Phenomenology of Polymer Solution Dynamics

PHENOMENOLOGY OF POLYMER SOLUTION DYNAMICS......Page 2
Title......Page 4
Copyright......Page 5
Dedication......Page 6
Contents......Page 8
Preface......Page 14
References......Page 17
1.1 Plan of the work......Page 18
1.2 Classes of model for comparison with experiment......Page 22
1.3 Interpretation of literature experimental results......Page 25
References......Page 26
2.1 Introduction......Page 27
2.2 Homogeneous sedimentation......Page 29
2.3 Probe sedimentation......Page 35
2.4 General properties: sedimentation......Page 43
References......Page 45
3.1 Introduction......Page 47
3.2 Basis of electrophoretic studies......Page 48
3.3 Electrophoresis using nucleic acid probes......Page 50
3.4 Videomicroscopy of DNA electrophoresis......Page 60
3.5 Electrophoresis of denatured polypeptides......Page 66
3.6 Particulate probes......Page 67
3.7 Triblock copolymer matrices......Page 73
3.8 Other electrophoretic experiments......Page 74
3.9 General properties: electrophoresis......Page 76
References......Page 81
4.1 Introduction......Page 86
4.2 Scattering and particle positions......Page 87
4.3 Nomenclature for diffusion coefficients......Page 90
4.4 Diffusion coefficients......Page 92
4.5 Calculation of diffusion coefficients......Page 93
4.5.2 Langevin interpretation......Page 94
4.5.3 Direct mechanical calculation......Page 98
4.5.4 Dynamic scaling length......Page 102
4.6 Rotational diffusion: segmental diffusion......Page 103
4.7 Interpretation of spectra......Page 104
References......Page 108
5.2 Motion in large-viscosity simple solvents......Page 111
5.3 Small-molecule translational diffusion in polymer solutions......Page 114
5.4 Small-molecule rotational diffusion in polymer solutions......Page 122
5.5 High-frequency viscoelasticity......Page 127
5.6 General properties: solvent dynamics......Page 128
References......Page 129
6.2 Depolarized light scattering......Page 133
6.3 Time-resolved optical polarization......Page 134
6.4 Magnetic resonance experiments......Page 143
6.5 General properties: segmental diffusion......Page 146
References......Page 148
7.1 Introduction......Page 151
7.2 End-to-end distances and relaxation times......Page 154
7.3 Chain dimensions and chain contraction......Page 161
7.4 Relaxation spectra – single mode......Page 166
7.5 Relaxation spectra – multiple modes and mode decompositions......Page 172
7.6 General properties: dielectric relaxation......Page 179
References......Page 185
8.1 Introduction......Page 188
8.2 Self-diffusion......Page 189
8.3 Tracer diffusion......Page 202
8.4 Other experimental studies......Page 221
8.5 General properties: single-chain dynamics......Page 224
References......Page 230
9.1 Introduction......Page 235
9.2 Light scattering spectroscopy......Page 236
9.3 Large probes......Page 238
9.4 Small probes......Page 247
9.5 Re-entrant phenomena......Page 250
9.6 Multiple relaxation modes......Page 253
9.7 Polyelectrolyte matrices......Page 257
9.8 Solvent quality......Page 260
9.9 Temperature dependence......Page 261
9.10 Hydroxypropylcellulose solutions......Page 264
9.11 Probe rotational diffusion......Page 274
9.12 Comparison of probe diffusion and polymer self-diffusion......Page 277
9.13 Particle tracking methods......Page 278
9.14 True microrheological measurements......Page 281
9.15 Probes in gels and biological systems......Page 284
9.16 Probe spectra interpreted with the Gaussian assumption......Page 286
9.17.1 Concentration dependence of Dp......Page 288
9.17.2 Quantitative parameter behavior......Page 289
9.17.3 Particle size effects......Page 291
9.17.4 Temperature dependence......Page 293
9.17.5 Probe diffusion, particle tracking, and true viscosity measurements......Page 294
9.17.6 Systems having multimodal spectra......Page 295
9.17.7 Probe diffusion and the solution viscosity......Page 296
