Macromolecules: 3 Physical structures and properties
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2008
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| Beschreibung: | XXXIV, 665 S. Ill., graph. Darst. |
| ISBN: | 9783527311743 |
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| 100 | 1 | |a Elias, Hans-Georg |d 1928- |e Verfasser |0 (DE-588)128433426 |4 aut | |
| 245 | 1 | 0 | |a Macromolecules |n 3 |p Physical structures and properties |c Hans-Georg Elias |
| 264 | 1 | |a Weinheim |b Wiley-VCH |c 2008 | |
| 300 | |a XXXIV, 665 S. |b Ill., graph. Darst. | ||
| 336 | |b txt |2 rdacontent | ||
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Datensatz im Suchindex
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| _version_ | 1806174262507077632 |
| adam_text | XXI
Table of Contents
Motto V
Preface VII
List of Symbols IX
Symbols for Languages IX
Mathematical Symbols IX
Symbols for Chemical Structures X
Averages and Other Markings X
Exponents and Superscripts X
Indices and Subscripts XI
Prefixes of Words XIII
Other Abbreviations XIV
Table of Contents XXI
1 Introduction 1
Literature to Chapter 1 4
2 Chemical Structure 7
2.1 Constitution 7
2.1.1 Definitions 7
2.1.2 Simple Polymer Chains 8
2.1.3 Polymer Architecture 9
Linear Polymers 9
Branched Polymers 10
Macromolecules with Higher Constitutional Dimensions . 11
2.2 Chemical Configuration 13
2.2.1 Basic Terms 13
2.2.2 Chemical Configurational Statistics 14
2.3 Molar Masses and Degrees of Polymerization 16
2.3.1 Overview 16
2.3.2 Statistical Weights 18
2.3.3 Simple Averages of Molar Masses 20
2.3.4 Hydrodynamic Averages of Molar Masses 21
Simple Hydrodynamic Averages 22
Complex Hydrodynamic Averages 22
2.3.5 Averages of Degrees of Polymerization 24
2.3.6 Averages of Other Properties 24
2.3.7 Moments of Distributions 25
2.3.8 Molecular Non-Uniformity 26
2.3.9 Constitutional Non-Uniformity 26
Sequence Lengths of Segments 27
Mass-average Molar Mass of Segments 28
2.3.10 Determination of Molar Masses 28
2.4 Distribution Functions 30
XXII Table of Contents
2.4.1 Types 30
2.4.2 Gaussian Distribution 31
2.4.3 Logarithmic Normal Distribution 34
2.4.4 Poisson Distribution 35
2.4.5 Schulz-Zimm and Schulz-Flory Distributions 36
2.4.6 Generalized Exponential Distributions 37
2.4.7 Determination of Molar Mass Distributions 37
Historical Notes to Chapter 2 39
Literature to Chapter 2 39
References to Chapter 2 40
3 Microconformations 41
3.1 Introduction 41
3.2. Local Conformations 42
3.2.1 Definitions 42
3.2.2 Rotational Potentials 43
3.2.3 Effect of Constitution 44
3.3 Sequences of Microconformations 46
3.3.1 Introduction 46
3.3.2 Helices 47
3.3.3 Constitution and Configuration Dependence 50
3.4 Optical Activity 53
3.4.1 Fundamentals 53
Circular Dichroism 53
Optical Activity 54
Optical Rotatory Dispersion 55
3.4.2 Structural Dependence 55
Poly(a-amino acid)s and Proteins 55
Poly(l-olefin)s 57
Copolymers 59
3.5 Transformation of Macroconformations 59
3.5.1 Phenomena 59
3.5.2 Thermodynamics 60
3.5.3 Kinetics 62
Historical Notes to Chapter 3 63
Literature to Chapter 3 64
References to Chapter 3 64
4 Macroconformations 65
4.1 Overview 65
4.1.1 Introduction 65
4.1.2 Macroconformations in Solution 66
Complete Helices in Solution 66
Helical Sections in Solution 67
4.2 Compact Molecules 68
4.2.1 Introduction 68
Table of Contents XXIII
4.2.2 Spheroids 69
Spheres 69
Ellipsoids 71
4.2.3 Rods 72
4.3 Molecular and Atomistic Modeling 73
4.3.1 Introduction 73
4.3.2 Methods 74
Group Increment Methods 74
Lattice Methods 75
Lattice-free Methods 76
4.3.3 Atomistic Force Fields 78
4.4 Unperturbed Coils of Linear Chains 81
4.4.1 Contour Lengths 82
4.4.2 End-to-end Distance and Radius of Gyration 83
4.4.3 Types of Coils 85
4.4.4 Molecular Models 85
Random-flight Chain 86
Freely Jointed Chain 88
Freely Rotating Chain 89
Chains with Restricted Rotation 91
Rotational Isomeric State 91
4.4.5 Flexibility of Chains 95
Steric Factor 95
Characteristic Ratio 96
Kuhnian Length 97
Persistence Length 98
4.4.6 Radius of Gyration 98
4.4.7 Coil Density 100
4.4.8 Distribution of End-to-End Distances 103
4.4.9 Worm-like Chains 104
4.5 Perturbed Coils of Linear Chains 107
4.5.1 Excluded Volumes 107
4.5.2 Expansion Factors 108
4.5.3 Helical Worm-like Chains 110
4.5.4 Molar Mass Dependence 110
4.5.5 Non-Uniformity Corrections 114
4.5.6 Temperature Dependence of Radii of Gyration 116
4.6 Cyclic Macromolecules 117
4.7 Branched Macromolecules 117
4.7.1 Introduction 117
4.7.2 Star Molecules 118
4.7.3 Comb Molecules 119
4.7.4 Dendrimers 121
4.8 Scaling 124
4.8.1 Local and Global Views 124
