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Physics and Chemistry of Interfaces

Physics and Chemistry of Interfaces

Hans-Jürgen Butt, Karlheinz Graf, Michael Kappl

ISBN: 978-3-527-60231-5

Aug 2004

156 pages

Select type: O-Book


Serving as a general introduction to surface and interface science, this book focuses on basic concepts rather than specific details, and on intuitive understanding rather than merely learning facts. The text reflects the fact that the physics and chemistry of surfaces is a diverse area of research that involves classical scientific and engineering disciplines. As such, it discusses fundamental subjects, such as thermodynamics of interfaces, as well as applied topics including wetting, friction, and lubrication.
Following an introduction to the most important techniques and methods, readers will be able to apply simple models to their own scientific problems. Furthermore, manifold high end technological applications are shown together with the basic scientific treatment, for example AFM, surface technology, biotechnology, microelectronics, and biomaterials.
The book is written with advanced students of chemistry, physics, materials science, chemical engineering and related subjects who have a basic knowledge of natural sciences and mathematics in mind. In addition, scientists and engineers who are not yet specialists in surface science but want to learn more about this important subject will equally benefit.

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.


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.



"A general yet comprehensive introduction to surface and interface science, this book focuses on essential concepts, and includes application from biotechnology to micoelectronics." (Materials World, Vol 12(2), Feb 2004)

"This textbook is really an excellent reference work for advanced students (and their teachers) in material science, chemistry, physics, biology, engineering, or for researchers needing background knowledge in this field. I believe that it should be considered mandatory reading for someone who wants to join this research area. It is very didactic, clear, concise, and well-organized...I really enjoyed reading the book...There are several other books dealing with surface and interface science, but this is probably the best for a general introduction to this subject." (ChemPhysChem)

"... the book is well worth a place on the shelf of material scientists and engineers involved in surface phenomena." (Materials World)

"... an excellent tool that is highly recommendable to students and experts equally." (TU Chemnitz)

"The book is highly recommended as a source of key information or inspiration and as an introduction to a fascinating and multi-facetted field of research and technology." (Advanced Materials)