Advances in Polymer Sciences Also Available Electronically 7
Aims and Scope 8
Preface 9
References 10
Obituary 11
Contents 13
Making Flory-Huggins Practical: Thermodynamics of Polymer-Containing Mixtures 15
1 Introduction 18
2 Extension of the Flory-Huggins Theory 19
2.1 Binary Systems 19
2.1.1 Polymer Solutions 19
Organic Solvents/Linear Homopolymers 19
Organic Solvents/Branched Homopolymers 30
Organic Solvents/Linear Random Copolymers 30
Polymer Solutions: Special Interactions 31
Water/Polysaccharides 31
Organic Solvents/Block Copolymers 32
2.1.2 Polymer Blends 32
2.1.3 Mixed Solvents 35
2.2 Ternary Systems 35
3 Measuring Methods 38
3.1 Vapor Pressure Measurements 38
3.2 Osmometry and Scattering Methods 39
3.3 Other Methods 40
4 Experimental Results and Modeling 41
4.1 Binary Systems 41
4.1.1 Polymer Solutions 41
Organic Solvents/Linear Homopolymers 41
Organic Solvents/Nonlinear Homopolymers 51
Organic Solvents/Linear Random Copolymers 52
Aqueous Solutions of Poly(vinyl methyl ether) 54
Swelling of Cellulose in Water 57
Aqueous Solutions of Pullulan and Dextran 59
Nonselective Solvent/Block Copolymers 60
4.1.2 Polymer Blends 62
Poly(vinyl methyl ether)/Polystyrene 62
Shape-Induced Polymer Incompatibility 64
4.1.3 Mixtures of Low Molecular Weight Liquids 66
4.2 Ternary Systems 67
4.2.1 Mixed Solvents 67
Simplicity 68
Cosolvency 68
Cononsolvency 69
Complex Behavior 70
4.2.2 Blend Solutions 71
Simplicity 71
Cosolvency 72
Cononsolvency 73
5 Conclusions 76
References 77
Aqueous Solutions of Polyelectrolytes: Vapor-Liquid Equilibrium and Some Related Properties 81
1 Introduction 88
2 Structure and Characterization of Polyelectrolytes 90
3 Experimental Data for the Vapor-Liquid Equilibrium of Aqueous Polyelectrolyte Solutions 94
3.1 Aqueous Solutions of a Single Polyelectrolyte 95
3.2 Aqueous Solutions of a Single Polyelectrolyte and a Low Molecular Weight Strong Electrolyte 99
4 Gibbs Energy of Aqueous Solutions of Polyelectrolytes 105
5 Thermodynamic Models 108
5.1 Cell Model of Lifson and Katchalsky 109
5.2 Counterion Condensation Theory of Manning 115
5.2.1 Contribution from the Polymer 117
5.2.2 Contribution from Condensed Counterions 118
5.2.3 Contribution from Free Counterions 120
5.2.4 Contribution from Coions 121
5.2.5 Contribution from Water 121
5.3 Modifications of Manning麓s Theory 122
5.4 NRTL Model of Nagvekar and Danner 123
5.5 Pessoa麓s Modification of the Pitzer Model 127
5.6 VERS-PE Model 131
6 Summary 145
References 145
Gas-Polymer Interactions: Key Thermodynamic Data and Thermophysical Properties 151
1 Introduction 152
2 Experimental Techniques 154
2.1 Gas Sorption and Solubility 154
2.1.1 Gravimetric Techniques 154
2.1.2 Coupled VW-pVT Technique 155
Vibrating-Wire Sensor 155
pVT Method and Pressure Decay Measurements 156
2.2 pVT-Calorimetry: Scanning Transitiometry 158
3 Gas-Polymer Interactions and Practical Applications 163
3.1 Evaluation of Gas Solubility and Associated Swelling 164
3.1.1 Coupled VW-pVT Method: Theory and Modeling 164
3.1.2 Selected Example: The {CO2 + MDPE} System 165
3.2 Gas-Polymer Interaction Energy 167
3.3 Thermophysical Properties at High Pressures 167
3.4 Phase Transition at High Pressures 175
3.4.1 First-Order Transitions 175
Melting/Crystallization at High Pressures (Hydrostatic Effect) 175
