Thermosetting Polymers (Plastics Engineering)

THERMOSETTING POLYMERS......Page 1
PREFACE......Page 6
CONTENTS......Page 8
1.1 THERMOPLASTIC AND THERMOSETTING POLYMERS......Page 12
CONTENTS......Page 0
1.2 ORGANIZATION OF THE BOOK......Page 15
2.1 GENERAL CONSIDERATIONS......Page 17
2.2.1 GENERAL ASPECTS......Page 19
2.2.2 ORGANIC ACID REACTIONS......Page 23
2.2.3 ISOCYANATE REACTIONS......Page 28
2.2.4 EPOXY REACTIONS......Page 35
2.2.5 FORMALDEHYDE REACTIONS......Page 40
2.2.6 SILANOL CONDENSATION......Page 45
2.2.7MISCELLANEOUS SYSTEMS......Page 47
2.3.1 DESCRIPTION OF THE DIFFERENT STAGES......Page 51
2.3.2 STYRENE COPOLYMERS AND POLYESTER ‘‘RESINS’’......Page 60
2.3.3 PHOTOPOLYMERIZATION OF (METH)ACRYLATES......Page 62
2.3.4 EPOXY REACTIONS......Page 63
2.3.5 OTHER RING-OPENING POLYMERIZATIONS (ROPS)......Page 70
2.3.6 MISCELLANEOUS......Page 73
REFERENCES......Page 76
3.1 INTRODUCTION......Page 78
3.1.1 GELATION......Page 79
3.1.2 POSTGEL STAGE......Page 83
3.1.3 MODELS OF NETWORK FORMATION......Page 85
3.2.1 A3 HOMOPOLYMERIZATION......Page 87
3.2.2 A4 + B2 STEPWISE POLYMERIZATION......Page 94
3.2.3 EXTENSION TO AF AND (AF + BG) STEPWISE POLYMERIZATIONS......Page 104
3.2.4 CYCLOTRIMERIZATION REACTIONS......Page 111
3.3 CHAINWISE POLYMERIZATIONS......Page 115
3.3.1 A2 HOMOPOLYMERIZATION......Page 116
3.3.2 A2 + AF CHAINWISE POLYMERIZATION......Page 119
3.4 HYDROLYTIC CONDENSATION OF ALKOXYSILANES......Page 125
NOTATION......Page 127
SUBSCRIPTS......Page 128
FURTHER READING......Page 129
4.1 INTRODUCTION......Page 130
4.2.1 PHENOMENOLOGICAL ASPECTS......Page 132
4.2.2 KINETIC ASPECTS......Page 135
4.2.3 GLASS TRANSITION TEMPERATURE AS A FUNCTION OF CONVERSION......Page 138
4.4.1 REGIONS OF THE CTT DIAGRAM......Page 145
4.4.2 ISOTHERMAL TRAJECTORIES......Page 146
4.4.3 POLYMERIZATION AT A CONSTANT HEATING RATE......Page 147
4.4.4 ADIABATIC TRAJECTORIES......Page 149
4.5 TIME–TEMPERATURE TRANSFORMATION (TTT) DIAGRAM......Page 150
NOTATION......Page 154
REFERENCES......Page 155
FURTHER READING......Page 156
5.1 INTRODUCTION......Page 157
5.2.1 PHENOMENOLOGICAL KINETIC EQUATIONS......Page 158
5.2.2 KINETIC EQUATIONS BASED ON A REACTION MODEL: STEPWISE POLYMERIZATIONS......Page 160
5.2.3 KINETIC EQUATIONS BASED ON A REACTION MODEL: CHAINWISE POLYMERIZATIONS......Page 164
5.3.1 EXPERIMENTAL MANIFESTATION OF THE EFFECT OF VITRIFICATION......Page 175
5.3.2 KINETIC MODELS INCLUDING DIFFUSION RATE CONSTANTS......Page 176
5.4 EXPERIMENTAL TECHNIQUES......Page 180
5.4.1 USE OF MODEL COMPOUNDS......Page 181
5.5 KINETIC EQUATIONS AND MASS BALANCES NOTATION......Page 192
GREEK LETTERS......Page 194
REFERENCES......Page 195
FURTHER READING......Page 196
6.1 INTRODUCTION......Page 197
6.2 EQUILIBRIUM MECHANICAL MEASUREMENTS......Page 198
6.3.1 SEARCH FOR AN EXPERIMENTAL CRITERION FOR GELATION......Page 199
6.3.2 EXPERIMENTAL EVIDENCE OF SINGULAR POWER LAWS AT THE GEL POINT......Page 202
6.3.3 SCALING LAWS AND GEL POINT DETERMINATION: A SEARCH FOR EXPONENTS......Page 203
