graphIn2015 Conference Book by Phantoms Foundation

December 03, 2015 Zaragoza (Spain)

GO Foundation is a private, globally focused not-for-profit organization devoted to accelerating the pace of graphene commercialization. We invest in innovation We advocate the industrial adoption of graphene materials and products We promote industry standards for graphene We offer expertise and facilities for collaborative development

With significant support from the Government of Canada and donations from major international organizations engaged in graphene technologies development, the GO Foundation’s Co-Founders are: U.S.-based NAATBatt International; the Phantoms Foundation of Spain, and; Grafoid Inc. of Canada. Go Foundation is based in Kingston, Ontario, Canada.

We empower the acceleration of graphene products to market Applications for development assistance and/or participation in the Foundation’s graphene cluster and related programs are available now through the GO Foundation Secretariat. Eligibility criteria are posted on the Foundation’s website at: www.gofoundation.ca

Index 3

Foreword Organising Committee Sponsors Exhibitors Contributions Keynote & Invited Oral ral Poster oster

4 4 4 5 7 16 28 8

Foreword For word On behalf of the Organising Committee, we take great pleasure in welcoming you to Zaragoza (Spain) for the 1st edition of the graphIn International Workshop (Graphene Industry – Challenges & Opportunities) Opportunities). This 1 day workshop aims at presenting the current state of the art and the opportunities of graphene opportunities graphene-based based materials and devices and its industrial challenges and opportunities, focusing on the most recent advances in technology developments and business opportunities in graphene commercialization.

This unique international event will provide a forum for sharing and developing innovations for the functional materials industries. The aim of graphIn will be to develop the relationships that will accelerate graphene industrial growth. This 1st edition has succeeded to bring together a large number of leading representatives of “graphene companies & labs”, sharing their market vision and business opportunities in diverse current market fields of graphene products and market applications. It will be the perfect place to get a complete overview into the state of the art and also to learn about the development of innovative and competitive commercial applications. The discussion in recent advances, difficulties and breakthroughs will be at his higher level. We are indebted to the following companies and government agencies for companies their financial support: American Elements, Grafoid Inc. and ICEX Spain Trade and Investment. We would also like to thank the exhibitors for their participation: Advanced Carbon Materials Dept. at Grupo Antolin Ingenieria, Applynano pplynano Solutions S.L., Avanzare Innovación Tecnológica, Centre for the Development of Industrial Technology (CDTI), GO Foundation, Grafoid Inc., Graphene Nanotech, S.L., Graphene Square Europe, Graphenea, GrapheneTech, Institut Catala de Nanociencia i Nanotecnología Nanotecnología (ICN2) and The Institute of Photonic Sciences (ICFO). In addition, thanks must be given to ETOPIA: Center for Art and Technology, Zaragoza Congresos, Ayuntamiento de Zaragoza, RENFE and the staff of the organising institutions whose hard work has helped planning this workshop orkshop orkshop.

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Antonio Correia (Phantoms Foundation, Spain) Stephan Roche (ICN2, Spain)

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Contributions list: Alphabetical order PAGE Jose A. Aguirre (Universidad de Málaga, Spain) Different biocompatibility of several graphene derivatives with dopaminergic cells at long term culture

Pilar Ariza (Universidad de Sevilla, Spain)

Oral Poster

Evaluation of electronic transport across grain boundaries in graphene

Ana Ballestar (Graphene Nanotech, S. L., Spain) Influence of SiC substrate modification on the growth of epitaxial graphene

Oral

17 29 18

Laurent Baraton (Engie CRIGEN, France) Keynote

Graphene and innovation for the energy industry: The point of view of a technology user

Francesco Bonaccorso (IIT, Italy)

8 8

Invited

Two-dimensional crystals for energy applications

Jérôme Borme (INL, Portugal) Development and use of single-layer CVD graphene in electrolyte-gated transistors and electrochemical devices for biosensing

Fernando Calle (ETSI Telecomunicación, UPM, Spain)

Invited Oral

Graphene foams: fabrication and applications

Iñigo Charola (Graphenea, Spain)

Invited

The Promises and Challenges of Graphene Oxides and CVD Sheets

Gordon Chiu (Grafoid Inc., Canada)

Keynote

Graphene and commercialization challenges

19 9 9

Sergi Claramunt Ruiz (Universitat Autònoma de Barcelona, Spain) Oral

High-throughput fabrication of graphene based electron devices over amorphous thin oxide layers

Roberto Clemente (Gnanomat, Spain)

Invited

A novel platform for graphene-tailored nanomaterials

20 10

Maria del Pilar De Miguel Ortega (CDTI, Spain) Centre for the Development of Industrial Technology: Funding opportunities for graphene in Spain

Oral

Poster

29 -

Daniel Domene-López (University of Alicante, Spain) Hardness characterization of graphene acrylic transparent nanocomposite coatings through Atomic Force Microscopy

Luc Duchesne (GO Foundation, Canada) GO Foundation: the power of Private Public Partnerships

Jose Antonio Garrido (ICN2, Spain) Graphene electronics for biomedical applications

Invited Invited

Rosa Garriga (Universidad de Zaragoza, Spain) Graphene oxide a new sensitive material for surface acoustic wave gas sensors

Julio Gómez (AVANZARE Innovacion Tecnologica S.L., Spain) Preparation of graphene and graphene epoxy composites

Lucía Gónzalez Bermúdez (EEA-GrapheneTECH, Spain) Low-cost, Green, Large Scale Manufacturing of Graphene

Marina González-Barriuso (Fundación Centro Tecnológico de Componentes, Spain) Synthesis of a graphene oxide- TiO2 nanocomposites for photocatalytic applications

Poster Invited Poster

Poster

30 10 32 33

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PAGE Anya Grushina (University of Geneva/DQMP, Switzerland) Quantum transport in high quality suspended graphene devices with advanced geometry

Poster

Invited

11 12

Celia Hernández Rentero (Universidad de Córdoba, Spain) Study of graphene nanosheets with three-dimensional morphology for use in Li-ion batteries

Frank Koppens (ICFO, Spain) Prototype demonstrators of graphene photodetector applications and future prospects

Iban Larroulet (Sensia, Spain) Graphene and nanotechnologies contributions to SPR in Sensia’s experience

Cesar Merino (Advanced Carbon Materials Dept. at Grupo Antolin Ingenieria, Spain) Suspensions of graphene sheets mechanochemically exfoliated from GANF carbon nanofibres

Edgar Muñoz (Instituto de Carboquímica ICB-CSIC, Spain) Graphene oxide as superior catalyst support for heterogeneous catalysis

Ana Navas (Instituto de Tecnologías Químicas de La Rioja (InterQuímica), Spain) Effect of the use of nanointermediates vs discrete nanoparticles in preparation of graphene nanocomposites

Invited

Poster

Oral

13 37 21

David A. Pacheco Tanaka (Tecnalia Research and Innovation, Spain) Graphene based capacitive deionization for an energy efficient desalination system (GRAPHESALT)

Poster

Oral

23 25

Javier Pascual (Universidad de Zaragoza / ICMA, Spain) Mechanical, tribological and chemical stability performance of a novel 1-2 layered graphene/UHMWPE composites

Alain Penicaud (Université de Bordeaux-CNRS-CRPP, France) Eau de Graphene: Additive Free, Single Layer Graphene in Water

Oral

Laura Saenz del Burgo (UPV/EHU, Spain) Relevance of graphene oxide nanoparticles in cell microencapsulation as a de novo producing drug organoid

María Simón (Universidad de Córdoba, Spain) Study of graphene from natural graphite for lithium batteries

Poster Poster

39 40

Gurpreet Singh (CICenergigune, Spain) Self-standing aerogels of SnO2-Graphene composites - Application as anode in lithium ion battery

Oral

Keynote

Oral

Wolfgang Templ (Alcatel-Lucent Deutschland AG, Germany) Telecommunication – a future area of application for new Graphene based components?

Elvira Villaro Ábalos (INTERQUÍMICA, Spain) Preparation, characterization and applications of highly reduce graphene oxide polyamide nanocomposites

Xiaoyue Xiao (China Innovation Alliance of the Graphene Industry (CGIA), China) From Improvement to innovation - the route of China's commercialization of Graphene

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Invited

KEYNOTE & INVITED CONTRIBUTIONS

Graphene and innovation for the energy industry: The point of view of a technology user Laurent Baraton, Louis Gorintin CRIGEN / Nanotech Energy â&#x20AC;&#x201C; Research & Technology Division - Engie, 361 av. du pdt Wilson â&#x20AC;&#x201C; BP 33 â&#x20AC;&#x201C; 93211 Saint Denis La Plaine Cedex, France

laurent.baraton@engie.com

Engie is the first independent power producer (IPP) in the world with a 115.3 GW of installed power-production capacity containing 16.5% of renewable energy. The group provides individuals, cities and businesses with highly efficient and innovative solutions largely based on its expertise in four sectors: renewable energy, energy efficiency, liquefied natural gas and digital technology. The potential technological breakthroughs offered by nanotechnologies open new prospective in fields such as gas detection and analysis, smart materials and energy conversion & storage. At CRIGEN, the Nanotech Energy taskforce is dedicated to the development of industrial grade technologies based on such innovations in order to secure future developments and create value in the activities and businesses of Engie. As such, we developed approaches to build bridges between

bleeding edge scientific research and everyday industrial needs. Graphene emerged as a promising platform for a large variety of applications, from rubber reinforcement to optoelectronics. As a consequence, we will look at graphene as an enabler, allowing to imagine, design and develop products that fits real industrial needs, opening B2B market opportunities. Through application examples, this talk will try to show that graphene based devices are extremely dependant to the quality of the starting material. This implies that the supply chain needed for the development of such industrial grade devices has to be secure from the very first link as much as it calls for standardization of the material.

KEYNOTE & INVITED CONTRIBUTIONS

Two-dimensional crystals for energy applications

F. Bonaccorso Istituto Italiano di Tecnologia, Graphene Labs, Via Morego 30, 16163 Genova, Italy

francesco.bonaccorso@iit.it

Energy conversion and storage applications are currently driving the development of new materials and processes,[1] able to improve the performance of existing devices or enable new ones [2,3,4,5] that are also environmentally benign. In this context, graphene and other two-dimensional (2D) crystals are emerging as promising materials [1-5]. A key requirement for applications such as flexible electronics and energy storage and conversion is the development of industrialscale, reliable, inexpensive production processes, [2] while providing a balance

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between ease of fabrication and final material quality with on-demand properties. Here, I will briefly show how solutionprocessing [2] can offer a simple and costeffective pathway to fabricate various 2D crystal-based flexible and energy devices, presenting huge integration flexibility compared to conventional methods. I will present an overview of graphene and other 2D crystals for flexible and printed (opto)electronic and energy applications, starting from solution processing of the raw

bulk materials, [2] the fabrication of large area electrodes [3] and their integration in the final devices [6,7,8,9]. References [1] A. C. Ferrari, F. Bonaccorso, et al., “Scientific and technological roadmap for graphene, related two-dimensional crystals, and hybrid systems” Nanoscale DOI: 10.1039/c4nr01600a (2014). [2] F. Bonaccorso, et al., Production and processing of graphene and 2d crystals. Materials Today, 15, 564-589, (2012). [3] F. Bonaccorso, et. al., Graphene photonics and optoelectronics, Nature Photonics 4, 611622, (2010). [4] F. Bonaccorso, Z. Sun, Solution processing of graphene, topological insulators and other 2d crystals for ultrafast photonics. Opt. Mater. Express 4, 63-78 (2014).

