile polymers is not considered to be adequate as electro-active materials. About thirty years ago, however, in the investigation of polymer gel actuator, we found poly(vinyl alcohol) (PVA) gel swollen with dimethyl sulphoxide (DMSO) can be actuated very efficiently by applying dc electric field.[2] Strain around 40% could be attained within a couple of tens of ms. Mechanism of the electrical deformation of the gel is explained based on the solvent drag in the gels. DMSO content of the gel is usually very high such as 98wt%, and is difficult to be stably held in the polymer matrix of PVA. In other words, DMSO is unable to be kept in the gel, is difficult from breeding out from the gel. The mechanism of the actuation has been proposed as solvent drag in the gel by an electric field and by the resulting asymmetric pressure distribution in the gel.[2] In the case of polyurethane (PU) and plasticizedpoly(vinyl chloride) (PVC), their excellent performance as an actuator has been revealed to be originated from asymmetric space charge distributions.[1] In the case of PVA-DMSO gel, although we have not investigated space charge distribution, the asymmetric pressure distribution has been considered to be the retarded +

Corresponding author. Tel.: + 81-268-24-4617. E-mail address: tohirai@shinshu-u.ac.jp, toshihirohirai@me.com 2 Present contact E-mail address: 3ES140175@s.kyushu-u.ac.jp

Page 317 of 1108

discharging on the cathode. Or in other words, an asymmetric space charge distribution in the PVA gel caused the bending actuation, too. These features have been published in several papers [3] and very recently it has been revealed the characteristic performances of PVA and PVC are resulted from colossal dielectric constant of them, particularly in the low frequency range such as less than 102 Hz. Particularly, the colossal dielectric constant appears in plasticized PVC as the results of extreme cooperative interaction between PVC and plasticizer. [1] Similar mechanism also works in PVA gels as will be presented in this paper. The characteristics can lead other novel functions to these conventional textile polymers, for instance, electro-optical functions that have never been expected on these polymers. In this paper, we will demonstrate that the PVA gel can induced light deflection by applying a dc electric field.

2. Experimental 2.1.

Materials

Gels are prepared using PVA purchased from Kuraray Co. DMSO and N-methyl pyrrolidone (NMP) are used as solvents, and are reagent grade purchased from Wako Chemical Inc. PVA-DMSO gels are prepared according to the procedure described elsewhere. [2] DMSO swollen PVA films were prepared by immersing PVA films in DMSO containing Petri dishes. For preparing PVANMP gels, PVA was heated and solubilized in NMP in prescribed Fig. 1: Preparation method of PVA-DMSO gels and PVA-NMP gels. weight ratio. PVA-NMP gels were prepared by cooling the NMP solutions. The cooling processes were carried out in transparent vessels in which the gels were prepared and the vessels were served as the cells for the measurement as they were.

2.2.

Measurements

Impedance analysis was carried out using Impedance analyser on PVA-DMSO gels and PVA-NMP gels. Measurements of electro-optical functions were carried out on PVA-NMP gels using the alignment illustrated in Fig. 3. Laser beam ďź&#x2C6;Îť =632.8nmďź&#x2030;was used. Polarizer was set before Fig. 2: Experimental set-up of electro-optical measurements. and after the cell, and the distance from cell to the screen wall is set 2m. Gel thickness or the distance between the electrodes was fixed at 8mm. Movement of laser spot was measured by applying a dc voltage between the electrodes.

3. Results and Discussion 3.1.

On the dielectric constant

The relationship between dielectric constant đ?&#x153;&#x20AC;đ?&#x153;&#x20AC;â&#x20AC;˛ and frequency are shown in Fig. 3. Frequency was ranged from 1Hz to 106Hz. PVC-DEA gels show far much larger values in the lower frequency range such as 10-6Hz to 10-1Hz. [3] Major difference among PVC-DEA gel, PVA-NMP, and PVA-DMSO gel is in the presence of cooperativity. Cooperativity and cooperativity-induced colossal dielectric constant have not been mentioned on these conventional materials. In the case of plasticized PVC, as an example in Fig.3 (a), PVC and DEA, both of them, shows low value of đ?&#x153;&#x20AC;đ?&#x153;&#x20AC;â&#x20AC;˛, but PVC-DEA gel shows far much 103 times larger value. [3] In the case of PVA-DMSO gel, it has excellent performance as electroactive actuator with huge and swift strain generation [2], although we had not carried out measurement of dielectric constant as we did not expect about the presence of cooperativity, in other words, we thought đ?&#x153;&#x20AC;đ?&#x153;&#x20AC;â&#x20AC;˛ value cannot exceed that of DMSO (around 40). However, as can be seen in Fig.3 (c), đ?&#x153;&#x20AC;đ?&#x153;&#x20AC;â&#x20AC;˛ shows a bit different feature. In the mid-range of frequency (from 103 Hz to 105 Hz), the value of đ?&#x153;&#x20AC;đ?&#x153;&#x20AC;â&#x20AC;˛ exceeds over 100 times larger that that of DMSO and 1000 times larger than that of PVA, and reaches 104 at 103 Hz. The tremendous enhancement of đ?&#x153;&#x20AC;đ?&#x153;&#x20AC;â&#x20AC;˛ can also explain the excellent

Page 318 of 1108

performance of PVA-DMSO gel as electroactive actuator, since electrically induced stress is proportional to the square of the applied electric field. ( ) We used to explain the phenomena according to the iondrag theory or charge-injection-solvent-drag theory. [2] However the solvent drag theory has difficulty in explaining the electrical actuation of plasticized PVC, since solvent migration is negligible in plasticized PVC. Enhancing đ?&#x153;&#x20AC;đ?&#x153;&#x20AC;â&#x20AC;˛ value by plasticizer or solvent co-existence can more consistently explain the both phenomena of PVC gel and PVA gel, and can be applied for other systems. PVA-DMSO gel is excellent material as actuator, but cannot hold DMSO stably in polymer matrix, and DMSO breeds out from gel body, particularly in the case of an electric field application. So we investigated the solvent, and employed NMP. The PVA-NMP gels are more stable, but show smaller deformation than PVA-DMSO gel. These characteristics are convenient for the observation of electro-optical function. Dielectric constant of PVA-NMP shows similar profile to PVA-DMSO gel as shown in Fig. 3 (b). value is about 10 times larger than that of DMSO at 103 Hz around. But value of the PVA gels cannot exceed that of solvent in the lower frequency range. In this sense, the values of PVA gels are solvent-limited, while that of PVC gel is cooperativity-controlled. (a)

(b)

(c)

Fig. 3: Dielectric constant of (a) plasticized PVC gel, (b) PVA-NMP gel, and (c) PVA-DMSO gel. (a) shows cooperative phenomenon between PVC and DEA, and the remarkable enhancement of was observed in low frequency range such as 1Hz. (b) and (c) also show cooperative phenomena in midrange such as 102-104 Hz in PVA-NMP gel and 103-105 Hz in PVA-DMSO gel. In (b) and (c), cannot exceed the value of of each solvent in low frequency range such as 1Hz. The cooperativity was extremely enhanced PVC-Plasticizer system.

3.2.

Electro-optical phenomena

In plasticized PVC or PVC gel, we investigated the presence of electro-optical function using a laser beam of nm, although the effect of colossal value of is observed at totally different range of frequency range of the light. The result was remarkable, and we observed a large Kerr effect-like light deflection about 30 times larger than nitrobenzene. [4] Although the mechanism has not been clarified yet, we expected the colossal value might have some relationship to the electro-optical function. PVA gels have much larger value than plasticized PVC gels does, so we expected the similar electrooptical phenomena in PVA gels. In Fig. 4, you can find remarkable laser beam deflection by PVA-NMP gel. Effect of position of incident light was also investigated and shown in Fig. 4. When the incident beam is near the cathode, the deflection of the modulated beam is the largest, the deflection of medium intensity was observed in the case of incident beam at the center of the cell, and the inverted deflection accompanying base line shifting to anode side was observed near the anode. These results in Fig. 4 revealed the presence of asymmetric refractive index gradient in the gel. Similar effect was also observed in plasticized PVC gels. Deflection distance from the home position of the laser spot was converted into angle and the relationship between angle ( ) and applied voltage (E) is plotted in Fig. 5.

Page 319 of 1108

Fig. 5: Electrically induced light deflection of PVA gel. Fig. 4: Electrically induced light deflection of PVA-NMP gel. Degree of deflection of modulated light (spot shift on the detection screen) strongly depends on the position of the incident light. Red plot 2 mm from cathode, Black plot is for the center (4mm from both electrode surfaces), and Blue plot for the 2mm from anode.

Dependence of equation below:

on the E is fitted by the

(1) For the comparison, the result on PVCDEA gel was shown in Fig. 6, and the curve fitted by the following equation;

(2) PVA-NMP gel in (1) is mostly linear function and PVC-DEA gel in (2) is just for the quadratic function.

Fig. 6: Electrically induced light deflection of PVC gel.

As the refractive index change (∆n) induced by the electric field can be described as follows, ∆n = aE + bE2, where a and b refer to Pockels effect and Kerr effect, respectively. [4] When the electrically induced modulation is small enough and refractive index change can be approximated proportional to θ. Then, we can say PVA-NMP gel has Pockels effect and PVC-DEA gel has Kerr effect in appearance. But we have to mention that the second order Kerr effect is about two times stronger in PVA-NMP gel compared to PVC-DEA gel. As the Pockels effect is far much stronger than Kerr effect PVA-NMP gel looks almost occupied by Pockels effect. Although detailed analysis necessary for more rigid confirmation of the phenomena, the event observed can provide new scope of the application of the gels, particularly for the conventional polymers.

4. References [1] M. Ali, T. Ueki, D. Tsurumi, T. Hirai, Influence of Plasticizer Content on the Transition of Electromechanical Behavior of PVC Gel Actuator. Langmuir 27, 7902-7908 (2011).

[2] T. Hirai, J. Zheng, M. Watanabe, H. Shirai, Electrically active polymer materials - application of non-ionic polymer gel and elastomers for artificial muscles. X. Tao, Ed., Smart Fibres, Fabrics and Clothing (2001), pp. 7-33.

[3] T. Hirai et al., in Electroactive Polymers: Advances in Materials and Devices, P. Vincenzini, S. Skaarup, Eds. (Trans Tech Publications Inc., Kreuzstrasse 10, 8635 Durnten-Zurich, Switzerland, 2013), Chapter 1: EAP Materials and Analysis of Physical Mechanisms, pp. 1-6. [4] H. Satou, T. Hirai, Electromechanical and electro-optical functions of plasticized PVC with colossal dielectric constant. SPIE Proceedings 8687, 868728-868721-868727 (2013). [5] W. Pyzuk, Polarizability of Rigid Rod Macromolecules with Dipolar Side Chains. A Nonlinear Dielectric Effect Study. Macromolecules 13, 153-157 (1980).

Page 320 of 1108

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

Viscosity and viscoelastic behaviour of high molecular weight polyacrylonitrile polymers 1

Jasjeet Kaur, 2Steve Agius and 1Keith Millington

CSIRO Manufacturing, 75 Pigdons Road, Waurn Ponds, VIC, 3216, Australia School of Engineering, Faculty of Science and Engineering and Built Environment, Deakin University, Waurn Ponds, VIC, 3216, Australia

Abstract: Rheology plays an important role in predicting the spinnability of the polymer solutions. A rheometer can provide information about the flow behaviour/viscometry and sol-gel transition/viscoelastic behaviour of polymer solutions, using a small amount of sample. Therefore some insight into how the polymer solution will behave during wet spinning can be obtained from rheology before actually spinning the solution. Keywords: Polyacrylonitrile (PAN), rheology, flow, viscoelastic, wet spinning

Introduction: Studying rheology prior to wet spinning of the polymer solutions can help to predict the spinning parameters that are required for production of a continuous fibre. Rheology provides information about the flow properties and sol-gel transition of the polymer solutions. These two processes form the two stages of the wet spinning process [1]. The first stage is to study how the polymer solution behaves when forced in one direction i.e. how it will flow through the spinneret. Here the viscosity of the polymer solution will play an important role, as it should not clog the spinneret holes, but the polymer content in the solution should be high enough to produce a highly crystalline fibre. The factors that determine the flow behaviour of the polymer solution in the wet spinning process are the temperature of the dope, the shear rate and polymer concentration [2]. The flow behaviour of the polymer solution can be studied as a function of these factors using a rheometer, before spinning the polymer solution. In the second stage of wet spinning, the polymer solution enters the coagulation bath kept at a controlled temperature and the polymer changes into the gel form [3]. This process is referred to as a sol-gel transition process. This process can be studied using a dynamic test in a rheometer. Sol/gel behaviour of the polymer solution in the coagulation bath will influence the diffusion behaviour of these solutions. The effect of temperature, relaxation time and linear viscoelastic region can be studied on the sol-gel behaviour of the polymer solutions. There are several factors that can influence the viscosity and viscoelastic behaviour of polymer solutions. These can be divided broadly as follows: the polymer characteristics, the temperature of the polymer dope, the shear force at which dope is extruded [4] and the type of solvent/non-solvent used. The polymer characteristics includes the polymer composition, sequence of co-monomer in the polymer chain, polymer structure [4], molecular weight, molecular weight distribution and presence of additives. The polymer structure includes variables such as tacticity, copolymerization and cross linking [1]. Hence rheology can help to achieve the characteristics of the polymer solution that will help produce a highly crystalline, defect-free and strong polyacrylonitrile (PAN) fibre that can be used as a precursor for carbon fibre.

Page 321 of 1108

Experimental: Materials: A polyacrylonitrile-based polymer was prepared in the laboratory via free radical polymerisation with high molecular weight (M w ) of >300,000 g/mol and polydispersity index (PDI) of 1.76. The acrylonitrile along with comonomers such as methyl acrylate and itaconic acid was added to a 7 litre reactor and then degassed using nitrogen and then vacuumed. The initiator AIBN (2, 2'-Azobisisobutyronitrile) was then added to the reaction mixture and then degassed again using nitrogen and then vacuumed. The reaction mixture was allowed to polymerise at 70oC for 3 hours.

Preparation of polymer solution: Various concentrations of PAN polymer solutions were prepared in dimethyl sulphoxide (DMSO), including 12 %, 14 % and 17 % in w/v ratio. The polymer was dissolved in DMSO using a shaker at 140 rpm and 58oC.

Rheological measurements: A Discovery HR3 hybrid rheometer was used for rheological measurements in the steady state and dynamic mode. A stainless steel sand-blasted 40 mm parallel plate geometry was used for the test. The sample was placed in between the two parallel plates. Low viscosity silicone oil was used to cover the sample from the sides to prevent evaporation of the solvent during the tests. The gap between the two plates used was 1000 Âľm. A new sample was used for each measurement. The system used in the tests was Peltier plate. In the steady state mode, viscosity was studied as a function of shear rate, and in the dynamic state the sol-gel transition was studied as a function of frequency.

Results and Discussion: 1) Effect of polymer concentration and temperature on flow behaviour of the polymer solution during first stage of wet spinning - To understand the effect of polymer concentration and temperature on flow behaviour, a flow test was performed. The shear rate chosen was 1/s. The viscosity of different polymer concentrations (12 %, 14 % and 17 % w/v) was measured at various different temperatures ranging from 25oC to 70oC. Figure 1 shows a plot of viscosity and polymer concentration. From the literature it has been reported that the spinnable viscosity of PAN polymer solution lies between 70-200 Pas. Therefore this plot determines that 17% PAN polymer concentration falls within the spinnable window for a temperature range of 25oC to 70oC, and is therefore spinnable. This also shows that 14 % PAN polymer concentration will be spinnable only at 25oC. It can also be seen from the plot that with increase in temperature the viscosity of the PAN polymer solutions decreases (Figure 1). Moreover the decrease in viscosity is higher at higher concentration (17%). This is because there are more polymer chains entangled at 17% PAN concentration. When the temperature increases these start to disentangle sooner and therefore disentangle in larger proportion. This leads to higher reduction in their viscosity when the temperature increases.

Figure 1: Graph shows viscosity at 1/s shear rate vs. polymer concentration for PAN solutions in DMSO

Page 322 of 1108

2) Effect of shear rate on flow behaviour of the polymer solutions during first stage of spinning - The effect of shear rate from 1 to 100/s can be seen on the flow behaviour of the polymer solutions in Figure 2.

Viscosity of 17% polymer conc.

250

25oC 40oC 50oC 60oC 70oC

200

150

100

0 1

100

Shear rate (1/s)

Figure 2: Graph of viscosity vs. shear rate for 17 % w/v PAN solution in DMSO

It can be seen that with increase in shear rate the viscosity of 17 % w/w polymer solution decreases. This depicts the shear thinning behaviour of the polymer solutions. From figure 2 it can be seen that beyond 10/s shear rate, the decrease in viscosity becomes independent of the polymer concentration. Moreover these polymer solutions show non-Newtonian behaviour i.e. the molecular chains become deformed on application of force and can show either an increase in viscosity (shear thickening) or a decrease in viscosity (shear thinning). In practice shear thinning behaviour is advantageous to the wet spinning process, and prevents clogging of the spinneret holes where shear stress increases.

3) Study of sol-gel transition using dynamic test to understand the second stage of wet spinning During the coagulation stage, the polymer solution changes into a gel at a certain temperature. Dynamic tests can help to determine the temperature that can drive this liquid to solid transition [5]. Figure 3 shows a

10000

1000

Crossover temperature at 10 Hz

100

Loss modulus (Pa)

Storage modulus (Pa)

10000

Storage modulus Loss modulus

1 0

Temperature (oC)

Figure 3: Graph of storage and loss modulus vs. temperature for 17 % PAN polymer solution at 10 Hz frequency and 1 % strain

Page 323 of 1108

plot of modulus against temperature for 17% w/v polymer solution. With the temperature decreasing from 60oC to 5oC, solid behaviour starts to dominate over liquid behaviour. The crossover point of the storage modulus and liquid modulus is seen at 30oC at 10 Hz frequency and 1 % strain. This behaviour explains why the coagulation bath needs to be kept at a lower temperature to induce gelation. This gelation is referred to as physical gelation that occurs due to aggregation of dipole-dipole interactions between the nitrile groups of the PAN chains [6] Strain of 1 % is chosen because the 17% polymer solution falls in the linear viscoelastic region at 1 % strain. This means that there is no change in the modulus with respect to the oscillation strain %. Moreover any change in the material properties at 1 % strain is due to the material itself and not due to the strain. This behaviour explains why the coagulation bath needs to be kept at a lower temperature to induce gelation. This gelation is referred to as physical gelation that occurs due to aggregation of dipole-dipole interactions between the nitrile groups of the PAN chains [6].

Conclusions: The flow behaviour and the sol-gel transition of PAN solutions during the wet spinning process can be determined by performing rheology tests. This improved understanding about the polymer solutions prior to spinning can prevent clogging of the spinneret holes and help to produce a high quality continuous fibre. From the flow tests, it can be concluded that 17 %w/v PAN solution falls within the spinnable range at temperatures ranging from 25oC to 70oC. Moreover this PAN-based polymer solution of MW 300,000 g/mol and polydispersity of 1.76 shows shear thinning behaviour. The dynamic tests showed that the coagulation bath temperature should be kept low, (< 30oC) in order to induce a sol-gel transition.

Acknowledgements: Authors acknowledge Jackie Y.Cai, Jill McDonnell, Lisa O’Brian and Colin Brackley who synthesised and provided polymers for this study.

References: [1] [2] [3]

[4] [5] [6]

M. Fujiyama and M. Kondou, "Effect of gelation on the flow processability of poly (vinyl chloride)," Journal of applied polymer science, vol. 90, pp. 1808-1824, 2003. L. Tan, A. Wan, and D. Pan, "Viscoelasticity of concentrated polyacrylonitrile solutions: effects of solution composition and temperature," Polymer International, vol. 60, pp. 1047-1052, 2011. W. Du, H. Chen, H. Xu, D. Pan, and N. Pan, "Viscoelastic behavior of polyacrylonitrile/dimethyl sulfoxide concentrated solution with water," Journal of Polymer Science Part B: Polymer Physics, vol. 47, pp. 1437-1442, 2009. R. Devasia, C. Nair, and K. Ninan, "Temperature and shear dependencies of rheology of poly (acrylonitrile‐co‐ itaconic acid) dope in DMF," Polymers for Advanced Technologies, vol. 19, pp. 1771-1778, 2008. L. Tan, S. Liu, and D. Pan, "Viscoelastic behavior of polyacrylonitrile/dimethyl sulfoxide concentrated solution during thermal-induced gelation," The Journal of Physical Chemistry B, vol. 113, pp. 603-609, 2008. M. Bercea, S. Morariu, and C.-E. Brunchi, "Rheological Investigation of Thermal-Induced Gelation of Polyacrylonitrile Solutions," International Journal of Thermophysics, vol. 30, pp. 1411-1422, 2009.

