Polymer Thermodynamics: Blends, Copolymers and Reversible Polymerization

Polymer Thermodynamics: Blends, Copolymers and Reversible Polymerization describes the thermodynamic basis for miscibility as well as the mathematical models used to predict the compositional window of miscibility and construct temperature versus volume-fraction phase diagrams. The book covers the binary interaction model, the solubility parameter approach, and the entropic difference model. Using equation of state (EOS) theories, thermodynamic models, and information from physical properties, it illustrates the construction of phase envelopes.

The book presents nine EOS theories, including some that take into account molecular weight effects. Characteristic values are given in tables. It uses the binary interaction model to predict the compositional window of miscibility for copolymer/homopolymer blends and blends of copolymers and terpolymers with common monomers. It discusses Hansen fractional solubility parameter values, six phase diagram types, the role of polymer architecture in phase behavior, and the mathematical framework for multiple glass transition temperatures found in partially miscible polymer blends. The author also illustrates biomedical and commercial applications of nanocomposites, the properties of various polymer alloys, Fick’s laws of diffusion and their implications during transient events, and the use of the dynamic programming method in the sequence alignment of DNA and proteins. The final chapter reviews the thermodynamics of reversible polymerization and copolymerization.

Polymer blends offer improved performance/cost ratios and the flexibility to tailor products to suit customers’ needs. Exploring physical phenomena, such as phase separation, this book provides readers with methods to design polymer blends and predict the phase behavior of binary polymer blends using desktop computers.

Key Features:

Describes thermodynamic models and EOS theories for polymers

Distinguishes compatibilized blends from miscible blends

Discusses negative pressure and negative thermal expansivity

Derives expressions for enthalpy and entropy of copolymerization, the chain sequence distribution of copolymers, and the Clapeyron equation for reversible polymerization

Covers natural polymer systems, copolymer/homopolymer blends, blends of copolymers and terpolymers with common monomers; and polymer nanocomposites

Presents the five laws of thermodynamics, glass transition temperature, and probability distributions Includes more than 500 end-of-chapter exercises

1. Introduction to Polymer Blends

History of Polymer Blends

Flory–Huggin’s Solution Theory—and Beyond

Miscible Polymer Blends

Partially Miscible Polymer Blends

Natural Polymers

Polymer Alloy

2. Equation of State Theories for Polymers

Small Molecules and Large Molecules

PVT Relations for Polymeric Liquids

Tait Equation

Flory, Orwoll, and Vrij Model

Prigogine Square-Well Cell Model

Lattice Fluid Model of Sanchez and Lacombe

Negative Coefficient of Thermal Expansion

3 Binary Interaction Model

Introduction

Compositional Window of Miscibility: Copolymer–Homopolymer

Compositional Window of Miscibility: Copolymers with Common Monomers

Compositional Window of Miscibility: Terpolymer System with Common Monomers

Compositional Window of Miscibility: Terpolymer and Homopolymer System without Common Monomers

Spinodal Curve from B Values and EOS

Copolymer/Homopolymer Blends of AMS–AN/PVC

Copolymer/Homopolymer Blends of AMS–AN with Other Copolymers

Intramolecular Repulsion as Driving Force for Miscibility–Mean Field Approach

4. Keesom Forces and Group Solubility Parameter Approach

Hildebrandt Solubility Parameter

Hansen Three-Dimensional Solubility Parameter

Specific Interactions

5. Phase Behavior

Introduction

LCST and UCST

Circular Envelope in Phase Diagram

Hourglass Behavior in Phase Diagrams

Molelucar Architechture

6. Partially Miscible Blends

Commercial Blends That Are Partially Miscible

Entropy Difference Model (ΔΔSm)

Estimates of Change in Entropy of Mixing at Glass Transition, ΔΔSm

Copolymer and Homopolymer Blend

Sequence Distribution Effects on Miscibility

7. Polymer Nanocomposites

Introduction

Commercial Products

Thermodynamic Stability

Vision and Reality

Fullerences

Carbon Nanotubes (CNT)

Morphology of CNTs

Nanostructuring Operations

Polymer Thin Films

Nanostructuring from Self-Assembly of Block Copolymers

Intercalated and Exfoliated Nanocomposites

8. Polymer Alloys

Introduction

PC/ABS Alloys

Nylon/ABS Alloys

PVC Alloys

Polyolefin Alloys

Natrual Polymer Alloy

9. Binary Diffusion in Polymer Blends

Introduction

Diffusion Phenomena

Fick’s First and Second Laws of Diffusion

Skylab Diffusion Demonstration Experiments

Bulk Motion, Molecular Motion, and Total Molar Flux

Stokes–Einstein Equation for Dilute Solutions

Diffusion in Solids

Diffusion Coefficient in Polymers

Transient Diffusion

Damped Wave Diffusion and Relaxation

Periodic Boundary Condition

10. Copolymer Composition

Introduction

Composition for Random Copolymers

Composition for Random Terpolymers

Reactivity ratios

Multicomponent Copolymerization—n Monomers

11. Sequence Distribution of Copolymers

Dyad and Triad Probabilities in Copolymer

Dyad and Triad Probabilities in Terpolymers

Sequence Alignment in DNA and Protein Sequences

12. Reversible Polymerization

Heat Effects during Polymerization

Ceiling Temperature during Reversible Polymerization

Subcritical Oscillations during Thermal Polymerization

Thermal Terpolymerization of Alphamethyl Styrene, Acrylonitrile, and Styrene

Reversible Copolymerization

Appendix A: Maxwell’s Relations

Appendix B: Five Laws of Thermodynamics

Appendix C: Glass Transition Temperature

Appendix D: Statistical Distributions