[5] G. Fiori, F. Bonaccorso, et al., Electronics based on two-dimensional materials. Nature Nanotech. 9, , 768-779, (2014). [6] F. Bonaccorso, et. al., Graphene, related twodimensional crystals, and hybrid systems for energy conversion and storage. Science, 347, 1246501 (2015). [7] J. Hassoun, F. Bonaccorso, et al. An advanced lithium-ion battery based on a graphene anode and a lithium iron phosphate cathode Nano Lett. 14, 4901-4906 (2014). [8] P. Robaeys, F. Bonaccorso, et al. Enhanced performance of polymer: fullerene bulk heterojunction solar cells upon graphene addition. Appl. Phys. Lett. 105, 083306 (2014). [9] F. Bonaccorso, et al., Functionalized Graphene as an Electron Cascade Acceptor for Air Processed Organic Ternary Solar Cells. Adv. Funct. Mater. 25, 3870, (2015).

The Promises and Challenges of Graphene Oxides and CVD Sheets Iñigo Charola Graphenea, Spain

i.charola@graphenea.com

graphenes to become successful, several things need to happen:

Material must be customized to the specific application Production must be scaled up to match application needs Price must reflect value in use

KEYNOTE & INVITED CONTRIBUTIONS

Graphenes will find many uses in both existing and new applications. A range of graphene production technologies are available but focus on a few promising platforms will be key to develop successful applications. This strategy will facilitate the use and advance the performance of graphene materials. For

Graphene and commercialization challenges Gordon Chiu Grafoid Inc., Canada

info@grafoid.com

Graphene is not your typical startup. There might be no roadmap and the business you think is there isn't exactly there. If you sell this material that won the Nobel Prize in 2010, it could lead to patents that doesn't involve you because you released all rights during the sale. Without sales, you won't last.

Welcome to the world of graphene, a paradigm shift in entrepreneurship.

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A Novel Platform for Graphene-Tailored Nanomaterials Roberto Clemente Gnanomat, Spain

info@gnanomat.com

Graphene has been identified not just as a nanomaterial with extraordinary physicalchemical properties but furthermore a cornerstone for the next revolution of nanomaterials by itself. However graphene is already in immature state and has not climbed from the academic laboratories to industry due to technologic barriers that need to be cleared in all the steps of the value chain of graphene.

Gnanomat possess a patented technology to address the technologic barriers mentioned. Our patented technology showed a fine alternative to exfoliate graphite into graphene of different qualities through a mechanical and clean method of liquid phase exfoliation (LPE). Moreover, and most importantly, Gnanomat has generated a strong proof of concept (PoC) not just to exfoliate graphene, but to efficiently combine this nanomaterial in polymeric matrixes, functionalize with metals and metal oxides as well. This extraordinary versatility allow us to offer a development platform to optimize tailor-made nanomaterials based on graphene and the potential to scale-up the production.

Preparation of graphene and graphene epoxy composites Julio Gomez AVANZARE Innovacion Tecnologica S.L:, Avda Lentiscares 4-6, Navarrete, Spain

KEYNOTE & INVITED CONTRIBUTIONS

julio@avanzare.es

The graphene material market, bulk graphene, graphene nanoplatelets and graphene films, will grow to 350 â&#x201A;Ź million in 2025. Their application in composites are the largest segment, followed by energy storage [1]. Currently, a variety of techniques have been developed to prepare graphene nanosheets (GNS), including the mechanical exfoliation, CVD, direct sonication, mechanochemical milling with surfactants and chemical wetting methods, however the performance of the graphene sheets and the composites produced by them is highly dependent on the size and defects content of the graphene. In this communication, 3 different methods for the production of bulk graphene or reduce graphene oxide: liquid exfoliation, reduced graphene oxides and high-expansion were

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compared with other production methods and products in the market. The complete characterization of graphene and highly reduce graphene oxide using TEM, SEM, AFM, XPS, DRX, Laser diffraction, etc will be presented. Epoxy resins are widely used in many industries thanks to its excellent mechanical, electrical and chemical properties [2]. There is a vast amount of literature regarding graphene/epoxy composites and its applications [3â&#x20AC;&#x201C;7]. Different types of graphene materials with variation in lateral size, defects and defects concentration, thickness, etc, have been used to obtain the graphene-epoxy composites. The different effect of the incorporation of liquid exfoliated graphene,

highly reduced graphene oxide and graphene nanoplatelets on the electrical, thermal conductivity and fire retardant properties of epoxy were investigated. properties Related to electrical properties, epoxyepoxy composites show lower percolation threshold limits than the previously reported values, opening a new range of applications and markets. Other factors as processing technique, the the compatibility between graphene and matrix and dispersion have an extremely high importance in the results. Conventional, continuous fibre reinforced polymer composites have made a huge impact over the past half century, in the aerospace, wind turbines turbines,, marine and oil/gas industries and recently in automotive industry. Processing techniques and final properties of hierarchical epoxy composites: infiltration and pre pre-pegs pegs were investigated.

References [1] Zh Ma, R. Kozarsky, M. Holman., GRAPHENE MARKET UPDATE. UPDATE. LUX RESEARCH (2014) [2] B. Qi, Z. Yuan, S. Lu, K. Liu, S. Li, L. Yang, et al., Fibers Polym. 15 (2014) 326 326–333. 333. [3] J. Liang, Y. Wang, Y. Huang, Y. Ma, Z. Liu, J. Cai, et al., Carbon 47 (2009) 922 922–925. 925. [4] R.J. Young, I.A. Kinloch, L. Gong, K.S. Novoselov, Compos. Sci. Technol. 72 (2012) 1459 1476. 1459–1476. [5] H. Yang, F. Li, C. Shan, D. Han, Q. Zhang, L. Niu, et al., J. Mater. Chem. 19 (2009) 4632 4632–4638. 4638. [6] S. Wang, P.J. Chia, L.L. Chua, L.H. Zhao, R.Q. Png, S. Sivaramakrishnan, M. Zhou, R.G.S. Goh, R.H. Friend, A.T.S. Wee, P.K.H. Ho, Adv. Mater. 20 (2008) 3440. [7] M.M. Gudarzi, F. Sharif, eXPRESS Polym. Lett. 6 (2012) 1017–1031. 1017 1031.

Prototype demonstrators of graphene photodetector applications and future prospects Frank Koppens ICFO -The -The Institute of Photonic Sciences The Barcelona Institute of Science and Technology Av. C.F. Gauss 3, Castelldefels (Barcelona) Spain

Graphene photodetectors are ideal for ultraultra sensitive detection of visible and infrared light [1,2], and at the same time they can be flexible and even partially transparent. This makes this detection system an enabler for unique applications [3,4].

Finally, we show the most recent progress on ultra fast graphene photodetectors for data ultra-fast communication applications.

Here, we will show working prototype demonstrators of several graphene-based demonstrators graphene based photodetection applications. One tangible example we present is a wearable health monitor that is flexible and transparent, and fully integrated with hybrid graphenegraphenequantum dot detectors. Additionally, we show the p progress rogress of monolithic integration of graphene with SiSi CMOS electronics for infrared imaging applications (such as night vision).

References [1] Hybrid 2D– 2D–0D 0D MoS2–PbS MoS2 PbS Quantum Dot Photodetectors. Kufer, Dominik, Ivan Nikitskiy, Tania Lasanta, Gabriele Navickaite, Frank HL

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KEYNOTE & INVITED CONTRIBUTIONS

frank.koppens@icfo.eu

Koppens, and Gerasimos Konstantatos, Advanced Materials 27, no. 1, 176-180 (2014) [2] Hybrid graphene-quantum dot phototransistors with ultrahigh gain. G. Konstantatos, M. Badioli, L. Gaudreau, J. Osmond, M. Bernechea, P. Garcia de Arquer, F. Gatti, F. H. L. Koppens, Nature Nanotechnology 7, 6, 363 (2012) [3] Photodetectors based on graphene, other two-dimensional materials and hybrid systems. Koppens, F. H. L., Mueller, T., Avouris, P., Ferrari, A. C., Vitiello, M. S., & Polini, M. Nature nanotechnology, 9(10), 780-793 (2014) [4] Science and technology roadmap for graphene, related two-dimensional crystals, and hybrid systems. Ferrari et al.,Nanoscale 7, no. 11 (2014)

[5] Picosecond photoresponse in van der Waals heterostructures. M. Massicotte, P. Schmidt, F. Vialla, K. G. SchĂ¤dler, A. Reserbat-Plantey, K. Watanabe, T. Taniguchi, K. J. Tielrooij and F. H. L. Koppens, Nature Nanotechnology, DOI: 10.1038/NNANO.2015.227 (2015). [6] Generation of photovoltage in graphene on a femtosecond timescale through efficient carrier heating. K. J. Tielrooij, L. Piatkowski, M. Massicotte, A. Woessner, Q. Ma, Y. Lee, K. S. Myhro, C. N. Lau, P. Jarillo-Herrero, N. F. van Hulst, and F. H. L. Koppens, Nature Nanotechnology 10, 437-443 (2015)

Graphene and Nanotechnologies contributions to SPR in Sensia's experience Iban Larroulet SENSIA, Spain

sensia@sensia.es

SENSIA is a technological leader company in the field of analytical instrumentation based on SPR (Surface Plasmon Resonance), for life sciences laboratories and environmental measurements.

device, the Indicator-G, leads to new unattained limits of detection, getting into the attomolar range, therefore bringing in new applications and diagnostic possibilities.

KEYNOTE & INVITED CONTRIBUTIONS

References Sensia has developed in 2014 an innovative SPR (Surface Plasmon Resonance) solution, using graphene biosensing and introducing on the market the first available commercial graphene biosensors, in a device whose microfluidics have been conceived to withstand the use of bacteria and/or of nanoparticles. The conception of the optical system enables extreme versatility, allowing the indifferent use of gold biosensors, of graphene coated biosensors, and of silica coated biosensors, with no required change of geometry of the optical platform, although the refractive indexes change. Several strategies of immobilization can be therefore used. The combination of graphene biosensors together with nanoparticles in Sensia's SPR

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[1] Oleksandr Zagorodko, Jolanda Spadavecchia , Aritz Yanguas Serrano Â§, Iban Larroulet , Amaia Pesquera, Amaia Zurutuza, Rabah Boukherroub , and Sabine Szunerits; Anal. Chem., 2014, 86, 1121111216 [2] Kostiantyn Turcheniuk, Charles-Henri Hage, Jolanda Spadavecchia, Aritz Yanguas Serrano, Iban Larroulet, Amaia Pesquera, Amaia Zurutuza, Mariano Gonzales Pisfil, Laurent Heliot, Julie Bouckaert, Rabah Boukherroub and Sabine Szunerits; J. Mater. Chem. B, 2015, 3, 375 [3] Oleksandr Zagorodko , Julie Bouckaert , Tetiana Dumych , Rostyslav Bilyy , Iban Larroulet , Aritz Yanguas Serrano , Dimitri Alvarez Dorta , Sebastien G. Gouin , StefanOvidiu Dima , Florin Oancea , Rabah Boukherroub , and Sabine Szunerits; Biosensors 2015.

