Carbon Nanotube–Polymer Composites 1 0 0 P F 7- 1 8 6 3 7 9 4 8 1 8 7 9 9/ 3 0 1 0. 1 oi: d g | or c. s s.r b u p p:// htt n o 3 1 d 20 deh nloaMarc Down 01 o d e h s bli u P View Online RSC Nanoscience & Nanotechnology Series Editors: Professor Paul O’Brien, , UK Professor Sir Harry Kroto FRS, University of Sussex, UK 1 Professor Ralph Nuzzo, University of Illinois at Urbana-Champaign, USA 0 0 P F 7- Titles in the Series: 1 68 1: Nanotubes and Nanowires 3 97 2: Fullerenes: Principles and Applications 4 8 3: Nanocharacterisation 1 8 7 4: Atom Resolved Surface Reactions: Nanocatalysis 9 9/ 5: Biomimetic Nanoceramics in Clinical Use: From Materials to Applications 3 0 1 6: Nanofluidics: Nanoscience and Nanotechnology 0. oi:1 7: Bionanodesign: Following Nature’s Touch d 8: Nano-Society: Pushing the Boundaries of Technology org | 9: Polymer-based Nanostructures: Medical Applications sc. 10: Metallic and Molecular Interactions in Nanometer Layers, Pores and bs.r Particles: New Findings at the Yoctolitre Level u p 11: Nanocasting: A Versatile Strategy for Creating Nanostructured Porous p:// Materials htt n 12: Titanate and Titania Nanotubes: Synthesis, Properties and Applications o 3 13: Raman Spectroscopy, Fullerenes and Nanotechnology 1 d 20 14: Nanotechnologies in Food nloadeMarch 1156:: UPonlryamveerlliNnganSoincoglmepCoeslilteGsebnyomEmicsu:lsMioincraonadnSduNspaennositoonols Dowon 01 1178:: PNhaangoetuNbaensoabnidotNecahnnoowloirgeys: 2nd Edition d he 19: Nanostructured Catalysts: Transition Metal Oxides s bli 20: Fullerenes: Principles and Applications, 2nd Edition u P 21: Biological Interactions with Surface Charge Biomaterials 22:NanoporousGold:FromanAncientTechnologytoaHigh-TechMaterial 23: Nanoparticles in Anti-Microbial Materials: Use and Characterisation 24:ManipulationofNanoscaleMaterials:AnIntroductiontoNanoarchitectonics 25: Towards Efficient Designing of Safe Nanomaterials: Innovative Merge of Computational Approaches and Experimental Techniques 26: Polymer–Graphene Nanocomposites 27: Carbon Nanotube–Polymer Composites How to obtain future titles on publication: A standing order plan is available for this series. A standing order will bring delivery of each new volume immediately on publication. For further information please contact: BookSalesDepartment,RoyalSocietyofChemistry,ThomasGrahamHouse, Science Park, Milton Road, Cambridge, CB4 0WF, UK Telephone: +44 (0)1223 420066, Fax: +44 (0)1223 420247 Email: [email protected] Visit our website at www.rsc.org/books View Online Carbon Nanotube–Polymer Composites Edited by 1 0 0 P Dimitrios Tasis F 7- Department of Materials Science, University of Patras, Greece 1 8 6 Email: [email protected] 3 7 9 4 8 1 8 7 9 9/ 3 0 1 0. 1 oi: d g | or c. s s.r b u p p:// htt n o 3 1 d 20 deh nloaMarc Down 01 o d e h s bli u P View Online 1 0 0 P F 7- 1 8 6 3 7 9 4 8 1 8 7 9 9/ 3 0 1 10. RSC Nanoscience & Nanotechnology No. 27 oi: d g | ISBN: 978-1-84973-568-1 c.or ISSN: 1757-7136 s s.r b pu A catalogue record for this book is available from the British Library p:// n htt # The Royal Society of Chemistry 2013 o 3 1 d 20 All rights reserved deh nloaMarc Apartfromfairdealingforthepurposesofresearchfornon-commercialpurposes Dowon 01 oDresfiogrnsparnivdatPeatsetnutdsyA, cctri1t9ic8i8smanodrthreevCieowpy,raigshtpearnmdiRtteeldatuedndRerighthtseRCegoupylartiigohnts, ed 2003,thispublicationmaynotbereproduced,storedortransmitted,inanyform h blis