Nanostructured Conductive Polymers

Nanostructured Conductive Polymers......Page 5
Contents......Page 7
Preface......Page 17
Foreword......Page 21
List of Contributors......Page 23
Part One......Page 27
1.1 Introduction......Page 29
1.2 Archeology and Prehistory......Page 33
1.3 The Dawn of the Modern Era......Page 34
1.4 The Materials Revolution......Page 38
1.5 Concluding Remarks......Page 39
References......Page 41
2.1 Introduction......Page 45
2.2.1 Preparation of Polyaniline Nanofibers......Page 47
2.2.2 Preparation of Polyaniline Nanotubes......Page 68
2.2.3 Preparation of Miscellaneous Polyaniline Nanostructures......Page 78
2.3.1 Structure and Properties of Polyaniline Nanofibers......Page 86
2.3.2 Structure and Properties of Polyaniline Nanotubes......Page 89
2.4.1 Processing......Page 90
2.4.2 Applications......Page 91
References......Page 100
3.1 Introduction: Inhomogeneity and Nanostructured Materials......Page 125
3.2.1 Introduction......Page 127
3.2.2 Atomic Force Microscopy (AFM), Kelvin Probe Force Microscopy (KFM), and Electric Force Microscopy (EFM)......Page 129
3.2.3 Current-Sensing Atomic Force Microscopy (CS-AFM)......Page 131
3.2.4 Scanning Tunneling Microscopy (STM) and Scanning Tunneling Spectroscopy (STS)......Page 135
3.2.5 Phase-Imaging Atomic Force Microscopy (PI-AFM) and High-Resolution Transmission Electron Microscopy (HRTEM): Studies of Local Crystallinity......Page 138
3.2.6 Near-Field Scanning Optical Microscopy (NSOM)......Page 150
3.3.1 Introduction......Page 154
3.3.2 EC-AFM Investigations of the Swelling/Deswelling of ECPs......Page 155
3.3.3 EC-STM Investigations of the Swelling/Deswelling of ECPs......Page 166
3.3.4 Scanning Electrochemical Microscopy (SECM) Investigations of ECPs......Page 167
3.4 The Origin of the Nanoscale Inhomogeneity of Conducting and Semiconducting Polymers......Page 170
References......Page 177
Part Two......Page 187
4.1 Introduction to Electrospinning Technology......Page 189
4.2 The Electrospinning Processing......Page 190
4.3.1 Solution Properties......Page 191
4.3.2 Process Conditions......Page 192
4.3.3 Ambient Conditions......Page 193
4.4.1 Polyaniline (PANI)......Page 194
4.4.2 Polypyrrole (PPy)......Page 201
4.4.3 Polythiophenes (PThs)......Page 205
4.4.4 Poly(p-phenylene vinylenes) (PPVs)......Page 209
4.4.5 Electrospun Nanofibers from Other Conductive Polymers......Page 212
4.5.1 Biomedical Applications......Page 213
4.5.2 Sensors......Page 220
4.5.3 Conductive Nanofibers in Electric and Electronic Applications......Page 223
References......Page 227
5.1 Introduction......Page 235
5.2 Carbon Nanotubes......Page 238
5.2.1 Synthesis of CNTs: Arc Discharge, Laser Ablation, Chemical Vapor Deposition......Page 240
5.2.2 Purification......Page 243
5.2.3 Separation Techniques for Metallic and Semiconducting Carbon Nanotubes......Page 245
5.2.4 Vibrational Properties of Carbon Nanotubes......Page 248
5.3 Synthesis of Composites Based on Conducting Polymers and Carbon Nanotubes......Page 250
5.3.1 Polyaniline/Carbon Nanotubes......Page 251
5.3.2 Polypyrrole/Carbon Nanotubes......Page 254
5.3.4 Poly(2,2\'-bithiophene)/Carbon Nanotubes\n......Page 255
5.3.5 Poly(N-vinylcarbazole)/Carbon Nanotubes......Page 256
5.3.7 Poly(p-phenylene) Vinylene/Carbon Nanotubes......Page 257
5.3.8 Polyacetylene/Carbon Nanotubes......Page 258
5.4.2 Covalently Functionalized Carbon Nanotubes with Conducting Polymers......Page 259
5.4.3 Conducting Polymers Doped with Carbon Nanotubes......Page 270
5.4.4 Noncovalent Functionalization of Carbon Nanotubes with Conducting Polymers......Page 273
5.5 Conclusions......Page 275
References......Page 276
6.1 Introduction......Page 287
6.2 FeOCl......Page 288
6.3 V2O5 Systems......Page 289
6.4 VOPO4.2H2O......Page 299
6.5 MoO3......Page 300
6.6 Layered Phosphates and Phosphonates......Page 303
6.7 Layered Rutiles......Page 305
6.9 Layered Titanates......Page 306
6.10 Graphite Oxide......Page 307
6.11 Conclusions......Page 309
References......Page 310
7.1 Introduction......Page 315
7.2 Oxidative Polymerization Combined with Metal-Ion Reduction (One-Pot Synthesis)......Page 316
7.3 Nanocomposite Formation by Means of Pre-Synthesized Metal Nanoparticles......Page 320
