Solids crystal defects

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. 

Crystal structure, crystal defects and chemical reactions. Most chemical reactions of interest to materials scientists involve at least one reactant in the solid state examples inelude surfaee oxidation, internal oxidation, the photographie process, electrochemieal reaetions in the solid state. All of these are critieally dependent on crystal defects, point defects in particular, and the thermodynamics of these point defeets, especially in ionic compounds, are far more complex than they are in single-component metals. I have spaee only for a superficial overview. 

So, by the 1990s, Professor Rao had been active in several of the major aspects which, together, were beginning to define materials chemistry crystal defects, phase transitions, novel methods of synthesis. Yet, although he has been president of the Materials Research Society of India, he does not call himself a materials chemist but remains a famous solid-state chemist. As with many new conceptual categories, use of the new terminology has developed sluggishly. 

Ionic solids, such as lithium fluoride and sodium chloride, form regularly shaped crystals with well defined crystal faces. Pure samples of these solids are usually transparent and colorless but color may be caused by quite small impurity contents or crystal defects. Most ionic crystals have high melting points. 

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. 

Thermoluminescence. Thermoluminescence is a property of some solids in which excitation by light or particle radiation is frozen in as trapped electrons and holes or a crystal defect. Subsequent heating allows relaxation of the excited state and emission... 

There is actually no sharp distinction between the crystalline and amorphous states. Each sample of a pharmaceutical solid or other organic material exhibits an X-ray diffraction pattern of a certain sharpness or diffuseness corresponding to a certain mosaic spread, a certain content of crystal defects, and a certain degree of crystallinity. When comparing the X-ray diffuseness or mosaic spread of finely divided (powdered) solids, the particle size should exceed 1 um or should be held constant. The reason is that the X-ray diffuseness increases with decreasing particle size below about 0.1 J,m until the limit of molecular dimension is reached at 1-0.1 nm (10-1 A), when the concept of the crystal with regular repetition of the unit cell ceases to be appropriate. 

The parameter c Eqn (2.1), is capable of variation by many orders of magnitude in ionic solids. In good solid electrolytes such as Na "-alumina and RbAg4l5, all of the Na /Ag ions are potentially mobile and hence c is optimised. At the other extreme, in pure, stoichiometric salts such as NaCl, ionic conduction depends on the presence of crystal defects, whether... 

The usefulness of quadrupolar effects on the nuclear magnetic resonance c I 7 yi nuclei in the defect solid state arises from the fact that point defects, dislocations, etc., give rise to electric field gradients, which in cubic ciystals produce a large effect on the nuclear resonance line. In noncubic crystals defects of course produce an effect, but it may be masked by the already present quadrupole interaction. Considerable experimental data have been obtained by Reif (96,97) on the NMR of nuclei in doped, cubic, polycrystalline solids. The effect of defect-producing impurities is quite... 

One area that takes advantage of many of the above formalisms is the application of HF theory to periodic solids. Periodic HF theory has been most extensively developed within the context of the crystal code (Dovesi et al. 2000) where it is available in RHF, UHF, and ROHF forms. Such calculations can be particularly useful for elucidating band structure in solids, assessing defect effects, etc. 

Reaction Cavities of Alkanones in Neat Solid Phases. The early report that irradiation of crystalline 7-tridecanone at 10°C does not result in discernible photoreaction [267] has been corroborated subsequently with other solid symmetrical n-alkanones [268]. However, careful scrutiny of the irradiated ketone reveals traces of Norrish II products in ratios which are very close to those found from photoreactions in solution. On this basis, it was concluded that the source of the photoproducts is reactions occurring at crystal defect sites. 

The crystal defects of the host lattice structure aid in the incorporation of chromophores. By increasing those defects, reactants can diffuse more easily through the product layers and the pigment is formed faster. The presence of mineralizers can also positively affect the solid-state reaction (24). A mineralizer is a compound that facilitates crystal growth during solid-state reactions by providing a local environment that makes the movement of reactants through the solids mixture easier. The incorporation of the chromophore into the host lattice usually results in the formation of a substitution, or less often an addition compound. 

The adsorbed species, which are considered to be adatoms, can diffuse to favorable low-energy sites and react, or they can be emitted into the gas phase. At sufficiently low temperatures, adatoms may have insufficient energy to diffuse and react or to be emitted into the gas phase. These adatoms will be codeposited with the compound film as crystal defects or as a second solid phase. As a result of these competing processes in the surface reaction zone, the growth rate and film composition depend on the flux and energy of the incident species and on the substrate temperature. 

Solids are usually polycrystalline, which means that they are built up of many small, individually ordered crystals. Crystal defects are caused by disarranged grain borders. 

The resolution of the atomic force microscope depends on the radius of curvature of the tip and its chemical condition. Solid crystal surfaces can often be imaged with atomic resolution. At this point, however, we need to specify what Atomic resolution is. Periodicities of atomic spacing are, in fact, reproduced. To resolve atomic defects is much more difficult and usually it is not achieved with the atomic force microscope. When it comes to steps and defects the scanning tunneling microscope has a higher resolution. On soft, deformable samples, e.g. on many biological materials, the resolution is reduced due to mechanical deformation. Practically, a real resolution of a few nm is achieved. 

After 14 years on the faculty of Imperial College, Jacobs moved from London, England, to London, Ontario, where his research program focused on the optical and electrical properties of ionic crystals, as well as on the experimental and theoretical determination of thermodynamic and kinetic properties of crystal defects.213 Over the years his research interests have expanded to include several aspects of computer simulations of condensed matter.214 He has developed algorithms215 for molecular dynamics studies of non-ionic and ionic systems, and he has carried out simulations on systems as diverse as metals, solid ionic conductors, and ceramics. The simulation of the effects of radiation damage is a special interest. His recent interests include the study of perfect and imperfect crystals by means of quantum chemical methods. The corrosion of metals is being studied by both quantum chemical and molecular dynamics techniques. 

Techniques of transmission electron microscopy have proved valuable in many areas of solid state science. Use of electron diffraction permits identification of crystal types, determination of unit cell sizes and characterization of crystal defects in the phases. Measurement of Energy Dispersive X-ray (EDS) line intensity allows calculation of the elemental composition of the phases. It is difficult to overestimate the value of such applications to metallic alloys, ceramic materials and electron-device alloys (T-4V Applications to coal and other fuels are far fewer, but the studies also show promise, both in characterization of mineral phases and in determination of organic constituents (5-9. This paper reports measurements on a particular feature of coal, the spatial variation of the organic sulfur concentration. 

This treatment of melting in confined geometries is obviously oversimplified and the molecular nature of the phases and interactions between the adsorbent walls and the adsorbate should be taken into account by considering not only the surface energies but also the exact nature of the solid phase (structure, crystalline orientation, crystal defects, and so on). 

Busenberg and Plummer (1985) also studied the coprecipitation of Na+ with calcite. Their conclusions agreed with previous concepts that normal solid solution coprecipitation was not occurring, and that the sodium was present at crystal defects. A major contribution of their work was to demonstrate the rate dependence of Na+ coprecipitation, and in doing so to resolve the differences in Na+ behavior observed in earlier studies. They also found that increasing concentrations of coprecipitated sulfate increased Na+ coprecipitation, probably by increasing lattice defects. 

Photomicrographs of solids produced at 2000 ppm total Mg2+ concentration are shown in Figure 11 which indicates that the solid particles are composed of ill-defined, needle-like platelets. Furthermore, Figure lib reveals serious crystal defects. The poor crystal properties were evidenced by an extremely low settling rate (less than 0.1 cm/min) and very few filter cake insoluble solids (less than 30%). 

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