Polymeric Liquids & Networks: Structure and Properties

✍ Scribed by William W. Graessley

• Publisher: Garland Science
• Year: 2003
• Tongue: English
• Leaves: 577
• Edition: 1
• Category: Library

✦ Synopsis

Polymeric Liquids and Networks: Structure and Properties is the first book of two by William W. Graessley that presents a unified view of flexible-chain polymer liquids and networks. The topics of both volumes range from equilibrium properties to dynamic response, finite deformation behavior and non-Newtonian flow. The second book will be titled Polymeric Liquids and Networks: Dynamics and Rheology. These various aspects of the field were developed over the past 70 years by researchers from many academic disciplines. The infusion of fresh viewpoints continually invigorated and enriched the field, making polymeric liquids and networks a truly interdisciplinary subject. The lack of a common terminology and perspective, however, has led to compartmentalization, making it difficult for a newcomer, even one technically trained, to gain a broad appreciation of the field and to see the relationships among its various parts. The aim of these two books, without diluting the substance, is to achieve a desired unity.Polymeric Liquids and Networks emphasizes fundamental principles and a molecular viewpoint. The conceptual basis of theories underlying each topical area is explained with derivations sometimes outlined briefly and sometimes given in detail. Technical terminology is kept to a minimum necessary for coherent presentation. The goal of the text is to provide an informed understanding rather than detailed technical proficiency. Theory, experiment, and simulation are woven together as appropriate for achieving a balanced view. The books are designed to serve academic and industrial needs, consolidating the understanding of topics with both practical and fundamental significance, and written from a technical but non-specialized perspective.The books deal mainly with non-polar and weakly polar species and largely with results derived from experiments on structurally well-defined systems. The objective is not to ignore the more complex systems, which are pervasive in both nature and industry and important in their own right. Much space is devoted to structural distributions, their characterization and their effect on properties. It is rather to provide a framework for better understanding of all polymeric liquids by identifying, in the simplest possible circumstances, the universal attributes of a chain-like and flexible molecular structure.