7.4 Metal Electrodeposition in Pre-Synthesized CPs......Page 323
7.4.1 Size and Size Distribution of Electrodeposited Metal Particles......Page 331
7.4.2 Spatial Distribution of Electrodeposited Metal Particles......Page 334
7.4.3 Number Density of Electrodeposited Metal Particles......Page 336
7.5.1 Use of the Polymer Material as Reductant......Page 338
7.5.2 Use of Additional Reductant......Page 346
7.6 Metallic-Based CP Composites for Electrocatalytic and Electroanalytic Applications......Page 347
References......Page 351
8.1 Synthetic Metals......Page 367
8.2 Nanostructured Conducting Polymers......Page 368
8.3 Spectroscopic Techniques......Page 370
8.3.1 Vibronic Techniques (UV-vis-NIR, FTIR, Raman, Resonance Raman)......Page 371
8.3.2 X-Ray Techniques (XANES, EXAFS AND XPS)......Page 372
8.4.1 Nanostructured Polyaniline and its Derivates......Page 375
8.4.2 Nanostructured Poly(Pyrrole)......Page 381
8.4.3 Nanostructured Poly(Thiophenes)......Page 384
8.4.4 Nanostructured Poly(Acetylene) and Poly(Diacetylene) and their Derivates......Page 387
8.5 Concluding Remarks......Page 390
References......Page 391
9.1 Introduction......Page 401
9.2.1 Basic Principles......Page 402
9.2.2 Imaging Modes......Page 403
9.2.3 Force Spectroscopy......Page 425
9.3 Concluding Remarks......Page 431
References......Page 432
10.1 Introduction......Page 437
10.2.1 Lithographical Methods......Page 438
10.2.2 Scanning-Probe-Based Techniques......Page 444
10.2.3 Template-Guided Growth or Patterning......Page 452
10.2.4 Other Methods......Page 462
10.3.1 Background......Page 469
10.3.2 Brief Summary of Transport in 3-D CP Materials......Page 470
10.3.3 Conductivity of CP Nanowires, Nanofibers, and Nanotubes......Page 472
10.4 Applications of Single Conducting Polymer Nanowires (CPNWs)......Page 475
10.4.1 CPNW Chemical and Biological Sensors......Page 476
10.4.2 CPNW Field-Effect Transistors......Page 479
10.4.3 CPNW Optoelectronic Devices......Page 481
References......Page 486
11.1 Introduction......Page 493
11.2.1 Hollow Spheres......Page 494
11.2.2 Tubes......Page 498
11.2.3 Others......Page 500
11.3.1 Hard-Template Method......Page 504
11.3.2 Soft-Template Method......Page 508
11.3.3 Micro- and Nanofabrication Techniques......Page 511
11.4 Properties and Applications of Micro- and Nanocontainers......Page 512
11.4.1 Chemical and Electrical Properties......Page 513
11.4.2 Encapsulation......Page 514
11.4.3 Drug Delivery and Controlled Release......Page 516
11.5 Conclusions......Page 520
References......Page 521
12.1 Introduction......Page 529
12.2.1 Solution-Based Oxidation Method......Page 532
12.2.2 Electropolymerization Method......Page 533
12.2.4 UV-Irradiation Technique......Page 534
12.4 Microstructure of the Conductive Polymer Nanocomposites......Page 535
12.5 Interaction between the Nanoparticles and the Conductive-Polymer Matrix......Page 536
12.6 Magnetic Properties of Conductive-Polymer Nanocomposites......Page 538
12.7 Electron Transport in Conductive-Polymer Nanocomposites......Page 541
12.8 Giant Magnetoresistance in Conductive-Polymer Nanocomposites......Page 546
12.9 Summary......Page 548
References......Page 550
13.1 Introduction......Page 557
13.1.1 Polymer: PCBM Solar Cells......Page 558
13.1.2 Polymer: Polymer Solar Cells......Page 559
13.2 Charge Transfer in Conjugated Polymers......Page 560
13.2.2 Charge Transfer at Semiconductor Heterojunctions......Page 561
13.2.3 Charge Transport......Page 563
13.2.4 Photoinduced Charge Transfer......Page 564
13.2.5 Onsager–Braun Model of Charge-Transfer State Dissociation......Page 566
13.2.7 Field-Assisted Charge Generation in Pristine Materials......Page 567
13.2.8 Charge Generation in Donor: Acceptor Blends......Page 568
13.2.9 Mechanisms of Charge-Transfer State Recombination......Page 570
13.3 Charge Generation and Recombination in Organic Solar Cells with High Open-Circuit Voltages......Page 571
13.3.1 Exciton Ionization at Polymer: Polymer Heterojunctions......Page 572
13.3.2 Photoluminescence from Charge-Transfer States......Page 573
13.3.3 The Nature of the Charge-Transfer States......Page 575
13.3.4 Probing the Major Loss Mechanism in Organic Solar Cells with High Open-Circuit Voltages......Page 576
