Polymer Thermodynamics: Liquid Polymer-Containing Mixtures (Advances in Polymer Science)

front-matter......Page 1
Polymer Thermodynamics......Page 3
Advances in Polymer Sciences Also Available Electronically......Page 7
Aims and Scope......Page 8
Preface......Page 9
References......Page 10
Obituary......Page 11
Contents......Page 13
Making Flory-Huggins Practical: Thermodynamics of Polymer-Containing Mixtures......Page 14
1 Introduction......Page 17
Organic Solvents/Linear Homopolymers......Page 18
Organic Solvents/Linear Random Copolymers......Page 29
Water/Polysaccharides......Page 30
2.1.2 Polymer Blends......Page 31
2.2 Ternary Systems......Page 34
3.1 Vapor Pressure Measurements......Page 37
3.2 Osmometry and Scattering Methods......Page 38
3.3 Other Methods......Page 39
Organic Solvents/Linear Homopolymers......Page 40
Organic Solvents/Nonlinear Homopolymers......Page 50
Organic Solvents/Linear Random Copolymers......Page 51
Aqueous Solutions of Poly(vinyl methyl ether)......Page 53
Swelling of Cellulose in Water......Page 56
Aqueous Solutions of Pullulan and Dextran......Page 58
Nonselective Solvent/Block Copolymers......Page 59
Poly(vinyl methyl ether)/Polystyrene......Page 61
Shape-Induced Polymer Incompatibility......Page 63
4.1.3 Mixtures of Low Molecular Weight Liquids......Page 65
4.2.1 Mixed Solvents......Page 66
Cosolvency......Page 67
Cononsolvency......Page 68
Complex Behavior......Page 69
Simplicity......Page 70
Cosolvency......Page 71
Cononsolvency......Page 72
5 Conclusions......Page 75
References......Page 76
Aqueous Solutions of Polyelectrolytes: Vapor-Liquid Equilibrium and Some Related Properties......Page 80
1 Introduction......Page 87
2 Structure and Characterization of Polyelectrolytes......Page 89
3 Experimental Data for the Vapor-Liquid Equilibrium of Aqueous Polyelectrolyte Solutions......Page 93
3.1 Aqueous Solutions of a Single Polyelectrolyte......Page 94
3.2 Aqueous Solutions of a Single Polyelectrolyte and a Low Molecular Weight Strong Electrolyte......Page 98
4 Gibbs Energy of Aqueous Solutions of Polyelectrolytes......Page 104
5 Thermodynamic Models......Page 107
5.1 Cell Model of Lifson and Katchalsky......Page 108
5.2 Counterion Condensation Theory of Manning......Page 114
5.2.1 Contribution from the Polymer......Page 116
5.2.2 Contribution from Condensed Counterions......Page 117
5.2.3 Contribution from Free Counterions......Page 119
5.2.5 Contribution from Water......Page 120
5.3 Modifications of Manning´s Theory......Page 121
5.4 NRTL Model of Nagvekar and Danner......Page 122
5.5 Pessoa´s Modification of the Pitzer Model......Page 126
5.6 VERS-PE Model......Page 130
References......Page 144
Gas-Polymer Interactions: Key Thermodynamic Data and Thermophysical Properties......Page 150
1 Introduction......Page 151
2.1.1 Gravimetric Techniques......Page 153
Vibrating-Wire Sensor......Page 154
pVT Method and Pressure Decay Measurements......Page 155
2.2 pVT-Calorimetry: Scanning Transitiometry......Page 157
3 Gas-Polymer Interactions and Practical Applications......Page 162
3.1.1 Coupled VW-pVT Method: Theory and Modeling......Page 163
3.1.2 Selected Example: The {CO2 + MDPE} System......Page 164
3.3 Thermophysical Properties at High Pressures......Page 166
Gas-Assisted Melting/Crystallization at High Pressures (Plasticizing Effect)......Page 174
3.4.2 Isotropic Transitions (Self-Assembling of Polymeric Structures Under High-Pressure Gas Sorption)......Page 177
Glass Transitions at High Pressures (Hydrostatic Effect)......Page 182
Gas-Assisted Glass Transitions at High Pressures (Plasticizing Effect)......Page 184
4 Conclusion......Page 187
References......Page 188
Interfacial Tension in Binary Polymer Blends and the Effects of Copolymers as Emulsifying Agents......Page 191
1 Introduction......Page 192
2 Methods of Measuring Interfacial Tension......Page 195
3.1 Experimental Studies of Polymer Interfacial Tension......Page 201
3.2 Theories of Polymer-Polymer Interfaces......Page 208
3.2.1 Semiempirical Theories of Polymer Interfaces......Page 211
3.2.2 Microscopic Theories of Polymer Interfaces......Page 214
3.2.3 Square-Gradient Approach......Page 221
Generalized Gradient Theory of Fluids......Page 222
The Square-Gradient Theory Applied to Polymer Interfaces......Page 225
3.2.4 Theories Near the Critical Point......Page 234
4.1 Copolymer Localization at the Polymer Blend Interface......Page 237
4.2 Experimental Studies on the Effect of Additives on Polymer-Polymer Interfacial Tension......Page 240
4.3 Theories of the Interfacial Behavior in Homopolymer/Homopolymer/Copolymer Blends......Page 250
4.3.1 The Noolandi and Hong Theory......Page 251
4.3.2 Leibler Theory for Nearly Compatible Systems......Page 256
Diblock Copolymer Additives......Page 258
Graft Copolymer Additives......Page 262
5 Concluding Remarks......Page 266
References......Page 270
Theory of Random Copolymer Fractionation in Columns......Page 282
1 Introduction......Page 285
2.1 Liquid-Liquid Phase Equilibrium of Copolymer Solutions......Page 287
2.2 Stepwise Fractionation Procedure......Page 295
2.3 Baker-Williams Fractionation......Page 299
2.4 Continuous Polymer Fractionation......Page 302
3.1 Liquid-Liquid Phase Equilibrium of Copolymer Solutions......Page 307
3.2 Stepwise Fractionation Procedure......Page 310
3.2.1 Influence of the Fractionation Strategy......Page 311
3.2.2 Influence of the Solvent Mixture......Page 313
3.2.3 Cross-Fractionation......Page 316
3.3 Baker-Williams Fractionation......Page 320
3.4 Continuous Polymer Fractionation......Page 327
4 Summary......Page 335
References......Page 336
Computer Simulations and Coarse-Grained Molecular Models Predicting the Equation of State of Polymer Solutions......Page 340
1 Introduction......Page 342
2.1 Atomistic Models......Page 344
2.2 Coarse-Grained Models in the Continuum and on the Lattice......Page 352
2.3 Mapping Atomistic Models to Coarse-Grained Models......Page 357
3.1 Molecular Dynamics......Page 366
3.2 Monte Carlo......Page 373
4,1 Alkanes in Carbon Dioxide......Page 377
4.2 Alkanes in Dipolar Solvents......Page 381
4.3 Solutions of Stiff Polymers and the Isotropic-Nematic Transition......Page 383
4.4 Solutions of Block Copolymers and Micelle Formation......Page 386
5 Conclusions and Outlook......Page 389
References......Page 391
Modeling of Polymer Phase Equilibria Using Equations of State......Page 399
2 Equations of State......Page 402
3 Estimation of Model Parameters......Page 409
4 Modeling of Homopolymer Systems......Page 411
5 Extension to Copolymers......Page 415
6 Accounting for the Influence of Polydispersity......Page 418
7 Summary......Page 424
References......Page 426
Index......Page 429