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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 | |
Free evaporation coefficients of solids | 11 | |
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 | |
Edge and screw dislocations | 33 | |
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 | |
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 | |
Dissociation cross-sections | 75 | |
Substrate heating by transmitted radiation | 77 | |
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 vapour phase refining and separation of metals | 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 | |
Vapour transport in flowing systems | 102 | |
Transport along a thermal gradient | 102 | |
Mass transport across a flowing gas | 103 | |
Material deposition from a flowing gas | 106 | |
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 of gases on solids | 119 | |
Surface structures of catalytic materials | 124 | |
Adsorption and the surface energies of metals | 125 | |
Bond mechanisms of adsorbed molecules | 126 | |
Supported metal catalysts | 128 | |
Examples of industrially important catalysts | 129 | |
Thermodynamics of the water--gas shift and steam reforming reactions | 129 | |
Kinetic factors in steam reforming | 132 | |
The Fischer-Tropsch production of organic molecules | 134 | |
The production of ammonia from its elements | 136 | |
The catalytic converter for automobile exhaust | 138 | |
Catalysis by metal oxides | 140 | |
Coupling reactions of methane | 142 | |
Reactors for catalytic processes | 143 | |
Bibliography | 145 | |
Part 2 | Rate processes in the solid state | 147 |
5 | Electrical charge and heat transport in solids | 149 |
The transport of electrons and positive holes | 149 | |
Metals and alloys | 149 | |
Electromigration in alloys | 153 | |
Elemental and compound semiconductors | 154 | |
Metal oxides | 158 | |
Thermal transport in condensed phases | 163 | |
Heat capacities | 164 | |
Thermal conductivity | 166 | |
Bibliography | 169 | |
6 | Rate processes in metals and alloys | 170 |
Structure and diffusion-controlled processes in metallic systems | 170 | |
The structures of metals | 170 | |
Volume diffusion in pure metals | 170 | |
Diffusion in inter-metallic compounds | 176 | |
Diffusion in alloys | 177 | |
Steady state creep in metals | 180 | |
Diffusion in interstitial solutions and compounds | 181 | |
Phase transformations in alloys | 184 | |
The decomposition of Austenite | 184 | |
Transformations in substitutional alloys | 188 | |
Order--disorder transformation | 189 | |
The age-hardening of copper--aluminium alloys | 190 | |
Spinodal decomposition of binary alloys | 190 | |
Metals and alloys in nuclear power reactors | 194 | |
Bibliography | 195 | |
Grain boundary and surface-driven properties in metallic systems | 195 | |
The measurement of the surface energies of metals | 196 | |
Diffusion in grain boundaries and dislocations | 197 | |
Surface diffusion on metals | 199 | |
Powder metallurgy | 201 | |
The production of metal powders | 201 | |
The sintering of solid metal particles | 204 | |
Hot pressing | 207 | |
Ostwald ripening | 209 | |
Grain growth in polycrystalline metals | 213 | |
Processing of powders to form metallic articles | 214 | |
Self-propagating combustion reactions | 216 | |
Inter-diffusion and interaction in thin film microelectronic structures | 219 | |
Bibliography | 221 | |
7 | Rate processes in non-metallic systems | 223 |
Diffusion in elemental semiconductors | 223 | |
Structures and diffusion in metal oxides | 224 | |
The measurement of diffusion coefficients in simple oxides | 229 | |
Surfaces and surface energies in ionic crystals | 232 | |
Sintering of metal oxides | 233 | |
The production and applications of ceramic oxide materials | 234 | |
Electroceramic oxides | 236 | |
Dielectric or ferroelectric oxides | 236 | |
Magnetic oxides | 237 | |
Solid electrolyte sensors and oxygen pumps | 239 | |
Solid oxide fuel cells and membranes | 244 | |
Ceramic superconductors | 247 | |
