Overview

Kinetics of Metal-Gas Interactions at Low Temperatures is devoted to the formation of a natural oxide film. This few nm thick surface layer is produced instantaneously if oxygen or water vapor is present in the gas atmosphere. It is responsible for the corrosion behavior, for wear and friction of metallic materials, as well as for hydrogen embrittlement or poisoning of catalytic surface reactions. Oxidation impedes experiments in surface sciences and production processes in modern thin-film technology. It can reliably be avoided only if expensive ultra-high vacuum techniques are applied. This monograph presents an introduction to the subject in a tutorial style. It demonstrates how complex metal-gas interactions can be analyzed by standard procedures of chemical kinetics.

Full Product Details

Author:   Eckehard Fromm
Publisher:   Springer-Verlag Berlin and Heidelberg GmbH & Co. KG
Imprint:   Springer-Verlag Berlin and Heidelberg GmbH & Co. K
Edition:   illustrated edition
Volume:   36
Dimensions:   Width: 15.50cm , Height: 1.80cm , Length: 23.50cm
Weight:   0.450kg
ISBN:  

9783540639756

ISBN 10:   3540639756
Pages:   206
Publication Date:   29 September 1998
Audience:   College/higher education ,  Professional and scholarly ,  Undergraduate ,  Postgraduate, Research & Scholarly
Format:   Hardback
Publisher's Status:   Active
Availability:   Out of stock  
The supplier is temporarily out of stock of this item. It will be ordered for you on backorder and shipped when it becomes available.

