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Table of Contents 1 Introduction To Macromolecules 1.1 What is a Macromolecule? 1 1.2 The Discovery of Macromolecules 3 1.3 The Structure of Macromolecules in Solution 4 1.4 The Remarkable Properties of Pure Bulk Polymers 7 1.5 Building New Materials Using Macromolecules 9 1.6 Suggestions for Further Reading 12 2 Describing Polymer Structure 2.1 Introduction 13 2.2 Geometric Structure of Macromolecules 15 2.3 Bond Probability Distributions 17 2.4 The Rotational Isomeric State Approximation 17 2.5 The Mean Squared End-To-End Distance 21 2.6 The Statistics of the Random Coil 25 2.7 Chain Flexibility and the Persistence Length 27 3 Measuring Polymer Structure 3.1 Introduction 29 3.2 Polymer Composition and Sequence Distribution 30 3.3 NMR Spectroscopy of Polymers 31 3.4 Measuring Local Conformations of Polymers 34 3.5 Vibrational Spectroscopy 34 3.6 Conformational Statistics of n-Hexane 36 3.7 Global Measures of the Chain Structure 37 3.8 Light Scattering from Dilute Polymer Solutions 38 4 The Macromolecular Basis of Rubber Elasticity 4.1 Introduction 41 4.2 The Thermodynamics of Ideal Rubber Elasticity 43 4.3 The Statistical Theory of Rubber Elasticity 45 4.4 The Thermoelastic Inversion Length 47 4.5 The Force of Extension of Real Rubber 48 5 Structure and Properties of Polymers in Dilute Solution 5.1 Introduction 49 5.2 Structure of Macromolecules in Dilute Solution 50 5.3 Flory Theory of Chain Expansion 54 5.4 Thermodynamics of Two Component Solutions 56 5.5 Osmotic Pressure 57 5.6 Flory Theory of the Second Virial Coefficient 59 5.7 Light Scattering From Two Component Solutions 61 5.8 Flory Theory of Light Scattering in Dilute Solution 63 5.9 Diffusion of Particles in Solution 66 5.10 Kirkwood Theory of Macromolecular Friction 68 5.11 Concentration Fluctuations and Mutual Diffusion 71 5.12 Viscosity of Dilute Polymer Solutions 75 5.13 The Effect of Molecular Weight Polydispersity 78 6 Structure and Properties of Polymers in Semi-Dilute Solution 6.1 Introduction 84 6.2 The Remarkable Behavior of Semi-Dilute Solutions 86 6.3 Microscopic Theory of Semi-Dilute Solutions 87 6.4 Viscosity in Semi-Dilute Solutions 90 6.5 Structure Near Overlap 91 7 Structure and Properties of Polymers in Concentrated Solution 7.1 Introduction 93 7.2 Flory-Huggins Theory of Concentrated Solutions 95 7.3 The Thermodynamics of Swollen Rubber: Gels 100 7.4 Light Scattering From Concentrated Solutions 101 7.5 Real Solutions and the Flory-Orwoll Theory 102 7.6 Diffusion in Concentrated Solutions 105 7.7 Viscoelasticity in Concentrated Polymer Solutions 106 8 Structure and Properties of Polymers in the Pure Amorphous Liquid State 8.1 Introduction 111 8.2 Free Volume and Viscosity 112 8.3 Viscosity of Low Molecular Weight Chain Liquids 113 8.4 Phenomenology of the Glass Transition 114 8.5 Temperature and Pressure Dependence of Relaxation Near the Glass Transition 119 9 Structure and Properties of Rodlike Polymers in Solution 9.1 Introduction 125 9.2 Characterization of Rodlike Polymers in Solution 126 9.3 Second Osmotic Virial Coefficient 128 9.4 Thermodynamics of Rodlike Polymer Solutions 129 10 Structure and Properties of Polyelectrolyte Chains in Solution 10.1 Introduction 133 10.2 Structure of Linear Polyelectrolyte Chains in 134 Dilute Solution 10.3 Thermodynamics of Polyelectrolyte Solutions 139 10.4 Viscosity of Polyelectrolyte Solutions 141

Library of Congress Subject Headings for this publication:

Polymers.