Suspensions of graphene sheets mechanochemically exfoliated from GANF carbon nanofibres C. Merino1, S. Blanco1, P. Merino1, E. del Rio2, V. León2, E. Vázquez2 1Grupo Antolin Ingeniería SA, Ctra. Madrid-Irún, Madrid Irún, km. 244.8, E09007 Burgos, Spain Departamento de Química Orgánica, Facultad de Ciencias y Tecnologías Químicas-IRICA, Químicas IRICA, Universidad de Castilla Castilla--La La Mancha, E13071 Ciudad Real, Spain

cesar.merino@grupoantolin.com

Graphene sheets have been obtained from graphite by ball milling with melamine [1]. The major disadvantage of graphite, as starting material, is the low efficiency of the exfoliation process due to the high number of stacked layers present in its structure. As an alternative route, we present an industrially scalable process to obtain few layer she sheets ets of graphene by using GANF carbon nanofibers as starting material [2]. GANF HR HR--CNFs CNFs present a singular helical ribbon graphitic structure, composed by a graphitic ribbon of approximately five graphene layers rolled along the fiber axis. This structure makes makes them very attractive as starting material for graphene production [3].

Figures

Figure 1: Scheme of mechanochemical exfoliation of GANF carbon nanofibres.

[1] Verónica León, Mildred Quintana, M. Antonia Herrero, Jose L. G. Fierro, Antonio de la Hoz, Maurizio Prato and Ester Vázquez. “Few “Few-layer layer graphenes from ballballmilling of graphite with melamine”. Chem. Commun., 47, pg. 10936 10936-- 10938 (2011) [2] Antonio Esaú Del Rio Rio-Castillo, Castillo, César Merino, Enrique Díez-Barra, Díez Barra, Ester Vázquez. “Selective suspension of single layer graphene mechanochemically exfoliated from carbon nanofibres”, Nano Research, Volume 7, Issue 7, pg 963 963-972 972 (2014). [3] Vera-Agulló Vera Agulló J, Varela Varela-Rizo Rizo H, Conesa JA, Almansa C, Merino C, Martin Martin-Gullón Gullón I. “Evidence for growth mechanism and helixhelix spiral cone structure of stacked-cup stacked cup carbon nanofibers“ nanofibers“ Carbon. 45, pp. 2751-8 2751 8 (2007)

Figure 2: Graphene sheets obtained from GANF HRHRCNFs.

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KEYNOTE & INVITED CONTRIBUTIONS

References

Telecommunication – a future area of application for new Graphene based components? Wolfgang Templ Alcatel-Lucent Deutschland AG, Germany

wolfgang.templ@alcatel-lucent.com

KEYNOTE & INVITED CONTRIBUTIONS

The progress of telecommunication during the past four decades mainly fuelled by the exponential increase of microelectronic integration density, which is concisely described by Moore’s Law, finally allows that nearly every individual on the globe can communicate to any other at any time no matter where and when. This trend is still ongoing: Global data traffic is still growing exponentially at increased pace – but our “traditional recipes” which we used to satisfy the increasing demands for telecommunication through the past decades are approaching their physical limits. The semiconductor based transistor device has reached the size of merely a few nanometers and further shrinking becomes increasingly difficult and expensive. The gain in physical performance narrows and can’t satisfy the requirements from future communication applications regarding costs, integration density and energy consumption. Consequently scientists are looking worldwide for alternatives based on new materials and components.

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In this situation Graphene based devices may offer a promising way out. With its superior physical properties Graphene could not only help to continue above outlined microelectronics success story. It moreover has unprecedented properties allowing for entirely new and different features and functionalities which may enable the growth of our communication network at affordable costs far into the future. Graphene based components also promise new solutions which help to reduce the environmental footprint of communication technologies. Today this material system is still in its infancy and still high efforts are needed to come to cost attractive components which can be fabricated in high quantities at affordable costs but first devices featuring superior performance indicate that the material can keep its promises.

From Improvement to Innovation – the Route of China’s Commercialization of Graphene Xiaoyue Xiao China Innovation Alliance of the Graphene Industry (CGIA), China

In 2015, China has speeded up the commercialization of graphene through the driving forces from government advocacy and increased marketing needs:

In March 2 of 2015, ZL-Oil announced a new lubricant modified with graphene. It increases the lubrication operation durability from 1000 miles to 5000 miles [1]. In April 18 of 2015, SuperC Technology Ltd launched 10,000 tons/year production line of graphene slurry, which is mainly used as conductive additives in Lithium battery [2]. In June 30 of 2015, Beijing Carbon Century Technology Ltd announced a graphene modified additives to improve engine combustion Testing results indicated that it saved gasline up to 10% [3]. In October 10 of 2015, CSR announced applications of newly developed graphene supercapacitors, Model 2.8V/30000F and Model 3.0V/12000F. The former can be used for trolleybus with continuation range up to 10 kilometers and charging time less than 1 minute. The later can be used for railroad car with continuation range up to 6 kilometers and charging time less than 30 seconds [4]. In October 2 of 2015, GNM announced a waist healing belt with the functions of warming and therapy, especially for seniors used in winter. This graphene

In the meantime, the Ministry of Science and Technology granted “National Industry Base of Graphene New Materials in Changzhou” in March of 2015 [7] and “National Torch Industry Base of Graphene and Carbon Materials in Qingdao” in August of 2015 [8]. The National “13-5” Project has set up a goal for graphene industry: during 2016 – 2020, 100 graphene industry parks will be built to create revenues up to 100 billion RMB of graphene products and revenues up to 1000 billion RMB of graphene related products. It focus on application areas of new energy and electrical cars, composite materials, coatings, energy saving and environment protection technologies, desalination, soft and foldable touch display screen, intelligent wearing materials etc.

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KEYNOTE & INVITED CONTRIBUTIONS

based belt can homogeneously reach to 35 ºC within 10 seconds, and its far IR irradiation spectrum is well coupling with human body that could improve blood circulation and relieve pain [5]. In October 28 of 2015, DT Nantech Ltd launched a 1000 tons/year production line of graphene slurry for applications in rubbers and tires. The graphene modified rubber/tires are not only improved with gas permeation rate but also thermal conductivity from 0.2 W/m K to 3 W/m K [6].

ORAL CONTRIBUTIONS

Different biocompatibility of several graphene derivatives with dopaminergic cells at long term culture Noela Rodriguez-Losada1, Rune Wendelbo2, Ernest Arenas3 and Jose A. Aguirre1 Department of Human Physiology, School of Medicine, University of Malaga, 29010 Malaga, Spain 2Abalonyx AS, Forskningsveien 1, 0373 Oslo, Norway 3 Department of Medical Biochemistry and Biophysics, Karolinska Institutet, SE-17177 Stockholm, Sweden 1

Jose.Aguirre@uma.es

measured at 560nm. The results demonstrated positive biocompatibility between the G-derivatives and SN4741 cells. We conclude that the use of our Gderivative scaffolds can enhance the neural differentiation towards neurons (TH positive) providing a cell growth microenvironments and appropriate synergistic cell guidance cues. This findings demonstrated that biocompatibility of scaffolds is a pre-requisite for generation of successful clinical application of graphene. It could offer a platform for neural stem cells and a promising approach for neural regeneration in the research of neurological diseases like PD. Long-term studies on the biological effects of graphene will now be performed for the development of therapeutic treatment as the goal. References [1] Li N., Zhang Q, Gao S. et a., 2013, Nature/Sci Rep. 3:1604. doi: 10.1038/srep01604 [2] Yan K., Li Y., Tan X., et al., 2013 [3] Small,2013, 9(9-10): 1492-1503]

ORAL CONTRIBUTIONS

The emerging carbon nanomaterial graphene (G) and its oxidized derivative graphene oxide (GO) have recently gained considerable attention in biomedical applications such as cancer therapy or biosensors. It has for example been demonstrated that G has an efficient bioconjugation with common biomolecules and activates cell differentiation of neuronal stem cells (Li et al., 2013). This way, G could acts as a physical support or scaffold to promote axonal sprout as a “deceleration” support for the DA cells derived from neural stem cells. Since GO in its multilayer form and with multiples carboxilate and epoxy groups seems to shows interesting biological properties (Yang et al., 2013) the aim of the present work has been to test different graphene derivatives searching for the best scaffold to be used in stem cell differentiation. For this purpose we have tested the cytotoxicity of GO and reduced GO, and specifically its biocompatibility with SN4741, a dopaminergic cells line derived from mouse substance nigra, measuring the effect in the cells at long term culture. The cells were cultured in Dulbecco’s modified Eagle’s medium 10% FCS (Gibco) to about 80% confluence. Cells were incubated applying 1.000 cells in 96-well microliter plates with graphene using three chemically different types of GO as powders and films: 1) GO, which is hydrophilic; 2) partially reduced GO (PRGO) which is hydrophobic and 3) fully reduced GO (FRGO), also hydrophobic, in five concentrations: 1 mg/ml; 0.1 mg/ml; 0.05 mg/ml; 0.02 mg/ml and 0.01 mg/ml, in each type of graphene. Cells were cultured with GO and cell viability was determined after 24 hours, 1 week and 2 weeks using the MTT assay (Roche) and cytotoxicitity was determined by the lactate dehydrogenase (LDH) (Roche) assay

graph In2015

Influence of SiC substrate modification on the growth of epitaxial graphene A. Ballestar1,2, A. García García-García García1,3, L. Serrano1,2, J. M. de Teresa2,4,5, M. R. Ibarra2,5, P. Godignon3 1Graphene Nanotech, S.L., Miguel Villanueva Villanueva 3, 26001 Logroño, Spain INA, LMA, Universidad de Zaragoza, Manuel Esquillor, 50018 Zaragoza, Spain 3 CNM-IMB-CSIC, CSIC, Campus UAB, Bellaterra, Bellaterra, 08193 Barcelona, Spain 4 ICMA, Universidad de Zaragoza, 50009 Zaragoza, Spain 5 Departamento Física de la Materia Condensada, Universidad de Zaragoza, 50009 Zaragoza, Spain 2

ana@gpnt.es

Since the isolation of graphene became accessible and the investigation of its properties revealed outstanding features [1,2], a large number of companies aiming the production of graphene graphene-based based materials and devices appeared in order to develop a new and powerful technology. However, the fabrication process of high quality graphene in an industrial scale remains as an open issue. The growth of graphene on Silicon Carbide (SiC) wafers is one of the most promising routes for bot both, h, production and integration into planar technology electronic applications [3 [3-5]. 5]. We fabricated epitaxial graphene on top of different types of SiC substrates. Of particular interest for electronic applications are those in which a bottom gate is ready tto o be used and

prepared prior to graphene growth. Different treatments such as implantation and doping have been used for substrate modification. We investigated the influence of these processes on the ultimate grown graphene by means of non-invasive non invasive techni techniques, ques, e.g. Raman spectroscopy and optical and atomic force microscopy (AFM). References [1] K. S. Novoselov et al., Nature Nature,, 306 (2004) 666 [2] K. S. Novoselov et al., Nature, 490 (2012) 192 [3] N. Camara et al., Appl. Phys. Lett., 93 (2008) 263102 [4] P. N. First, First, MRS Bulletin, Bulletin, 35 (2010) 296 [5] D. Waldmann et al., Nature Mat., 10 (2011) 357

ORAL CONTRIBUTIONS

Figures

Figure 1: Results obtained after characterization of graphene grown on an implated SiC substrate. (a) Optical image of the sample surface. (b) Raman spectra measured at the positions indicated in the inset picture. (c) AFM topography of an area of the sample. (d) Zoom in 3D image of the area indicated in (c). (e) Profile taken at the gray line line shown on (c).

