Preface ........................................................ xi
Preface to the First Edition ................................. xiii
1 Introduction ................................................. 1
1.1 Polymers ................................................ 1
1.2 Applications of Polymers ................................ 2
1.3 Polymer-Based Industries ................................ 3
1.4 Feedstocks for Polymers ................................. 9
1.5 Polymer Science and Technology ......................... 12
1.6 Trends ................................................. 15
Keywords .................................................... 17
Problems .................................................... 17
References .................................................. 18
2 Basic Structures of Polymers ................................ 21
2.1 Classification Schemes ................................. 21
2.2 Bonding ................................................ 22
2.3 Single Molecules ....................................... 25
2.4 Network Molecules ...................................... 28
2.5 Thermodynamics of Binary Systems ....................... 29
2.6 Cohesive Energy Density and Solubility Parameter ....... 34
Appendix .................................................... 41
Keywords .................................................... 44
Problems .................................................... 44
References .................................................. 48
3 Physical States and Transitions ............................. 51
3.1 Physical States ........................................ 51
3.2 Conformation of Single Chains in Solution .............. 52
3.3 Phase Separation in Polymer Mixtures ................... 54
3.4 Transitions in Pure Polymers ........................... 59
3.5 Amorphous Polymers ..................................... 62
3.6 Plasticization ......................................... 68
3.7 Cryslallinity .......................................... 69
3.8 Conformation of Single Chains in Crystals .............. 73
3.9 Spherulites and Drawing ................................ 74
3.10 Crystallization ........................................ 78
3.11 Transition Temperatures ................................ 79
3.12 Block Copolymers ....................................... 86
3.13 Liquid Crystal Polymers ................................ 86
3.14 Gels ................................................... 89
Keywords .................................................... 90
Problems .................................................... 91
References .................................................. 94
4 Polymer Formation ........................................... 99
4.1 Polymerization Reactions ............................... 99
4.2 Functionality ......................................... 100
4.3 Step and Chain Growth Polymerizations ................. 101
4.4 Chain Polymerization .................................. 104
4.5 Ionic Polymerization .................................. 118
4.6 Controlled Radical Polymerization ..................... 128
4.7 Insertion Polymerization .............................. 130
4.8 Step Growth Polymerization ............................ 135
4.9 Ring-Opening Polymerization ........................... 144
4.10 Copolymerization ...................................... 146
4.11 Biosynthesis of Polymers .............................. 154
4.12 Polymer Modification .................................. 159
Keywords ................................................... 161
Problems ................................................... 163
References ................................................. 171
5 Polymerization Processes ................................... 177
5.1 Design Criteria ....................................... 177
5.2 Bulk Polymerization ................................... 181
5.3 Solution Polymerization ............................... 183
5.4 Suspension Polymerization ............................. 193
5.5 Emulsion Polymerization ............................... 194
5.6 Comparison of Polymerization Methods .................. 201
Keywords ................................................... 202
Problems ................................................... 203
References ................................................. 206
6 The Molecular Weight of Polymers ........................... 209
6.1 Molecular Weight Distribution and Average Molecular
Weight ................................................ 209
6.2 Theoretical Distributions ............................. 212
6.3 Empirical Distribution Models ......................... 217
6.4 Measurement of Distribution ........................... 220
6.5 Measurement of Molecular Weight ....................... 227
6.6 Number-Average Molecular Weight Methods ............... 228
6.7 Weight-Average Molecular Weight Methods ............... 235
Appendices ................................................. 241
Keywords ................................................... 243
Problems ................................................... 244
References ................................................. 249
7 Viscous Flow ............................................... 251
7.1 Introduction .......................................... 251
7.2 Viscosity ............................................. 252
7.3 Polymer Shapes in Solution ............................ 260
7.4 Effect of Concentration and Molecular Weight .......... 274
7.5 Effect of Temperature and Pressure .................... 280
7.6 Normal Stress Differences in Shear .................... 282
7.7 Models for Non-Newtonian Row .......................... 287
7.8 Viscometry ............................................ 291
7.9 Rheometry ............................................. 296
7.10 Turbulent Flow ........................................ 315
Appendices ................................................. 319
Keywords ................................................... 321
Problems ................................................... 324
References ................................................. 331
8 Mechanical Properties at Small Deformations ................ 337
8.1 Elasticity in Various Geometries ...................... 337
8.2 Rubber Elasticity ..................................... 340
8.3 Viscoelasticity - Maxwell Model ....................... 349
8.4 Dynamic Measurements .................................. 356
8.5 Real Polymers - Five Regions of Viscoelasticity ....... 360
8.6 Generalized Maxwell Model ............................. 362
8.7 Effect of Molecular Weight ............................ 365
8.8 Effect of Crystallinity ............................... 367
8.9 Effect of Fillers ..................................... 369
8.10 Other Transitions ..................................... 369
Appendices ................................................. 370
Keywords ................................................... 373
Problems ................................................... 374
References ................................................. 379
9 Ultimate Properties ........................................ 383
9.1 Failure Tests ......................................... 383
9.2 Constant-Rate-of-Strain Tests ......................... 385
9.3 Breaking Energy ....................................... 387