6.3.4 DETERMINATION OF THE SECOND PHENOMENON: VITRIFICATION......Page 205
6.4.1 DIELECTRIC PARAMETERS AND REACTION......Page 208
6.4.2 CAN THE GELATION PHENOMENON BE OBSERVED FROM DIELECTRIC MEASUREMENTS?......Page 210
6.5 MAIN CONCLUSIONS......Page 212
NOTATION......Page 214
REFERENCES......Page 215
7.1.1 WHY THIS QUESTION?......Page 217
7.1.2 WHAT ARE INHOMOGENEITIES?......Page 218
7.1.3 HOW TO CHARACTERIZE INHOMOGENEITIES?......Page 219
7.1.4 AIM OF THIS CHAPTER......Page 221
7.2.1 IDEAL NETWORKS FROM STEPWISE POLYMERIZATIONS......Page 222
7.2.2 BUT THE STEP-POLYMERIZATION PROCESS CAN ALSO INDUCE INHOMOGENEITIES......Page 223
7.3.1 CHAINWISE POLYMERIZATION IS INTRINSICALLY AN INHOMOGENEOUS PROCESS......Page 228
7.3.2 NETWORK FORMATION IN THE CASE OF FREE-RADICAL POLYMERIZATION......Page 229
7.3.3 CONCLUSIONS ON THE CHAIN-POLYMERIZATION MECHANISM......Page 232
7.4.1 ARE CURED THERMOSETS INHOMOGENEOUS?......Page 233
7.4.2 IS THERE AWA Y TO CONTROL INHOMOGENEITIES?......Page 234
REFERENCES......Page 235
8.1 INTRODUCTION......Page 237
8.2.1 SOLUBILITY OF MAIN MODI.ERS USED......Page 238
8.2.2 DESCRIPTION OF THE REACTION-INDUCED PHASE SEPARATION PROCESS......Page 243
8.2.3 CONTROL OF GENERATED MORPHOLOGIES......Page 248
8.3.3 CORE-SHELL PARTICLES......Page 252
8.3.4 MISCELLANEOUS MODI.ERS......Page 253
NOTATION......Page 256
REFERENCES......Page 257
9.1 INTRODUCTION......Page 259
9.2 EXAMPLES OF PROCESSING TECHNOLOGIES......Page 260
9.3.1 SELECTION OF THE INITIAL TEMPERATURE......Page 262
9.3.2 CONTROL OF THE TEMPERATURE RISE......Page 263
9.4 CURE IN HEATED MOLDS......Page 266
9.5 AUTOCLAVE MOLDING OF GRAPHITE/EPOXY COMPOSITES......Page 274
9.6 FOAMING......Page 279
9.7 SHELL MOLDING (CRONING PROCESS)......Page 283
9.8CONCLUSIONS......Page 289
NOTATION......Page 290
REFERENCES......Page 291
FURTHER READING......Page 292
10.1 INTRODUCTION......Page 293
10.2.1 VOLUMETRIC PROPERTIES......Page 295
10.2.2 COHESIVE PROPERTIES......Page 301
10.2.3 LOCAL MOBILITY......Page 305
10.3.1 INTRODUCTION......Page 310
10.3.2 ‘‘IDEAL’’ NETWORKS......Page 311
10.3.3 HOMOGENEOUS, NONIDEAL NETWORKS......Page 318
10.3.4 INHOMOGENEOUS, ‘‘NONIDEAL’’ NETWORKS......Page 320
10.4.1 INTRODUCTION......Page 321
10.4.2 ENTROPIC ELASTICITY......Page 322
10.4.3 PROPERTIES LINKED TO THE SEGMENTAL MOBILITY......Page 327
10.5 CONCLUSIONS......Page 329
NOTATION......Page 330
REFERENCES......Page 332
11.1 INTRODUCTION......Page 334
11.2.1 BULK MODULUS......Page 337
11.2.2 SHEAR MODULUS......Page 340
11.2.3 TENSILE MODULUS......Page 341
11.2.4 POISSON’S RATIO......Page 343
11.2.5 ANTIPLASTICIZATION......Page 345
11.3.1 INTRODUCTION......Page 347
11.3.2 TRANSITIONS......Page 349
11.3.3 MODELING THE VISCOELASTIC BEHAVIOR IN THE FREQUENCY DOMAIN......Page 352
11.3.4 PRACTICAL USE OF COLE–COLE PLOTS. CHARACTERISTICS OF THERMOSETS......Page 355
11.3.5 TIME–TEMPERATURE RELATIONSHIPS......Page 356
11.4 CONCLUSIONS......Page 358
REFERENCES......Page 359
