Physics and Chemistry of Interfaces

Physics and Chemistry of Interfaces......Page 4
Preface......Page 8
Contents......Page 10
1 Introduction......Page 16
2.1 Microscopic picture of the liquid surface......Page 19
2.2 Surface tension......Page 20
2.3.1 Curved liquid surfaces......Page 23
2.3.2 Derivation of the Young–Laplace equation......Page 25
2.3.3 Applying the Young–Laplace equation......Page 26
2.4 Techniques to measure the surface tension......Page 27
2.5 The Kelvin equation......Page 30
2.6 Capillary condensation......Page 32
2.7 Nucleation theory......Page 35
2.8 Summary......Page 38
2.9 Exercises......Page 39
3.1 The surface excess......Page 41
3.2.1 Internal energy and Helmholtz energy......Page 44
3.2.2 Equilibrium conditions......Page 45
3.2.3 Location of the interface......Page 46
3.2.5 Free surface energy, interfacial enthalpy and Gibbs surface energy......Page 47
3.3 The surface tension of pure liquids......Page 49
3.4 Gibbs adsorption isotherm......Page 50
3.4.1 Derivation......Page 51
3.4.2 System of two components......Page 52
3.4.3 Experimental aspects......Page 53
3.4.4 The Marangoni effect......Page 54
3.5 Summary......Page 55
3.6 Exercises......Page 56
4.1 Introduction......Page 57
4.2.1 The Poisson–Boltzmann equation......Page 58
4.2.2 Planar surfaces......Page 59
4.2.3 The full one-dimensional case......Page 61
4.2.4 The Grahame equation......Page 64
4.3.1 Limitations of the Poisson–Boltzmann theory......Page 65
4.3.2 The Stern layer......Page 67
4.4 The Gibbs free energy of the electric double layer......Page 69
4.5 Summary......Page 70
4.6 Exercises......Page 71
5.1 Electrocapillarity......Page 72
5.1.1 Theory......Page 73
5.1.2 Measurement of electrocapillarity......Page 75
5.2 Examples of charged surfaces......Page 76
5.2.1 Mercury......Page 77
5.2.2 Silver iodide......Page 78
5.2.3 Oxides......Page 80
5.2.4 Mica......Page 81
5.2.5 Semiconductors......Page 82
5.3.1 Potentiometric colloid titration......Page 83
5.3.2 Capacitances......Page 86
5.4.1 The Navier–Stokes equation......Page 87
5.4.2 Electro-osmosis and streaming potential......Page 88
5.4.3 Electrophoresis and sedimentation potential......Page 91
5.5 Types of potentials......Page 92
5.7 Exercises......Page 94
6.1 Van der Waals forces between molecules......Page 95
6.2.1 Microscopic approach......Page 99
6.2.2 Macroscopic calculation — Lifshitz theory......Page 102
6.2.3 Surface energy and Hamaker constant......Page 107
6.3.1 The Derjaguin approximation......Page 108
6.3.2 The disjoining pressure......Page 110
6.4 Measurement of surface forces......Page 111
6.5.1 General equations......Page 113
6.5.2 Electrostatic interaction between two identical surfaces......Page 116
6.5.3 The DLVO theory......Page 117
6.6.1 The solvation force and confined liquids......Page 119
6.6.2 Non DLVO forces in an aqueous medium......Page 121
6.7.1 Properties of polymers......Page 122
6.7.2 Force between polymer coated surfaces......Page 123
6.8 Spherical particles in contact......Page 126
6.9 Summary......Page 130
6.10 Exercises......Page 131
7.1.1 The contact angle......Page 133
7.1.2 Derivation......Page 134
7.1.4 Complete wetting......Page 136
7.2.1 Capillary rise......Page 137
7.2.2 Particles in the liquid–gas interface......Page 138
7.2.3 Network of fibres......Page 140
7.3.1 Experimental methods......Page 141
7.3.2 Hysteresis in contact angle measurements......Page 143
7.3.3 Surface roughness and heterogeneity......Page 144
7.4 Theoretical aspects of contact angle phenomena......Page 146
7.5.1 Wetting......Page 148
7.5.2 Dewetting......Page 152
7.6.1 Flotation......Page 153
7.6.2 Detergency......Page 155
7.6.3 Microfluidics......Page 156
7.6.4 Adjustable wetting......Page 157
7.8 Exercises......Page 159
8.1 Introduction......Page 160
8.2.1 The substrate structure......Page 161
8.2.2 Surface relaxation and reconstruction......Page 162
8.2.3 Description of adsorbate structures......Page 164
8.3 Preparation of clean surfaces......Page 165