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Graphene foams: fabrication and applications Fernando Calle, J. Pedrós, A. Boscá, S. Ruiz-Gómez, L. Pérez, J. Martínez Instituto de Sistemas Optoelectrónicos y Microtecnología, Universidad Politécnica de Madrid Avda Compluetense 30, 28040 Madrid, Spain

fernando.calle@upm.es

Graphene stands out by many different properties (electrical, optical, structural, mechanical, thermal, etc.), which combinations allow to improve device performance or enable new applications. Graphene can be prepared by several techniques. Chemical vapor deposition (CVD) using catalytic metal foils or films has demonstrated very good results for high quality single or few-layer 2D graphene. Similarly, 3D graphene structures may also be grown by CVD on Cu or Ni metal foams or sponges, showing a high surface that enables a number of devices for many application fields. The graphene foam (GF) processing involves three steps: material growth, substrate removal and, eventually, functionalization. We are using plasma enhanced CVD (PECVD) to grow the graphene coating on a metal foam acting as a catalytic mesh. The coating thickness depends on the metal substrate and the growth conditions (gases ratio, growth time, etc.). A free-standing GF (see figure 1) is obtained by wet etching the metal substrate. Finally, the GF may be functionalized by different techniques and materials (polymerisation, electrodeposition,

sol-gel), either to modify the graphene properties and/or to provide robustness to the 3D structure. In this work we will discuss several applications of GFs, with a particular interest in the challenges and technological issues and requirements. Most of our work has been devoted to the fabrication of different types of electrodes for supercapacitors, either by filling the GF with a hierarchical polymer nanostructure, or different oxides by electrodeposition or sol-gel. GFs are also been exploited to enhance the properties of batteries. Other possibilities are being pursued in the energy field, such as energy harvesting produced by the flow of a polar liquid through the GF, or hydrogen storage. Finally, we will review some additional applications in electronics, instrumentation, environment or biotechnology. Acknowledgements: This work has been supported by Repsol (Programme Inspire) and Ministerio de Economía y Competitividad (Project No. ENE2013-47904-C3-1).

Figures

Figure 1: SEM pictures with increased magnification of a graphene foam deposited on nickel by CVD, after metal removal.

graph In2015

ORAL CONTRIBUTIONS

Free-standing G-foam

High-throughput fabrication of graphene based electron devices over amorphous thin oxide layers Sergi Claramunt, Qian Wu, Marc Porti, Anna Ruiz, Albert Crespo, Montserrat NafrĂa, Xavier Aymerich Electronic Engineering Department, Universitat AutĂ˛noma de Barcelona, 08193 Bellaterra, Spain

ORAL CONTRIBUTIONS

sergi.claramunt@uab.cat

Graphene, a one atom thick layer of carbon first discovered by Geim and Novoselov in 2004 [1], may be a component of future electron devices thanks to its formidable physical and electrical properties. For example, its high carrier mobility will be useful for the fabrication of field-effect transistors (GFETs) for radiofrequency applications [2]. Another field of applications could be resistive random access memories (RRAM) where the inclusion of graphene between the electrodes and insulator could control the variability of the memories [3], basically thanks to the low reactivity of the graphene layers. On the other hand, the morphology of the graphene layers makes this material an ideal candidate to be included in an industrial CMOS like fabrication process. In spite of that, the electronic integration of graphene still has some challenges that need to be solved before being able to be processed at industrial level. For example, the transference of chemical vapor deposition (CVD) synthetized graphene from the Cu catalyst to the target substrate has to be improved, as its final quality depends largely on this step process. In this work we present the high-throughput fabrication of graphene-based devices over amorphous thin oxide layers (HfO2 and Al2O3). First, 1x1cm2 commercial available graphene is transferred over the target substrates [4], that are composed of a thin oxide layer grown using Atomic Layer Deposition (ALD, 6.6 nm of HfO2 or 6 nm Al2O3) over a pdoped silicon substrate as a bottom contact. After the graphene layer is ready, Au/Ti contact electrodes are deposited by evaporation. The definition is done by laser lithography in order to have the maximum flexibility and avoid the fabrication of physical masks. After the deposition of the metal electrodes, the graphene channel is defined for the case of the GFETs, or for the case of memory devices the etching of the

graph In2015

exposed graphene by Reactive Ion Etching (RIE) is only Needed. The morphology of the graphene layer is characterized by Scanning Electron Microscopy (SEM) and at the nanoscale using a Atomic Force Microscope. The devices were electrically characterized using a Semiconductor Parameter Analyzer. First, the transference process of graphene is studied using HfO2 as a target substrate. We found that some steps are needed to be added to the conventional transference process in order to obtain a high quality continuous graphene layer, for example, a thermal treatment of the polymer/graphene stack to avoid the formation of wrinkles and holes or the cleaning of the graphene layer using acetic acid instead of acetone in order to eliminate as much PMMA as possible. After the improvement of the transfer process, GFETs and MGIS structures were fabricated and characterized. We found that, although the graphene layer is continuous and homogeneous, the lithographic process may damage the underlying graphene under the electrodes, as can be seen in the different behavior of the memories. References [1] K.S. Novoselov, A. K. Geim, S. V Morozov, D. Jiang, Y. Zhang, S. V Dubonos, I. V Grigorieva, A. A. Firsov, Science 306 (2004) 666 [2] F. Schwierz, Nat. Nanotechnol. 5 (2010) 487 [3] H. Tian, H.Y. Chen, B. Gao, S. Yu, J. Liang, Y. Yang, D. Xie, J. Kang, T.L. Ren, Y. Zhang, H.S.P. Wong, Nano Lett. 13 (2013) 651 [4] A. Reina, H. Son, L. Jiao, B. Fan, M.S. Dresselhaus, Z. Liu, J. Kong, J. Phys. Chem. C 112 (2008) 17741

Centre for the Development of Industrial Technology: Funding opportunities for graphene in Spain Mª del Pilar de Miguel Ortega CDTI, C/ Cid, 4, 28001 Madrid, Spain

mariapilar.demiguel@cdti.es

The Centre for the Development of Industrial Technology (CDTI) is a Public Business Entity, answering to the Ministry of Economy and Competitiveness, which fosters the technological development and innovation of Spanish companies. It is the entity that channels the funding and support applications for national and international R&D&i projects of Spanish companies. The CDTI thus seeks to contribute to improving the technological level of the Spanish companies by means of implementing the following activities: Financial and economic-technical assessment of R&D projects implemented by companies. Managing and fostering Spanish participation in international technological cooperation programmes. Fostering international business technology transfer and support services for technological innovation. Supporting the setting up and consolidating technological companies.

CDTI provides companies with its own funding and facilities access to third-party financing (Bank Line for Funding Technological Innovation and Subsidies of the EU R&D Framework Programme) for national and international research and development projects. In addition, the CDTI is empowered as the competent entity to issue binding motivated reports of the projects funded by any of its lines (Royal Decree 2/2007). These documents will provide greater legal security to Spanish companies with an approved project and funded by the CDTI when seeking tax rebates for costs incurred in the R&D activities of those projects. It should be noted that in recent years, research and development in nanotechnology can be included within the key funding objectives under CDTI schemes. Thus, different funding instruments have been used to finance this innovative field such as R&D projects, CIEN, FEDERINNTERCONECTA, NEOTEC at national level as well as international programmes.

Effect of the use of nanointermediates vs discrete nanoparticles in preparation of graphene nanocomposites Instituto de Tecnologías Químicas de La Rioja (Inter-Química), Spain Departamento de Química – Centro de Investigación en Síntesis Química. Universidad de La Rioja, Spain 3Departamento de Química Inorgánica y Técnica, Facultad de Ciencias UNED, Spain 4Avanzare Innovación Tecnológica S.L., Spain

anavas@interquimica.org

Due to the extremely low density of bulk graphene and related materials such as reduce graphene oxide RGO, its handling and manipulation is often complicated and delicate, producing a high nanoparticle

release to the atmosphere. Therefore, in order to try to decrease the health and safety impact of these materials caused by the exposure during its use and manipulation, it has been carried out a study

graph In2015

ORAL CONTRIBUTIONS

A Navas1,2, E Villaro1,3, J Gómez4 1

of the release of nanoparticles of RGO to the atmosphere during the complete process of preparation of epoxy matrix RGO. For that we have prepare dispersion of RGO or direct use of these nanolayers and compare and quantify the release. Nanointermediates are the predispersion of discrete nanoparticles in a solid, liquid or polymer form. These intermediate products with nanoscale features, are nowadays the tool for the industrialization of the nanomaterials. Three ways of introducing graphene into the composite have been assessed to compare the exposure in each scenario: direct use of the graphene in bulk powder, and two types of graphene nanointermediates: predispersion at higher concentration in the epoxy resin, and pressed graphene in pellet form.

ORAL CONTRIBUTIONS

In order to select sampling equipment, we have considered the penetration of the particles in the respiratory tract. The particles are divided into three fractions depending on the penetration in the respiratory system conditioned by the size of the particle: inhalable fraction (the fraction of airborne material that enters by nose and mouth during breathing, and is therefore available for deposition anywhere in the respiratory tract), thoracic fraction (the fraction of inhaled airborne material penetrating beyond the larynx) and respirable fraction (the inhaled airborne material that penetrates to the lower gas exchange region of the lung).

cases, studies were conducted to characterize the particles, sizes, distributions and shapes with a scanning electron microscope (SEM). Thanks to the energy dispersive analyzer (EDX) attached to the microscope, we were able to make compositional studies of particles encountered (figure 2). And a study gravimetric was carried out with samples collected with IOM sampler, for the simulation and calculation of the concentration of particles in air (airborne particulate matter). After analysing all samples from the three cases, it has been observed great advantages of using nanointermediates compared to graphene powder. In addition to simplification and time savings in the use of these nanoparticles. References [1] General methods for sampling and gravimetric analysis of respirable, thoracic and inhalable aerosols. Health and Safety Executive. www.hsl.gov.uk

Figures

Due to the particle size of the graphene material to study, the measurements were performed of the inhalable fraction, where the deposit from particulate matter should be able to produce a biological effect. For that reason, the equipment that has been used in this case has been the IOM sampler (figure 1), that offers the requirements needed for this measurement.

Figure 1: IOM inhalable dust sampler

During the different phases of the nanocomposite preparation, they have taken air samples and superficial zones which were subsequently analyzed. In all

Figure 2: SEM picture of IOM filter with RGO particle.

graph In2015

Mechanical, tribological and chemical stability performance of a novel 1-2 layered graphene/UHMWPE composites Pascual, F.J.1; Alonso, P.J.2; L. Quiles3; P. Castell3; Puertolas, J.A.1 Department of Materials Science and Technology, I3A, Universidad de Zaragoza, Zaragoza, Spain 2Aragón Materials Science Institute, ICMA, Universidad de Zaragoza-CSIC, Zaragoza, Spain 3AITIIP Technological Center, Zaragoza, Spain

jpascual@unizar.es

Methods and Materials: Uniaxial tensile tests (n=4) were carried out according to ASTM D638M (UNEEN ISO 527-2) in an Instron machine (model 5565) at a constant displacement rate of 10 mm/min. Izod tests were carried out by Cemitec (Noain, Spain). Differential Scanning Calorimetry (DSC) were performed heating in air from 20 to 200 °C at 10 °C/min in a Q200 Thermal Analysis DSC. Wear ball-on-disk test (n≤3) were performed in a TRB tribometer (CSM instruments, Peseux, Switzerland) for 24 hours. Rotating UHMWPE sample disks, 20 mm in diameter, were immersed in diluted bovine serum at 37ºC and opposed to an alumina ball, 6 mm in diameter. The load applied was 5 N resulting in a contact pressure of 37 MPa. The radius of the circular track was 4 mm and the sliding speed was 0.05 m/s. Worn volume is calculated by confocal microscopy using a SENSOFAR PLU 2300 optical imaging profiler. Electron Paramagnetic Resonance (EPR) measurements were taken at room temperature in a Bruker Elexsys E580 spectrometer working at X-band. The microwave power was 0.2 mW and the modulation amplitude 0.1 mT. Prismatic shape samples (2x2x10 mm3) were fixed with vacuum grease to a methacrylate sample holder.

