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Fundamental Principles of Polymeric Materials. Edition No. 3

  • Book

  • 432 Pages
  • June 2012
  • John Wiley and Sons Ltd
  • ID: 2170883

New edition brings classic text up to date with the latest science, techniques, and applications

With its balanced presentation of polymer chemistry, physics, and engineering applications, the Third Edition of this classic text continues to instill readers with a solid understanding of the core concepts underlying polymeric materials. Both students and instructors have praised the text for its clear explanations and logical organization. It begins with molecular-level considerations and then progressively builds the reader's knowledge with discussions of bulk properties, mechanical behavior, and processing methods.

Following a brief introduction, Fundamental Principles of Polymeric Materials is divided into four parts:

  • Part 1: Polymer Fundamentals

  • Part 2: Polymer Synthesis

  • Part 3: Polymer Properties

  • Part 4: Polymer Processing and Performance

Thoroughly Updated and Revised

Readers familiar with the previous edition of this text will find that the organization and style have been updated with new material to help them grasp key concepts and discover the latest science, techniques, and applications. For example, there are new introductory sections on organic functional groups focusing on the structures found in condensation polymerizations. The text also features new techniques for polymer analysis, processing, and microencapsulation as well as emerging techniques such as atom transfer radical polymerization.

At the end of each chapter are problems - including many that are new to this edition - to test the reader's grasp of core concepts as they advance through the text. There are also references leading to the primary literature for further investigation of individual topics.

A classic in its field, this text enables students in chemistry, chemical engineering, materials science, and mechanical engineering to fully grasp and apply the fundamentals of polymeric materials, preparing them for more advanced coursework.