✦ Table of Contents

Cover......Page 1
Polymeric Liquids and Networks......Page 5
Contents......Page 9
Preface......Page 15
1.1 Molecular Nature of Polymers......Page 19
1.2 Polymeric Structure......Page 24
1.2.1 Chemical Microstructure......Page 25
1.2.3 Rotational States......Page 28
1.3 Polymeric Properties......Page 30
1.3.1 Species Dependence......Page 31
Viscosity.......Page 32
Viscoelastic behavior.......Page 34
1.4 Macromolecular Heterogeneity......Page 35
1.4.1 Averages......Page 36
1.4.2 Distribution Functions......Page 38
Exponential distribution.......Page 39
Distributions from branching and scission.......Page 40
Empirical distribution functions.......Page 43
1.5 Molecular Simulations......Page 45
REFERENCES......Page 46
CHAPTER 2 Molecular Liquids......Page 47
2.1.1 Intermolecular Forces......Page 53
2.1.2 Terminology......Page 56
2.1.3 Statistical Thermodynamics......Page 58
2.1.4 Pair Distributions and Intermolecular Energy......Page 61
2.1.5 Principles of Elastic Scattering......Page 64
2.1.6 The Structure Factor......Page 70
2.2.1 Scattering by Pure Liquids......Page 73
2.2.2 The van der Waals Liquid......Page 77
2.2.3 Hard-Sphere Liquids......Page 79
2.3.1 The Longuet-Higgins and Widom Model......Page 81
2.3.2 Cell Models......Page 84
2.3.3 Lattice Models......Page 85
2.3.4 Reduced Equations of State......Page 87
2.3.5 Cohesive Energy and Internal Pressure......Page 88
REFERENCES......Page 91
3.1 Thermodynamics of Liquid Mixtures......Page 95
3.2 Liquid-Liquid Phase Behavior......Page 101
3.3 Molecular Aspects of Mixing......Page 107
3.4 Simple Mixtures......Page 112
3.4.1 Properties of the Interaction Parameter......Page 114
3.4.2 Phase Behavior......Page 116
3.4.3 Observations......Page 118
3.5 Regular Mixtures......Page 121
3.5.1 Commentary......Page 123
3.5.2 Volume Change on Mixing......Page 125
3.6 The Free Volume Effect......Page 127
3.6.1 Modified FOV Theory......Page 129
3.6.2 The Free Volume Interaction Parameter......Page 132
3.6.3 Commentary......Page 134
REFERENCES......Page 135
CHAPTER 4 The Random Coil Model......Page 139
4.1 Random Walks......Page 141
4.1.1 Average End-to-End Distance......Page 142
4.1.2 Radius of Gyration......Page 143
4.2 Polymer Chains......Page 146
4.2.1 Locally Restricted Conformations......Page 147
4.2.2 Step Length Definitions......Page 150
4.3 Nonlinear Molecules......Page 154
4.3.1 Branched Chains......Page 155
4.3.2 Macrocycles......Page 158
4.5 Conformational Distributions......Page 160
4.5.1 The End-to-End Vector Distribution......Page 161
4.5.2 The Gaussian Form......Page 165
4.5.3 Mass Distribution for Gaussian Coils......Page 166
4.6.1 Mechanical Properties......Page 167
4.6.2 Thermodynamic Properties......Page 168
4.7.1 Form Factors......Page 170
Random coil molecules.......Page 172
Pair distributions.......Page 173
General properties.......Page 174
4.7.2 Structure Factors......Page 176
One-component systems.......Page 177
Incompressible mixtures.......Page 178
REFERENCES......Page 183
5.1 Thermodynamic Characterization Methods......Page 185
5.1.1 Osmotic Pressure......Page 186
5.1.2 Light Scattering......Page 189
Fundamentals.......Page 190
Dilute solutions.......Page 193
Scattering method comparisons.......Page 200
5.2 Dynamic Characterization Methods......Page 202
5.2.1 Dynamic Light Scattering......Page 203
5.2.2 Viscometry......Page 207
5.3.1 Size Exclusion Chromatography......Page 210
5.3.2 Multidetector Methods......Page 215
REFERENCES......Page 217
6.1 Intramolecular Interactions......Page 221
6.1.1 Excluded Volume......Page 222
Pervaded volume and self-concentration.......Page 223
Self-exclusion.......Page 226
6.1.2 Hydrodynamic Interaction......Page 235
6.2 Linear Polymers......Page 240
6.2.1 Limiting Size Ratios......Page 241
6.2.2 Expansion Factors......Page 242
6.2.3 Good Solvent Master Curves......Page 245
Master curve forms.......Page 249
Onset molecular weights.......Page 250
6.3 Branched and Macrocyclic Polymers......Page 253
Regular stars.......Page 255
Rings.......Page 257
Combs.......Page 261
6.3.2 Lightly Branched Statistical Structures......Page 265
