Diffusion of Reactive Molecules in Solids and

Expert coverage of the physics and mathematics of diffusion-reactions in solids and melts This book presents a unified treatment of diffusion and reaction in a wide variety of oxides-with a special emphasis on the reactive molecules of water, hydrogen, and oxygen. The author proposes new ways of understanding diffusion and reaction in oxides and in silica glass, presents new mathematical treatments of diffusion-reaction, and offers a new discussion of the oxidation state. Helpful data tables cover the activation energies of water and oxygen diffusion in oxides; the diffusion of dopants in silicon; the ionic porosity of crystalline and amorphous oxides; and the diffusion of a large number of elements in silicon. The book features advanced discussions of: * Diffusion and reaction in solids and in relation to solid structure * Diffusion and reaction of water in silica glass, quartz, obsidian, and all oxides * Diffusion and reaction of hydrogen in oxides * Diffusion and reaction of oxygen in oxides * The oxidation state * Diffusion in silicon Diffusion of Reactive Molecules in Solids and Melts presents an up-to-date and comprehensive survey of the subject written for geologists, professionals working in fiber optics, graduate students, and researchers in materials science and solid-state physics.

ROBERT H. DOREMUS, PhD, is Professor of Glass and Ceramics in the Materials Science and Engineering Department at Rensselaer Polytechnic Institute in Troy, New York. He is also the author of Glass Science, Second Edition (Wiley-Interscience), among other books.

Preface.

1. Introduction.

1.1. Importance.

1.2. Defects.

1.3. Diffusion-Reaction Mechanisms.

1.4. Outline of the Book.

1.5. Omissions.

References.

2. Diffusion Without Chemical Reaction.

2.1. Introduction.

2.2. Fundamental Diffusion Equations.

2.3. Infinite and Semi-Infinite Geometries.

2.4. Plane Sheet.

2.5. Permeation Through a Membrane.

2.6. Diffusion Coefficient a Function of Concentration.

References.

3. Diffusion and Reaction with Local Equilibrium.

3.1. Introduction.

3.2. Reaction Experiments.

3.3. Exchange Experiments.

3.4. Pressure Effects.

3.5. Moving Boundary-Tarnishing Reactions.

References.

4. Diffusion and Nonequilibrium Reactions.

4.1. Introduction.

4.2. No Local Equilibrium, Forward Reaction Only.

4.3. No Local Equilibrium, First-Order Forward and Reverse Reactions.

4.4. No Equilibrium, First-Order Forward Reaction, Second-Order Reverse Reaction.

4.5. No Local Equilibrium, Tracer Diffusion.

4.6. Time Ranges of Validity of Equations.

4.7. Surface Exchange.

References.

Appendix: Error Functions of Complex Argument.

5. Structure and Sizes of Atoms and Molecules.

5.1. Introduction.

5.2. Electron Distributions Around Atoms and Molecules.

5.3. Sizes of Gaseous Atoms and Molecules Dissolved in Solids and Melts.

5.4. Sizes of Ions in Solids and Melts, and Openness of Solid Structures.

5.5. Monoxides. References.

6. Diffusion and Reaction of Water in Silica Glass.

6.1. Introduction.

6.2. Structure of Silica Glass.

6.3. Gas Solubility in Silica Glass.

6.4. Experiments of Roberts and Co-Workers at Temperatures of 700 to 1200oC.

6.5. Experiments of Spitzer and Ligenza at 650oC, and Rigo et al. from 400 to 900oC.

6.6. Experiments of Wakabayashi and Tomozawa at 350 and 450oC.

6.7. Experiments of Rauch et al. and Lanford et al. at Temperatures of 200 to 90oC.

6.8. Discussion.

References.

7. Diffusion, Reaction, and Exchange of Water in Quartz.

7.1. Introduction.

7.2. Structure of Quartz.

7.3. Experiments of Kats on Hydrogen-Deuterium Exchange.

7.4. Experiments on 18O-16O Exchange.

7.5. Experiments of Dersch and Rauch at Temperatures of 200oC and Lower.

7.6. Discussion.

References.

