Preface xi
Useful Constants xvi
Symbols and Some Basic Abbreviations xvii
About the Companion Web Site xx
1 Introduction to Colloid and Surface Chemistry 1
1.1 What are the colloids and interfaces? Why are they important? Why do we study them together? 1
1.1.1 Colloids and interfaces 3
1.2 Applications 4
1.3 Three ways of classifying the colloids 5
1.4 How to prepare colloid systems 6
1.5 Key properties of colloids 7
1.6 Concluding remarks 7
Appendix 1.1 8
Problems 9
References 10
2 Intermolecular and Interparticle Forces 11
2.1 Introduction - Why and which forces are of importance in colloid and surface chemistry? 11
2.2 Two important long-range forces between molecules 12
2.3 The van der Waals forces 15
2.3.1 Van der Waals forces between molecules 15
2.3.2 Forces between particles and surfaces 16
2.3.3 Importance of the van der Waals forces 21
2.4 Concluding remarks 25
Appendix 2.1 A note on the uniqueness of the water molecule and some of the recent debates on water structure and peculiar properties 26
References for the Appendix 2.1 28
Problems 29
References 33
3 Surface and Interfacial Tensions - Principles and Estimation Methods 34
3.1 Introduction 34
3.2 Concept of surface tension - applications 34
3.3 Interfacial tensions, work of adhesion and spreading 39
3.3.1 Interfacial tensions 39
3.3.2 Work of adhesion and cohesion 43
3.3.3 Spreading coefficient in liquid-liquid interfaces 44
3.4 Measurement and estimation methods for surface tensions 45
3.4.1 The parachor method 46
3.4.2 Other methods 48
3.5 Measurement and estimation methods for interfacial tensions 50
3.5.1 "Direct" theories (Girifalco-Good and Neumann) 51
3.5.2 Early "surface component" theories (Fowkes, Owens-Wendt, Hansen/Skaarup) 52
3.5.3 Acid-base theory of van Oss-Good (van Oss et al., 1987) - possibly the best theory to-date 57
3.5.4 Discussion 59
3.6 Summary 60
Appendix 3.1 Hansen solubility parameters (HSP) for selected solvents 61
Appendix 3.2 The "phi" parameter of the Girifalco-Good equation (Equation 3.16) for liquid-liquid interfaces. Data from Girifalco and Good (1957, 1960) 66
Problems 67
References 72
4 Fundamental Equations in Colloid and Surface Science 74
4.1 Introduction 74
4.2 The Young equation of contact angle 74
4.2.1 Contact angle, spreading pressure and work of adhesion for solid-liquid interfaces 74
4.2.2 Validity of the Young equation 77
4.2.3 Complexity of solid surfaces and effects on contact angle 78
4.3 Young-Laplace equation for the pressure difference across a curved surface 79
4.4 Kelvin equation for the vapour pressure, P, of a droplet (curved surface) over the "ordinary" vapour pressure Psat for a flat surface 80
4.4.1 Applications of the Kelvin equation 81
4.5 The Gibbs adsorption equation 82
4.6 Applications of the Gibbs equation (adsorption, monolayers, molecular weight of proteins) 83
4.7 Monolayers 86
4.8 Conclusions 89
Appendix 4.1 Derivation of the Young-Laplace equation 90
Appendix 4.2 Derivation of the Kelvin equation 91
Appendix 4.3 Derivation of the Gibbs adsorption equation 91
Problems 93
References 95
5 Surfactants and Self-assembly. Detergents and Cleaning 96
5.1 Introduction to surfactants - basic properties, self-assembly and critical packing parameter (CPP) 96
5.2 Micelles and critical micelle concentration (CMC) 99
5.3 Micellization - theories and key parameters 106
5.4 Surfactants and cleaning (detergency) 112
5.5 Other applications of surfactants 113
5.6 Concluding remarks 114
Appendix 5.1 Useful relationships from geometry 115
Appendix 5.2 The Hydrophilic-Lipophilic Balance (HLB) 116
Problems 117
References 119
6 Wetting and Adhesion 121
6.1 Introduction 121
6.2 Wetting and adhesion via the Zisman plot and theories for interfacial tensions 122
6.2.1 Zisman plot 122
6.2.2 Combining theories of interfacial tensions with Young equation and work of adhesion for studying wetting and adhesion 124
6.2.3 Applications of wetting and solid characterization 130
6.3 Adhesion theories 141
6.3.1 Introduction - adhesion theories 141
6.3.2 Adhesive forces 144
6.4 Practical adhesion: forces, work of adhesion, problems and protection 147
6.4.1 Effect of surface phenomena and mechanical properties 147
6.4.2 Practical adhesion - locus of failure 148
6.4.3 Adhesion problems and some solutions 149
6.5 Concluding remarks 154
Problems 155
References 160
7 Adsorption in Colloid and Surface Science - A Universal Concept 161
7.1 Introduction - universality of adsorption - overview 161
7.2 Adsorption theories, two-dimensional equations of state and surface tension-concentration trends: a clear relationship 161
7.3 Adsorption of gases on solids 162
7.3.1 Adsorption using the Langmuir equation 163
7.3.2 Adsorption of gases on solids using the BET equation 164
7.4 Adsorption from solution 168
7.4.1 Adsorption using the Langmuir equation 168
7.4.2 Adsorption from solution - the effect of solvent and concentration on adsorption 171
7.5 Adsorption of surfactants and polymers 173
7.5.1 Adsorption of surfactants and the role of CPP 173
7.5.2 Adsorption of polymers 174
7.6 Concluding remarks 179
Problems 180
References 184
8 Characterization Methods of Colloids - Part I: Kinetic Properties and Rheology 185