9.4 Creep Failure ......................................... 388
9.5 Fatigue ............................................... 388
9.6 Reduced-Variable Failure Correlations ................. 389
9.7 Fracture of Glassy Polymers ........................... 391
9.8 Heterophase Systems ................................... 395
Keywords ................................................... 408
Problems ................................................... 409
References ................................................. 410
10 Some General Properties of Polymer Systems ................. 413
10.1 Design Criteria ....................................... 413
10.2 Compounding ........................................... 414
10.3 Hardness .............................................. 416
10.4 Density ............................................... 416
10.5 Thermal Properties .................................... 417
10.6 Electrical Properties ................................. 420
10.7 Optical Properties .................................... 428
Keywords ................................................... 430
Problems ................................................... 431
References ................................................. 432
11 Degradation and Stabilization of Polymer Systems ........... 435
11.1 Degrading Agencies .................................... 435
11.2 Phase Separation and Interfacial Failure .............. 440
11.3 Polymer Degradation ................................... 441
11.4 Antioxidants and Related Compounds .................... 448
11.5 Stabilizers for Irradiated Systems .................... 453
11.6 Ablation .............................................. 455
Keywords ................................................... 459
Problems ................................................... 459
References ................................................. 460
12 Fabrication Processes ...................................... 463
12.1 The Fabricator ........................................ 463
12.2 Raw Material Forms .................................... 464
12.3 Mixing ................................................ 465
12.4 Coatings and Adhesives ................................ 471
12.5 Photoresists: An Application of Polymers to
Microelectronics ...................................... 486
12.6 Application of Polymers in Medicine ................... 491
Keywords ................................................... 497
Problems ................................................... 499
References ................................................. 500
13 Fabrication Processes: Extrusion and Molding ............... 511
13.1 Extrusion in General .................................. 511
13.2 Extrusion of Rat Film, Sheet, and Tubing .............. 515
13.3 Fibers ................................................ 523
13.4 Laminates ............................................. 529
13.5 Compression Molding ................................... 531
13.6 Injection Molding ..................................... 534
13.7 Injection-Molding Simulations ......................... 539
13.8 Other Molding Processes ............................... 542
13.9 Foams ................................................. 552
13.10 Sheet Forming ........................................ 563
Keywords ................................................... 565
Problems ................................................... 567
References ................................................. 568
14 Recycling and Resource Recovery ............................ 571
14.1 Waste Generation and Disposal ......................... 571
14.2 Identification and Separation ......................... 574
14.3 Down-Cycling .......................................... 580
14.4 Monomer Recovery ...................................... 582
14.5 Hydrogenation. Pyrolysis, and Gasification ............ 584
14.6 Incineration with Energy Recovery ..................... 585
14.7 Degradable Polymers ................................... 588
14.8 Prospects ............................................. 592
Keywords ................................................... 594
Problems ................................................... 595
References ................................................. 596
15 Carbon Chain Polymers ...................................... 599
15.1 Introduction .......................................... 599
15.2 The Polyolefins ....................................... 602
15.3 The Acrylonitrile-Butadiene-Styrene Group ............. 607
15.4 The Diene Polymers .................................... 615
15.5 The Vinyls ............................................ 622
15.6 The Acrylics .......................................... 627
15.7 The Fluorocarbon Polymers ............................. 630
Keywords ................................................... 633
Problems ................................................... 634
References ................................................. 635
16 Heterochain Polymers ....................................... 639
16.1 Introduction .......................................... 639
16.2 Polyesters ............................................ 639
16.3 Polyethers ............................................ 646
16.4 Polysaccharides ....................................... 652
16.5 Poly amides and Related Polymers ...................... 656
16.6 Aldehyde Condensation Polymers ........................ 669
16.7 Polymers Based on Isocyanate Reactions ................ 672
16.8 Silicones ............................................. 675
16.9 Polyphosphazenes ...................................... 680
16.10 Engineering Resins and High-Performance Polymers ..... 681
16.11 Thermoplastic Elastomers ............................. 684
Keywords ................................................... 686
Problems ................................................... 688
References ................................................. 689
17 Analysis and Identification of Polymers .................... 693
17.1 The Purpose of Polymer Analysis ....................... 693
17.2 Infrared and Ultraviolet Spectroscopy ................. 694
17.3 Differential Thermal Methods .......................... 696
17.4 Other Methods of Thermal Analysis ..................... 702
17.5 Nuclear Magnetic Resonance Spectroscopy ............... 703
17.6 Miscellaneous Spectroscopic Methods ................... 707
17.7 Chemical Tests and Identification Schemes ............. 707
Keywords ................................................... 708
Problems ................................................... 708
References ................................................. 709
Appendices .................................................... 711
1 List of Symbols ......................................... 713
2 Typical Properties of Polymers Used for Molding and
Extrusion ............................................... 727
3 Typical Properties Reported for Some Commercial
Textile Fibers .......................................... 733
4 Major Markets for Selected Plastics and Rubber .......... 735
Equivalents for Selected SI Quantities ........................ 737
Index ......................................................... 739
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