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Phase equilibria and thermal expansion of CaTiO$$_{3}$$ doped with neptunium

ネプツニウムを添加したCaTiO$$_{3}$$の相平衡と熱膨張

佐藤 剛*; 山下 利之; 松井 恒雄*

Sato, Tsuyoshi*; Yamashita, Toshiyuki; Matsui, Tsuneo*

CaTiO$$_{3}$$及びCa(Ti,Al)O$$_{3}$$とNpO$$_{2}$$の相関係をX線回折法により調べた。用いた試料はAr-8%$$_{2}$$中1773Kで調製したものである。単相の固溶体がCaTiO$$_{3}$$及びCa(Ti,Al)O$$_{3}$$についてそれぞれ、0-7.5モル%Np及び1-10モル%Npで得られた。TiをAlで置換することにより、Npの固溶量は増加する。Npの固溶挙動をUやPuと比較し、添加物の酸化状態やイオン半径の観点から議論した。Np添加CaTiO$$_{3}$$の熱膨張を室温から1273Kの範囲で、高温X線回折法により測定した。試料の体積膨張係数は組成によらずほぼ一定であり、Npの添加によるCaTiO$$_{3}$$の安定化は見られなかった。これは、顕著な安定化が観測されているPuを添加したCaTiO$$_{3}$$とは、大きく異なっている。

Phase relationships between NpO$$_{2}$$ and CaTiO$$_{3}$$ or Ca(Ti, Al)O$$_{3}$$ were investigated by X-ray diffraction (XRD) analysis, using specimens prepared at 1773 K in Ar-8%H$$_{2}$$. Single phase solid solutions were formed 0-7.5 mol%Np and 1-10 mol%Np for CaTiO$$_{3}$$ and Ca(Ti, Al)O$$_{3}$$, respectively. By substituting Al for Ti in CaTiO$$_{3}$$, Np solubility in Ca(Ti, Al)O$$_{3}$$ increased. Solubility of Np was compared with those of U and Pu, and was discussed with oxidation states and ionic radii of dopants. Thermal expansions of (Ca,Np)TiO$$_{3}$$ were measured from room temperature to 1273 K in Ar-8%H$$_{2}$$ using high-temperature XRD technique. These specimens showed nearly the same value of volumetric thermal expansion coefficients, suggesting that the incorporation of tetravalent Np into CaTiO$$_{3}$$ had practically no effect on stabilization of the crystal lattice. This finding was in a marked contrast to that of Pu doped CaTiO$$_{3}$$, where pronounced stabilization in the crystal was observed by incorporating Pu into CaTiO$$_{3}$$.

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パーセンタイル:80.62

分野:Materials Science, Multidisciplinary

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