Medical grade GUR1050 UHMWPE powder was gently supplied by Celanese (Irving, USA) with an average particle size of 150 µm. The nearmonolayer graphene used in this work is considered to be 1-2-layered graphene and was provided by Avanzare (Spain). It was blended with the UHMWPE to concentrations of 0.1, 0.3, and 0.5 wt% in a ball mill for 8 hours at 400 rpm to obtain a homogeneous dispersion. The consolidation process was carried out using a 15 Ton press with hot plates (Specac, UK) for 30 minutes at 175°C under 15 MPa pressure, followed by cooling in air down to 40°C under the same pressure. Samples were denoted as GUR1050+X%GR1-2L, where X stands for the weight % of reinforcements in the polymer matrix. Some composites underwent a further high temperature thermal treatment in a vacuum oven (LTE, UK) for 8 hours at 240°C and were denoted GUR1050+X%GR1-2L HT. Some specimens were gamma irradiated in Aragogamma (Spain) to a final dose of 90 kGy. Results: Tensile performance of the untreated composites showed a slight increase in secant modulus for all GR1-2L amounts and yield stress remained unchanged. However, fracture stress, fracture strain and work to fracture decreased as additive amount increased. For example, at the lower concentration, 0.1 wt%, the decrease was about 20%. Conversely, Izod impact toughness pertained the unloaded metrics until the 0.5 wt%, where a diminution of about 40% arisen. When thermal treatment is considered, both secant modulus and yield stress underwent a considerable increase of 30% and 10%, respectively, for all the percentages. For the 0.1wt% composite, fracture stress, fracture strain and work to fracture kept similar values to the pristine GUR1050 while Izod impact toughness increased about 10%. On the other hand, the 0.5%wt composite showed a reduction of about 20% in fracture stress, fracture strain and work to fracture compared to pristine polyethylene. Compared to the thermally untreated equivalent, the improvement in properties is evident, ranging from 20-50%.

graph In2015

ORAL CONTRIBUTIONS

Introduction: UHMWPE-based composites have been eveloped as an alternative to the current highly crosslinked UHMWPE obtained by gamma or electron beam irradiation and stabilized by thermal treatments or antioxidants [1]. The first and unique commercially available implantablegrade carbon reinforced UHMWPE was a mechanically blended short carbon fiber composite, known as Poly II [2]. Several attempts to improve the UHMWPE have been attained in the recent years by blending with carbon-based materials [3]. Graphene materials are new and potential candidates for reinforcement polymers owing to their high strength close to 130 GPa, stiffness around 1TPa and excellent thermal conductivity. In the present work, we evaluate the UHMWPE composites based on 1-2 layered graphene from a mechanical, tribological and chemical stability point of view.

Form DSC data, we can infer that Tm (136.9 ºC) and the degree of crystallinity (48.1 %) practically remain constant with the addition of GR1-2L up to 0.5 wt %. High temperature thermal treatment increases the Tm about 1.25 °C, the crystallinity in about 2% for the composites. Ball-on-disk tribological tests reveal that coefficient of friction did not show any significant difference for the untreated composites. However, a strong reduction (about 50%) in friction coefficient of the composites when the high temperature thermal treatment was applied, as shown in Table 1. Worn areas considered to be the “floaded” area, i.e. the area results from substracting the area placed over the surface level of the unworn sample from the total worn area. Table 1. Friction coefficient (µ) and wear factor (k) of GUR1050/GR1-2L composites. Material

ORAL CONTRIBUTIONS

GUR1050 GUR1050+0.1%GR1-2L GUR1050+0.3%GR1-2L GUR1050+0.5%GR1-2L GUR1050 HT GUR1050+0.1%GR1-2L HT GUR1050+0.3%GR1-2L HT GUR1050+0.5%GR1-2L HT

µ (2000-4000 m) 0.085±0.013 0.093±0.023 0.087±0.007 0.082±0.016 0.059±0.002 0.047±0.002 0.047±0.002 0.049±0.002

k 10−6 (mm3/Nm) 2.41 ± 0.07 2.60 ± 0.45 2.44 ± 0.75 2.51 ± 0.98 N/A N/A N/A N/A

In order to study chemical stability, EPR spectra have been measured before and after irradiating the samples. Prior to irradiation, no signals were detected in any case while a complex spectrum was observed after irradiating the sample with a 90 kGy dose. Figure 1 show the spectra observed in composite samples with different content of 1-2 layered graphene. For comparison purposes the EPR spectra of pristine UHMWPE (PE) and of a MWCNT/UHMWPE composite with a 0.5 % content of Nanocyl™ NC7000 labelled as NCYL) have been also include in the figure. The spectra observed in all the cases are similar and they consists of a dominant central signal (g ≈ 2, and a peak-to-peak width of about 1 mT), labelled with S, and other one with complex structure that is marked with stars, similar to observed in [4]. So, the starlabelled signal is associated to more stable polyallyl radicals and the S-labelled one to oxygencentered radicals [5]. However the relative intensities of these contributions are markedly different that that previously found. The S signal results dominant in the present case while the polyallyl contribution is markedly lower. Moreover no intensity variation is observed in this last signal with the addition of either CNT or different amounts of graphene.

graph In2015

On the other hand the intensity of the S-signal is affected by the presence of the carbonaceous materials. Its intensity decreases as the graphene content increases. It has been summarized in Figure 2 where the peak-to-peak height (Ypp) of the S-signal (normalized to its values in neat UHMWPE) is plot as a function of the graphene content. However this decrease is less than that found when CNT are added as it is depicted by open circles. Conclusion: The present work proposes a high temperature thermally treated 1-2 layeredgraphene/UHMWPE composite as an alternative to current HXLPs. A very strong reduction in friction coefficient (≈50%) and a noticeable improvement in secant modulus (≈30%) and yield stress (≈10%) have been found. Additionally, in EPR tests, it has been found a reduction in free radicals when the composite is γ-irradiated comparable to the MWCNT /UHMWPE one. Additional studies concerning bioactivity of wear debris should be programmed before to consider the proposed composite material as a potential substitute to highly crosslinked UHMWPEs.

References [1] Kurtz S, UHMWPE Biomaterials Hanbook. AP 2009. [2] Farling G, inventor; Zimmer Inc., assignee. (1977) U. S. Patent No. 4, 055,862. [3] Puértolas JA and Kurtz SM. J Mech Behav Biomed Mater 39 (2014) 129-145. [4] Potts JR, Polymer 52 (2011) 5-25. [5] Martínez-Morlanes MJ et al. Carbon 50 (2012) 2442-2452. [6] Castel P et al. J. Mater Sci. 48 (2013) 6549-6557. Figures

Figure 1: EPR spectra of γ–irradiated samples.

Figure 2: Normalized peak-topeak height (Ypp) of the Ssignal for the GR1-2L/UHMWPE composites.

Eau de Graphene: Additive Free, Single Layer Graphene in Water Alain Penicaud1,2, George Bepete1,2, Eric Anglaret3, Carlos Drummond1,2 1 CNRS, CRPP, UPR 8641, F33600 Pessac, France Univ. Bordeaux, CRPP, UPR 8641, F33600 Pessac, France 3Laboratoire Charles Coulomb, Univ. Montpellier, F34000 France 2

penicaud@crpp-bordeaux.cnrs.fr

Full exfoliation of graphite to form thermodynamically stable, negatively charged, graphene (graphenide) flakes in solution can be achieved by dissolution of graphite intercalation compounds (GICs) in low boiling point aprotic organic solvents under inert atmosphere [1,2] . We now report that, under certain conditions, graphenide can be transferred to water as single layer graphene. The organic solvent can then be evaporated to remain with an aqueous graphene suspension of ca 0.1 g/L concentration under ambient atmosphere. The Raman spectra (2.33 eV laser) collected in situ on such dispersions show bands at 1343, 1586, 1620 and 2681 cm-1 corresponding to the D, G, D’ and 2D bands of graphene respectively. The 2D band at 2681 cm-1 is well fitted with a sharp lorentzian line (∼28 cm-1) which is a hallmark of single layer graphene [3]. We have thus succeeded in preparing air stable, bulk suspensions of single layer graphene in water [4].

References [1] A. Catheline et al., Soft Matter, 12, (2012) 7882 [2] C. Drummond & A. Penicaud, Acc. Chem. Res. 46 (2013) 129 [3] Y.Y. Wang et al. J. Phys. Chem. C., 112 (2008) 10637 [4] G. Bepete, C. Drummond, A. Pénicaud, European patent, June 12, 2014, EP14172164

Figures

Figure 1: Vials of Eau de Graphene (graphene water)

Self-standing aerogels of SnO2-Graphene composites – Application as anode in lithium ion battery Gurpreet Singh1, Cristina Botas1, Daniel Carriazo1,2, Teófilo Rojo1,3 1CICenergigune, Miñano, Alava, Spain IKERBASQUE, Basque Foundation for Science, Bilbao, Spain 3Departamento de Química Inorgánica, Facultad de Ciencia y Tecnología (UPV/EHU), Bilbao, Spain 2

Lithium-ion batteries (LIBs) are the key components of portable electronic devices and electric vehicles. High energy density lithium ion batteries are required for their future applications in electronic market, as the needs of the market are more demanding. Graphene and graphene based materials have gained the interest due to their good properties such as mechanical flexibility and high electrical

ORAL CONTRIBUTIONS

gsingh@cicenergigune.com

conductivity, surface area and chemical diffusivity of Li. Graphene has been studied in the batteries in the past and their challenge has been demonstrated over the past couple of years [1, 2]. On the other hand metallic Tin based materials have also attracted great attention due to their good electrochemical properties when used as anode for LIBs, mainly due to theoretical specific capacity (993 mAh g-1) of Sn, low

graph In2015

cost and low toxicity [2]. However, Sn shows several problems: i) large volume changes during the lithiation/delithiation process (which can be up to 300 %); ii) high degradation and low cyclability due to these volume changes; iii) high decomposition of the electrolyte due to high reactivity of Sn nanoparticles. Different Sn/C composites have been developed to overcome these problems and improve the stability of Sn anodes. These carbon matrixes are reported to buffer the volume change of Sn during charge/discharge. [2]

CR2032 type coin cells were used to analyze the electrochemical properties of the composite cathode. Cells were fabricated inside a glove box under Argon atmosphere with H2O and O2 level < 0.1 ppm. 1.2 M LiPF6 solution in ethylene carbonate and dimethyl carbonate 1:1 (v/v) solution with VC as additive was used as electrolyte. Lithium metal foil was used as counter/reference and glass fiber as separator. Self-standing rGO and Sn/SnO2@rGO composite (without any binder and any support) were used as anodes. The reversible specific capacity of Sn/SnO2@rGO was 650 mAh g-1 at 50 mA g-1 after 40 cycles and 420 mAh g-1 at 1A g-1. The pure rGO specific capacity was 298 mAh•g-1 after 40 cycles at 50 mA g-1 (Fig. 1) [4].

The aim of this work, was to evaluate reduce graphene oxide (rGO) and a novel composite of SnO2@rGO (binder free) as selfstanding anodes for LIBs. SnO2@rGO composites were synthesized in two steps: i) freeze-drying and ii) thermal reduction of a mixture of SnSO4 and graphene oxide suspension, previously prepared by modified Hummer method. [3] The pure rGO was prepared following the same procedure. The materials have been characterized by XRD, XPS and SEM. Homogeneous distribution of 50–200 nm particles of SnO2 in the graphene matrix has been observed.