Page 324 of 1108

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

Stability of red rare earth luminous fiber emission spectra Yanan Zhu, Mingqiao Ge (School of Textile and Clothing, Jiangnan University, Wu Xi 214122 China)

Abstract: Rare earth strontium aluminate luminous fiber is a novel functional fiber. In order to investigate emission light color stability of rare earth luminous fiber containing red organic fluorescent pigment, several kinds of rare earth strontium aluminate luminous fibers were prepared by using rare-earth strontium aluminate as the rare-earth luminescent material and fiber-forming polymers such as polymer polyethylene terephthalate (PET) as a matrix and combining them with red organic fluorescent pigment and functional additives. Fluorescence spectrophotometer was used to characterize the resulting samples. Results showed that the shape and the peak of emission showed little change, but the emission intensity became weaker as the treatment time increased. Keywords: Rare earth luminous fiber, Red organic fluorescent pigment, Emission spectra, SrAl 2 O 4 :Eu2+, Dy3+

1. Introduction Rare earth luminous ﬁber is a novel functional fiber, which is made of rare-earth luminescent material and fiber-forming polymer as main raw materials and it was successfully attracted great research interest since being invented in 2004. The ﬁber has excellent luminescence intensity, a long afterglow time, and is free from harmful radiation [1-2]. It absorbs ultraviolet or the visible light for ten minutes, and then can emit light continually for more than ten hours after removal of excitation resource. It has a wide range of applications, because of its potential to play a vital role in various fields such as embroidery, plush toys, and so on for its excellent luminous properties [3-4]. Alkaline earth aluminates xMO⋅yAl 2 O 3 :Eu2+, RE3+ (M = Ca, Sr, Ba) are functional inorganic materials with strong luminescence at the blue/green regions [5-7]. They show high quantum efficiency, long afterglow life, and good chemical stability. Recently, great progresses have been made in aluminate rare earth luminescent materials due to its good water resistance and excellent chemical stability. Phosphor, which is the cure material, used in the luminous fiber is mainly SrAl 2 O 4 :Eu2+, Dy3+ currently [2,3]. The color of fiber’s emitting light is rather monotonous at present, which limits the development of rare earth strontium aluminate luminous fibers. It is well known that Rhodamine B is derivatives of the xanthene dyes class, which are among the oldest and most commonly used of all synthetic dyes that, of their applications were using in cloth and food coloring[8].The special photophysics properties of these types of molecules cause the vast and increasing up applications in chemistry and physics. And the luminous fiber that can emit red light in the darkness was fabricated through doping red organic fluorescent pigments (the core dye is Rhodamine B). This fiber would inevitably encounter various external conditions in the actual application process, such as air, light, temperature changes, moisture and so on, which are likely to affect its emission spectra, thereby affecting its emission light color. So its emission stability is an important characteristic. But the stability of red rare earth luminous fiber’s emission spectra is not known until now and it is not reported in other literatures. In order to investigate the stability of emission spectra of rare earth luminous fiber doping red organic fluorescent pigments. In this study, SrAl 2 O 4 :Eu2+, Dy3+ was prepared by means of solid-state reaction, and rare earth luminous fibers were prepared through melt spinning by mixing SrAl 2 O 4 :Eu2+, Dy3+ and PET chips together, and the emission spectra was tested.

2. Experimental

Page 325 of 1108

2.1 Materials SrCO 3 (AR), Al 2 O 3 (GR), Eu 2 O 3 (99.99%), Dy 2 O 3 (99.9%), H 3 BO 3 (AR) and organic fluorescent pigments were purchased from Sinopharm Chemical Reagent Co., Ltd China. Polyethylene terephthalate (PET) chips were purchased from Wu Xi Taiji Industry Co, Ltd. (Wuxi, China), and functional additives were supplied by Jiangsu Guoda Complete Wiring Equipment Co,Ltd.(Wuxi, China). The structure of basic organic fluorescent dye used in preparing organic fluorescent pigment was shown in Figure. 1.

Figure.1. Molecular structure of organic fluorescent dye

2.2 Preparation of SrAl 2 O 4 :Eu2+, Dy3+ SrAl 2 O 4 :Eu2+, Dy3+ was prepared by solid-state reaction by using SrCO 3 , Al 2 O 3 , H 3 BO 3 , Eu 2 O 3 and Dy 2 O 3 of analytical reagent (A.R) grade as the starting materials. Appropriate amounts of raw materials were mixed and dissolved in appropriate amounts of absolute ethanol, followed by ultrasonic dispersion for 30 min in order to get a homogeneous mixture. Then the hybrid was dried at 100 °C for 24 h, ground in planetary high-energy ball mill and heated to high temperature 1400 °C for 4 h under a reducing atmosphere, and then re-milled the sintered products and sieved to get the desired samples.

2.3 Preparation of PET-SrAl 2 O 4 :Eu2+, Dy3+- red organic fluorescent pigment PET chips were dried in an oven at 110 ºC for 24 h, and then mixed with a scheduled mass of rare-earth luminescent material functional addictives (dispersant) in a high-speed mixer. The mixtures were then extruded in a twin-screw master batch producer at 270-290 ºC to get master batches for spinning application. After being dried at 110 ºC, the master batches were melted and spun to obtain the luminous fiber, incorporating the strontium aluminate luminescent agent at 5 wt% and red organic fluorescent pigment at 0.5 wt%.

2.4 Characterization 2.4.1 Luminous properties The emission spectra of all the samples were measured at room temperature through using a fluorescence spectrophotometer (HITACHI 650-60, Japan) with a Xe flash lamp as an excitation source; the slit was 2.5 nm in width; the excitation wavelength was from 200 nm to 700 nm and the scan speed was 120 nm/min.

3. Results and discussion 3.1 Durability of PET-SrAl 2 O 4 :Eu2+, Dy3+- red organic fluorescent pigment

Intensity/a.u

0 month 3 month 6 month 9 month 12 month

450

500

550 600 Wavelength/nm

650

700

Figure.2 Emission spectra of luminous fiber placed at room temperature for different time

The emission spectra of PET-SrAl 2 O 4 :Eu2+, Dy3+- red organic fluorescent pigment samples are shown in Fig.2, which were placed at room temperature for 12 months, respectively, and the emission spectra of the samples were tested every three months. It is well known that the shape and the intensity of the emission spectra of PET-SrAl 2 O 4 :Eu2+, Dy3+- red organic

Page 326 of 1108

fluorescent pigment samples are due to the number of electrons, which belong to SrAl 2 O 4 :Eu2+, Dy3+ and red organic fluorescent pigment, that transit to the excited state and the energy level of this state. As we all know, when the SrAl 2 O 4 :Eu2+, Dy3+- red organic fluorescent pigment are irradiated in the same excitation light, then the number of electrons and the energy level of the excited state are the same. From Fig.2 it can be seen that luminous fibers were excited in the same condition and the emission spectra of samples were a broad band emission accompanied with the peaks around λ=520 nm and 580 nm , which is due to the 5d–4f transition of Eu2+ ions of SrAl 2 O 4 :Eu2+, Dy3+ and the characteristic emission of the red organic fluorescent pigments. All the samples had similar emission spectra with the strontium aluminate luminescent agent at 5 wt% and red organic fluorescent pigment at 0.5 wt%. Regardless of the change of the storage time, the position of the emission peak and the shape showed no change, indicating that the change of the storage time hardly influences the crystal structure of SAOED and the red organic fluorescent pigment. From the analysis above we obtained the conclusion that the emission properties were stable no matter how long it has been placed in the same atmosphere.

3.2 Light fastness of PET-SrAl 2 O 4 :Eu2+, Dy3+- red organic fluorescent pigment

Intensity/a.u

0小时 1小时 2小时 3小时 4小时 5小时

450

500

550 600 Wavelength/nm

650

700

Figure.3 Emission spectra of luminous fiber exposed to direct sunlight for different time

Light fastness has been to be a subject of great interest in textile industry since the fabrics are widely used in automobile colored upholstery and are exposed to direct sunlight and temperature above 50 oC. Figure.3 shows the emission spectra of PET-SrAl 2 O 4 :Eu2+, Dy3+- red organic fluorescent pigment samples that were exposed to direct sunlight and temperature at 50 oC for different time. From Figure.3, it can be seen that the emission spectra of rare earth luminous fiber containing red organic fluorescent pigment had a similar emission spectrum with each other under the same condition just different time. The shape and the peak of emission showed little change, but the emission intensity became weaker as the time exposed to direct sunlight and temperature at 50 oC increased. It was mainly related to the luminescence properties of SrAl 2 O 4 :Eu2+, Dy3+ and red organic fluorescent pigment. As is mentioned above, the luminescence of rare-earth luminescent material is generated by the transition of 4f electrons of rare-earth ion. When it was excited by the sunlight, the electrons transited between 4f and 5d shells. Therefore, the matrix lattice structure of SrAl 2 O 4 :Eu2+, Dy3+ were not changed, which ensured the luminescence properties of SrAl 2 O 4 :Eu2+, Dy3+.

3.3 Acid and alkali resistance of PET-SrAl 2 O 4 :Eu2+, Dy3+- red organic fluorescent pigment

Page 327 of 1108

450

500

550 600 Wavelength/nm

(1) acid treatment

650

0 min 0.5 min 1 min 3 min 5 min

Intensity/a.u

0 min 0.5 min 1 min 3 min 5 min

700

450

500

550 600 Wavelength/nm

650

700

(2) alkali treatment

Figure.4 Emission spectra of luminous fiber with acid-alkali treatment for different time Figure.4 shows the emission spectra of luminous fiber with acid and alkali treatment for different time. From Figure.4 it can be seen that the principle of emission spectra were similar with each other containing two emission peaks around 520 nm and 580 nm. However, the emission intensity was different from one another as the acid treatment time changed. The intensity of emission peak around 520 nm dropped and emission peak around 580 nm increased greatly at first and then decreased gradually when the treatment time was over 0.5 minute. We deemed that SrAl 2 O 4 :Eu2+, Dy3+ and red organic fluorescent pigment on the surface of the luminous fiber, and when luminous fiber was dipping in the acid-alkali solution, it would penetrate to the internal of the fluorescent pigment, which might influence the polarity of fluorescent pigment. And it will lead to more and more electrons transited between the ground state and the excited state of fluorescent pigment. But as the treatment time increased, the acid-alkali solution penetrating to the internal of the luminous fiber increased, which would cause the structure change of the pigment. SrAl 2 O 4 :Eu2+, Dy3+ will be hydrolysis when it faced with acid or alkali.

3.4 Washable performance of PET-SrAl 2 O 4 :Eu2+, Dy3+- red organic fluorescent pigment

Intensity/a.u

0h 1h 2h 3h

450

500

550 600 Wavelength/nm

650

700

Figure.5 Emission spectra of luminous fiber after being washing for different time

Emission spectra of luminous fiber after being washing for different time are shown in Figure.5. From Figure.5 it can be seen that the emission intensity of PET-SrAl 2 O 4 :Eu2+, Dy3+- red organic fluorescent pigment after being washed for more than one hour was lower than that of the luminous fiber without washing. And when it was washed for more than one hour, the luminous fibers have similar emission spectra with the same emission intensity and the same shape. It was deemed that there would be two reasons for this phenomenon. Firstly, one of the possible reasons could be ascribed to the fact that part of SrAl 2 O 4 :Eu2+, Dy3+ and red organic fluorescent pigment moved to the surface of the luminous fiber and easily affected by washing. When it was being washed, the particles would drop down, which caused the emission intensity decreased. Secondly, the particles inside the fiber were less affected by washing, which resulted in little change of the emission spectra as the washing time increased.

4. Conclusions

Page 328 of 1108

In order to investigate the emission property stability of PET-SrAl 2 O 4 :Eu2+, Dy3+- red organic fluorescent pigment. SrAl 2 O 4 :Eu2+, Dy3+ was prepared by means of solid-state reaction, and rare earth luminous fibers were prepared through melt spinning by mixing SrAl 2 O 4 :Eu2+, Dy3+, organic fluorescent pigments (Rhodamine B) and polymer polyethylene terephthalate (PET) chips together, and it was treated in different environments. The emission properties were studied through testing their emission spectra. The conclusions are summed up as follows: (1) The emission properties were stable no matter how long it has been placed in the same atmosphere. (2) The shape and the peak of emission showed little change, but the emission intensity became weaker as the time exposed to direct sunlight and temperature at 50 oC increased, and when the luminous fiber is exposed to the sunlight for more than 3 hours, its emission intensity and shape has little change. (3) The emission intensity of PET-SrAl 2 O 4 :Eu2+, Dy3+- red organic fluorescent pigment was obviously influenced by the acid-alkali solution. (4) Washing time had a certain effects on the emission intensity of PET-SrAl 2 O 4 :Eu2+, Dy3+- red organic fluorescent pigment. Even in the same washing conditions just with different washing time, the luminous fiber would possess emission spectral line with different intensity.

5. References: [1] YanhongYan ,Mingqiao Ge. Morphology and spectral characteristics of a luminous fiber containing a rare earth strontium aluminate . Text Res J 1819, 82 (2012). [2] Mingqiao Ge, Xuefeng Guo, Yanhong Yan. Preparation and study on the structure and properties of rare-earth luminescent fiber. Text Res J 677, 82 (2012). [3] Jishu Zhang, Mingqiao Ge. Effect of polymer matrix on the spectral characteristics of spectrum-fingerprint anti-counterfeiting fiber. J Text I 767, 9 (2011). [4] Xuefeng Guo, Mingqiao Ge, Jumei Zhao. Photochromic properties of rare-earth strontium aluminate luminescent fiber. Fiber Polym 875, 7(2011). [5] Wei Xie, Jun Quan, Haoyi Wu, Lexi Shao, Changwei Zou, Jun Zhang, Xiaoyu Shi, Yinhai Wang. Structure and luminescence properties of SrAl 2 O 4 :Eu2+, Dy3+ by Ba2+ and Ca2+ co-doping. J Alloy Compd 97, 514 (2012). [6] B.M. Mothudi , O.M. Ntwaeaborwa, J.R. Botha, H.C. Swart. Photoluminescence and phosphorescence properties of MAl2O4:Eu2+, Dy3+ (M=Ca, Ba, Sr) phosphors prepared at an initiating combustion temperature of 500 째C. Physica B: Condensed Matter 4440, 404(2009). [7] PingTing Ji, XiangYing Chen, Ye Qin Wu. Encapsulating MAl2O4:Eu2+, Dy3+ (M = Sr, Ca, Ba) phosphors with triethanolamine to enhance water resistance. Appl Surf Sci 1888, 258 (2011). [8] JahanbakhshGhasemi, AliNiazi, MikaelKubista. Thermodynamics study of the dimerization equilibria of rhodamine B and 6G in different ionic strengths by photometric titration and chemometrics method. Spectrochim Acta A 649, 62 (2005).

Page 329 of 1108

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

Structure and Properties of Fibers Manufactured from Liquid Crystalline Poly(2-cyano-1,4-phenylene terephthalamide)-based Copolymers Seong Jun Yu, Doo Hyun Baik and Young Gyu Jeong + Department of Advanced Organic Materials and Textile System Engineering Chungnam National University, Daejeon 34134, Republic of Korea

Abstract. Poly(2-cyano-1,4-phenylene terephthalamide) (cyPPTA) and its copolymers with different hydroquinone (HQ) contents of 2-10 mol% were synthesized by using phosphorylation-based polycondensation reaction and their fibers were manufactured by a wet-spinning technique. The intrinsic viscosities of the cyPPTA-based copolymers synthesized in NMP/CaCl 2 was found to be much higher than those of the materials synthesized in DMAc/LiCl. For the fibers manufactured from the liquid crystalline solution dopes of NMR/CaCl 2 , the thermal stability and tensile mechanical properties decreased with the increase of the HQ content in the cyPPTA-based copolymers. Keywords: cyPPTA, liquid crystalline, phosphorylation, thermal property, mechanical property.

1. Introduction Poly(p-phenylene terephthalamide) (PPTA) fibers are well known as typical super fibers because of their excellent thermal stability, mechanical modulus, and chemical resistance. Since PPTA is soluble dominantly in strong acids or in highly polar solvents with inorganic salt, a variety of modified PPTA-based fibers have been investigated by introducing functional side groups and/or comonomer units on the chain backbone to improve their processability using less harmful organic solvents. In the reactions of synthesizing PPTA and its modified polymers, terephthaloyl chloride (TPC) and p-phenylene diamine (PPD) have been chosen as two main monomers. On the other hand, phosphorylation reaction has been considered as an alternative way to synthesize aromatic polyamides by adopting terephthalic acid (TPA) monomer instead of TPC. The usage of TPA monomer has several advantages such as less susceptibility to moisture and cost-effectiveness. In this study, we synthesized poly(2-cyano-1,4-phenylene terephthalamide) (cyPPTA) and its copolymers containing different hydroquinone (HQ) contents via phosphorylation-based polycondensation and manufactured fibers using these synthetic polymer. The molecular structures, thermal and mechanical properties of the fibers were investigated as a function of the HQ content.

2. Experimental 2.1.

Materials and synthesis

2-cyano-1,4-phenylenediamine (cyPPD, Miwon co.), terephthalic acid (TPA, Aldrich Com.), and hydroquinone (HQ, Aldrich Com.) were used as monomers for synthesizing cyPPTA and its copolymers containing different HQ contents. Triphenyl phosphite (TPP, Aldrich Com.) and pyridine (Py, Aldrich Com.) were adopted as catalysts for the phosphorylation-based polycondensation. N-methyl-2-pyrrolidone (NMP, Samchun Com.)/anhydrous calcium chloride (CaCl 2 , Samchun Com.) and dimethylacetamide (DMAc, Samchun Com.)/lithium chloride (LiCl, Samchun Com.) were used as polar organic solvent systems for the polymerization. cyPPTA and its copolymers were synthesized by a phosphorylation-assisted polymerization, as shown schematically in Fig. 1. TPP and Py catalysts were added into NMP/CaCl 2 or DMAc/LiCl solvent system, and TPA, cyPPD and HQ monomers were then added. Phosphorylation-based polycondensation reaction was then +

Corresponding author. Tel.: + 82-42-821-6617. E-mail address: ygjeong@cnu.ac.kr.

Page 330 of 1108

carried out at 100 °C. After the polymerization, the reaction products were washed with acetone and distilled water to remove the residual solvent.

Fig. 1: Synthesis scheme for cyPPTA and its copolymers with different hydroquinone moiety contents.

2.2.

Fabrication and characterization of fibers

The cyPPTA and its copolymer fibers were manufactured by a wet-spinning process. For the purpose, the NMP/CaCl 2 –based solution dopes including cyPPTA and its copolymers were manufactured and they were spun into a coagulation bathe at a speed of 1 ml/min. The thermal degradation properties of cyPPTA and its copolymer fibers were investigated by a thermogravimetric analyser (TGA-N-1000, Scinco) under N 2 condition at a heating rate of 10 °C/min. Using Ubbelohde viscometer, their intrinsic viscosity was confirmed. The crystalline structures of the solution dopes and associated fibers were characterized by using a polarized optical microscope (S38, Bimience). The tensile mechanical properties of the fibers were examined by using a universal tensile machine (Instron 4467) at room temperature at an extension rate of 8 mm/min.

3. Results and discussion The synthesis conditions and resulting intrinsic viscosity of cyPPTA and its polymers at different organic solvent systems of NMP/CaCl 2 and DMAc/LiCl are summarized in Table 1. It was found that intrinsic viscosities of the polymers synthesized in NMP/CaCl 2 were much higher than those of materials polymerized in DMAc/LiCl. It demonstrates that NMP/CaCl 2 solvent system make cyPPTA polymers higher degree of polymerization during the phosphorylation-based reaction. In addition, for the copolymers with higher HQ comonomer content, the intrinsic viscosity was lower, which might be caused by the fact that the HQ component in the copolymer backbone contributes to diminish the hydrogen bonding between cyPPTA chains and to endow cyPPTA with the chain flexibility. Table 1: Synthesis condition and intrinsic viscosity of cyPPTA and its copolymers Synthesis condition Sample code

cyPPD (mmol)

HQ (mmol)

TPA (mmol)

TPP (mmol)

Pyridine (mmol)

cyPPTA-100 cyPPTA-98 cyPPTA-96 cyPPTA-94 cyPPTA-92 cyPPTA-90

25.0 24.5 24.0 23.5 23.0 22.5

0.0 0.5 1.0 1.5 2.0 2.5

25.0 25.0 25.0 25.0 25.0 25.0

50.0 50.0 50.0 50.0 50.0 50.0

72.0 72.0 72.0 72.0 72.0 72.0

Intrinsic viscosity NMP or DMAc (ml) 51.4 51.4 51.4 51.4 51.4 51.4

LiCl or CaCl 2 (mmol) 36.0 36.0 36.0 36.0 36.0 36.0

NMP/ CaCl 2

DMAc/ LiCl

3.6 3.1 2.7 2.6 2.1 1.9

2.7 2.2 1.4 1.3 0.4 0.1

Fig. 1 shows POM images of NMP/CaCl 2 solutions containing different cyPPTA and its copolymers concentrations. For cyPPTA-100, cyPPTA-98, and cyPPTA-96 exhibited liquid crystalline structure at 10 wt% polymer concentration. On the other hand, with increasing the HQ comonomer contents in the copolymers, the liquid crystalline morphology was observed at higher polymer concentrations in NMP/CaCl 2 solutions. The TGA thermograms of the cyPPTA and its copolymer fibers are presented in Fig. 2. The thermal decomposition temperature as well as char yield at 800 °C was found to decrease with the increase of HQ

Page 331 of 1108

contents in the cyPPTA-based copolymers. In addition, the tensile strength and strain to break the fibers decreased with the increase of the HQ comonomer, which might be caused by the decreased hydrogen bonding as well as lower degree of polymerization of the cyPPTA-based copolymers.