4.8.2 Fractals 126
XXIV Table of Contents
4.8.3 Self-similarity 127
A-4 Appendix to Chapter 4 129
A-4.1 Freely Rotating Chains 129
A-4.2 Distribution of End-to-End Distances 130
A-4.3 End-to-End Distance and Radius of Gyration 131
Historical Notes to Chapter 4 133
Bibliography of Force Fields 134
Literature to Chapter 4 135
References to Chapter 4 137
5 Scattering Methods 139
5.1 Overview 139
5.2 Static Light Scattering: Rayleigh Range 140
5.2.1 Fundamentals 140
5.2.2 Copolymers 144
5.2.3 Concentration Dependence 146
5.2.4 Mixed Solvents 147
5.3 Static Light Scattering: Debye Range 150
5.3.1 Introduction 150
5.3.2 Scattering Functions 150
5.3.3 ZimmPlot 153
5.3.4 Effect of Particle Shape 154
Spheres 154
Rods 154
Random Coils 155
Worm-like Chains 157
Star Molecules 158
Comb Molecules 159
5.4 Small-Angle X-Ray Scattering 160
5.4.1 Fundamentals 160
5.4.2 Scattering Functions 162
Linear Chains 162
Branched Polymers 164
5.5 Small-Angle Neutron Scattering 166
5.5.1 Fundamentals 166
5.5.2 Experimental Results 168
Historical Notes to Chapter 5 170
Literature to Chapter 5 170
References to Chapter 5 171
6 Disordered Condensed Systems 173
6.1 Amorphous Polymers 173
6.1.1 Structure 173
6.1.2 Density 176
6.2 Polymer Melts 178
6.2.1 Microconformations 178
Table of Contents XXV
6.2.2 Macroconformations 179
6.2.3 Entanglement of Polymer Chains 180
6.2.4 Temperature Dependence of Radii of Gyration 181
6.3 Semi-Concentrated Solutions 183
6.3.1 Concentration Ranges 183
6.3.2 Temperature Dependence of Coil Dimensions 184
6.3.3 Blobs 185
6.3.4 Radii of Gyration of Star Molecules 188
Historical Notices to Chapter 6 189
Literature to Chapter 6 189
References to Chapter 6 190
7 Crystalline States 191
7.1 Crystal Structures 191
7.1.1 Definitions of a Crystal 191
7.1.2 Lattice Structures 191
7.1.3 Symmetry Properties 193
7.1.4 Crystal Structure by X-Ray Diffraction 194
7.1.5 Lattice Constants 197
7.1.6 Lattice Structures 199
7.1.7 Polymorphism 201
7.1.8 Isomorphism 202
7.1.9 Unit Cells 202
7.2 Structure of Crystallites 203
7.2.1 Fringed Micelles 203
7.2.2 Polymer Single Crystals 204
7.2.3 Structure of Folds 206
7.2.4 Structure of Lamellae 208
7.3 Crystallization 210
7.3.1 Formation of Nuclei 210
Homogeneous Nucleation 210
Heterogeneous Nucleation 211
Nucleation Agents 212
Crystallization from Solution 213
Crystallization from Melts 215
7.3.2 Crystallization Rates 215
7.4 Morphology 219
7.4.1 Spherulites 219
7.4.2 Other Superstructures 220
7.4.3 Factors Controlling Crystallization 221
7.5 Crystallinity 224
7.5.1 Ideal Crystals 224
7.5.2 Crystallizability and Crystallinity 224
7.5.3 Lattice Defects 225
7.5.4 One-Phase and Two-Phase Models 225
7.5.5 X-Ray Diffraction 226
XXVI Table of Contents
7.5.6 Density 227
7.5.7 Calorimetry 228
7.5.8 Infrared Spectrometry 228
7.5.9 Indirect Methods 229
7.6 Orientation 229
7.6.1 X-Ray Interference 230
7.6.2 Optical Birefringence 230
7.6.3 Propagation of Ultrasound 232
7.6.4 Infrared Dichroism 232
7.6.5 Polarized Fluorescence 233
Historical Notes to Chapter 7 234
Literature to Chapter 7 235
References to Chapter 7 237
8 Mesophases 239
8.1 Introduction 239
8.1.1 Types of Mesophases 239
8.1.2 Other Mesophases 239
8.2 Mesomorphic States 240
8.2.1 Mesogens 241
8.2.2 Order in Domains 242
8.3 Lyotropic Liquid-Crystalline Polymers 244
8.3.1 Survey 244
8.3.2 Phase Separation 246
Onsager Theory 246
Flory Theory 247
8.3.3 Chemical Potentials 250
8.3.4 Orientation of Mesogens 253
8.3.5 Amphotropic Liquid Crystals 255
8.4 Thermotropic Liquid-Crystalline Polymers 257
8.4.1 Structural Requirements 257
8.4.2 Physical Structure of SCLCPs 258
8.4.3 Properties of Mesophases 260
8.5 Block Polymers 261
8.5.1 Survey 261
8.5.2 Thermotropic Domains 262
8.5.3 Lyotropic Structures 266
8.6 Ionomers 267
Historical Notes to Chapter 8 269
Literature to Chapter 8 269
References to Chapter 8 271
9 Polymers in and at Interfaces 273
9.1 Surface of Polymers 273
9.1.1 Fundamentals 273
9.1.2 Surface Composition 273
Table of Contents XXVII
9.2 Interfacial Tension 275
9.2.1 Determination of Interfacial Tension 275
9.2.2 Time Effects 277
9.2.3 Surface Tension of Polymer Melts 279
9.2.4 Interfacial Tension between Polymer Melts 280
9.2.5 Surface Tension of Polymer Solutions 280
9.2.6 Critical Surface Tension Solid-Liquid 281
9.3 Thin Layers of Polymers 283
9.4 Adsorption on Surfaces 286
9.4.1 Fundamentals 286
9.4.2 Methods 287
9.4.3 Time Dependence 287
9.4.4 Adsorption Equilibria 288
9.5 Polymer Brushes 290
9.5.1 Repulsive Forces 290
9.5.2 Blob Theory 291
Historical Notes to Chapter 9 293
Literature to Chapter 9 294
References to Chapter 9 295