References......Page 297
10.1 Introduction......Page 304
10.2 Single-particle diffusion......Page 307
10.3 Dynamic structure factor and mutual diffusion......Page 310
10.4 Rotational diffusion......Page 314
10.5 Viscosity......Page 318
10.6 Viscoelastic properties......Page 324
10.7 General properties: colloid dynamics......Page 328
References......Page 332
11.1 Introduction......Page 337
11.2.1 Theoretical expectations......Page 338
11.2.2 Phenomenology of S(q,t): near-dilute solution......Page 340
11.2.3 Phenomenology of S(q,t): small q......Page 341
11.2.4 Phenomenology of S(q,t): larger c and q......Page 343
11.3 Neutral polymer slow modes......Page 346
11.3.1 Physical nature of the slow mode......Page 347
11.3.2 Slow mode in good solvents......Page 350
11.3.3 Slow mode in Theta solvents......Page 353
11.4 The polyelectrolyte slow mode......Page 354
11.5 Thermal diffusion and Soret coefficients......Page 356
11.6 Nondilute ternary systems......Page 358
11.7 Inelastic neutron scattering......Page 360
11.8 General properties: dynamic structure factor......Page 361
References......Page 367
12.1 Introduction......Page 372
12.2.1 Stretched-exponential behavior......Page 374
12.2.2 The solutionlike-meltlike transition......Page 382
12.2.3 Molecular weight dependence......Page 394
12.2.4 Effect of chain topology......Page 397
12.2.5 Solvent quality......Page 399
12.2.6 Effect of temperature......Page 400
12.3.1 Functional form of η(c,M)......Page 402
12.3.2 Effect of chain topology......Page 404
12.3.3 Effect of solvent quality......Page 405
12.3.4 Quantitative behavior of the scaling parameters......Page 406
12.4 Conclusions......Page 409
References......Page 410
13.1 Remarks......Page 414
13.2 Temporal scaling ansatz for viscoelastic behavior......Page 415
13.3  Phenomenology of the dynamic moduli......Page 420
13.4 Phenomenology of shear thinning......Page 435
13.5 Concentration and molecular weight effects......Page 444
13.5.1 Material-dependent parameters from G\'(ω) and G\"(ω)......Page 445
13.5.2 Scaling parameters from η(κ)......Page 449
13.5.3  Validation of the Kronig–Kramers relations......Page 452
13.6 Optical flow birefringence......Page 453
13.7 General properties: viscoelasticity......Page 454
References......Page 458
14.1 Normal stress differences......Page 462
14.2 Memory-effect phenomena......Page 465
14.2.1 Relaxations after change in shear rate......Page 466
14.2.2 Relaxations after time-dependent strains......Page 467
14.2.3 Extensional viscosity......Page 468
14.3.1 Shear banding......Page 469
14.3.2 Nonquiescent strain relaxation......Page 470
14.3.4 Fourier-transform rheology......Page 471
14.4 Remarks......Page 472
References......Page 473
15.2 Sedimentation......Page 476
15.3 Electrophoresis......Page 478
15.4 Light scattering spectroscopy......Page 480
15.5 Solvent and small-molecule motion......Page 481
15.6 Segmental dynamics......Page 482
15.7 Dielectric relaxation and chain dimensions......Page 483
15.8 Single-chain diffusion......Page 484
15.9 Probe diffusion......Page 485
15.10 Colloid dynamics......Page 486
15.11 The dynamic structure factor......Page 488
15.12 Low-shear viscosity......Page 489
15.13 Viscoelasticity......Page 490
16.2 Comparison with scaling and exponential models......Page 492
16.3 Parametric trends......Page 494
16.4 Transitions......Page 495
16.5 Comparison of colloid and polymer dynamics......Page 498
16.6 How do polymers move in nondilute solution?......Page 501
16.7 Hydrodynamic interactions in solution......Page 503
16.8 Length scales in polymer solutions......Page 505
16.9 Effect of chain topology......Page 506
16.10 Other constraints......Page 507
References......Page 508
17: Afterword: hydrodynamic scaling model for polymer dynamics......Page 511
References......Page 514
Index......Page 516