Table of Contents

PREFACE xiii

PREFACE TO THE SECOND EDITION xv

ACKNOWLEDGMENTS xvii

1 INTRODUCTION 1

Problems 7

References 7

PART I. POLYMER FUNDAMENTALS 9

2 TYPES OF POLYMERS 11

2.1 Reaction to Temperature 11

2.2 Chemistry of Synthesis 12

2.3 Structure 19

2.4 Conclusions 30

Problems 30

Reference 34

3 MOLECULAR STRUCTURE OF POLYMERS 35

3.1 Types of Bonds 35

3.2 Bond Distances and Strengths 35

3.3 Bonding and Response to Temperature 37

3.4 Action of Solvents 38

3.5 Bonding and Molecular Structure 39

3.6 Stereoisomerism in Vinyl Polymers 40

3.7 Stereoisomerism in Diene Polymers 42

3.8 Summary 44

Problems 44

References 45

4 POLYMER MORPHOLOGY 46

4.1 Amorphous and Crystalline Polymers 47

4.2 The Effect of Polymer Structure, Temperature, and Solvent on Crystallinity 48

4.3 The Effect of Crystallinity on Polymer Density 49

4.4 The Effect of Crystallinity on Mechanical Properties 50

4.5 The Effect of Crystallinity on Optical Properties 51

4.6 Models for the Crystalline Structure of Polymers 53

4.7 Extended Chain Crystals 56

4.8 Liquid Crystal Polymers 57

Problems 59

References 60

5 CHARACTERIZATION OF MOLECULAR WEIGHT 61

5.1 Introduction 61

5.2 Average Molecular Weights 62

5.3 Determination of Average Molecular Weights 66

5.4 Molecular Weight Distributions 75

5.5 Gel Permeation (or Size-Exclusion) Chromatography (GPC, SEC) 79

5.6 Summary 85

Problems 86

References 89

6 THERMAL TRANSITIONS IN POLYMERS 91

6.1 Introduction 91

6.2 The Glass Transition 91

6.3 Molecular Motions in an Amorphous Polymer 92

6.4 Determination of Tg 92

6.5 Factors that Influence Tg 95

6.6 The Effect of Copolymerization on Tg 97

6.7 The Thermodynamics of Melting 97

6.8 The Metastable Amorphous State 100

6.9 The Influence of Copolymerization on Thermal Properties 101

6.10 Effect of Additives on Thermal Properties 102

6.11 General Observations about Tg and Tm 103

6.12 Effects of Crosslinking 103

6.13 Thermal Degradation of Polymers 103

6.14 Other Thermal Transitions 104

Problems 104

References 106

7 POLYMER SOLUBILITY AND SOLUTIONS 107

7.1 Introduction 107

7.2 General Rules for Polymer Solubility 107

7.3 Typical Phase Behavior in Polymer–Solvent Systems 109

7.4 The Thermodynamic Basis of Polymer Solubility 110

7.5 The Solubility Parameter 112

7.6 Hansen’s Three-Dimensional Solubility Parameter 114

7.7 The Flory–Huggins Theory 116

7.8 Properties of Dilute Solutions 118

7.9 Polymer–Polmyer-Common Solvent Systems 121

7.10 Polymer Solutions, Suspensions, and Emulsions 121

7.11 Concentrated Solutions: Plasticizers 122

Problems 124

References 126

PART II. POLYMER SYNTHESIS 129

8 STEP-GROWTH (CONDENSATION) POLYMERIZATION 131

8.1 Introduction 131

8.2 Statistics of Linear Step-Growth Polymerization 132

8.3 Number-Average Chain Lengths 133

8.4 Chain Lengths on a Weight Basis 136

8.5 Gel Formation 137

8.6 Kinetics of Polycondensation 142

Problems 143

References 145

9 FREE-RADICAL ADDITION (CHAIN-GROWTH) POLYMERIZATION 146

9.1 Introduction 146

9.2 Mechanism of Polymerization 147

9.3 Gelation in Addition Polymerization 148

9.4 Kinetics of Homogeneous Polymerization 149

9.5 Instantaneous Average Chain Lengths 153

9.6 Temperature Dependence of Rate and Chain Length 155

9.7 Chain Transfer and Reaction Inhibitors 157

9.8 Instantaneous Distributions in Free-Radical Addition Polymerization 160

9.9 Instantaneous Quantities 165

9.10 Cumulative Quantities 166

9.11 Relations Between Instantaneous and Cumulative Average Chain Lengths for a Batch Reactor 169

9.12 Emulsion Polymerization 173

9.13 Kinetics of Emulsion Polymerization in Stage II, Case 2 176

9.14 Summary 180

Problems 180

References 183

10 ADVANCED POLYMERIZATION METHODS 185

10.1 Introduction 185

10.2 Cationic Polymerization 185

10.3 Anionic Polymerization 186

10.4 Kinetics of Anionic Polymerization 192

10.5 Group-Transfer Polymerization 194

10.6 Atom Transfer Radical Polymerization 195

