Dynamics of Surfactant Self-Assemblies: Micelles, Microemulsions, Vesicles and Lyotropic Phases (Surfactant Science)

Cover......Page 1
Contents......Page 13
PREFACE......Page 15
REFERENCES......Page 18
List of Contributors......Page 19
Introduction to Surfactants and Surfactant Self-Assemblies......Page 21
I. Surfactants and Self-Assemblies of Surfactants......Page 22
II. Adsorbed Surfactant Layers on Solid Surfaces......Page 26
A. Theoretical Aspects......Page 28
B. Experimental Aspects......Page 32
D. Water-Soluble Polymer/Surfactant Systems......Page 36
IV. Microemulsions......Page 37
V. Vesicles......Page 41
VI. Lyotropic Liquid Crystals (Mesophases)......Page 46
VII. Conclusion: Importance of Dynamic Aspects of Surfactant Self-Assemblies......Page 50
References......Page 51
Methods for the Study of the Dynamics of Surfactant Self-Assemblies......Page 57
I. Introduction......Page 58
A. Principle......Page 59
1. Single-Step Processes......Page 61
2. Multistep Processes......Page 63
C. Relaxation Amplitudes......Page 64
D. Chemical Relaxation Techniques......Page 65
1. T-jump......Page 66
2. p-jump......Page 68
3. Shock Tube......Page 71
4. E-jump......Page 72
5. Ultrasonic Absorption......Page 73
6. Stopped-Flow......Page 76
III. Time-Resolved Luminescence Quenching......Page 78
IV. Nuclear Magnetic Resonance (NMR)......Page 82
V. Electron Spin Resonance (ESR)......Page 84
VI. Rheology......Page 86
B. Fluctuation Spectroscopy......Page 88
References......Page 89
Dynamics in Micellar Solutions of Surfactants......Page 95
I. Introduction......Page 97
1. Basic Assumptions......Page 101
2. Relaxation Time for the Exchange Process......Page 104
3. Relaxation Time for the Micelle Formation/Breakdown......Page 106
1. Exchange Process......Page 107
2. Micelle Formation/Breakdown......Page 109
C. Relaxation Amplitudes......Page 111
D. Extension to Mixed Micelles......Page 112
E. Other Theoretical Treatments of Micellar Kinetics......Page 113
A. General Observations......Page 114
B. Information Gained from Studies of the Exchange Process......Page 121
C. Information Gained from Studies of the Micelle Formation/Breakdown......Page 130
D. Dynamics of Giant Micelles......Page 133
A. Preliminary Remarks......Page 135
B. Mixed Systems with Two Surfactants......Page 136
C. Mixed Systems with One Surfactant and One Cosurfactant......Page 138
1. Studies of Surfactant and Cosurfactant Exchanges......Page 139
2. Studies of the Formation/Breakdown of the Mixed Cosurfactant/Surfactant Micelles......Page 141
A. Rate Constants for the Exchange of the Solubilizate......Page 144
B. Effect of Solubilizates on the Micelle Dynamics......Page 149
A. Reminder on Polymer/Surfactant Systems......Page 150
B. Surfactant Exchange from Polymer-Bound Micelles......Page 152
C. Kinetics of Formation/Breakdown of Polymer-Bound Micelles......Page 156
A. Counterion Exchange Kinetics......Page 158
B. Micellar Kinetics at the Approach of a Critical Point......Page 160
C. Micellar Kinetics in the Presence of Cyclodextrins......Page 161
D. Dynamic Surface Tension and Micelle Formation/Breakdown Kinetics......Page 162
IX. Conclusions and Summary......Page 163
References......Page 166
Contents......Page 181
I. Introduction......Page 182
II. Theoretical Aspects of the Dynamics of Micelles of Block Copolymers......Page 186
A. AWK Theory for the Dynamics of Surfactant Micelles and Main Conclusions Drawn from Results for Surfactant Solutions......Page 187
B. Analytical Treatments of the Dynamics of Block Copolymer Micelles......Page 190
C. Dynamic Monte Carlo Simulations......Page 192
III. Dynamics of Block Copolymer Micelles: Historical Aspects, Methods of Investigation and General Observations......Page 195
A. Qualitative Features......Page 197
1. Exchange Rate Constants......Page 205
2. Micelle Formation/Breakdown......Page 210
A. General Considerations......Page 212
B. Dynamics of Copolymer Micelles in Aqueous and Hydro-Organic Solution......Page 213
C. Dynamics of Copolymer Micelles in Organic Solutions......Page 221
VI. Dynamics of Exchange of Solubilizates in Micellar Solutions of Block Copolymers......Page 229
A. Rate of Release (Exit) of Solubilizates from Block Copolymer Micelles......Page 231
B. Rate of Entry of Solubilizates into Block Copolymer Micelles......Page 234
A. Telechelic Polymers......Page 236
B. Comblike Polymers......Page 238
VIII. Dynamics of Miscellaneous Processes Occurring in Block Copolymers Systems......Page 240
IX. General Conclusions......Page 242
REFERENCES......Page 244
Contents......Page 253
I. Introduction......Page 254
II. General Points Concerning Microemulsions Structure, Phase Behavior, and Dynamics......Page 256
A. Global Motions of the Individual Aggregates......Page 258
B. Diffusion of Single Components......Page 260
