Fundamentals of Polymer Engineering, Revised and Expanded

Cover Page......Page 1
Title: Fundamentals of Polymer Engineering, Second Edition......Page 2
ISBN: 0824708679......Page 3
Preface to the Second Edition......Page 8
Preface to the First Edition......Page 9
Contents......Page 12
1.1 DEFINING POLYMERS......Page 19
1.2 CLASSIFICATION OF POLYMERS AND SOME FUNDAMENTAL CONCEPTS......Page 22
1.3.1 Addition Polymers......Page 34
1.3.2 Condensation Polymers......Page 35
1.4 MOLECULAR-WEIGHT DISTRIBUTIONS......Page 37
1.5 CONFIGURATIONS AND CRYSTALLINITY OF POLYMERIC MATERIALS......Page 40
1.6 CONFORMATION OF POLYMER MOLECULES......Page 45
1.7 POLYMERIC SUPPORTS IN ORGANIC SYNTHESIS [11-13]......Page 47
1.8 CONCLUSION......Page 56
PROBLEMS......Page 57
2.2 EFFECT OF TEMPERATURE ON POLYMERS [1^4]......Page 63
2.2.1 Chain Flexibility......Page 65
2.2.2 Interaction Between Polymers......Page 66
2.2.4 Nature of Primary Bondings......Page 67
2.3 ADDITIVES FOR PLASTICS......Page 68
2.4.1 Natural Rubber......Page 79
2.4.2 Polyurethane Rubbers......Page 81
2.4.3 Silicone Rubbers......Page 83
2.5 CELLULOSE PLASTICS......Page 84
2.6 COPOLYMERS AND BLENDS [9-11]......Page 86
2.7 CROSS-LINKING REACTIONS......Page 90
2.8 ION-EXCHANGE RESINS......Page 98
2.9 CONCLUSION......Page 107
REFERENCES......Page 108
PROBLEMS......Page 109
3.1 INTRODUCTION......Page 121
3.2 ESTERIFICATION OF HOMOLOGOUS SERIES AND THE EQUAL REACTIVITY HYPOTHESIS [1,4,5]......Page 123
3.3 KINETICS OF A-R-B POLYMERIZATION USING EQUAL REACTIVITY HYPOTHESIS [2]......Page 125
3.4 AVERAGE MOLECULAR WEIGHT IN STEP-GROWTH POLYMERIZATION OF ARB MONOMERS......Page 129
3.5 EQUILIBRIUM STEP-GROWTH POLYMERIZATION [15-18]......Page 134
3.6 MOLECULAR-WEIGHT DISTRIBUTION IN STEP-GROWTH POLYMERIZATION......Page 136
3.7 EXPERIMENTAL RESULTS......Page 143
APPENDIX 3.1: THE SOLUTION OF MWD THROUGH THE GENERATING FUNCTION TECHNIQUE IN STEP-GROWTH POLYMERIZATION......Page 158
REFERENCES......Page 161
PROBLEMS......Page 163
4.1 INTRODUCTION [1,2]......Page 171
4.2 ANALYSIS OF SEMIBATCH REACTORS [1,3]......Page 174
4.2.1 Vapor-Liquid Equilibrium Governed by Raoult’s Law......Page 176
4.2.2 Volume of Reaction Mass......Page 177
4.2.3 Performance of the Semibatch Reactors......Page 178
4.3 MWD OF ARB POLYMERIZATION IN HOMOGENEOUS CONTINUOUS-FLOW STIRRED-TANK REACTORS [4]......Page 184
4.4 ADVANCED STAGE OF POLYMERIZATION [5-11]......Page 187
4.5 CONCLUSION......Page 192
APPENDIX 4.1 SIMILARITY SOLUTION OF STEP-GROWTH POLYMERIZATION IN FILMS WITH FINITE MASS TRANSFER [12]......Page 193
PROBLEMS......Page 199
5.1 INTRODUCTION......Page 206
5.2.1 Initiation......Page 210
5.2.2 The Propagation Reaction......Page 213
5.2.3 Termination of Polymer Radicals......Page 214
5.3 KINETIC MODEL OF RADICAL POLYMERIZATION [5,6]......Page 215
5.4 AVERAGE MOLECULAR WEIGHT IN RADICAL POLYMERIZATION......Page 217
5.5 VERIFICATION OF THE KINETIC MODEL AND THE GEL EFFECT IN RADICAL POLYMERIZATION......Page 219
5.6 EQUILIBRIUM OF RADICAL POLYMERIZATION [29]......Page 228
5.7 TEMPERATURE EFFECTS IN RADICAL POLYMERIZATION......Page 233
5.8.1 Cationic Polymerization......Page 234
5.8.3 Initiation in Cationic Polymerization......Page 237
5.8.4 Propagation, Transfer, and Termination in Cationic Polymerization......Page 239
5.9.1 Initiation in Anionic Polymerization......Page 240
5.9.3 Kinetic Model for Anionic Polymerization [31-35]......Page 242
5.10 ZIEGLER-NATTA CATALYSTS IN STEREOREGULAR POLYMERIZATION [43-56]......Page 244
