Physics and Chemistry of Interfaces

Preface; 1 Introduction; 2 Liquid surfaces; 2.1 Microscopic picture of the liquid surface; 2.2 Surface tension; 2.3 Equation of Young and Laplace; 2.3.1 Curved liquid surfaces; 2.3.2 Derivation of the Young-Laplace equation; 2.3.3 Applying the Young-Laplace equation; 2.4 Techniques to measure the surface tension; 2.5 The Kelvin equation; 2.6 Capillary condensation; 2.7 Nucleation theory; 2.8 Summary; 2.9 Exercises; 3 Thermodynamics of interfaces; 3.1 The surface excess; 3.2 Fundamental thermodynamic relations; 3.2.1 Internal energy and Helmholtz energy; 3.2.2 Equilibrium conditions; 3.2.3 Location of the interface; 3.2.4 Gibbs energy and definition of the surface tension; 3.2.5 Free surface energy, interfacial enthalpy and Gibbs surface energy; 3.3 The surface tension of pure liquids; 3.4 Gibbs adsorption isotherm; 3.4.1 Derivation; 3.4.2 System of two components; 3.4.3 Experimental aspects; 3.4.4 The Marangoni effect; 3.5 Summary; 3.6 Exercises; 4 The electric double layer; 4.1 Introduction; 4.2 Poisson-Boltzmann theory of the diffuse double layer; 4.2.1 The Poisson-Boltzmann equation; 4.2.2 Planar surfaces; 4.2.3 The full one-dimensional case; 4.2.4 The Grahame equation; 4.2.5 Capacity of the diffuse electric double layer; 4.3 Beyond Poisson-Boltzmann theory; 4.3.1 Limitations of the Poisson-Boltzmann theory; 4.3.2 The Stern layer; 4.4 The Gibbs free energy of the electric double layer; 4.5 Summary; 4.6 Exercises; 5 Effects at charged interfaces; 5.1 Electrocapillarity; 5.1.1 Theory; 5.1.2 Measurement of electrocapillarity; 5.2 Examples of charged surfaces; 5.2.1 Mercury; 5.2.2 Silver iodide; 5.2.3 Oxides; 5.2.4 Mica; 5.2.5 Semiconductors; 5.3 Measuring surface charge densities; 5.3.1 Potentiometric colloid titration; 5.3.2 Capacitances; 5.4 Electrokinetic phenomena: The zeta potential; 5.4.1 The Navier-Stokes equation; 5.4.2 Electro-osmosis and streaming potential; 5.4.3 Electrophoresis and sedimentation potential; 5.5 Types of potentials; 5.6 Summary; 5.7 Exercises; 6 Surface forces; 6.1 Vander Waals forces between molecules; 6.2 The van der Waals force between macroscopic solids; 6.2.1 Microscopic approach; 6.2.2 Macroscopic calculation Lifshitz theory; 6.2.3 Surface energy and Hamaker constant; 6.3 Concepts for the description of surface forces; 6.3.1 The Derjaguin approximation; 6.3.2 The disjoining pressure; 6.4 Measurement of surface forces; 6.5 The electrostatic double-layer force; 6.5.1 General equations; 6.5.2 Electrostatic interaction between two identical surfaces; 6.5.3 The DLVO theory; 6.6 Beyond DLVO theory; 6.6.1 The solvation force and confined liquids; 6.6.2 Non DLVO forces in an aqueous medium; 6.7 Steric interaction; 6.7.1 Properties of polymers; 6.7.2 Force between polymer coated surfaces; 6.8 Spherical particles in contact; 6.9 Summary; 6.10 Exercises; 7 Contact angle phenomena and wetting; 7.1 Young's equation; 7.1.1 The contact angle; 7.1.2 Derivation; 7.1.3 The line tension; 7.1.4 Complete wetting; 7.2 Important wetting geometries; 7.2.1 Capillary rise; 7.2.2 Particles in the liquid-gas interface; 7.2.3 Network of fibres; 7.3 Measurement of the contact angle; 7.3.1 Experimental methods; 7.3.2 Hysteresis in contact angle measurements; 7.3.3 Surface roughness and heterogeneity; 7.4 Theoretical aspects of contact angle phenomena; 7.5 Dynamics of wetting and dewetting; 7.5.1 Wetting; 7.5.2 Dewetting; 7.6 Applications; 7.6.1 Flotation; 7.6.2 Detergency; 7.6.3 Microfluidics; 7.6.4 Adjustable wetting; 7.7 Summary; 7.8 Exercises; 8 Solid surfaces; 8.1 Introduction; 8.2 Description of crystalline surfaces; 8.2.1 The substrate structure; 8.2.2 Surface relaxation and reconstruction; 8.2.3 Description of adsorbate structures; 8.3 Preparation of clean surfaces; 8.4 Thermodynamics