[PDF] [2011] Polymer Thermodynamics Liquid Polymer-Containing Mi torrent

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Making Flory-Huggins Practical: Thermodynamics of Polymer-Containing Mixtures, by B. A. Wolf*Aqueous Solutions of Polyelectrolytes: Vapor-Liquid Equilibrium and Some Related Properties, by G. Maurer, S. Lammertz, and L. Ninni Schäfer*Gas-Polymer Interactions: Key Thermodynamic Data and Thermophysical Properties, by J.-P. E. Grolier, and S. A.E. Boyer*Interfacial Tension in Binary Polymer Blends and the Effects of Copolymers as Emulsifying Agents, by S. H. Anastasiadis*Theory of Random Copolymer Fractionation in Columns, by Sabine Enders*Computer Simulations and Coarse-Grained Molecular Models Predicting the Equation of State of Polymer Solutions, by K. Binder, B. Mognetti, W. Paul, P. Virnau, and L. Yelash*Modeling of Polymer Phase Equilibria Using Equations of State, by G. Sadowski



Contents

Making Flory-Huggins Practical: Thermodynamics of Polymer-Containing Mixtures

1 Introduction

2 Extension of the Flory-Huggins Theory

2.1 Binary Systems

2.1.1 Polymer Solutions

Organic Solvents/Linear Homopolymers

Organic Solvents/Branched Homopolymers

Organic Solvents/Linear Random Copolymers

Polymer Solutions: Special Interactions

Water/Polysaccharides

Organic Solvents/Block Copolymers

2.1.2 Polymer Blends

2.1.3 Mixed Solvents

2.2 Ternary Systems

3 Measuring Methods

3.1 Vapor Pressure Measurements

3.2 Osmometry and Scattering Methods

3.3 Other Methods

4 Experimental Results and Modeling

4.1 Binary Systems

4.1.1 Polymer Solutions

Organic Solvents/Linear Homopolymers

Organic Solvents/Nonlinear Homopolymers

Organic Solvents/Linear Random Copolymers

Aqueous Solutions of Poly(vinyl methyl ether)

Swelling of Cellulose in Water

Aqueous Solutions of Pullulan and Dextran

Nonselective Solvent/Block Copolymers

4.1.2 Polymer Blends

Poly(vinyl methyl ether)/Polystyrene

Shape-Induced Polymer Incompatibility

4.1.3 Mixtures of Low Molecular Weight Liquids

4.2 Ternary Systems

4.2.1 Mixed Solvents

Simplicity

Cosolvency

Cononsolvency

Complex Behavior

4.2.2 Blend Solutions

Simplicity

Cosolvency

Cononsolvency

5 Conclusions

References

Aqueous Solutions of Polyelectrolytes: Vapor-Liquid Equilibrium and Some Related Properties

1 Introduction

2 Structure and Characterization of Polyelectrolytes

3 Experimental Data for the Vapor-Liquid Equilibrium of Aqueous Polyelectrolyte Solutions

3.1 Aqueous Solutions of a Single Polyelectrolyte

3.2 Aqueous Solutions of a Single Polyelectrolyte and a Low Molecular Weight Strong Electrolyte

4 Gibbs Energy of Aqueous Solutions of Polyelectrolytes

5 Thermodynamic Models

5.1 Cell Model of Lifson and Katchalsky

5.2 Counterion Condensation Theory of Manning

5.2.1 Contribution from the Polymer

5.2.2 Contribution from Condensed Counterions

5.2.3 Contribution from Free Counterions

5.2.4 Contribution from Coions

5.2.5 Contribution from Water

5.3 Modifications of Manning´s Theory

5.4 NRTL Model of Nagvekar and Danner

5.5 Pessoa´s Modification of the Pitzer Model

5.6 VERS-PE Model

6 Summary

References

Gas-Polymer Interactions: Key Thermodynamic Data and Thermophysical Properties

1 Introduction

2 Experimental Techniques

2.1 Gas Sorption and Solubility

2.1.1 Gravimetric Techniques

2.1.2 Coupled VW-pVT Technique

Vibrating-Wire Sensor

pVT Method and Pressure Decay Measurements

2.2 pVT-Calorimetry: Scanning Transitiometry

3 Gas-Polymer Interactions and Practical Applications

3.1 Evaluation of Gas Solubility and Associated Swelling

3.1.1 Coupled VW-pVT Method: Theory and Modeling

3.1.2 Selected Example: The {CO2 + MDPE} System

3.2 Gas-Polymer Interaction Energy

3.3 Thermophysical Properties at High Pressures

3.4 Phase Transition at High Pressures

3.4.1 First-Order Transitions

Melting/Crystallization at High Pressures (Hydrostatic Effect)