8.1 Introduction - importance of kinetic properties 185
8.2 Brownian motion 185
8.3 Sedimentation and creaming (Stokes and Einstein equations) 187
8.3.1 Stokes equation 187
8.3.2 Effect of particle shape 188
8.3.3 Einstein equation 190
8.4 Kinetic properties via the ultracentrifuge 191
8.4.1 Molecular weight estimated from kinetic experiments (1 = medium and 2 = particle or droplet) 193
8.4.2 Sedimentation velocity experiments (1 = medium and 2 = particle or droplet) 193
8.5 Osmosis and osmotic pressure 193
8.6 Rheology of colloidal dispersions 194
8.6.1 Introduction 194
8.6.2 Special characteristics of colloid dispersions' rheology 196
8.7 Concluding remarks 198
Problems 198
References 201
9 Characterization Methods of Colloids - Part II: Optical Properties (Scattering, Spectroscopy and Microscopy) 202
9.1 Introduction 202
9.2 Optical microscopy 202
9.3 Electron microscopy 204
9.4 Atomic force microscopy 206
9.5 Light scattering 207
9.6 Spectroscopy 209
9.7 Concluding remarks 210
Problems 210
References 210
10 Colloid Stability - Part I: The Major Players (van der Waals and Electrical Forces) 211
10.1 Introduction - key forces and potential energy plots - overview 211
10.1.1 Critical coagulation concentration 213
10.2 van der Waals forces between particles and surfaces - basics 214
10.3 Estimation of effective Hamaker constants 215
10.4 vdW forces for different geometries - some examples 217
10.4.1 Complex fluids 219
10.5 Electrostatic forces: the electric double layer and the origin of surface charge 219
10.6 Electrical forces: key parameters (Debye length and zeta potential) 222
10.6.1 Surface or zeta potential and electrophoretic experiments 223
10.6.2 The Debye length 225
10.7 Electrical forces 228
10.7.1 Effect of particle concentration in a dispersion 229
10.8 Schulze-Hardy rule and the critical coagulation concentration (CCC) 230
10.9 Concluding remarks on colloid stability, the vdW and electric forces 233
10.9.1 vdW forces 233
10.9.2 Electric forces 234
Appendix 10.1 A note on the terminology of colloid stability 235
Appendix 10.2 Gouy-Chapman theory of the diffuse electrical double-layer 236
Problems 238
References 242
11 Colloid Stability - Part II: The DLVO Theory - Kinetics of Aggregation 243
11.1 DLVO theory - a rapid overview 243
11.2 DLVO theory - effect of various parameters 244
11.3 DLVO theory - experimental verification and applications 245
11.3.1 Critical coagulation concentration and the Hofmeister series 245
11.3.2 DLVO, experiments and limitations 247
11.4 Kinetics of aggregation 255
11.4.1 General - the Smoluchowski model 255
11.4.2 Fast (diffusion-controlled) coagulation 255
11.4.3 Stability ratio W 255
11.4.4 Structure of aggregates 257
11.5 Concluding remarks 264
Problems 265
References 268
12 Emulsions 269
12.1 Introduction 269
12.2 Applications and characterization of emulsions 269
12.3 Destabilization of emulsions 272
12.4 Emulsion stability 273
12.5 Quantitative representation of the steric stabilization 275
12.5.1 Temperature-dependency of steric stabilization 276
12.5.2 Conditions for good stabilization 277
12.6 Emulsion design 278
12.7 PIT - Phase inversion temperature of emulsion based on non-ionic emulsifiers 279
12.8 Concluding remarks 279
Problems 280
References 282
13 Foams 283
13.1 Introduction 283
13.2 Applications of foams 283
13.3 Characterization of foams 285
13.4 Preparation of foams 287
13.5 Measurements of foam stability 287
13.6 Destabilization of foams 288
13.6.1 Gas diffusion 289
13.6.2 Film (lamella) rupture 290
13.6.3 Drainage of foam by gravity 291
13.7 Stabilization of foams 293
13.7.1 Changing surface viscosity 293
13.7.2 Surface elasticity 293
13.7.3 Polymers and foam stabilization 295
13.7.4 Additives 296
13.7.5 Foams and DLVO theory 296
13.8 How to avoid and destroy foams 296
13.8.1 Mechanisms of antifoaming/defoaming 297
13.9 Rheology of foams 299
13.10 Concluding remarks 300
Problems 301
References 302
14 Multicomponent Adsorption 303
14.1 Introduction 303
14.2 Langmuir theory for multicomponent adsorption 304
14.3 Thermodynamic (ideal and real) adsorbed solution theories (IAST and RAST) 306
14.4 Multicomponent potential theory of adsorption (MPTA) 312
14.5 Discussion. Comparison of models 315
14.5.1 IAST - literature studies 315
14.5.2 IAST versus Langmuir 315
14.5.3 MPTA versus IAST versus Langmuir 317
14.6 Conclusions 317
Acknowledgments 319
Appendix 14.1 Proof of Equations 14.10a,b 319
Problems 319
References 320
15 Sixty Years with Theories for Interfacial Tension - Quo Vadis? 321
15.1 Introduction 321
15.2 Early theories 321
15.3 van Oss-Good and Neumann theories 331
15.3.1 The two theories in brief 331
15.3.2 What do van Oss-Good and Neumann say about their own theories? 333
15.3.3 What do van Oss-Good and Neumann say about each other's theories? 334
15.3.4 What do others say about van Oss-Good and Neumann theories? 335
15.3.5 What do we believe about the van Oss-Good and Neumann theories? 338
15.4 A new theory for estimating interfacial tension using the partial solvation parameters (Panayiotou) 339
15.5 Conclusions - Quo Vadis? 344
Problems 345
References 349
16 Epilogue and Review Problems 352
Review Problems in Colloid and Surface Chemistry 353
Index 358
