Conducting Polymers, Fundamentals and Applications

by Chandrasekhar, Prasanna

• ISBN13: 9780792385646
• ISBN10: 0792385640
• eBook ISBN(s): 9781461552451
• Format: Hardcover
• Copyright: 1999-08-01
• Publisher: Kluwer Academic Pub
• More Book Details
• Purchase Benefits

Summary

Conducting polymers (CPs) is a relatively new field utilizing the unique electronic properties of a class of easily synthesized, primarily organic materials with the predominant property of high and controllable conductivity and subsidiary properties emanating from this conductivity and the associated causative electronic structure. Conducting Polymers, Fundamentals and Applications: A Practical Approach deals with the practical fundamentals and applications of conducting polymers. Written from a pedagogical point of view and at a very basic level this book provides a thorough grounding in CPs. Readers will find this book may be used as the basis for further work, as a reference, or as a text supplementing advanced undergraduate- or graduate-level courses.

Table of Contents

List of Common Abbreviations	xxv
Foreword	xxxiii
Lawrence Dalton
Preface	xxxv
PART I: FUNDAMENTALS	1	(430)
Basics of Conducting Polymers (CPs)	3	(20)
What are Conducting Polymers (CPs)?	4	(5)
Definitions and Examples	4	(3)
Excluded Materials Classes (Those Not Treated as CPs in this Book)	7	(2)
Historical	9	(1)
Basic Characteristics of CPs, Doping and Structure	10	(6)
Conductivity Classification of Materials	10	(2)
Doping and Dopants	12	(3)
Doping Types	15	(1)
Real and Idealized Structures	16	(1)
Basics of CP Synthesis	16	(7)
Categories and Classes of Syntheses	16	(1)
Representative Syntheses- Chemical	17	(3)
Representative Syntheses- Electrochemical	20	(1)
Simple Representation of Mechanisms	20	(2)
Problems and Exercises	22	(1)
Semiconductor Models for CPs	23	(20)
Conventional Semiconductors and CPs	23	(3)
Conventional Semiconductors	23	(2)
CPs as Semiconductors	25	(1)
Structural Distortions: Polarons, Bipolarons and Solitons	26	(8)
Band Structure Evolution	34	(3)
Densities of States and Wavevector Representations	37	(1)
Correlation of Optical Spectra to Band Structure	38	(3)
Theoretical and Practical Aspects	41	(2)
Problems and Exercises	41	(2)
Basic Electrochromics of CPs	43	(34)
Basics of Electrochromism and Spectroelectro-chemistry of CPs	43	(5)
Basics	43	(1)
Spectral Regions	44	(1)
Elementary Electrochemistry of CPs as Basis for Electrochromism	45	(1)
Basic Methodology for Transmission-and Reflectance-Mode Electrochromism	46	(2)
UV-VIS-NIR and IR Spectroelectrochemical Measurements	48	(17)
Transmission-Mode SPELs	48	(4)
Reflection-Mode Data	52	(4)
IR-Region Data	56	(9)
Other Electrochromic Parameters of Interest	65	(7)
Other Measurements	72	(5)
Problems and Exercises	75	(2)
Electrochemistry of CPs	77	(24)
Basics	78	(3)
Introduction	78	(1)
Basic Methodology	78	(1)
Electrolytes and Electrodes	79	(2)
Basic Voltammetric Parameters and Information of Interest	81	(8)
Cyclic Voltammograms (CVs)	81	(1)
Electrochemical Windows	82	(1)
Scan Rate Dependencies	83	(1)
Other Parameters From CVs, Peak Broadening	83	(1)
Surface-Active Behavior	84	(2)
Charge Capacities	86	(1)
Dopant and Structural Relationships	86	(3)
Reversibility	89	(1)