10 Thermodynamics of Polymer Solutions 297
10.1 Chemical Thermodynamics 297
10.1.1 Introduction 297
10.1.2 Thermodynamic Classification of Solutions 297
10.1.3 Solubility Parameters 299
Solubility Parameters of Solvents 299
Solubility Parameters of Polymers 300
Enthalpy of Mixing 302
10.1.4 Molecular Considerations 303
Self-association of Solvent Molecules 304
Solvation 304
Preferential Solvation 305
10.1.5 Rate of Dissolution 306
10.2 Statistical Thermodynamics 307
10.2.1 Introduction 307
10.2.2 Lattice Theory 308
Enthalpy of Mixing 308
Interaction Parameter 309
Entropy of Mixing 310
Gibbs Energy of Mixing 312
Chemical Potentials 312
Summary 313
10.2.3 Phase Separation 314
Solutions of Amorphous Polymers 314
Quasi-binary Systems 316
Fractionation 317
XXVIII Table of Contents
Cloud Point Titrations 318
Precipitation Fractionation of Polymers 319
Polymer Mixtures in Solution 320
Polymer Blends 320
Critical Miscibility Temperatures 321
Solutions of Crystalline Polymers 323
10.3 Osmotic Pressure 325
10.3.1 Fundamentals 325
10.3.2 Membrane Osmometry 326
Semipermeable Membranes 326
Non-semipermeable Membranes 327
10.3.3 Ebullioscopy and Cryoscopy 328
10.3.4 Vapor Phase Osmometry 330
10.4 Virial Coefficients 330
10.4.1 Fundamentals 330
10.4.2 Lattice Theory 332
10.4.3 Effect of Excluded Volume 335
10.4.4 Effect of Molar Mass 335
10.4.5 Effect of Temperature 336
10.4.6 Osmotic Pressure of Semi-concentrated Solutions 337
10.5 Association and Self-association 339
10.5.1 Fundamentals 339
10.5.2 Open Self-association 340
10.5.3 Closed Self-association 343
10.5.4 Complexation of Polymers with Small Molecules 346
10.5.5 Polymer-Polymer Complexes 348
10.6 Polyelectrolytes 351
10.6.1 Structure of Polyelectrolyte Solutions 351
10.6.2 Thermodynamic Activity 352
10.6.3 Osmotic Pressure 354
10.7 Gels 356
10.7.1 Survey 356
10.7.2 Swelling of Chemically Crosslinked Neutral Gels 357
10.7.3 Swelling of Electrically Charged, Chemically Crosslinked Gels 358
10.7.4 Physically Crosslinked Gels 359
Historical Notes to Chapter 10 360
Literature to Chapter 10 361
References to Chapter 10 364
11 Transport in Solution , 365
11.1 Translational Diffusion 365
11.1.1 Introduction 365
11.1.2 Measurements 366
Classic Method 366
Dynamic Light Scattering 368
11.1.3 Friction Coefficients of Translation 370
Table of Contents XXIX
Spheres 370
Ellipsoids 370
Rods 371
Random Coils 372
11.1.4 Diffusion Coefficients 375
Spheres 375
Rigid Rods 376
Random Coils 377
11.1.5 Concentration Dependence, Dilute Solutions 377
11.1.6 Concentration Dependence, Semi-concentrated Solutions .... 378
11.17 Structured Flow 380
11.2 Sedimentation 381
11.2.1 Fundamentals 381
11.2.2 Sedimentation Rate 383
Sedimentation Coefficients 383
Concentration Dependence 384
Molar Mass Dependence 387
11.2.3 Sedimentation Equilibrium 389
11.2.4 Sedimentation Equilibrium in Density Gradients 389
11.3 Field-Flow Fractionation 390
11.4 Electrophoresis 391
Historical Notes to Chapter 11 392
Literature to Chapter 11 392
References to Chapter 11 394
12 Viscosity of Dilute Solutions 395
12.1 Fundamentals 395
12.1.1 Definitions 395
12.1.2 Experimental Methods 396
12.2 Concentration Dependence 399
12.2.1 Non-Electrolytes 399
12.2.2 Polyelectrolytes 402
12.3 Intrinsic Viscosities 405
12.3.1 Averages 405
12.3.2 Hydrodynamic Volumes 406
12.3.3 Spheres 407
12.3.4 Ellipsoids 408
12.3.5 Rods 410
12.3.6 Unperturbed Coils 411
Exponents a 411
Values of Kv 412
Hydrodynamic Radii 413
12.3.7 Perturbed Coils 416
12.3.8 Branched Polymer Molecules 417
Randomly Branched Polymers 419
Dendrimers 420
XXX Table of Contents
Hyperbranched Polymers 421
Comb Polymers 421
Star Polymers 421
12.3.9 Polyelectrolytes 422
A-12 Appendix to Chapter 12: Flory Constants 423
Historical Notes to Chapter 12 424
Literature to Chapter 12 425
References to Chapter 12 425
13 Thermal Properties 427
13.1 Fundamentals 427
13.1.1 Introduction 427
13.1.2 Thermodynamic States 427
13.1.3 Order of Thermal Transitions 428
13.1.4 Experimental Methods 430
13.2 Mobility of Molecules 433
13.2.1 Thermal Expansion 433
13.2.2 Heat Capacity 434
13.2.3 Thermal Conductivity 436
13.2.4 Thermal Relaxations 437
13.3 Melting 438
13.3.1 Fundamentals 438
13.3.2 Effect of Morphology 439
Definition of Melting Temperature 439
Effect of Heating Rate 440
Effect of Crystallite Size 441
13.3.3 Molar Mass Dependence 442
13.3.4 Effect of Constitution 444
13.4 Transitions of Liquid Crystals 448
13.4.1 Thermal States 448
13.4.2 Molar Mass Dependence 451
13.4.3 Thermodynamic Quantities 451
13.5 Glass Transformations 452
13.5.1 Free Volumes 454
13.5.2 Molecular Interpretations 455
