《Mechanical behavior of high polymers》求取 ⇩

A. Introduction1

Ⅰ. Phenomenological Discussion1

1. The Geometry of Stress1

Transformation of Coordinates4

2. The Geometry of Small Strains8

3. Theory of Elasticity. Relationship between Stress and Strain in an Ideal Elastic Material10

A. Homogeneous Stress10

The 21 Independent Elastic Constants12

Alternative Methods of Representation for Elastic Properties of Isotropic Bodies14

Problems Involving Simple Geometry16

B. Nonhomogeneous Stresses16

The Special Case When μ?λ19

C. Large Deformations20

4. The Flow of Newtonian Liquids23

A. Homogeneous Shear Stress23

B. Nonhomogeneous Stresses25

Flow of a Newtonian Liquid through a Capillary Tube29

Flow of a Newtonian Liquid between Concentric Cylinders Undergoing Relative Rotation31

5. Non-Newtonian Fluids and Plasticity32

A. Homogeneous Shear Stress32

The Question of the Yield Point34

B. Behavior of a Non-Newtonian Liquid Subjected to Nonuniform Stresses35

Flow of a Non-Newtonian Liquid through a Capillary Tube36

Rotating Cylinder Viscometer38

C. The Determination of Flow Curves39

D. Extension of the Hydrodynamic Concepts Embodied in the Differential Equations of Viscous Flow43

Appendix: Nonlinearity in Stress-Strain Relationships44

6. Thixotropy: Flow Accompanied by Structure Changes45

7. Coulomb Friction52

8. Combinations of Elasticity and Flow, and Inertial Effects53

A. Maxwellian Relaxation54

B. Retarded Elastic Response57

C. Inertial Elasticity and Damped Inertial Elasticity59

Ⅱ. Simple Molecular Mechanisms Involved in Elasticity and Flow62

1. The Mechanism of Elastic Displacement in Crystalline Solids62

A. Change of Elastic Constants with Temperature65

B. Types of Forces66

2. Liquid Flow—a Mechanism of Response to Stress67

A. The Structure of Simple Liquids68

B. Diffusion70

C. Viscous Flow71

The Question of Momentum Transfer; Relation of Gas Viscosity to Liquid Viscosity74

D. The Softening Point and Apparent Second Order Transition Point in Amorphous Materials75

The Softening Point77

Volume Changes80

The Viscosity of Liquid and Glass, Detailed Theory83

Force Fields and Stress Fields86

Bibliography90

B. The Plastoelastic Behavior of Amorphous Linear High Polymers93

Ⅰ. Introduction93

Ⅱ. Structure and Diffusion of Linear Amorphous Polymers94

1. Configurations94

2. Equilibrium Distribution among Configurations98

3. Diffusion101

Ⅲ. Effect of Shear Stress—Qualitative Introductory Treatment103

1. Introduction103

2. Analysis of Four-Parameter Model107

A. Significance of Elements; Magnitude and Temperature De-pendence of Parameters107

The Modulus G1107

The Modulus G2108

A Note on the "Gaslike" Nature of Rubber Elasticity112

Magnitude and Temperature Dependence of η2 and η3113

B. Range of Behaviors Described by Model A116

The Apparent Second Order Transition and Softening Point of Amorphous Polymers120

