Physical Properties of Macromolecules -- Contents -- Preface -- Part One Glass Transitions in Amorphous Polymers -- 1. Glass Transitions in Amorphous Polymers: Basic Concepts -- 1.1 Phase Transitions in Amorphous Materials -- 1.2 Volume-Temperature and Enthalpy-Temperature Relations in the Vicinity of First-Order and Second-Order Phase Transitions: Discontinuous Thermophysical Properties at T(m) and T(g) -- 1.3 The Equilibrium Glassy State -- 1.4 Physical Aging, Densification, and Volume and Enthalpy Relaxation -- 1.5 Temperature-Pressure Differential Phase Equilibrium Relations for First-Order Processes: The Clapeyron Equation -- 1.6 Temperature-Pressure Differential Phase Equilibrium Relations for Second-Order Processes: The Ehrenfest Equations -- 1.7 Compositional Dependence of T(g) via Entropy Continuity -- 1.8 Compositional Dependence of T(g) via Volume Continuity -- 1.9 Linear Least Squares Analysis of the Gordon-Taylor Equation and Other T(g)-Composition Relations for Binary Mixtures -- 1.10 Free Volume Concepts -- 1.11 Temperature Dependence of Fractional Free Volume -- 1.12 Compositional Dependence of Fractional Free Volume and Plasticizer Efficiency for Binary Mixtures -- 1.13 Fractional Free Volume Analysis of Multicomponent Mixtures: Compositional Dependence of the Glass TransitionTemperature -- 1.14 Molecular Weight Dependence of Fractional Free Volume -- 1.15 Experimental Design to Test the Molecular Weight Dependence of Fractional Free Volume and T(g) -- 1.16 Pressure Dependence of Fractional Free Volume -- 1.17 Effect of Particle Size or Film Thickness on the Glass Transition Temperature -- 1.18 Effect of the Glass Transition on Surface Tension -- References -- Problems -- 2. Diffusion in Amorphous Polymers Near the Glass Transition Temperature -- 2.1 Diffusion on a Lattice.

2.2 Overview of the Relation Between Fractional Free Volume and Diffusive Motion of Liquids and Gases Through Polymeric Membranes -- 2.3 Free Volume Theory of Cohen and Turnbull for Diffusion in Liquids and Glasses -- 2.4 Free Volume Theory of Vrentas and Duda for Solvent Diffusion in Polymers Above the Glass Transition Temperature -- 2.5 Influence of the Glass Transition on Diffusion in Amorphous Polymers -- 2.6 Analysis of Half-Times and Lag Times via the Unsteady State Diffusion Equation -- 2.7 Example Problem: Effect of Molecular Weight Distribution Functions on Average Diffusivities -- References -- 3. Lattice Theories for Polymer-Small-Molecule Mixtures and the Conformational Entropy Description of the Glass Transition Temperature -- 3.1 Lattice Models in Thermodynamics -- 3.2 Membrane Osmometry and the Osmotic Pressure Expansion -- 3.3 Lattice Models for Athermal Mixtures with Excluded Volume -- 3.4 Flory-Huggins Lattice Theory for Flexible Polymer Solutions -- 3.5 Chemical Stability of Binary Mixtures -- 3.6 Guggenheim's Lattice Theory of Athermal Mixtures -- 3.7 Gibbs-DiMarzio Conformational Entropy Description of the GlassTransition for Tetrahedral Lattices -- 3.8 Lattice Cluster Theory Analysis of Conformational Entropy and the Glass Transition in Amorphous Polymers -- 3.9 Sanchez-Lacombe Statistical Thermodynamic Lattice Fluid Theory of Polymer-Solvent Mixtures -- Appendix: The Connection Between Exothermic Energetics and Volume Contraction of the Mixture -- References -- Problems -- 4. dc Electric Field Effects on First- and Second-Order PhaseTransitions in Pure Materials and Binary Mixtures -- 4.1 Electric-Field-Induced Alignment and Phase Separation -- 4.2 Overview -- 4.3 Electric Field Effects on Low-Molecular-Weight Molecules and Their Mixtures -- 4.4 Electric Field Effects on Polymers and Their Mixtures.

4.5 Motivation for Analysis of Electric Field Effects on PhaseTransitions -- 4.6 Theoretical Considerations -- 4.7 Summary -- Appendix: Nomenclature -- References -- 5. Order Parameters for Glasses: Pressure and Compositional Dependence of the Glass Transition Temperature -- 5.1 Thermodynamic Order Parameters -- 5.2 Ehrenfest Inequalities: Two Independent Internal Order Parameters Identify an Inequality Between the Two Predictions for the Pressure Dependence of the Glass Transition Temperature -- 5.3 Compositional Dependence of the Glass Transition Temperature -- 5.4 Diluent Concentration Dependence of the Glass Transition Temperature via Classical Thermodynamics -- 5.5 Compositional Dependence of the Glass Transition Temperature via Lattice Theory Models -- 5.6 Comparison with Other Theories -- 5.7 Model Calculations -- 5.8 Limitations of the Theory -- References -- Problem -- 6. Macromolecule-Metal Complexes: Ligand Field Stabilization and Glass Transition Temperature Enhancement -- 6.1 Ligand Field Stabilization -- 6.2 Overview -- 6.3 Methodology of Transition-Metal Coordination in Polymeric Complexes -- 6.4 Pseudo-Octahedral d(8) Nickel Complexes with Poly(4-vinylpyridine) -- 6.5 d(6) Molybdenum Carbonyl Complexes with Poly(vinylamine) that Exhibit Reduced Symmetry Above the Glass Transition Temperature -- 6.6 Cobalt, Nickel, and Ruthenium Complexes with Poly(4-vinylpyridine) and Poly(L-histidine) that Exhibit Reduced Symmetry in the Molten State -- 6.7 Total Energetic Requirements to Induce the Glass Transition via Consideration of the First-Shell Coordination Sphere in Transition Metal and Lanthanide Complexes -- 6.8 Summary -- 6.9 Epilogue -- Appendix: Physical Interpretation of the Parameters in the Kwei Equation for Synergistic Enhancement of the Glass Transition Temperature in Binary Mixtures -- References.