13.5.3 Effect of Constitution 458
Linear Chains of Homopolymers 458
Branched Polymers 460
Dendrimers 461
13.5.4 Plasticizing 461
External Plasticizing 461
Internal Plasticizing 463
Crosslinked Polymers 465
13.5.5 Static and Dynamic Glass Temperatures 466
13.6 Other Transformations and Relaxations 469
Historical Notes to Chapter 13 470
Table of Contents XXXI
Literature to Chapter 13 470
References to Chapter 13 471
14 Transport in Polymers 473
14.1 Introduction 473
14.2. Transport in Fluid Polymer Phases 474
14.2.1 Solvents in Concentrated Polymer Solutions 474
14.2.2 Polymers in Melts 475
14.2.3 Reptation of Polymer Chains 477
14.2.4 Polymer Chains in Polymer Matrices 479
14.3 Permeation Through Polymers 481
14.3.1 Overview 481
14.3.2 Permeability Coefficients 482
14.3.3 Permeation of Gases 484
14.3.4 Permeation of Liquids 486
14.4 Transport of Polymers Through Porous Membranes 487
14.4.1 Membranes 487
14.4.2 Diffusion Through Pores 487
Historical Notes to Chapter 14 489
Literature to Chapter 14 489
References to Chapter 14 490
15 Melt Viscosity 491
15.1 Deformation 491
15.2 Viscometry 494
15.2.1 Types of Viscosity 494
15.2.2 Viscometers 494
15.3 Newtonian Shear Viscosities 496
15.3.1 Melt Viscosities of Linear Polymers 496
15.3.2 Rouse Theory 497
15.3.3 Corrections for the Rouse Range 499
15.3.4 Reptation 500
15.3.5 Non-linear Macromolecules 502
15.4 Non-Newtonian Shear Viscosity 503
15.4.1 Overview 503
15.4.2 Rheometry 505
15.4.3 Melt Elasticity 508
15.5 Elongational Viscosity 509
15.5.1 Fundamentals 509
15.5.2 Elongational Viscosity of Melts 510
15.5.3 Elongational Viscosity of Solutions 511
Appendix to Chapter 15: Capillary Viscometry 514
Historical Notes to Chapter 15 514
Literature to Chapter 15 515
References to Chapter 15 516
XXXII Table of Contents
16 Elasticity 517
16.1. Introduction 517
16.2 Tensile Properties 519
16.2.1 Basic Terms 519
Nominal Tensile Properties 519
True Stress-Strain Curves 521
Stress Softening 521
16.2.2 Hooke sLaw 522
16.2.3 Poisson s Ratio 523
16.2.4 Testing 525
Tensile Moduli 525
Flexural Moduli 528
Lattice Moduli 529
16.2.5 Types of Deformation 530
16.3 Energy Elasticity 533
16.3.1 Generalized Hooke Equation 534
16.3.2 Linear Elasticity Theory 535
Stresses 535
Deformations 536
16.3.3 Stiffness Constants and Compliance Constants 537
Orthotropic Bodies 538
Oriented Bodies 539
Isotropic Bodies 541
16.3.4 Theoretical Moduli 542
16.3.5 Real Moduli of Elasticity 545
Mixing Rules 546
Takayanagi Models 547
Effect of Processing 549
16.4 Entropy Elasticity 549
16.4.1 Phenomena 549
16.4.2 Entropy-elasticity of Single Molecules 551
16.4.3 Chemical Thermodynamics 552
16.4.4 Statistical Thermodynamics 555
16.4.5 Models 557
16.4.6 Uniaxial Extension 559
16.4.7 Biaxial Extension 560
16.4.8 Elongation of Real Networks 560
16.4.9 Shearing of Networks 563
Historical Notes to Chapter 16 565
Literature to Chapter 16 566
References to Chapter 16 567
17 Viscoelasticity 569
17.1 Introduction 569
17.1.1 Overview 569
17.1.2 Definitions 569
Table of Contents XXXIII
17.2 Yield Point 572
17.2.1 Considere Construction 572
17.2.2 Molecular Reasons for Yielding 573
17.2.3 Yield Points and Necking 576
17.2.4 Flow Criteria 577
17.3 Flow Range 579
17.3.1 Crazes and Shear Bands 579
17.3.2 Effect of Entanglement Density 579
17.3.3 Proportion of Crazes and Shear Bands 580
17.3.4 Large Elongations 582
17.3.5 Yielding as a Flow Process 584
17.4 Creep and Relaxation 586
17.4.1 Two-parameter Models 586
17.4.2 Stress Relaxation 588
17.4.3 Creep Experiment 590
17.4.4 Three-and Four-parameter Models 591
17.4.5 Boltzmann Superposition Principle 594
17.5 Dynamic Deformations 596
17.5.1 Forced Oscillations 596
17.5.2 Free Oscillations 598
17.5.3 Complex Moduli 599
17.5.4 Dynamic Moduli of Solid Polymers 602
17.5.5 Shear Storage Moduli of Polymer Melts 603
17.5.6 Shear Storage Moduli of Solutions 606
A-17 Appendic: Alternating Deformations 608
Historical Notes to Chapter 17 609
Literature to Chapter 17 610
References to Chapter 17 611
18 Fracture 613
18.1 Introduction 613
18.1.1 Definitions 613
18.1.2 Test Methods 614
18.1.3 Effect of Molar Mass 615
18.1.4 Stress Cracking 617
18.2 Fracture Strengths 619
18.2.1 Introduction 619
18.2.2 Fracture of Brittle Polymers 620
18.2.3 Initiation of Fracture 623
18.2.4 Fracture Propagation 624
18.2.5 Theoretical Fracture Strengths 626
18.3 Real Fracture Strengths 628
18.3.1 Introduction 628
18.3.2 Critical Stress Intensity Factors 629
18.3.3 Fracture Toughness 631
18.3.4 Fracture of Ductile Polymers 631
XXXIV Table of Contents
18.3.5 Impact Strength 633
