Vacancy point defects precipitation

If tlie level(s) associated witli tlie defect are deep, tliey become electron-hole recombination centres. The result is a (sometimes dramatic) reduction in carrier lifetimes. Such an effect is often associated witli tlie presence of transition metal impurities or certain extended defects in tlie material. For example, substitutional Au is used to make fast switches in Si. Many point defects have deep levels in tlie gap, such as vacancies or transition metals. In addition, complexes, precipitates and extended defects are often associated witli recombination centres. The presence of grain boundaries, dislocation tangles and metallic precipitates in poly-Si photovoltaic devices are major factors which reduce tlieir efficiency. 

Figure 1.1 Defects in crystalline solids (a) point defects (interstitials) (b) a linear defect (edge dislocation) (c) a planar defect (antiphase boundary) (d) a volume defect (precipitate) (e) unit cell (filled) of a structure containing point defects (vacancies) and (/) unit cell (filled) of a defect-free structure containing ordered vacancies. ...

AGbo > [ AGa0, almost pure metal A is precipitated in the internal reduction zone. The reaction at the front is induced by a point defect flux which stems from the difference in oxygen potentials (point defect concentration) between the internal reaction front and the external surface. The reaction front and surface act as source and sink for the point defect flux. For example, when we assume that (A,B)0 contains transition-metal ions (e.g., (Ni,Mg)0), the defects are cation vacancies and compensating electron holes. The (reducing) external surface acts as a vacancy sink according to the reaction... 

Defect structure of neutron-irradiated Fe-Cr alloys contains free vacancies, SIA, VC, pure dislocation loops, dislocation loops decorated by Cr atoms, and vacancy-Cr complexes as well as Cr precipitates depending on the irradiation regime (Malerba et al. 2008). The CD model in our study is close to the model proposed by Christien and Barbu (2004), where the CD simulations are first performed for the free vacancies, SIAC, and point defect clusters and then for the precipitates, taking into account the steady state values of the free point defects concentrations obtained in the first step. In addition, we take into account the Cr-effect on the SIA diffusivity according to the density functional theory (DFT) calculations (Terentyev et al. 2008). 

Since the details of these equations are explained elsewhere, only key ideas are briefly described here. One of these is to classify the solute atom clusters into irradiation-induced clusters and irradiation-enhanced clusters. Irradiation-induced clusters correspond to solute atom clusters with or without Cu atoms, whose formation mechanism is assumed to be the segregation of solute atoms based on point defect cluster or matrix damage (heterogeneous nucleation). On the other hand, the irradiation-enhanced clusters correspond to so-called CRPs (Cu-rich precipitates) or CELs (Cu-enriched clusters), and the formation mechanism is the clustering of Cu atoms above the solubility limit enhanced by the excess vacancies introduced by irradiation. This model also assumes that the formation of solute atom clusters and matrix damage is not independent to each other, which is a very different model from the conventional two-feature models as described in the previous sections. Another key idea is the introduction of a concept of a thermal vacancy contribution in the diffusivity model. This idea is essentially identical to that shown in Rg. 11.11. This is a direct modeling of the results of atomic-level computer simulations. ... 

The four nickel materials in Eqs. 13.1 and 13.2 are distinct phases and have been characterized bothelectrochemically and by the XRD patterns exhibited in the chemically precipitated phases. A point defect, nonstoichiometric, structural model correctly describes the structure and interactions of nickel electrode active materials (22). In this model, the intercalated water is incorporated as interlameUar protons, with the oxygen effectively adding to the Ni02 layers. The model introduces nickel vacancies that explain the empirical Ni/O ratios (less than 1/2). The Raman spectra gives no indication of water in the lattice as the excess protons and alkali cations... 

A suitable classification of crystalline defects can be achieved by first considering the so-called point defects and then proceeding to higher-dimensional defects. Point defects are atomic defects whose effect is limited only to their immediate surroundings. Examples are vacancies in the regular lattice, or interstitial atoms. Dislocations are classified as linear or one-dimensional defects. Grain boundaries, phase boundaries, stacking faults, and surfaces are two-dimensional defects. Finally, inclusions or precipitates in the crystal matrix can be classified as three-dimensional defects. 

Numerous studies have attempted to elucidate the role of Mo in the passivity of stainless steel. It has been proposed from XPS studies that Mo forms a solid solution with CrOOH with the result tiiat Mo is inhibited from dissolving trans-passively [9]. Others have proposed that active sites are rapidly covered with molybdenum oxyhydroxide or molybdate salts, thereby inhibiting localized corrosion [10]. Yet another study proposed that molybdate is formed by oxidation of an Mo dissolution product [11]. The oxyanion is then precipitated preferentially at active sites, where repassivation follows. It has also been proposed that in an oxide lattice dominated by three-valent species of Cr and Fe, ferrous ions will be accompanied by point defects. These defects are conjectured to be canceled by the presence of four- and six-valent Mo species [1]. Hence, the more defect-free film will be less able to be penetrated by aggressive anions. A theoretical study proposed a solute vacancy interaction model in which Mo " is assumed to interact electrostatically with oppositely charged cation vacancies [ 12]. As a consequence, the cation vacancy flux is gradually reduced in the passive film from the solution side to the metal-film interface, thus hindering vacancy condensation at the metal-oxide interface, which the authors postulate acts as a precursor for localized film breakdown [12]. 

In order to elucidate whether such a precipitate can trap positrons, the positron affinities A+ for the host material and the precipitate were calculated [154], The A+ values were found to be relatively high and the positron lifetimes very short for perfect MC carbides. This fact confirms that perfect MC (M s Cr, V, Ti, Mn, Fe, Zr, Nb) carbides are very dense materials that cannot trap positrons when embedded in the Fe matrix. In general, from a PAS point of view, radiation damage can be interpreted as a combination of radiation-induced point defects, dislocations and small vacancy clusters [129,130] that occur mainly in the region of the precipitate-matrix interface. 

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