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Oxygen potential representation of (U,Ce)O$$_{2 pm x}$$

(U,Ce)O$$_{2 pm x}$$の酸素ポテンシャル式

鈴木 紀一  ; 村上 龍敏 ; 廣岡 瞬 ; Nelson, A.*; McClellan, K.*; 加藤 正人   

Suzuki, Kiichi; Murakami, Tatsutoshi; Hirooka, Shun; Nelson, A.*; McClellan, K.*; Kato, Masato

Ce含有率5%, 20%, 30%の(U,Ce)O$$_{2 pm x}$$の酸素ポテンシャル測定データについて、Kroger-Vink diagramを用いてxと酸素分圧Po2の関係を調べた。定比組成近傍では、xは$$P_{rm O2}$$$$^{+1/2}$$(酸化側), $$P_{rm O2}$$$$^{-1/2}$$(還元側)に比例することが分かった。これは、定比組成近傍ではイオンの真性化が支配的であることを示している。また、より還元側において、Ce含有率5%ではxは$$P_{rm O2}$$$$^{-1/4}$$、20%及び30%ではxは$$P_{rm O2}$$$$^{-1/6}$$に比例することが分かった。また、これらの結果を基に欠陥濃度を評価し、O/M比, 温度, Ce含有率をパラメータとして、酸素ポテンシャルの実験結果をよく再 現する式を得た。

The relationship between equilibrium oxygen partial pressure, $$P_{rm O2}$$, and deviation from stoichiometric composition, x, was evaluated using a Kroger-Vink diagram. It was found that x was proportional to $$P_{rm O2}$$$$^{+1/2}$$ and $$P_{rm O2}$$$$^{-1/2}$$ near stoichiometry for all compositions. This suggests that intrinsic ionization is dominant near stoichiometry. Also, in the reducing region, x was proportional to $$P_{rm O2}$$$$^{-1/4}$$ for 20 and 30% of Ce, and was proportional to $$P_{rm O2}$$$$^{-1/6}$$ for 5% of Ce. Defect reactions and defect concentrations were evaluated by the relationship between x and $$P_{rm O2}$$$$^{1/n}$$. Then, the oxygen potential expression was derived using the defect concentrations as functions of O/M ratio, temperature and Ce content. The calculated values reproduced experimental values well.

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