Nanostructured Conductive Polymers

Ali Eftekhari is Professor of Chemistry and Director of the Avicenna Institute of Technology in Cleveland (USA). He received his PhD at Trinity College (Ireland). From 2000 to 2002, he was a researcher at Nirvan Co. (USA) working on an environmental project under support of former Vice-President Al Gore. From 2002 to 2004, Professor Eftekhari was senior researcher at KICR (USA), working on a joint corporate project based in United States and Iran. For the next two years, he was Head of the Electrochemistry Division at the Materials and Energy Research Center in Iran. Since 2007, Ali Eftekhari has been Professor of Chemistry and Director of Avicenna Institute of Technology. He is the editor of four books including Nanostructured Materials in Electrochemistry (Wiley) and editor of the book Boltzmann Philosophy of Science. Professor Eftekhari is Editor of the Journal of Nanomaterials and has been chairman or on the Editorial Advisory Boards of several conferences. His research interests include electrochemistry, nanoscience and nanotechnology, statistical physics, condensed matter physics, philosophy, the history of science, management and science policy.

• Preface xvForeword xixList of Contributors xxiPart One 11 History of Conductive Polymers 3J. Campbell Scott1.1 Introduction 31.2 Archeology and Prehistory 71.3 The Dawn of the Modern Era 81.4 The Materials Revolution 121.5 Concluding Remarks 13Acknowledgments 15References 152 Polyaniline Nanostructures 19Gordana Ćirić-Marjanović2.1 Introduction 192.2 Preparation 212.2.1 Preparation of Polyaniline Nanofibers 212.2.2 Preparation of Polyaniline Nanotubes 422.2.3 Preparation of Miscellaneous Polyaniline Nanostructures 522.3 Structure and Properties 602.3.1 Structure and Properties of Polyaniline Nanofibers 602.3.2 Structure and Properties of Polyaniline Nanotubes 632.4 Processing and Applications 642.4.1 Processing 642.4.2 Applications 652.5 Conclusions and Outlook 74References 743 Nanoscale Inhomogeneity of Conducting-Polymer-Based Materials 99Alain Pailleret and Oleg Semenikhin3.1 Introduction: Inhomogeneity and Nanostructured Materials 993.2 Direct Local Measurements of Nanoscale Inhomogeneity of Conducting and Semiconducting Polymers 1013.2.1 Introduction 1013.2.2 Atomic Force Microscopy (AFM), Kelvin Probe Force Microscopy (KFM), and Electric Force Microscopy (EFM) 1033.2.3 Current-Sensing Atomic Force Microscopy (CS-AFM) 1053.2.4 Scanning Tunneling Microscopy (STM) and Scanning Tunneling Spectroscopy (STS) 1093.2.5 Phase-Imaging Atomic Force Microscopy (PI-AFM) and High-Resolution Transmission Electron Microscopy (HRTEM): Studies of Local Crystallinity 1123.2.6 Near-Field Scanning Optical Microscopy (NSOM) 1243.3 In situ Studies of Conducting and Semiconducting Polymers: Electrochemical Atomic Force Microscopy (EC-AFM) and Electrochemical Scanning Tunneling Microscopy (EC-STM) 1283.3.1 Introduction 1283.3.2 EC-AFM Investigations of the Swelling/Deswelling of ECPs 1293.3.3 EC-STM Investigations of the Swelling/Deswelling of ECPs 1403.3.4 Scanning Electrochemical Microscopy (SECM) Investigations of ECPs 1413.4 The Origin of the Nanoscale Inhomogeneity of