Imperfect crystallization

The physical properties of tellurium are generally anistropic. This is so for compressibility, thermal expansion, reflectivity, infrared absorption, and electronic transport. Owing to its weak lateral atomic bonds, crystal imperfections readily occur in single crystals as dislocations and point defects. 

Faraday Society, Discussion No. 28 (1959b) Crystal Imperfections and the Chemical Reactivity of Solids (Aberdeen University Press). 

So important are lattice imperfections in the reactions of solids that it is considered appropriate to list here the fundamental types which have been recognized (Table 1). More complex structures are capable of resolution into various combinations of these simpler types. More extensive accounts of crystal defects are to be found elsewhere [1,26,27]. The point which is of greatest significance in the present context is that each and every one of these types of defect (Table 1) has been proposed as an important participant in the mechanism of a reaction of one or more solids. In addition, reactions may involve structures identified as combinations of these simplest types, e.g. colour centres. The mobility of lattice imperfections, which notably includes the advancing reaction interface, provides the means whereby ions or molecules, originally at sites remote from crystal imperfections and surfaces, may eventually react. 

References to the profitable exploitation of microscopic techniques in kinetic studies can be found in the work of Thomas and co-workers [91, 206—210], Herley et al. [211] and of Flanagan and his collaborators [212,213]. The rates of advance of reaction interfaces have been measured from direct observations on single crystals and the kinetic parameters so obtained are compared with results for mass loss determinations. The effects of the introduction of crystal imperfections and the role of such species in mechanisms of reaction are also considered. 

A. Guinier, Diffraction In Crystals, Imperfect Crystals, and Amorphous Bodies, Dover, New York, 1963. 

Considering the crystal imperfections that are typically found in all crystals, the crystal quality of organic pigments is a major concern. The external surface of any crystal exhibits a number of defects, which expose portions of the crystal surface to the surrounding molecules. Impurities and voids permeate the entire interior structure of the crystal. Stress, brought about by factors such as applied shear, may change the cell constants (distances between atoms, crystalline angles). It is also possible for the three dimensional order to be incomplete or limited to one or two dimensions only (dislocations, inclusions). 

On the role of crystal imperfections in photographic sensitivity. Z. Physik 138, 381 (1954). 

The primary consideration we are missing is that of crystal imperfections. Recall from Section 1.1.4 that virtually all crystals contain some concentration of defects. In particular, the presence of dislocations causes the actual critical shear stress to be much smaller than that predicted by Eq. (5.17). Recall also that there are three primary types of dislocations edge, screw, and mixed. Althongh all three types of dislocations can propagate through a crystal and result in plastic deformation, we concentrate here on the most common and conceptually most simple of the dislocations, the edge dislocation. 

This model can also be applied to hysteresis that arises from chemical heterogeneity however, this time the surface is assumed to be smooth and to contain concentric rings of different chemical composition and hence different 0 s. Actual heterogeneity may arise from impurities concentrated at the surface, from crystal imperfections, or from differences in the properties of different crystal faces. The distribution of such heterogeneities on an actual surface will obviously be more complex than the model considers, but the qualitative features of hysteresis are explained by the model nevertheless. Johnson and Dettree (1969) present additional details of model experiments of this sort. 

Crystal Reid stabilization energy (CFSE), 399—401, 408-413 Crystal lattices, and efficiency of packing, 118-122 Crystallography, 74-85 Crystals, imperfections in, 263-265... 

Solid state reactions occur mainly by diffusional transport. This transport and other kinetic processes in crystals are always regulated by crystal imperfections. Reaction partners in the crystal are its structure elements (SE) as defined in the list of symbols (see also [W. Schottky (1958)]). Structure elements do not exist outside the crystal lattice and are therefore not independent components of the crystal in a thermodynamic sense. In the framework of linear irreversible thermodynamics, the chemical (electrochemical) potential gradients of the independent components of a non-equilibrium (reacting) system are the driving forces for fluxes and reactions. However, the flux of one independent chemical component always consists of the fluxes of more than one SE in the crystal. In addition, local reactions between SE s may occur. 

Experiments demonstrate that along crystal imperfections such as dislocations, internal interfaces, and free surfaces, diffusion rates can be orders of magnitude faster than in crystals containing only point defects. These line and planar defects provide short-circuit diffusion paths, analogous to high-conductivity paths in electrical systems. Short-circuit diffusion paths can provide the dominant contribution to diffusion in a crystalline material under conditions described in this chapter. 

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