Fundamental Principles of Polymeric Materials

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  • Edition: 3rd
  • Format: Hardcover
  • Copyright: 2012-05-22
  • Publisher: Wiley

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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

Prefacep. xiii
Preface to the Second Editionp. xv
Acknowledgmentsp. xvii
Introductionp. 1
Problemsp. 1
Referencesp. 7
Polymer Fundamentalsp. 9
Types of Polymersp. 11
Reaction to Temperaturep. 11
Chemistry of Synthesisp. 12
Structurep. 19
Conclusionsp. 30
Problemsp. 30
Referencep. 34
Molecular Structure of Polymersp. 35
Types of Bondsp. 35
Bond Distances and Strengthsp. 35
Bonding and Response to Temperaturep. 37
Action of Solventsp. 38
Bonding and Molecular Structurep. 39
Stereoisomerism in Vinyl Polymersp. 40
Stereoisomerism in Diene Polymersp. 42
Summaryp. 44
Problemsp. 44
Referencesp. 45
Polymer Morphologyp. 46
Amorphous and Crystalline Polymersp. 47
The Effect of Polymer Structure, Temperature, and Solvent on Crystallinityp. 48
The Effect of Crystallinity on Polymer Densityp. 49
The Effect of Crystallinity on Mechanical Propertiesp. 50
The Effect of Crystallinity on Optical Propertiesp. 51
Models for the Crystalline Structure of Polymersp. 53
Extended Chain Crystalsp. 56
Liquid Crystal Polymersp. 57
Problemsp. 59
Referencesp. 60
Characterization of Molecular Weightp. 61
Introductionp. 61
Average Molecular Weightsp. 62
Determination of Average Molecular Weightsp. 66
Molecular Weight Distributionsp. 75
Gel Permeation (or Size-Exclusion) Chromatography (GPC, SEC)p. 79
Summaryp. 85
Problemsp. 86
Referencesp. 89
Thermal Transitions in Polymersp. 91
Introductionp. 91
The Glass Transitionp. 91
Molecular Motions in an Amorphous Polymerp. 92
Determination of Tgp. 92
Factors that Influence Tgp. 95
The Effect of Copolymerization on Tgp. 97
The Thermodynamics of Meltingp. 97
The Metastable Amorphous Statep. 100
The Influence of Copolymerization on Thermal Propertiesp. 101
Effect of Additives on Thermal Propertiesp. 102
General Observations about Tg and Tmp. 103
Effects of Crosslinkingp. 103
Thermal Degradation of Polymersp. 103
Other Thermal Transitionsp. 104
Problemsp. 104
Referencesp. 106
Polymer Solubility and Solutionsp. 107
Introductionp. 107
General Rules for Polymer Solubilityp. 107
Typical Phase Behavior in Polymer-Solvent Systemsp. 109
The Thermodynamic Basis of Polymer Solubilityp. 110
The Solubility Parameterp. 112
Hansen's Three-Dimensional Solubility Parameterp. 114
The Flory-Huggins Theoryp. 116
Properties of Dilute Solutionsp. 118
Polymer-Polmyer-Common Solvent Systemsp. 121
Polymer Solutions, Suspensions, and Emulsionsp. 121
Concentrated Solutions: Plasticizersp. 122
Problemsp. 124
Referencesp. 126
Polymer Synthesisp. 129
Step-Growth (Condensation) Polymerizationp. 131
Introductionp. 131
Statistics of Linear Step-Growth Polymerizationp. 132
Number-Average Chain Lengthsp. 133
Chain Lengths on a Weight Basisp. 136
Gel Formationp. 137
Kinetics of Polycondensationp. 142
Problemsp. 143
Referencesp. 145
Free-Radical Addition (Chain-Growth) Polymerizationp. 146
Introductionp. 146
Mechanism of Polymerizationp. 147
Gelation in Addition Polymerizationp. 148
Kinetics of Homogeneous Polymerizationp. 149
Instantaneous Average Chain Lengthsp. 153
Temperature Dependence of Rate and Chain Lengthp. 155
Chain Transfer and Reaction Inhibitorsp. 157
Instantaneous Distributions in Free-Radical Addition Polymerizationp. 160
Instantaneous Quantitiesp. 165
Cumulative Quantitiesp. 166
Relations Between Instantaneous and Cumulative Average Chain Lengths for a Batch Reactorp. 169
Emulsion Polymerizationp. 173
Kinetics of Emulsion Polymerization in Stage II, Case 2p. 176
Summaryp. 180
Problemsp. 180
Referencesp. 183
Advanced Polymerization Methodsp. 185