Acknowledgment: The authors thank European Commission (Graphene Flagship) for their financial support.

References [1] Z. Wu, G. Zhoua, L.Yina, W. R., F. Lia, H. Cheng. Nano Energy, 1 (2012) 107 [2] J. Qin, C. He, N. Zhao, Z. Wang, C. Shi, E. Liu, J. Li. ACS Nano, 8 (2014) 1728 [3] C. Botas, P. Álvarez, C. Blanco, R. Santamaría, M. Granda, et al. Carbon, 50 (2012) 275 [4] C. Botas, D. Carriazo, G. Singh, T. Rojo, J. Mater. Chem. A, 3 (2015) 13402

1800 1600 1400 1200 1000 800 600 400 200 0

80 60

41 Cycle number

50mA/g

1 A/g

0.8A/g

0.4 A/g

50mA/g

0.2 A/g

Current density:

0.1 A/g

ORAL CONTRIBUTIONS

Discharge Capacity Sn/SnO2@rGO Discharge Capacity rGO Coulombic efficiency rGO

20 0

Figure1: Charge-discharge and columbic efficiency curves measured using rGO and SnO2@rGO samples as binder-free electrodes.

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Coulombic Efficiency (%)

100 Charge Capacity Sn/SnO2@rGO Charge Capacity rGO Coulombic efficiency Sn/SnO2@rGO

75mA/g

Capacity (mA h/g)

Figures

Preparation, characterization and applications of highly reduce graphene oxide polyamide nanocomposites Elvira Villaro Ábalos1,2, Julio Gómez Cordón3, Jesus Ruben Berenguer4 Instituto de Tecnologías Químicas Emergentes de La Rioja; San Francisco, 11, 26370 Navarrete, La Rioja, Spain 2Departamento de Química Inorgánica y Técnica, UNED. Senda del Rey, 9, 28040 Madrid, Spain 3Avanzare Innovación Tecnologica S.L. Avda Lentiscares 4-6 Navarrete, La Rioja, Spain 4Departamento de Químicas. Universidad de La Rioja, Madre de Dios, 53 26006, Logroño, Spain

evillaro@interquimica.org

Thermochemical reduction of graphene oxide can be used to produce large quantities of highly-reduced graphene oxide (HRGO) for potential application in electronics, optoelectronics, composite materials and energy-storage devices. In polymer nanocomposites, graphene (or HRGO) is probably the most promising nanofiller due to its high surface area, aspect ratio, tensile strength, thermal and electrical conductivity, EMI shielding ability, flexibility and transparency[1]. In particular, high values of electrical and thermal conductivity have been reported derived from ultra-fast transfer of charge carriers due to its high specific surface area and strong interaction between adjacent carbon atoms and monolayer structure[2]. We have prepared graphene oxide (GO) using two different grades of graphite as starting materials (with different lateral size) by modified Hummer´s method[3]. The prepared GO has been reduced by a combination of chemical and thermal methods with the aim to decrease the number of sp3 defects and the oxygen content.

predispersion systems to optimize the properties of the nanocomposites. The electrical conductivity measurements and dielectric relaxation processes have been performed using Electrochemical Impedance Spectroscopy (EIS). We have also characterized the thermal conductivity of these nanocomposites. We will present the results studying the influence of the lateral size, thickness, oxygen content, defects and defects type in the electrical and thermal performance. We are able to prepare very high electrical conductivity nanocomposites (higher than 1 S/m) at low loads, and the percolation threshold has been achieved at less than 0,7%v for the lower oxygen content HRGO nanocomposites. This result is significantly better that other graphene materials and CNT nanocomposites produced by compounding or insitu polymerization; opening a new frame of applications in conductive polymers for their use in several industrial products[4].

We have prepared thermoplastic nanocomposites by melt compounding using unreinforced polyamide-6 (PA6) as matrix, studying dispersion of the HRGO in the matrix and the physical and mechanical properties of the HRGO nanocomposites. We have studied the processing parameters and

[1] Potts J. R., Dreyer D. R., Bielawski C. W., Ruoff R., S., Graphene-based polymer nanocomposites Polymer 2011; 52: 5-25 [2] Geim A. K., Novoselov K. S., The rise of graphene Nat. Mater. 2007; 6: 183 [3] W.S., Offeman R.E., Preparation of graphitic oxide. J Am Chem Soc. 1958; 80: 1339 [4] He and Tjong Nanoscale Research Letters 2013, 8:132; Polymer 50 (2009) 5103–5111

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ORAL CONTRIBUTIONS

References We have characterized the obtained highly reduced graphene oxides (HRGOs), by XRD, XPS, Raman and microscopic techniques (SEM, FE-SEM, TEM, HR-TEM, AFM) to determine key aspects as number of layers, lateral size, defects and oxygen content.

POSTER CONTRIBUTIONS

Evaluation of Electronic Transport Across Grain Boundaries in Graphene M.P. Ariza1, J.P. Mendez2 and F. Arca1 1ETSI, Universidad de Sevilla, Spain Graduate Aeronautical Laboratories, California Institute of Technology, USA

mpariza@us.es

In the field of electronics, due to its excellent mechanical and electrical properties, graphene has become the most promising material for the production of next generation electronic components. However, with all the research findings up to date, owing to the fact that defect-free graphene presents a lack of band gap, it is well known the limited use of this material for semiconductor-based applications, such as field effect transistors. Many attempts have been successfully made to engineer band gaps in graphene, such as doped or uniaxial strained membranes and manufactured nanoribbons. In this work, we focus on a new innovative way to introduce relevant transport gaps in graphene associated with

the existence of asymmetrical grain boundaries in the lattice. First, we have identified stable grain boundary structures by recourse of a computational tool based on the Landauer-Büttiker formalism. The electronic transport across these grain boundaries is then evaluated based on a tight binding model. In addition, in order to validate our results against ab initio-based calculations, we have also employed the density functional formalism and the nonequilibrium Green’s function method implemented in TRANSIESTA code. As main result, we have found that some asymmetric grain boundary structures provide a moderate transport gap, up to ~ 1eV.

Hardness characterization of graphene acrylic transparent nanocomposite coatings through Atomic Force Microscopy D. Domene1, R. Sarabia1, G. Ramos-Fernandez1, I. Rodríguez2, J.C. García-Quesada1, I. Martin-Gullon1 University of Alicante, PO box 99, 03080 Alicante, Spain 2Applynano Solutions, Alicante Scientific Park, Spain

ddl5@alu.ua.es

electrostatic dissipative properties while keeping transparency [4]. Anti-scratch properties are usually monitored through hardness characterization. Polymer based coatings are regularly tested through the Wolf-Wilburn test (ISO15184), a simple standard where the film hardness is ranked depending on which pencil from a set of 20 of different hardness begins to produce an scratch on the film. One of the problems of this standard is that high performance coatings are out of scale, and then it is difficult to study how nanoreinforced formulations perform. On the other hand, atomic force microscopy (AFM) is a high

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UV-Photocure acrylic resins are of recent growing interest for applications such as paints, coatings, adhesives and inks due to the easier procesability, and lower energy and cost of photo curing versus thermal curing [1]. Photocuring acrylic resins formulations based on urethane diacrylate are used as high performance antiscratching glass coatings [2], and transparent nanocomposites with on nanosilica are on development [3]. Monolayer or few-layered graphene are idoneous materials for getting the double functionality of improving hardness with respect to the neat resin and giving

versalite technique valid for the characterization of well-varied properties. Specifically, the atomic probe, with an adequate diamond cantilever, used in contact mode can be used for either indentation on a polymer film (in and out and measuring the interacting force) or dragging the probe after it was indented at same force, and exploring with AFM in tapping mode the stratch produced. The present work studies the effect the role of highly exfoliated graphene oxide onto photocuring acrylic nanocomposites, where Wolf-Wilburn hardness of neat resin is above 9H. AFM equipment was able to characterized and monitor the scratch resistance, quantifying the effect in terms of wear volume, as shown in AFM tapping mode, per same force, as produced by AFM in contact mode. As a consequence,

our group is working now in establishing an scale for the hardness, studying coatings below 9H, for the extrapolation for coatings above 9H, as samples treated in the present contribution. References [1] Castelvetro, V., M. Molesti, and P. Rolla. Macromolecular Chemistry and Physics, 2002. 203(10-11): p. 1486-1496. [2] Zhang, H., L. Tang, Z. Zhang, et al. Tribology International, 2010. 43(1–2): p. 83-91. [3] Amerio, E., P. Fabbri, G. Malucelli, et al. Progress in Organic Coatings, 2008. 62(2): p. 129-133 [4] Sangermano, M., S. Marchi, L. Valentini, et al. Macromolecular Materials and Engineering, 2011. 296(5): p. 401-407.

Graphene oxide a new sensitive material for surface acoustic wave gas sensors I. Sayago1, D. Matatagui2, M.J. Fernández1, J.L. Fontecha1, M.C. Horrillo1, J.P. Santos1, R. Garriga3, E. Muñoz4 Instituto de Tecnologías Físicas y de la Información ITEFI-CSIC, Madrid, Spain CCADET, Universidad Nacional Autónoma de México (UNAM), México D.F. Departamento de Química Física, Universidad de Zaragoza, Zaragoza, Spain 4 Instituto de Carboquímica ICB-CSIC, Zaragoza, Spain 1

rosa@unizar.es

POSTER CONTRIBUTIONS

Graphene oxide (GO) is an attractive material that has been studied these last few years as sensitive layer in the chemical gas sensors. GO combines 2D structural features of the graphene and the presence of oxygen-containing functional groups (mainly, epoxide, hydroxyl and carbonyl groups) to potentially interact with a great variety of analytes. Chemical gas sensors offer a wide variety of advantages over the conventional analytical instruments such as low cost, short response time, easy manufacturing, and small size. In this context, surface acoustic wave (SAW) sensors have gained enormous interest due to their high sensitivity, high resolution, high stability and a frequency output signal which is easy to process [1-2]. Besides, they operate at room temperature and, therefore, the GO thermal reduction can be prevented.

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SAW sensors consist of a set of interdigitated electrodes (IDTs) onto the surface of a piezoelectric substrate forming a delay line (DL). The IDTs convert incoming electrical radio frequency (RF) signals into surface acoustic waves which propagate along the surface of the device. The sensitive layer is deposited onto the piezoelectric substrate. The principle of a SAW device is very simple, when the gas molecules are adsorbed on a sensitive layer, the velocity and amplitude of the surface waves change. The velocity changes can be calculated indirectly by measuring the frequency shifts due to the vapour adsorption. The main goal of the present study is to establish the potential applicability of GO as sensitive layer of SAW sensor [3]. The sensor based on GO is tested for the detection of dimethyl methylphosphonate (DMMP) in air

Gutch, G. Lal, K.D. Vyas, D.C. Gupt. Sens. Actuators B 135 (2009) 399. [3] I. Sayago et al., submitted. [4] S.L. Bartelt-hunt, Bartelt hunt, D.R.U. Knappe, M.A. Barlaz, Critical Reviews in Environmental Science and Technology, 38 (2008) 112.

atmosphere at room temperature. Dimethyl methylphosphonate is a sarin sarin-simulant simulant used in the production of chemical weapons [4]. References [1] D.S. Ballantine Jr., R.M. White, S.J. Martin, A.J. Ricco, E.T. Zellers, G.C. Frye, H. Woltjen, Acoustic Wave Sensors Sensorsâ&#x20AC;&#x201C;Theory, Theory, Design and PhysicoPhysico-Chemical Chemical Applications, Academic Press, New York 1997. [2] A.T. Nimal, Nimal, U. Mittal, M. Singh, M. Khaneja, G.K. Kannan, J.C. Kapoor, V. Dubey, P.K.

