Surface defects, effects

Chemical stabilization involves removing the concentration of surface hydroxyls and surface defects, such as metastable three-membered rings, below a critical level so that the surface is not stressed by rehydroxylation in use. Thermal stabilization involves reducing the surface area sufficiently to enable the material to be used at a given temperature without reversible stmctural changes. The mechanisms of thermal and chemical stabilization are interrelated because of the extreme effects that surface hydroxyls and chemisorbed water have on stmctural changes. Full densification of gels, such as the... 

An effect which is frequently encountered in oxide catalysts is that of promoters on the activity. An example of this is the small addition of lidrium oxide, Li20 which promotes, or increases, the catalytic activity of dre alkaline earth oxide BaO. Although little is known about the exact role of lithium on the surface structure of BaO, it would seem plausible that this effect is due to the introduction of more oxygen vacancies on the surface. This effect is well known in the chemistry of solid oxides. For example, the addition of lithium oxide to nickel oxide, in which a solid solution is formed, causes an increase in the concentration of dre major point defect which is the Ni + ion. Since the valency of dre cation in dre alkaline earth oxides can only take the value two the incorporation of lithium oxide in solid solution can only lead to oxygen vacaircy formation. Schematic equations for the two processes are... 

The condition of the test metal is important. Clean metal samples with uniform finishes are preferred. The accelerating effects of surface defects lead to deceptive results in samples. The ratio of the area of a defect to the total surface area of the metal is much higlier in a sample than in any metal in service. This is an indication of the inaccuracy of tests made on metals with improper finishes. The sample metal should have the same type of heat treatment as the metal to be used in service. Different heat treatments have different effects on corrosion. Heat treatment may improve or reduce the corrosion resistance of a metal in an unpredictable manner. For the purpose of selectivity, a metal stress corrosion test may be performed. General trends of the performance of a material can be obtained from such tests however, it is difficult to reproduce the stress that actually will occur during service. 

The catalytic properties of the shock-modified rutile whose defect properties have been reported in previous sections of this chapter have been studied in a flow reactor used to measure the oxidation of CO by Williams and coworkers [82G01, 86L01]. As shown in Fig. 7.7 the effect of shock activation is substantial. Whereas the unshocked material displays such low activity that an effect could only be observed at the elevated temperature of 400 °C, the shock-modified powder shows substantially enhanced catalytic activity with the extent of the effect depending on the shock pressure. After a short-time transient is annealed out, the activity is persistent for about 8 h. Although the source of the surface defects that cause the activity is not identified, the known annealing behavior of the point defects indicates that they are not responsible for the effect. 

In another study [31] it has been reported that haze of LLDPE is mainly a consequence of light scattered by the spherulites. Thus, origin of poor clarity is not the same in LLDPE as in HP LDPE. In HP LDPE the haze is produced by surface defects coming from processing rheology [48,54,55]. Processing variables, therefore, do not have the same effect on LLDPE as they do on HP LDPE. 

Structural properties of materials Sub-lattice Substrate Surface phonoas Surface defects m transition metals Surface segregation SupeqDlastic properties and lic[uid phase effect Susceptibility... 

Firstly, they might be expected to have an effect when corrosion occurs under conditions of active (film-free) anodic dissolution and is not limited by the diffusion of oxygen or some other species in the environment. However, if the rate of active dissolution is controlled by the rate of oxygen diffusion, or if, in general terms, the rate-controlling process does not take place at the metal surface, the effect of crystal defects might be expected to be minimal. 

As the surface smoothing and levelling effects are somewhat limited, the use of acid cleaners prior to anodising or electropainting, where surface defects can be enhanced, is not common. 

In this work, effects of atmosphere during calcination process on photoactivities for decomposition of ethylene were investigated. TiOa were prepared by sol-gel and then calcined under Na plus increasing amounts of O2 at temperature 723 K. Conversion of ethylene increased with increasing sirface defect. Increasing this defect occurred when amount of O2 during calcination process increased. Surface defect of Ti02 samples was determined by CO2-TPD and ESR, while XRD, SEM, TEM and BET were used to characterize other physical properties of TiOa samples. 

In this work, effect of atmosphere during calcination process on surface defect was investigated using photocatalytic activity for oxidation of ethylene. CO2-TPD and ESR were used to determine this surface defect. 

Tenne R, Wold A (1985) Passivation of recombination centers in n-WSe2 yields high efficiency (>14%) photoelectrochemical cell. Appl Phys Lett 47 707-709 Chaparro AM, Salvador P, Peter LM (1995) The role of surface defects in the photooxidation of iodide at n-MoSe2 evidence for a local autocatalytic effect. J Phys Chem 99 6677-6683... 

Molecular dynamics simulations have also been used to study the effect of the presence of surface defects and the distribution of ions at the electrochemical double layer. The classical approach described previously has been challenged in recent times through the use of models that involve the calculation of both atomic and the electronic structures of the interface, as made by J. W. Halley et al. (1998). 

In above sections the main attention has been paid to adsorption-caused change in electrophysical characteristics of semiconductor adsorbent caused by surface charging effects. However, as it was mentioned in section 1.6, the change in electrophysical characteristics of such adsorbents can be caused by other mechanisms, e.g. by direct interaction of absorbate with the surface defects provided (as in the case of oxide adsorbents) by superstoichiometric atoms of metals and oxygen... 

In summary, intratracheal instillation of CNTs has shown that their potential in eliciting adverse pulmonary effects is influenced by exposure time, CNT dose, CNT biopersistence, surface defects, and metal contamination [71, 72]. Despite the use of surfactants, all studies showed that intratracheal instillation caused major difficulties due to the agglomerative nature of CNTs in a biological environment. More realistic exposure methods, namely inhalation rather than intratracheal administration, are therefore needed for determining the pulmonary toxicity [59, 65, 73]. Several investigations have been performed by using administration different from intra-... 

Enhanced chemical reactivity of solid surfaces are associated with these processes. The cavitational erosion generates unpassivated, highly reactive surfaces it causes short-lived high temperatures and pressures at the surface it produces surface defects and deformations it forms fines and increases the surface area of friable solid supports and it ejects material in unknown form into solution. Finally, the local turbulent flow associated with acoustic streaming improves mass transport between the liquid phase and the surface, thus increasing observed reaction rates. In general, all of these effects are likely to be occurring simultaneously. 

The electron spin resonance (ESR) technique has been extensively used to study paramagnetic species that exist on various solid surfaces. These species may be supported metal ions, surface defects, or adsorbed molecules, ions, etc. Of course, each surface entity must have one or more unpaired electrons. In addition, other factors such as spin-spin interactions, the crystal field interaction, and the relaxation time will have a significant effect upon the spectrum. The extent of information obtainable from ESR data varies from a simple confirmation that an unknown paramagnetic species is present to a detailed description of the bonding and orientation of the surface complex. Of particular importance to the catalytic chemist... 

It is interesting to observe that a fair correlation can be found between the pore size evaluated by the Washbum-Laplace model and the pore size evaluated by the BJH model of nitrogen adsorption in the case of SBA-15 [12] and other materials with interconnected pores [13], In the case of gas adsorption, the surface defects are filled at a lower pressure and do not affect the pressure of capillary condensation [10]. However, the BJH model does not take into account the effects of curvature on condensation and systematically underevaluates the size of the mesopores [7, 14]. 

A surface peak effect has been observed during Rb and Sr diffusion in vitreous silica (13). Such large near-surface concentrations are postulated to result from the exposure at the glass surface of a greater number of interstices or defects over which diffusion can occur. This would lead to steep penetration curves observed in some XPS profiles of glass. 

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