8.4.1 Surface stress and surface tension......Page 168
8.4.2 Determination of the surface energy......Page 169
8.4.3 Surface steps and defects......Page 172
8.5 Solid–solid boundaries......Page 174
8.6.2 Electron microscopy......Page 177
8.6.3 Scanning probe microscopy......Page 179
8.7 Diffraction methods......Page 182
8.7.2 Diffraction with electrons, X-rays, and atoms......Page 183
8.8.1 Spectroscopy using mainly inner electrons......Page 186
8.8.2 Spectroscopy with outer electrons......Page 188
8.8.3 Secondary ion mass spectrometry......Page 189
8.9 Summary......Page 190
8.10 Exercises......Page 191
9.1.1 Definitions......Page 192
9.1.2 The adsorption time......Page 193
9.1.3 Classification of adsorption isotherms......Page 194
9.1.4 Presentation of adsorption isotherms......Page 196
9.2.1 Heats of adsorption......Page 197
9.2.2 Differential quantities of adsorption and experimental results......Page 199
9.3.1 The Langmuir adsorption isotherm......Page 200
9.3.2 The Langmuir constant and the Gibbs energy of adsorption......Page 203
9.3.4 The BET adsorption isotherm......Page 204
9.3.5 Adsorption on heterogeneous surfaces......Page 207
9.3.6 The potential theory of Polanyi......Page 208
9.4.1 Measurement of adsorption isotherms......Page 210
9.4.2 Procedures to measure the specific surface area......Page 213
9.4.3 Adsorption on porous solids — hysteresis......Page 214
9.4.4 Special aspects of chemisorption......Page 216
9.5 Adsorption from solution......Page 217
9.6 Summary......Page 218
9.7 Exercises......Page 220
10.1 Introduction......Page 221
10.2 Chemical vapor deposition......Page 222
10.3.1 Self-assembled monolayers......Page 224
10.3.2 Physisorption of Polymers......Page 227
10.3.3 Polymerization on surfaces......Page 230
10.4 Etching techniques......Page 232
10.6 Exercises......Page 236
11.1.1 Introduction......Page 238
11.1.2 Amontons’ and Coulomb’s Law......Page 239
11.1.3 Static, kinetic, and stick-slip friction......Page 241
11.1.4 Rolling friction......Page 243
11.1.5 Friction and adhesion......Page 244
11.1.7 Techniques to measure friction......Page 245
11.1.9 Microscopic friction......Page 247
11.2.1 Hydrodynamic lubrication......Page 251
11.2.2 Boundary lubrication......Page 253
11.2.3 Thin film lubrication......Page 254
11.2.4 Lubricants......Page 255
11.3 Wear......Page 256
11.4 Summary......Page 259
11.5 Exercises......Page 260
12.1 Surfactants......Page 261
12.2.1 The critical micelle concentration......Page 265
12.2.2 Influence of temperature......Page 267
12.2.3 Thermodynamics of micellization......Page 268
12.2.4 Structure of surfactant aggregates......Page 270
12.2.5 Biological membranes......Page 273
12.3.1 General properties......Page 274
12.3.2 Formation......Page 276
12.3.3 Stabilization......Page 277
12.3.4 Evolution and aging......Page 280
12.3.5 Coalescence and demulsification......Page 282
12.4.1 Size of droplets......Page 283
12.4.2 Elastic properties of surfactant films......Page 284
12.4.3 Factors influencing the structure of microemulsions......Page 285
12.5.1 Classification, application and formation......Page 287
12.5.3 Soap films......Page 289
12.5.4 Evolution of foams......Page 292
12.6 Summary......Page 293
12.7 Exercises......Page 294
13.1 Introduction......Page 295
13.2 Phases of monomolecular films......Page 298
13.3.1 Optical methods......Page 301
13.3.2 X-ray reflection and diffraction......Page 302
13.3.3 The surface potential......Page 305
13.3.4 Surface elasticity and viscosity......Page 307
13.4 Langmuir–Blodgett transfer......Page 308
13.5 Thick films – spreading of one liquid on another......Page 310
13.7 Exercises......Page 312
14 Solutions to exercises......Page 314
A.1.2 Laue condition......Page 336
A.1.3 The reciprocal lattice......Page 338
A.2 Diffraction at Surfaces......Page 340
A.3 Intensity of diffraction peaks......Page 342
B Symbols and abbreviations......Page 346
Bibliography......Page 350
Index......Page 370