Fig. 1: POM images of NMP/CaCl 2 solutions containing various polymer concentrations.

100

Weight (% )

cyPPTA-100 cyPPTA-98 cyPPTA-96 cyPPTA-94 cyPPTA-92 cyPPTA-90

0 0

200

400

600

800

Temperature ( C)

Fig. 2: TGA thermograms of the fibers manufactured from cyPPTA and its copolymers by a wet-spinning process.

4. References [1] S. J.Yu, D. H. Baik, and Y. G. Jeong, Fiber. Polym., 2014, 15, 2447. [2] F. Higashi, S.-I. Ogata, and Y. Aoki, J. Polym. Sci. Pol. Chem., 1982, 20, 2081.

Page 332 of 1108

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

Studies on Tensile and Flexural Properties of Hemp/PBTG Biocomposites Young Shin Park and Chang Whan Joo + Department of Advanced Organic Material and Textile System Engineering, Chungnam National University, Daejeon, 305-764, Korea

Abstract. In this study, poly(butylene terephthalate-co-glutarate) (PBTG) of aliphatic-aromatic polyesters was used as matrix to fabricate Hemp/PBTG composites by the compression molding method with different volume fraction of hemp fibers and PBTG resins. We have investigated the tensile and flexural properties of the fabricated composites by experimental and theoretical procedures. For the prediction of mechanical properties of the Hemp/PBTG composites, the well-known Tsai-Pagano model and the modified shear-lag model have been considered to predict the tensile modulus and flexural modulus of the Hemp/PBTG composites. Meanwhile, the morphological structure and chemical structure of the composites were observed by SEM and ATR. Interfacial shear strength, tensile properties and flexural properties were measured by universal testing machine. Keywords: aliphatic-aromatic polyester, PBTG, hemp fibers, biocomposites

1. Introduction Petrochemical-based polymers have been used in industrial fields due to various advantages such as high functionality, low density, good durability and easy processability, but they have problems for the resource exhaustion and environment pollution by the incineration and landfill.[1,2] The polymers keeping the degradable properties have attracted attention as a way to solve the problems of petrochemical-based polymers. Well-known degradable polymers are poly(lactic acid) (PLA) and poly(capro lactone) (PCL), and which has been applied in the medical fields as scaffold, drug delivery system and suture, because their biodegradability and biocompatibility are excellent.[3-5] However, PLA and PCL are hard to replace petrochemical-based polymers due to low mechanical properties and high production costs. Alternatively, aliphatic-aromatic polyesters, i.e., poly(butylene adipate-co-terephthalate) (PBAT), was proposed and have similar degradability and degradation rate without the toxic substance by comparison with PLA.[6] Aliphatic polyesters were developed with several improving ways through polymerization and functionalization to supplement disadvantages of vegetable-based polymers. Among the improving ways, poly(butylene adipate-co-terephtalate) (PBAT) was synthesized as enhanced degradable polymer including physical and thermal properties[7]. Witt[8] worked degradable tests of PBAT films in composting conditions, and assessed that there was no toxic emission. Also, Weng[9] studied degradation properties of PLA and PBAT films under the soil, and reported that both polymers showed similar degradability and degradation rate. However, the researches of aliphatic-aromatic polyesters are in initial step yet, and are lacked of related literatures more than others degradable polymers. Thus, Multi-Modal studies about various aliphatic-aromatic polyesters are demanded to promote replacement of vegetable or petrochemical polymers. In addition, degradable polymers are applied to make biocomposites for enhancing mechanical properties by adding the vegetable fibers having many advantages such as low density, high strength and biodegradability[10]. Especially, hemp fibers are suitable for reinforcement of composites due to high tensile strength and water resistance, and cost-effective owing to rapid growth. Hu [11] prepared composites by stacking PLA films and hemp fibers, and tensile strength and tensile modulus of composites at the 40% of fiber volume fraction were improved as 1.5 times and 2.4 times compared to PLA films, respectively. Also, Yu[12] fabricated PLA/ramie +

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

Page 333 of 1108

composites using the hot press, and investigated impacts of adding PBTG on properties of composites. Tensile strength and flexural strength of PLA resins were enhanced as 1.4 times by the addition of ramie fibers. On the other hand, matrix of biocomposites reinforced by hemp fibers was used as PLA resins, and researches of aliphatic-aromatic polyesters for biocomposites were still not enough and there is a lack of the study of degradable composites composed of aliphatic-aromatic polyesters and natural fibers. The purpose of this study was to fabricate Hemp/PBTG composites with poly(butylene terephthalate-coglutarate) (PBTG) as matrix to design degradable composites. And their tensile properties and flexural properties with different fiber volume fraction were investigated using the theoretical predictions and the experimental measurements.

2. Experiment 2.1. Materials This study used Poly(butylene terephthalate-co-glutarate)(PBTG) and hemp fibers as matrix and reinforcement, respectively. PBTG resins are copolymer of poly(butylene terephthalate)(PBT) and glutaric acid(GA), and were supplied from Huvis Co. in Korea. Intrinsic viscosity(IV) and weight-average molecular weight(M w ) of PBTG resins were 0.85ă&#x17D;&#x2014;/g and 24,000, and density was 1.12g/ă&#x17D;¤. Hemp fibers were cultivated from China, and fiber length was cut as 10ă&#x17D;&#x153;. For the surface modification, hemp fibers were immersed in NaOH 5wt% solution for 4 hours, and hemi-cellulose and lignin in cellulose fibers were removed. After the NaOH treatment, hemp fibers were washed few times, and then were dried in vacuum oven at 80â&#x201E;&#x192; for 24 hours.

2.2. Sample preparation Hemp webs were fabricated using the wet-lay method, and then were dried in vacuum oven at 60â&#x201E;&#x192; for 48 hours. PBTG resins were melt to make films by the hot-press machine after milling resins, and the used temperature, pressure and time were 210â&#x201E;&#x192;, 10ă&#x17D;Ť and 1min, respectively. And then Hemp webs and PBTG films were stacked in metal mold of 180x180x3ă&#x17D;Ł and were compressed using the process condition.

2.3. Characterization Surface structure of hemp fibers and fractured cross sectional structure of composites were observed by scanning electron microscopy (JSM-7000F, JEOL, Japan), and effect of alkali treatment on hemp fibers was measured by the ATR-IR(ALPHA-P, Bruker Optic GmgH, Germany). Interfacial strength between hemps fibers and PBTG resins were evaluated using the micro droplet method by universal testing machine (Instron 4467, Instron, USA), and interfacial shear strength and critical fiber length were calculated by the equations(2.1) and (2.2). Ď&#x201E;=

đ?&#x2018;&#x192;đ?&#x2018;&#x192;đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;?đ?&#x2018;? đ?&#x153;&#x2039;đ?&#x153;&#x2039;đ?&#x153;&#x2039;đ?&#x153;&#x2039;đ?&#x153;&#x2039;đ?&#x153;&#x2039;

(2.1)

đ?&#x153;&#x17D;đ?&#x153;&#x17D;đ?&#x2018;&#x201C;đ?&#x2018;&#x201C;

đ?&#x2018;&#x2122;đ?&#x2018;&#x2122;đ?&#x2018;?đ?&#x2018;? = 2đ?&#x153;?đ?&#x153;? đ??ˇđ??ˇ (2.2) Where, P pull is pull-out load, D and L are diameter and embedded length of fibers. Tensile and flexural properties of composites were measured by universal testing machine (Instron 4467, Instron, USA) according to ASTM D638 and D790, respectively.

3. Results and Discussion 3.1. Chemical structure and interfacial strength by alkali treatment Chemical structure of cellulose fibers consist of crystal cellulose, amorphous hemicellulose, and lignin. The composition change of hemp fiber by alkali treatment is shown in Figure 1. Depending on alkali treatment, Chemical structure was changed and it was observed at 1250, 1440, 1630, 1730, and 2910cm-1. At 1250 and 1440cm-1, absorption peak mean stretching vibration of C-O and bending vibration of CH 2 in lignin. At 1730 and 2910cm-1, absorption peak indicate stretching vibration of C=O and C-H in hemicellulose. Therefore, these results confirm that lignin and hemicellulose in hemp fiber was removed according to alkali treatment. As shown in Figure 2, the graph of interfacial strength of hemp fiber and PBTG resin were observed. The

Page 334 of 1108

interfacial shear strength of non-treated hemp fiber is 6.07㎫, and critical fiber length is 1.57㎜. After Alkali treatment, interfacial shear strength increased to 11.21㎫ and critical fiber length decreased to 1.12㎜. Thus, according to alkali treatment, shear strength of hemp fiber and PBTG were improved by increasing surface friction and decreasing hydrophilic contents.

1630

Interfacial shear strength(MPa)

2910

1250 1440

1730

4000

3500

3000

2500

2000

1500

1000

500

Wavenumber(cm-1)

20 Interfecial shear strength Critical fiber length 15

Untreatment

Critical fiber length(mm)

Absorbance

Untreatment Treatment

Treatment

Fig. 1: Chemical structure of hemp fibers by alkali treatment. Fig. 2: Interfacial shear strength and critical fiber length of hemp fibers by alkali treatment.

3.2. Tensile properties Figure 3 is results of the tensile strength and modulus of hemp/PBTG composites with different fiber volume fraction. In Figure 3 (a) and (b), the predict value of tensile strength and modulus were represented with linear function and it was proportional to volume fraction of fibers. Tensile strength of the composite showed similar to the predicted values from theoretical equations of Piggott and Nairn at below the fiber volume fraction 0.2, and tensile strength was lower than predicted values at the above 0.3. Meanwhile, tensile modulus of composite was increased in proportion to volume fraction of fibers, and it cannot reach the predicted modulus excepting Halpin-Tsai and Tsai-Pagano equation. The difference between the predicted and measured value in tensile strength of composites was appeared since an effect of increases of contact point on penetration of resins at high volume fraction, and load transfer was decreased by the reduction of distance between fibers and non-uniform distribution of fibers. However, tensile modulus was affected by increasing strain from the yield point of thermoplastic. 10 Rule of mixture Rule of mixture(Piggott) Shear-lag(Nairn) Experiment

150

Tensile modulus(GPa)

Tensile strength(MPa)

200

100

0.1

0.2

0.3

0.4

Rule of mixuture Halpin-Tsai Tsai-Pagano Shear-lag(Piggott) Shear-lag(Nairn) Shear-lag(Mendel) Experiment

0.1

0.2

0.3

0.4

Fiber volume fraction Fiber volume fraction (a) Tensile strength (b) Tensile modulus Fig. 3: Tensile strength and modulus of hemp/PBTG composites with different fiber volume fraction.

3.3. Flexural property The flexural strength and flexural modulus of hemp/PBTG composite is shown in Figure 4. Flexural strength of composites was enhanced by hemp fibers as maximum 1.5 times at volume fraction 0.2. The difference of flexural modulus was enhanced as increasing fiber volume fraction. The flexural modulus of composite is results of 3-dimension analysis about vertical load since effect of 2-dimensional structure enhanced hemp fibers is lower than tensile modulus. We confirmed that optimum fiber volume fraction was 0.2 from the results of flexural strength and flexural modulus.

Page 335 of 1108

3.5

Flexural modulus(GPa)

Flexural strength(MPa)

Shear-lag(Shibata) Experiment

2.5

1.5

1 0

0.1

0.2

0.3

Fiber volume fraction

0.4

0.1

0.2

0.3

0.4

Fiber volume fraction

(a) Flexural strength (b) Flexural modulus Fig. 4: Flexural strength and modulus of hemp/PBTG composites with different fiber volume fraction

4. Conclusion The biocomposites were fabricated by consisting hemp and PBTG films and their tensile properties and flexural properties with different fiber volume fraction were evaluated and Hemp fibers were prepared by alkali treatment and results are below. 1. Lignin and hemi cellulose of hemp fibers was removed by the alkali treatment, and interfacial shear strength between hemp fibers and PBTG resin was improved from 6.07㎫ to 11.21㎫ as 1.8 times due to the removal of hydrophilic element and the increase in surface friction. 2. At below the fiber volume fraction 0.2, tensile properties showed similar to the predicted values, and tensile strength showed high contribution of fiber distribution more than tensile modulus. 3. In the fiber volume fraction 0.2, tensile strength and flexural strength of composites were enhanced as 2.6 times and 1.5 times, and showed greatest values. Consequently, theoretical predictions and experimental results showed the conformity at the below fiber volume fraction 0.2, and we confirmed that optimum fiber volume fraction was 0.2 from the results of tensile strength and flexural strength.

5. Reference [1] A. A. Shah, F. Hasan, A. Hameed and S. Ahmed, “Biological Degradation of Plastic: A Comprehensive Review”, Biotechnology Advances, 2008, 26, 246-265. [2] B. Parrish, R. B. Breitenkamp and T. Emrick, “PEG- and Peptide-Grafted Aliphatic Polyesters by Click Chemistry”, Journal of the American Chemical Society, 2005, 127(20), 7404-7410. [3] H. J. Sung, C. Meredith, C. Johnson and Z. S. Galis, “The Effect of Scaffold Degradation Rate on Three dimensional Cell Growth and Angiogenesis”, Biomaterials, 2004, 25, 5735-5742. [4] M. Sun, P. J. Kingham A. J. Reid, S. J. Armstrong, G. Terenghi and S. Downes, “In Vitro and In Vivo Testing of Novel Ultrathin PCL and PCL/PLA Blend Films as Peripheral Nerve Conduit”, Journal of Biomedical Materials Research Part A, 2010, 93A(4), 1470-1481. [5] D. Cohn and A. H. Salomon, “Designing Biodegradable Multi block PCL/PLA Thermoplastic Elastomers”, Biomaterials, 2005, 26, 2297-2305. [6] R. Herrera, L. Franco, A. Rodriguez-Galan and J. Puiccali, “Characterization and Degradation Behavior of Poly(butylene adipateco-terephthalate)s”, Journal of Polymer Science: Part A, 2002, 40, 4141-4157. [7] U. Witt, T. Eining, M. Tamato, I. Kleeberg, W. D. Decker and R. J. Muller, “Biodegrdation of Aliphactic-aromatic Copolyesters: Evaluation of the Finer Biodegradability and Ecotoxicological Impact of Degradation Intermediates”, Chemosphere, 2001, 44, 289299. [8] Y. X. Weng, W. J. Jin, Q. Y. Meng, L. Wang and Y. Z. Wang, “Biodegradation Behavior of Poly(butylene adipate-co-terephthalate) (PBAT), Poly(lactic acid) (PLA), and Their Blend under Soil Conditions”, Polymer Testing, 2013, 32(5), 918-826. [9] T. Sen and H. N. Jagannatha Reddy, “Various Industrial Applications of Hemp, Kinaf, Flax and Ramie Natural Fibers”, International Journal of Innovation, Management and Technology, 2011, 2(3), 192-198. [10] R. Hu and J. K. Lim, “Fabrication and Mechanical Properties of Completely Biodegradable Hemp Fiber Reinforced Polylactic Acid Composites”, Journal of Composite Materials, 2007, 41(13), 1655-1669. [11] R. Masirek, Z. Kulinski, D. Chionna, E. Piorkowska and M. Pracella, “Composites of Poly(L-lactide) with Hemp Fibers: Morphology and Thermal and Mechanical Properties”, Journal of Applied Polymer Science, 2007, 105, 255-268.

Page 336 of 1108

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

Study on solid erosion properties of fiber-reinforced thermoplastics with high heat-resistant properties Bing Liu1 and Limin Bao1,* 1

Faculty of Textile Science and Technology, Shinshu University,3-15-1 Tokida, Ueda, Nagano 3868567,Japan

Abstract: Solid erosion properties of fiber-reinforced thermoplastics (FRTPs) made from two different kinds fibers and resins were investigated using angular alumina abrasives at a constant impact velocity but varying impact angles. According to some references, the theoretical equation was also obtained in this paper. The comparison results between experimental results and theoretical results showed obtained equation can characterize erosion properties of ductile materials well. Keywords: solid erosion property, FRTP, theoretical equation

1. Introduction Recently, fiber reinforced composite materials based on high performance thermoplastics, such as polyphenylene sulfide (PPS), polyether-etherketone (PEEK) have been investigated by lots of researchers due to better mechanical properties, high heat resistant properties and recyclable property [1]. Fiber reinforced composite materials have been applied in aircraft construction because it can decrease the weight of these vehicles, which can increase the effective utilization ratio of fuel. In many aircraft application, these materials encounter wear and damage process because lots of solid particles contain in the air. Similarly, if the surface of these materials was hit by particles for a long time, the temperature will increase sharply. Hence, a study on the erosion behavior of such composite materials with high heat-resistant properties is important [2]. There are lots of researches related with solid particle erosive wear property of fiber reinforced thermoplastics [3,4], however, a lot is just reported on the erosion rate of prepared composite materials but not much on erosion mechanism of these materials. Erosion behavior of materials takes long time for us to get wear rate at different impact angles, so how to evaluate wear rate of different composite materials effectively at all impact angles become very important. In this paper, the surface of damaged samples was observed under the help of SEM and on the basis of previous research, the theoretical equation was assumed. Erosion behavior of FRTPs based on two different kinds fibers and resins were investigated and obtained experimental results were compared with theoretical results. The comparison results showed obtained equation can characterize erosion properties of ductile materials well.

2. Experimental 2.1.

Materials

The PBO fabric with a plain weave used for reinforcement in this paper was Zylon速 High Modulus (HM), purchased from Toyobo Co., Japan. The Aramid fabric with a plain weave was Technora速, purchased from Teijin Co., Japan. Two kinds of the thermoplastic resins were used in this paper. One is crystalline co-polyester (PET) obtained from Toyobo Co. The other is polyetherimide (PEI) was purchased from Sigma-Aldrich, USA. The required solvent was N-Methyl-2-pyrrolidone (NMP) for both PET and PEI. It was obtained from the Kanto Chemical Corresponding author. Tel.: +81-0268-21-5423 E-mail address: baolimin@shinshu-u.ac.jp.

Page 337 of 1108

Co., Japan.

2.2.

Composites manufacturing

Firstly PET and PEI were dissolved in NMP using a hot-plate magnetic stirrer (Coring PC-420D) at the same weight percentage (20 wt%). A hand lay-up impregnation method was used for pre-impregnation of the reinforcing fabric with the matrix solution. Then the fabric with resin solution was put into a vacuum oven after hand lay-up pre-impregnation. The surface of attained prepreg sheets was uneven after the temperature decrease to ambient temperature. Surface smoothness was conducive to the next preparation of composite materials, so they were thermal treated by using hot-press machine (table-type test press, SA-302, Tester Sangyo Co.), which also could press out excess resin. The hot press temperatures were 200°C and 290°C respectively for PET and PEI with the same pressure that was 0.12MPa. Lastly, the prepreg sheets were cut into a certain size to make them accord with metallic mold. Then to acquire composites, the metallic mold was pressed under the temperature of the same as the preparation of prepreg sheets, but the hot press pressure and time became 3.74MPa and 30min.

2.3.

Erosion experiment

A schematic diagram of erosion testing system is present in Fig. 1. The sample was fixed on the metal stage. Solid particles were held in a hopper, and fed into the air stream by a micro-feeder that can keep the constant feed rate. The velocity of compressed air, which was created by an air compressor was controlled by adjusting the inlet pressure of the gun nozzle.

Fig. 1 Schematic diagram of experimental apparatus

The distance between the air gun nozzle and sample was 40mm, the impact time was determined as 30min, impact velocity of particle in this experiment was 127.4m/s. Weight loss of before and after the erosion testing were measured by a precision balance, in order to evaluate the erosion damage of the prepared materials.

3. Theoretical equation assumption Based on the other papers [5], the erosion behavior around α=20º is an important impact angle to ductile material when assume the theoretical equation, hence, α=20º was determined as a dividing line to discuss. Step 1: α≤20° Vp Sinα (the vertical component of velocity) almost has no effect on the materials, because just caused the elastic deformation; When Vp Cosα (the horizontal component of velocity) left from the surface of composite materials, the speed was not zero. In order to make the calculation simple, the residual velocity was assumed as V（α）=√(α/20) Vp Cosα. Step 2: 20°<α≤90° According to normal observation of damaged samples’ surface, hairiness became more with the increase of impact angle. So we guessed that the erosion behavior was related with Sinα. Hence, α DVp2Cos α2 20 Evp 2 sin α2 +D’vp 2 Sinα Cos α2

Ec = Ec =

α≤20° 20° < � ≤ 90°

A theoretical curve can be obtained according to the above equation, the comparison between theoretical

Page 338 of 1108

results and experimental results were shown in Fig. 2. As observed in Fig. 2, we can confirm that obtained equation can characterize erosion properties of ductile materials well.