Conducting and Semiconducting Polymers 144References 151Part Two 1614 Nanostructured Conductive Polymers by Electrospinning 163Ioannis S. Chronakis4.1 Introduction to Electrospinning Technology 1634.2 The Electrospinning Processing 1644.3 Electrospinning Processing Parameters: Control of the Nanofiber Morphology 1654.3.1 Solution Properties 1654.3.2 Process Conditions 1664.3.3 Ambient Conditions 1674.4 Nanostructured Conductive Polymers by Electrospinning 1684.4.1 Polyaniline (PANI) 1684.4.2 Polypyrrole (PPy) 1754.4.3 Polythiophenes (PThs) 1794.4.4 Poly(p-phenylene vinylenes) (PPVs) 1834.4.5 Electrospun Nanofibers from Other Conductive Polymers 1864.5 Applications of Electrospun Nanostructured Conductive Polymers 1874.5.1 Biomedical Applications 1874.5.2 Sensors 1944.5.3 Conductive Nanofibers in Electric and Electronic Applications 1974.6 Conclusions 201References 2015 Composites Based on Conducting Polymers and Carbon Nanotubes 209M. Baibarac, I. Baltog, and S. Lefrant5.1 Introduction 2095.2 Carbon Nanotubes 2125.2.1 Synthesis of CNTs: Arc Discharge, Laser Ablation, Chemical Vapor Deposition 2145.2.2 Purification 2175.2.3 Separation Techniques for Metallic and Semiconducting Carbon Nanotubes 2195.2.4 Vibrational Properties of Carbon Nanotubes 2225.3 Synthesis of Composites Based on Conducting Polymers and Carbon Nanotubes 2245.3.1 Polyaniline/Carbon Nanotubes 2255.3.2 Polypyrrole/Carbon Nanotubes 2285.3.3 Poly(3,4-ethylenedioxythiophene)/Carbon Nanotubes 2295.3.4 Poly(2,2 0 -bithiophene)/Carbon Nanotubes 2295.3.5 Poly(N-vinylcarbazole)/Carbon Nanotubes 2305.3.6 Polyfluorenes/Carbon Nanotubes 2315.3.7 Poly(p-phenylene) Vinylene/Carbon Nanotubes 2315.3.8 Polyacetylene/Carbon Nanotubes 2325.4 Vibrational Properties of Composites Based on Conducting Polymers and Carbon Nanotubes 2335.4.1 Conducting Polymer/Carbon Nanotube Bilayer Structures 2335.4.2 Covalently Functionalized Carbon Nanotubes with Conducting Polymers 2335.4.3 Conducting Polymers Doped with Carbon Nanotubes 2445.4.4 Noncovalent Functionalization of Carbon Nanotubes with Conducting Polymers 2475.5 Conclusions 249Acknowledgments 250References 2506 Inorganic-Based Nanocomposites of Conductive Polymers 261Rabin Bissessur6.1 Introduction 2616.2 FeOCl 2626.3 V 2 O 5 Systems 2636.4 Vopo 4 .2h 2 O 2736.5 MoO 3 2746.6 Layered Phosphates and Phosphonates 2776.7 Layered Rutiles 2796.8 Layered perovskites 2806.9 Layered Titanates 2806.10 Graphite Oxide 2816.11 Conclusions 283Acknowledgements 284References 2847 Metallic-Based Nanocomposites of Conductive Polymers 289Vessela Tsakova7.1 Introduction 2897.2 Oxidative Polymerization Combined with Metal-Ion Reduction (One-Pot Synthesis) 2907.3 Nanocomposite Formation by Means of Pre-Synthesized Metal Nanoparticles 2947.4 Metal Electrodeposition in Pre-Synthesized CPs 2977.4.1 Size and Size Distribution of Electrodeposited Metal Particles 3057.4.2 Spatial Distribution of Electrodeposited Metal Particles 3087.4.3 Number Density of Electrodeposited Metal Particles 3107.5 Chemical Reduction of Metal Ions in Pre-Polymerized CP Suspensions or Layers 3127.5.1 Use of the Polymer Material as Reductant 3127.5.2 Use of Additional Reductant 3207.6 Metallic-Based