8. Diffusion and Reaction of Water in Rhyolite Glass (Obsidian).

8.1. Introduction.

8.2. Diffusion-Reaction Model.

8.3. Analysis of High-Temperature Diffusion Profiles.

8.4. Analysis of Low-Temperature Profiles.

8.5. Discussion.

References.

Appendix.

9. Diffusion and Reaction of Water in Oxides.

9.1. Introduction.

9.2. Equations.

9.3. Diffusion of Water in Pyrope and Calcite.

9.4. Comparison of Experimental Activation Energies for Diffusion of Water in Oxides with Ionic Porosity.

References.

10. Speciation of Water in Silicate Glasses and Melts.

10.1. Introduction.

10.2. Langmuir Model for Speciation.

10.3. Comparison with Experiment.

10.4. Solubility of Water.

10.5. Partial Molar Volume.

10.6. Discussion.

References.

11. Hydrogen in Oxides.

11.1. Introduction.

11.2. Hydrogen in Silica Glass.

11.3. Hydrogen in Fiber Optic Cables of Silica.

11.4. Hydrogen in Multicomponent Silicate Glasses.

11.5. Hydrogen in Crystalline Oxides.

References.

12. Diffusion of Oxygen in Nominally Dry Oxides.

12.1. Introduction.

12.2. Diffusion of Oxygen in Silica Glass.

12.3. Molecular Transport of Oxygen.

12.4. Oxygen Transport by Ions.

12.5. Experimental Activation Energies.

12.6. Further Considerations of Mechanisms.

12.7. Diffusion of Oxygen in Nominally Dry Silicate Melts.

References.

13. Oxidation State.

13.1. Introduction.

13.2. Dissolved Gases.

13.3. Metals and Oxygen.

13.4. Ions with Multiple Valence States and the Phase Rule.

13.5. Oxidation with Transport of Cations.

References.

14. Diffusion in Silicon: Fast and Intermediate Diffusers.

14.1. Introduction.

14.2. Classification of Diffusing Atoms.

14.3. Interstitials, Vacancies, and Fast Diffusers in Silicon.

14.4. Exchange or Kick-Out Mechanism and Diffusion of Intermediate Diffusers in Single-Crystal, Dislocation-Free Silicon.

14.5. Influence of Dislocations in Silicon on Intermediate Diffusers.

14.6. Diffusion in Amorphous Silicon.

14.7. Summary and Subsequent Chapters.

References.

15. Diffusion of Hydrogen in Silicon.

15.1. Introduction.

15.2. Mechanisms of Hydrogen Diffusion in Silicon.

15.3. Equations.

15.4. Comparison with Experiments.

15.5. Discussion.

References.

16. Diffusion of Oxygen and Silicon in Silicon: Silicon Monoxide Model.

16.1. Introduction.

16.2. Structure of Dissolved SiO.

16.3. Infrared Spectra and Dichroism.

16.4. Diffusion of Oxygen, Infrared Dichroism, and Internal Friction.

16.5. Fast Diffusion of Oxygen.

16.6. Diffusion of Silicon.

16.7. Conclusions.

References.

17. Diffusion of Group III, IV, and V Elements in Silicon.

17.1. Introduction.

17.2. Diffusion Coefficients and Activation Energies for Group III, IV, and V Elements.

17.3. Mechanisms of Diffusion and Reaction.

17.4. Concentration Dependence of Effective Diffusion Coefficients of Group III and V Elements in Silicon.

17.5. Internal Friction of Silicon.

17.6. Influence of Other Factors on Dopant Diffusion in Silicon.

References.

18. Diffusion in Germanium.

18.1. Introduction.

18.2. Measurements of Diffusion Coefficients in Germanium and Silicon.

18.3. Diffusion Profiles in Germanium.

18.4. Mechanisms of Diffusion in Germanium.

References.

Appendix.

Author Index.

Subject Index.

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Diffusion of Reactive Molecules in Solids and Melts

Summary

Author Biography

Table of Contents

Supplemental Materials