12.1 INTRODUCTION......Page 361
12.2.1 CLASSICAL TESTS......Page 362
12.2.2 FRACTURE MECHANICS......Page 365
12.2.3 DUCTILE-BRITTLE TRANSITION......Page 367
12.3.1 DEFORMATION MECHANISMS......Page 368
12.3.3 INFLUENCE OF THE STRESS STATE ON YIELDING STRESS AND YIELDING CRITERIA......Page 369
12.3.4 YIELDING THEORIES AND IN.UENCE OF PHYSICAL PARAMETERS (T, E)......Page 372
12.3.5 INFLUENCE OF NETWORK STRUCTURE ON YIELDING......Page 377
12.4.1 STATIC FAILURE......Page 382
12.4.2 INFLUENCE OF TEST VARIABLES (T,E) ON THE FRACTURE OF NETWORKS......Page 386
12.4.3 IMPACT STRENGTH OF THERMOSETS......Page 387
12.4.4 FATIGUE FAILURE OF THERMOSETS......Page 390
12.5 CONCLUSIONS......Page 394
NOTATION......Page 395
GREEK LETTERS......Page 396
REFERENCES......Page 397
13.1 INTRODUCTION......Page 400
13.2.1 ROLE OF THE INCLUSIONS IN THE INITIATION STEP (BEFORE THE APPEARANCE OF AN INTRINSIC DEFECT OR CRACK)......Page 401
13.2.2 ROLE OF THE PARTICLES DURING CRACK PROPAGATION......Page 403
13.3.1 FRACTURE MODELING OF RUBBER-MODI.ED EPOXY NETWORKS......Page 406
13.3.2 IN.UENCE OF NETWORK STRUCTURE AND MORPHOLOGY ON FRACTURE PROPERTIES OF EPOXY NETWORKS......Page 408
13.3.3 RUBBER TOUGHENING OF VINYL ESTER (VE) AND UNSATURATED POLYESTERS (UP)......Page 413
13.4.1 GENERALITIES......Page 414
13.4.2 INFLUENCE OF STRUCTURAL PARAMETERS ON THE TOUGHENING OF THERMOSETS BY INITIALLY MISCIBLE TPS......Page 415
13.4.3 TOUGHENING BY TP POWDERS......Page 416
13.5 TOUGHENING BY CORE-SHELL RUBBER (CSR) PARTICLES......Page 417
13.5.1 DESIGN OF THE CORE-SHELL RUBBER PARTICLES......Page 418
13.5.2 SPECIFIC TOUGHENING MECHANISMS WITH CSR PARTICLES......Page 419
13.5.3 INFLUENCE OF CSR STRUCTURAL PARAMETERS......Page 420
13.5.4 INFLUENCE OF MATRIX TG ON TOUGHNESS AND TOUGHENING MECHANISMS......Page 421
13.5.6 CONCLUSIONS......Page 422
13.6.1 USE OF LIQUID-CRYSTALLINE POLYMERS (LCP)......Page 423
13.6.2 RUBBER PLUS THERMOPLASTIC – TOUGHENED NETWORKS......Page 424
13.7 CONCLUSIONS......Page 425
NOTATION......Page 426
REFERENCES......Page 427
14.1 INTRODUCTION......Page 431
14.2.1 REVERSIBLE AND IRREVERSIBLE; PHYSICAL AND CHEMICAL AGING......Page 433
14.2.2 HYDROPHILICITY......Page 434
14.2.3 DIFFUSION......Page 439
14.2.4 PHYSICAL CONSEQUENCES OF WATER ABSORPTION......Page 441
14.2.5 MECHANICAL CONSEQUENCES OF WATER ABSORPTION......Page 443
14.3.1 THE‘‘IDEAL’’ CASEOF HYDROLYSIS......Page 444
14.3.2 DETERMINATION OF THE CONVERSION DEGREE IN THERMOSETS......Page 446
14.3.3 STRUCTURE–REACTIVITY RELATIONSHIPS......Page 448
14.3.4 LIFETIME CRITERION......Page 450
14.3.5 SOME ‘‘NONIDEAL’’ CASES OF HYDROLYTIC AGING......Page 451
14.4.1 INTRODUCTION, DEFINITIONS......Page 457
14.4.2 A BASIC KINETIC MODEL TO BEGIN THE STUDY OF POLYMER AGING......Page 458
14.4.3 STRUCTURE–STABILITY RELATIONSHIPS......Page 465
14.4.4 PRACTICAL ASPECTS OF THERMAL AGING: LIFETIME PREDICTION......Page 472
14.5 CONCLUSIONS......Page 476
GREEK LETTERS......Page 477
REFERENCES......Page 478