13.3.5 Geminate Recombination of Interfacial Charge-Transfer States into Triplet Excitons......Page 578
13.4 Conclusions and Outlook......Page 581
References......Page 582
Part Three......Page 589
14.1 Introduction......Page 591
14.2 Nanowires and Nanotubes......Page 592
14.3 Nanogaps and Nanojunctions......Page 594
14.4 Nanofibers and Nanocables......Page 596
14.5 Nanofilms......Page 598
14.6 Metallic Nanoparticle/Conducting-Polymer Nanocomposites......Page 600
14.7 Metal-Oxide Nanoparticles/Conducting-Polymer Nanocomposites......Page 601
14.8 Carbon Nanotube Nanocomposites......Page 603
14.9 Nanoparticles......Page 605
14.10 Nanoporous Templates......Page 608
14.11 Application Summaries......Page 609
14.12 Conclusions......Page 619
References......Page 620
15.1 Introduction......Page 625
15.2.2 Bilayer and Trilayer Actuators......Page 626
15.2.3 Linear Actuators and the Inclusion of Metal Contacts......Page 628
15.2.4 Out-of-Plane Actuators......Page 629
15.3 Modelling Mechanical Performance and Developing Device Applications......Page 630
15.3.1 Modelling of Conducting-Polymer Actuation......Page 631
15.3.2 Applications of Conducting-Polymer Actuators......Page 633
15.4.1 Chain Alignment......Page 636
15.4.2 Anisotropy......Page 638
15.4.4 Conformational Changes......Page 640
15.5.1 Effect of Ion Size......Page 641
15.5.2 Ionic Liquids......Page 642
15.5.3 Ions Producing Large Actuation Strains......Page 643
15.6.1 Blends of Two Conducting Polymers......Page 645
15.6.3 Carbon Nanotubes......Page 646
15.6.5 Other Interpenetrating Networks......Page 647
15.7 Prospects for Nanostructured Conducting-Polymer Actuators......Page 648
References......Page 649
16.1 Introduction......Page 657
16.2 Protection Mechanisms Induced by Conducting Polymers......Page 659
16.2.1 Displacement of the Electrochemical Interface......Page 660
16.2.2 Ennobling the Metal Surface......Page 663
16.2.3 Self-healing Effect with Doping Anions as Corrosion Inhibitors......Page 671
16.2.4 Barrier Effect of the Polymer......Page 676
16.3.1 Coatings Consisting of a Conducting Primer Deposited by Electropolymerization......Page 682
16.3.2 Coatings Made from Conducting-Polymer Formulations......Page 688
16.4 Nanostructured Conducting-Polymer Coatings and Anticorrosion Protection......Page 691
16.4.1 Improving ECP Adhesion to Oxidizable Metals......Page 692
16.4.2 Nanostructured Surfaces Displaying Superhydrophobic Properties......Page 693
16.5 Conclusions......Page 697
References......Page 698
17.1 Introduction......Page 707
17.2.1 Synthesis by Cyclic Voltammetry......Page 708
17.2.2 Synthesis by Potentiostat......Page 712
17.2.3 Synthesis by Galvanostat......Page 716
17.3.1 Electrocatalysis by Pure Nanostructured Conducting Polymers......Page 718
17.3.2 Electrocatalysis at the Electrodes of Conducting-Polymer Nanocomposites......Page 721
17.4 Conclusion......Page 726
References......Page 727
18.1 Introduction......Page 733
18.2.1 Electrode Coatings......Page 734
18.2.2 Alternate Applications......Page 735
18.3.1 Conduction Mechanism......Page 737
18.3.2 Conventional Components......Page 738
18.3.3 Biofunctional Additives......Page 740
18.4 Fabrication of Nanostructured Conductive Polymers......Page 741
18.4.1 Electrodeposition......Page 743
18.4.2 Chemical Synthesis......Page 744
18.4.3 Alternate Processing Techniques......Page 746
18.5.1 Surface Properties......Page 750
18.5.3 Electrical Properties......Page 751
18.5.4 Biological Performance......Page 752
18.6 Interfacing with Neural Tissue......Page 753
18.7 Conclusions......Page 754
References......Page 755
19.1 Introduction......Page 763
19.2.1 Materials and Equipment......Page 768
19.2.2 Preparation of Nanocomposite (Nanotube Grease)......Page 771
19.3.1 Thermal and Electrical Properties of Nanocomposites (Nanotube Greases)......Page 774
19.3.2 Rheological Investigation of Nanocomposite (Nanotube Grease)......Page 776
19.3.3 Nanocomposites (Nanotube Greases) with Magnetically Sensitive Nanoparticles......Page 780
19.3.4 Electrical Conductivities of Various Nanofillers (Nanotubes)......Page 785
Acknowledgments......Page 787
References......Page 788
Index......Page 791
Color Plates......Page 803