Fundamental Principles of Polymeric Materials

by Brazel, Christopher S.; Rosen, Stephen L.

• ISBN13: 9780470505427
• ISBN10: 0470505427
• Edition: 3rd
• Format: Hardcover
• Copyright: 2012-05-22
• Publisher: Wiley

Summary

Fundamental Principles of Polymeric Materials is an introduction to the field of polymers that balances chemistry, physics, and engineering applications. Updating the classic Second Edition (1993) that continues to find use in introductory polymer courses, this revised edition focuses on new technologies that use polymers, new feedstocks, polymers derived from biological sources, new strategies for polymerizations, and analysis of polymers. Furthermore, this edition includes new homework problems and examples as well as new ideas and concepts, while remaining friendly to students new to the polymer field.

Author Biography

Christopher S. Brazel, PhD, CHE, is Associate Professor of Chemical and Biological Engineering at The University of Alabama. His research interests include stimuli-responsive polymers, composite materials with magnetic nanoparticles, targeted block copolymer micelles, gels and networks for drug delivery, and microencapsulation. Previously, Dr. Brazel was a Fulbright Distinguished Scholar and Visiting Professor at the Institute for Science and Technology in Medicine, Keele University, UK. Stephen L. Rosen, PhD, CHE, is a former Professor of Chemical Engineering at the University of Missouri-Rolla. Dr. Rosen authored the two previous editions of Fundamental Principles of Polymeric Materials.