Table of Contents

1 Introduction.- 2 Principles of Reaction Kinetics.- 2.1 Equilibria of Chemical Reactions.- 2.2 Structure of Reaction Models.- 2.2.1 Reaction Partial Steps.- 2.2.2 Rate Equations of Partial Reactions.- 2.2.3 Combining the Partial Steps.- 2.2.4 Mathematical Solution of the Problem.- 2.2.5 Steady-State Conception.- 2.2.6 Rate Determining Step.- 2.2.7 Concluding Remarks.- 2.3 Characteristics of Reaction Partial Steps.- 2.3.1 Molecular Adsorption or Physisorption.- 2.3.2 Chemisorption.- 2.3.3 Formation of Lattice Defects.- 2.3.4 Formation of the Reaction Product.- 2.3.5 Diffusion Processes.- 2.3.6 Electronic Currents.- 2.3.7 Ionic Fluxes.- 2.3.8 Initial Stage of Oxidation.- 3 Experimental Techniques.- 3.1 Initial State of Metal Surfaces and UHV Experiments.- 3.2 Volumetric and Manometric Methods.- 3.3 Quartz Crystal Microbalance.- 3.4 Ellipsometry.- 3.5 Energetic Ion Scattering.- 3.5.1 Rutherford Backscattering Spectroscopy.- 3.5.2 Elastic Recoil Detection Analysis.- 3.5.3 Nuclear Reaction Analysis.- 3.6 X-Ray Reflectivity.- 3.7 Surface-Analytical Methods.- 4 Hydrogen Reactions.- 4.1 Experimental Results.- 4.1.1 Metal-Hydrogen Systems.- 4.1.2 Hydrogen Solution in Metals.- 4.1.3 Hydride Formation.- 4.2 Hydrogen Solution in Metals.- 4.2.1 Reaction Mechanism, Partial Steps.- 4.2.2 Transport of H2 Molecules in the Gas Phase.- 4.2.3 Desorption of Physisorbed Molecules.- 4.2.4 Dissociation of Physisorbed H2 Molecules.- 4.2.5 Recombination and Desorption of Chemisorbed Hydrogen Atoms.- 4.2.6 Surface Penetration, Forward Reaction.- 4.2.7 Surface Penetration, Backward Reaction.- 4.2.8 Diffusion in the Metal Phase.- 4.3 Hydride Formation.- 4.3.1 Reaction Mechanism, Partial Steps.- 4.3.2 Physisorption and Chemisorption.- 4.3.3 Transition from Chemisorption to the Hydride Subsurface.- 4.3.4 Diffusion in the Hydride Phase.- 4.3.5 Formation of the Hydride Phase.- 4.4 Computer Simulation of Advanced Models.- 4.4.1 Structure of the Model.- 4.4.2 Procedure of the Numeric Solution.- 4.4.3 Discussion of Results for Absorption.- 4.4.4 Conclusions.- 4.4.5 Desorption.- 5 Low-Temperature Oxidation.- 5.1 Experimental Results.- 5.2 Rate Laws Proposed in the Literature.- 5.2.1 Parabolic Law.- 5.2.2 Inverse Logarithmic Law.- 5.2.3 Linear Law.- 5.2.4 Logarithmic Law.- 5.3 Partial Steps of the Oxidation Reaction.- 5.3.1 Reaction Mechanisms.- 5.3.2 Charge Distribution and Electric Fields.- 5.3.3 Reactions at the Metal/Oxide Interface.- 5.3.4 Reactions at the Oxide Surface.- 5.4 Relations and Constants Used in Model Calculations.- 5.4.1 Equation of Continuity.- 5.4.2 Steady-State Condition.- 5.4.3 Principle of Coupled Currents.- 5.4.4 Structure of the Models.- 5.4.5 Numerical Procedures.- 5.5 Example of a Model Considering Space Charges.- 5.5.1 Equilibria of the Interface Reactions.- 5.5.2 Ion Currents.- 5.5.3 Electronic Currents.- 5.5.4 Mathematical Treatment.- 5.6 Models Neglecting Space Charges.- 5.6.1 Ion Current in the Homogeneous Field.- 5.6.2 Electrostatic Phenomena.- 5.6.3 Surface Penetration.- 5.6.4 Configuration of the Models.- 5.7 Detailed Presentation of a Model with Metal Interstitials as Mobile Defects.- 5.7.1 Equilibrium and Rate Equations.- 5.7.2 Surface Charges.- 5.7.3 The Potential V Across the Layer.- 5.7.4 Calculation of Concentrations, Currents, and the Oxide Growth Curve.- 5.7.5 Standard Oxide Growth Curve.- 5.7.6 Concentration of Reacting Species and Partial Fluxes.- 5.8 Results of Model Calculations, Parameter Variations.- 5.8.1 Effective Charge of Metal Interstitials.- 5.8.2 Ion Current.- 5.8.3 Surface Penetration.- 5.8.4 Effective Electron Mass.- 5.8.5 Energy U of the Conduction Band Distance.- 5.8.6 Energy W of the Chemisorption Level.- 5.8.7 Equilibrium Constant of Physisorption.- 5.8.8 Oxygen Pressure.- 5.8.9 Temperature.- 5.9 Effects of the Defect Structure of the Oxide.- 5.9.1 Models with Oxygen Interstitials, Space Charge Effects.- 5.9.2 Effect of the Oxygen Pressure.- 5.9.3 Models with Oxygen Vacancies and Metal Vacancies.- 5.10 Simulation of Experiments with the Volumetric Method.- 5.10.1 Reaction Model.- 5.10.2 Results of Model Calculations.- 5.11 Reaction Mechanisms of Low-Temperature Oxidation.- 5.11.1 Fundamentals of the Mechanism.- 5.11.2 Physisorbed Oxygen.- 5.11.3 Defect Formation and Oxide Formation.- 5.11.4 Electronic Structure and Electronic Currents.- 5.11.5 Effects not Considered by the Models.- 5.11.6 Approximations for Estimated Oxidation Curves.- 5.11.7 Experimental Results and Model Calculations.- 5.11.8 Conclusions.- 6 Poisoning of Hydrogen Reactions.- 6.1 Experimental Results.- 6.1.1 Wire Samples.- 6.1.2 Film Samples.- 6.1.3 Powder Samples.- 6.1.4 General Trends.- 6.2 Stability of Oxide Layers at Elevated Temperatures.- 6.2.1 Structure of the Model.- 6.2.2 Results.- 6.2.3 Conclusions.- 6.3 Surface Layer of Constant Thickness.- 6.3.1 Absorption, Dissociation and Permeation Control.- 6.3.2 Discussion of the Mechanism.- 6.3.3 Desorption, Surface and Permeation Controlled.- 6.3.4 Absorption, Permeation and Diffusion Control.- 6.4 Contamination Layers Growing During Exposure.- 6.4.1 Poisoning by Chemisorption Layers.- 6.4.2 Poisoning by Oxide Layers.- 6.4.3 Hydrogen Absorption in H2/O2 Gas Mixtures.- 6.4.4 Estimate of Exposure Time and H2 Absorption Before Poisoning.- Appendices.- A Chemical Potentials and Standard States.- A.1 Chemical Potentials.- A.1.1 Definitions.- A.2 Standard States and Standard Reactions.- A.2.1 Elements.- A.2.3 Physisorption.- A.2.4 Molecular Chemisorption.- A.2.5 Atomic Chemisorption.- A.2.6 Metal Interstitials.- A.2.7 Metal Vacancy.- A.2.8 Oxygen Interstitials.- A.2.9 Oxygen Vacancy.- A.2.10Other Compounds.- B Equilibria of Charged Species.- B.1 Poisson Equation.- B.2 Dipole Layers.- B.3 Space Charges.- B.3.3 Conclusions.- B.4 Mott Potential.- B.4.1 Oxygen Molecules as Acceptors.- B.4.2 Oxygen Atoms as Acceptors.- B.4.3 Pressure Independent Acceptor Sites.- B.4.4 Conditions for the Existence of a Mott Equilibrium Potential.- B.5 Equilibria in Oxide Layers.- C Electronic Currents.- C.1 Tunneling.- C.2 Hopping Mechanism.- C.3 Semiconduction.- D Ionic Currents.- D.1 Basic Equations.- D.1.1 Zero Concentration Gradient.- D.1.2 Zero Field Current.- D.1.3 High Field Transport Equation.- D.1.4 Steady State Current in a Homogeneous Field.- D.2 Space Charge Effects.- D.3 Coupled Currents.- E Units, Material Constants.- Symbols.- References.

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