ALCOCK, C. B. (2000). Thermochemical Processes - Principles and Models.pdf

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Thermochemical Processes
Principles and Models
Thermochemical Processes
Principles and Models
C.B. Alcock DSc, FRSC
OXFORD AUCKLAND BOSTON JOHANNESBURG MELBOURNE NEW DELHI
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Butterworth-Heinemann
Linacre House, Jordan Hill, Oxford OX2 8DP
225 Wildwood Avenue, Woburn, MA 01801-2041
A division of Reed Educational and Professional Publishing Ltd
First published 2001
C.B. Alcock 2001
All rights reserved. No part of this publication
may be reproduced in any material form (including
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Applications for the copyright holder’s written permission
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to the publishers
British Library Cataloguing in Publication Data
Alcock, C. B.
Thermochemical processes:principles and models
1 Thermodynamics
2 Chemical processes
3 Materials at high
temperatures
I Title
660.2 0 969
Library of Congress Cataloguing in Publication Data
Alcock, C. B.
Thermochemical processes:principles and models/C.B. Alcock.
p. cm.
Includes bibliographical references.
ISBN 0 7506 5155 5
1 Thermodynamics
2 Chemical processes
3 Materials at high temperatures
I Title
TP155.2.T45 T47 2000
660 0 .2969 – dc21
00-049367
ISBN 0 7506 5155 5
Typeset by Laser Words, Chennai, India
Printed in Great Britain
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Contents
Preface
xi
Part 1: Processes with gaseous reaction control
1
1 Vapour deposition processes 3
Vapour deposition for the preparation of thin films
3
Vapour pressure data for the elements
4
The kinetic theory of a gas in a container
4
Molecular effusion 6
Vapour deposition of elements 6
The deposition rate on a cool substrate
8
Vapour deposition of alloys 8
Vapour deposition of compounds 10
Other techniques for the preparation of thin films 16
Single and epitaxial films in semiconducting systems
16
Thin film production by the sputtering of metals
17
The production of nanoparticles 20
Coating with thin diamond films 22
Plasma evaporation and pyrolysis of carbon to form Fullerenes
23
Materials science and the formation of thin films
24
The formation of nuclei from the vapour phase
24
The formation of a film from nuclei
28
Grain growth in the initial deposit
30
Point defects in solids 31
Interfacial energies in solid systems
35
Bibliography 38
Appendix: Vapour pressure data for the elements 38
2 Gaseous reaction kinetics and molecular decomposition
42
Theories of reaction kinetics 42
Thermal energies and the structures of molecules
43
The collision theory of gaseous reactions
45
Transition state theory of gaseous reactions
47
Empirical estimates of the activation energy
49
The order of chemical reactions
50
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vi Contents
Time dependence of the extent of reaction
52
Chain reactions 52
Combustion chain reactions 53
Chain reactions in the combustion of gaseous fuels
56
Fuel/air mixing in combustion systems 58
The thermal efficiencies of combustion engines
59
Bibliography 62
Molecular dissociation and chain reactions in chemical vapour deposition
62
Thermochemical data for the dissociation of gaseous molecules
63
Bond character in gaseous heteronuclear compounds
64
Hybridization of covalent bonds 66
Bond energies of gaseous polyvalent metal halides 67
Thermal decomposition of hydrides and organometallic compounds
68
Bibliography 71
Radiation and electron decomposition of molecules
72
Photochemical reactions 73
Radiation and convection cooling of the substrate
82
Laser production of thin films 82
Molecular decomposition in plasma systems
84
Bibliography 85
3 Vapour phase transport processes
86
Vapour transport processes 86
Thermodynamics and the optimization of vapour phase transport
86
The direction of vapour transport across a thermal gradient
89
The choice of halogen in transport reactions 91
The thermodynamics of the vapour phase transport of compounds
93
Multicomponent thermodynamics in gaseous systems
95
Sintering by vapour phase transport
99
Grain growth by vapour phase transport
100
Transport along a thermal gradient 102
Transport and thermal properties of gases 108
Equations of state for ideal and real gases 112
Molecular interactions and the properties of real gases
114
Bibliography 117
4 Heterogeneous gas – solid surface reactions
118
The zeroth order reaction 118
Adsorption and the surface energies of metals
125

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