A. Reminder of the Case of Simple Micelles......Page 261
B. Exchange Dynamics in Microemulsions......Page 263
A. Motion of Hydrophobic or Hydrophilic Chains of Surfactant Molecules......Page 268
B. Mobility of Confined Water......Page 269
A. The Percolation Concept and Film Rigidity......Page 270
B. Effect of Temperature......Page 272
C. Effect of Salinity......Page 273
D. Effect of Additives......Page 276
E. Droplet Percolation and Bicontinuity......Page 277
F. Kinetics of Droplet Coalescence and Exchange of Matter between Droplets......Page 279
G. Droplet Clustering and Rate of Exchange between Clusters......Page 287
A. Interfacial Dynamics and Droplet Deformation......Page 290
B. Temperature-Induced Change of Film Curvature......Page 292
C. Rearrangements Following a Fast Change of Composition: Rate of Dissolution of Excess Dispersed Phase Below the Saturation Limit......Page 295
D. Electric Field-Induced Dynamics of Microemulsions......Page 303
VIII. Implications of the Dynamic Behavior of Microemulsions in Some Specific Domains......Page 305
REFERENCES......Page 309
contents......Page 319
I. Introduction......Page 320
1. Flip-Flop......Page 326
2. Lateral Diffusion......Page 329
B. Transport of Lipids and Other Molecules Between Vesicles (Exchange)......Page 331
C. Transport across Lipid Vesicle Bilayers......Page 335
III. Kinetic Studies of the Vesicle-to- Micelle and Micelle-to-Vesicle Transformations......Page 340
IV. Fatty-Acid and Mixed Phospholipid/Fatty Acid Vesicle Systems......Page 352
V. Dynamic Changes Associated with Vesicle Phase Transitions......Page 354
VI. Effect of Applied Electric Fields on the Properties of Vesicle Bilayers......Page 356
VII. Conclusions......Page 357
References......Page 358
Dynamics of Lyotropic Liquid Crystal Phases of Surfactants and Lipids and of Transitions Between These Phases......Page 367
I. Introduction......Page 368
A. Dynamics of the L3 Phase......Page 371
1. Transition from the La Phase to the Bicontinuous Cubic Phase (V1) and V1 Æ La Transition......Page 374
2. Other Phase Transitions......Page 375
A. Dynamics of Lamellar-to-Lamellar Phase Transitions......Page 376
B. Dynamics of the Lamellar-to-Inverted Hexagonal (H2) Phase Transition......Page 384
C. Dynamics of Transitions Involving the Inverse Cubic Phases Q2......Page 387
IV. Kinetics of Shear-Induced Phase Transitions......Page 390
V. Conclusions......Page 392
REFERENCES......Page 394
Contents......Page 399
I. Introduction......Page 400
A. Dynamic Surface Excess and Surface Tension......Page 401
1. Selection of Surfactants......Page 402
2. Experimental Techniques......Page 403
C. Dynamic Surface Properties of CmTAB Solutions......Page 407
1. Surfactant Solutions Below the cmc......Page 412
2. Surfactant Solutions above the cmc......Page 414
E. General Observations for Other Ionic Surfactants......Page 416
A. Optical Reflectometry and the Wall-Jet Cell......Page 417
1. Surfactant Chain Length Effects......Page 420
2. Influence of Electrolytes......Page 423
3. The Slow Adsorption Region (SAR)......Page 425
4. Evidence for Kinetic Trapping......Page 427
1. The Electrostatic Concentration Span......Page 429
4. Adsorption Kinetics and the Adsorption Isotherm......Page 431
B. Solid-Liquid Interfaces......Page 432
REFERENCES......Page 433
Contents......Page 439
I. Introduction......Page 440
A. Dilute Solutions of Spherical Micelles......Page 441
B. Viscoelastic Solutions of Rod-Shaped Micelles......Page 443
C. Flow Properties of Surfactant Mesophases......Page 445
A. Short Reminder on Micellar Kinetics......Page 447
B. Relaxation Properties of Entangled Solutions of Rodlike Micelles......Page 448
B. Methods of Investigation......Page 455
C. Maxwell Model for Viscoelastic Solutions......Page 458
D. Experimental Results......Page 460
V. Nonlinear Viscoelastic Properties of Entangled Solutions of Rod- Shaped Micelles......Page 464
A. Analytical Solutions for Steady-State Shear Flow......Page 465
B. Transient Flow......Page 469
VI. Shear-Induced Phase Transitions......Page 471
VII. Instabilities of Flow (Shear Banding)......Page 476
VIII. Conclusions and Prospects......Page 479
References......Page 480
Reaction Processes in Self-Assembly Systems......Page 495
II. Theoretical Considerations of Reactions in Micellar Systems......Page 496
III. Metal Complex Formation......Page 500
IV. Metal Extraction......Page 503
V. Catalysis of Organic Reactions by Micelles......Page 506
B. Metal-Ligand Complex Formation......Page 508
C. Preparation of Nanoparticles......Page 511
D. Separation Processes and Extraction......Page 512
VII. The Matrix Effect......Page 513
VIII. Polymerization in Vesicle Systems......Page 514
IX. Enzyme Processes......Page 515
X. The Future......Page 518
REFERENCES......Page 519
Index......Page 529