CP Composites for Electrocatalytic and Electroanalytic Applications 321List of Acronyms 325References 3258 Spectroscopy of Nanostructured Conducting Polymers 341Gustavo M. do Nascimento and Marcelo A. de Souza8.1 Synthetic Metals 3418.2 Nanostructured Conducting Polymers 3428.3 Spectroscopic Techniques 3448.3.1 Vibronic Techniques (UV-vis-NIR, FTIR, Raman, Resonance Raman) 3458.3.2 X-Ray Techniques (XANES, EXAFS AND XPS) 3468.4 Spectroscopy of Nanostructured Conducting Polymers 3498.4.1 Nanostructured Polyaniline and its Derivates 3498.4.2 Nanostructured Poly(Pyrrole) 3558.4.3 Nanostructured Poly(Thiophenes) 3588.4.4 Nanostructured Poly(Acetylene) and Poly(Diacetylene) and their Derivates 3618.5 Concluding Remarks 364Acknowledgements 365References 3659 Atomic Force Microscopy Study of Conductive Polymers 375Edgar Ap. Sanches, Osvaldo N. Oliveira Jr, and Fabio Lima Leite9.1 Introduction 3759.2 AFM Fundamentals and Applications 3769.2.1 Basic Principles 3769.2.2 Imaging Modes 3779.2.3 Force Spectroscopy 3999.3 Concluding Remarks 405Acknowledgments 406References 40610 Single Conducting-Polymer Nanowires 411Yixuan Chen and Yi Luo10.1 Introduction 41110.2 Fabrication of Single Conducting-Polymer Nanowires (CPNWs) 41210.2.1 Lithographical Methods 41210.2.2 Scanning-Probe-Based Techniques 41810.2.3 Template-Guided Growth or Patterning 42610.2.4 Other Methods 43610.3 Transport Properties and Electrical Characterization 44310.3.1 Background 44310.3.2 Brief Summary of Transport in 3-D CP Materials 44410.3.3 Conductivity of CP Nanowires, Nanofibers, and Nanotubes 44610.3.4 Summary 44910.4 Applications of Single Conducting Polymer Nanowires (CPNWs) 44910.4.1 CPNW Chemical and Biological Sensors 45010.4.2 CPNW Field-Effect Transistors 45310.4.3 CPNW Optoelectronic Devices 45510.5 Summary and Outlook 460References 46011 Conductive Polymer Micro- and Nanocontainers 467Jiyong Huang and Zhixiang Wei11.1 Introduction 46711.2 Structures of Micro- and Nanocontainers 46811.2.1 Hollow Spheres 46811.2.2 Tubes 47211.2.3 Others 47411.3 Preparation Methods and Formation Mechanisms 47811.3.1 Hard-Template Method 47811.3.2 Soft-Template Method 48211.3.3 Micro- and Nanofabrication Techniques 48511.4 Properties and Applications of Micro- and Nanocontainers 48611.4.1 Chemical and Electrical Properties 48711.4.2 Encapsulation 48811.4.3 Drug Delivery and Controlled Release 49011.5 Conclusions 494References 49512 Magnetic and Electron Transport Behaviors of Conductive-Polymer Nanocomposites 503Zhanhu Guo, Suying Wei, David Cocke, and Di Zhang12.1 Introduction 50312.2 Magnetic Polymer Nanocomposite Preparation 50612.2.1 Solution-Based Oxidation Method 50612.2.2 Electropolymerization Method 50712.2.3 Two-Step Deposition Method 50812.2.4 UV-Irradiation Technique 50812.3 Physicochemical Property Characterization 50912.4 Microstructure of the Conductive Polymer Nanocomposites 50912.5 Interaction between the Nanoparticles and the Conductive-Polymer Matrix 51012.6 Magnetic Properties of Conductive-Polymer Nanocomposites 51212.7 Electron Transport in Conductive-Polymer Nanocomposites 51512.8 Giant Magnetoresistance in Conductive-Polymer Nanocomposites 52012.9 Summary 52212.9.1 