Solvent and pH Effects, Mixed Solvents, Dopants	89	(3)
Relation with Semiconductor Properties	92	(2)
Other Voltammetric Methods	94	(1)
CA, CC and Diffusion Coefficients	94	(2)
Complex Film Thickness and Dopant Effects	96	(2)
Modified Electrodes	98	(3)
Problems and Exercises	98	(3)
Advanced Polymerization Concepts	101	(42)
Electrochemical Polymerization	102	(13)
Mechanisms	102	(1)
Generic Electropolymerization Mechanism	102	(2)
Factors Favoring Polymerization and No Polymerization	104	(3)
Mechanistic Notation and Rate Expressions	107	(3)
Solvents and Electrodes	110	(1)
Potentiostatic, Galvanostatic Polymerizations, Threshold Concentrations	111	(1)
Dopants	112	(1)
Electrochemical Monitoring of Polymerization	113	(2)
Chemical Polymerization	115	(9)
Mechanisms and General	115	(2)
Optimization in Solution Polymerizations	117	(1)
Synopsis of Chemical Syntheses	118	(4)
Unique Chemical Polymerization Methods	122	(2)
Dopants, and Alternative Doping Techniques	124	(5)
Common Dopants	124	(2)
Uncommon or Unusual Dopants	126	(1)
Alternative Doping Techniques	127	(2)
Template-Based Polymerizations	129	(7)
Nanoscale Polymerizations	136	(2)
True Copolymerizations	138	(2)
Bulk and Commercial Production	140	(3)
Problems and Exercises	142	(1)
Conduction Models For CPs	143	(30)
Introduction and General Aspects	144	(6)
Experimental Measurements Substantiating Conduction Models	144	(1)
Nature of Conduction and Relation with CP Morphology	145	(3)
Temperature, Frequency, Doping Dependencies	148	(1)
Temperature Dependencies	148	(1)
Frequency Dependencies	148	(1)
Doping Dependencies	148	(1)
Practical Aspects	149	(1)
Conduction Models	150	(5)
Mott Variable Range Hopping (VRH) Model	150	(2)
Sheng Model	152	(1)
Kivelson and Other Models	152	(2)
Relationship of All Models	154	(1)
Experimental Correlations	155	(18)
General	155	(1)
Temperature Dependencies	155	(4)
Frequency Dependencies, Microwave Measurements	159	(3)
Thermopower and Hall Effect Measurements	162	(2)
Pressure Dependencies	164	(3)
Stretching, Anisotropy, Crystallinity, Molecular Weight Effects	167	(2)
Activation Energies and Mobilities	169	(2)
Minor Structural Effects	171	(1)
Problems and Exercises	172	(1)
Theoretical Treatments of CPs	173	(34)
Aims of this Chapter	174	(1)
One-Dimensional Systems and Peierls Instability	174	(1)
Overview of Theoretical Methods Used	175	(2)
Extended Huckel and Related Methods	177	(1)
The Veh Method	178	(5)
AB Initio, Combination AB Initio/Semiempirical Studies	183	(2)
Methods Using SSH Hamiltonians	185	(1)
Methods Considering e-e, e-p Correlations	186	(3)
Appendix 7-1: Selected Calculated Band Structures	189	(7)
Appendix 7-2: Selected Methodology, Calculation Details, and Relevant Equations	196	(11)
Extended Huckel (EH)	196	(1)
LCAO/ETB (Extended Tight Binding)	197	(1)
VEH	197	(2)
Strictly Ab Initio Methods	199	(1)
Representative Combination Ab Initio/Semi-Empirical Methods	199	(1)
The SSH Hamiltonian	199	(1)
Methods Considering e-e, e-p Correlations	200	(6)
Problems and Exercises	206	(1)
Solubility and Processing of CPs	207	(22)
Introductory Remarks and Truly Soluble CPs	208	(1)
Note on Commonality with Material in Other Chapters	208	(1)
Truly Soluble and Processible CPs	208	(1)
Most Common Processing Methods	208	(1)
Solutions in Unusual or Difficult Solvents	209	(1)
