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$$^{155}$$Gd M$"o$ssbauer spectroscopic and powder X-ray diffraction study of CeO$$_{2}$$ - GdO$$_{1.5}$$ solid solution

セリアーガドリニア固溶体系の$$^{155}$$Gdメスバウアー分光法及び粉末X線回折法による研究

中村 彰夫; 今井 和貴*; 井川 直樹; 岡本 芳浩; 山本 悦嗣; 松川 史郎*; 高橋 正*

Nakamura, Akio; imai, kazutaka*; Igawa, Naoki; Okamoto, Yoshihiro; Yamamoto, Etsuji; Matsukawa, Shiro*; Takahashi, Masashi*

Powder X-ray diffractometry and $$^{155}$$Gd-M$"o$ssbauer spectroscopy have been applied to the Ce$$_{1-y}$$Gd$$_{y}$$O$$_{2-y/2}$$ prepared at 1450$$^{circ}$$C. The former shows that this system forms a complete solid solution being the disordered defect-fluorite type in the smaller y range than 0.30 and the order C-type beyond y = 0.30. Its marked positive non-Vegardianity was consistently interpreted as a generalized Vegard-law behaviour of this distortion-dilated solid solution having Gd$$^{3+}$$ - oxygen vacancy association. The latter also clarifies that in the ordered C-type phase with decreasing y the 8b-site $$^{155}$$Gd-M$"o$ssbauer intensity steadily diminishes and vanishes at y = 0.50, indicating that the more-distorted minor 8b Gd$$^{3+}$$ in C-type GdO$$_{1.5}$$ is being preferentially replaced with Ce$$^{4+}$$.

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