Materials Design Perspective 524References 52413 Charge Transfer and Charge Separation in Conjugated Polymer Solar Cells 531Ian A. Howard, Neil C. Greenham, Agnese Abrusci, Richard H. Friend, and Sebastian Westenhoff13.1 Introduction 53113.1.1 Polymer: PCBM Solar Cells 53213.1.2 Polymer: Polymer Solar Cells 53313.1.3 Polymer: Inorganic Nanoparticle Solar Cells 53413.2 Charge Transfer in Conjugated Polymers 53413.2.1 Excitons as the Primary Photoexcitations 53513.2.2 Charge Transfer at Semiconductor Heterojunctions 53513.2.3 Charge Transport 53713.2.4 Photoinduced Charge Transfer 53813.2.5 Onsager–Braun Model of Charge-Transfer State Dissociation 54013.2.6 Charge Formation from High-Lying Singlet States in a Pristine Polymer 54113.2.7 Field-Assisted Charge Generation in Pristine Materials 54113.2.8 Charge Generation in Donor: Acceptor Blends 54213.2.9 Mechanisms of Charge-Transfer State Recombination 54413.3 Charge Generation and Recombination in Organic Solar Cells with High Open-Circuit Voltages 54513.3.1 Exciton Ionization at Polymer: Polymer Heterojunctions 54613.3.2 Photoluminescence from Charge-Transfer States 54713.3.3 The Nature of the Charge-Transfer States 54913.3.4 Probing the Major Loss Mechanism in Organic Solar Cells with High Open-Circuit Voltages 55013.3.5 Geminate Recombination of Interfacial Charge-Transfer States into Triplet Excitons 55213.3.6 The Exchange Energy of Interfacial Charge-Transfer States in Semiconducting Polymer Blends 55513.4 Conclusions and Outlook 555Acknowledgements 556References 556Part Three 56314 Nanostructured Conducting Polymers for (Electro)chemical Sensors 565Anthony J. Killard14.1 Introduction 56514.2 Nanowires and Nanotubes 56614.3 Nanogaps and Nanojunctions 56814.4 Nanofibers and Nanocables 57014.5 Nanofilms 57214.6 Metallic Nanoparticle/Conducting-Polymer Nanocomposites 57414.7 Metal-Oxide Nanoparticles/Conducting-Polymer Nanocomposites 57514.8 Carbon Nanotube Nanocomposites 57714.9 Nanoparticles 57914.10 Nanoporous Templates 58214.11 Application Summaries 58314.12 Conclusions 593References 59415 Nanostructural Aspects of Conducting-Polymer Actuators 599Paul A. Kilmartin and Jadranka Travas-Sejdic15.1 Introduction 59915.2 Mechanisms and Modes of Actuation 60015.2.1 Ion Movement and Conducting-Polymer Electrochemistry 60015.2.2 Bilayer and Trilayer Actuators 60015.2.3 Linear Actuators and the Inclusion of Metal Contacts 60215.2.4 Out-of-Plane Actuators 60315.2.5 Effect of Synthesis Conditions 60415.3 Modelling Mechanical Performance and Developing Device Applications 60415.3.1 Modelling of Conducting-Polymer Actuation 60515.3.2 Applications of Conducting-Polymer Actuators 60715.4 Effect of Morphology and Nanostructure upon Actuation 61015.4.1 Chain Alignment 61015.4.2 Anisotropy 61215.4.3 Porosity 61415.4.4 Conformational Changes 61415.5 Solvent and Ion Size Effects to Achieve Higher Actuation 61515.5.1 Effect of Ion Size 61515.5.2 Ionic Liquids 61615.5.3 Ions Producing Large Actuation Strains 61715.6 Nanostructured Composite Actuators 61915.6.1 Blends of Two Conducting Polymers 61915.6.2 Graphite 62015.6.3 Carbon Nanotubes 62015.6.4 Hydrogels 62115.6.5 Other Interpenetrating Networks 62115.7 