Historical Notes to Chapter 18 635
Literature to Chapter 18 636
References to Chapter 18 637
19 Appendix 639
19.1 SI Physical Quantities and Units 639
19.2 Common Physical Quantities and Units 643
19.3 Concentrations 646
19.4 Ratios of Physical Quantities 646
19.4 Constitution and Names of Polymer Molecules 647
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XXI
Table of Contents
Motto V
Preface VII
List of Symbols IX
Symbols for Languages IX
Mathematical Symbols IX
Symbols for Chemical Structures X
Averages and Other Markings X
Exponents and Superscripts X
Indices and Subscripts XI
Prefixes of Words XIII
Other Abbreviations XIV
Table of Contents XXI
1 Introduction 1
Literature to Chapter 1 4
2 Chemical Structure 7
2.1 Constitution 7
2.1.1 Definitions 7
2.1.2 Simple Polymer Chains 8
2.1.3 Polymer Architecture 9
Linear Polymers 9
Branched Polymers 10
Macromolecules with Higher Constitutional Dimensions . 11
2.2 Chemical Configuration 13
2.2.1 Basic Terms 13
2.2.2 Chemical Configurational Statistics 14
2.3 Molar Masses and Degrees of Polymerization 16
2.3.1 Overview 16
2.3.2 Statistical Weights 18
2.3.3 Simple Averages of Molar Masses 20
2.3.4 Hydrodynamic Averages of Molar Masses 21
Simple Hydrodynamic Averages 22
Complex Hydrodynamic Averages 22
2.3.5 Averages of Degrees of Polymerization 24
2.3.6 Averages of Other Properties 24
2.3.7 Moments of Distributions 25
2.3.8 Molecular Non-Uniformity 26
2.3.9 Constitutional Non-Uniformity 26
Sequence Lengths of Segments 27
Mass-average Molar Mass of Segments 28
2.3.10 Determination of Molar Masses 28
2.4 Distribution Functions 30
XXII Table of Contents
2.4.1 Types 30
2.4.2 Gaussian Distribution 31
2.4.3 Logarithmic Normal Distribution 34
2.4.4 Poisson Distribution 35
2.4.5 Schulz-Zimm and Schulz-Flory Distributions 36
2.4.6 Generalized Exponential Distributions 37
2.4.7 Determination of Molar Mass Distributions 37
Historical Notes to Chapter 2 39
Literature to Chapter 2 39
References to Chapter 2 40
3 Microconformations 41
3.1 Introduction 41
3.2. Local Conformations 42
3.2.1 Definitions 42
3.2.2 Rotational Potentials 43
3.2.3 Effect of Constitution 44
3.3 Sequences of Microconformations 46
3.3.1 Introduction 46
3.3.2 Helices 47
3.3.3 Constitution and Configuration Dependence 50
3.4 Optical Activity 53
3.4.1 Fundamentals 53
Circular Dichroism 53
Optical Activity 54
Optical Rotatory Dispersion 55
3.4.2 Structural Dependence 55
Poly(a-amino acid)s and Proteins 55
Poly(l-olefin)s 57
Copolymers 59
3.5 Transformation of Macroconformations 59
3.5.1 Phenomena 59
3.5.2 Thermodynamics 60
3.5.3 Kinetics 62
Historical Notes to Chapter 3 63
Literature to Chapter 3 64
References to Chapter 3 64
4 Macroconformations 65
4.1 Overview 65
4.1.1 Introduction 65
4.1.2 Macroconformations in Solution 66
Complete Helices in Solution 66
Helical Sections in Solution 67
4.2 Compact Molecules 68
4.2.1 Introduction 68
Table of Contents XXIII
4.2.2 Spheroids 69
Spheres 69
Ellipsoids 71
4.2.3 Rods 72
4.3 Molecular and Atomistic Modeling 73
4.3.1 Introduction 73
4.3.2 Methods 74
Group Increment Methods 74
Lattice Methods 75
Lattice-free Methods 76
4.3.3 Atomistic Force Fields 78
4.4 Unperturbed Coils of Linear Chains 81
4.4.1 Contour Lengths 82
4.4.2 End-to-end Distance and Radius of Gyration 83
4.4.3 Types of Coils 85
4.4.4 Molecular Models 85
Random-flight Chain 86
Freely Jointed Chain 88
Freely Rotating Chain 89
Chains with Restricted Rotation 91
Rotational Isomeric State 91
4.4.5 Flexibility of Chains 95
Steric Factor 95
Characteristic Ratio 96
Kuhnian Length 97
Persistence Length 98
4.4.6 Radius of Gyration 98
4.4.7 Coil Density 100
4.4.8 Distribution of End-to-End Distances 103
4.4.9 Worm-like Chains 104
4.5 Perturbed Coils of Linear Chains 107
4.5.1 Excluded Volumes 107
4.5.2 Expansion Factors 108
4.5.3 Helical Worm-like Chains 110
4.5.4 Molar Mass Dependence 110
4.5.5 Non-Uniformity Corrections 114
4.5.6 Temperature Dependence of Radii of Gyration 116
4.6 Cyclic Macromolecules 117
4.7 Branched Macromolecules 117
4.7.1 Introduction 117
4.7.2 Star Molecules 118
4.7.3 Comb Molecules 119
4.7.4 Dendrimers 121
4.8 Scaling 124
4.8.1 Local and Global Views 124
4.8.2 Fractals 126
XXIV Table of Contents
4.8.3 Self-similarity 127
A-4 Appendix to Chapter 4 129
A-4.1 Freely Rotating Chains 129
A-4.2 Distribution of End-to-End Distances 130
A-4.3 End-to-End Distance and Radius of Gyration 131
Historical Notes to Chapter 4 133
Bibliography of Force Fields 134
Literature to Chapter 4 135
References to Chapter 4 137
5 Scattering Methods 139
5.1 Overview 139
5.2 Static Light Scattering: Rayleigh Range 140
