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New defect-crystal-chemical approach to non-Vegardianity and complex defect structure of fluorite-based MO$$_{2}$$-LnO$$_{1.5}$$ solid solutions (M$$^{4+}$$=Ce, Th; Ln$$^{3+}$$=Lanthanide), 1; Model description and lattice-parameter data analysis

蛍石型MO$$_{2}$$-LnO$$_{1.5}$$固溶体の非ヴェガード性及び複雑な欠陥構造への新しい欠陥構造化学的アプローチ(M$$^{4+}$$=Ce, Th; Ln$$^{3+}$$=ランタノイド),1; モデルの記述と格子定数データの解析

中村 彰夫

Nakamura, Akio

Lattice parameter data of defect fluorite (DF) solid solutions between MO$$_{2}$$ and LnO$$_{1.5}$$ (M=Ce, Th; Ln=Y, Gd, Eu, Sm, Nd, La) exhibit marked positive deviation from Vegard law. Their detailed analysis shows that this is a generalized non-Vegardian behavior of these oxygen-vacancy (V$$_{rm O}$$) type distortionally-dilated solid solutions with non-random oxygen coordination around the cations: The M=Ce and Th shift to the opposite non-randomness for the larger Ln: strongly Ce-V$$_{rm O}$$ associative in the former and extremely Ln-V$$_{rm O}$$ associative in the latter. Given compatibility with ion-packing model, this can also provide us with their metal-oxygen bond-length data. The author describes here such random to non-random model extension and its-based main $$a$$$$_{rm 0}$$ including their comparison with reported local-structure, thermodynamic data of these systems.

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パーセンタイル:40.4

分野:Chemistry, Physical

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