Template Based and Sulfonated CPs	210	(5)
Template Based ``Soluble'' CPs	210	(3)
``Self-Doped'' and Other Sulfonated CP Systems	213	(2)
Long Chain Alkyl Substituted Poly (Thiophenes)	215	(1)
Poly (Diacetylenes) As Processible CPs	215	(1)
Use of Other Solubilizing Groups	216	(2)
Processing and Coating of CPs VIA in situ Polymerization	218	(1)
General	218	(1)
Textile and Fiber Coating	218	(1)
Melt and Other Heat Processibility	219	(2)
Techniques Using Colloidal Solutions	221	(2)
Precursor Routes	223	(1)
Langmuir-Blodgett Films of CPs	223	(3)
Direct Vapor Deposition	226	(1)
Other New Deposition Methods	226	(3)
Problems and Exercises	227	(2)
Structural Aspects, Morphology and Fiber/Film Processing	229	(24)
General Considerations in Morphology	230	(8)
Idealized and Real Structures, Chain Defects and Order	230	(1)
Polymerization Conditions	230	(2)
Rotational Barriers	232	(1)
Molecular Weight (MWt)	232	(2)
Fibrillar and Globular Morphology	234	(1)
Doping Effects	235	(2)
Effects of Fundamental Structure and Substituents	237	(1)
Fibers and Oriented Films	238	(10)
Preparation: Fibers	238	(1)
General Considerations in Fiber Preparation	238	(1)
Representative Procedures in Detail	239	(2)
Preparation: Oriented Films	241	(1)
Enhancement of Conductivity, Conductivity Anisotropy	242	(1)
Mechanical Properties	243	(2)
Crystallinity	245	(2)
True Single-Crystal Character	247	(1)
Thermochromism and Solvatochromism	248	(5)
Problems and Exercises	251	(2)
``Composites'' (Blends) and Copolymers	253	(22)
Introduction and Definitions	254	(2)
Definitions	254	(2)
Synopsis of Types of Syntheses	256	(1)
In Situ Chemical Polymerizations	256	(5)
Chemical Polymerization via Sorption of Monomer	256	(1)
Chemical Polymerization via Sorption of Oxidant	257	(1)
Solution Evaporative Polymerization	258	(1)
Catalytic and Other In Situ Chemical Polymerization	259	(2)
In Situ Electrochemical Polymerizations	261	(1)
Direct Polymer Blends	262	(2)
Blending in Solution	262	(1)
Melt-Blending	263	(1)
Composite Fibers	264	(1)
True Copolymers	265	(7)
Interpenetrating Polymer Networks	272	(3)
Problems and Exercises	272	(3)
Characterization Methods and Salient Results: PART 1	275	(54)
Introduction, Outline of Skeletal Characterization	276	(1)
Conductivity and Related Measurements	277	(9)
Ex-Situ DC Conductivity of Powders, Films and Fibers	277	(3)
In-Situ DC Conductivity	280	(1)
Electrochemical Impedance Spectroscopy (EIS) and AC Conductivity	281	(5)
Thermopower Measurements	286	(1)
Infrared Measurements	286	(3)
Molecular Weight	289	(2)
Indirect Methods	289	(1)
Gel Permeation Chromatography (GPC)	290	(1)
Viscosity	290	(1)
Light Scattering	290	(1)
Raman Spectroscopy	291	(6)
Thermal and Environmental Stability Measurements	297	(9)
Thermogravimetric Analysis (TGA)	297	(4)
Differential Scanning Calorimetry (DSC)	301	(2)
Other Thermal and Environmental Stability Test Methods	303	(3)
X-Ray Photoelectron Spectroscopy	306	(4)
Nuclear Magnetic Resonance Methods	310	(5)
ESR	315	(8)
Basics of ESR of CPs	315	(1)
P(Py) and Poly(thiophenes)	316	(3)
Poly(acetylene)	319	(1)
P(ANi)s	320	(1)
Photo-Induced ESR	321	(1)
Other CPs	322	(1)
Endor	323	(1)
Electron Energy Loss Spectroscopy (EELS)	324	(5)
Problems and Exercises	326	(3)
Characterization Methods and Salient Results: PART 2	329	(42)