5.2.1 Fundamentals 140
5.2.2 Copolymers 144
5.2.3 Concentration Dependence 146
5.2.4 Mixed Solvents 147
5.3 Static Light Scattering: Debye Range 150
5.3.1 Introduction 150
5.3.2 Scattering Functions 150
5.3.3 ZimmPlot 153
5.3.4 Effect of Particle Shape 154
Spheres 154
Rods 154
Random Coils 155
Worm-like Chains 157
Star Molecules 158
Comb Molecules 159
5.4 Small-Angle X-Ray Scattering 160
5.4.1 Fundamentals 160
5.4.2 Scattering Functions 162
Linear Chains 162
Branched Polymers 164
5.5 Small-Angle Neutron Scattering 166
5.5.1 Fundamentals 166
5.5.2 Experimental Results 168
Historical Notes to Chapter 5 170
Literature to Chapter 5 170
References to Chapter 5 171
6 Disordered Condensed Systems 173
6.1 Amorphous Polymers 173
6.1.1 Structure 173
6.1.2 Density 176
6.2 Polymer Melts 178
6.2.1 Microconformations 178
Table of Contents XXV
6.2.2 Macroconformations 179
6.2.3 Entanglement of Polymer Chains 180
6.2.4 Temperature Dependence of Radii of Gyration 181
6.3 Semi-Concentrated Solutions 183
6.3.1 Concentration Ranges 183
6.3.2 Temperature Dependence of Coil Dimensions 184
6.3.3 Blobs 185
6.3.4 Radii of Gyration of Star Molecules 188
Historical Notices to Chapter 6 189
Literature to Chapter 6 189
References to Chapter 6 190
7 Crystalline States 191
7.1 Crystal Structures 191
7.1.1 Definitions of a Crystal 191
7.1.2 Lattice Structures 191
7.1.3 Symmetry Properties 193
7.1.4 Crystal Structure by X-Ray Diffraction 194
7.1.5 Lattice Constants 197
7.1.6 Lattice Structures 199
7.1.7 Polymorphism 201
7.1.8 Isomorphism 202
7.1.9 Unit Cells 202
7.2 Structure of Crystallites 203
7.2.1 Fringed Micelles 203
7.2.2 Polymer Single Crystals 204
7.2.3 Structure of Folds 206
7.2.4 Structure of Lamellae 208
7.3 Crystallization 210
7.3.1 Formation of Nuclei 210
Homogeneous Nucleation 210
Heterogeneous Nucleation 211
Nucleation Agents 212
Crystallization from Solution 213
Crystallization from Melts 215
7.3.2 Crystallization Rates 215
7.4 Morphology 219
7.4.1 Spherulites 219
7.4.2 Other Superstructures 220
7.4.3 Factors Controlling Crystallization 221
7.5 Crystallinity 224
7.5.1 Ideal Crystals 224
7.5.2 Crystallizability and Crystallinity 224
7.5.3 Lattice Defects 225
7.5.4 One-Phase and Two-Phase Models 225
7.5.5 X-Ray Diffraction 226
XXVI Table of Contents
7.5.6 Density 227
7.5.7 Calorimetry 228
7.5.8 Infrared Spectrometry 228
7.5.9 Indirect Methods 229
7.6 Orientation 229
7.6.1 X-Ray Interference 230
7.6.2 Optical Birefringence 230
7.6.3 Propagation of Ultrasound 232
7.6.4 Infrared Dichroism 232
7.6.5 Polarized Fluorescence 233
Historical Notes to Chapter 7 234
Literature to Chapter 7 235
References to Chapter 7 237
8 Mesophases 239
8.1 Introduction 239
8.1.1 Types of Mesophases 239
8.1.2 Other Mesophases 239
8.2 Mesomorphic States 240
8.2.1 Mesogens 241
8.2.2 Order in Domains 242
8.3 Lyotropic Liquid-Crystalline Polymers 244
8.3.1 Survey 244
8.3.2 Phase Separation 246
Onsager Theory 246
Flory Theory 247
8.3.3 Chemical Potentials 250
8.3.4 Orientation of Mesogens 253
8.3.5 Amphotropic Liquid Crystals 255
8.4 Thermotropic Liquid-Crystalline Polymers 257
8.4.1 Structural Requirements 257
8.4.2 Physical Structure of SCLCPs 258
8.4.3 Properties of Mesophases 260
8.5 Block Polymers 261
8.5.1 Survey 261
8.5.2 Thermotropic Domains 262
8.5.3 Lyotropic Structures 266
8.6 Ionomers 267
Historical Notes to Chapter 8 269
Literature to Chapter 8 269
References to Chapter 8 271
9 Polymers in and at Interfaces 273
9.1 Surface of Polymers 273
9.1.1 Fundamentals 273
9.1.2 Surface Composition 273
Table of Contents XXVII
9.2 Interfacial Tension 275
9.2.1 Determination of Interfacial Tension 275
9.2.2 Time Effects 277
9.2.3 Surface Tension of Polymer Melts 279
9.2.4 Interfacial Tension between Polymer Melts 280
9.2.5 Surface Tension of Polymer Solutions 280
9.2.6 Critical Surface Tension Solid-Liquid 281
9.3 Thin Layers of Polymers 283
9.4 Adsorption on Surfaces 286
9.4.1 Fundamentals 286
9.4.2 Methods 287
9.4.3 Time Dependence 287
9.4.4 Adsorption Equilibria 288
9.5 Polymer Brushes 290
9.5.1 Repulsive Forces 290
9.5.2 Blob Theory 291
Historical Notes to Chapter 9 293
Literature to Chapter 9 294
References to Chapter 9 295
10 Thermodynamics of Polymer Solutions 297
10.1 Chemical Thermodynamics 297
10.1.1 Introduction 297
10.1.2 Thermodynamic Classification of Solutions 297
10.1.3 Solubility Parameters 299
Solubility Parameters of Solvents 299
Solubility Parameters of Polymers 300
Enthalpy of Mixing 302
10.1.4 Molecular Considerations 303
Self-association of Solvent Molecules 304
Solvation 304
Preferential Solvation 305
10.1.5 Rate of Dissolution 306