orbyanymeans,withoutthepriorpermissioninwritingofTheRoyalSocietyof Pu Chemistry or the copyright owner, or in the case of reproduction in accordance withthetermsoflicencesissuedbytheCopyrightLicensingAgencyintheUK,or in accordance with the terms of the licences issued by the appropriate Reproduction Rights Organization outside the UK. Enquiries concerning reproduction outside the terms stated here should be sent to The Royal Society of Chemistry at the address printed on this page. The RSC is not responsible for individual opinions expressed in this work. Published by The Royal Society of Chemistry, Thomas Graham House, Science Park, Milton Road, Cambridge CB4 0WF, UK Registered Charity Number 207890 For further information see our web site at www.rsc.org Printed in the United Kingdom by Henry Ling Limited, Dorchester, DT1 1HD, UK 5 0 0 P F 7- Preface 1 8 6 3 7 9 4 8 1 8 7 9 9/ 3 0 1 0. The combination of carbon nanotube special properties (structural and 1 oi: conductive) makes them the ideal filler material in various polymer matrices d g | for a wide range of applications. With the aim of mimicking the conditions c.or existinginmetalrod-reinforcedconcrete,Ajayanandco-workersreportedthe s s.r first ever fabrication of a carbon nanotube/polymer composite in 1994. Since b pu then, there have been some thousands of works published, revealing the p:// potential of polymers reinforced with one-dimensional graphitic nanostruc- htt n tures. In the early years of related research, as-prepared carbon nanotube o 3 material was actually a mixture of different metallicities, diameters and 1 ded h 20 lengths, not to mention the presence of impurities and sidewall defects. nloaMarc Furthermore, self-aggregation phenomena due to van der Waals interactions Down 01 afonudndatloachkamofpecrhtehmeichaolmaoffgienniteyoubsetdwiseternibuthtieonfilolefrthaengdrathpehitmicantraixnohsatrvuectbuereens o d within a polymer matrix. Finally, due to their relatively short length and the e h blis presence of sidewall defects, carbon nanotubes are normally curled, and Pu therefore individual tubes embedded in a polymer only exhibit a fraction of their potential. Thus, the superb properties of the graphitic nanomaterial have been partially translated into high stiffness and conductivity polymer composites. Only in recent years have been great advances towards the development of multifunctional carbon nanotube/polymer assemblies. The purpose of this book is to summarize the basic principles of carbon nanotube chemistry in relation to the fabrication of polymer composites, but also tohighlightsome ofthemost remarkableadvancesthat haveoccurred in the topic during the last recent years. Indeed, the rapid advances in the chemical functionalization of carbon nanotubes have paved the way towards thefabricationofhybridpolymer-basedassemblieswithenhancedpotentialin a wide range of applications. Recent studies have shown that such carbon RSCNanoscience&NanotechnologyNo.27 CarbonNanotube-PolymerComposites EditedbyDimitriosTasis #TheRoyalSocietyofChemistry2013 PublishedbytheRoyalSocietyofChemistry,www.rsc.org v View Online vi Preface nanotube/polymercompositesexhibitinterestingactivities,assupercapacitors, battery electrodes, organic light-emitting diodes, photovoltaic cells, actuators andinfraredsensors,aswellasconductivecoatings.Alltheseaspectsofcarbon nanotube/polymer composite science are summarized in the different chapters collected in this book. Two additional chapters are devoted to a related and 5 00 very important field, namely the development of characterization tools for P F carbon nanotube/polymer samples. 