Microwave Properties	330	(9)
Interest in CPs, Properties Covered, Frequencies	330	(1)
Parameters of Interest, and Cavity Perturbation Measurements	330	(2)
Network Analyzer Based Methods	332	(1)
Transmission and Reflection Measurements	333	(1)
EMI Shielding Effectiveness (EMI-SE) Measurements	333	(1)
Radar Cross Section (RCS)	334	(1)
Salient Results	334	(5)
Photo/Electro-Luminescence, Photo-Induced Properties	339	(12)
Methods	339	(1)
Salient Results	340	(11)
Third Order Nonlinear Optical (NLO) Properties	351	(12)
The NLO Effect and Practical Requirements	351	(1)
Methodology	352	(1)
Salient Results: Third Order NLO Effects	353	(8)
Salient Results: Second Order NLO Effects	361	(1)
Salient Results: Decay Times of Excited States	361	(2)
Magnetic Susceptibility	363	(3)
Miscellaneous Methods	366	(5)
Problems and Exercises	369	(2)
Classes of CPs: PART 1	371	(22)
Note on Chapter Focus	372	(1)
Poly(Acetylenes) (P(Ac)s)	372	(5)
Simple Syntheses and Basic Properties	372	(1)
Doping of P(Ac)	373	(1)
Orientation of P(Ac)	374	(1)
Special Syntheses	375	(1)
Substituted P(Ac)s	376	(1)
Poly(Diacetylenes) (P(DiAc)s)	377	(4)
Poly(Pyrroles) (P(Py)s)	381	(2)
Chemical Polymerizations	381	(1)
Electrochemical Syntheses	382	(1)
Substituted P(Py)s	383	(1)
Poly(Anilines) (P(ANi)s)	383	(4)
Structure and Nomenclature	383	(2)
Representative Chemical Syntheses	385	(1)
Electrochemical Synthesis	386	(1)
P(ANi) Derivatives	387	(1)
Other Poly(Aromatic Amines)	388	(5)
Problems and Exercises	391	(2)
Classes of CPs: PART 2	393	(38)
Note on Chapter Focus	394	(1)
Poly(Thiophenes)(P(T)'s)	394	(6)
Chemical Syntheses	394	(1)
Electrochemical Syntheses	395	(3)
Properties	398	(2)
Derivatives of Poly(Thiophenes)	400	(9)
P(ITN) and Poly(naphtho[c]thiophene)	401	(2)
Poly(thienylene vinylenes) P(TV)s	403	(3)
Other Poly(thiophene) (P(T)) Derivatives	406	(3)
Poly(p-Phenylene)s (P(PP)s) and Derivatives	409	(13)
Poly(p-phenylene) P(PP)	409	(3)
Poly(phenylene vinylene) (P(PV))	412	(8)
Poly(phenylene sulfide) (P(PS)), Poly(phenylene oxide) (P(PO)) and Related Poly(phenylene chalcogenide)s	420	(2)
Poly(Azulenes)	422	(1)
Ladder Polymers: BBL, BBB, PBT, PBO	423	(3)
Poly(Quinolines) and Derivatives	426	(2)
Other Polymers	428	(3)
Problems and Exercises	428	(3)
PART II: APPLICATIONS	431	(214)
Batteries	433	(20)
Types of Batteries Incorporating CPs	434	(3)
Summary of Applications	434	(1)
Advantages of CPs	434	(1)
Battery Parameters and Performance	434	(3)
Li Secondary Batteries	437	(4)
Principles	437	(2)
Li/CP Batteries	439	(1)
Problems Associated with Li/CP Batteries	440	(1)
Poly(Acetylene) (P(Ac))	441	(1)
Poly(Pyrrole) (P(Py))	442	(2)
Poly(Aniline) (P(ANi))	444	(2)
Poly(Thiophenes) (P(T)s)	446	(1)
Other CPs	446	(1)
Non-Li-Batteries	447	(2)
Commercialization of CP-Based Batteries	449	(4)
Problems and Exercises	452	(1)
Light Emitting Diodes (LEDs)	453	(30)
Introduction	454	(1)
Principles of CP-Based LEDs	455	(4)
Varieties of CPs Used	459	(1)
Exemplary Device Assembly	459	(1)
Addressing Problems and Tailoring Performance	460	(3)
Tailoring of Color	463	(10)
AC-Driven LEDs	473	(2)
LEDs Emitting Polarized Light	475	(1)
Submicron and Other Specialty Applications	476	(1)
Additional Developments Relating to Device and Commercial Applications	477	(3)
