Chapter 1 STRUCTURE OF POLYMER CHAIN 1
1.1 Introduction 1
1.1.1 Introduction to Polymer Science 1
1.1.2 From Small Molecules to Big Molecules 2
1.1.3 Future Topics for Polymer Science 5
1.1.4 Major Characteristics of Polymer Structure 6
1.1.5 Contents of Polymer Structure 6
1.2 Short-range Structure of Polymer Chain 7
1.2.1 The Chemical Composition of Repeating Units 7
1.2.2 Bonding Methods of Monomers 9
1.2.3 Branch and Cross-liking of Polymer Chain 11
1.2.4 Sequential Structure of Copolymer 12
1.2.5 Configuration of Polymer Chain 14
1.3 Long-range Structure of Polymer Chain 17
1.3.1 Size and Shape of Polymer Chain 17
1.3.2 Internal Rotation and Conformation of Polymer Chain 18
1.3.3 Flexibility of Polymer Chain 18
1.3.4 Factors of Influence on Polymer Chain Flexibility 19
1.4 Conformation Statistics of Polymer Chain 21
1.4.1 Geometry Calculation of Average Square End-to-end Distance 23
1.4.2 Statistical Calculation of Average Square End-to-end Distance 25
1.4.3 Characteristics of Polymer Chain Flexibility 27
1.4.4 Radius of Gyration of Polymer Chain 28
1.4.5 Wormlike Chain 29
Chapter 2 CONDENSED STATE STRUCTURE OF POLYMERS 32
2.1 Van Der Waals Force and Hydrogen Bonding 32
2.1.1 Primary Bonds 32
2.1.2 Seconary-bond Forces 33
2.1.3 Intermolecular Forces and Physical Properties 34
2.2 Form and Structure of Crystalline Polymers 36
2.2.1 Morphology of Crystalline Polymers 36
2.2.2 Conformation and Unit Cell of Crystalline Polymers 39
2.3 Structural Models of Polymers 48
2.3.1 Structural Models of Crystalline Polymers 48
2.3.2 Struetural Model of Amorphous Polymers 52
2.4 Crystalline Processes of Crystalline Polymers 56
2.4.1 Structure and Ability of Polymer 56
2.4.2 Crystallization Process of Polymers 57
2.4.3 The Rate of Crystallization and Its Measurement Methods 57
2.4.4 The Avrami Equation 60
2.4.5 The Degree of Crystallinity 62
2.4.6 Experimental Determination of Crystallinity 63
2.5 Crystallization Thermodynamics of Polymers 64
2.5.1 Melting Phenomena and the Melting Temperature 64
2.5.2 Theory of Melting Point Depression 67
2.5.3 Example Calculation of Melting Point Depression 68
2.5.4 Experimental Thermodynamic Parameters 68
2.5.5 Entropy of Melting 68
2.5.6 The Hoffnan-Weeks Equilibrium Melting Temperature 70
2.5.7 Effect of Chemical Structure On the Melting Temperature 70
2.6 Oriented Structure of Polymers 72
2.6.1 The Production of Orientation in Synthetic Polymers 73
2.6.2 Deliberate Orientation by Processing in the Solid State 73
2.6.3 Deliberate Orientation by Processing in the Fluid State 75
2.6.4 Cold Drawing and the Natural Draw Ratio 77
2.6.5 Oriented Polymers-models and Properties 77
2.6.6 Highly Oriented Polymers and Ultimate Moduli 81
2.7 Liquid-crystal Polymers 83
2.7.1 Introduction 83
2.7.2 Types of Mesophases for Small Molecules 83
2.7.3 Types of Liquid-crystal Polymers 85
2.7.4 The Processing of Liquid-crystal Polymers 86
2.7.5 The Properties and Applications of Liquid-crystal Polymers 88
2.8 Structure and Properties of Blending Polymers 91
2.8.1 Conditions for Polymer-polymer Miscibility 91
2.8.2 Experimental Detection of Miscibility 96
2.8.3 Compatibilisation and Examples of Polymer Blends 98
2.8.4 Morphology 100
2.8.5 Properties and Applications 100
Chapter 3 PROPERTIES OF POLYMER SOLUTIONS 104
3.1 Dissolution of Polymers 104
3.1.1 Dissolution Process 104
3.1.2 Cohesive Energy Density and Thermodynamics for Polymer Dissolution 105
3.2 Thermodynamics of Polymer Solutions 109
3.2.1 The Ideal Solution 109
3.2.2 Statistical Thermodynamics of Mixing 109
3.2.3 Dilute Solutions 110
3.2.4 Values for the Flory-Huggins Parameterx1 112
3.2.5 A Worked Example for the Free Energy of Mixing 113
3.3 Semidilute Polymer Solutions 114
3.3.1 The Dilute to Semidilute Transition 114
3.3.2 Semidilute Regime Scaling Laws 115
3.3.3 The Correlation Length，ξ，in the Semidilute Solution 115
3.4 Concentrated Polymer Solutions 116
3.4.1 Plasticization of Polymers 116
3.4.2 Spinning Solutions 117
3.4.3 Gels 118