5.11 KINETIC MECHANISM IN HETEROGENEOUS STEREOREGULAR POLYMERIZATION......Page 248
5.12 STEREOREGULATION BY ZIEGLER-NATTA CATALYST......Page 250
5.13 RATES OF ZIEGLER-NATTA POLYMERIZATION......Page 251
5.13.1 Modeling of Stationary Rate......Page 252
5.13.2 Modeling of the Initial Rates of Stereoregular Polymerization......Page 253
5.14 AVERAGE CHAIN LENGTH OF THE POLYMER IN STEREOREGULAR POLYMERIZATION......Page 256
5.15 DIFFUSIONAL EFFECT IN ZIEGLER-NATTA POLYMER [45,46,49]......Page 258
5.16 NEWER METALLOCENE CATALYSTS FOR OLEFIN POLYMERIZATION [57-60]......Page 260
REFERENCES......Page 262
PROBLEMS......Page 266
6.1 INTRODUCTION......Page 273
6.2 DESIGN OF TUBULAR REACTORS [1-13]......Page 274
6.2.1 Moments of Radical and Dead Polymers [12,13]......Page 278
6.2.2 Control of Molecular Weight [8-13]......Page 288
6.3 COPOLYMERIZATION [14-25]......Page 291
6.4 RECYCLING AND DEGRADATION OF POLYMERS [26-33]......Page 303
APPENDIX 6.1 SOLUTION OF EQUATIONS DESCRIBING ISOTHERMAL RADICAL POLYMERIZATION......Page 305
REFERENCES......Page 311
PROBLEMS......Page 312
7.1 INTRODUCTION......Page 317
7.2 AQUEOUS EMULSIFIER SOLUTIONS......Page 318
7.2.1 Polymerization in Water Emulsion......Page 320
7.3 SMITH AND EWART THEORY FOR STATE II OF EMULSION POLYMERIZATION [1,2]......Page 322
7.3.1 Case I: Number of Free Radicals per Polymer Particle Is Small Compared with Unity......Page 324
7.3.2 Case II: No Transfer of Polymer Radicals out of the Particle Through Di¡usion Combined with a High Termination Rate......Page 325
7.4 ESTIMATION OF THE TOTAL NUMBER OF PARTICLES, Nt......Page 331
7.5 MONOMER CONCENTRATION IN POLYMER PARTICLES, [M]......Page 333
7.5.1 Experimental Results......Page 335
7.6 DETERMINATION OF MOLECULAR WEIGHT IN EMULSION POLYMERIZATION [17,18 ]......Page 337
7.7 EMULSION POLYMERIZATION IN HOMOGENEOUS CONTINUOUS-FLOW STIRRED-TANK REACTORS [8 ]......Page 342
7.8 TIME-DEPENDENT EMULSION POLYMERIZATION......Page 344
7.9 CONCLUSIONS......Page 352
REFERENCES......Page 353
PROBLEMS......Page 354
8.1 INTRODUCTION......Page 358
8.2 END-GROUP ANALYSIS......Page 360
8.3 COLLIGATIVE PROPERTIES......Page 361
8.4 LIGHT SCATTERING......Page 368
8.5 ULTRACENTRIFUGATION......Page 372
8.6 INTRINSIC VISCOSITY......Page 376
8.7 GEL PERMEATION CHROMATOGRAPHY......Page 382
REFERENCES......Page 387
PROBLEMS......Page 389
9.1 INTRODUCTION......Page 392
9.2 CRITERIA FOR POLYMER SOLUBILITY......Page 394
9.3 THE FLORY -HUGGINS THEORY......Page 397
9.3.1 Entropy Change on Mixing......Page 398
9.3.2 Enthalpy Change on Mixing......Page 402
9.3.3 Free-Energy Change and Chemical Potentials......Page 404
9.3.4 Phase Behavior of Monodisperse Polymers......Page 406
9.3.5 Determining the Interaction Parameter......Page 408
9.3.6 Calculating the Binodal......Page 411
9.3.7 Strengths and Weaknesses of the Flory -Huggins Model......Page 413
9.4 FREE-VOLUME THEORIES......Page 414
9.5 THE SOLUBILITY PARAMETER......Page 416
9.6 POLYMER BLENDS......Page 419
REFERENCES......Page 421
PROBLEMS......Page 423
10.1 INTRODUCTION......Page 425
10.2 PROBABILITY DISTRIBUTION FOR THE FREELY JOINTED CHAIN......Page 426
10.3 ELASTIC FORCE BETWEEN CHAIN ENDS......Page 433
10.4 STRESS-STRAIN BEHAVIOR......Page 436
10.5 THE STRESS TENSOR (MATRIX)......Page 438
10.6 MEASURES OF FINITE STRAIN......Page 441
10.7 THE STRESS CONSTITUTIVE EQUATION......Page 445
10.8 VULCANIZATION OF RUBBER AND SWELLING EQUILIBRIUM......Page 447
10.9 CONCLUSION......Page 450
REFERENCES......Page 451
PROBLEMS......Page 452
11.1 INTRODUCTION......Page 455
11.2.1 Homogeneous Nucleation......Page 461
