Rate processes in non-metallic systems

The technology of silicon and germanium production has developed rapidly, and knowledge of die self-diffusion properties of diese elements, and of impurity atoms has become reasonably accurate despite die experimental difficulties associated widi die measurements. These arise from die chemical affinity of diese elements for oxygen, and from die low values of die diffusion coefficients. 

Because of die rigidity and directionality of die covalent bonds die energies of self-diffusion have been found to be higher diaii diose of metals. In die case of silicon, it appears drat a furdier complication is drat an intersti-tialcy mechanism predominates above 1000°C. Below diis teiiiperamre, bodi elements appear to self-diffuse by atom-vacancy exchange as for die metals. 

Quite extraordinary diffusion coefficients of impurities from odier parts of die Periodic Table are found, and especially in die important case of lidiium or copper diffusion, where die eidiancement over self-diffusion is by six to eight orders of magnitude. This indicates diat diese atoms do not form part of die sp network in die sUmcture, but more closely resemble separate atoms in die sp iiiaUix. 

The incorporation of oxygen eidier on die surface due to die presence of a SiOa layer, or widiiii die volume following diffusion away from die surface. 

It will be noted that because of the low self-diffusion coefficients the numerical values for representations of self-diffusion in silicon and germanium by Anhenius expressions are subject to considerable uncertainty. It does appear, however, that if this representation is used to average most of the experimental data the equations are for silicon 

The incorporation of oxygen either on the surface due to the presence of a Si02 layer, or within the volume following diffusion away from the surface, 

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Processes in which solids play a rate-determining role have as their principal kinetic factors the existence of chemical potential gradients, and diffusive mass and heat transfer in materials with rigid structures. The atomic structures of the phases involved in any process and their thermodynamic stabilities have important effects on these properties, since they result from the distribution of electrons and ions during the process. In metallic phases it is the diffusive and thermal capacities of the ion cores which are prevalent, the electrons determining the thermal conduction, whereas it is the ionic charge and the valencies of the species involved in non-metallic systems which are important in the diffusive and the electronic behaviour of these solids, especially in the case of variable valency ions, while the ions determine the rate of heat conduction. 

This review is structured as follows. In the next section we present the theory for adsorbates that remain in quasi-equilibrium throughout the desorption process, in which case a few macroscopic variables, namely the partial coverages 0, and their rate equations are needed. We introduce the lattice gas model and discuss results ranging from non-interacting adsorbates to systems with multiple interactions, treated essentially exactly with the transfer matrix method, in Sec. II. Examples of the accuracy possible in the modehng of experimental data using this theory, from our own work, are presented for such diverse systems as multilayers of alkali metals on metals, competitive desorption of tellurium from tungsten, and dissociative... 

Whilst carbon and stainless steels are commonly used materials of construction, increasing use is being made of non-metallic and rubber lined equipment. The selection of the material of construction should take into account the cases of the worst process conditions that may occur under foreseeable conditions and should be applied to all components including valves, pipe fittings, instruments and gauges. Both composition (e.g., chlorides, moisture) and temperature deviations can have a significant direct effect on the rate of corrosion. The operator should demonstrate that procedures are in place to ensure that potential deviations in process conditions such as fluid temperature, pressure and composition are identified and assessed in relation to the selection of materials of construction for piping systems. 

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