Fig. 2 The comparison between theoretical value and experimental value

4. Results Erosion behavior of fiber reinforced thermoplastics was affected by impact angles. The theoretical equation obtained in this paper can characterize erosion properties of ductile materials well. Similarly, if the experimental conditions are very different from the experimental conditions in this paper, it is necessary to pay attention when using it.

5. Reference [1] M. Sharma, J. Bijwe, et al, Exploring potential of micro-raman spectroscopy for correlating graphitic distortion in carbon fibers with stresses in erosive wear studies of PEEK composites, wear, 270, 791-799, 2011. [2] R. Rattan and J. Bijwe, Influence of impingement angle on solid particle erosion of carbon fabric reinforced polyetherimide composite, wear, 262, 568-574, 2007. [3] A.P. Harsha and A.A. Thakre, Investigation on solid particle erosion behavior of polyetherimide and its composites, wear, 262, 807-818, 2007. [4] U.S. Tewari, A.P. Harsha, et al, Solid particle erosion of unidirectional carbon fiber reinforced polyetheretherketone composites, wear, 252, 992-1000, 2002. [5] J.G.A. Bitter. A study of erosion phenomena Part 2, 6, 169-190,1963.

Page 339 of 1108

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

Synthesis and Characterization of Poly (L-lactide) – Poly (εcaprolactone) Segmented Block Copolymers Choong Hee Hong, Dae Gil Eom, Jae Ho Min, Chan Sol Kang, and Doo Hyun Baik* Department of Advanced Organic Materials and Textile System Engineering, Chungnam National University, Korea *dhbaik@cnu.ac.kr

Abstract. A series of poly (L-lactide) – poly (ε-caprolactone) segmented block copolymers were synthesized

via three-step polymerizatiom procedures. Firstly, ε-caprolactone was ring opened by polytetramethylene ether glycol (PTMEG) with stannous octoate. The synthesized HO-PCL-PTMEG-OH was ‘B’ block of segmented block copolymers. Secondly, using this ‘B’ block, L-lactide - ‘B’ block - L-lactide (‘ABA’ type) of PLA triblock copolymer was synthesized. Thirdly, the obtained ABA triblock copolymer was reacted with diisocyanate. Consequently, the segmented block copolymers synthesized and characterized using fouriertransform infrared (FT-IR) spectroscopy, differential scanning calorimetry (DSC), and nuclear magnetic resonance(1H NMR).

Keywords: PLA, PCL, PTMEG, segmented block copolymer, diisocyanate

1. Introduction Poly (L-lactide) (PLA) is an eco-friendly material and its raw material, L-lactic acid, is produced by crops such as corn and beets. PLA is a biodegradable aliphatic polyester derived from renewable resources that has gained much interest in recent years. PLA is a thermoplastic polymer, having high tensile strength and excellent elastic modulus compared to poly(ethylene terephtalate)[1]. But PLA is a brittle material with low elongation at break and impact strength, unsuitable for applications requiring mechanical toughness[2]. This weakness might be improved by blending or copolymerization of PLA with lower glass transition temperature polymers, such as poly(ε-caprolactone)(PCL) and polytetramethylene ether glycol(PTMEG). PCL and PTMEG as typical aliphatic polyesters, are biodegradable, biocompatible, and nontoxic. In this paper, to improve mechanical properties of PLA, we have synthesized PLA segmented block copolymers.

2. Experiments 2.1.

Materials

2.2.

Synthesis

L-lactide was supplied by Purac Biochem. ε-caprolacton, PTMEG with number average molecular weight (M n ) of 2000 g/mol, Tin(Ⅱ) 2-ethylhexanoaate (Sn(Oct) 2 ) and 1,6-hexamethylene diisocyanate (HDI) were purchased from Sigma-Aldrich and used without further treatments. Methylenediphenyl 4,4’-diisocyanate (MDI) was purchased from TCI. All the solvents such as chloroform, toluene, and dichloromethane were purchase from Sigma Aldrich.

PLA and its copolymers were synthesized by ring opening polymerization (ROP), in bulk. PLA-PCL segmented block copolymers were synthesized via three steps; ‘B’ block, ‘ABA’ block, and multiblock. In the first step ROP, ε-caprolacton and PTMEG were reacted with Sn(Oct) 2 as a catalyst. Dihydroxyl-terminated PCL-PTMEG-PCL oligomers were used as macroinitiator in the second step ROP. In the second step ROP, synthesized oligomers and L-lactide were reacted with Sn(Oct) 2 . ‘ABA’ type of PLA-PCL-PLA was synthesized. Finally, the prepared dihydroxyl-terminated PLA-PCL-PLA were coupled via chain extension using diisocyante. The procedure for the synthesis of the PLA-PCL multiblock is shown in Scheme 1.

Page 340 of 1108

Scheme 1. Synthesis of PLA segmented block copolymer

2.3.

Characterization

Thermal properties of synthesized polymers were investigated by DSC. Each polymer’s intrinsic viscosity was confirmed by Ubbelohde viscometer(30 ℃, chloroform), and their mechanical properties were measured by Instron®.

3. Results & Discussion Table 1 shows synthesizing profile and sample code of PLA segmented block copolymers. According to those results, the intrinsic viscosity of PLA copolymers was decreased with increasing PTMEG content of PCL diol. Plus, as increasing diisocyanate content, segmented block copolymer’s intrinsic viscosity increased. In addition, compare to MDI ABA-2 and HDI-2ABA-2, using HDI as a chain extender, get high intrinsic viscosity. Table 1. Sample code of PLA copolymers

Page 341 of 1108

Figure 1 shows DSC heating thermograms of PLA copolymers, where there shows endotherms were observed on DSC thermograms. In figure 1, there are not considered large difference among the copolymers. Even though, their condition is different, thermal property is similar. Because their chemical structure is similar and few urethane bond is in the segmented block copolymer. And the second DSC thermograms, glass transition temperature decreased with increasing HDI content because of ether group and urethane bond in the main chain, which is related with mechanical properties.

ABA diol-2 HDI-2 ABA-2 MDI ABA-2

Endo

HDI-1 ABA-2 HDI-2 ABA-2 HDI-3 ABA-2

100

120

140

160

Temperature(oC)

100

120

140

160

Temperature(oC)

Figure 1. DSC thermograms of PLA copolymers

Figure 2 displays the tensile stress-strain curves of PLA copolymers. In figure 2, compare to ABA diol and segmented block copolymers, segmented block copolymers have large strain better than ABA diol. It seems to urethane bond in segmented block copolymer and their repeating unit is more effective in strain. On the other hand, there are not large differences in stress. And the second curves, increasing HDI contents, strain is dramatically increased. Because, when HDI content is increased, urethane bond also increase. The mechanical properties corresponding to PLA copolymers are summarized in Table 2.

HDI-1 ABA-2 HDI-2 ABA-2 HDI-3 ABA-2

Stress(MPa)

MDI ABA-2 HDI-2 ABA-2 ABA diol-2

Strain(%)

Figure 2. Stress-strain curves of PLA copolymers

Table 2. Mechanical properties of PLA copolymer films

Page 342 of 1108

4. Conclusion In this study, PLA copolymers were synthesized by two-step ring opening polymerization of L-lactide and Îľ-caprolactone. Segmented block copolymers were characterized by intrinsic viscosity, DSC and InstronÂŽ. Increasing the HDI content in the copolymers, the glass transition temperature decreased. Also, increasing the HDI content their strain is dramatically increased which is related to chemical structure of segmented block copolymer. As a result, it seems that the mechanical properties of PLA copolymers can be finely adjusted by tuning the copolymer composition and chemical structure.

5. References [1] Chao Zeng and Jie Ren, J Polym Sci, 2012, 125, 2564-2576 [2] Chao Zeng and Nai-wen Zhang J Therm Anal Calorim, 2013, 111, 633-646

Page 343 of 1108

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

Synthesis and Characterization of Polyacrylonitrile-based Terpolymers as Carbon Fiber Precursors Eunbin Lee, Won Ho Park and Young Gyu Jeong + Department of Advanced Organic Materials and Textile System Engineering Chungnam National University, Daejeon 34134, Republic of Korea

Abstract. Although polyacrylonitrile (PAN) is considered as one of the most widely used precursors for manufacturing high performance carbon fibers (CFs), the use of PAN homopolymer is restricted due to its low spinnability and stabilization. In order to improve the processability and stabilization of PAN, in the present study, we have manufactured a series of PAN-based copolymers with different concentration of 1vinylimidazole and itaconic acid by solution polymerization, and have investigated their molecular structures and thermal properties as potential precursors for high performance CFs. Keywords: carbon fiber, polyacrylonitrile, 1-vinylimidazole, itaconic acid

1. Introduction Carbon fibers (CFs) are finding an important place in high-technology applications including aerospace, military, and automobile, because of their exceptionally high mechanical strength, elastic modulus, thermal stability, and chemical/ environmental resistance. Polyacrylonitrile (PAN) is one of the most widely used precursor polymers for making high performance CFs. However, the use of pristine PAN homopolymer is restricted due to its low spinnability and stabilization [1]. Thus PAN precursors for CFs usually incorporate comonomers such as methyl acrylate (MA), methyl methacrylate (MMA), vinyl acetate (VA), and itaconic acid (IA). It has been reported that the presence of acrylate comonomer improves solubility, spinnability, and drawability of PAN copolymers and modifies the fiber morphology. It was also reported that smaller acrylate side chain in the precursor can contribute to improved mechanical properties of the final CFs. Especially, IA comonomer has been incorporated in the precursor backbone for enhancing the solubility and promoting the thermo-oxidative stabilization, which plays a crucial role in the properties of resulting CFs. On the other hand, the copolymerization reactions involving 1-vinylimidazole (VIM) and its derivatives have stimulated great interest due to the wide possibilities of the preparation of new PAN-based precursors. These materials showed unique properties such as ion exchange and complex behavior, catalytic, biological and physiological activities, and heat resistance. In the present study, we have synthesized a series of AN/VIM/IA terpolymers by using solution polymerization technique and have characterized their molecular structures by adopting 1H NMR and FT-IR spectroscopy. We have also manufactured precursor fibers via solution spinning of terpolymers and have investigated their processability associated with stabilization and carbonization for obtaining high performance CFs.

2. Experimental 2.1.

Synthesis of PAN-based copolymers

A series of PAN-based terpolymers were synthesized by using solution polymerization. Acrylonitrile (AN), 1-vinylimidazole (VIM) and itaconic acid (IA) were polymerized in the presence of azobisisobutyronitrile (AIBN) initiator at 70 째C for 16 hrs in nitrogen atmosphere. The monomer feed composition for synthesizing the copolymers was summarized in Table 1. After the polymerization, the copolymers were precipitated in deionized water, filtered, and washed with methanol to remove residual monomers.

Corresponding author. Tel.: + 82-42-821-6617. E-mail address: ygjeong@cnu.ac.kr.

Page 344 of 1108

2.2.

Characterization

The PAN-based copolymers were characterized with aids of 1H NMR spectrometer (JNM-AL 400, JEOL Ltd) and FT-IR spectrometer (Nicolet iS10, Thermo Scientific). The thermal properties of the copolymers were characterized by using a thermogravimetric analyser (TGA-N-1000, Scinco) under nitrogen and air atmosphere at a heating rate of 10 Â°C/min. Table 1: The feed compositions for synthesizing PAN-based copolymers with different VIM and IA compositions Feed composition (mol%)

Sample code AV AVI_1 AVI_2 AVI_3 AVI_4

AN 80 80 80 80 80

VIM 20 19 18 17 16

IA 0 1 2 3 4

3. Results and discussion 3.1.

Structure characterization

Fig. 1 shows 1H NMR spectra of PAN-based copolymers with different VIM and IA compositions. The methylene groups of the copolymer backbone chain were observed at 1.8-2.2 ppm. The methyne groups associated with AN and VIM linkages of the copolymers appeared at 3.1-3.2 ppm and 4.2-4.6 ppm, respectively. The protons of imidazole ring were detected at 6.9-8.0 ppm. The hydroxyl and methylene protons of the carboxylic groups of IA component were observed at 9.5-9.6 ppm and 1.3-1.5 ppm, respectively [2]. The area of peaks appearing at 6.9-8.0 ppm decreased with the decrease of VIM composition in the PAN-based copolymers from 20 to 16 mol%, whereas the peak area at 1.3-1.5 ppm increased with the increase of IA composition from 1 to 4 mol%.

Fig. 1: 1H NMR spectra of PAN-based copolymers with different VIM and IA compositions: (a) AV; (b) AVI_1; (c) AVI_2; (d) AVI_3; (e) AVI_4.

The FT-IR spectra of PAN-based copolymers were shown in Fig. 2. The Câ&#x2030;ĄN stretching bands were observed clearly at ~2243 cm-1 and the CH 2 stretching bands of the copolymer backbone were detected at ~2922 cm-1. In addition, the C-N ring stretching and C-H ring in-phase bending of VIM component were detected at ~1229 cm-1 and ~1082 cm-1, respectively. The C=O stretching band was also detected at ~1718 cm-

Page 345 of 1108

Transmittance (a.u.)

and its intensity increased with the increment of the IA composition in the copolymers [3]. Overall, from the NMR and FT-IR spectra, it is reasonable to contend that PAN-based copolymers with various compositions are successfully synthesized via the solution polymerization.

AV AVI_1 AVI_2 AVI_3 AVI_4

3000

2500

2000

1500

1000

-1

wavenumber (cm )

Fig. 2: FT-IR spectra of PAN-based copolymers with different VIM and IA compositions.

3.2.

Thermal property

The TGA thermograms of PAN-based copolymers with different comonomer compositions were shown in Fig. 3. The TGA curves in Fig. 3(A) display three main steps in weight loss: the first weight loss at ~300 째C is caused by the remaining moisture; the second weight loss at 300-450 째C is associated with the dehydrogenation; the last weight loss at 650-800 째C is due to the degradation of polymer backbone. With increasing the IA composition in the copolymers, the cyclization reaction to form a stable ladder structure was accelerated and thus the residue at high temperature at 800 째C increased [4]. The residue at air condition was also higher for the copolymers with higher IA composition, although it was somewhat lower than that under nitrogen condition.

Fig. 3: TGA curves of PAN-based copolymers with different VIM and IA compositions under (A) nitrogen and (B) air atmosphere.

4. References [1] Devasia R, Reghunadhan Nair CP, Sivadasan P, Ninan KN, Polym. Int., 2005, 54(8), 1110-1118. [2] Nursel P, Zakir MO, Olgun G, Macromol. Chem. Phys., 2004, 205(8), 1088-1195. [3] Qin O, Lu C, Haojing W, Kaixi L, Polym. Degrad. Stab., 2008, 93(8), 1415-1421. [4] Danyun L, Kesaven D, Li XD, Choi WK, Seo MK, Kim BS, Carbon Lett., 2014, 15(4), 290-294.

Page 346 of 1108

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

The chemical modification of Oxy-PAN nanofibrous web by sodium hydroxide solution Seung Hyun Lee, Min Hee Kim, Seoho Lee, Hanna Park and Won Ho Park + Department of Advanced Organic Materials and Textile System Engineering, Chungnam National University

Abstract. Oxy-PAN nanofibrous webs fabricated by electrospinning were firstly stabilized by heat treatment, and subsequently hydrolyzed with various sodium hydroxide solution concentrations to impart the ability to highly absorb water. This was achieved through the chemical conversion of the nitrile groups on the surface of the PAN nanofibrous web. Attenuated total reflection infrared spectroscopy (ATR-IR) and X-ray photoelectron spectroscopy (XPS) were used to confirm the chemical conversion on the surfaces of hydrolyzed Oxy-PAN (H-PAN) before and after hydrolysis. Water uptake was used to determine the water absorbing capacity. Also, the dimensional stability of H-PAN was observed by optical microscopy.

Keywords: Polyacrylonitrile, Hydrolysis, Nanofibers, Electrospinning, Oxy-PAN etc.

1. Introduction Super-absorbent polymers (SAPs) are often prepared by minimal crosslinking of hydrophilic polymers. It can absorb an extremely large amount of water compared to most hydrophilic materials, and the absorbed water is hardly removable even under some pressure. SAPs are widely used in various applications such as hygienic, foods, cosmetics, agriculture and architecture. Polyacrylonitrile (PAN) is one of the most important fiber forming polymers. PAN fibers have many outstanding properties including their high strength, abrasion resistance, and good insect resistance. The stabilization process of PAN fiber is normally performed in the temperature range of 200 ~ 300â&#x201E;&#x192; under an oxidative atmosphere. During the process, PAN precursor fibers experience significant chemical and physical changes. Therefore, the stabilized PAN (Oxy-PAN) fibers are chemically and thermally stable while they are exposed to low or high temperature and alkaline solution. There are many methods of manufacturing SAP such as hydrolysis, graft polymerization and crosslinking. One of the common methods for manufacturing a SAP was hydrolysis of PAN, and SAPs were commonly prepared in a granular shape and powders. It is desirable for fibers to possess high surface areas in many applications such as reinforcing fibers in composite, filter materials, and absorbent materials. The PAN nanofibers with high surface area can be a promising precursor for SAP application. However, this hydrolysis method has a difficulty to maintain the nanofibrous structure of PAN. To overcome this drawback, Oxy-PAN nanofibrous webs fabricated by electrospinning were firstly stabilized by heat treatment, and subsequently hydrolyzed with various sodium hydroxide solution concentrations to impart the ability to highly absorb water. This was achieved through the chemical conversion of the nitrile groups on the surface of the PAN nanofibrous web. Attenuated total reflection infrared spectroscopy (ATR-IR) and X-ray photoelectron spectroscopy (XPS) were used to confirm the chemical conversion on the surfaces of hydrolyzed Oxy-PAN (H-PAN) before and after hydrolysis. Water uptake was used to determine the water absorbing capacity. Also, the dimensional stability of H-PAN was observed by optical microscopy.

Corresponding author. Tel.: + 82-42-821- 6613. E-mail address: parkwh@cnu.ac.kr.

Page 347 of 1108

2. Experimental 2.1.

Materials

Polyacrylonitrile was supplied from Taekwang Industrial Co., Korea. N,N-Dimethylformamide (DMF, Daejung Co., Korea.) was used as the solvent. Sodium hydroxide solution was purchased from Samchun Co., Korea.

2.2.

Electrospinning of PAN nanofibrous web

PAN nanofibrous web was prepared by electorspinning. The electrospinning solution was prepared by dissolving the PAN powder in DMF. The as-prepared solution was then loaded into a syringe and electrospun into nanofibers collected by a rolling substrate, using a commercial electrospinning device. The distance and voltage between the needle and the cylindrical collector were 10 – 15 cm and 10 – 18 kV.

2.3.

Preparation of Oxy-PAN nanofibrous web

Fig. 1(A) showed stabilization process of PAN nanofibrous web. The PAN nanofibrous web was heated in a furnace at 210 - 230℃ for 10 – 120 min in the presence of air.

2.4.

Preparation of hydrolyzed Oxy-PAN nanofibrous web

Fig. 1(B) showed hydrolysis process of Oxy-PAN nanofibrous web. The process was carried out in a NaOH aqueous solution at 50℃. The hydrolysed Oxy-PAN nanofibrous web was washed with distilled water/ethanol until neutral pH and dried overnight in vacuum at 100℃

2.5.

Characterizations

Chemical functionalities of samples were characterized by Attenuated total reflection infrared spectroscopy (ATR-IR) and X-ray photoelectron spectroscopy (XPS) was used to confirm the chemical conversion on the surfaces of hydrolyzed Oxy-PAN before and after hydrolysis. The PAN nanofibrous web before and after treatments was observed under a field-emission scanning electron microscope (SEM) after being coated with platinum sputtering.

Fig. 1: Mechanism of (A) stabilization of PAN nanofibrous web and (B) hydrolysis of Oxy-PAN nanofibrous web

3. Results and discussion 3.1.

ATR-IR spectra of Oxy-PAN nanofibrous web

The spectra of Oxy-PAN nanofibrous web before and after hydrolysis was shown in Fig. 2. Evidently, the intensity of the broad adsorption band at 3351 cm-1 corresponded to the stretching vibration of –OH. This indicates the introduction of the –OH groups on the surface of the hydrolyzed Oxy-PAN nanofibrous web. As the reaction time increased, the intensities of two absorption peaks at 1668 cm-1, 1573 cm-1 were increased. The peak at 1573 cm-1 indicates the existence of imine –C=N- conjugated sequences in the hydrolyzed Oxy-

Page 348 of 1108

PAN nanofibrous web. The intensity of the peak at 1668 cm-1 corresponded to the stretching vibration of the carbonyl of the carboxylic acid. Since only a fraction of the nitrile groups converted to the imine and carboxylic acid groups. This is evident by the decrease in the intensity of the peak at 2241 cm-1. .