3.5 Polyelectrolyte Solutions 120
3.6 Miscibility of Polymer Blends 121
3.6.1 Phase Diagrams 123
3.6.2 Thermodynamics of Phase Separation 124
3.6.3 An Example Calculation:Molecular Weight Miscibility Limit 124
3.7 Hydrodynamics Properties of Polymer Solutions 125
3.7.1 The Diffusion of Polymer in Solutions 125
3.7.2 Viscose Flow of Polymer in Solutions 126
Chapter 4 MOLECULAR WEIGHT AND MOLECULAR WEIGHT DISTRIBUTION OF POLYMERS 132
4.1 Polymer Size and Shape 132
4.2 Molecular Weight Averages 132
4.3 Determination Methods of Molecular Weight 133
4.3.1 End-group Analyses 133
4.3.2 Osmotic Pressure 134
4.3.3 Light Scattering 137
4.3.4 Flight Time 145
4.3.5 Viscometry 150
4.4 Determination Methods of Molecular Weight Distribution 154
4.4.1 Phase Separation and Fractionation 154
4.4.2 Gel Permeation Chromatography 154
Chapter 5 MOLECULAR CHAIN MOTION 164
5.1 Introduction to Molecular Chain Motion 164
5.1.1 Simple Mechanical Relationships and Their Concepts 164
5.1.2 Polymer Relaxation and Transition 167
5.1.3 Polymer Molecular Chain Relaxation and Transition 170
5.2 The Glass Transition 173
5.2.1 Introduction 173
5.2.2 Methods of Measuring Transitions in Polymers 174
5.2.3 Theories of the Glass Transition 179
5.2.4 Factors of Influence on Glass Transition Temperature 190
5.3 Viscosity Flow of Polymer 206
5.3.1 Characteristics of Viscosity Flow 206
5.3.2 Measure of Shear Viscosity 212
5.3.3 Factors of Influence on Viscosity Flow Temperature 217
Chapter 6 MECHANICAL BEHAVIOUR OF POLYMERS 226
6.1 Mechanical Behaviour of Amorphous and Crystalline Polymers 226
6.1.1 Basic Physical Quantities Describing Mechanical Behaviour 226
6.1.2 Several Common Terms of Mechanical Properties 229
6.1.3 Tensile Properties of Various Polymers 234
6.1.4 Yield of Polymers 237
6.1.5 Fracture and Theoretical Strength of Polymers 240
6.1.6 Factors Affecting the Actual Strength of Polymers 243
6.2 Mechanical Behaviour of Elastic Polymers 250
6.2.1 Application Temperature Range of Rubbers 250
6.2.2 Characteristics of Elasticity 251
6.2.3 Phenomenological Descriptions of Rubber Elasticity 255
6.2.4 Thermodynamic Analysis of Rubber Elasticity 260
6.2.5 Statistical Thermodynamics of Rubber Elasticity 263
6.2.6 Effects of the Structure of Cross-links and Networks on the Rubber Elasticity 265
6.2.7 Internal Energy Effects on the Rubber Elasticity 268
6.2.8 Ultimate Properties of Rubber 270
6.3 Mechanical Relaxation of Polymers:Viscoelasticity 270
6.3.1 Mechanical Relaxation Phenomenon of Polymers 271
6.3.2 Mechanical Models for Viscoelasticity 273
6.3.3 The Relationship between Viscoelasticity and Time and Temperature:Time-temperature Equivalence Principle 275
6.3.4 The Boltzmann Superposition Principle(BSP) 277
Chapter 7 ELECTRICAL AND OPTICAL PROPERTIES OF POLYMERS 283
7.1 Electrical Polarization and Dielectric Constant of Polymers 284
7.1.1 Polarization of Dielectric Media in Electric Field 284
7.1.2 Interpreting Polarization Effect of Polymer from Molecular Level 285
7.1.3 Relation between Dielectric Constant and Molecular Polarizability 286
7.1.4 The Dielectric Constants of Polymers 288
7.2 Dielectric Loss of Polymers 291
7.2.1 Dielectric Relaxation and Dielectric Loss 291
7.2.2 Characterization of Dielectric Loss 291
7.2.3 Some Factors Effecting on Dielectric Relaxation and Dielectric Loss 292
7.2.4 Spectra of Dielectric Relaxation in Solid Polymers 295
7.3 Conduction in Polymers 298
7.3.1 Characterization of Electric Conduction 298
7.3.2 Conductive Characteristics of Polymers 299
7.3.3 Volume Resistivity and Surface Resistivity 299
7.3.4 Dependence Relation between Conduction and Structure in Solid Polymer 300
7.3.5 Influence of Other Factors 305
7.4 Dielectric Breakdown of Polymers 306
7.4.1 Dielectric Breakdown and Dielectric Strength 306
7.4.2 Dielectric Breakdown Mechanisms of Polymer 307
7.5 Electrostatic Charge Phenomena on Polymer 309
7.6 Optical Properties of Polymers 310
7.6.1 Transparency and Colourlessness 310
7.6.2 The Refractive Index 311