Figures 500 0

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Frecuency shift (HZ)

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Low-cost, Green, Large Scale Manufacturing of Graphene Lucía González Bermúdez, Cesar Quispe, Ana Suárez, Pedro Martín EEA-GrapheneTECH, Maria de Luna 11, Nave 1, Zaragoza, Spain

lgonzalez@graphene-Tech.net

Chemical exfoliation leads to graphene oxide (GO) with very poor electrical conductivity, which, if further reduced to increase conductivity (reduced graphene oxide, rGO), tends to lead graphene defective, not fully reduced and carrying many non-carbon elements from the hazardous chemicals used (as in Hummers o Brodie methods), hence limiting its quality for potential industrial uses. In contrast, mechanical exfoliation protocols use shear forces to separate graphene stacks in graphite and are currently producing nonoxidised graphene nanoplatalets (GNPs) with a broad range of quality, number of layers, conductivity, surface area and mechanical performance depending on the success degree of exfoliation. As a result mechanical exfoliation appears to be the most promising route for the mass manufacturing of high quality bulk graphene.

GPx multigraphene is produced with different numbers of standardized layers (ranging 5-40 layers), achieving specific surface areas among 100-700 m2 / g.

Our Graphene production takes place in manufacturing process, "top down" graphite exfoliation, at low cost and in a manner friendly to the environment; accordingly, the quality of nanoplates Graphene obtained is highly commercial.

GPx multigraphene as coatings (paints) multiple properties are improved: The 2/3 scratch resistance, increased yields between 15-20%, a considerable increase in the corrosion resistance.

Thanks to the quality and diversity of our product, we achieve to service customer demand specifically, modifying and functionalizing our graphene, because our main focus is customer satisfaction. Gpx multigraphene supports almost all polymers; tested potential applications have shown improvements of up to 40% in epoxy resins, in the module flexibility. GPx multigraphene as additive has achieved reinforce the mechanical properties in all types polymers tested, improving the traction coefficient, impact, and friction and melt flow.

POSTER CONTRIBUTIONS

Figures

Figure 1: GrapheneTECH Comparison.

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Synthesis of a graphene oxide- TiO2 nanocomposites for photocatalytic applications M. González-Barriuso1, L. Astoreca1, P. Ribao2, M. J. Rivero2, C. Manteca1, A. Yedra1 Fundación Centro Tecnológico de Componentes (CTC). Parque Científico y Tecnológico de Cantabria (PCTCAN), Spain 2Department of Chemical and Biomolecular Engineering, University of Cantabria, Santander, Spain

The availability of drinking water is a factor of the highest priority to human existence. However, it is estimated that 780 million people lack access to safe drinking water, and therefore are forced to rely on sources of unsafe biologically water. Therefore, reuse of this resource is gaining great importance in certain regions of the world, and therefore a sustainable method for disinfecting water for this purpose is necessary [1], [2]. There is great concern about this issue, since emergent contaminants are been detected in wastewater treatment plant effluents. However, the conventional technology is inadequate given the complexity of the degradation of these new contaminants. For this reason, humanity is developing new technologies for the treatment of these waters. These novel technologies are photocatalytic oxidation, adsorption processes / separation and bioremediation included. The solution proposed by this research is to implement a technology that improves the efficiency of photocatalysts used today in photocatalytic processes. To do this, nanotechnology is been used. The idea is to improved TiO2 photocatalytic activity combining it with graphene oxide. The graphene oxide-TiO2 nanocomposites have a bigger specific surface area due to graphene oxide contribution, the absorption of a range of wave lengths larger and the suppression of charges recombination. This suppression of charges recombination is related to the excellent electrical properties of graphene. Graphene acts as an electron acceptor [3].

material have been studied. The graphene oxide-TiO2 nanocomposites were prepared by hydrothermal and mechanic synthesis. Previously, graphene oxide was synthesized from highly oriented graphite by a Hummers’ modified method [4]. This nanocomposites have been characterized by atomic force microscopy (AFM), BET isotherm adsorption, FTIR spectroscopy and thermogravimetry. These analysis prove that the graphene oxide sheets are decorated by TiO2 nanoparticles. Also, degradation photocatalytic experiments were done above two pollutants: dissolve organic carbon (DOC) and dicloroacetic acid (DCA) analysis. These show an improved in the photocatalytic activity of the nanocomposite compared to the titanium oxide. References [1] H. Wang et al. (2013). Graphene-based materials: Fabrication, characterization and application for the decontamination of wastewater and wastegas and hydrogen storage/generation. Advances in Colloid and Interface Science, 195-196. 19-40. [2] P. Fernández-Ibáñez et al. (2014). Solar photocatalytic desinfection of water using titanium dioxide graphene composites. Chemical Engineering Journal, 261. 36-44. [3] R. Leary, A. Westwood. (2011). Carbonaceous nanomaterials for the enhancement of TiO2 photocatalysis. Carbon, 49. 741-772 [4] M. González-Barriuso et al. (2015). Synthesis and characterization of reduced graphene oxide from graphite waste and HOPG. Materials Research Innovations, 19. 192-195.

Different methods for the synthesis of graphene oxide-TiO2 nanocomposites and its preliminary assessment as photocatalytic

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POSTER CONTRIBUTIONS

Keywords: Graphene oxide, photocatalysis, titanium dioxide

Figures

Figure 1: AFM images and topographic profile of a graphene oxide-TiO2 nanocomposite sample synthesized in this work.

Quantum transport in high quality suspended graphene devices with advanced geometry Anya Grushina, DongKeun Ki, Alberto Morpurgo University of Geneva, DQMP, Quai Ernest-Ansermet 24, Geneva 1205, Switzerland

POSTER CONTRIBUTIONS

grushinast@gmail.com

Suspended graphene provides an opportunity to explore intrinsic low-energy properties of graphene and its multilayers due to its high quality and decoupled substrate [1]. The progress in sample fabrication makes advanced geometry accessible for graphene devices. Ballistic electron transport and charge carriers collimation in monolayers with induced potential barriers create an environment for "electron optics" [2]. We show an additional bottom gate forming a Fabry-Pérot (FP) cavities between the contacts and controlled p-n interface in monolayer graphene. The device exhibits ballistic behavior on 1 µm scale, one magnitude longer than previously reported samples. A clear FP interference pattern is consistent with estimated cavity size (Fig.1,a) and undergoes a π-shift in small magnetic field (Fig.1,b) – a signature of chiral charge carriers in graphene [3]. Having established the method for fabrication of high quality suspended graphene [4], we design

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multiterminal devices (inset on Fig.2b) to probe transport phenomena close to charge neutrality point (CNP) in few-layer graphene. High-quality tetralayer graphene becomes strongly insulating in zero magnetic field (Fig.2,a), with thermal activation behavior of the gap (Fig.2,b) [5]. We interpret such behavior as symmetry breaking of the underlying ground state due to electronelectron interactions with a similar mechanism as suggested for bilayer graphene samples [6-8]. Based on our observations and previously reported high quality trilayers remaing conducting [9] we suggest that interactions around CNP exhibit an even-odd effect, opening a gap in graphene with even number of layers.

References [1] X. Du et.al., Nature Nanotechnology, 3 (2008) 491-495 [2] A. Young and P. Kim, Annual Review of Condensed Matter Physics, 2, (2011) 101-120 [3] A. Grushina, D.-K. Ki, A.F. Morpurgo, Applied Physics Letters, 102 (2013) 223102 [4] D.-K. Ki and A.F. Morpurgo, Nano Letters, 13 (2013) 5165-5170 [5] A. Grushina et.al, Nature Communications, 6 (2015) 6419 [6] J. Velasco et.al., Nature Nanotechnology, 7 (2012) 156-160

[7] W. Bao et.al., Proceedings of National Academy of Science, 109 (2012) 10802-10805 [8] F. Freitag et.al., Physics Review Letters 108 (2012) 076602 [9] W. Bao et.al., Nature.Physics 7(12) (2011) 948-952

Figures

Figure 2: a, Temperature dependence of the conductance G as a function of charge carrier density n reveals a highly insulating state at low temperatures in tetralayer graphene; b, Minimum conductance Gmin as a function of inverse temperature 1/T shows thermally activated behavior Gmin = exp(-EA/kBT) with activation energy EA = 14.6 K; inset shows multiterminal sample geometry

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POSTER CONTRIBUTIONS

Figure 1: a, Resistance R as a function of charge carrier n density shows oscillations due to Fabry-PĂŠrot interference; b, Shift of the interference pattern in magnetic field B

Study of graphene nanosheets with three-dimensional morphology for use in Li-ion batteries Celia Hernández Rentero, Oscar Vargas, Álvaro Caballero, Julián Morales Dpto. Química Inorgánica e Ingeniería Química, Instituto de Química Fina y Nanoquímica, Universidad de Córdoba, Spain

q12herec@uco.es

Graphene is a material that is attracting a lot of interest in recent years, with great prospects thanks to its various applications. Remarkable is the use of graphene-based materials as electrodes for lithium-ion batteries. Three dimensional graphenes (3DG) offer advantages over the graphene monolayer and other three-dimensional carbons, e.g. nanotubes, because they are easier and cheaper to prepare, and more efficient [1].

mAh g-1), but retention of the capacity along cycling was poor. On the other hand, G3D with mixed synthesis (hydrothermal treatment and chemical reducing agent) provided lower capacities (comparable to the graphite´s ones) but better capacity retention. Finally, the G3D synthesized by using a reducing agent and not hydrothermal tretamen had an intermediate behavior.

In this work we have studied different 3DG in order to examine their properties in energy storage systems. Four ways to prepare hydrogels from graphite oxide have been selected: i) by exfoliation based on hydrothermal treatment; ii) and iii) by chemical reduction and subsequent hydrothermal exfoliation, and iv) by chemical treatments.

[1] Vargas, O.; Caballero, A.; Morales, J.; Elia, G. A.; Scrosati, B.; Hassoun, J., Electrochemical performance of a graphene nanosheets anode in a high voltage lithium-ion cell. Physical Chemistry Chemical Physics 2013, 15 (47), 20444-20446. [2] Wang, G.; Shen, X.; Yao, J.; Park, J., Graphene nanosheets for enhanced lithium storage in lithium ion batteries. Carbon 2009, 47 (8), 20492053.