7- 81 Thedifferentchaptersofthepresentbookhavebeendeliveredbyprominent 6 73 expertsandIwouldliketosincerelythankallofthemfortheireffortandtheir 9 84 enthusiasm to participate to this journey. My gratitude is extended to the 1 78 Royal Society of Chemistry (RSC) for its high standard of support in this 9 9/ adventure and to all of the RSC members who contributed to the process 3 0 1 regarding the efficient handling of all the chapters. Especially, I would like to 0. oi:1 acknowledge the help of Mrs Rosalind Searle and Dr Merlin Fox during the d wholeeditingprocess.Further,IwouldliketothanktheRSCDesignteamfor g | or the design of the front cover image. c. s s.r b u p p:// htt n o 3 1 d 20 deh nloaMarc Down 01 o d e h s bli u P 7 0 0 P 7-F Contents 1 8 6 3 7 9 4 8 1 8 7 9 9/ Chapter 1 Conducting Polymer-based Carbon Nanotube Composites: 3 0 1 Preparation and Applications 1 0. oi:1 Sang-Ha Hwang, Jeong-Min Seo, In-Yup Jeon, Young-Bin g | d Park and Jong-Beom Baek or c. s 1.1 Discovery of Conducting Polymers 1 s.r b 1.2 Synthesis of Conducting Polymers 2 u p p:// 1.3 Conductivity and Doping of Conducting Polymers 3 htt 1.4 Conducting Polymers as Carbon Nanotube (CNT) n o Composite Matrices 6 3 d 201 1.5 ApplicationsofCNT/ConductingPolymerComposites 9 deh 1.5.1 Supercapacitors 9 nloaMarc 1.5.2 Rechargeable Lithium-ion Battery Electrodes 12 Dowon 01 11..55..34 POhrgoatonvicolLtaigichtD-eemviictetisng Diodes (OLEDs) 1164 d he 1.6 Conclusions 17 s bli Acknowledgements 17 u P References 18 Chapter 2 Actuators and Infrared Sensors Based on Carbon Nanotube– Polymer Composites 22 Jian Chen 2.1 Introduction 22 2.2 Shape-Memory CNT–Polymer Composites 23 2.2.1 IR Heating of CNT–SMP composites 25 2.2.2 Inductive Heating of CNT–SMP composites 28 2.2.3 Resistive Heating of CNT–SMP composites 28 RSCNanoscience&NanotechnologyNo.27 CarbonNanotube-PolymerComposites EditedbyDimitriosTasis #TheRoyalSocietyofChemistry2013 PublishedbytheRoyalSocietyofChemistry,www.rsc.org vii View Online viii Contents 2.3 Shape-Changing CNT–Polymer Composites 31 2.3.1 Light-driven Shape-changing CNT–Polymer Composites 32 2.3.2 Electroactive Shape-changing CNT–Polymer Composites 36 7 00 2.4 CNT–Polymer Composite IR Sensors 42 P F 2.5 Conclusions 44 7- 81 Acknowledgements 45 6 73 References 45 9 4 8 1 8 7 9 Chapter 3 Photoelectrical Responses of Carbon Nanotube–Polymer 9/ 03 Composites 51 1 0. Yumeng Shi and Lain-Jong Li 1 oi: d g | 3.1 Introduction 51 or c. 3.2 Band Structure and Chirality Dependence 52 s s.r 3.3 Band-to-band Transition of SWNTs 53 b pu 3.4 Wrapping SWNTs with Polymers 56 p:// 3.5 Energy Transfer from Photosensitive Polymers to htt n SWNTs 58 o 3 3.6 PhotoelectricResponsesfromtheSWNTsCoatedwith 1 d 20 Photosensitive Polymers 58 deh Downloan 01 Marc 33..66..12 PSEWhleocNttorTosesOntasptititcioveFeleoPcrotcrleoynmMiceircDsroesvciocepsyB(EasFeMd o)n 59 o d Measurement of SWNT–Polymer 63 e sh 3.6.3 The Ability for Hole and Electron bli u Discrimination in SWNTs 64 P 3.7 Conclusions 69 References 69 Chapter4 ChemicalFunctionalisationofCarbonNanotubesforPolymer Reinforcement 72 Yurii K. Gun’ko 4.1 Introduction 72 4.2 Non-covalent Functionalisation of CNTs 73 4.3 Covalent Functionalisation 77 4.3.1 ‘‘Grafting From’’ Approach 79 4.3.2 ‘‘Grafting To’’ Approach 81 4.4 Combination of Non-covalent