Gas-Assisted Melting/Crystallization at High Pressures (Plasticizing Effect)

3.4.2 Isotropic Transitions (Self-Assembling of Polymeric Structures Under High-Pressure Gas Sorption)

3.4.3 Glass Transitions

Glass Transitions at High Pressures (Hydrostatic Effect)

Gas-Assisted Glass Transitions at High Pressures (Plasticizing Effect)

4 Conclusion

References

Interfacial Tension in Binary Polymer Blends and the Effects of Copolymers as Emulsifying Agents

1 Introduction

2 Methods of Measuring Interfacial Tension

3 Interfacial Tension in Binary Polymer Blends

3.1 Experimental Studies of Polymer Interfacial Tension

3.2 Theories of Polymer-Polymer Interfaces

3.2.1 Semiempirical Theories of Polymer Interfaces

3.2.2 Microscopic Theories of Polymer Interfaces

3.2.3 Square-Gradient Approach

Generalized Gradient Theory of Fluids

The Square-Gradient Theory Applied to Polymer Interfaces

3.2.4 Theories Near the Critical Point

4 Copolymers as Emulsifying Agents in Polymer Blends

4.1 Copolymer Localization at the Polymer Blend Interface

4.2 Experimental Studies on the Effect of Additives on Polymer-Polymer Interfacial Tension

4.3 Theories of the Interfacial Behavior in Homopolymer/Homopolymer/Copolymer Blends

4.3.1 The Noolandi and Hong Theory

4.3.2 Leibler Theory for Nearly Compatible Systems

4.3.3 Leibler Theory for Strongly Incompatible Systems and Its Modification

Diblock Copolymer Additives

Graft Copolymer Additives

5 Concluding Remarks

References

Theory of Random Copolymer Fractionation in Columns

1 Introduction

2 Theory

2.1 Liquid-Liquid Phase Equilibrium of Copolymer Solutions

2.2 Stepwise Fractionation Procedure

2.3 Baker-Williams Fractionation

2.4 Continuous Polymer Fractionation

3 Results and Discussion

3.1 Liquid-Liquid Phase Equilibrium of Copolymer Solutions

3.2 Stepwise Fractionation Procedure

3.2.1 Influence of the Fractionation Strategy

3.2.2 Influence of the Solvent Mixture

3.2.3 Cross-Fractionation

3.3 Baker-Williams Fractionation

3.4 Continuous Polymer Fractionation

4 Summary

References

Computer Simulations and Coarse-Grained Molecular Models Predicting the Equation of State of Polymer Solutions

1 Introduction

2 Molecular Models for Polymers and Solvents

2.1 Atomistic Models

2.2 Coarse-Grained Models in the Continuum and on the Lattice

2.3 Mapping Atomistic Models to Coarse-Grained Models

3 Basic Aspects of Simulation Methods

3.1 Molecular Dynamics

3.2 Monte Carlo

4 Modeling the Phase Behavior of Some Polymer Solutions: Case Studies

4,1 Alkanes in Carbon Dioxide

4.2 Alkanes in Dipolar Solvents

4.3 Solutions of Stiff Polymers and the Isotropic-Nematic Transition

4.4 Solutions of Block Copolymers and Micelle Formation

5 Conclusions and Outlook

References

Modeling of Polymer Phase Equilibria Using Equations of State

1 Introduction

2 Equations of State

3 Estimation of Model Parameters

4 Modeling of Homopolymer Systems

5 Extension to Copolymers

6 Accounting for the Influence of Polydispersity

7 Summary

References

Index