10.2 Statistical Thermodynamics 307
10.2.1 Introduction 307
10.2.2 Lattice Theory 308
Enthalpy of Mixing 308
Interaction Parameter 309
Entropy of Mixing 310
Gibbs Energy of Mixing 312
Chemical Potentials 312
Summary 313
10.2.3 Phase Separation 314
Solutions of Amorphous Polymers 314
Quasi-binary Systems 316
Fractionation 317
XXVIII Table of Contents
Cloud Point Titrations 318
Precipitation Fractionation of Polymers 319
Polymer Mixtures in Solution 320
Polymer Blends 320
Critical Miscibility Temperatures 321
Solutions of Crystalline Polymers 323
10.3 Osmotic Pressure 325
10.3.1 Fundamentals 325
10.3.2 Membrane Osmometry 326
Semipermeable Membranes 326
Non-semipermeable Membranes 327
10.3.3 Ebullioscopy and Cryoscopy 328
10.3.4 Vapor Phase Osmometry 330
10.4 Virial Coefficients 330
10.4.1 Fundamentals 330
10.4.2 Lattice Theory 332
10.4.3 Effect of Excluded Volume 335
10.4.4 Effect of Molar Mass 335
10.4.5 Effect of Temperature 336
10.4.6 Osmotic Pressure of Semi-concentrated Solutions 337
10.5 Association and Self-association 339
10.5.1 Fundamentals 339
10.5.2 Open Self-association 340
10.5.3 Closed Self-association 343
10.5.4 Complexation of Polymers with Small Molecules 346
10.5.5 Polymer-Polymer Complexes 348
10.6 Polyelectrolytes 351
10.6.1 Structure of Polyelectrolyte Solutions 351
10.6.2 Thermodynamic Activity 352
10.6.3 Osmotic Pressure 354
10.7 Gels 356
10.7.1 Survey 356
10.7.2 Swelling of Chemically Crosslinked Neutral Gels 357
10.7.3 Swelling of Electrically Charged, Chemically Crosslinked Gels 358
10.7.4 Physically Crosslinked Gels 359
Historical Notes to Chapter 10 360
Literature to Chapter 10 361
References to Chapter 10 364
11 Transport in Solution , 365
11.1 Translational Diffusion 365
11.1.1 Introduction 365
11.1.2 Measurements 366
Classic Method 366
Dynamic Light Scattering 368
11.1.3 Friction Coefficients of Translation 370
Table of Contents XXIX
Spheres 370
Ellipsoids 370
Rods 371
Random Coils 372
11.1.4 Diffusion Coefficients 375
Spheres 375
Rigid Rods 376
Random Coils 377
11.1.5 Concentration Dependence, Dilute Solutions 377
11.1.6 Concentration Dependence, Semi-concentrated Solutions . 378
11.17 Structured Flow 380
11.2 Sedimentation 381
11.2.1 Fundamentals 381
11.2.2 Sedimentation Rate 383
Sedimentation Coefficients 383
Concentration Dependence 384
Molar Mass Dependence 387
11.2.3 Sedimentation Equilibrium 389
11.2.4 Sedimentation Equilibrium in Density Gradients 389
11.3 Field-Flow Fractionation 390
11.4 Electrophoresis 391
Historical Notes to Chapter 11 392
Literature to Chapter 11 392
References to Chapter 11 394
12 Viscosity of Dilute Solutions 395
12.1 Fundamentals 395
12.1.1 Definitions 395
12.1.2 Experimental Methods 396
12.2 Concentration Dependence 399
12.2.1 Non-Electrolytes 399
12.2.2 Polyelectrolytes 402
12.3 Intrinsic Viscosities 405
12.3.1 Averages 405
12.3.2 Hydrodynamic Volumes 406
12.3.3 Spheres 407
12.3.4 Ellipsoids 408
12.3.5 Rods 410
12.3.6 Unperturbed Coils 411
Exponents a 411
Values of Kv 412
Hydrodynamic Radii 413
12.3.7 Perturbed Coils 416
12.3.8 Branched Polymer Molecules 417
Randomly Branched Polymers 419
Dendrimers 420
XXX Table of Contents
Hyperbranched Polymers 421
Comb Polymers 421
Star Polymers 421
12.3.9 Polyelectrolytes 422
A-12 Appendix to Chapter 12: Flory Constants 423
Historical Notes to Chapter 12 424
Literature to Chapter 12 425
References to Chapter 12 425
13 Thermal Properties 427
13.1 Fundamentals 427
13.1.1 Introduction 427
13.1.2 Thermodynamic States 427
13.1.3 Order of Thermal Transitions 428
13.1.4 Experimental Methods 430
13.2 Mobility of Molecules 433
13.2.1 Thermal Expansion 433
13.2.2 Heat Capacity 434
13.2.3 Thermal Conductivity 436
13.2.4 Thermal Relaxations 437
13.3 Melting 438
13.3.1 Fundamentals 438
13.3.2 Effect of Morphology 439
Definition of Melting Temperature 439
Effect of Heating Rate 440
Effect of Crystallite Size 441
13.3.3 Molar Mass Dependence 442
13.3.4 Effect of Constitution 444
13.4 Transitions of Liquid Crystals 448
13.4.1 Thermal States 448
13.4.2 Molar Mass Dependence 451
13.4.3 Thermodynamic Quantities 451
13.5 Glass Transformations 452
13.5.1 Free Volumes 454
13.5.2 Molecular Interpretations 455
13.5.3 Effect of Constitution 458
Linear Chains of Homopolymers 458
Branched Polymers 460
Dendrimers 461
13.5.4 Plasticizing 461
External Plasticizing 461
Internal Plasticizing 463
Crosslinked Polymers 465
13.5.5 Static and Dynamic Glass Temperatures 466
13.6 Other Transformations and Relaxations 469
Historical Notes to Chapter 13 470
Table of Contents XXXI
Literature to Chapter 13 470
References to Chapter 13 471