Gas-Assisted Melting/Crystallization at High Pressures (Plasticizing Effect) 175
3.4.2 Isotropic Transitions (Self-Assembling of Polymeric Structures Under High-Pressure Gas Sorption) 178
3.4.3 Glass Transitions 183
Glass Transitions at High Pressures (Hydrostatic Effect) 183
Gas-Assisted Glass Transitions at High Pressures (Plasticizing Effect) 185
4 Conclusion 188
References 189
Interfacial Tension in Binary Polymer Blends and the Effects of Copolymers as Emulsifying Agents 192
1 Introduction 193
2 Methods of Measuring Interfacial Tension 196
3 Interfacial Tension in Binary Polymer Blends 202
3.1 Experimental Studies of Polymer Interfacial Tension 202
3.2 Theories of Polymer-Polymer Interfaces 209
3.2.1 Semiempirical Theories of Polymer Interfaces 212
3.2.2 Microscopic Theories of Polymer Interfaces 215
3.2.3 Square-Gradient Approach 222
Generalized Gradient Theory of Fluids 223
The Square-Gradient Theory Applied to Polymer Interfaces 226
3.2.4 Theories Near the Critical Point 235
4 Copolymers as Emulsifying Agents in Polymer Blends 238
4.1 Copolymer Localization at the Polymer Blend Interface 238
4.2 Experimental Studies on the Effect of Additives on Polymer-Polymer Interfacial Tension 241
4.3 Theories of the Interfacial Behavior in Homopolymer/Homopolymer/Copolymer Blends 251
4.3.1 The Noolandi and Hong Theory 252
4.3.2 Leibler Theory for Nearly Compatible Systems 257
4.3.3 Leibler Theory for Strongly Incompatible Systems and Its Modification 259
Diblock Copolymer Additives 259
Graft Copolymer Additives 263
5 Concluding Remarks 267
References 271
Theory of Random Copolymer Fractionation in Columns 283
1 Introduction 286
2 Theory 288
2.1 Liquid-Liquid Phase Equilibrium of Copolymer Solutions 288
2.2 Stepwise Fractionation Procedure 296
2.3 Baker-Williams Fractionation 300
2.4 Continuous Polymer Fractionation 303
3 Results and Discussion 308
3.1 Liquid-Liquid Phase Equilibrium of Copolymer Solutions 308
3.2 Stepwise Fractionation Procedure 311
3.2.1 Influence of the Fractionation Strategy 312
3.2.2 Influence of the Solvent Mixture 314
3.2.3 Cross-Fractionation 317
3.3 Baker-Williams Fractionation 321
3.4 Continuous Polymer Fractionation 328
4 Summary 336
References 337
Computer Simulations and Coarse-Grained Molecular Models Predicting the Equation of State of Polymer Solutions 341
1 Introduction 343
2 Molecular Models for Polymers and Solvents 345
2.1 Atomistic Models 345
2.2 Coarse-Grained Models in the Continuum and on the Lattice 353
2.3 Mapping Atomistic Models to Coarse-Grained Models 358
3 Basic Aspects of Simulation Methods 367
3.1 Molecular Dynamics 367
3.2 Monte Carlo 374
4 Modeling the Phase Behavior of Some Polymer Solutions: Case Studies 378
4,1 Alkanes in Carbon Dioxide 378
4.2 Alkanes in Dipolar Solvents 382
4.3 Solutions of Stiff Polymers and the Isotropic-Nematic Transition 384
4.4 Solutions of Block Copolymers and Micelle Formation 387
5 Conclusions and Outlook 390
References 392
Modeling of Polymer Phase Equilibria Using Equations of State 400
1 Introduction 403
2 Equations of State 403
3 Estimation of Model Parameters 410
4 Modeling of Homopolymer Systems 412
5 Extension to Copolymers 416
6 Accounting for the Influence of Polydispersity 419
7 Summary 425
References 427
Index 430