Mobility of defects

A theoretical analysis of the experimental kinetics for Vk centres in KC1-Tl, as well as for self-trapped holes in a-Al203 and Na-salt of DNA, is presented in [55]. The fitting of theory to the experimental curves is shown in Fig. 4.4. Partial agreement of theory and experiment observed in the particular case of Vk centres was attributed to the violation of the continuous approximation in the diffusion description. This point is discussed in detail below in Section 4.3. Note in conclusion that the fact of the observation of prolonged increase in recombination intensity itself demonstrated slow mobility of defects. In the case of pure irradiated crystals, it is a strong... 

Therefore, the observed process (I) could be related to the cooperative dynamics of glycerol in the supercooled phase, while process (II) is most likely related to the crystalline phase of glycerol and is the result, similar to water, of the mobility of defects in the crystalline lattice [200]. The temperature dependence of the relaxation time for dehydrated glycerol is compared in Fig. 23 with those for the usual behavior of glycerol, which has absorbed some water from the atmosphere. 

Simultaneously, we could consider the mobility of defects as (T). In these expressions,... 

The much greater mobility of defects in wustite causes this layer to be very thick compared with the magnetite and haematite layers. In fact the relative thicknesses of FeO Fe304 Fe203 are in the ratio of roughly 95 4 1 at 1000... 

In order to understand the rate of alignment, the mobility of defects must be considered. Movement of all defects must be accomplished by climb and glide of edge dislocations at the defect. Examples are shown in Fig. 34. Climb is motion in the layer plane and glide is motion transverse to the layers. Consider a pair of... 

The imique resolving power of STM can provide important new information on the atomic-scale realm and on the dynamics of nanostructures. For example, the mobility of defects such as oxygen vacancies on Ti02 surfaces (which become mobile after O2 exposure) can be explored. For the diffusion of O2 molecules on rutile Ti02 (110) surfaces (which plays an important role in understanding (photo)catalytic activity), a charge-transfer-induced diffusion mechanism for the adsorbed O2 molecules was observed. 

Where is the ratio of the irradiated to unirradiated elastic modulus. The dislocation pinning contribution to the modulus change is due to relatively mobile small defects and is thermally annealable at 2000°C. Figure 13 shows the irradiation-induced elastic modulus changes for GraphNOL N3M. The low dose change due to dislocation piiming (dashed line) saturates at a dose <1 dpa. 

In addition, for two coaxial armchair tubules, estimates for the translational and rotational energy barriers (of 0.23 meV/atom and 0.52 meV/atom, respectively) vvere obtained, suggesting significant translational and rotational interlayer mobility of ideal tubules at room temperature[16,17]. Of course, constraints associated with the cap structure and with defects on the tubules would be expected to restrict these motions. The detailed band calculations for various interplanar geometries for the two coaxial armchair tubules basically confirm the tight binding results mentioned above[16,17]. 

Our picture of the transport process in these thick oxide layers is that there is a uniform concentration gradient of defects (cation vacancies and positive holes) across the layer. But it is important to notice that the oxidation flux is exactly twice that to be expected if diffusion alone were responsible for the transport of cation vacancies. The reason for this is, of course, that the more mobile positive holes set up an electric field which assists the transport of the slower-moving cation vacancies. 

In most cases of practically useful ionic conductors one may assume a very large concentration of mobile ionic defects. As a result, the chemical potential of the mobile ions may be regarded as being essentially constant within the material. Thus, any ionic transport in such a material must be predominantly due to the influence of an internal electrostatic potential gradient,... 

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. 

The variations of dielectric constant and of the tangent of the dielectric-loss angle with time provide information on the mobility and concentration of charge carriers, the dissociation of defect clusters, the occurrence of phase transitions and the formation of solid solutions. Techniques and the interpretation of results for sodium azide are described by Ellis and Hall [372]. 

It is appropriate to emphasize again that mechanisms formulated on the basis of kinetic observations should, whenever possible, be supported by independent evidence, including, for example, (where appropriate) X-ray diffraction data (to recognize phases present and any topotactic relationships [1257]), reactivity studies of any possible (or postulated) intermediates, conductivity measurements (to determine the nature and mobilities of surface species and defects which may participate in reaction), influence on reaction rate of gaseous additives including products which may be adsorbed on active surfaces, microscopic examination (directions of interface advance, particle cracking, etc.), surface area determinations and any other relevant measurements. 

Jacobs et al. [59,925,926] (Fig. 17). While this scheme conveniently summarizes many features of the observed behaviour, a number of variations or modifications of the mechanisms indicated have been proposed. Maycock and Pai Vemeker [924,933] emphasize the possible role of point defects and suggest, on the evidence of conductivity measurements, that the initial step may be the transfer of either a proton or an electron. Boldyrev et al. [46] suggest that proton conduction permits rapid migration of HC104 within the reactant and this undergoes preferential decomposition in distorted regions. More recently, the ease of proton transfer and the mobilities of other species in or on AP crystals have been investigated by a.c. [360] and d.c. [934] conductivity measurements. Owen et al. [934] could detect no surface proton conductivity and concluded that electron transfer was the initial step in decomposition. At the present time, these inconsistencies remain unresolved. 

In spite of the absence of periodicity, glasses exhibit, among other things, a specific volume, interatomic distances, coordination number, and local elastic modulus comparable to those of crystals. Therefore it has been considered natural to consider amorphous lattices as nearly periodic with the disorder treated as a perturbation, oftentimes in the form of defects, so such a study is not futile. This is indeed a sensible approach, as even the crystals themselves are rarely perfect, and many of their useful mechanical and other properties are determined by the existence and mobility of some sort of defects as well as by interaction between those defects. Nevertheless, a number of low-temperamre phenomena in glasses have persistently evaded a microscopic model-free description along those lines. A more radical revision of the concept of an elementary excitation on top of a unique ground state is necessary [3-5]. 

Several routes have been used to produce defect sites on MgCl2 surfaces One way is to grow the MgCl2 film at low temperatures so that the mobility of the MgCl2 is too low to allow for the formation of a fully epitaxial film. However, a major problem of this procedure is the tendency to produce films containing pinholes, which change the reactivity of the system [21]. Another option is to bombard the surface either with electrons or ions [22,87-90,106,107]. 

From a structural point-of-view the bulk metallic state, that is, fee lattice (with varying densities of defects such as twins and stacking faults) is generally established in gold nanoparticles of about 10 nm diameter and upwards. However, such particles still display many unusual physical properties, primarily as the result of their small size. Shrinking the size of gold particles has an important effect it increases both the relative proportion of surface atoms and of atoms of even lower coordination number, such as edge atoms [49] and these atoms in turn are relatively mobile and reactive. 

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