POSTER CONTRIBUTIONS

The materials obtained were characterized by techniques that provided insights related to the structure, morphology, texture, thermal stability and composition. We concluded that a pore system has been formed due to the partial removal of functional groups and the subsequent exfoliation of graphite oxide. In the study as electrodes in Li-ion batteries the results showed not a direct link between the synthesis method and the electrochemical behavior. The measurements were performed in galvanostatic regime at a rate of 149 mA g-1, between 3.00-0.01 V [2]. For the first cycle, some of the 3D graphenes had a tendency to deliver high capacities exceeding the theoretical capacity (744 mAh / g), which is common in disordered carbons. In all cases high values of irreversible capacity were obtained, between 880 and 300 mAh/g. The G3D synthesized by hydrothermal treatment delivered high discharge capacity values (higher than the graphite´s ones, 300

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References

Figures

Figure 1: SEM image of G3D synthesized by hydrothermal treatment showing the flower-like threedimensional morphology

Graphene oxide as superior catalyst support for heterogeneous catalysis Andrés Seral-Ascaso1, Asunción Luquin2,3, María Jesús Lázaro1, Rosa Garriga4, Germán F. de la Fuente5, Mariano Laguna2, Edgar Muñoz1 1Instituto de Carboquímica ICB-CSIC, Zaragoza, Spain Instituto de Síntesis Química y Catálisis Homogénea (Universidad de Zaragoza-CSIC), Zaragoza, Spain 3Universidad Pública de Navarra, Pamplona, Spain 4Departamento de Química Física, Universidad de Zaragoza, Zaragoza, Spain 5Instituto de Ciencia de Materiales de Aragón (Universidad de Zaragoza-CSIC), Zaragoza, Spain

edgar@icb.csic.es

GNP decoration process. GO, that exhibits high microporosity, behaves differently probably because the microporosity present in the dry solid drastically decreased when the material was highly exfoliated in water, leading to a huge surface area available for the GNP deposition. Moreover, the large number of oxygen functional groups (hydroxyl, carbonyl, phenol, and epoxide groups, 44.9 wt.% O content) of GO allowed a good GO dispersibility in water. The presence of these oxygen-containing functional groups in GO may also assist the GNP deposition and, eventually, may favor the gold-carbon hybrid/reactants interaction, so they may also further account for the superior catalytic performance of the Au-GO hybrids [1]. This work has been supported by the regional Government of Aragón, Spain (Project PI119/09, and Research Groups funding). This work has been funded in part by the European Commission through projects FP7 Grant agreement # 280658 and LIFE11/ENV/ES 560.

References [1] A. Seral-Ascaso, A. Luquin, M.J. Lázaro, G.F. de la Fuente, M. Laguna, E. Muñoz, Appl. Catal. A 456 (2013) 88.

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Graphene oxide (GO) offers appealing features such as their 2D structure and the presence of oxygen functional groups for its use as support for heterogeneous catalysis. In this work we show that GO offers superior catalyst support performance when compared to a variety of carbon supports (single-walled and multi-walled carbon nanotubes, graphite, graphitic cones, nanodiamond, ordered mesoporous carbon, carbon xerogel, carbon black, activated carbon, and laser-ablation produced carbon foam). We show that these carbon materials could be efficiently used as supports for gold nanoparticle (AuNP)-based catalysts for the hydroamination of phenylacetylene with aniline. Carbon supports were decorated with AuNPs synthesized by in situ reduction of chloroauric acid (H[AuCl4]) in water. The synthesized gold-carbon hybrids worked remarkably well as catalysts for the targeted reaction. Conversion values as high as 79% were achieved by suitably adjusting the gold:carbon support w/w ratios. Our results indicate that the catalytic activity strongly depends on gold:carbon support w/w ratios and on the structure and textural properties and dispersibility of the carbon supports used. The best gold-carbon catalyst performance in terms of conversion values and low carbon support content has been achieved when using GO as well as supports (carbon black, carbon nanotubes, and nanodiamond) that combine high BET surface areas, well-developed mesoporosity, and good dispersibility in water during the

Graphene based capacitive deionization for an energy efficient desalination system (GRAPHESALT) David A. Pacheco Tanaka1, Yolanda Belaustegui1, Pablo Benguria1, Olivier Lorain2 Tecnalia Reseach and Innovation, Mikeletegi 2, DonostiaDonostia-San San Sebatian 20009, Spain 2Polymem, 3 rue de Iâ&#x20AC;&#x2122;industrie-Zone Zone de VIC 31320, Castanet Tolosan, France

Pablo.benguria@tecnalia.com

Graphesalt is a project inside the Graphene Flagship involving Tecnalia and Polymem. Graphesalt focuses on developing a sustainable desalination process based on Capacitive Deionization technology (CDI) using graphene/metal oxide electrodes to diminish the salt concentration from saline water (seawater, brackish water, industrial water), with the ai aim m of surpassing the state of the art efficiency of reverse osmosis. Among the emerging desalination approaches, capacitive deionization (CDI) is one of the most promising technologies. The advantages of CDI include lower operating costs and energy consump consumption, tion, lack of secondary pollution and easy regeneration and maintenance. CDI technology has its roots in supercapacitor technology and uses pairs of oppositely placed porous electrodes which store ions upon applying an electrical voltage difference.

POSTER CONTRIBUTIONS

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The research research is organized in three work packages. The first one, will concern the development and characterization of high specific surface area and capacitance electrodes, this work package will be done by Tecnalia. The second one will imply the construction of of the laboratory CDI system, this WP will be realized by Polymem, which has the expertise in membrane pilot plant construction and Tecnalia. And, in the last one, the performance of the CDI system for salts electroadsorption and electrodesorption, charge a and nd energy consumption will be evaluated; this work package will be done by Tecnalia and Polymem. Acknowledgments The work has received founding from the European Union Seventh Framework Programme under grant agreement 604391 Graphene Flagship

Relevance of graphene oxide nanoparticles in cell microencapsulation as a de novo producing drug organoid Laura Saenz del Burgo Burgo*, *, Jesús Ciriza*, Argia Acarregui, Haritz Gurruchaga, Gorka Orive, Rosa María Hernández, Jose Luis Pedraz NanoBioCel Group, Laboratory of Pharmaceutics, School of Pharmacy, University of the Basque Country UPV/EHU, Vitoria Vitoria-Gasteiz, Gasteiz, Spain The Biomedical Research Networking Centre on Bioengineering, Biomaterials and Nanomedicine (CIBER (CIBER-BBN) BBN),, Spain *Both Both authors contributed equally to the development of the present work

joseluis.pedraz@ehu.es

References [1] Ciriza, J., Saenz del Burgo, L., VirumbralesVirumbrales Muñoz, M., Ochoa, I., Fernandez, LJ., Orive, G., Hernández, MR., Pedraz, JL., International Journal of Pharmaceutics, 493 (2015) 260-270 260 [2] Orive, G.; Santos, E.; Pedraz, J. L.; Hernandez, R. M., Adv Drug Deliv Rev, 67-68 67 68 (2013) 3-14. 3 14. [3] Basta, G.; Montanucci Montanucci,, P.; Luca, G.; Boselli, C.; Noya, G.; Barbaro, B.; Qi, M.; Kinzer, K. P.; Oberholzer, J.; Calafiore, R., Diabetes Care, 34(11) (2011) 2406-9. 2406 [4] Goenka, S.; Sant, V.; Sant, S., J Control Release, 173 (2013) 75 75-88. [5] Lee, W. C.; Lim, C. H.; Shi, H.; Tang, L. A.; A. Wang, Y.; Lim, C. T.; Loh, K. P., ACS Nano, 5(9) (2011) 7334-41. 7334 [6] Li, N.; Zhang, Q.; Gao, S.; Song, Q.; Huang, R.; Wang, L.; Liu, L.; Dai, J.; Tang, M.; Cheng, G., Sci Rep, 3 (2013) 1604. [7] Ruiz, O. N.; Fernando, K. A.; Wang, B.; Brown, N. A.; Luo, P. G.; M McNamara, cNamara, N. D.; Vangsness, M.; Sun, Y. P.; Bunker, C. E., ACS Nano 5(11) (2011) 8100 8100-7.

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Figure 1: Viability of encapsulated C2C12 myoblasts in graphene oxideoxide [0-100 [0 100 µg/ml] APA microcapsules. A) Metabolic activity (CCK8) and B) Cell membrane integrity assay (LDH), both expressed as the ratio between day 8 and 1 after microencapsulation.

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POSTER CONTRIBUTIONS

Cell microencapsulation implies the immobilization of cells within a polymeric matrix surrounded by a semipermeable membrane that allows the bidirectional diffusion of nutrients and oxygen inside the microcapsules and the release of waste and therapeutic molecules molecules to the outside. Therefore, cell microencapsulation represents a great promise for the development of long long--term term de novo synthesized drug delivery systems. In fact, the microencapsulation of different types of cells is being investigated for the tre treatment atment of several human diseases. Most efforts are focused on chronic and degenerative diseases as this strategy could become an alternative to some commonly used parenteral treatments that need to be repeatedly administered. However, several challenges need need to be overcome before it can be translated extensively into the clinic. For instance, the long term cell survival inside the microcapsules. On this regard, graphene oxide has shown to promote the proliferation of different cell types both in two and three three dimension cultures. Consequently, the aim of this work was to combine the use of graphene oxide together with the cell microencapsulation technology and analyze the biocompatibility of this chemical compound with erythropoietin producing myoblasts enclosed enclosed in alginate alginate-poly poly-LL-lysine lysine (APA) microcapsules. We have determined the best graphene oxide concentrations that are able to enhance the viability of the cells in vitro and demonstrated in vivo, vivo, that cells microencapsulated in graphene oxide containing APA APA microcapsules are able to increase the hematocrit of C57BL/6J above controls. These results provide a relevant step for the future clinical application of graphene oxide on cell microencapsulation.

Study of Gra Graphene phene from Natural Graphite for Lithium Batteries María Simón, Simón, Alvaro Caballero, Julián Morales y Óscar Vargas Dpto. Química Inorgánica e Ingeniería Química, Instituto de Química Fina y Nanoquímica, Campus de Rabanales, Universidad de Córdoba. 14071 Córdoba, Spain

p12sigam@uco.es

POSTER CONTRIBUTIONS

The modern commitment between energy consumption and sustainability presents a sort of technical challenges, among them the need of storage. Graphene is presented as a key material to face such a challenge. The theoretical energy storage capacity of graphene graphene has been calculated as the double than that for graphite, due to the possibility of storing Li+ in both faces of the graphene sheet [1]. Graphene Graphene-based based materials are among the most studied materials for energy storage in lithium batteries [2]. Mass prod production uction of graphene from graphite at low cost is essential. Natural graphite is cheaper than synthetic; moreover graphene production from untreated natural graphite decreases costs, since extracting graphite from the minerals usually involves an expensive p purification urification process. On the other hand, there are huge stocks of natural graphite minerals on earth. Although, in the last decade natural graphite production is growing the estimated production could be maintained for over 200 years at current rates [3]. In this study, graphene nanosheets were synthesized from untreated natural graphite from Huelma, Jaén (Spain). Graphite oxide (GO) was prepared by using modified Hummers method, then Graphene nanosheet (GNS) were prepared applying thermal exfoliation unde underr inert nitrogen atmosphere at 300ºC. The synthesized materials were characterized structurally, morphologically and in terms of chemical composition. The natural graphite sample contains 45-50% 45 50% by weight of carbon, and the rest is composed of elements such such as silicon, iron, calcium and oxygen. These elements are present as calcium carbonate, quartz and clinoferrosillite. In the synthesized materials, GO and GNS, calcium disappears due to chemical treatment, although other impurities remain. The energy storage storage capacity is evaluated using the material as electrode in rechargeable lithium batteries.

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The results have confirmed that the theoretical capacity of graphene nanosheets is double than that obtained for graphite. In addition, the impurities in the sample do not affect the electrochemical sample properties of the electrode. Comparing these results with a similar study with synthetic samples, natural graphite and the graphene derived from it have demonstrated excellent energy properties; the capacity values even surpass some reported for other graphene materials obtained by similar methods from pure synthetic graphite. References [1] Y.Zhu, S.Murali, W.Cai, X.Li, J.W.Suk, J.R.Poots, R.S.Ruoff, Graphene and graphene oxide: synthesis, properties and applicatons, Adv.Mater. 22 (2010) 39063906 3924. [2] M.Liang, L.Zhi Graphene Graphene-based based electrode materials for rechargeable lithium batteries, Journal of Materials Chemistry, 19 (2009) 5871 5878. 5871-5878. [3] S. Moores, “Flake Graphite Basic Basic-Supply, Supply, Demand Price”, London, (2014)

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