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By Gschneidner K.A. (ed.)

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The mysterious non-stoichiometric characteristics of the lanthanide higher oxides are related to these intrinsic features of the 4f electron band structures. Unfortunately, at present time only the electron band structures of CeO2 , Ce2 O3 , and PrO2 have been calculated. 4. , 2005). , 1966; Hyde and Eyring, 1965; Bevan and Kordis, 1964). 1 Phase diagrams with bi-variant parameters: temperature and oxygen partial pressure The binary phase diagrams of CeOx –O2 , PrOx –O2 , and TbOx –O2 system can be found, for example, in Haire and Eyring review article (Haire and Eyring, 1994).

The Zr cations have fixed valence 4+ and they are not ordered. The oxygen vacancies in this oxide are distributed around the reduced cerium cations. Therefore, the probability of an oxygen site being vacant for the tetrahedron with Zr should be different, and then the modules for constructing the structure are limited. The composition domains are inevitable. Figure 38 is the high resolution electron microscopic image of this phase (Kang, 2006). FIGURE 37 model.

The proposal structure is shown in Figure 36. C. Kang FIGURE 35 FIGURE 36 Electron diffraction pattern of the Ce19 O34 phase. The proposed structure of the Ce19 O34 phase. Lanthanide Higher Oxides: The Contributions of Leroy Eyring 41 modules in the n = 7 phases are not completely dissociated (Kang and Eyring, 1997a, 1997b). 10 From the binary oxide to the ternary oxide The binary lanthanide higher oxides, CeOx , PrOx , and TbOx have oxygendeficient, fluorite-related structures. In these structures the cations occupy the same positions in the structure, and they have same valence flexibility.

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