Surfaces dislocations

By way of example, Volume 26 in Group III (Crystal and Solid State Physics) is devoted to Diffusion in Solid Metals and Alloys, this volume has an editor and 14 contributors. Their task was not only to gather numerical data on such matters as self- and chemical diffusivities, pressure dependence of diffusivities, diffusion along dislocations, surface diffusion, but also to exercise their professional judgment as to the reliability of the various numerical values available. The whole volume of about 750 pages is introduced by a chapter describing diffusion mechanisms and methods of measuring diffusivities this kind of introduction is a special feature of Landolt-Bornstein . Subsequent developments in diffusion data can then be found in a specialised journal. Defect and Diffusion Forum, which is not connected with Landolt-Bdrnstein. 

As in metals, dislocation, surface, and grain boundary diffusion can be important. Grain boundary diffusion, in particular, can lead to diffusion coefficients that are 10 to 10 times greater than the bulk diffusion coefficient. However, the effect is not the same for both cations and anions. In some systems, only the ion that is expected to be present in excess at the grain boundary will exhibit enhanced grain boundary diffusion. 

Since its formulation, solid state theory has been concerned also with non-strictly-periodic systems, due principally to the theoretical and technological importance of defects (point impurities, color centers, dislocations, surfaces, etc.). However, most of these theoretical studies and approaches exploit the results of the ideal periodic crystal as the basic ingredient on which to include impurity effects. 

Strain rate Twins subboundaries Dislocations Surface roughness (noches, surface cracks) ... 

In summary, the factors that affect crystal growth in inorganic solutions are (i) level of supersaturation, (ii) mechanistic processes (screw-dislocations, surface nucleation, surface reactions, bulk diffusion, and dehydration), (iii) concentration of other (coprecipitating) ions and molecules in the system, (iv) pH and temperature. 

Actual crystal planes tend to be incomplete and imperfect in many ways. Nonequilibrium surface stresses may be relieved by surface imperfections such as overgrowths, incomplete planes, steps, and dislocations (see below) as illustrated in Fig. VII-5 [98, 99]. The distribution of such features depends on the past history of the material, including the presence of adsorbing impurities [100]. Finally, for sufficiently small crystals (1-10 nm in dimension), quantum-mechanical effects may alter various physical (e.g., optical) properties [101]. 

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. 

The density of dislocations is usually stated in terms of the number of dislocation lines intersecting unit area in the crystal it ranges from 10 cm for good crystals to 10 cm" in cold-worked metals. Thus, dislocations are separated by 10 -10 A, or every crystal grain larger than about 100 A will have dislocations on its surface one surface atom in a thousand is apt to be near a dislocation. By elastic theory, the increased potential energy of the lattice near... 

W. T. Read, Jr., Dislocations in Crystals, McGraw-Hill, New York, 1953. Solid Surfaces, ACS Symposium Series No. 33, American Chemical Society, Washington, DC, 1961. 

We have considered briefly the important macroscopic description of a solid adsorbent, namely, its speciflc surface area, its possible fractal nature, and if porous, its pore size distribution. In addition, it is important to know as much as possible about the microscopic structure of the surface, and contemporary surface spectroscopic and diffraction techniques, discussed in Chapter VIII, provide a good deal of such information (see also Refs. 55 and 56 for short general reviews, and the monograph by Somoijai [57]). Scanning tunneling microscopy (STM) and atomic force microscopy (AFT) are now widely used to obtain the structure of surfaces and of adsorbed layers on a molecular scale (see Chapter VIII, Section XVIII-2B, and Ref. 58). On a less informative and more statistical basis are site energy distributions (Section XVII-14) there is also the somewhat laige-scale type of structure due to surface imperfections and dislocations (Section VII-4D and Fig. XVIII-14). 

Figure C2.11.6. The classic two-particle sintering model illustrating material transport and neck growtli at tire particle contacts resulting in coarsening (left) and densification (right) during sintering. Surface diffusion (a), evaporation-condensation (b), and volume diffusion (c) contribute to coarsening, while volume diffusion (d), grain boundary diffusion (e), solution-precipitation (f), and dislocation motion (g) contribute to densification.

There are two mechanisms by which a phase change on the ground-state surface can take place. One, the orbital overlap mechanism, was extensively discussed by both MO [55] and VB [47] formulations, and involves the creation of a negative overlap between two adjacent atomic orbitals during the reaction (or an odd number of negative overlaps). This case was temied a phase dislocation by other workers [43,45,46]. A reaction in which this happens is... 

The ultimate trapping site for a photoelectron is influenced by the high dielectric constant of silver haUde (ca 12.5, 11.15, and 7.15 for AgBr, AgCl, and P-AgI, respectively), the negative surface charge, and relative trap depths. Interior traps located at point defects on dislocation lines are probably not as... 

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