6.3.3 Highly Branched Structures......Page 267
Daoud-Cotton model.......Page 269
Many-arm star properties.......Page 272
Colloidal analogies.......Page 273
6.4 Concentration Regimes......Page 275
REFERENCES......Page 277
CHAPTER 7 Polymer Solutions......Page 283
7.1.1 Chain Dimensions in Polymer Melts......Page 284
Excluded volume screening.......Page 287
Concentration dependence.......Page 291
Semidilute-concentrated crossover.......Page 292
Observations.......Page 294
7.2 Osmotic Pressure beyond Overlap......Page 296
7.2.1 Flory-Huggins Predictions......Page 298
7.2.2 Scaling Analysis......Page 301
7.2.3 Experimental Observations......Page 302
7.3.1 Correlation Length......Page 304
7.3.2 The Random Phase Approximation......Page 311
7.3.3 Interpretation Alternatives......Page 313
7.3.4 Branch-Induced Ordering......Page 314
7.4 The Interaction Parameter......Page 315
Vapor composition and sorption.......Page 316
Osmometry.......Page 317
Scattering.......Page 318
7.4.2 Interpretation of χ......Page 322
Free volume effects.......Page 324
Impact on dilute solutions.......Page 330
Athermal solutions.......Page 331
7.5.1 Upper Critical Behavior......Page 332
7.5.2 Lower Critical Behavior......Page 338
7.5.3 Scattering and Criticality......Page 341
7.5.4 The Ginzburg Criterion......Page 347
REFERENCES......Page 353
CHAPTER 8 Polymer Blends......Page 359
8.1 Molecular Interactions......Page 361
8.2 Isotopic Blends......Page 365
8.2.1 Isotopic Interactions......Page 366
Experimental aspects.......Page 367
8.2.2 Temperature Dependence of the Interactions......Page 370
8.2.3 Some Properties of χHD......Page 373
8.3 Polyolefin Blends......Page 374
8.3.1 Measurements......Page 375
8.3.2 Observations......Page 377
8.3.3 Solubility Parameters......Page 382
Molecular considerations.......Page 385
PVT measurements.......Page 387
Simulations.......Page 390
Temperature dependence.......Page 393
Pressure dependence.......Page 395
Molecular weight dependence.......Page 396
Composition dependence.......Page 397
8.3.5 Irregular Blends......Page 399
8.4 Hydrocarbon Polymer Blends......Page 403
8.4.1 Inter-Family Blends.......Page 406
8.4.2 Intra-Family Blends......Page 407
8.4.3 Commentary......Page 409
8.5.1 Sequencing Effects......Page 411
8.5.2 Mean Composition Effects......Page 412
8.6 Blends with Specific Associations......Page 417
REFERENCES......Page 421
CHAPTER 9 Network Structure and Elasticity......Page 427
9.1 Equal Reactivity and Random Linking......Page 429
9.1.1 Network Connectivity......Page 431
9.1.3 Linking Statistics......Page 436
9.2 Structurally Related Observables......Page 438
9.2.1 Pre-Gelation Region......Page 439
9.2.2 The Gel Curve......Page 441
9.3 Elasticity-Related Properties......Page 445
9.3.1 Active Junctions and Strands......Page 446
9.3.2 Topological and Dynamics-Related Properties......Page 449
9.3.3 Architectural Characterization......Page 453
9.4 General Considerations on Network Elasticity......Page 454
9.5 The Affine Network......Page 459
9.5.1 The Logarithmic Contribution......Page 461
9.5.2 Effects of Temperature and Volume Change......Page 463
9.5.3 Network Pressure......Page 464
9.6 The Phantom Network......Page 465
9.7 The Entangled Network......Page 470
9.7.1 Modulus Magnitude......Page 471
9.7.2 Experimental Tests......Page 474
REFERENCES......Page 484
CHAPTER 10 Network Properties......Page 489
10.1 Stress-Strain Behavior......Page 490
10.1.1 The Mooney-Rivlin Form......Page 494
10.1.2 Swelling and Supercoiling Effects......Page 497
10.1.3 The Ferry-Kan Formulation......Page 505
10.2 Swelling Equilibrium......Page 508
10.3 Thermoelasticity......Page 519
10.4 Observations on Networks......Page 526
Neutron scattering.......Page 527
10.5 Modeling Uncrossability......Page 532
10.5.1 Topological Classification......Page 537
10.5.2 Slip-Links......Page 540
10.5.4 Tube Models......Page 542
Affine models.......Page 544
Constant mesh density models.......Page 545
Nonaffine models.......Page 546
10.5.5 Commentary......Page 548
REFERENCES......Page 549
Appendix A —Symbols......Page 555
Subject Index......Page 561
Author Index......Page 567