Structured Fluids Polymers, Colloids, Surfactants

by Witten, Thomas A.; Pincus, Philip A.

• ISBN13: 9780198526889
• ISBN10: 0198526881
• Format: Hardcover
• Copyright: 2004-03-25
• Publisher: Oxford University Press

Summary

Over the last thirty years, the study of liquids containing polymers, surfactants or colloidal particles has developed from a loose assembly of facts into a coherent discipline with substantial predictive power. These liquids expand our conception of what condensed matter can do. Such structured-fluid phenomena dominate the physical environment within living cells. This book teaches how to think of these fluids from a unified point of view, showing the far-reaching effects of thermal fluctuations in producing forces and motions. Keeping mathematics to a minimum, the book seeks the simplest explanations that account for the distinctive scaling properties of these fluids. An example is the growth of viscosity of a polymer solution as the cube of the molecular weight of the constituent polymers. Another is the hydrodynamic radius of a colloidal aggregate, which remains comparable to its geometrical radius even though the density of particles in the aggregate becomes arbitrarily small. The book aims for a simplicity, unity and depth not found in previous treatments. The text is supplemented by numerous figures, tables and problems to aid the student.

Author Biography

Thomas A. Witten was an assistant professor at the University of Michigan and a staff scientist at Exxon Research and Engineering before joining the University of Chicago in 1989 as a professor of physics.