Part Two Semicrystalline Polymers and Melting Transitions -- 7. Basic Concepts and Molecular Optical Anisotropy in Semicrystalline Polymers -- 7.1 Spherulitic Superstructure -- 7.2 Comments about Crystallization -- 7.3 Spherulitic Superstructures that Exhibit Molecular Optical Anisotropy -- 7.4 Interaction of a Birefringent Spherulite with Polarized Light -- 7.5 Interaction of Disordered Lamellae with Polarized Light -- 7.6 Interaction of Disordered Lamellae with Unpolarized Light -- 7.7 Molecular Optical Anisotropy of Random Coils and Rigid Rod-Like Polymers -- 7.8 Birefringence of Rubbery Polymers Subjected to External Force Fields -- 7.9 Chain Folding, Interspherulitic Connectivity, and Mechanical Properties of Semicrystalline Polymers -- References -- Problems -- 8. Crystallization Kinetics via Spherulitic Growth -- 8.1 Nucleation and Growth -- 8.2 Heterogeneous Nucleation and Growth Prior to Impingement -- 8.3 Avrami Equation for Heterogeneous Nucleation that Accounts for Impingement of Spherulites -- 8.4 Crystallization Kinetics and the Avrami Equation for Homogeneous Nucleation of Spherulites -- 8.5 Linear Least Squares Analysis of the Kinetics of Crystallization via the Generalized Avrami Equation -- 8.6 Half-Time Analysis of Crystallization Isotherms -- 8.7 Maximum Rate of Isothermal Crystallization -- 8.8 Thermodynamics and Kinetics of Homogeneous Nucleation -- 8.9 Temperature Dependence of the Crystallization Rate Constant -- 8.10 Optimum Crystallization Temperatures: Comparison Between Theory and Experiment -- 8.11 The Energetics of Chain Folding in Semicrystalline Polymer-Polymer Blends that Exhibit Multiple Melting Endotherms -- 8.12 Melting Point Depression in Polymer-Polymer and Polymer-Diluent Blends that Contain a High-Molecular-Weight Semicrystalline Component -- References -- Problems.

9. Experimental Analysis of Semicrystalline Polymers -- 9.1 Semicrystallinity -- 9.2 Differential Scanning Calorimetry: Thermograms of Small Molecules that Exhibit Liquid Crystalline Phase Transitions Below the Melting Point -- 9.3 Isothermal Analysis of Crystallization Exotherms via Differential Scanning Calorimetry -- 9.4 Kinetic Analysis of the Mass Fraction of Crystallinity via the Generalized Avrami Equation -- 9.5 Measurements of Crystallinity via Differential Scanning Calorimetry -- 9.6 Analysis of Crystallinity via Density Measurements -- 9.7 Pychnometry: Density and Thermal Expansion Coefficient Measurements of Liquids and Solids -- References -- Problems -- Part Three Mechanical Properties of Linear and Crosslinked Polymers -- 10. Mechanical Properties of Viscoelastic Materials: Basic Concepts in Linear Viscoelasticity -- 10.1 Mathematical Models of Linear Viscoelasticity -- 10.2 Objectives -- 10.3 Simple Definitions of Stress, Strain, and Poisson's Ratio -- 10.4 Stress Tensor -- 10.5 Strain and Rate-of-Strain Tensors -- 10.6 Hooke's Law of Elasticity -- 10.7 Newton's Law of Viscosity -- 10.8 Simple Analogies Between Mechanical and Electrical Response -- 10.9 Phase Angle Difference Between Stress and Strain and Voltage and Current in Dynamic Mechanical and Dielectric Experiments -- 10.10 Maxwell's Viscoelastic Constitutive Equation -- 10.11 Integral Forms of Maxwell's Viscoelastic Constitutive Equation -- 10.12 Mechanical Model of Maxwell's Viscoelastic Constitutive Equation -- 10.13 Four Well-Defined Mechanical Experiments -- 10.14 Linear Response of the Maxwell Model during Creep Experiments -- 10.15 Creep Recovery of the Maxwell Model -- 10.16 Linear Response of the Maxwell Model during Stress Relaxation -- 10.17 Temperature Dependence of the Stress Relaxation Modulus and Definition of the Deborah Number.

10.18 Other Combinations of Springs and Dashpots.