10.7 Heterogeneous Stereospecific Polymerization 196

10.8 Grafted Polymer Surfaces 202

10.9 Summary 203

Problems 203

References 205

11 COPOLYMERIZATION 207

11.1 Introduction 207

11.2 Mechanism 207

11.3 Significance of Reactivity Ratios 209

11.4 Variation of Composition with Conversion 210

11.5 Copolymerization Kinetics 216

11.6 Penultimate Effects and Charge-Transfer Complexes 216

11.7 Summary 217

Problems 217

References 219

12 POLYMERIZATION PRACTICE 220

12.1 Introduction 220

12.2 Bulk Polymerization 220

12.3 Gas-Phase Olefin Polymerization 225

12.4 Solution Polymerization 226

12.5 Interfacial Polycondensation 228

12.6 Suspension Polymerization 229

12.7 Emulsion Polymerization 232

12.8 Summary 234

Problems 234

References 235

PART III. POLYMER PROPERTIES 237

13 RUBBER ELASTICITY 239

13.1 Introduction 239

13.2 Thermodynamics of Elasticity 239

13.3 Statistics of Ideal Rubber Elasticity 246

13.4 Summary 248

Problems 248

References 249

14 INTRODUCTION TO VISCOUS FLOW AND THE RHEOLOGICAL BEHAVIOR OF POLYMERS 250

14.1 Introduction 250

14.2 Basic Definitions 251

14.3 Relations Between Shear Force and Shear Rate: Flow Curves 252

14.4 Time-Dependent Flow Behavior 254

14.5 Polymer Melts and Solutions 255

14.6 Quantitative Representation of Flow Behavior 256

14.7 Temperature Dependence of Flow Properties 259

14.8 Influence of Molecular Weight on Flow Properties 262

14.9 The Effects of Pressure on Viscosity 263

14.10 Viscous Energy Dissipation 264

14.11 Poiseuille Flow 265

14.12 Turbulent Flow 268

14.13 Drag Reduction 269

14.14 Summary 271

Problems 271

References 274

15 LINEAR VISCOELASTICITY 276

15.1 Introduction 276

15.2 Mechanical Models for Linear Viscoelastic Response 276

15.3 The Four-Parameter Model and Molecular Response 285

15.4 Viscous or Elastic Response? The Deborah Number 288

15.5 Quantitative Approaches to Model Viscoelasticity 289

15.6 The Boltzmann Superposition Principle 293

15.7 Dynamic Mechanical Testing 297

15.8 Summary 304

Problems 304

References 307

16 POLYMER MECHANICAL PROPERTIES 308

16.1 Introduction 308

16.2 Mechanical Properties of Polymers 308

16.3 Axial Tensiometers 309

16.4 Viscosity Measurement 311

16.5 Dynamic Mechanical Analysis: Techniques 316

16.6 Time–Temperature Superposition 323

16.7 Summary 329

Problems 329

References 332

PART IV. POLYMER PROCESSING AND PERFORMANCE 335

17 PROCESSING 337

17.1 Introduction 337

17.2 Molding 337

17.3 Extrusion 344

17.4 Blow Molding 347

17.5 Rotational, Fluidized-Bed, and Slush Molding 348

17.6 Calendering 349

17.7 Sheet Forming (Thermoforming) 350

17.8 Stamping 351

17.9 Solution Casting 351

17.10 Casting 351

17.11 Reinforced Thermoset Molding 352

17.12 Fiber Spinning 353

17.13 Compounding 355

17.14 Lithography 358

17.15 Three-Dimensional (Rapid) Prototyping 358

17.16 Summary 359

Problems 359

References 360

18 POLYMER APPLICATIONS: PLASTICS AND PLASTIC ADDITIVES 361

18.1 Introduction 361

18.2 Plastics 361

18.3 Mechanical Properties of Plastics 362

18.4 Contents of Plastic Compounds 363

18.5 Sheet Molding Compound for Plastics 371

18.6 Plastics Recycling 373

Problems 374

References 374

19 POLYMER APPLICATIONS: RUBBERS AND THERMOPLASTIC ELASTOMERS 375

19.1 Introduction 375

19.2 Thermoplastic Elastomers 375

19.3 Contents of Rubber Compounds 376

19.4 Rubber Compounding 379

References 379

20 POLYMER APPLICATIONS: SYNTHETIC FIBERS 380

20.1 Synthetic Fibers 380

20.2 Fiber Processing 380

20.3 Fiber Dyeing 381

20.4 Other Fiber Additives and Treatments 381

20.5 Effects of Heat and Moisture on Polymer Fibers 381

21 POLYMER APPLICATIONS: SURFACE FINISHES AND COATINGS 383

21.1 Surface Finishes 383

21.2 Solventless Coatings 385

21.3 Electrodeposition 387

21.4 Microencapsulation 387

Problem 389

References 389

22 POLYMER APPLICATIONS: ADHESIVES 390

22.1 Adhesives 390

References 394

INDEX 395

Authors

Christopher S. Brazel Stephen L. Rosen University of Toledo.