鉱物結晶学の多様化：新たな広がりと挑戦　　４．都市鉱物（材料科学）希土類ケイ酸塩酸素アパタイト中の酸化物イオン伝導経路

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タイトル別名
  • Conduction Pathway of Oxide Ions in Rare-Earth Silicate Oxyapatites
  • 希土類ケイ酸塩酸素アパタイト中の酸化物イオン伝導経路
  • キドルイ ケイ サンエン サンソ アパタイト チュウ ノ サンカブツ イオン デンドウ ケイロ

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Apatite-type RE9.33(SiO4)6O2 rare-earth silicate compounds are of great interest for their oxide ion conductivity at moderate temperatures. Crystallographic space group and structural parameters of La/Nd9.33(SiO4)6O2 were investigated based on single-crystal X-ray diffraction data at room temperature for La9.33(SiO4)6O2 and at various temperatures from 150 to 900 K for Nd9.33(SiO4)6O2. Based on the most accurate diffraction data to date, these compounds have an apatite prototype structure (space group P63/m) with no symmetry lowering, site splitting nor interstitial oxide ion in the structure. Most striking feature of the structure is large anisotropy in thermal motions of the oxide ion at the anion channel site. Even at room temperature, the mean-square displacement of the channel oxide ion in La9.33(SiO4)6O2 is 16 times larger in [001] than those normal to the direction. Not striking but important point is that there is no sign of interstitial oxide ion which had been proposed as a charge carrier in La9.33(SiO4)6O2 and related compounds. These findings imply straight migration of oxide ion inside the channel as a primary mechanism of oxide-ion conductivity in these compounds. Size and shape of the anion channel might be a key to achieve high oxide-ion conductivity in these compounds.

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