C. Model B: an Equivalent of Model A125

Ⅳ. Effect of Shear Stress—More Refined and Quantitative Treatment127

1. Phenomenological Necessity for Distribution of Retardation Times127

A. Complex Phenomena Resulting from a Distribution of Retar-dation Times130

B. The Fundamental Partial Differential Equation132

C. An Equivalent Representation for Model C134

2. Molecular Theory of the Viscoelastic Spectrum of an Amorphous Linear Polymer134

A. Different Kinds of "Segments"143

B. Effect of Molecular Weight on Viscoelastic Spectrum145

C. Effect of Polydispersity upon the Viscoelastic Spectrum148

D. Effect of Chemical Constitution152

Two-Phase Theories of Polymer Structure164

The Concept of "Internal Stress"165

3. The Empirical Four-Parameter Model166

More Detailed Empirical Models171

4. Interdependence and Nonlinearity of Plastoelastic Elements172

Ⅴ. Shear Stress: The Dynamics of Viscoelastic Behavior176

1. Case (1)—Constant Stress178

2. Case (2)—Constant Deformation181

3. Case (3)—Constant Rate of Deformation183

4. Case (4)—Response to Stresses Varying Sinusoidally with Time189

5. Analogy with Electrical Networks193

General Use of Impedance Function197

6. The Principle of Superposition198

7. Hysteresis and Heat Loss in Cyclic Elastic Deformations200

A. Mechanical Nonequilibrium201

B. Thermal Nonequilibrium202

C. Phase Nonequilibrium203

Ⅵ. Nonhomogeneous and Combined Stresses204

1. Introduction204

2. Extension to Viscoelastic Materials207

3. Case in Which f(σ,t) Can Be Factored210

4. General Case211

5. "Accessible" and "Inaccessible" States of Strain213

6. Special Cases215

7. Large Strains218

Ⅶ. Optical Effects in Strained Amorphous Polymers—Photoelasticity220

Bibliography228

C. Three-Dimensional Cross-Linked Polymers234

Ⅰ. Introduction234

Ⅱ. Mechanical Behavior of Idealized Network Types236

1. Loose Regular Networks Containing Material of Low Molecular Weight236

A. Equilibrium Behavior236

B. The Tetrahedral Model for the Network Structure of Rubber243

C. Theory of Guth and James246

D. Network Defects. Influence of Molecular Weight of Original Linear Polymer on Elastic Properties of a Network257

Network Entanglements257

Intramolecular Cross Linkages259

Terminal Chains: The Effect of Initial Molecular Weight259

E. Nonequilibrium Behavior261

2. Loose Regular Networks Containing Linear Polymer Molecules264

3. Loose Irregular Networks266

4. Tight Networks267

Ⅲ. The Formation of Three-Dimensional Polymers268

1. Polycondensation Reactions268

A. Solution of the Recurrence Relationship277

B. Distribution of Species with Respect to Complexity (z)278

C. The Sol—Gel Ratio279

D. Number Average and Weight Average Complexities281

E. Distribution of Species with Respect to Size282

2. Cross Linking of a Linear Polymer284

A. Special Case: Monodisperse Polymer284

The Sol—Gel Ratio286

Number Average and Weight Average Molecular Weights287

B. General Case: Arbitrary Initial Distribution Curve287

3. Polymerization Reactions Involving Divinyl Compounds292

A. Copolymerization of Vinyl Compounds294

Nonmathematical Predictions Concerning Copolymerization296

B. Definition of Symmetry and Independence298

C. Polymerization of a Symmetrical Divinyl Compound299

D. Polymerization of an Unsymmetrical Divinyl Compound300

E. Copolymerization of a Vinyl Monomer with a Symmetrical Divinyl Monomer302

F. Copolymerization of a Vinyl Monomer with an Unsymmetrical Divinyl Monomer304

Ⅳ. Structures and Mechanical Properties of Actual Three-Dimensional Polymers304

1. Vulcanized Rubber304

Nonequilibrium Behavior312

2. Phenol-Formaldehyde and Related Resins317

3. Wool321

Ⅴ. Chemical Change Accompanying Viscoelastic Response321

1. Additional Cross Linking during Deformation322

2. Rupture of Cross Links during Deformation322

3. Breaking and Re-forming of Cross Links during Deformation323

A. Continued Cure of Phenolic Resins during Creep325

B. Stress Relaxation in Vulcanized Rubbers326

4. Dynamic Interchange of van der Waals' Linkages336

Bibliography337

D. Crystallization of High Polymers340

Ⅰ. Structure342

Ⅱ. Thermodynamics of High Polymer Crystallization345

Equilibrium Considerations346

Ⅲ. Kinetics of High Polymer Crystallization351

Ⅳ. Effect of Specific Molecular Structure Factors on the Crystallization of High Polymers356

1. Effect of Molecular Weight and Cross Linking on Crystallization359

2. Effect of Low Molecular Weight Materials on High Polymer Crystal-lization360

Ⅴ. Effect of Crystallinity and the Crystallization Process on the Mechanical Properties of High Polymers362

1. Mechanical Properties of the Crystallites362

2. Mechanical Properties of a Polycrystalline Polymer, without Phase Change363

3. Mechanical Properties of a Polycrystalline Polymer, with Phase Change365

A. Crystallization during Elastic Deformation365

Mack Elasticity370

B. Effect of Crystallization on Flow in Rubber373

C. Crystallization of Polyvinylidene Chloride374

D. Effect of Crystallization on the Elastic Behavior of Nylon376

E. Other Examples378

The Creep and Recovery Behavior of Nylon402

Ⅵ. Mechanical Behavior of Wool414

Bibliography424

E. Plasticization and Solution: Systems Containing High Polymers and Materials of Low Molecular Weight427

Ⅰ. Introduction427

Ⅱ. Arrangement of Molecules in Amorphous Mixtures427

Localized and Directed Forces428

Ⅲ. Effect of Low Molecular Materials on Viscoelastic Properties of High Polymers in Concentrated Systems431

The Random Mixture431

The Typical Plasticized Polar Polymer433

Effect of Molecular Structure of the Plasticizer450

Ⅳ. Dilute Polymer Solutions454

1. The Staudinger Equations456

2. Dependence of Viscosity on Concentration459

3. Dependence of Viscosity on Molecular Weight462

4. Dependence of Viscosity on Rate of Shear467

5. Effect of Temperature and Solvent Type on Intrinsic Viscosity of High Polymer Solutions468

Bibliography472

F. Ultimate Strength and Related Properties476

Ⅰ. Introduction476

1. A Mathematical Difficulty476

2. A Structural Difficulty476

3. An Experimental Difficulty477

Ⅱ. Geometric Considerations478

Ⅲ. Time Effects481

1. Breaking Time as a Function of Stress481

A. Combination of Geometric and Time Complexity484

B. Response to Different Stress Sequences (Hypothetical)485

C. Ultimate Strength from the Stress-Strain Curve488

2. Impact Strength491

Ⅳ. Correlation between Structure and Tensile Strength493

1. Dependence on Molecular Weight493

2. Influence of Molecular Weight Distribution495

3. Influence of Crystallization and Orientation on Tensile Strength500

4. Effect of Environmental Conditions515

Bibliography525

Appendix Ⅰ. Tensor Representation of Stress and Strain534

Appendix Ⅱ. Various Mathematical Methods of Specifying Viscoelastic Prop-erties537

Appendix Ⅲ. Tensor Treatment of Nonhomogeneous Stresses in Viscoelastic Media557

Appendix Ⅳ. Experimental Methods in the Scientific Mechanical Testing of . High Polymers565

Subject Index571