Table of Contents

1 Overview	1	(12)
1.1 Introduction	1	(1)
1.2 A gallery of structured fluids	2	(4)
1.2.1 Self-organization	2	(2)
1.2.2 Rheology	4	(1)
1.2.3 Scaling	5	(1)
1.3 Types of structured fluids	6	(5)
1.3.1 Colloids	6	(1)
1.3.2 Aggregates	7	(1)
1.3.3 Polymers	7	(2)
1.3.4 Surfactant assemblies	9	(1)
1.3.5 Association	10	(1)
1.4 The chapters to follow	11	(1)
References	11	(2)
2 Fundamentals	13	(28)
2.1 Statistical physics	13	(14)
2.1.1 Thermal equilibrium	13	(4)
2.1.2 Probability and work	17	(5)
2.1.3 Lattice gas	22	(2)
2.1.4 Approach to equilibrium	24	(3)
2.2 Magnitude of a liquid's response	27	(4)
2.3 Experimental probes of structured fluids	31	(8)
2.3.1 Macroscopic responses	31	(3)
2.3.2 Probes of spatial structure	34	(4)
2.3.3 Probes of atomic environment	38	(1)
Solution to Problem 2.1	39	(1)
References	40	(1)
3 Polymer molecules	41	(42)
3.1 Types of polymers	41	(6)
3.1.1 Monomers	42	(1)
3.1.2 Architecture	43	(2)
3.1.3 Polymerization	45	(2)
3.2 Random-walk polymer	47	(7)
3.2.1 End-to-end probability	48	(6)
3.3 Interior structure	54	(7)
3.3.1 Scattering	56	(5)
3.4 Self-avoidance and self-interaction	61	(14)
3.4.1 Local and global avoidance	62	(2)
3.4.2 Estimating D	64	(3)
3.4.3 Self-interaction and solvent quality	67	(5)
3.4.4 Universal ratios	72	(1)
3.4.5 Polyelectrolytes	73	(2)
Appendix A: Dilation symmetry	75	(4)
Appendix B: Polymeric solvents and screening	79	(3)
References	82	(1)
4 Polymer solutions	83	(30)
4.1 Dilute solutions	83	(2)
4.2 Semidilute solutions	85	(5)
4.2.1 Structure	86	(1)
4.2.2 Energy	87	(3)
4.2.3 Concentrated solutions and melts	90	(1)
4.3 Motion in a polymer solution	90	(19)
4.3.1 Brownian motion of a sphere	90	(4)
4.3.2 Intrinsic viscosity	94	(2)
4.3.3 Polymer in dilute solution: hydrodynamic opacity	96	(2)
4.3.4 Internal fluctuations	98	(1)
4.3.5 Hydrodynamic screening	98	(1)
4.3.6 Semidilute diffusion	99	(3)
4.3.7 Semidilute self-diffusion without entanglement	102	(1)
4.3.8 Motion with entanglements	103	(2)
4.3.9 Stress relaxation and viscosity	105	(4)
4.4 Conclusion	109	(1)
Appendix A: Origin of the Oseen tensor	109	(1)
Solution to Problem 4.5 (Deriving permeability)	110	(1)
References	111	(2)
5 Colloids	113	(38)
5.1 Attractive forces: why colloids are sticky	114	(8)
5.1.1 Induced-dipole interactions	114	(2)
5.1.2 Solid bodies	116	(1)
5.1.3 Perturbation-Attraction Theorem	117	(3)
5.1.4 Depletion forces	120	(2)
5.2 Repulsive forces	122	(10)
5.2.1 Steric stabilization	123	(4)
5.2.2 Electrostatic stabilization	127	(5)
5.3 Organized states	132	(3)
5.3.1 Colloidal crystals	132	(1)
5.3.2 Lyotropic liquid crystals	133	(1)
5.3.3 Fractal aggregates	134	(1)
5.3.4 Anisotropic interactions	134	(1)
5.4 Colloidal motion	135	(2)
5.4.1 Electrophoresis	136	(1)
5.4.2 Soret effect	137	(1)
Appendix A: Perturbation attraction in a square-gradient medium	137	(2)
Appendix B: Colloidal aggregates	139	(10)
References	149	(2)
6 Interfaces	151	(22)
6.1 Probes of an interface	151	(2)
6.2 Simple fluids	153	(8)
6.2.1 Interfacial energy	153	(3)
6.2.2 Contact angle	156	(2)
6.2.3 Wetting dynamics	158	(1)
6.2.4 Surface heterogeneity	159	(1)
6.2.5 Other interfacial flows	160	(1)
6.3 Solutes and interfacial tension	161	(2)
6.3.1 Fluid mixtures	162	(1)
6.4 Polyatomic solutes	163	(8)
6.4.1 Polymer adsorption	163	(2)
6.4.2 Concentration profile	165	(2)
6.4.3 Hard wall	167	(1)
6.4.4 Kinetics of adsorption	168	(1)
6.4.5 Surface interaction	168	(1)
6.4.6 Flow	168	(3)
6.5 Conclusion	171	(1)
References	171	(2)
7 Surfactants	173	(40)
7.1 Introduction	173	(1)
7.2 Mixing principles	174	(4)
7.2.1 Positivity	175	(1)
7.2.2 Additivity	175	(1)
7.2.3 Ordering: like dissolves like	176	(1)
7.2.4 Reciprocity	176	(1)
7.2.5 Transitivity	177	(1)
7.2.6 Effect of permanent dipoles: water	177	(1)
7.2.7 Effect of charges: ionic separation	177	(1)
7.3 Surfactant molecules	178	(2)
7.4 Surfactants in solution: micelles	180	(6)
7.4.1 Open aggregation: wormlike micelles	182	(3)
7.4.2 Open aggregation: two-dimensional micelles	185	(1)
7.4.3 Aggregation kinetics	185	(1)
7.5 Micelle interaction	186	(6)
7.5.1 Energy of two-dimensional micelles	188	(3)
7.5.2 Energy to confine a fluctuating membrane	191	(1)
7.6 Mixing immiscible liquids: microemulsions	192	(6)
7.6.1 Interfacial tension	195	(2)
7.6.2 Emulsions and foams	197	(1)
7.7 Amphiphilic polymers	198	(5)
7.7.1 Micelle size	199	(2)
7.7.2 Other copolymers	201	(1)
7.7.3 Polymeric amphiphiles in solution	202	(1)
7.8 Dynamics and rheology	203	(7)
7.8.1 Wormlike entanglement and relaxation	204	(2)
7.8.2 Rheology of lamellar solution	206	(1)
7.8.3 Shear-induced restructuring	207	(3)
Appendix: Gauss-Bonnet Theorem	210	(1)
References	211	(2)
Index	213