Synthesis and Properties of Ni<sup>2+</sup>-Substituted Tetrasilicic Fluorine Micas

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  • KITAJIMA Kunio
    Department of Chemistry and Material Engineering, Shinshu University
  • IHARA Yoshihiro
    Department of Chemistry and Material Engineering, Shinshu University
  • TAKUSAGAWA Nobuo
    Department of Chemistry and Material Engineering, Shinshu University

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Other Title
  • Ni<sup>2+</sup>置換フッ素四ケイ素雲母の合成と性質
  • Ni2 + チカン フッソ 4 ケイソ ウンモ ノ ゴウセイ ト セイシツ

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Various Ni2+-substituted tetrasilicic micas having high contents of Ni2+, such as KNiMgLi(Si4O10)F2, KNi2Li(Si4O10)F2 and KNi2.5(Si4O10)F2, were synthesized at ca. 900°C through solid-state reaction techniques. Lattice constants a, b, c decreased with increasing Ni2+-substitutions, reflecting the decrease in the ionic radius of Ni2+ against Mg2+. UV-visible spectra of Ni2+-micas were very similar to those of [Ni(H2O)6]2+, This can be explained in terms of the nephelauxetic series F-<H2O<Oa (apical oxygen) as well as the spectrochemical series F-<H2O<Oa. IR spectra showed that the tetrahedral distortion changes with increasing Ni2+-substitutions, i.e., the interatomic distance of Si-Oa lengthens while that of Si-Ob (basal oxygen) shortens. Ni2+-micas exhibited paramagnetism when the Ni2+ content was smaller than 2.0 mol in octahedral sites, however, antiferromagnetism seemed to appear at larger substitutions of 2.5 mol Ni2+ per formula unit.

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