11.2.2 Heterogeneous Nucleation......Page 462
11.3 OVERALL CRYSTALLIZATION RATE......Page 465
11.4.1 Isothermal Quiescent Crystallization......Page 468
11.4.2 Nonisothermal Quiescent Crystallization......Page 472
11.5 POLYMER CRYSTALLIZATION IN BLENDS AND COMPOSITES......Page 474
11.6 MELTING OF CRYSTALS......Page 477
11.7 INFLUENCE OF POLYMER CHAIN EXTENSION AND ORIENTATION......Page 480
11.8 POLYMERS WITH LIQUID-CRYSTALLINE ORDER......Page 482
11.9 STRUCTURE DETERMINATION......Page 485
11.9.1 Mass Fraction Crystallinity......Page 487
11.9.2 Spherulite Size......Page 489
11.9.3 Polymer Chain Orientation......Page 492
11.10 WORKING WITH SEMICRYSTALLINE POLYMERS......Page 497
11.11 CONCLUSION......Page 498
REFERENCES......Page 499
PROBLEMS......Page 502
12.1 INTRODUCTION......Page 505
12.2 STRESS-STRAIN BEHAVIOR......Page 506
12.2.1 Influence of Variables such as Molecular Weight and Temperature......Page 512
12.3 THE GLASS TRANSITION TEMPERATURE......Page 515
12.4 DYNAMIC MECHANICAL EXPERIMENTS......Page 519
12.5 TIME-TEMPERATURE SUPERPOSITION......Page 522
12.6 POLYMER FRACTURE......Page 526
12.7 CRAZING AND SHEAR YIELDING......Page 529
12.8 FATIGUE FAILURE......Page 534
12.9 IMPROVING MECHANICAL PROPERTIES......Page 536
REFERENCES......Page 538
PROBLEMS......Page 541
13.1 INTRODUCTION......Page 544
13.2 FUNDAMENTALS OF MASS TRANSFER......Page 545
13.3.1 Diffusion in the Liquid Phase......Page 549
13.3.2 Diffusion in Solid Polymers......Page 554
13.4 DIFFUSIVITY OF SPHERES AT INFINITE DILUTION......Page 560
13.5 DIFFUSION COEFFICIENT FOR NON-THETA SOLUTIONS......Page 564
13.6 FREE-VOLUME THEORY OF DIFFUSION IN RUBBERY POLYMERS......Page 565
13.7 GAS DIFFUSION IN GLASSY POLYMERS......Page 570
13.8 ORGANICVAPORDIFFUSIONINGLASSY POLYMERS:CASE II DIFFUSION......Page 575
13.9 POLYMER-POLYMER DIFFUSION......Page 578
13.10 CONCLUSION......Page 582
REFERENCES......Page 583
PROBLEMS......Page 587
14.1 INTRODUCTION......Page 591
14.2 VISCOMETRIC FLOWS......Page 594
14.3 CONE-AND-PLATE VISCOMETER......Page 596
14.4 THE CAPILLARY VISCOMETER......Page 602
14.5 EXTENSIONAL VISCOMETERS......Page 607
14.6 BOLTZMANN SUPERPOSITION PRINCIPLE......Page 610
14.7 DYNAMIC MECHANICAL PROPERTIES......Page 613
14.8 THEORIES OF SHEAR VISCOSITY......Page 616
14.9 CONSTITUTIVE BEHAVIOR OF DILUTE POLYMER SOLUTIONS......Page 623
14.9.1 Elastic Dumbell Model......Page 624
14.9.2 Multiple Bead ^Spring Models......Page 632
14.10 CONSTITUTIVE BEHAVIOR OF CONCENTRATED SOLUTIONS AND MELTS......Page 633
14.10.1 Lodge ’s Rubberlike Liquid......Page 634
14.10.2 Other Single-Integral Equations......Page 636
REFERENCES......Page 640
PROBLEMS......Page 644
15.1 INTRODUCTION......Page 648
15.2 EXTRUSION......Page 649
15.2.1 Screw Geometry......Page 651
15.2.2 Solids-Conveying Zone......Page 652
15.2.3 Melting Zone......Page 657
15.2.4 The Melt Zone......Page 660
15.2.5 Overall Extruder Simulation......Page 663
15.2.6 ExtrudersasMixers......Page 664
15.3 INJECTION MOLDING......Page 669
15.3.1 Mold Filling......Page 674
15.3.2 Mold Packing and Cooling......Page 682
15.3.3 Molding Microstructure......Page 684
15.4 FIBER SPINNING......Page 685
15.4.1 Single-Filament Model......Page 688
15.4.2 Steady-State Behavior of Single Filaments......Page 691
15.4.3 Multifilament Spinning and Other Concerns......Page 697
REFERENCES......Page 698
PROBLEMS......Page 702
B......Page 705
D......Page 706
G......Page 707
M......Page 708
Q......Page 709
R,S......Page 710
W,X,Y,Z......Page 711
Back Page......Page 712