Imperfections of crystals

The powder patterns obtained by X-ray diffraction and selected area electron diffraction do represent averages over very large numbers of particles but the averaging over size, orientation and imperfection of crystals removes much of the important information, especially that on the correlations of properties,e.g, the orientational relationship of adjacent crystal regions or the dependence of twinning on size. 

As the temperature of calcination in air was raised, Dx increased at first and then became constant above 500° on the contrary, A changed in just the adverse way ij, however, stayed constant throughout. These results indicate synthetically that calcination in air causes the growth of palladium particles, but no diminution of the imperfection of crystals. 

Raman spectroscopy is primarily a structural characterization tool. The spectrum is more sensitive to the lengths, streng ths, and arrangement of bonds in a material than it is to the chemical composition. The Raman spectmm of crystals likewise responds more to details of defects and disorder than to trace impurities and related chemical imperfections. 

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. 

The nature of the material to be studied, which means its degree of crystallinity and perfectness of crystal structure, may have a significant effect on the thermoanalytical behavior. In spite of identical chemical composition of a certain material the variations with respect to structure, imperfections, grain boundaries, etc. are almost infinite. Of course many of these will not show in normal thermogravimetric analysis, with very sensitive apparatus characteristically different TG curves18, 19 may be obtained however. As an example Fig. 26 shows the thermal decomposition of hydrozincite, Zn5(OH)6(003)2, whereby equal amounts of samples from natural origin and synthetic preparations are compared. 

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

Note 4 The degree of crystallinity can be determined by several experimental techniques among the most commonly used are (i) X-ray diffraction, (ii) calorimetry, (iii) density measurements, and (iv) infrared spectroscopy (IR). Imperfections in crystals are not easily distinguished from the amorphous phase. Also, the various techniques may be affected to different extents by imperfections and interfacial effects. Flence, some disagreement among the results of quantitative measurements of crystallinity by different methods is frequently encountered. 

Diffraction properties of crystals are determined by X-ray analysis which is covered in Chapters 4 and 5. Imperfections within the crystal are indicated by high mosaicity exhibited by broadening of diffraction spots and diffuse scattering. Prolonged exposure of protein and protein-DNA crystals to X-rays causes loss of diffraction due to radiation damage. 

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. 

Between the regions of strong absorption by electronic and vibrational transitions there is a region of high transparency where absorption is dominated by impurities and imperfections. Artificial crystals of MgO are thus quite transparent to visible light. This transparent region can be made more interest-... 

In semi-crystalline polymers the interaction of the matrix and the tiller changes both the structure and the crystallinity of the interphase. The changes induced by the interaction in bulk properties are reflected by increased nucleation or by the formation of a transcrystalline layer on the surface of anisotropic particles [48]. The structure of the interphase, however, differs drastically from that of the matrix polymer [49,50]. Because of the preferred adsorption of large molecules, the dimensions of crystalline units can change, and usually decrease. Preferential adsorption of large molecules has also been proved by GPC measurements after separation of adsorbed and non-attached molecules of the matrix [49,50]. Decreased mobility of the chains affects also the kinetics of crystallization. Kinetic hindrance leads to the development of small, imperfect crystallites, forming a crystalline phase of low heat of fusion [51]. 

It turns out to be simple. Nature rarely works with crystals as ideal as the ones considered in Section 7.12.3. Crystals are grown, e.g., from a melt, and in the general rush of crystallization, the majority of crystals grow with built-in defects and imperfections in the way in which their atoms are arranged. It is one type of these imperfections that contains the secret of nonvanishing, self-perpetuating steps. The... 

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