The redistribution of fission products in UO[subscript 2] nuclear fuels | 249 | |
Bibliography | 250 | |
8 | Gas-solid reactions | 251 |
The oxidation of metals and compounds | 251 | |
The parabolic rate law | 251 | |
The linear and logarithmic rate laws | 252 | |
Oxidation of metals forming more than one oxide | 253 | |
The oxidation of nickel: volume and grain boundary diffusion | 254 | |
The oxidation of silicon | 255 | |
Complex oxide formation in the oxidation of alloys | 256 | |
Internal oxidation of alloys | 257 | |
The theory of the parabolic oxidation law | 260 | |
The carburizing and oxidation of transition metals | 262 | |
The oxidation of metallic carbides and silicides | 266 | |
The oxidation of silicon carbide and nitride | 268 | |
Bibliography | 269 | |
9 | Laboratory studies of some important industrial reactions | 270 |
The reduction of haematite by hydrogen | 270 | |
Erosion reactions of carbon by gases | 271 | |
The combustion of coal | 273 | |
The oxidation of FeS--parabolic to linear rate law transition | 274 | |
Oxidation of complex sulphide ores--competitive oxidation of cations | 275 | |
The kinetics of sulphation roasting | 276 | |
Heat transfer in gas--solid reactions | 277 | |
Industrial reactors for iron ore reduction to solid iron | 279 | |
The industrial roasting of sulphides | 281 | |
The corrosion of metals in multicomponent gases | 283 | |
Bibliography | 285 | |
Appendix | Thermodynamic data for the Gibbs energy of formation of metal oxides | 285 |
Part 3 | Processes involving liquids | 289 |
10 | Physical properties and applications of liquid metals | 291 |
The structures and mechanism of diffusion of liquid metals | 291 | |
Thermophysical properties of liquid metals | 294 | |
Viscosities of liquid metals | 294 | |
Surface energies of liquid metals | 295 | |
Thermal conductivity and heat capacity | 296 | |
The production of metallic glasses | 297 | |
Liquid metals in energy conversion | 300 | |
Liquid phase sintering of refractory materials | 301 | |
Bibliography | 304 | |
The production of crystalline semiconductors | 304 | |
Zone refining of semiconducting elements | 304 | |
11 | Physical and chemical properties of glassy and liquid silicates | 307 |
Metal solubilities in silicate glasses | 310 | |
The production of silicate glasses and glass-containing materials | 310 | |
The production of porcelains | 311 | |
Ceramic electrical insulators | 313 | |
The production of glass-ceramics | 313 | |
Cements | 314 | |
Optical fibres | 315 | |
Chalcogenide glasses | 315 | |
Bibliography | 316 | |
12 | The structures and thermophysical properties of molten salts | 317 |
Hot corrosion of metals by molten salts | 319 | |
Molten carbonate fuel cells | 321 | |
Bibliography | 322 | |
13 | Extraction metallurgy | 323 |
The principles of metal extraction | 324 | |
Metal--slag transfer of impurities | 324 | |
The electron balance in slag--metal transfer | 327 | |
Bubble formation during metal extraction processes | 328 | |
The corrosion of refractories by liquid metals and slags | 329 | |
Extractive processes | 330 | |
The production of lead and zinc | 330 | |
Co-production of lead and zinc in a shaft furnace | 332 | |
The ironmaking blast furnace | 333 | |
The reduction of stable oxides in carbon arc furnaces | 335 | |
Steelmaking and copper production in pneumatic vessels | 337 | |
Steel | 337 | |
Copper | 339 | |
The reduction of oxides and halides by reactive metals | 341 | |
Magnesium | 341 | |
Chromium | 342 | |
Manganese | 343 | |
Heat losses in crucible reactions | 344 | |
Zirconium | 345 | |
Uranium | 346 | |
The electrolysis of molten salts | 347 | |
Magnesium | 347 | |
Sodium | 347 | |
Aluminium | 348 | |
Refractory metals | 349 | |
Bibliography | 349 | |
14 | The refining of metals | 351 |
The effect of slag composition on impurity transfer | 351 | |
The thermodynamics of dilute solutions | 354 | |
The refining of lead and zinc | 356 | |
The separation of zinc and cadmium by distillation | 357 | |
De-oxidation of steels | 360 | |
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