tailieunhanh - Kinetics of Materials - R. Balluff S. Allen W. Carter (Wiley 2005) WW Part 6

Tham khảo tài liệu 'kinetics of materials - r. balluff s. allen w. carter (wiley 2005) ww part 6', kỹ thuật - công nghệ, cơ khí - chế tạo máy phục vụ nhu cầu học tập, nghiên cứu và làm việc hiệu quả | ATOMIC MODELS FOR DIFFUSIVITIES 181 Crystal Self-Diffusion in Nonstoichiometric Materials. Nonstoichiometry of semiconductor oxides can be induced by the material s environment. For example materials such as FeO illustrated in Fig. NiO and CoO can be made metal-deficient or O-rich in oxidizing environments and TiO2 and ZrO2 can be made O-deficient under reducing conditions. These induced stoichiometric variations cause large changes in point-defect concentrations and therefore affect diffusivities and electrical conductivities. In pure FeO the point defects are primarily Schottky defects that satisfy massaction and equilibrium relationships similar to those given in Eqs. and . When FeO is oxidized through the reaction FeO 02 FeOi z each o atom takes two electrons from two Fe ions as illustrated in Fig. according to the reactions 2Fe 2Fe 2e 1 _ io2 2e- O - corresponding to the combined reaction 2Fe o2 2Fe 0 Electrical neutrality requires that a cation vacancy be created for every o atom added as in Fig. this combined with site conservation becomes 2Fe e o2 2Fepe 0Ỗ v e Figure Addition of a neutral o atom to FeO to produce O-rich metal-deficient oxide a An o atom receives two electrons from Fe ions in the bulk material b The final structure contains defects in the form of two Fe ions and a cation Fe vacancy. 182 CHAPTER 8 DIFFUSION IN CRYSTALS which can be written in terms of holes h in the valence band created by the loss of an electron from an Fe ion producing an Fe ion ỉ 2 o v- Fe Fe e - Fepe Equation predicts a relationship between the cation vacancy site fraction and the oxygen gas pressure. The equilibrium constant for this reaction is important for oxygen-sensing materials . Fẹl. _ g-AG kr Pc 2 For the regime in which the dominant charged defects are the oxidation-induced cation vacancies and their associated holes the electrical neutrality condition is e 2 V e Therefore .

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