Introduction to Polymer Viscoelasticity

The revised fourth edition of the text that offers a thorough understanding of viscoelastic behavior, essential for the proper utilization of polymers

The thoroughly revised and updated fourth edition of Introduction to Polymer Viscoelasticity is the classic resource on the topic of molecular viscoelasticity. This important text bridges the gap between primers on polymer science and advanced research–level monographs. The authors assume a molecular, rather than a mechanical approach, and provide a strong grounding in the fundamental concepts, detailed derivations, and particular attention to assumptions, simplifications, and limitations.

Revisions to the updated fourth edition feature the inclusion of new measurement techniques, coverage of biopolymer viscoelasticity, and a vital discussion of the relationship between mechanical polymer properties and viscoelastic functions. In addition, the text contains two entirely new sections that address modern areas of viscoelastic measurement: large amplitude oscillatory shear (LAOS) and microrheology. The authors explain principles, corresponding equations, and experimental methods with supporting real–life applications and the text has supporting data available with a supplementary website. This important resource:

Offers a completely revised and updated guide to molecular viscoelasticity Includes coverage of measurement techniques (nano–indentation, atomic force microscopy (AFM), and diffusing wave spectroscopy (DWS)), biopolymer viscoelasticity Explores the relationship between mechanical polymer properties and viscoelastic functions Offers two new sections that address modern areas of viscoelastic measurement: large amplitude oscillatory shear (LAOS) and microrheology

Written for polymer and materials scientists, chemical engineers, physical chemists, product design engineers, mechanical engineers, and students, Introduction to Polymer Viscoelasticity is the go–to resource for understanding the most current research and developments in the field.

Preface to the Fourth Edition

Preface to the Third Edition

Preface to the Second Edition

Preface to the First Edition

1. Introduction

PROBLEMS, 6

GENERAL REFERENCE TEXTS, 7

REFERENCES, 8

2. Phenomenological Treatment of Viscoelasticity

A. ELASTIC MODULUS, 9

B. TRANSIENT EXPERIMENTS, 21

C. DYNAMIC EXPERIMENTS, 25

1. Low–Strain Measurements, 25

2. Large Amplitude Oscillatory Shear (LAOS), 30

3. Microrheology, 34

D. BOLTZMANN SUPERPOSITION PRINCIPLE, 38

E. RELATIONSHIP BETWEEN THE CREEP COMPLIANCE AND THE STRESS RELAXATION MODULUS, 43

F. RELATIONSHIP BETWEEN STATIC AND DYNAMIC PROPERTIES, 44

APPENDIX 2–1. Connecting Creep Compliance and Stress Relaxation Modulus Using Laplace Transforms, 45

APPENDIX 2–2. Borel s Theorem, 48

APPENDIX 2–3. Geometries for the Measurement of Viscoelastic Functions, 49

1. Linear Motion Geometries, 49

2. Rotational Motion Geometries, 53

PROBLEMS, 57

REFERENCES, 64

3. Viscoelastic Models

A. MECHANICAL ELEMENTS, 66

1. Maxwell Model, 68

2. Voigt Model, 74

3. Generalized Maxwell Model, 76

4. Voigt–Kelvin model, 79

B. DISTRIBUTIONS OF RELAXATION AND RETARDATION TIMES, 81

C. MOLECULAR THEORIES THE ROUSE MODEL, 84

D. APPLICATION OF FLEXIBLE–CHAIN MODELS TO SOLUTIONS, 93

E. THE ZIMM MODIFICATION, 94

F. EXTENSION TO BULK POLYMER, 96

G. REPTATION, 108

APPENDIX 3–1: MANIPULATION OF THE ROUSE MATRIX, 112

PROBLEMS, 117

REFERENCES, 123

4. Time Temperature Correspondence

A. FOUR REGIONS OF VISCOELASTIC BEHAVIOR, 125

B. TIME TEMPERATURE SUPERPOSITION, 133

C. MASTER CURVES, 136

D. THE WLF EQUATION, 136

E. MOLECULAR INTERPRETATION OF VISCOELASTIC RESPONSE, 143

PROBLEMS, 144

REFERENCES, 149

5. Transitions and Relaxation in Amorphous Polymers

A. PHENOMENOLOGY OF THE GLASS TRANSITION, 150

B. THEORIES OF THE GLASS TRANSITION, 155

1. Free–Volume Theory, 155

2. Thermodynamic Theory, 158

3. Kinetic Theories, 164

C. STRUCTURAL PARAMETERS AFFECTING THE GLASS TRANSITION, 166

D. RELAXATIONS IN THE GLASSY STATE, 172

E. RELAXATION PROCESSES IN NETWORKS, 176

1. Physical Relaxation, 176

2. Chemical Processes, 177

F. BIOPOLYMER VISCOELASTICITY, 180

1. Biopolymer Sources, 180

2. Humidity Control, 181

3. Examples of Biopolymer Viscoelastic Response, 183

PROBLEMS, 189

REFERENCES, 196

6. Elasticity of Rubbery Networks

A. THERMODYNAMIC TREATMENT, 199

B. STATISTICAL TREATMENT, 205

1. Derivation, 205

2. Energy Contribution, 216

C. PHENOMENOLOGICAL TREATMENT, 220

D. FACTORS AFFECTING RUBBER ELASTICITY, 224

1. Effect of Degree of Crosslinking, 224

2. Effect of Swelling, 226

3. Effect of Fillers, 229

4. Effect of Strain–Induced Crystallization, 232

APPENDIX 6–1. Statistics of a Polymer Chain, 234

APPENDIX 6–2. Equation of State for a Polymer Chain, 240

PROBLEMS, 242

REFERENCES, 246

7. Dielectric and NMR Methods

A. DIELECTRIC METHODS, 249

1. Phenomenology, 250

2. Molecular Interpretation of Dielectric Constant, 257

3. Interfacial Polarization, 264

4. Application to Polymers, 265

5. Experimental Methods, 268

6. Application of Dielectric Relaxation to Poly (methyl methacrylate), 272

7. Comparisons between Mechanical and Dielectric Relaxation for Polymers, 273

B. NUCLEAR MAGNETIC RESONANCE METHODS, 274

PROBLEMS, 280

REFERENCES, 282

Answers to Selected Problems

CHAPTER 2, 284

CHAPTER 3, 296

CHAPTER 4, 304

CHAPTER 5, 308

CHAPTER 6, 312

CHAPTER 7, 320

List of Major Symbols

List of Files on Website

Author Index

Subject Index

Montgomery T. Shaw, PhD, is Emeritus Distinguished Professor of Chemical Engineering at the University of Connecticut. Among his books are the prior edition of Introduction to Polymer Viscoelasticity and Introduction to Polymer Rheology, both published by Wiley.

William J. MacKnight, PhD, is a Professor Emeritus at the University of Massachusetts Amherst, where he was formerly the co–Principal Investigator for the Center for UMass/Industry Research on Polymers (CUMIRP). He has been a co–author for each edition of Introduction to Polymer Viscoelasticity, all published by Wiley.