Introductionp. 185
Cationic Polymerizationp. 185
Anionic Polymerizationp. 186
Kinetics of Anionic Polymerizationp. 192
Group-Transfer Polymerizationp. 194
Atom Transfer Radical Polymerizationp. 195
Heterogeneous Stereospecific Polymerizationp. 196
Grafted Polymer Surfacesp. 202
Summaryp. 203
Problemsp. 203
Referencesp. 205
Copolymerizationp. 207
Introductionp. 207
Mechanismp. 207
Significance of Reactivity Ratiosp. 209
Variation of Composition with Conversionp. 210
Copolymerization Kineticsp. 216
Penultimate Effects and Charge-Transfer Complexesp. 216
Summaryp. 217
Problemsp. 217
Referencesp. 219
Polymerization Practicep. 220
Introductionp. 220
Bulk Polymerizationp. 220
Gas-Phase Olefin Polymerizationp. 225
Solution Polymerizationp. 226
Interfacial Polycondensationp. 228
Suspension Polymerizationp. 229
Emulsion Polymerizationp. 232
Summaryp. 234
Problemsp. 234
Referencesp. 235
Polymer Propertiesp. 237
Rubber Elasticityp. 239
Introductionp. 239
Thermodynamics of Elasticityp. 239
Statistics of Ideal Rubber Elasticityp. 246
Summaryp. 248
Problemsp. 248
Referencesp. 249
Introduction to Viscous Flow and the Rheological Behavior of Polymersp. 250
Introductionp. 250
Basic Definitionsp. 251
Relations Between Shear Force and Shear Rate: Flow Curvesp. 252
Time-Dependent Flow Behaviorp. 254
Polymer Melts and Solutionsp. 255
Quantitative Representation of Flow Behaviorp. 256
Temperature Dependence of Flow Propertiesp. 259
Influence of Molecular Weight on Flow Propertiesp. 262
The Effects of Pressure on Viscosityp. 263
Viscous Energy Dissipationp. 264
Poiseuille Flowp. 265
Turbulent Flowp. 268
Drag Reductionp. 269
Summary .271
Problemsp. 271
Referencesp. 274
Linear Viscoelasticityp. 276
Introductionp. 276
Mechanical Models for Linear Viscoelastic Responsep. 276
The Four-Parameter Model and Molecular Responsep. 285
Viscous or Elastic Response? The Deborah Numberp. 288
Quantitative Approaches to Model Viscoelasticityp. 289
The Boltzmann Superposition Principlep. 293
Dynamic Mechanical Testingp. 297
Summaryp. 304
Problemsp. 304
Referencesp. 307
Polymer Mechanical Propertiesp. 308
Introductionp. 308
Mechanical Properties of Polymersp. 308
Axial Tensiometersp. 309
Viscosity Measurementp. 311
Dynamic Mechanical Analysis: Techniquesp. 316
Time-Temperature Superpositionp. 323
Summaryp. 329
Problemsp. 329
Referencesp. 332
Polymer Processing and Performancep. 335
Processingp. 337
Introductionp. 337
Moldingp. 337
Extrusionp. 344
Blow Moldingp. 347
Rotational, Fluidized-Bed, and Slush Moldingp. 348
Calenderingp. 349
Sheet Forming (Thermoforming)p. 350
Stampingp. 351
Solution Castingp. 351
Castingp. 351
Reinforced Thermoset Moldingp. 352
Fiber Spinningp. 353
Compoundingp. 355
Lithographyp. 358
Three-Dimensional (Rapid) Prototypingp. 358
Summaryp. 359
Problemsp. 359
Referencesp. 360
Polymer Applications: Plastics and Plastic Additivesp. 361
Introductionp. 361
Plasticsp. 361
Mechanical Properties of Plasticsp. 362
Contents of Plastic Compoundsp. 363
Sheet Molding Compound for Plasticsp. 371
Plastics Recyclingp. 373
Problemsp. 374
Referencesp. 374
Polymer Applications: Rubbers and Thermoplastic Elastomersp. 375
Introductionp. 375
Thermoplastic Elastomersp. 375
Contents of Rubber Compoundsp. 376
Rubber Compoundingp. 379
Referencesp. 379
Polymer Applications: Synthetic Fibersp. 380
Synthetic Fibersp. 380
Fiber Processingp. 380
Fiber Dyeingp. 381
Other Fiber Additives and Treatmentsp. 381
Effects of Heat and Moisture on Polymer Fibersp. 381
Polymer Applications: Surface Finishes and Coatingsp. 383
Surface Finishesp. 383
Solventless Coatingsp. 385
Electrodepositionp. 387
Microencapsulationp. 387
Problemp. 389
Referencesp. 389
Polymer Applications: Adhesivesp. 390
Adhesivesp. 390
Referencesp. 394
Indexp. 395
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