and Covalent Approaches 83 4.5 Main Techniques for Fabrication of CNT–Polymer Composites 85 4.5.1 Solution Processing of Composites 86 View Online Contents ix 4.5.2 Melt Processing 86 4.5.3 In Situ Polymerisation Processing 87 4.5.4 ProcessingofCompositesBasedonThermosets 89 4.5.5 Coagulation Spinning and Electrospinning 90 4.5.6 Buckypaper-based Approaches 91 7 00 4.5.7 Layer-by-layer (LBL) Technique 92 P F 4.5.8 Swelling Under Ultrasound Technique 93 7- 81 4.6 Influence of Nanotube Functionalisation on 6 73 Mechanical Properties of CNT–Polymer Composites 93 9 84 4.7 Role of Fabrication and Processing Techniques in 1 78 Reinforcement of Polymers by CNTs 100 9 9/ 4.7.1 Mechanical Properties of Solution-processed 3 0 1 Composites 100 0. oi:1 4.7.2 Mechanical Properties of Melt-processed d Composites 101 g | or 4.7.3 Mechanical Properties of Composites Based on sc. Thermosetting Polymers 103 bs.r 4.7.4 Mechanical Properties of Composites Prepared u p p:// by In Situ Polymerisation 104 htt 4.7.5 Mechanical Properties of Composites Fibres on Prepared by Spinning 105 3 d 201 4.7.6 Mechanical Properties of Composites Prepared deh Using Buckypaper 106 nloaMarc 4.7.7 Mechanical Properties of Composites Prepared Dowon 01 4.8 ConclusUiosninsgaLndBLFuAtuprperoOaucthlook 110078 d e References 110 h s bli u P Chapter 5 Polymer-grafted Carbon Nanotubes via ‘‘Grafting From’’ Approach 120 Chao Gao, Zheng Liu, Liang Kou and Xiaoli Zhao 5.1 Linear Polymer-functionalized Carbon Nanotubes (CNTs) 120 5.1.1 AtomTransferRadicalPolymerization(ATRP) Approach to Polymer-grafted CNTs 120 5.1.2 Reversible-addition Fragmentation Chain- transfer (RAFT) Polymerization Approach to Polymer-grafted CNTs 142 5.1.3 Nitroxide-mediated Radical Polymerization (NMRP) Approach to Polymer-grafted CNTs 146 5.1.4 Ring-opening Polymerization (ROP) Approach to Polymer-grafted CNTs 148 5.1.5 Ring-opening Metathesis Polymerization (ROMP) Approach to Polymer-grafted CNTs 155 View Online x Contents 5.1.6 Anionic Polymerization Approach to Polymer- grafted CNTs 157 5.1.7 Other ‘‘Grafting From’’ Methods to Polymer- grafted CNTs 158 5.1.8 Binary-grafting Approach to Polymer-grafted 7 00 CNTs 160 P F 5.2 Dendritic Polymer-functionalized CNTs 162 7- 81 5.2.1 Self-condensing Vinyl (Co)Polymerization 6 73 (SCVP/SCVCP) 165 9 84 5.2.2 ROP Approach 166 1 78 5.2.3 Polycondensation Approach 169 9 9/ 5.3 Concluding Remarks 173 3 0 1 Acknowledgements 173 0. oi:1 References 173 d g | or c. Chapter 6 Metallic Single-walled Carbon Nanotubes for Electrically s s.r Conductive Materials and Devices 182 b pu Ankoma Anderson, Fushen Lu, Mohammed J. Meziani and p:// Ya-Ping Sun htt n o 3 6.1 Introduction 182 1 d 20 6.2 Harvesting Metallic SWNTs 184 deh Downloan 01 Marc 6.3 E66..l33ec..12tricCCaloolymmCppooossniidtteeussctwwiviittehhNNSaeonpnoa-rceaontmreidpchoMesdietetSasWllicNSTWs NTs 111999151 o d 6.4 Transparent Conductive Coatings and Films 197 e sh 6.5 Perspective 203 bli u Acknowledgements 204 P References 204 Chapter 7 Characterization of Dispersability of Industrial Nanotube MaterialsandtheirLengthDistributionBeforeandAfterMelt Processing 212 B. Krause, M. Mende, G. Petzold, R. Boldt and P. Po¨tschke 7.1 Introduction 212 7.2 Experimental 213 7.2.1 Materials 213 7.2.2 Centrifugal Separation Analysis (CSA) 214 7.2.3 Melt Processing 215 7.2.4 Morphological Characterization 216 7.3 Results and Discussion 216 7.3.1 Characterization of the Dispersability of CNT Materials 216