``LECs'' and Other Device Types	480	(3)
Problems and Exercises	482	(1)
Sensors	483	(26)
Modes of Sensing with CPs	484	(1)
Conductometric-Mode Sensors	484	(6)
Potentiometric Sensing	490	(2)
Amperometric Sensing	492	(6)
Conductometric/Amperometric Sensing with Micro Sensors	498	(3)
Voltammetric Sensing	501	(2)
Gravimetric-Mode Sensing	503	(1)
Optical-Mode Sensing	504	(2)
Other Sensing Modes	506	(2)
Commercial Implementation	508	(1)
Problems and Exercises	508	(1)
Electro-Optic and Optical Devices	509	(18)
Device Types and Motivations for Development	509	(1)
Waveguides	510	(7)
Other Second-Order NLO Applications	517	(1)
Semiconductor/CP (SC/CP) Interfaces	518	(5)
CP-Based Lasers	523	(1)
Other Optical Devices	524	(1)
Practical Implementation	525	(2)
Problems and Exercises	526	(1)
Microwave- and Conductivity-Based Technologies	527	(16)
Introduction, Applications Covered, Frequencies	527	(1)
Electromagnetic Impulse (EMI) Shielding	528	(3)
Electrostatic Discharge and Antistatic	531	(1)
Microwave Absorption and Radar Cross Section (RCS) Reduction	532	(2)
Comprehensive Properties' Studies	534	(2)
Conductive Textiles	536	(3)
Microwave Smoke	539	(1)
Microwave Welding	540	(3)
Problems and Exercises	541	(2)
Electrochromic Devices	543	(20)
Introduction and Device Types	543	(2)
Visible-Region Devices	545	(9)
Structure	545	(1)
Function of Devices, Laboratory vs. Actual Devices	546	(2)
Examples of Actual, Functional Devices	548	(6)
IR-Region Devices	554	(6)
Other Spectral Regions	560	(3)
Problems and Exercises	561	(2)
Electrochemomechanical and Chemomechanical Devices	563	(10)
Introduction, History, and Principles	563	(1)
Artificial Muscles	564	(3)
Other Electrochemomechanical Actuation	567	(3)
Chemomechanical Actuators and Sensors	570	(3)
Problems and Exercises	571	(2)
Corrosion Protection	573	(18)
Principles, Driving Forces and History	574	(4)
Principles of Other Anti-Corrosion Methods	574	(1)
Driving Forces Behind Development	574	(1)
Principles of CP Anti-Corrosion Coatings	575	(2)
Brief Historical Development	577	(1)
Advantages of CP Coatings	578	(1)
Candidates and Methods	578	(1)
Most-Studied Candidates and Coating Methodology	578	(1)
Testing Methodology	579	(1)
Salient Results	579	(9)
P(ANi)'s	579	(6)
Other Poly(Aromatic Amines)	585	(3)
Other CPs	588	(1)
Prognosis for the Future	588	(3)
Problems and Exercises	589	(2)
Semiconductor-, Lithography-, and Electrically-Related Applications	591	(36)
Lithography and Photopatterning	592	(4)
Lithography	592	(2)
Other Photopatterning	594	(2)
Other Related Applications	596	(1)
Photovoltaics, Heterojunctions and PECs	596	(16)
Use of CPs in General	596	(1)
PVs, Heterojunctions, Diodes	597	(12)
Photoelectrochemical Cells (PECs)	609	(3)
Capacitors	612	(4)
Electrolytic and Electroless Metal Plating	616	(1)
CP-Based ``Molecular Electronic Devices''	617	(10)
Problems and Exercises	624	(3)
Catalysis and Drug/Chemical Delivery	627	(10)
Introduction and Common Features	627	(1)
Catalysis	628	(3)
Drug/Chemical Delivery	631	(6)
Problems and Exercises	634	(3)
Membranes	637	(8)
Introduction	637	(1)
Ion Permeation and Exchange	638	(2)
Chemical/Drug Permeation	640	(1)
Gas Separation	640	(5)
Problems and Exercises	644	(1)
Literature Cited	645	(58)
Index	703	(16)
About the Author	719