14 Transport in Polymers 473
14.1 Introduction 473
14.2. Transport in Fluid Polymer Phases 474
14.2.1 Solvents in Concentrated Polymer Solutions 474
14.2.2 Polymers in Melts 475
14.2.3 Reptation of Polymer Chains 477
14.2.4 Polymer Chains in Polymer Matrices 479
14.3 Permeation Through Polymers 481
14.3.1 Overview 481
14.3.2 Permeability Coefficients 482
14.3.3 Permeation of Gases 484
14.3.4 Permeation of Liquids 486
14.4 Transport of Polymers Through Porous Membranes 487
14.4.1 Membranes 487
14.4.2 Diffusion Through Pores 487
Historical Notes to Chapter 14 489
Literature to Chapter 14 489
References to Chapter 14 490
15 Melt Viscosity 491
15.1 Deformation 491
15.2 Viscometry 494
15.2.1 Types of Viscosity 494
15.2.2 Viscometers 494
15.3 Newtonian Shear Viscosities 496
15.3.1 Melt Viscosities of Linear Polymers 496
15.3.2 Rouse Theory 497
15.3.3 Corrections for the Rouse Range 499
15.3.4 Reptation 500
15.3.5 Non-linear Macromolecules 502
15.4 Non-Newtonian Shear Viscosity 503
15.4.1 Overview 503
15.4.2 Rheometry 505
15.4.3 Melt Elasticity 508
15.5 Elongational Viscosity 509
15.5.1 Fundamentals 509
15.5.2 Elongational Viscosity of Melts 510
15.5.3 Elongational Viscosity of Solutions 511
Appendix to Chapter 15: Capillary Viscometry 514
Historical Notes to Chapter 15 514
Literature to Chapter 15 515
References to Chapter 15 516
XXXII Table of Contents
16 Elasticity 517
16.1. Introduction 517
16.2 Tensile Properties 519
16.2.1 Basic Terms 519
Nominal Tensile Properties 519
True Stress-Strain Curves 521
Stress Softening 521
16.2.2 Hooke'sLaw 522
16.2.3 Poisson's Ratio 523
16.2.4 Testing 525
Tensile Moduli 525
Flexural Moduli 528
Lattice Moduli 529
16.2.5 Types of Deformation 530
16.3 Energy Elasticity 533
16.3.1 Generalized Hooke Equation 534
16.3.2 Linear Elasticity Theory 535
Stresses 535
Deformations 536
16.3.3 Stiffness Constants and Compliance Constants 537
Orthotropic Bodies 538
Oriented Bodies 539
Isotropic Bodies 541
16.3.4 Theoretical Moduli 542
16.3.5 Real Moduli of Elasticity 545
Mixing Rules 546
Takayanagi Models 547
Effect of Processing 549
16.4 Entropy Elasticity 549
16.4.1 Phenomena 549
16.4.2 Entropy-elasticity of Single Molecules 551
16.4.3 Chemical Thermodynamics 552
16.4.4 Statistical Thermodynamics 555
16.4.5 Models 557
16.4.6 Uniaxial Extension 559
16.4.7 Biaxial Extension 560
16.4.8 Elongation of Real Networks 560
16.4.9 Shearing of Networks 563
Historical Notes to Chapter 16 565
Literature to Chapter 16 566
References to Chapter 16 567
17 Viscoelasticity 569
17.1 Introduction 569
17.1.1 Overview 569
17.1.2 Definitions 569
Table of Contents XXXIII
17.2 Yield Point 572
17.2.1 Considere Construction 572
17.2.2 Molecular Reasons for Yielding 573
17.2.3 Yield Points and Necking 576
17.2.4 Flow Criteria 577
17.3 Flow Range 579
17.3.1 Crazes and Shear Bands 579
17.3.2 Effect of Entanglement Density 579
17.3.3 Proportion of Crazes and Shear Bands 580
17.3.4 Large Elongations 582
17.3.5 Yielding as a Flow Process 584
17.4 Creep and Relaxation 586
17.4.1 Two-parameter Models 586
17.4.2 Stress Relaxation 588
17.4.3 Creep Experiment 590
17.4.4 Three-and Four-parameter Models 591
17.4.5 Boltzmann Superposition Principle 594
17.5 Dynamic Deformations 596
17.5.1 Forced Oscillations 596
17.5.2 Free Oscillations 598
17.5.3 Complex Moduli 599
17.5.4 Dynamic Moduli of Solid Polymers 602
17.5.5 Shear Storage Moduli of Polymer Melts 603
17.5.6 Shear Storage Moduli of Solutions 606
A-17 Appendic: Alternating Deformations 608
Historical Notes to Chapter 17 609
Literature to Chapter 17 610
References to Chapter 17 611
18 Fracture 613
18.1 Introduction 613
18.1.1 Definitions 613
18.1.2 Test Methods 614
18.1.3 Effect of Molar Mass 615
18.1.4 Stress Cracking 617
18.2 Fracture Strengths 619
18.2.1 Introduction 619
18.2.2 Fracture of Brittle Polymers 620
18.2.3 Initiation of Fracture 623
18.2.4 Fracture Propagation 624
18.2.5 Theoretical Fracture Strengths 626
18.3 Real Fracture Strengths 628
18.3.1 Introduction 628
18.3.2 Critical Stress Intensity Factors 629
18.3.3 Fracture Toughness 631
18.3.4 Fracture of Ductile Polymers 631
XXXIV Table of Contents
18.3.5 Impact Strength 633
Historical Notes to Chapter 18 635
Literature to Chapter 18 636
References to Chapter 18 637
19 Appendix 639
19.1 SI Physical Quantities and Units 639
19.2 Common Physical Quantities and Units 643
19.3 Concentrations 646
19.4 Ratios of Physical Quantities 646
19.4 Constitution and Names of Polymer Molecules 647 |
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| index_date | 2024-07-02T19:11:19Z |
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