Fig. 2: ATR-IR spectra of (A) Oxy-PAN nanofibrous web, (B) hydrolysed at 50℃ for 5 h, (C) hydrolysed at 50℃ for 10 h and (D) hydrolysed at 50℃ for 15 h

4. References [1] P. Kampalanonwat, P. Supaphol, Ind. Eng. Chem. Res. 2011, 50, 11912-11921 [2] S. Zhang, S. Chen, Q. Zhang, P. Li, C. Yuan, React. Funct. Polym. 2008, 68, 891-898 [3] K. Lee, J. Li, B. Fei, J. Xin, Polym. Degrad. Stabil. 2014, 105, 80-85 [4] S. Deng, R. Bai, J. P. Chen, J. Colloid Interface Sci. 2003, 260, 265-272 [5] G. P. Karpacheva, L. M. Zemtsov, G. N. Bondarenko, A. D. Litmanovich, N. A. Plate, Polym. Sci. Ser. A+. 2000, 42, 620-625

Page 349 of 1108

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

Effects of carbonization temperature on properties of PAN-based carbon fiber Jong Sung Won 1, Hyun Jae Lee 1, Da Young Jin 1, Jun Young Yoon 2, Tae Sang Lee 2 and Seung Goo Lee 1 + 1

Department of Advanced Organic Materials and Textile System Engineering, Chungnam National University, Gung-dong, Yuseong-gu, Dajeon, Korea 2 Kolon industries, INC., KOLON Tower, 11, Kolon-ro, Gwacheon-si, Gyeonggi-do, Korea

Abstract. In this study, PAN-based carbon fibers were produced by carbonization at 5 different temperature conditions. And changes of various characteristics of the carbon fibers prepared according to each condition were studied. Morphologies of carbon fibers were observed using scanning electron microscopy (SEM), and thermal characteristics were analyzed thermogravimetric analyzer (TGA). X-ray diffraction (XRD) was used to analyze the crystalline characteristics. Mechanical properties were measured by universal testing machine. According to these analyses, the optimal carbonization temperature for preparation of PAN-based carbon fiber was obtained.

Keywords: PAN-based carbon fiber, carbonization, oxidation test.

1. Introduction PAN The carbon fiber is a fibrous carbon material having a carbon content of 90wt%. The strength of the carbon fiber is 10 times that of iron and weight is 25% of the iron, 70% of aluminium[1-2]. Also, carbon fiber has high thermal conductivity, low thermal expansion coefficient and excellent electrical conductivity. Therefore, they are used in various industries such as break of the aircraft, heat insulation materials, space aircraft, heat-resistance materials in nuclear reactor, rocket nozzle etc [3-5]. Carbon fibers are classified as rayon-based, PAN-based, and pitch-based carbon fiber according to the precursor used in the preparation. Among them, PAN-based carbon fiber is manufactured by using a polyacrylonitrile (PAN) fiber as a precursor. PAN-base carbon fiber has highest economic efficiency and is stronger than other type of precursor-based carbon fiber. PAN fiber is most suitable precursors for producing high performance carbon fibers because of its higher melting point and greater carbon yield than other precursors. For this reason, the majority of all carbon fibers used today are made from PAN precursor [6-7]. Developing of carbon fiber from PAN fiber precursor is generally subjected to 2 processes. The first step is a stabilization process (200째C~300째C, oxidizing condition). In this step, the PAN fiber is stretched and simultaneously oxidized, and thermoplastic PAN is converted to non-plastic ladder compound through intramolecular cyclization reaction. The second is the carbonization process (temperature below 1800째C, inert atmosphere). In this step, chemical composition and physical properties of the carbon fiber are changed and about 50% of weight of carbon fiber is removed as vapour, ammonia, hydrogen cyanide, CO, CO 2 , N 2 , CH 4 etc. And cross-link is formed by intramolecular cyclization reaction [8-9]. In this study, PAN-based carbon fibers were produced by carbonization at 5 different carbonization temperature conditions. And changes of various characteristics of the prepared carbon fibers were analyzed by scanning electron microscopy (SEM), thermogravimetric analyzer (TGA), X-ray diffraction (XRD) and universal testing machine (UTM).

2. Experiments +

Corresponding author. Tel.: + 82-10-3404-6150. E-mail address: lsgoo@cnu.ac.kr.

Page 350 of 1108

2.1.

Preparation of carbon fiber

Figure 1 shows the manufacturing process of PAN-based carbon fiber. Carbonization was carried out in a nitrogen atmosphere. Table 1 shows the carbonization conditions of the PAN-based carbon fiber. Drive draw rate is for controlling the tension at the same level, which means the drive speed difference in the oxidation step (drive 2~4) and whole process including the oxidation step (drive 1~7).

Fig. 1: Schematics of manufacturing process of carbon fiber from PAN precursor

Table 1: Carbonization condition of PAN-based carbon fiber Test No. Drive draw rate

Test-2

Test-3

Test-4

Test-5

Drive 2~4

%, Oxi.

-3.1%

-0.1%

-8.9%

Drive 1~7

%, Total

-5.0%

-3.7%

-12.2%

Low temperature (째C) Furnaces High temperature (째C)

2.2.

Test-1

Zone #1

450

Zone #2

650

Zone #3

800

Zone #4

850

Zone #1

1000

1050

1200

1150

1200

Zone #2

1200

1300

1350

1400

Zone #3

1450

1550

1500

1550

1600

Zone #4

1300

1500

1650

1750

1800

Characterization

The surface and cross sectional morphologies of prepared carbon fibers were observed by using the scanning electron microscopy (SEM, S-4800, Hitachi). The x-ray diffraction (XRD, D/MAX-2200, Rigaku) was used to determine the crystalline characteristics of prepared carbon fibers. To analyze the thermal properties of the carbon fibers, the oxidation test was conducted using the thermogravimetric analyzer (TGA). To analyze the mechanical properties, tensile test was conducted using the universal testing machine (Model 4467, Instron)

3. Results and discussion Figure 2 shows the XRD analysis results. According to increase of carbonization temperature, the crystallinity tends to increase. This is because the amorphous structure of carbon fibers decreased and the crystalline molecular structure increased with the increase of carbonization temperature. In general, the increase in the crystallinity results in an increase of the mechanical properties [10]. Also, the lattice spacing and the crystal size were calculated using the Bragg equation and Scherrer equation, respectively. The Bragg equation are shown in Formula 1 and the Scherrer equation are shown in Formula 2. The lattice spacing was not a significant change, but crystal size increased according to increase of carbonization temperature. The lattice spacing and the crystal size affect the thermal properties of carbon fibers [11].

Page 351 of 1108

Fig. 2: XRD patterns of PAN-based carbon fibers prepared under various carbonization temperatures

nλ = 2d∙sinθ

(1)

L = Kλ / (β∙cosθ)

(2)

Figure 3 show the mechanical properties of carbon fibers. Tensile strength and tensile modulus of carbon fiber increased according to increase of carbonization temperature. This is because the increase of the crystallinity of carbon fiber by increase of carbonization temperature. In general, the increase of crystallinity results in improving mechanical properties. However, in spite of highest crystallinity, the carbon fiber prepared at carbonization temperature of 1800°C indicates a significant reduction in tensile strength. The reason for this result is that the defects of carbon fiber caused by high temperature.

Fig. 3: Tensile strength and tensile modulus of PAN-based carbon fibers prepared under various carbonization temperatures

Weight reduction of the prepared carbon fibers according to oxidation reaction was investigated by TGA in air atmosphere. Weight reduction by oxidation tended to decrease with increase of carbonization temperature. This result can be explained on the basis of the crystal size. Crystal size of carbon fiber increased according to increase of carbonization temperature. When the crystal size increased, the activation energy increased, thus the oxidation reaction rate becomes slow [11].

4. Conclusion In this study, the PAN-based carbon fiber was prepared at various carbonization temperatures. And the prepared PAN-based carbon fibers were characterized by XRD, UTM and TGA. Crystalline characteristics

Page 352 of 1108

were analysed by XRD. Mechanical properties and thermal properties were investigated by UTM and TGA, respectively. As a result, found out that the crystallinity and crystal size of carbon fibers increased according to increase of carbonization temperature. Further, Obtain results that tensile strength, tensile modulus and oxidation resistance of carbon fiber was improved with increase of carbonization temperature. However, the carbon fiber prepared at carbonization temperature of 1800째C indicates a significant reduction in tensile strength. Through these results, carbonization temperature of 1750째C was identified as an optimal condition for preparing of PAN-based carbon fiber.

5. Acknowledgement This study was supported by 'Hybrid and Super Fiber Materials Specialist Training Program' from Korea Institute for Advanced of Technology.

6. References [1] O. P. Bahl and L. M. Manocha, Characterization of oxidized PAN fibers, Carbon, 12, 1974, pp. 417. [2] A. D. Cato and D. D. Edie, Flow Behavior of Mesophase Pitch, Carbon, 41, 2003, pp. 1411. [3] L. L. Hong, A. Moshonov and J. D. Muzzy, Electrochemical polymerization of xylene derivatives on carbon fiber, Poly. Compos., 12, 1991, pp. 191-195. [4] L. T. Drzal and M. Madhukar, Fibre-matrix adhesion and its relationship to composite mechanical properties, J. Mater. Sci., 28, 1993, pp. 569-610. [5] M. S. Dresselhaus and G. Dresselhaus, Intercalation compounds of graphite, Adv. Phys., 30, 1981, 139-326. [6] S. Chand, Review Carbon fibers for composites, J. Mater. Sci., 35, 2000, pp. 1303-1313. [7] Z. Wangxi, L. Jie and W. Gang. Evolution of structure and properties of PAN precursors during their conversion to carbon fibers. Carbon, 41, 2013, pp. 2805-2812. [8] E. Fitzer, W. Frohs and M. Heine, Optimization of stabilization and carbonization treatment of PAN fibers and structural characterization of the resulting carbon fibers, Carbon, 24, 1986, pp. 387-395. [9] H. G. Chae and M. L. Minus, A. Rasheed, and S. Kumar, Stabilization and carbonization of gel spun polyacrylonitrile / single wall carbon nanotube composite fibers, Polymer, 48, 2007, pp. 3781-3789. [10] M. K. Ismail, On the reactivity, structure, and porosity of carbon fibers and fabrics, Carbon, 29, 1991, pp. 777-792. [11] P. Gao, H. Wang and Z. Jin, Study of oxidation properties and decomposition kinetics of three-dimensional (3-D) braided carbon fiber, Thermochimica Acta, 414, 2004, pp 59-63.

Page 353 of 1108

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

The Effects of Heat-Treatment Temperature on Carbonization Behavior of Heterocyclic Aromatic Polymer ChanSol Kang, Seung Won Kim, Min Jung Paik, Chae Won Park, Sun Hong Kim, and Doo Hyun Baik* 1

Department of Advanced Organic Materials & Textile System Engineering, Chungnam National University, Korea *dhbaik@cnu.ac.kr

Abstract. Polyhydroxyamide (PHA) and polybenzoxazole (PBO) were converted into carbonaceous materials via low-temperature carbonization process with different heat-treatment temperatures (HTTs). The obtained carbonized PHA and PBO (called C-PHA and C-PBO) were characterized by IR, Raman, WAXD, SEM, and TEM to understand the relations between the carbon layered structures and the carbonization process with HTT of them. According to FT-IR results, it is likely to assume that both the PHA and PBO particles were successfully converted into C-PHA and C-PBO above 800 °C without the oxidative stabilization step. It was observed that two different diffraction peaks of C-PHA and C-PBO located at 2θ ~ 24.03° (002) and 44.18° (100) corresponding to the typical carbon materials. In addition, TEM images revealed that the PBO-based CPs treated at 1200 °C have significant carbon layer structures. Keywords: polyhydroxyamide, polybenzoxazole, heat-treatment temperature, carbonization behaviour, morphological features

1. Introduction Commercially available carbon fibers are generally prepared from the pyrolysis of precursor fibers such as polyacrylonitrile (PAN)-, pitch-, and phenol-based fibers. During the conversion from PAN-based precursor fibers to carbon fibers, the heat-treatment conditions such as processing heat-treatment temperatures and gas environments are significantly crucial for the final properties of carbon fibers. In general, heat-treatment process can be classified into three regions: oxidative stabilization, carbonization, graphitization. Among these stages, the oxidative stabilization is especially one of the most necessary stages, which directly affects the carbon yield as well as the final properties of carbon fibers. However, the large amount of heat energy and time consumed and the significant CO 2 released to prepare stable ladder structure. Therefore, oxidative stabilization process should be finely tuned in terms of energy consumption. Recently, carbon fibers prepared from the aromatic rigid-rod polymer have attracted great interest from academic points of view owing to their superior heat resistant properties. Since various rigid-rod polymer precursors including aromatic and/or heterocyclic aromatic structure can be carbonized without the oxidative stabilization stage, they provide the efficient processing technique in terms of energy savings, unlike PAN precursor[1]. The main objective of this study is to investigate the structures and carbonization behavior of rigid-rod polymers as a function of heat-treatments temperature by adopting IR, Raman, WAXD, and TEM.

2. Experimental 2.1.

Materials

3,3’-dihydroxybenzidine (DHB, > 99.0 %) was purchased from Wakayama Seika Kogyo Co. (Japan). Isophthaloyl chloride (IPC, 99.0 %) and anhydrous N,N-dimethyl acetamide (DMA c , 99.8 %) were purchased from Sigma-Aldrich Co. (USA), and lithium chloride (LiCl, 99.0 %) was purchased from Junsei Chemical Co. (Japan), respectively, which normally used to synthesize the PHA particles.

2.2.

Preparation of C-PHA and C-PBO

Page 354 of 1108

The PHA particles were synthesized using low-temperature solution polycondensation method and the PBO particles were prepared through intramolecular cyclization reaction of PHA particles at 350 °C for an hour, as reported in previous study[2]. In addition, to manufacture the C-PHA and C-PBO, the carbonization process of PHA and PBO was carried out under nitrogen atmosphere with different temperatures of 600, 700, 800, 900, 1000, 1100, and 1200 °C for an hour, respectively.

2.3.

Characterization

To confirm the chemical structures of PHA and PBO particles, and their structural changes as a function of HTTs, FT-IR Spectroscopy (Thermo, Nicolet IS50, USA) was examined at room temperature. The Raman spectra were obtained over a spectral range of 100-4000 cm-1 equipment with the multichannel air cooled CCD and InGaAs array detector, power output of 120 mW, and 514 nm excitation wavelength laser. To observe the structural evolution of the C-PHA and C-PBO with different HTTs, WAXD was measured With nickel-filtered Cu-K α radiation (λ=1.542 Å) generated at 40 kV and 100 mA. The structural changes of morphology and carbon layered structure in C-PHA and C-PBO were characterized with aid of a TEM (JEOL, JEM 2100, Japan).

3. Results and Discussion Figure 1 shows FT-IR spectra of the C-PHA and C-PBO with different HTTs. For Figure 1 (A), it can be observed that the typical characteristic bands of PHA particles gradually disappeared with higher HTTs and totally vanished above 800 °C. Similarly, the PBO particles also disappeared above 800 °C, as shown in Figure 1 (B). It indicates that the main-chain scission of the PHA and PBO structures occurred at high temperature, followed by some secondary reactions such as hydrogen transfer, cross-linking, and rearrangement with increasing HTTs, yielding the several aromatic compounds caused by recombination and aromatization reactions[4]. Accordingly, it is likely to assume that both the PHA and PBO particles were successfully converted into CPs without the oxidative stabilization step above 800 °C.

Figure 1. FT-IR spectra of C-PHA (A) and C-PBO (B) with several HTTs: (a) 600 °C; (b) 700 °C; (c) 800 °C; (d) 900 °C; (e) 1000 °C; (f) 1100 °C; (g) 1200 °C.

Page 355 of 1108

To investigate the changes of the carbon layered structure in the C-PHA and C-PBO, X-ray diffraction patterns of C-PHA and C-PBO as a function of HTTs are presented in Figure 2. Overall, it was observed that two different diffraction peaks of C-PHA and C-PBO appeared at 2θ ~ 24.03° and 44.18° ascribing to (002) and (100) planes of the typical carbon materials, respectively[3]. In general, a weak broad diffraction peak (d 002 ) is related to the turbostratic carbon structure with randomly oriented carbon layered structure which would be developed with increasing HTT, forming the more ordered and compact carbon layered structure and presenting a sharp diffraction peak. In addition, a broad diffraction peak may indicate that the stacking height of the carbon layered structure is markedly small. As shown in Figure 2 (A), it could be observed that X-ray diffraction patterns of C-PHA with HTT have broad peaks at the same positions (d 002 and d 101 ) and almost did not change the intensity of them, suggesting that all the samples have the similar degree of stacking height. This result means that small hexagonal layers have been already formed in the C-PHA and C-PBO above 800 °C. However, it was confirmed that the interlayer spacings of the C-PHA (d 002 = 0.368 nm) and C-PBO (d 002 = 0.359 nm) manufactured in this study were larger than that of a general turbostratic carbon structure (d 002 = 0.345 nm), implying the lower degree of stacking height of the carbon materials, as above mentioned. Consequently, it is though that the C-PHA and C-PBO carbonized above 800 °C have similarly developed lattice texture of graphite.

Figure 2. XRD patterns of the C-PHA (A) and C-PBO (B) with different HTTs. When a certain type of disordered carbon structures is carbonized at high temperature, both well-ordered graphitic carbon structures and less-ordered turbostratic carbon structures are formed simultaneously[4]. To have deeper understanding on the structural changes of PBO-based CPs with different HTTs, TEM images of PBO-based CPs are obtained as illustrated in Figure 3. Overall, it was confirmed that the carbon layered structure in PBO-based CPs were increasingly developed with increasing HTT. In general, such type of structure has been prepared from the carbonization process of rod-like polymeric precursors such as poly(pphenylene terephthalamide) (PPTA), polyimide (PI), and polybenzimidazole (PBI). As shown in Figure 3, PBO-based CPs treated at 1200 °C have well-ordered graphitic carbon structures, which indicates that they have a number of aromatic layers containing both well-ordered graphitic carbon structures and less-ordered turbostratic carbon structures and were tightly stacked parallel and equidistant, which is consistent with the XRD results. Therefore, it is concluded that PBO-based CPs treated at 1200 °C have higher graphitic carbon structures.

Page 356 of 1108

Figure 3. TEM images of the carbonized PBO heat-treated at 1200 °C.

4. Conclusions PHA and PBO particles were changed into CPs through low-temperature carbonization step with several HTTs. FT-IR spectra identified that both the PHA and PBO particles were successfully converted into CPs above 800 °C without the oxidative stabilization procedure. XRD analysis revealed that two different diffraction peaks of C-PHA and C-PBO showed at 2θ ~ 24.03° (002) and 44.18° (100) assigning to the typical carbon materials. TEM images observed that the PBO-based CP heat-treated at 1200 °C have the distinct carbon layered structure. The details on carbonization are also the aim of further investigation, especially 1) the optimal carbonization conditions need to be identified, and 2) the structure and property relationships of the carbon fibers need to be clarified. The temperature-increasing rate and procedure, as well as the resulting structure change the ladder-like polymer to the turbostratic carbon, are important factors enhancing the mechanical properties of the carbon fibers.

5. References [1] I. Karacan and L. Erzurumluoglu, Fibers and Polymers, 2015, 16(5), 961-974. [2] C. S. Kang, M. J. Paik, C. W. Park, and D. H. Baik, Fibers and Polymers, 2015, 16(2), 239-244. [3] C. C. Han, J. T. Lee, and H. Chang, Chem. Mater., 2001, 13, 4180-4186. [4] Q. Gao, F. Qu, W. Zheng, and H. Lin, J Porous Mater., 2013, 20, 983-988.

Page 357 of 1108

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

The Functional Properties of PET/ Rayon Staple Fiber Made Woven Fabrics with ACC@Ag Powders K. B. Chenga, J. C. Chen b, J. T. Chang a, J. Y. Liu a, C. M. Wu c, K. C. Leed a

Department of Fiber and Composite Materials, Textile and Material Industry Research Center, Feng Chia University, Taichung 407, Taiwan b Graduate Institute of Materials Science and Technology, Vanung University, Chungli, Taiwan, R.O.C c Department of Materials Science and Engineering, National Taiwan University of Science and Technology, Taipei 10607, Taiwan, R.O.C d Department of Textile Engineering, Chinese Culture University, Taipei 11114, Taiwan, R.O.C Corresponding author: K. B Cheng (kbcheng@fcu.edu.tw)

Abstract. In this study, the fabrication of nano silver doped activated coir charcoal particles (ACC @Ag) were proposed using chemical reduction method. Certain amount of ACC@Ag was added into the spinning solution after de-foaming process to fabricate viscose rayon staple fibers using wet spinning method in this study. The 1.25d*38mm viscose rayon/ACC@Ag staple fibers was then blended with 1.5d*1.5in polyester staple fibers to fabricate PET/ Rayon/ACC@Ag with 50%/50% blending ratio and 30â&#x20AC;&#x2122;S and 40â&#x20AC;&#x2122;S linear density using ring spinning process. The blended yarns are expected to be used for the fabrics with antibacterial, warm retention, odor absorption and antistatic properties. This ring blended yarns was then used as the raw material to fabricate woven fabrics with anti-bacterial and anti-electrostatic properties which comply with JIS and AATCC standards. The influences of woven structures, fabric constitutions on the temperature difference, antibacterial, odor absorption and anti-electrostatic properties of woven fabrics were also investigated. Finally, the potential applications of the fabrics fabricated will also be proposed and suggested in this study.

