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Synthsis, structure and physical property of vanadate garnets

Research Project

Project/Area Number 14540449
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Petrology/Mineralogy/Science of ore deposit
Research InstitutionYamaguchi University

Principal Investigator

IISHI Kazuake  Yamaguchi University, Faculty of Science, Professor, 理学部, 教授 (60034716)

Project Period (FY) 2002 – 2005
Project Status Completed (Fiscal Year 2005)
Budget Amount *help
¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 2005: ¥400,000 (Direct Cost: ¥400,000)
Fiscal Year 2004: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 2003: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 2002: ¥1,700,000 (Direct Cost: ¥1,700,000)
KeywordsVanadate garnet / Crystal chemistry / Solid solution / Flux method / Morphplogy / Surface kinetics / 構造解析 / イオン半径 / モルホロジー / 抵抗加熱型FZ単結晶育成装置 / SHG結晶 / Li_3VO_4 / リートベルト構造解析 / ヤーン・テラー効果 / HSAB原理
Research Abstract

1 Experiments were conducted to synthesize vanadate garnets of the following 5 types ; Type3:{A^+_2A^<2+>}[M^<2+>M^<3+>]-(V_3)O_<12>, Type 4:{A^+A^<2+>_2}[M^+M^<3+>](V_3)O_<12>, Type 5:{A^+A^<2+>_2}[M^<2+>_2](V_3)O_<12>, Type 6:{A^<2+>_3}[M^+M^<2+>](V_3)O_<12> and Type 7:{□_<0.5>A^<2+>_<2.5>}[M^<2+>_2](V_3)O_<12>, where A^+=Li^+,Cu^+,Na^+,Ag^+ and K^+;A^<2+>=Cd^<2+>,Ca^<2+>,Sr^<2+> and Pb^<2+>;M^+=Li^+;M^<2+>=Ni^<2+>,Mg^<2+>,Co^<2+>,Cu^<2+>,Zn^<2+>,Mn^<2+> and Cd^<2+>;M^<3+>=Cr^<3+> and Fe^<3+>. New variations of {Na_2Ca}[NiFe^<3+>](V_3)O_<12>,{A^+Ca_2}[LiCr^<3+>](V_3)O_<12>, where A^+=Li^+ and Na^+,{A^+Ca_2}[LiFe^<3+>](V_3)O_<12>, where A^+=Li^+,Cu^+,Na^+ and Ag^+,{LiCa_2}[M^<2+>_2](V_3)O_<12>, where M^<2+>=Co^<2+> and Mn^<2+>,{KCa_2}[Mn_2](V_3)O_<12>,{Ca_3}[LiCd](V_3)O_<12> and {Pb_3}[LiM^<2+>](V_3)O_<12>, where M^<2+>=Mg^<2+>,Co^<2+>,Zn^<2+>,Mn^<2+> and Cd^<2+> were prepared as phase-pure garnets for the first time. Garnets were formed only a few in both types 3 and 4. In types 5,6 … More and 7, the variety of garnets formed was greatly limited by the replacement of Ca^<2+> by Sr^<2+> as compared with that being not so much limited by the replacement of Ca^<2+> by Pb^<2+>, though the effective ionic radius of Pb^<2+> is larger than that of Sr^<2+>. This is ascribed to "the hard and soft acids and bases principle". In types 5,6 and 7, in the case of M^<2+>=Cu^<2+>, the variety of garnets formed was fairly limited due to the "the Jahn-Teller effect of Cu^<2+>".
2 The morphologies of vanadate garnets (NaCa_2M_2V_3O_<12>,M=Ni,Mg or Co) were studied by growing well-formed crystals from sodium vanadate flux. The first rank F-faces were determined by growing crystals at low supersaturation levels and were found to be the {110} face at lower temperature and the {211} face at higher temperature. This change was ascribed to a change in the ratio of the bond lengths at the octahedral site to that of the dodecahedral site with increasing temperature. When crystals grew larger in the lower temperature region, predominantly {211} faces appeared in addition to {110} faces, whereas in the higher temperature region, {110} faces were predominant over {211} faces. The reason for these phenomena was ascribed to the surface kinetics caused by an increase in the rate of mineral nutrient transport to the surface of the crystal with increasing crystal size. Less

Report

(5 results)
  • 2005 Annual Research Report   Final Research Report Summary
  • 2004 Annual Research Report
  • 2003 Annual Research Report
  • 2002 Annual Research Report
  • Research Products

    (12 results)

All 2006 2004 2003 Other

All Journal Article (11 results) Publications (1 results)

  • [Journal Article] Isomorphous substitutions in vanadate garnets2006

    • Author(s)
      K.Iishi
    • Journal Title

      Neues Jahrbuch fur Mineralogie Abhandlung 18(In press)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Annual Research Report 2005 Final Research Report Summary
  • [Journal Article] Morphology of flux-grown vanadate garnets2006

    • Author(s)
      K.Iishi
    • Journal Title

      Journal of Crystal Growth 290(In press)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Annual Research Report 2005 Final Research Report Summary
  • [Journal Article] Isomorphous substitutions in vanadate garnets2006

    • Author(s)
      Iishi, K.
    • Journal Title

      Neues Jahrbuch fur Mineralogie Abhandlung Vol.18(in press)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Morphology of flux-grown vanadate garnets2006

    • Author(s)
      Iishi, K.
    • Journal Title

      Journal of Crystal Growth Vol.290(in press)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Single crystal X-ray diffraction study of the vanadate garnet Ca_2NaZn_2V_3O_<12>2004

    • Author(s)
      A.Nakatsuka
    • Journal Title

      Materials Research Bulletin 39

      Pages: 949-956

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary 2004 Annual Research Report
  • [Journal Article] The Crystal structure of synthetic palenzoanite Ca_2NaMn_2V_3O_<12>2004

    • Author(s)
      A.Nakatsuka
    • Journal Title

      Applied Mineralogy, Pecchio et al. (eds) 2004 ICAM-BR, Sao Paulo

      Pages: 631-634

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Single crystal X-ray diffraction study of the vanadate garnet Ca_2NaZn_2V_3O_<12>2004

    • Author(s)
      Nakatsuka, A.
    • Journal Title

      Materials Research Bulletin Vol.39

      Pages: 949-956

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] The crystal structure of synthetic paleuzoanite Ca_2NaMn_2V_3O_<12>2004

    • Author(s)
      Nakatsuka, A.
    • Journal Title

      Applied Mineralogy(Pecchio, et al.(eds))(CAM-BR, Sao Paulo)

      Pages: 631-634

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] The crystal structure of synthetic palenzoanite Ca_2NaMn_2V_3O_<12>2004

    • Author(s)
      A.Nakatsuka
    • Journal Title

      Applied Mineralogy, 2004 ICAM-BR, Sao Paulo (Pecchio et al.(eds))

      Pages: 631-634

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Vanadate garnet, Ca_2NaMg_2V_3O_<12>2003

    • Author(s)
      A.Nakatsuka
    • Journal Title

      Acta Crystallographica Section C 59

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Vanadate garnet, Ca_2NaMg_2V_3O_<12>2003

    • Author(s)
      Nakatsuka, A.
    • Journal Title

      Acta Crystallographica Section C Vol.59

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Publications] A.Nakatsuka, Y.Ikuta, A.Yoshiasa, K.Iishi: "Vanadate garnet, Ca_2NaMg_2V_3O_<12>"Acta Crystallographica Section C. 59. i133-i135 (2003)

    • Related Report
      2003 Annual Research Report

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Published: 2002-04-01   Modified: 2016-04-21  

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