Table of Contents

Preface	p. xiii
Preface to the Second Edition	p. xv
Acknowledgments	p. xvii
Introduction	p. 1
Problems	p. 1
References	p. 7
Polymer Fundamentals	p. 9
Types of Polymers	p. 11
Reaction to Temperature	p. 11
Chemistry of Synthesis	p. 12
Structure	p. 19
Conclusions	p. 30
Problems	p. 30
Reference	p. 34
Molecular Structure of Polymers	p. 35
Types of Bonds	p. 35
Bond Distances and Strengths	p. 35
Bonding and Response to Temperature	p. 37
Action of Solvents	p. 38
Bonding and Molecular Structure	p. 39
Stereoisomerism in Vinyl Polymers	p. 40
Stereoisomerism in Diene Polymers	p. 42
Summary	p. 44
Problems	p. 44
References	p. 45
Polymer Morphology	p. 46
Amorphous and Crystalline Polymers	p. 47
The Effect of Polymer Structure, Temperature, and Solvent on Crystallinity	p. 48
The Effect of Crystallinity on Polymer Density	p. 49
The Effect of Crystallinity on Mechanical Properties	p. 50
The Effect of Crystallinity on Optical Properties	p. 51
Models for the Crystalline Structure of Polymers	p. 53
Extended Chain Crystals	p. 56
Liquid Crystal Polymers	p. 57
Problems	p. 59
References	p. 60
Characterization of Molecular Weight	p. 61
Introduction	p. 61
Average Molecular Weights	p. 62
Determination of Average Molecular Weights	p. 66
Molecular Weight Distributions	p. 75
Gel Permeation (or Size-Exclusion) Chromatography (GPC, SEC)	p. 79
Summary	p. 85
Problems	p. 86
References	p. 89
Thermal Transitions in Polymers	p. 91
Introduction	p. 91
The Glass Transition	p. 91
Molecular Motions in an Amorphous Polymer	p. 92
Determination of Tg	p. 92
Factors that Influence Tg	p. 95
The Effect of Copolymerization on Tg	p. 97
The Thermodynamics of Melting	p. 97
The Metastable Amorphous State	p. 100
The Influence of Copolymerization on Thermal Properties	p. 101
Effect of Additives on Thermal Properties	p. 102
General Observations about Tg and Tm	p. 103
Effects of Crosslinking	p. 103
Thermal Degradation of Polymers	p. 103
Other Thermal Transitions	p. 104
Problems	p. 104
References	p. 106
Polymer Solubility and Solutions	p. 107
Introduction	p. 107
General Rules for Polymer Solubility	p. 107
Typical Phase Behavior in Polymer-Solvent Systems	p. 109
The Thermodynamic Basis of Polymer Solubility	p. 110
The Solubility Parameter	p. 112
Hansen's Three-Dimensional Solubility Parameter	p. 114
The Flory-Huggins Theory	p. 116
Properties of Dilute Solutions	p. 118
Polymer-Polmyer-Common Solvent Systems	p. 121
Polymer Solutions, Suspensions, and Emulsions	p. 121
Concentrated Solutions: Plasticizers	p. 122
Problems	p. 124
References	p. 126
Polymer Synthesis	p. 129
Step-Growth (Condensation) Polymerization	p. 131
Introduction	p. 131
Statistics of Linear Step-Growth Polymerization	p. 132
Number-Average Chain Lengths	p. 133
Chain Lengths on a Weight Basis	p. 136
Gel Formation	p. 137
Kinetics of Polycondensation	p. 142
Problems	p. 143
References	p. 145
Free-Radical Addition (Chain-Growth) Polymerization	p. 146
Introduction	p. 146
Mechanism of Polymerization	p. 147
Gelation in Addition Polymerization	p. 148
Kinetics of Homogeneous Polymerization	p. 149
Instantaneous Average Chain Lengths	p. 153
Temperature Dependence of Rate and Chain Length	p. 155
Chain Transfer and Reaction Inhibitors	p. 157
Instantaneous Distributions in Free-Radical Addition Polymerization	p. 160
Instantaneous Quantities	p. 165
Cumulative Quantities	p. 166
Relations Between Instantaneous and Cumulative Average Chain Lengths for a Batch Reactor	p. 169
Emulsion Polymerization	p. 173
Kinetics of Emulsion Polymerization in Stage II, Case 2	p. 176
Summary	p. 180
Problems	p. 180
References	p. 183
Advanced Polymerization Methods	p. 185
Introduction	p. 185
Cationic Polymerization	p. 185
Anionic Polymerization	p. 186
Kinetics of Anionic Polymerization	p. 192
Group-Transfer Polymerization	p. 194
Atom Transfer Radical Polymerization	p. 195
Heterogeneous Stereospecific Polymerization	p. 196
Grafted Polymer Surfaces	p. 202
Summary	p. 203
Problems	p. 203
References	p. 205
Copolymerization	p. 207
Introduction	p. 207
Mechanism	p. 207
Significance of Reactivity Ratios	p. 209
Variation of Composition with Conversion	p. 210
Copolymerization Kinetics	p. 216
Penultimate Effects and Charge-Transfer Complexes	p. 216
Summary	p. 217
Problems	p. 217
References	p. 219
Polymerization Practice	p. 220
Introduction	p. 220
Bulk Polymerization	p. 220
Gas-Phase Olefin Polymerization	p. 225
Solution Polymerization	p. 226
Interfacial Polycondensation	p. 228
Suspension Polymerization	p. 229
Emulsion Polymerization	p. 232
Summary	p. 234
Problems	p. 234
References	p. 235
Polymer Properties	p. 237
Rubber Elasticity	p. 239
Introduction	p. 239
Thermodynamics of Elasticity	p. 239
Statistics of Ideal Rubber Elasticity	p. 246
Summary	p. 248
Problems	p. 248
References	p. 249
Introduction to Viscous Flow and the Rheological Behavior of Polymers	p. 250
Introduction	p. 250
Basic Definitions	p. 251
Relations Between Shear Force and Shear Rate: Flow Curves	p. 252
Time-Dependent Flow Behavior	p. 254
Polymer Melts and Solutions	p. 255
Quantitative Representation of Flow Behavior	p. 256
Temperature Dependence of Flow Properties	p. 259
Influence of Molecular Weight on Flow Properties	p. 262
The Effects of Pressure on Viscosity	p. 263
Viscous Energy Dissipation	p. 264
Poiseuille Flow	p. 265
Turbulent Flow	p. 268
Drag Reduction	p. 269
Summary .271
Problems	p. 271
References	p. 274
Linear Viscoelasticity	p. 276
Introduction	p. 276
Mechanical Models for Linear Viscoelastic Response	p. 276
The Four-Parameter Model and Molecular Response	p. 285
Viscous or Elastic Response? The Deborah Number	p. 288
Quantitative Approaches to Model Viscoelasticity	p. 289
The Boltzmann Superposition Principle	p. 293
Dynamic Mechanical Testing	p. 297
Summary	p. 304
Problems	p. 304
References	p. 307
Polymer Mechanical Properties	p. 308
Introduction	p. 308
Mechanical Properties of Polymers	p. 308
Axial Tensiometers	p. 309
Viscosity Measurement	p. 311
Dynamic Mechanical Analysis: Techniques	p. 316
Time-Temperature Superposition	p. 323
Summary	p. 329
Problems	p. 329
References	p. 332
Polymer Processing and Performance	p. 335
Processing	p. 337
Introduction	p. 337
Molding	p. 337
Extrusion	p. 344
Blow Molding	p. 347
Rotational, Fluidized-Bed, and Slush Molding	p. 348
Calendering	p. 349
Sheet Forming (Thermoforming)	p. 350
Stamping	p. 351
Solution Casting	p. 351
Casting	p. 351
Reinforced Thermoset Molding	p. 352
Fiber Spinning	p. 353
Compounding	p. 355
Lithography	p. 358
Three-Dimensional (Rapid) Prototyping	p. 358
Summary	p. 359
Problems	p. 359
References	p. 360
Polymer Applications: Plastics and Plastic Additives	p. 361
Introduction	p. 361
Plastics	p. 361
Mechanical Properties of Plastics	p. 362
Contents of Plastic Compounds	p. 363
Sheet Molding Compound for Plastics	p. 371
Plastics Recycling	p. 373
Problems	p. 374
References	p. 374
Polymer Applications: Rubbers and Thermoplastic Elastomers	p. 375
Introduction	p. 375
Thermoplastic Elastomers	p. 375
Contents of Rubber Compounds	p. 376
Rubber Compounding	p. 379
References	p. 379
Polymer Applications: Synthetic Fibers	p. 380
Synthetic Fibers	p. 380
Fiber Processing	p. 380
Fiber Dyeing	p. 381
Other Fiber Additives and Treatments	p. 381
Effects of Heat and Moisture on Polymer Fibers	p. 381
Polymer Applications: Surface Finishes and Coatings	p. 383
Surface Finishes	p. 383
Solventless Coatings	p. 385
Electrodeposition	p. 387
Microencapsulation	p. 387
Problem	p. 389
References	p. 389
Polymer Applications: Adhesives	p. 390
Adhesives	p. 390
References	p. 394
Index	p. 395
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