Solid interstitial

Zone melting causes impurities to migrate to one end of a cylindrical metal sample by generating a narrow molten zone and moving it repeatedly in one direction along the cylinder axis. Impurities more soluble in the liquid phase (metals, some halides, and carbon) move in the direction of zone travel, while those more soluble in the solid (interstitials) move in the opposite direction. This technique produces pure rare earth metals . ... 

Dislocation theory as a portion of the subject of solid-state physics is somewhat beyond the scope of this book, but it is desirable to examine the subject briefly in terms of its implications in surface chemistry. Perhaps the most elementary type of defect is that of an extra or interstitial atom—Frenkel defect [110]—or a missing atom or vacancy—Schottky defect [111]. Such point defects play an important role in the treatment of diffusion and electrical conductivities in solids and the solubility of a salt in the host lattice of another or different valence type [112]. Point defects have a thermodynamic basis for their existence in terms of the energy and entropy of their formation, the situation is similar to the formation of isolated holes and erratic atoms on a surface. Dislocations, on the other hand, may be viewed as an organized concentration of point defects they are lattice defects and play an important role in the mechanism of the plastic deformation of solids. Lattice defects or dislocations are not thermodynamic in the sense of the point defects their formation is intimately connected with the mechanism of nucleation and crystal growth (see Section IX-4), and they constitute an important source of surface imperfection. 

Materials that contain defects and impurities can exhibit some of the most scientifically interesting and economically important phenomena known. The nature of disorder in solids is a vast subject and so our discussion will necessarily be limited. The smallest degree of disorder that can be introduced into a perfect crystal is a point defect. Three common types of point defect are vacancies, interstitials and substitutionals. Vacancies form when an atom is missing from its expected lattice site. A common example is the Schottky defect, which is typically formed when one cation and one anion are removed from fhe bulk and placed on the surface. Schottky defects are common in the alkali halides. Interstitials are due to the presence of an atom in a location that is usually unoccupied. A... 

Leaching is the removal of a soluble fraction, in the form of a solution, from an insoluble, permeable sohd phase with which it is associated. The separation usually involves selective dissolution, with or without diffusion, but in the extreme case of simple washing it consists merely of the displacement (with some mixing) of one interstitial liquid by another with which it is miscible. The soluble constituent may be solid or liquid and it may be incorporated within, chemically combined with, adsorbed upon, or held mechanically in the pore structure of the insoluble material. The insoluble sohd may be massive and porous more often it is particulate, and the particles may be openly porous, cellular with selectively permeable cell walls, or surface-activated. 

A crystalline solid is never perfect in that all of tire lattice sites are occupied in a regular manner, except, possibly, at the absolute zero of temperature in a perfect crystal. Point defects occur at temperatures above zero, of which the principal two forms are a vacant lattice site, and an interstitial atom which... 

Fig. 7.7. Solid-solution structures. In interstitial solutions small atoms fit into the spaces between large atoms. In substitutional solutions similarly sized atoms replace one another. If A-A, A-B and B-B bonds hove the some strength then this replacement is random. But unequal bond strengths con give clustering or ordering.

Crystalline solids at temperatures above absolute zero are never perfeet in that all lattiee sites are oeeupied in a eompletely regular manner. Imperfeetions exist. Formation of sueh sites is endothermie a small quantity of energy is required. Point defeets oeeur, of whieh the prineipal two are a vacant lattiee site, and an interstitial atom that oeeupies a volume between a group of atoms on normal sites that affeets erystal purity (see Hull and Baeon, 2001, for a detailed exposition). 

If the pressure of O2 above a crystalline oxide is increased, the oxide-ion activity in the solid can be increased by placing the supernumerary ions in the interstitial positions, e.g. ... 

In some metal components it is possible to form oxides and carbides, and in others, especially those with a relatively wide solid solubility range, to partition the impurity between the solid and the liquid metal to provide an equilibrium distribution of impurities around the circuit. Typical examples of how thermodynamic affinities affect corrosion processes are seen in the way oxygen affects the corrosion behaviour of stainless steels in sodium and lithium environments. In sodium systems oxygen has a pronounced effect on corrosion behaviour whereas in liquid lithium it appears to have less of an effect compared with other impurities such as C and Nj. According to Casteels Li can also penetrate the surface of steels, react with interstitials to form low density compounds which then deform the surface by bulging. For further details see non-metal transfer. 

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