Prospects for Nanostructured Conducting-Polymer Actuators 622References 62316 Electroactive Conducting Polymers for the Protection of Metals against Corrosion: from Micro- to Nanostructured Films 631Pierre Camille Lacaze, Jalal Ghilane, Hyacinthe Randriamahazaka and Jean-Christophe Lacroix16.1 Introduction 63116.2 Protection Mechanisms Induced by Conducting Polymers 63316.2.1 Displacement of the Electrochemical Interface 63416.2.2 Ennobling the Metal Surface 63716.2.3 Self-healing Effect with Doping Anions as Corrosion Inhibitors 64516.2.4 Barrier Effect of the Polymer 65016.3 Conducting-Polymer Coating Techniques for Usual Oxidizable Metals: Performances of Conducting-Polymer-Based Micron-Thick Films for Protection against Corrosion 65616.3.1 Coatings Consisting of a Conducting Primer Deposited by Electropolymerization 65616.3.2 Coatings Made from Conducting-Polymer Formulations 66216.4 Nanostructured Conducting-Polymer Coatings and Anticorrosion Protection 66516.4.1 Improving ECP Adhesion to Oxidizable Metals 66616.4.2 Nanostructured Surfaces Displaying Superhydrophobic Properties 66716.5 Conclusions 671Acknowledgement 672References 67217 Electrocatalysis by Nanostructured Conducting Polymers 681Shaolin Mu and Ya Zhang17.1 Introduction 68117.2 Electrochemical Synthetic Techniques of Nanostructured Conducting Polymers 68217.2.1 Synthesis by Cyclic Voltammetry 68217.2.2 Synthesis by Potentiostat 68617.2.3 Synthesis by Galvanostat 69017.3 Electrocatalysis at Nanostructured Conducting-Polymer Electrodes 69217.3.1 Electrocatalysis by Pure Nanostructured Conducting Polymers 69217.3.2 Electrocatalysis at the Electrodes of Conducting-Polymer Nanocomposites 69517.4 Conclusion 700References 70118 Nanostructured Conductive Polymers as Biomaterials 707Rylie A. Green, Sungchul Baek, Nigel H. Lovell, and Laura A. Poole-Warren18.1 Introduction 70718.2 Biomedical Applications for Conductive Polymers 70818.2.1 Electrode Coatings 70818.2.2 Alternate Applications 70918.3 Polymer Design Considerations 71118.3.1 Conduction Mechanism 71118.3.2 Conventional Components 71218.3.3 Biofunctional Additives 71418.4 Fabrication of Nanostructured Conductive Polymers 71518.4.1 Electrodeposition 71718.4.2 Chemical Synthesis 71818.4.3 Alternate Processing Techniques 72018.5 Polymer Characterization 72418.5.1 Surface Properties 72418.5.2 Mechanical Properties 72518.5.3 Electrical Properties 72518.5.4 Biological Performance 72618.6 Interfacing with Neural Tissue 72718.7 Conclusions 728References 72919 Nanocomposites of Polymers Made Conductive by Nanofillers 737Haiping Hong, Dustin Thomas, Mark Horton, Yijiang Lu, Jing Li, Pauline Smith, and Walter Roy19.1 Introduction 73719.2 Experimental 74219.2.1 Materials and Equipment 74219.2.2 Preparation of Nanocomposite (Nanotube Grease) 74519.3 Results and Discussion 74819.3.1 Thermal and Electrical Properties of Nanocomposites (Nanotube Greases) 74819.3.2 Rheological Investigation of Nanocomposite (Nanotube Grease) 75019.3.3 Nanocomposites (Nanotube Greases) with Magnetically Sensitive Nanoparticles 75419.3.4 Electrical Conductivities of Various Nanofillers (Nanotubes) 75919.4 Conclusion 761Acknowledgments 761References 762Index 765