ゲルマニウムスピネルの研究(第3報)

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The cation distribution in CO_2GeO_4-CoM2O_4 and CO_2GeO_4-CO_2RO_4 systems (Co-I group), and in Ni2 GeO_4-NiM_2O_4 and Ni_2 GeO_4-Ni_2R O_4 systems (Ni-I group), where M = Al or Cr, and R = Sn or Ti, has been studied by lattice constant variation, reflectance spectra and pattern fitting method of X-ray diffraction diagrams. The cation distribution in Co_<1.2>Zn_<0.8> GeO_4-Co_<0.6>Zn_<0.4>M_2 O_4 and Co_<1.2> Zn_<0.8>GeO_4-CO_<1.2>Zn_<0.8>RO_4(Co-II group) and in NI_<1.2>Zn_<0.8>GeO_4-Nl_<0.6>Zn_<0.4>M_2O_4 Ni_<0.8>Zn_<1.2> GeO_4- Ni_<0.8> Zn_<1.2>RO_4 (Ni-II group), where M=Al or Cr, and R=Sn or Ti, has also been studied. These results are summarized as follows. (1) Spinel type solid solutions with the 6-coordinated sites occupied by Ge^<4+> ions are formed over the entire ranges of C0-II and Ni-II groups. (2) In the Cr-, Al- and Sn-systems of Co-I and Ni-I groups, no spinel type solid solutions near CO_2GeO_4 and Ni_2GeO_4 compositions are observed. But in the Ti-system of Co-I and Ni-I groups, spinel type solid solutions in which Ti^<4+> ions are substituted for Ge^<4+> ions in the 4-coordinated sites are formed. In the composition range near the other end members of CoAl_2O_4, CoCr_2O_4, Co_2TIO_4 and Co_2SnO_4(Co-I group) spinel type solid solutions m which Ge^<4+> occupy the 6 coordinated sites are formed over the wide range. In the composition range near the end members of NiCr_2O_4 or NiAl_2O_4 (Ni-I group), spinel type solid solution are formed over narrow range. The cation distributions i,1 the spinel type solid solutions were accounted for by the site preference of cations and Pauling's electrostatic valence rule. We proposed that this rule is one of the most important factors for determining the cation distribution in the spinel structure.
社団法人日本セラミックス協会の論文
1990-09-01

ゲルマニウムスピネルの研究(第3報)

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