of solid surfaces; 8.4.1 Surface stress and surface tension; 8.4.2 Determination of the surface energy; 8.4.3 Surface steps and defects; 8.5 Solid-solid boundaries; 8.6 Microscopy of solid surfaces; 8.6.1 Optical microscopy; 8.6.2 Electron microscopy; 8.6.3 Scanning probe microscopy; 8.7 Diffraction methods; 8.7.1 Diffraction patterns of two-dimensional periodic structures; 8.7.2 Diffraction with electrons, X-rays, and atoms; 8.8 Spectroscopic methods; 8.8.1 Spectroscopy using mainly inner electrons; 8.8.2 Spectroscopy with outer electrons; 8.8.3 Secondary ion mass spectrometry; 8.9 Summary; 8.10 Exercises; 9 Adsorption; 9.1 Introduction; 9.1.1 Definitions; 9.1.2 The adsorption time; 9.1.3 Classification of adsorption isotherms; 9.1.4 Presentation of adsorption isotherms; 9.2 Thermodynamics of adsorption; 9.2.1 Heats of adsorption; 9.2.2 Differential quantities of adsorption and experimental results; 9.3 Adsorption models; 9.3.1 The Langmuir adsorption isotherm; 9.3.2 The Langmuir constant and the Gibbs energy of adsorption; 9.3.3 Langmuir adsorption with lateral interactions; 9.3.4 The BET adsorption isotherm; 9.3.5 Adsorption on heterogeneous surfaces; 9.3.6 The potential theory of Polanyi; 9.4 Experimental aspects of adsorption from the gas phase; 9.4.1 Measurement of adsorption isotherms; 9.4.2 Procedures to measure the specific surface area; 9.4.3 Adsorption on porous solids hysteresis; 9.4.4 Special aspects of chemisorption; 9.5 Adsorption from solution; 9.6 Summary; 9.7 Exercises; 10 Surface modification; 10.1 Introduction; 10.2 Chemical vapor deposition; 10.3 Soft matter deposition; 10.3.1 Self-assembled monolayers; 10.3.2 Physisorption of Polymers; 10.3.3 Polymerization on surfaces; 10.4 Etching techniques; 10.5 Summary; 10.6 Exercises; 11 Friction, lubrication, and wear; 11.1 Friction; 11.1.1 Introduction; 11.1.2 Amontons' and Coulomb's Law; 11.1.3 Static, kinetic, and stick-slip friction; 11.1.4 Rolling friction; 11.1.5 Friction and adhesion; 11.1.6 Experimental Aspects; 11.1.7 Techniques to measure friction; 11.1.8 Macroscopic friction; 11.1.9 Microscopic friction; 11.2 Lubrication; 11.2.1 Hydrodynamic lubrication; 11.2.2 Boundary lubrication; 11.2.3 Thin film lubrication; 11.2.4 Lubricants; 11.3 Wear; 11.4 Summary; 11.5 Exercises; 12 Surfactants, micelles, emulsions, and foams; 12.1 Surfactants; 12.2 Spherical micelles, cylinders, and bilayers; 12.2.1 The critical micelle concentration; 12.2.2 Influence of temperature; 12.2.3 Thermodynamics of micellization; 12.2.4 Structure of surfactant aggregates; 12.2.5 Biological membranes; 12.3 Macroemulsions; 12.3.1 General properties; 12.3.2 Formation; 12.3.3 Stabilization; 12.3.4 Evolution bandaging; 12.3.5 Coalescence and demulsification; 12.4 Microemulsions; 12.4.1 Size of droplets; 12.4.2 Elastic properties of surfactant films; 12.4.3 Factors influencing the structure of microemulsions; 12.5 Foams; 12.5.1 Classification, application and formation; 12.5.2 Structure of foams; 12.5.3 Soap films; 12.5.4 Evolution of foams; 12.6 Summary; 12.7 Exercises; 13 Thin films on surfaces of liquids; 13.1 Introduction; 13.2 Phases of monomolecular films; 13.3 Experimental techniques to study monolayers; 13.3.1 Optical methods; 13.3.2 X-ray reflection and diffraction; 13.3.3 The surface potential; 13.3.4 Surface elasticity and viscosity; 13.4 Langmuir-Blodgett transfer; 13.5 Thick films - spreading of one liquid on another; 13.6 Summary; 13.7 Exercises; 14 Solutions to exercises; Appendix; A Analysis of diffraction patterns; A.1 Diffraction at three dimensional crystals; A.1.1 Bragg condition; A.1.2 Laue condition; A.1.3 The reciprocal lattice; A.1.4 Ewald construction; A.2 Diffraction at Surfaces; A.3 Intensity of diffraction peaks; B Symbols and abbreviations; Bibliography; Index