Colloidal Dispersions

W. B. RUSSEL
D. A. SAVILLE
W. R. SCHOWALTER
Department of Chemical Engineering
Princeton University

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CAMBRIDGE UNIVERSITY
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New York Port Chester
Melbourne Sydney

PRESS

CONTENTS
Frontispiece
Preface
units ana pnysicai constants
Mathematical symbols

xiii
XVI

xviii

1
1.1
1.2
1.3
1.4
1.5

A Survey of Colloidal Dispersions

Colloidal phenomena
Historical notes
Recent developments
The classification of colloids
An overview
References

1
1
7
9
12
14
18

2
2.1
2.2
2.3

Hydrodynamics
Introduction
Description of the motion of continuous media
Two simple flow fields
Steady laminar shear
Potential flow past a sphere
Characteristics of Stokes flow
Singular solutions to the Stokes equations
Dynamics of isolated spheres
Unsteady translation of spheres
Two spheres translating through a quiescent fluid
Two spheres in a shear flow
Summary
References
Problems

21
21
22
25
25
28
30
31
35
42
44
53
60
62
63

Brownian Motion
Introduction
The Langevin equation
Brownian motion and diffusion

65
65
66
68

2.4
2.5
2.6
2.7
2.8
2.9
2.10

3
3.1
3.2
3.3

viii

Contents

3.4
3.5
3.6
3.7

Measurement by photon correlation spectroscopy

Pair interactions
Brownian dynamics
Summary
References
Problems

4
4.1
4.2
4.3
4.4
4.5
4.6
4.7
4.8
4.9
4.10
4.11
4.12

Electrostatics
Introduction
Electrostatic
fields
Boundary conditions
The electric stress tensor
The origins of interfacial charge
The Gouy-Chapman model of the diffuse layer
The diffuse layer near a flat plate
The diffuse layer around a sphere
Repulsion between charged plates
Repulsion between charged spheres
Tests of the Gouy-Chapman theory
Summary
References
Problems

88
88
89
92
94
96
99
101
109
111
115
120
123
124
126

5
5.1
5.2
5.3
5.4
5.5

Dispersion forces
Introduction
Intermolecular forces and the microscopic theory
Overview of the continuum theory
Dielectric response of materials
Theory for flat plates
Solution of the boundary value problem
Interaction potential
Effect of electrolyte
Calculations for specific materials
Geometrical effects: the Derjaguin approximation
Direct measurements
A simplified approximation for flat plates
Interactions between spheres
Summary
References
Problems

129
129
130
136
138
142
142
145
146
147
149
150153
156
158
159
160

5.6
5.7
5.8
5.9
5.10
5.11

72
76
82
84
85
86

Contents
6
6.1
6.2

6.3

6.4
6.5

6.6

7
7.1

7.2

7.3

7.4

ix

Forces due to soluble polymer

Introduction
Polymers in solution
General features
Thermodynamic functions
Self-consistent field theory
Application to bulk solutions
Terminally anchored polymers
Structure of isolated layers
Interactions between layers: ideal solutions
Interactions between layers: good and poor solvents
Experimental results
Non-adsorbing polymer
Adsorbing polymer
Structure of isolated layers
Interactions between adsorbed layers
Summary
References
Problems

162
163
164
164
168
172
176
176
176
181
183
186
189
194
194
201
205
206
209

Electrokinetic phenomena
Introduction
Examples of electrokinetic phenomena
A model problem
Electrophoresis
Scale analysis
A thick diffuse layer
A thin diffuse layer
Electrophoresis with an equilibrium diffuse layer
Effects due to deformation of the diffuse layer
Measurements of electrophoretic mobilities
Comparisons between theory and experiment
Electrical conductivity of dilute suspensions
Maxwell's theory
Diffuse layer effects
Comparisons between theory and experiment
Dilute suspensions with alternating electric
fields
The leaky dielectric
Maxwell-Wagner theory
Behavior of suspensions of colloidal particles

211
211
211
212
215
216
219
220
222
223
227
229
231
231
232
235
238
239
241
243

Contents
7.5

Summary
References
Problems

252
253
256

8
8.1
8.2
8.3
8.4
8.5
8.6
8.7
8.8

Electrostatic stabilization
Introduction
Interparticle potential and criteria for stability
Conservation equations for probability densities
Initial stage of Brownian
flocculation
Predictions of the stability ratio
Measurements of doublet formation rates
Growth and structure of large
floes
Doublet formation in shear
flows
Diffusion dominated flocculation: Pe<^\
Convection dominated flocculation: Pe$>l
Growth of large aggregates in shear
Criteria for mechanical stability
Experimental studies of shear
flocculation
Summary
References
Problems

258
258
260
262
267
271
274
279
289
289
292
298
299
303
305
305
308

Polymeric stabilization
Introduction
Criteria for stability
Interaction potential between spheres with polymer
layers
Stability with respect to dispersion forces
Critical flocculation point
Measurements of critical flocculation point
Summary
References
Problems

310
310
312

Equilibrium phase behavior

Introduction
The statistical mechanical approach
Equilibrium properties of dilute suspensions
Perturbation theory
Suspensions of hard spheres
Disorder-order transition for charged spheres

329
329
332
334
335
338
343

8.9
8.10
8.11

9
9.1
9.2

9.3
9.4

10
10.1
10.2
10.3
10.4
10.5
10.6

313
315
316
319
327
327
328

Contents
10.7

xi

Phase transitions induced by dissolved polymer

Application of the perturbation theory
Hard spheres in ideal polymer solutions
Electrostatically stabilized dispersions
Polymerically stabilized dispersions
Summary
References
Problems

349
350
352
353
357
360
361
364

Particle capture
Introduction
Capture efficiency and the filter coefficient
Scale analysis
Capture of non-Brownian particles
Inertial capture
Capture with attractive forces
Capture with electrostatic repulsion
Capture of Brownian particles
Experimental measurements
Experiments with rotating discs
Experiments with packed beds
Summary
References
Problems

366
366
367
370
374
375
377
380
383
387
388
389
391
391
393

12
12.1
12.2
12.3
12.4
12.5
12.6
12.7
12.8

Sedimentation
Introduction
Ensemble average velocities
Monodisperse suspensions of spheres
Polydisperse suspensions of spheres
Theory of batch settling
Hard spheres at infinite Peclet number
Hard spheres at finite Peclet number
Summary
References
Problems

394
394
396
400
405
411
414
423
425
426
427

13
13.1
13.2

Diffusion
Introduction
Gradient diffusion of monodisperse spheres

429
429
432

10.8

11
11.1

11.2

11.3
11.4

11.5

xii

Contents

13.3
13.4
13.5
13.6
13.7

Equilibrium in the presence of an external potential

Principles of photon correlation spectroscopy
Initial decay of the autocorrelation functions
Wavenumber-dependent diffusion coefficient
Summary
References
Problems

437
441
444
447
452
453
454

14
14.1
14.2
14.3
14.4
14.5
14.6
14.7
14.8
14.9
14.10
14.11
14.12

Rheology
Introduction
Characterization of rheological behavior
Dimensional analysis
Hard spheres
Charged spheres
Polymerically stabilized spheres
Weakly flocculated dispersions
Motivation for pair interaction theories
Non-equilibrium microstructure
Macroscopic stresses
Results and comparison with experiment
Summary
References
Problems

456
457
464
466
471
477
481
488
488
493
497
503
503
505

Appendix A: Measured properties

Appendix B: Vector and tensor notation

507
508

Author index
Subject index

511
517