Concepts in Polymer Thermodynamics, Volume II

Preface Introduction References Elements of Thermodynamics of Mixtures 2.1 Fundamentals 2.1.1 The Laws of Thermodynamics 2.1.2 Thermodynamic Functions and Relations 2.1.3 Mixtures 2.1.4 Composition Variables 2.2 Phase Equilibria 2.2.1 Phases 2.2.2 Gibbs Phase Rule 2.2.3 Free Energy of Mixing 2.2.4 Phase Stability 2.2.5 Phase Diagrams 2.2.6 Multicomponent Mixtures 2.2.7 Crystallizable Components 2.3 Ideal Mixtures 2.4 Regular Mixtures 2.4.1 Deviations from Ideality 2.4.2 Regular Mixtures 2.5 Solubility Parameters 2.5.1 Group Contribution Methods 2.5.2 Topological Contributions 2.6 Lattice Theories 2.6.1 Entropy of Mixing 2.6.2 Heat of Mixing References Basic Thermodynamics of Polymeric Mixtures 3.1 Polymers 3.1.1 Introduction 3.1.2 Molecular Weight Distributions 3.2 Single Chain Statistics 3.2.1 The Ideal Chain 3.2.2 Real Chains 3.2.3 A Real Chain in a Solvent 3.2.4 A Real Chain in the Melt 3.3 Ideal Polymer Mixtures 3.3.1 Introduction 3.3.2 Ideal Polymeric Mixtures 3.3.3 Derivation of the Flory-Huggins Entropy of Mixing 3.3.4 Alternative Derivations 3.3.5 Huggins Correction 3.4 Regular Polymer Mixtures 3.4.1 Generalized Regular Polymer Mixtures 3.5 Phase Diagrams 3.6 The Effect of Moleculr Weight Distributions 3.6.1 Introduction 3.6.2 Spinodal and Critical Point 3.6.2 Binodal and Flash Calculations 3.6.4 Example References Polymer Thermodynamic Models 4.1 Introduction 4.2 Flory-Huggins Models 4.3 Equation-of-State Models 4.3.1 Key Concepts 4.3.1.1 Helmholtz Free Energy 4.3.1.2 Corresponding States 4.3.1.3 Cell Partition Function 4.3.1.4 Chain Flexibility Parameter 4.3.2 The Flory EoS Theory 4.3.3 Hole Models 4.3.3.1 Key Concepts 4.3.3.2 Holes and Huggins 4.4. Specific Interaction Models 4.4.1 Key Concepts 4.4.2 Interaction Strengths 4.4.3 Generalizations 4.5 The (n=0) Vector Model 4.6 Prism Theory References Computer Simulations 5.1 Introduction 5.2 Computer Simulations and Statistical Mechanics 5.2.1 Introduction 5.2.2. The Boltzmann Distribution 5.2.3 Ensembles 5.3 Molecular Dynamics 5.4 Monte Carlo Simulations 5.5 Simulation of Small Systems 5.5.1 Periodic Boundary Conditions 5.6 Simulations of Polymeric Systems 5.6.1 Single Chain Simulations 5.6.2 Simulations of Many Chains References Experimental Findings 6.1 Introduction 6.2 Experimental Techniques 6.2.1 Scattering Techniques 6.2.1.1 Cloud Point Methods 6.2.1.2 Spinodal Decomposition 6.2.1.3 Light Scattering 6.2.1.4 Dilute Polymer Solutions 6.2.1.5 Neutron Scattering 6.2.2 Heats of Mixing 6.2.3 Glass Transition Temperature 6.3 Experimental Results and Model Validations 6.3.1 Polymer Solutions 6.3.1.1 Polystyrene in Cyclohexane 6.3.1.2 Other Polymer Solutions 6.3.2 Polymer Blends 6.3.2.1 Polystyrene in Polyvinyl Methyl Ether 6.3.2.2 Some Typical Polymeric Mixtures References List of Symbols Index