Keywords: Viscose Rayon, Nano ACC@Ag particle, Blended Yarns, Anti-bacterial and Anti-electrostatic Properties, Warm Retention, Idol Absorption

1. Introduction Supported submicron mineral inorganic particles play an important role in fiber production and environmental protection, such as in functional fibers. Specific stabilization of the dispersed support particles has been achieved by optimizing the interaction between novel metal and support particle. However, there is still no general method for the stabilization of particle again sintering problem. [1] In this study, a new process is proposed and developed to overcome the stabilization problem of the dispersed support particle. This process has successfully demonstrated its applicability to the fabrication of rayon/ ACC@Ag staple fiber. In recent years, the combination of inorganic particle with fiber and polymer composite material has attracted more and more attention because of the advancement and development of functional composite film and fiber. One of the most prevalent classes of composite material is to combine the inorganic particles which act as functional filler in organic matrix. Because of the specific function of inorganic particles, the incorporation of organic/inorganic polymer or fiber, with small amount of inorganic particle addition, can greatly improve the functional properties of conventional polymer materials.

Page 358 of 1108

Porous carbon with high specific surface area can be produced through alkaline activation and has drawn much attention in the last few decades [2]. In this alkaline activation process, NaOH and KOH are commonly used to produce porous carbon with micro pores and much higher specific surface area [3]. Although the theoretical reaction mechanism of alkaline activation occurs at 800oC, however, most KOH activation of porous carbon are conducted by gasification process to remove CO and CO2 from the charcoal [4]. The waste coir shell was selected in this study to produce porous coir charcoal, because of the availability of large quantity waste coir shell and the good to recycle and reutilize waste material.

2. Experimental 2.1 Materials 1. Antimony(

â&#x2026;˘) Oxide

2. Potassium hydroxide 3. Polyvinyl Pyrrolidone, PVP 4. Coir charcoal particles were fabricated by wet ball mill method, D 50 at 820nm 5. KOH, for activating the coir charcoal particles 6. Silver Nitrate, AgNO 3 for fabricating the Nano Ag particles with 20nm 7. 1.25 denier and 1.5 inch length viscose rayon staple fibers with ACC@Ag particles 8. 1.5denier and 1.5inch length polyester staple fibers for blending with rayon/ACC@Ag fibers

2.2 Experimental Equipments 1. UV/visible Spectrophotometer for testing the absorption of UV 2. Ultrasonic Cleaner was used for particles dispersion 3. Magnetic Stirrer for making the particles disperse into the solution evenly 4. X-ray diffraction analysis: MAC Science X-ray Diffractometer. 5. Specific Surface Area & Pore Size Distribution Analyzer: ASAP, Model No. 2020 6. Differential Scanning Calorimeter, (DSC): TA, Model No.Q20 7. Thermogravimetreic Analyzer, TGA: NETZSCH , Model No.TG 209 F3 Tarsus 8. SP-830 Spectrophotometer 9. Switzerland AGEMA Thermovision 900 camera

2.3 Fabrication of ACC@Ag Core Shell Particle [1] Coir charcoal particles were prepared from waste coir shell using steam activation process with the help of furnace heating. Prior to coir charcoal particles preparation, waste coir shell was dried in an oven at 120oC for 24 hour to remove moisture. In carbonization process, the dried waste coir shell was heated in a 900oC for 1 hour. To reduce the particle size of the coir charcoal, the coir charcoal were ground in a ball mill machine for 8 hours. The average particle size (D 50 ) of the coir charcoal was measured as 820 nm. The ground coir charcoal was then dispersed in deionized water with the help of acrylic series dispersant.

Page 359 of 1108

Activated coir charcoal (ACC) was prepared from ground coir charcoal using chemical method. The activation process was done by reacting coir charcoal with KOH at 100oC. Colloidal silver particles with average size of approximately 32 nm are synthesized by reducing method. These colloids nano silver covered (surrounded) ACC core particles were prepared using AgNO3 solution to form mono-dispersed ACC@Ag particles. In this study, AgNO3 solutions with various concentrations, 0.005 M, 0.01 M, 0.02 M and 0.04 M, were mixed with ACC core particles in liquid phase to form mono-dispersed ACC@Ag particles. Furthermore, a silane coupling agent was use to improve the interface problem and uniform distribution among nano Ag, active coir charcoal particles and rayon matrix. It is believed that the ACC@Ag core shell particles prepared using the modified process may have better dispersing characteristic, more reliable and stable, and better odor absorption, anti-bacteria, anti-electrostatic, and warm capabilities.

3. Results and Discussions 3. 1 Morphology and Structure of the ACC@Ag Core Shell Particles Fig.1 shows the TEM morphology of Ag particle doped activated coir charcoal particle (ACC@Ag). Nano Ag particles of average 20nm uniformly dispersed on the tiny hole of activated coir charcoal can be clearly observed. As shown in Figure 1, ACC@Ag particle is composed of many nano Ag (deep color) doped around the tiny holes of the ACC (light color). The ACC@Ag core shell was found to have a complex structure and irregular shape formed from layered deposit. The procedure for the preparation of spinning process of Rayon/ ACC@Ag staple fibers was proposed [5]. 50%:50% PET/Rayon and PET/ Rayon ACC@Ag with 30’S (19.7 tex) and 40’S (14.8 tex) ring yarns were spun by ring spinning process. Polyester/ACC@Ag Rayon blended yarns with 50%:50% (commercial polyester: Rayon/ ACC@Ag staple fibers) blended ratio were used as warp and weft yarns to fabricate woven fabrics by using hand loom method. As shown in Table 1, 8 kinds of woven fabrics with different warp and weft yarn constitutions were fabricated in this study. These fabrics were tested and compared for their odor absorption, anti-bacteria, antielectrostatic, and warming capability functions. The warp and weft density of A, B, C, D woven fabrics (30’S (19.7 tex) ring yarn) are 120 ends/inch and 100 picks/inch respectively with 2/2 twill structure. For samples E, F, G, H (40’S (14.8 tex) ring yarn), the warp and weft density are 130 ends/inch and 100 picks/inch with 2/2 twill structure. For samples D and H, woven fabrics were fabricated with PET/ACC@Ag Rayon as the warp yarns and 50%/50% regular polyester/ rayon and PET/ ACC@Ag Rayon as the weft yarns alternatively by 1/1 picking method. Sample A is constituted from regular 50%/50% Polyester/Rayon blended ring yarns with 30’S as the warp and weft yarns. Sample B blended the PET/ACC@Ag Rayon with 30’S as the warp and weft yarns. ACC@Ag Rayon means nano silver particles dope on the coir charcoal particles which is added into the rayon fiber. Sample C blended PET/ACC@Ag Rayon with 30’S as the warp yarns and regular 50%/50% Polyester/ Rayon with 30’S as the weft yarns. Sample D blended the PET/ACC@Ag Rayon with 30’S as the warp yarns and 50%/50% regular polyester/ rayon and PET/ ACC@Ag Rayon with 30’S as the weft yarns alternatively by 1/1 picking method. Sample E is constituted from regular 50%/50% Polyester/Rayon blended ring yarns with 40’S as the warp and weft yarns. Sample F is constituted from PET/ ACC@Ag Rayon with 40’S as the warp and weft yarns. Sample G interweave PET/ ACC@Ag Rayon staple fibers with 40’S as the warp yarns and regular 50%/50% Polyester/ Rayon with 40’S as the weft yarns. Sample H blended the 50% PET staple and 50% ACC@AgRayon with 40’S as the warp yarns and 50%/50% regular polyester/ rayon and PET/ ACC@Ag Rayon with 40’S as the weft yarns alternatively by 1/1 picking method. The woven fabrics might be recommended to use as clothes or apparels in winter and autumn period such as sports wear, shirt, jacket, sock, trousers, and under wears etc.

Page 360 of 1108

3.3 Effect of ACC@Ag content on thermal absorption and diffusion characteristics of woven fabrics The thermal conservation and warming capability of the woven fabrics made with the different amount of Ag@ ACC particles were measured using a Switzerland AGEMA Thermovision 900 camera. The measured results were determined based upon the FTTS-FA-010 (Specified Requirements of Far Infrared Textiles) standard. A 250W halogen lamp was used as the heating source and directed to the surface of specimens at 45o angle and 100cm for 10 min and turned off. The surface temperature of the test samples were recorded every minute at the beginning of the test and lasted for 20 minutes. The initial surface temperature of the sample tested was controlled at 25oC (T 0 ). After 10min of irradiating, the surface temperature difference, i.e. T 10 -T 0 , is called thermal absorption period which can be characterized as the thermal conservation property. At the end of 20min test, the surface temperature difference, i.e. T 10 T 20 , is called thermal diffusion period. The temperature difference between initial and 20min measurement, T 20 -T 0 , can be characterized as the warming capability of the fabric. The test results are listed in Table 2 and Figures 2 and 3. From the test results, it was found that the higher ACC@Ag content, the better thermal absorption and diffusion capabilities of the fabrics. For fabrics made with PET/ACC@Ag Rayon (B, C, D, and F, G, H), their thermal absorption, diffusion and warming capabilities are much better than the fabric made with PET/Rayon. This is believed to be due to the addition of ACC@Ag particles. Because of the higher ACC@Ag particles content in fabric B than in fabrics C and D, it also has better thermal absorption and diffusion capabilities than fabrics C and D. By comparing Figures 6 and 7, samples B, C and D have better thermal absorption and diffusion capabilities than fabrics F, G and H. This is probably due to the higher fabric weight of samples B, C and D (30’s, 170.5g/cm2) than that of fabrics F, G and H (40’s, 130.5g/cm2). However, for cost consideration, samples C and D is cheaper than sample B and Fabrics fabricated with 40’s are cheaper than those made with 30’S, because of less PET/ ACC@Ag Rayon in the woven fabrics. Table 2 and Figure 2 and 3 show the higher ACC@Ag content have the better thermal absorption and diffusion ability. Furthermore, T10-T0 temperature raising rate increases with increasing the ACC@Ag core shell particles content; presumably due to much higher thermal conductivity and lower thermal diffusitivity of the coir charcoal particles with multi- porous. However, the sample B shows the better thermal absorption and diffusion than the other A samples since has much more the ACC@Ag content in the PET/ ACC@Ag rayon blended yarns and not significance with C and D samples. Furthermore, the sample F shows the better thermal absorption and diffusion than the other E, G, H samples since has much more the ACC@Ag content in the PET/ ACC@Ag rayon blended yarns. Comparison the woven fabrics with 30’S and 40’S yarn kinds, the former one has better warm retention ability than latter one. Since the thickness of woven fabrics with 30’S is heavier and thicker than 40’S. For cost consideration, the sample C and D is better selection, since the amount of PET/ ACC@Ag Rayon is less than the sample B and 30’S yarn price is cheaper than 40’S.

3.4 Effects of ACC@Ag and fabric constitutions on the functional properties of woven fabrics The surface resistivity of woven fabrics fabricated in this study was tested based upon AATCC 100 and ASTM 257 standard “Test methods for D-C Resistance of Conductance of Insulating Material”. As shown in Table 3, woven fabrics fabricated with 30’s ring yarn (A, B, C and D) generally have lower resistivity than those fabricated with 40’s ring yarn. This is because that woven fabrics with higher ACC@Ag particles content also has better electrical conductivity and higher specific surface area. The lowest surface resistivity

Page 361 of 1108

(4.3E+10) was measured for sample B which has the highest ACC@Ag content in the woven fabric. The test results listed in Table 4 also show the woven fabrics prepared can achieve anti-electrostatic level required by AATCC 100 and ASTM 257 standard. Table 4 shows the sample F, G and H woven fabrics show 94% stink absorption ratio, and have the better stink absorption than the other fabrics since the multi-porous activated coir charcoal particles content in rayon yarns. It is because the multi-porous active coir charcoal contribution. AATCC Test Method 90-1982 (Agar plate method) was followed to conduct antibacterial test. In this test, 2.8cm in diameter of PET/ Rayon and PET/ ACC@Ag rayon woven fabrics was cut and put in the center of bacteria growth medium. After 18hr of growing period, the growth of bacteria on woven fabrics can be determined by the murky color and its extent. Figure 4 shows that sample B has the best anti-bacteria characteristic within the four samples tested because of its widest inhibition zone. This is believed to be due to the function of nano silver particles that evenly doped on the multi-porous active coir charcoal. Sample D shows only minor anti-bacteria effect but significant. As shown in Figure 4, no inhibition zone can be identified for Sample A and C which also mean no anti-bacteria function for these two woven fabrics.

4. Conclusions The wet spinning system for fabricating the rayon/ ACC@Ag staple fibers and PET/ ACC@Ag staple yarn with 30’s and 40’S were spun by ring spinning system successfully. In producing PET/ ACC@Ag staple yarns with improved performance over equivalent PET/Rayon staple yarns. 1. ACC@Ag core shell particles were fabricated by modified reduction method successfully and distributed in rayon staple fibers uniformly. 2. Rayon staple fibers with ACC@Ag (1.25 denier and 38mm length) were fabricated by wet spinning process successfully. 3. Polyester blended with rayon/ACC@Ag staple fibers then produced the 30’S and 40’S blended yarns by ring spinning process successfully. 4. Eight kinds of polyester/ ACC@Ag rayon woven fabrics with the different constitutions were produced by hand loom successfully. 5. The effects of SR, temperature difference, stink absorption ratio, antibacterial and anti-static of woven fabrics could be improved, and increased with increasing the ACC@Ag particles and Polyester/ ACC@Ag yarn content, yarn count and fabric thickness. Sample B woven fabric shows the best performance in this paper.

6. The Polyester/ ACC@Ag rayon woven fabrics could be recommended to use as clothes or apparels in winter and autumn seasons such as shirt, jacket, sock, trousers, and under wears etc.

References 1. Pablo M. Arnal, Massimiliano Comotti, and Ferdi Schuth, High-Temperature-Stable Catalysts by Hollow Sphere Encapsulation, Angew. Chem. Int. Ed. 2006, 45, 8224–8227 2. Takahata T, Toda I, Ono H, Ohshio S, Himeno S et al. Detailed Structural Analyses of KOH activated carbon from waste coffee beans. Jpn J Appl Phys 2009; 48:117001. 3. Lill-Rodena Ma, Cazorla-Amoros D, Linares- Solano A. Understanding chemical reactions between carbons and NaOH and KOH: an insight into the chemical activation mechanism. Carbon 2003; 41: 267275. 4. Wigmans T. Industrial aspects of production and use of activated carbon. Carbon 1989; 27: 13-22.

Page 362 of 1108

5. John L. Hathawayt, Man Made Fiber- Science and Technology, Viscose Rayon Textile Fibers, Volume 2, John Willy and Sons, Inc.,1967, P7-42. 6. Taiwan Textile Research Institute, FTTS-FA-010 Infra Red Thermal Image Testing Standard. 7. ASTM 257, Surface Resistivity Testing Standard. 8. Taiwan Textile Research Institute, FTTS-FA-018-2008 Stink Absorption Testing Standard. 9. AATCC 100 & AATCC147, Anti-bacteria Testing Standard. 10. CNS 12915, Tensile Properties of the Woven Fabric Testing Standard.

Acknowledgement We would like to thank for National Science Council (100-2221-E-035-023-) financial support and experiment work done by I/O composites Lab., Department of Fiber and Composite Materials, Textile and Materials Industry Research Center, Feng Chia University, Taichung, Taiwan.

Figure 1 Morphology of ACC@Ag core shell particle Table 1 The specifications of woven fabrics with Polyester/Rayon/ ACC@Ag blended yarns Code A

Warp and Weft Density 120epi*100ppi

120epi*100ppi

Warp and Weft Yarn Count Warp Yarn：PET/Rayon 50%/50% 30’S Weft Yarn：PET/Rayon 50%/50%30’S Fabric Weight: 170.5g/m2 Warp Yarn：PET/ACC@Ag Rayon 30’S Weft Yarn： PET/ACC@Ag Rayon 30’S Fabric Weight: 172.4 g/m2 Warp Yarn：PET/ACC@Ag Rayon 30’S Weft Yarn：PET/ Rayon 50%/50% 30’S Fabric Weight: 171.5 g/m2 Warp Yarn：PET/ACC@Ag Rayon 30’S

Page 363 of 1108

130epi*100ppi

Weft Yarn：PET/ACC@Ag Rayon 30’S+ PET/ Rayon 50%/50% 30’S Fabric Weight: 172.2 g/m2 Warp Yarn：PET/Rayon 40’S Weft Yarn：PET/Rayon 40’S Fabric Weight: 133.5 g/m2 Warp Yarn：PET/ ACC@Ag Rayon 40’S Weft Yarn：PET/ ACC@Ag Rayon 40’S Fabric Weight: 135.6 g/m2 Warp Yarn：PET/ ACC@Ag Rayon 40’S Weft Yarn：PET/Rayon 40’S Fabric Weight: 134.2 g/m2 Warp Yarn：PET/ ACC@Ag Rayon 40’S/ Weft Yarn：PET/Rayon 40’s+ PET/ ACC@Ag Rayon 40’S (50%/50%) Fabric Weight: 134.8 g/m2

Figure 2 Thermal image temperature differences of woven fabrics from A to D

Page 364 of 1108

E F G H

Figure 3 Thermal image temperature differences of woven fabrics from E to H

Page 365 of 1108

Table 2 Thermal image temperature difference with the different woven fabrics constitutions Samples A B C D E F G H

T 10 -T 0 , oC 10.90 20.70 19.28 19.57 5.17 17.38 13.73 15.87

T 20 -T 0 , oC 2.68 4.09 4.24 4.45 1.23 3.72 1.10 2.78

T 10 -T 20 , oC 8.22 16.61 15.04 15.12 3.49 13.66 12.63 13.09

Table 3 The surface resistivity (SR) of the woven fabrics

S R

A B 5.5E+1 4.3E+1 0 0

C D 5.6E+1 5.4E+1 0 0

E 6.1E+1 0

Table 4 The stink absorption of the woven fabrics A B C D SA 71 86 71 86

F 6.4E+1 0

E 86

Unit: 立/cm2 G H 5.2E+1 5.2E+1 0 0

F 94

Unit: % G H 94 94

Figure 4 The image of the anti-bacteria effects on the sample B, D, A respectively

Page 366 of 1108

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

The Heating and Cooling Behaviours of Needle-Punched Nonwoven Fabrics with Wool and Silver-Coated Polyamide Fibres E. Sancak1,2, M. S. Özen1,2, N. Soin2, M. Akalın1, T. H. Shah2, A. Zarei2, E. Siores2

Marmara University, Technology Faculty, Department of Textile Engineering, İstanbul, TURKEY 2 Institute for Materials Research and Innovation (IMRI), University of Bolton, Bolton, UK

Abstract. In recent years, a wide range of textile materials has been used to provide heat in many industrial and clothing applications. The degree of comfort provided by textile products used for garments depends on several factors, one of them being their performance in heating and cooling. It is known that the types of fibre and the production methods used for a material are the main factors determining the heating and cooling behaviours of textile structures. The heating and cooling behaviours of nonwoven fabrics are very important not only for their thermal qualities but also for comfort and protection against adverse weather conditions. This paper investigates the thermal behaviours of needle-punched nonwoven fabrics produced from conductive silver-coated staple polyamide fibres and wool fibres by using nonwoven fabric production techniques and carding, cross-lapper and needle-punching machines. In the first production batch, nonwoven fabric was produced with 100% conductive silver-coated polyamide fibres. In the second batch, the conductive silver-coated staple polyamide fibres were blended with wool fibres in a 50/50 ration. The temperature variations of these nonwoven fabrics were measured by a thermocouple in close contact with a 1x1 inch in sample for 4,000 seconds to explore personal thermal management via Joule heating. The results obtained from these thermal measurements of the nonwoven fabrics were then compared with each other. The results show that the variation in temperature of the nonwoven fabrics increased with the testing time. It was found that the external surface and inside areas of nonwoven fabrics displayed different temperature values. The test results clearly show that needle-punched nonwoven fabrics can be used for thermal management.

Keywords: Nonwovens, Conductive Textiles, Thermo-mechanical behavior, Protective Textiles, Heating

1. Introduction Functional textiles that are manufactured mainly for the purpose of protection are referred to as “protective textiles” and are used to provide thermal comfort and for their anti-freezing qualities. Today, we have many forms and methods of using energy, but 47% of global energy continues to be spent on indoor heating alone, and 42% of that specifically for residential building heating. If heating and insulation could be designed specifically for humans as individuals, a vast amount of energy could be saved. This optimal energy-saving approach is called “personal thermal management”. In the past metallic wires were used in fabrics that can be heated and for personal heating garments. The first documented evidence for the use of metallic wires in textile clothing is found in World War II. Nowadays, more sophisticated conductive yarns that contain all the properties of textile yarns are being produced. The manufacture of conductive yarns has contributed to textiles finding increasing application in the field of electrical components and electronics. Further textile actuators such as heating fabrics have also been used in numerous and varied fields such as sports, leisure, medicine. Heating textiles can be deployed for household use, such as in heated floors, walls and roofs etc. These textiles are also used for other industrial or technical purposes such as motorbike gloves, heating pads, leisure and sport garments and in the automotive industry. They are also used in medical fields such as electrotherapy treatment, medical blankets for maintaining a patient’s body temperature, strain sensors and motion-capturing devices [1-9]. Temperature control is one of the most important functions of clothes. Most of heating elements use the principle of Joule heating, which is generated when an electric current is passed through a conductive material.

Page 367 of 1108

All conductive materials are heating elements in principle. Conductive materials such as metals and conducting polymers are already being used in textiles designed as antistatic materials, for electromagnetic interference shielding, heating, the transmission of electrical signals and in sensors. The heating material used is the most important factor in designing heat-radiating textiles. Heating elements are divided into two categories by shape: sheet-type heating elements and wire-type heating elements. However the voltage is supplied, the temperature of the heat radiated and the capacity of the battery are problems which need to be examined before selecting the heating material. The temperature of the heating materials depends on the thermal power given off by the textile. Clothing heated by the textiles can ensure an appropriate temperature gradient between the body and the environment. The required temperature gradient can be obtained either by passive or active clothing. Passive clothing is not suitable where a high amount of work is required, because layers and layers of clothing hinder the movement of the wearer. Active clothing can react to changes in metabolism or climate conditions. In the past, the following were used as heating elements in active clothing: metallic heating elements, graphite elements, conductive rubbers, and water heater systems. The use of such heaters was subject to many limitations: the increased mass of the clothing, the rigidity of systems, the limitations on the evaporation/extraction of sweat, etc. Textile heating elements can be manufactured from any type of textile products such as nonwoven fabric, knitted fabric, woven fabric and embroidery. Heating elements made of nonwoven fabric have, however, proved to be of little use, owing to the high electrical resistance of conductive nonwoven fabric. The resistance of heating elements made of woven fabric is lower than that of a heating element of the same dimensions made of knitted fabric due to the structure of these materials [1,2,10-13].

2. Experimental Study 2.1.

Materials

In the experimental study, needle-punched nonwoven fabrics were produced from Silver.STAT6.7dtex silver-coated staple polyamide (procured from the R-Stat SAS Company/France) and wool fibres by using an Automatex needle-punching line consisting of carding, cross-lapper and needle-punch machines.

2.2.

Production of Needle Punched Nonwoven Fabric

An Automatex laboratory-type needle-punching line, consisting of carding, cross-lapper and needlepunching machines, was used for the production of nonwoven fabrics from 6.7dtex silver-coated staple polyamide and wool fibre. Production of the needle-punched nonwoven fabrics was carried out continuously and the working speed of the carding machine was kept at 15m/min. The width of carding machine was approximately 50cm. The wool-type carding machine and its various parts are shown in Figure 1. The carding machine and needle-punching machine parameters used for the production of the nonwoven fabrics are given in Table 1 and Table 2 respectively. This band transfers the material to successive needle-punching machine; the speed of the latter determines the weight per square meters of the finished product. Table 1. Working Parameters of Carding Machine

Table 2. Working Parameters of Needle Punching Machine

Figure 1. Automatex Needle Punching Production Line

Page 368 of 1108

The PNNF-Ag/PA66 coded nonwoven fabric was produced from 6.7dtex silver-coated staple polyamide by using the machine settings mentioned above. The other PNNF-Ag/PA66/W nonwoven fabric sample was composed of three layers. Two of these were nonwoven fabric manufactured with wool fibres and the other one was prepared from 6.7dtex silver-coated staple polyamide. In first stage of production of the PNNFAg/PA66/W nonwoven fabric sample, the three layers were prepared separately. After that, these layers were needle-punched together. The cross-section and longitudinal views of the PNNF-Ag/PA66/W and PNNFAg/PA66 sample fabrics are shown in Figure 2.

Figure 2. a) Longitudinal view of PNNF-Ag/PA66 sample fabric; b) Cross-section view of PNNFAg/PA66 sample fabric; c) Longitudinal view of PNNF-Ag/PA-66/W sample fabric; d) Cross-section view of PNNF-Ag/PA66/W sample fabric

2.3.

Joule Heating Measurement

The Joule heating effect in the nonwoven fabrics was measured using a Farnell PDD3502A Dual 35V, 2A power supply and PICO TC-08 8 channel thermocouple data logger. A sample size of 1x1 inch was connected to the power supply using two adhesive copper tapes attached to each end of sample for electrical contacts with the fabric sample with the thermocouple mounted on the top surface and inside the fabric.

Figure 3. Testing set-up for the Joule heating measurements

3. Results And Discussion The temperature variations in the nonwoven fabrics were measured for 4,000 seconds to examine personal thermal management via Joule heating and then the heating and cooling temperature values were recorded. As shown in Figure 4, the results obtained from thermal measurements of the nonwoven fabrics were then compared with each other.

Page 369 of 1108

Figure 4. a) Comparison of temperature evolution for interior and surface of PNNF-Ag/PA66 fabric sample; b) Comparison of temperature evolution for interior and surface of PNNF-Ag/PA66/W fabric sample; c) Comparison of temperature evolution for interior of PNNF-Ag/PA66 and PNNF-Ag/PA66/W fabric samples; d) Comparison of temperature evolution for surface of PNNF-Ag/PA66 and PNNF-Ag/PA66/W fabric samples

Figure 4(a) compares the temperature evolution of the interior and surface of PNNF-Ag/PA66 coded nonwoven fabrics. The temperature of the surface was greater than the interior temperature by around 2 0C in the period when power was applied, which was between 0 and 2000 sec. The highest temperatures of the interior and surface of the fabrics were 33 and 35 0C respectively. The heat increased on the inside and surface of the nonwoven fabric between 0 and 2000 sec. The temperature curves were stable between 1000 and 2000 sec. Both the interior and surface of nonwoven fabrics showed a similar temperature behaviour in the cooling period, which was between 2000 and 4000 sec. Figure 4(b) compares the temperature evolution of the interior and surface of PNNF-Ag/PA66W coded nonwoven fabrics. The temperature of the interior was greater than the surface temperature by around 4 0C in the period when power was applied, which was between 0 and 2000 sec. The highest temperatures of the surface and interior of the fabrics were 32 and 36 0C respectively. The heat increased on the inside and surface of nonwoven fabrics from 0 to 2000 sec. The temperature curves were stable between 1000 and 2000 sec. Examining the heating behaviour of the samples in the cooling period, between 2000 and 4000 sec, less heat was lost from the interior than from the surface. Figure 4(c) compares the temperature evolution of the interior of the PNNF-Ag/PA66 and PNNFAg/PA66W coded nonwoven fabrics. The interior temperature of PNNF-Ag/PA66W was greater than that of PNNF-Ag/PA66 by around 4 0C for the period when power was applied, which was between 0 and 2000 sec. The highest inside temperature values obtained were 32 and 36 0C for PNNF-Ag/PA66 and PNNF-Ag/PA66W, respectively. The heat increased on the interior of the PNNF-Ag/PA66 and PNNF-Ag/PA66W nonwoven fabrics from 0 to 2000 sec. The temperature curves were stable between 1000 and 2000 sec. Examining the

Page 370 of 1108

heating behaviour of the interior in the cooling period, between 2000 and 4000 sec, much more heat was lost from PNNF-Ag/PA66 than from PNNF-Ag/PA66W. Figure 4(d) compares the temperature evolution for the surface of the PNNF-Ag/PA66 and PNNFAg/PA66W coded nonwoven fabrics. The surface temperature of PNNF-Ag/PA66W was less than PNNFAg/PA66 by around 4 0C in the period when power was applied, which was between 0 and 2000 sec. The highest surface temperature values obtained were 36 and 32 0C for PNNF-Ag/PA66 and PNNF-Ag/PA66W respectively. The heat increased on the surface of PNNF-Ag/PA66 and PNNF-Ag/PA66W nonwoven fabrics from 0 to 2000 sec. The temperature curves were stable between 1000 and 2000 sec. Examining the heating behaviour of the interior in the cooling period, between 2000 and 4000 sec, less heat was lost from PNNFAg/PA66 than from PNNF-Ag/PA66W.

4. Conclusions In this study, the thermal evolution for NNF-Ag/PA66 and PNNF-Ag/PA66W nonwoven fabrics was investigated. The temperature variations of nonwoven fabrics were measured via Joule heating for 4000 seconds to examine the capacity for personal thermal management. The results show that the variation of temperature of these nonwoven fabrics increased with the testing time. Also, the interior of the PNNFAg/PA66W nonwoven fabric achieved a greater heat than the interior of the PNNF-Ag/PA66 nonwoven fabric during the heating and cooling periods because of the insulating properties of wool. On the other hand, the surface of the PNNF-Ag/PA66W nonwoven fabric attained less heat than the surface of PNNF-Ag/PA66 nonwoven fabric during the heating and cooling periods. In addition, the surface and inside areas of the nonwoven fabrics displayed different temperature values related to their compositional properties. The results clearly show that the needle-punched nonwoven fabrics can be used for thermal management. These structures are currently used for industrial and technical purposes such as heated floors, walls and roof, heating pads, leisure garments, medical blanket and sport garments as well as in the automotive industry.

References 1- Hamdani S.T.A., Potluri P., Fernando A. “The-Mechanical Behavior of Textile Heating Fabric Based on Silver Coated Polymeric Yarn” Materials, Doi: 10.3390/ma6031072, 2013, 1072-1089. 2- Ultra Heating Fabric, Available online: http://www.adafruit.com/datasheets/Ultra%20Heating%20Fabric.pdf 3- Hsu, P. C., X. Liu, C. Liu, X. Xie, H. R. Lee, A. J. Welch, T. Zhao and Y. Cui (2015). "Personal thermal management by metallic nanowire-coated textile." Nano Letter 15(1): 365-371. 4- Scott, R.A. Textiles for Protection; Woodhead Publishing: Cambridge, UK, 2005; pp. 378–397. 5- Scott, R.A. The technology of electrically heated clothing. Ergonomics 1988, 31, 1065–1081. 6- Alagirusamy, R.; Eichhoff, J.; Gries, T.; Jockenhoevel, S. Coating of conductive yarns for electrotextile applications. J. Text. Inst. 2012, 104, 1–8. 7- Droval, G.; Glouannec, P.; Feller, J.F.; Salagnac, P. Simulation of electrical and thermal behaviour of conductive polymer composites heating elements. J. Thermophys. Heat Transf. 2005, 19, 375–381. 8- El-Tantawy, F.; Kamada, K.; Ohnabe, H. In situ network structure, electrical and thermal properties of conductive epoxy resin–carbon black composites for electrical heater applications. Mater. Lett. 2002, 56, 112–126. 9- Lee, J.Y.; Park, D.W.; Lim, J.O. Polypyrrole-coated woven fabric as a flexible surface-heating element. Macromol. Res. 2003, 11, 481–487. 10- Hao, L.; Yi, Z.; Li, C.; Li, X.; Yuxiu, W.; Yan, G. Development and characterization of flexible heating fabric based on conductive filaments. Measurement 2012, 45, 1855–1865. 11- Nakad, Z.; Jones, M.; Martin, T.; Shenoy, R. Using electronic textiles to implement an acoustic beamforming array: A case study. Pervasive Mob. Comput. 2007, 3, 581–606. 12- Cho, G. Smart Clothing: Technology and Applications; CRC Press: Boca Raton, FL, USA, 2010; Volume 30, pp. 89–113. 13- Kayacan, O.; Bulgun, E.Y. Heating behaviors of metallic textile structures. Int. J. Cloth. Sci. Technol. 2009, 21, 127–136.

Page 371 of 1108

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

Thermal Protective Performance of the Air Layer in Firefighter’s Protective Clothing Seung-Tae Hong 1 +, Hae-Hyoung Kim 1 Young-Soo Kim 2, Pyoung-Kyu Park 2, Hyung-Seob Kim 3 and Seung-Joon Yoo 3 1

Korea Fire Institute, 331 Jisamro, Giheung-gu, Yongin-si, Gyeonggi-do, 446-909, Korea San-Cheong, #53 Jungbudaero 1960, Yangji-myun, Cheoin-gu, Yongin-si, Gyeonggi-do, 449-828, Korea 3 Seonam University, 7-111, Pyeongchon-gil, Songak, Asan, 336-922, Korea

Abstract. Thermal protective performance of the air layer in firefighter’s protective clothing was investigated. The thermal protective performance test was carried out in the firefighter’s protective clothing composed of 3 layers by the method fixed in ASTM D 4108 (convection), ISO 6942 (radiation) and ISO 17492(convection and radiation). Convection, radiation and both were respectively used as thermal heat fluxes. The outer shell was composed of aramid (60%) and PBI (40%). The mid-layer was composed of an aramid and a PTFE (polytetrafluoroethylene) film. The liner (felt) was composed of 100% of aramid. The liner was replaced by the air layer to reduce the weight of the clothing. When the air layer was over 3 mm, the thermal protective performance (TPP) rating for the flame exposure satisfied the KFI (Korea Fire Institute) standard. Radiant heat transfer index (RHTI) for the radiant exposure satisfied the ISO 11613 standard in over 2 mm of the air layer. The heat transfer index (HTI) for combined flame and radiant exposure satisfied the ISO 11613 standard in over 3 mm of the air layer. In the future, new microporous materials such as aerogel, nano-fiber etc. will be applied to improve the comfort by reducing the weight of protective clothing. Keywords: Thermal Protective performance, Protective Clothing, Air layer

1. Introduction Firefighter’s protective clothing should be designed to perform several functions, the most important of which is protection against heat and flames. Protection against moisture is also important. Protective clothing ensembles for structural firefighting typically consist of a flame-resistant outer shell, a middle layer (moisture barrier) and an inner liner. Heat and fire in different forms are the most important hazards in firefighting. There are three basic mechanisms of heat transfer, namely conduction, convection and radiation. Three mechanisms of heat transfer in fire are shown in Fig 1. While it is probable that all three contribute in every fire, it is often found that one predominates at a given stage, or in a given location. The thermal hazards in ground fire conditions are usually radiant or convective energy from open flames[1]. Convective heat transfer involves movement of the fluid medium. It occurs at all stages in a fire but is particularly important early on when thermal radiation levels are low. Radiative heat transfer requires no intervening medium between the heat source and the receiver. It is the transfer of energy by electromagnetic waves. It becomes the dominant mode of heat transfer in fires as the fuel bed diameter increases beyond about 0.3 m[2]. In this work, convection, radiation and both were respectively used as thermal heat fluxes for performance tests. We have investigated the thermal protective performance of the air layer in firefighter’s protective clothing.

2. Experimental Firefighter’s protective clothing manufactured by San-Cheong was used in all performance tests. The protective clothing consists of 3 layers (outer shell, mid-layer, liner). Materials for each layer are shown in Table 1. The liner was replaced by air layer to reduce the weight of the clothing. The performance test was carried out with increasing the thickness of air layer.

Page 372 of 1108

Table 1: Materials of firefighter’s protective clothing Layer Outer shell Mid layer Liner(felt)

Material Aramid 60% + PBI1 40% Aramid / PTFE2 Aramid 100%

PBI = polybenzimidazoles, 2PTFE = polytetrafluoroethylene

Prior to testing, the specimens were conditioned for 24 h at a temperature of 20 ± 2℃ and a relative humidity of 65 ± 2% in accordance with ISO 139. All tests were carried out in an atmosphere having a temperature of 10℃ to 30℃ and a relative humidity of 15% to 80% and which is free from draughts. The average value for 3 specimens was calculated in all tests.

2.1.

Thermal Protective Performance(TPP)

Thermal protective performance test was carried out by a standard fixed in ASTM D 4108[3]. Exposure heat flux was set to 8.3 ± 0.2 W/cm2 (2.0 ± 0.05 cal/cm2·sec). The exposure energy to the thermal end point is the TPP rating (W/cm2 or cal/cm2·sec) and is calculated as follows: TPP rating = F×T (1) 2 2 Where, F = exposure heat flux, W/cm (cal/cm ·sec) T = exposure time, sec

2.2.

Radiant Heat Transfer Index(RHTI)

Radiant heat transfer index was measured by the method fixed in ISO 6942[4]. Incident heat flux density was set to 40 kW/m2.

2.3.

Heat Transfer Index(HTI)

Heat transfer index was measured by the method fixed in ISO 17492[5]. Thermal-flux source consists of a convective thermal-flux source and a radiant thermal-flux source. Total heat flux for the exposure energy was set to 80 ± 2 kW/m2 and half of that amount was radiant component.

3. Results and Discussion Firefighter’s protective clothing used in this study was composed of 3 layers. Outer shell protects human body against fire layer. Mid-layer is a moisture barrier to protect inner layer from getting wet. Liner is a thermal barrier insulating the body from the heat. The liner was changed by the air layer to reduce the weight of the clothing. Thermal protective performance (TPP) rating for the flame exposure (ASTM D 4108) was measured. TPP ratings with an increase in the thickness of the air layer are shown in Fig. 2. The thickness of the air layer changed from 1 mm to 10 mm. TPP rating should be over 30 cal/cm2 in order to satisfy the KFI (Korea Fire Institute) standard[6]. The value ‘30’ means, firefighters need at least 15 sec to escape from the fire. When the thickness of the air layer was over 3 mm, the TPP rating satisfied the KFI standard. Radiant heat transfer index (RHTI) for the radiant exposure (ISO 6942) was measured. RHTI values with an increase in the thickness of the air layer are shown in Fig 3. RHTI 12 and RHTI 24 mean the times for temperature rises of 12℃ and 24℃ in the calorimeter. The RHTI 24 value should be over 22 sec and the difference between RHTI 24 and RHTI 12 is over 6 sec in order to satisfy the ISO 11613 standard[7]. When the thickness of the air layer was over 2 mm, the RHTI 12 and RHTI 24 satisfied the ISO 11613 standard. Heat transfer index (HTI) for combined flame and radiant exposure was also measured. HTI values with an increase in the thickness of the air layer are shown in Fig 4. HTI 12 and HTI 24 mean the times for temperature rises of 12℃ and 24℃ in the calorimeter. The HTI 24 value should be over 17.5 sec in order to satisfy the ISO 11613 standard. When the thickness of the air layer was over 3 mm, the HTI 24 satisfied the ISO 11613 standard. HTI for existing protective clothing was also measured by the method fixed in ISO 17492. The HTI 24 values for before and after replacing a liner by the air layer were compared in Fig. 5. The HTI 24 of B(before)

Page 373 of 1108

was higher than that of A(after) which was replaced by the air layer(10 mm). Though the application of the air layer for the existing protecting clothing did not improve the thermal protecting performance, the performance satisfied the KFI and ISO standards. The contradiction between protection and comfort is probably the most pronounced for firefighter’s protective clothing. The weight of protecting clothing has been getting higher to improve the protection performance. Nowadays, the main goal for the development of new materials for protective clothing is usually the improvement of ergonomics and thermal comport while maintaining the protection level. In this study, the air was considered as a light material. Heat conductivity of the air is about 1/10 of general fibers. A lot of attentions have been currently focused on microporous barrier materials and synthetic fibers of high performance in manufacturing garments for fire resistance. The volume ratio of air in aerogel is over 95% and nano-fiber has lower density and larger specific surface area per unit volume than general fibers. In the future, new microporous materials such as aerogel, nano-fiber etc. will be applied to improve the comfort by reducing the weight of protective clothing.

4. References [1] R. E. Scott, Textiles for Protection, Woodhead Publishing Ltd., Cambridge (2005) [2] D. Drysdale, An Introduction to Fire Dynamics, 2nd ed., John Wiley & Sons, Chichester (1998) [3] ASTM D 4108, “Standard Test Method for Thermal Protective Performance of Materials for Clothing by OpenFlame Method”, American Society for Testing Materials (1987) [4] ISO 6942, 3rd ed., “Protective Clothing - Protection against Heat and Fire - Method of Test: Evaluation of Materials and Material Assemblies When Exposed to a Source of Radiant Heat”, International Organization for Standardization (2002) [5] ISO 17492, 1st ed., “Clothing for Protection against Heat and Flame – Determination of Heat Transmission on Exposure to both Flame and Radiant Heat”, International Organization for Standardization (2003) [6] KFI Standard for Firefighter’s Clothing, Korea Fire Institute, 165 (2014) [7] ISO 11613, 1st ed., “Protective Clothing for Firefighters – Laboratory Test Methods and Performance Requirements”, International Organization for Standardization (1999)

Page 374 of 1108

Fig. 1: Three mechanisms (conduction, convection and radiation) of heat transfer in fire

Fig. 2: TPP rating with an increase in the thickness of the air layer.

Fig. 4: HTI with an increase in the thickness of the air layer.

Fig. 3: RHTI with an increase in the thickness of the air layer.

Fig. 5: HTI 24 before and after replacing a liner by the air layer. A: after(10 mm air layer) B: before

Page 375 of 1108

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

Three Dimensional Composite Prepared by Vacuum-assisted Resin Transfer Molding Young Ah Kang 1 +, Seung Hee Oh 1 and Jong S. Park 1 1

Department of Organic Material and Polymer Engineering, Dong-A University, Busan 604-714, Korea.

Abstract. Three dimensional hybrid fabric composed of ultrahigh molecular weight polyethylene (UHMWPE) and polyethylene terephthalate (PET) was knitted by Raschel Warp Knitting method, which can be applied in civil engineering and construction uses. UHMWPE/PET hybrid fabric-reinforced composites were prepared by vacuum-assisted resin transfer molding (VaRTM) apparatus with a newly designed mold. Unsaturated polyester resin was used as a matrix, which involved pre-curing for 24 h at room temperature and then post-curing at different temperatures from 80 to 120 째C. For the obtained three-dimensional composites, the weight ratio of fiber-to-matrix in the composite reached about 60 wt%, as estimated by TGA.

Keywords: VaRTM, fiber-reinforced composites, UHMWPE/PET hybrid fabrics.

1. Introduction Vacuum-assisted resin transfer molding (VaRTM) has been proposed as a more advanced process for manufacturing large composite structures. Uddin et al. [1-3] introduced VaRTM used a single-sided-mold technology to infuse resin into fabric, which could then be used to wrap large structures (e.g., bridge girders and columns). VaRTM involves vacuum infusion in a rigid, closed molding. The fiber reinforcement is compressed by the pressure of the atmosphere, and thus pressed tightly against the rigid surface of the mold. The VaRTM process is associated with low tooling cost and facilitates the production of high quality, defectfree structures. The VaRTM process has been successfully used to make large parts with complex shapes, as well as for unique architecture with high structural performance. Using this method, the vacuum expels air and VOC from the preform assembly and allows the resin to flow into the preform. A pressure of up to 1 atm provides the driving force for the resin to impregnate the dry preforms, and the compression force to compact the composite to the desired volume fraction of reinforcementto-matrix. Accordingly, a high volume fraction of fiber reinforcement can be optimized to yield superior toughness and strength in a more flexible composite structure. However, these properties may be influenced by the extent to which the resin has cured, particularly after curing at room temperature. Cain et al. [4] investigated time-dependent properties of composite structure created using VaRTM, and defined the postcuring effects. In this study, a three-dimensional composite reinforced by a hybrid knitted fabric composed of ultrahigh molecular weight polyethylene (UHMWPE) and polyethylene terephthalate (PET) was produced using an inhouse prepared VaRTM apparatus. Though UHMWPE has numerous useful properties (light weight, high strength, yield strength as high as 2.4 GPa, and specific gravity as low as 0.97), it has been seldom adopted as a fiber reinforcement in composites due to its poor thermal resistance. The composite was prepared by precuring for 24 h at room temperature, and then post-curing in a range from 80 to 120 째C. These post-curing temperatures were carefully selected to correspond with the relaxation of UHMWPE [5, 6]. For the VaRTM method, several processing factors influence the preparation and properties of the composite, such as curing temperature and time, and fabric preform structure. Structure and mechanical properties of the composite were

Corresponding author. Tel.: + 82-51-200-7544. E-mail address: yakang@dau.ac.kr.

Page 376 of 1108

investigated through scanning electronic microscopy (SEM), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), tensile and flexural test.

2. Experimental 2.1.

Materials

Unsaturated polyester resin (HF-123NHL, AEKYUNG CHEMICAL Co., Ltd.) was used as matrix material, and methyl ethyl ketone peroxide of 1.0 v% was used as a catalyst which initiates the crosslinking of unsaturated polyester resins in composites. The three-dimensional fabric (UHMWPE/PET 25, which was kindly provided by DAERIM TEX Co., LTD. (Korea), was used as received without additional cleaning. The fabric was warp knitted with UHMWPE and PET filament by means of Raschel Warp Knitting machine.

2.2.

Preparation of Composite

Schematic diagram of the VaRTM apparatus equipped with a newly designed mold is shown, in which a 3dimensional aluminum mold (300×300×30 mm) was used for the preparation of UHMWPE/PET fabric reinforced composites (Fig. 1). A 2 mm-thick Teflon plate with lots of Teflon cylinders (20φ×20mm) was placed in the mold so as to produce the 3-dimensional composite. In the mold, double rubber gaskets were sited around the perimeter of the mold to provide a tight seal.

Fig. 1: Schematic of the VaRTM apparatus for preparation of 3-dimensinal composite.

Resin and initiator were mixed at a ratio of 100:1 by volume, and the mixture was stirred at room temperature for 5 min to combine thoroughly the resin and initiator. Two vacuum pumps were used: Pump 1 was to compact the preform by maintaining a constant vacuum, and Pump 2 was to inject the resin into the mold. The resin mixture was injected into cavities in the mold at room temperature, under constant vacuum. Residual air bubbles in the mold were extracted into a resin trap tank. The composite was cured for 2 h and 24 h under the constant vacuum and under free vacuum at room temperature, respectively, which was referred to as pre-curing, and then was post-cured at 80, or 120°C for 60 min. The reinforcement (3-dimensional knitted fabric) and the obtained composite were shown in Fig.2

Fig. 2: Photographs of reinforcement (left) and composite (right).

2.3.

Characterizations

The thermal properties of the composites were measured using a thermogravimetric analyser (TGA Q500, TA Instrument) at a ramping rate of 10°C/min under nitrogen flow. The viscoelastic behavior of the composites and neat resin films were measured using a dynamic mechanical analyzer (DMA Q800, TA Instrument) in a frequency mode of 1 Hz, at a ramping rate of 4 °C/min under nitrogen flow. The tensile and flexural properties of the composites and neat resin film were measured using an Instron 56969 CRE testing machine according

Page 377 of 1108

to KS M ISO 527-4 and KS M ISO 178 procedures, respectively, at a test speed of 2 mm/min. Cross-sections of composite fractured by the tensile test were observed with a scanning electron microscope (SEM, Hitachi S3500N). The surfaces of the composites were coated with thin gold film to increase their conductance before SEM measurements.

3. Results and Discussion TGA scans with temperature for fabric, neat resin, and composite are shown in Fig. 3. The UHMWPE/PET hybrid fabric started a primary decomposition around 400°C, with weight loss of about 8% prior to the onset of main decomposition. It is attributed presumably to the evaporation of oiling agents added in the spinning and weaving processes. The decomposition curve of hybrid fabric was not separated because of the nearly same decomposition temperature of both components, UHMWPE and PET. The neat polyester resin was decomposed mostly around from 350 to 430°C and left ashes below about 5%. The decomposition curves of neat resin showed little difference between pre-curing and post-curing. Meanwhile, the composite started decomposition in two stages at over 300°C. These weight losses involved the matrix resin component at temperatures from 300 to 350°C (the first stage) and the UHMWPE/PET hybrid fabric reinforcement component at temperatures from 400 to 450°C (the second stage). The weight ratio of reinforcement-to-matrix can be approximately estimated from the weight loss of the composite, and the ratio reached about 60 wt%.

Fig. 3: TGA thermograms of fabric, resin, and composite.

4. References [1] N. Uddin, “Developments in Fiber-Reinforced Polymer (FRP) Composites for Civil Engineering”, Chapter 4, Woodhead Publishing, May 2013. [2] K. N. Indira, P. Jyotishkumar, and S. Thomas, Fiber. Polym., 13, 1319 (2012). [3] S. Laurenzi, A. Grilli, M. Pinna, F. De Nicola, G. Cattaneo, and M. Marchetti, Compos Part B-Eng., 57, 47 (2014). [4] J. J. Cain, N. L. Post, J. J. Lesko, S. W. Case, Y. N. Lin, J. S. Riffle, and P. E. Hess, J. Eng. Mater. Technol., 128, 34 (2005). [5] Y. P. Khanna, E. A. Turi, T. J. Taylor, V. V. Vickroy, and R. F. Abbott, Macromolecules, 18, 1302 (1985). [6] C. S. Lee, J. Y. Jho, K. Choi, and T. W. Hwang, Macromol. Res., 12, 141 (2004).

5. Acknowledgement This research was supported by the Ministry of Science, ICT and Future Planning of Korea, from the RCT (Regional Connection Technology) support program (Grant No. R0002902) supervised by the KIAT (Korea Institute for Advancement of Technology).

Page 378 of 1108

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

Transverse Modulus of Carbon Fibre by Compression and Nanoindentation Hillbrick, L.K 1+, Huson, M.G 1, Naylor, G.R.S 1, Lucas, S 1, Mangalampalli, K 2 and Bradby, J 2 1

CSIRO Manufacturing The Australian National University

Abstract. Lightweight, high strength, high modulus carbon fibre reinforced polymer composites are increasingly being used for structural applications in a broad range of industries, including aerospace, military, engineering and sporting equipment. Computer simulation techniques are often used to predict the elastic behaviour experienced by carbon fibre composite materials whilst in service and under load. These simulation techniques typically require knowledge about the elastic behaviour of the composite’s constituent materials. The most challenging is measuring the transverse modulus of the reinforcing carbon fibre, due to its small diameter. This paper reports on two approaches for determining the transverse modulus; nano-indentation and transverse compression of the cylindrical fibre. Since several different theoretical models have been proposed for the calculation of the transverse modulus of fibres from compression experiments, compression tests have been carried out on model elastic cylinders of poly(methyl methacrylate), as well as cuboids machined from the cylinders. The transverse modulus of the cylinders was determined directly from compression experiments on the cuboids and indirectly by fitting the different models to the cylinder compression data. Results from both the transverse compression and nano-indentation techniques are discussed, including the difficulties associated with these techniques, such as instrument compliance and the release of internal stresses during machining.

Keywords: transverse modulus, carbon fibre, compression, nano-indentation

1. Introduction The compression of a cylindrical fibre between parallel plates is a widely reported method for determining the transverse compression properties of a highly oriented fibre. At least seven analytical models are reported in the literature and have been used by researchers to interpret the transverse compressive behaviour of various fibres in terms of their Young’s modulus (axial, E L and transverse, E T ), contact half width (b), the load per unit length (F), the radius of curvature (R) of the cylinder and Poisson’s ratio (ν) (Table 1). These models make a number of assumptions in their derivations, such as the system being in a state of plane strain and whether the stress distribution is elliptical or parabolic. The models proposed by Lundberg (equation 2), Phoenix et al. (equation 4) and Jawad and Ward (equation 6) can be shown to be indistinguishable from one another provided b<<R. Although these models have been used by researchers to determine the transverse modulus of fibres, there has been very little attempt to evaluate the validity of the different models. In order to compare the models, the transverse compression curves of poly (methyl methacrylate) (PMMA) cylinders were analysed using all of the models and the results compared to the transverse modulus obtained directly from the compression of the cuboids machined from the cylinders. The model deemed to best describe the compression was used to analyse the transverse compression curves of individual carbon fibres, compressed using a commercial nano-indenter fitted with a flat ended probe. Transverse modulus of carbon fibres was also determined from nano-indentation experiments.

2. Experimental PMMA cylindrical rod (EFM Plastics), with a diameter of 25 mm, was cut into six lengths of 50 mm. Four of six samples were retained as cylinders (cylinders 1-4) and two were machined into cuboids. +

Corresponding author. Tel.: + 61-352-464 802 E-mail address: linda.hillbrick@csiro.au

Page 379 of 1108

The dimensions of each side of the cuboids were 14.9 mm. After testing, cylinders 3 and 4 were machined to form smaller cylinders with diameters of 17 mm and 20 mm respectively and retested. Compression of the PMMA samples was carried out on an Instron tester (model 5967) fitted with an Advanced Non-Contacting Video Extensometer (model 2663-821). Samples were compressed both axially and transversely at a rate of 25%/min to a strain level of 2-5% and data was collected using Bluehill 3 software. The reflective spots used by the video extensometer were placed on metal plates, directly above and below the samples. Transverse modulus was obtained by fitting the equations in Table 1 to the transverse compression curves of each cylinder using the experimentally determined values of E L (Table 2) and ν L = 0.399. For the Cheng equation ν T was assumed to be equal to ν L . The data was fitted in the region from 0.5 to 1.5% strain. Residual stress in the PMMA was assessed by viewing the samples under crossed polars, both before and after machining. Table 1: Models relating the transverse compression (U) of anisotropic cylinders to the applied force per unit length (F) Year

Equation

Ref.

Equ #

1907

4F  1 ν  − π  E T E L

  2 R  1   Ln +    b  3 

Foppl [1]

1949

4 F  1 ν L2  − π  E T E L

  4 R  1   Ln −    b  2 

Lundberg [2]

Morris [3]

Phoenix & Skelton [4]

Sherif et al. [5]

Jawad & Ward [6]

Cheng et al. [7]

1968

1974

1978

2004

4F πb 2

4 F  1 ν L2  R    sinh −1    − π  E T E L   b 

4 F  1 ν L2  − π  E T E L

1976

2 L

 2R  1   sinh −1  −   b  2 

4 F  1 ν L2   2 R  1    Ln − +  π  ET E L   b  2 

4 F  1 ν L2  − π  E T E L

(

 R   sinh −1   + 0.19  b  

)

2 2  ν T ν L 2    ν 2  b 2 + R 2 − R R +  1 − L b 2 Ln b + R + R  −  −    b  E T E L    ET E L 

Micro-compression of individual IM7 carbon fibres (Hexcel) were carried out on a commercial Hysitron Instrumented Indenter, Hysitron 3D OmniProbe High load TI 950 TriboIndenter (Minneapolis, USA), fitted with a 50 µm diameter flat ended, truncated conical probe with a 60ᵒ included angle. The carbon fibres were fixed onto a SiC (single crystal, 6H polytype) substrate by nail polish and the system calibrated by indentation with a Berkovich indenter on quartz. Nano-indentation was used to determine the transverse modulus of IM7 carbon fibre embedded in 977-3 epoxy matrix. The same Hysitron TriboIndenter, fitted with a Berkovich diamond indenter, with an end radius of ≈100 nm, was used. A partial unloading (80%) experiment was performed with the load increasing in 13 steps from 1000 μN up to a maximum load of 10000 μN. Each load cycle comprised 1 s loading, 1 s holding and 1 s unloading. The modulus was determined by analysing the unloading region of the load-displacement curves using the method of Oliver and Pharr [8].

3. Results and Discussion The axial moduli for the machined PMMA cuboids and cylinders were consistently larger than that measured for the original 25 mm diameter PMMA cylinders (Fig.1A). Examination of the samples under crossed polars (Fig.1B) showed that residual stress was present in all samples, as indicated by the coloured bands (stress decreases in the order blue, red, yellow, white and black). The stress was greatest in the unmachined cylinders and diminished as the extent of machining increased. Researchers studying soda-lime glass [9] observed that reducing the tensile stress in a sample led to an increased modulus, suggesting that this is the most likely explanation for the increased modulus of the machined samples.

Page 380 of 1108

Axial Modulus (MPa)

3900

cuboid

3700

Cylinder 1 Cylinder 2

3500

Cylinder 3 3300

Cylinder 4

3100 2900 0

100

200

300

400

500

600

PMMA Cross sectional area (mm 2 )

Fig. 1: (A) Axial moduli (E L ) as a function of PMMA cross-sectional area (B) Residual stress patterns in PMMA. Diagonally from top left: original cylinder, 20mm cylinder, 17 mm cylinder and cuboid

An overestimation of E L by 10% leads to an overestimation in E T of only 1.1% so the increased axial modulus of the cuboid, potentially due to the release of residual stress during machining, may not have great implications in calculating the transverse modulus using the models. However any change in transverse modulus, as a result of reduced residual stress, will have significant implications in the evaluation of the models and thereby the choice of preferred model. Given these differences in axial modulus, the value of the specific cylinder being tested was used in analysing the cylinder transverse compression data to determine its transverse modulus. No significant effect of residual stress on the transverse modulus was found (P > 0.1), as shown by comparing the transverse modulus of Cylinder 3M with its un-machined parent Cylinder 3 (Table 2). This was regardless of which model was used to calculate the transverse modulus. This validates using the transverse modulus of the cuboid to evaluate the models. The average transverse modulus (E T ) measured for the cuboid was 2657 MPa (CV 5.3%). The transverse modulus of each cylinder, as predicted by the various models, is shown in Table 2. The Foppl model and the models developed by Jawad and Ward, as well as the mathematically equivalent models derived by Phoenix et al. and Lundberg predicted transverse modulus values that were closest to the value measured for the cuboids. The values were respectively 2% greater and 3% lower. The Sherif, Morris and Cheng models predicted values that differed from the cuboid modulus by approximately 8%, 10% and 20% respectively. Table 2. Axial (E L ) and transverse moduli (E T ) of PMMA cylinders calculated using a range of models. Values in brackets are coefficient of variation. EL E T (MPa) (MPa) Lundgren Phoenix & Skelton Jawad & n n Cheng Morris Ward Foppl Sherif 1 346 1 5 9 0 Cylinder 1 2165 (1.7) 2441 (1.6) 2622 (1.6) 2752 (1.6) 2903 (1.5) (2. 4) 1 330 1 1 2 0 Cylinder 2 2082 (1.4) 2347 (1.4) 2521 (1.3) 2646 (1.3) 2790 (1.3) (3. 3) 1 310 1 0 1 0 Cylinder 3 2098 (2.3) 2369 (2.3) 2541 (2.3) 2665 (2.2) 2808 (2.2) (1. 7)

Page 381 of 1108

1 0

Cylinder 4 Cylinder 3M Machined D 1 7 m m

1 0

320 6 (1. 3) 373 5 (1. 6)

1 0

Average

2167 (4.4)

2442 (4.4)

2617 (4.3)

2743 (4.2)

2889 (4.1)

2154 (4.0)

2422 (4.0)

2603 (3.9)

2733 (3.8)

2883 (3.8)

2581 (1.8)

2708 (1.8)

2855 (1.8)

2133 (1.9)

2404 (1.8)

Cylinder 4M is awaiting testing

The compression curves obtained for the compression of individual carbon fibres on the Hysitron Triboindenter were reasonably repeatable, however the shape of the compression curves were not consistent with any of the proposed models (Fig. 2A). Forcing a fit of the Jawad and Ward model in the region between 0.5 and 1.5% strain resulted in a calculated transverse modulus of only 1200 MPa which is much lower than would be expected for a carbon fibre. Accurate calibration and correction for instrument compliance was identified as an issue.

Young's Modulus (GPa)

Curve predicted by the Jawad and Ward equation

17 1

11 Indent No.

Fig. 2: (A) Hysitron load compression curves for six IM7 carbon fibres compared to an expected curve based on the Jawad &Ward equation with E T = 21 GPa, E L = 276 GPa, ν = 0.4 and d = 5.2 µm (B) Transverse modulus of six IM7 carbon fibres embedded in 977-3 epoxy matrix using nano-indentation

The results from nano-indentation tests are shown in Fig. 2B. The average transverse modulus of the IM7 carbon fibres was 20.7 ± 0.8 GPa.. The compliance of the underlying matrix has been removed by extrapolating the data to zero load. Fig 2A includes the expected curve based on the nano-indentation transverse modulus.

4. Conclusion The experimental transverse compression curves of the PMMA cylinders were analysed using the compression models. The best models were those by Foppl, Jawad and Ward, Phoenix and Skelton and Lundgren that gave an average transverse modulus within 3% of the value obtained by direct compression of the cuboid. The shapes of the transverse compression curves obtained for IM7 carbon fibres on the Hysitron were not consistent with any of the proposed models and more work is needed to solve the calibration and compliance issues. The transverse modulus of IM7 measured via the nano-indentation technique was 20.7 ± 0.8 GPa.

5. 1. 2.

References Foppl, A., Die wichtigsten lehren der hoheren elastizitatstheorie. Vorlesungen uber Technische Mechanik, 1907. Section 6 Various Applications: p. 311-372. Lundberg, G., Cylinder compressed between two plane bodies. 1949, SKF: Goteborg. As cited in McCallion, H. and N. Truong, The deformation of rough cylinders compressed between smooth flat surfaces of hard blocks. Wear, 1982. 79(3): p. 347-361. Morris, S., The determination of the lateral-compression modulus of fibres. The Journal of the Textile Institute, 1968. 59(11): p. 536-547.

Page 382 of 1108

4. 5. 6. 7.

8. 9.

Phoenix, S.L. and J. Skelton, Transverse compressive moduli and yield behavior of some orthotropic, highmodulus filaments. Textile Research Journal, 1974. 44(12): p. 934-940. Sherif, S.M., L.J. Segerlind and J.S. Frame, An equation for the modulus of elasticity of a radially compressed cylinder. Transactions of the American Society for Agricultural Engineers, 1976. 19(4): p. 782-791. Jawad, S.A. and I.M. Ward, The transverse compression of oriented nylon and polyethylene extrudates. Journal of Materials Science, 1978. 13(7): p. 1381-1387. Cheng, M., W.M. Chen and T. Weerasooriya, Experimental investigation of the transverse mechanical properties of a single kevlar KM2 fiber. International Journal of Solids and Structures, 2004. 41(22-23): p. 6215-6232. Oliver, W.C. and G.M. Pharr, An improved technique for determining hardness and elastic-modulus using load and displacement sensing indentation experiments. Journal of Materials Research, 1992. 7(6): p. 1564-1583. Kese, K.O., Z.C. Li and B. Bergman, Influence of residual stress on elastic modulus and hardness of soda-lime glass measured by nanoindentation. Journal of Materials Research, 2004. 19(10): p. 3109-3119.

Page 958 of 1108

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.

Page 962 of 1108

[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.