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A CORRELATION BETWEEN THE STRUCTURAL RELAXATION AND THE ELECTRICAL CONDUCTIVITY OF SEMICONDUCTING VANADATE GLASSES

Research Project

Project/Area Number 08640743
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field 機能・物性・材料
Research InstitutionKYUSHU UNIVERSITY

Principal Investigator

NISHIDA Tetsuaki  Kyushu University, Department of Chemistry, Faculty of Science, Research Associate, 理学部, 助手 (10112286)

Co-Investigator(Kenkyū-buntansha) MAEDA Yonezo  Kyushu University, Department of Chemistry, Faculty of Science, Professor, 理学部, 教授 (30037262)
HARA Kazuhiro  Kyushu University, Department of Applied Science, Faculy of Engineering, Associa, 工学部, 助教授 (00180993)
ICHIKAWA Fusao  Kyushu University, Department of Physics, Faculty of Science, Research Associate, 理学部, 助手 (30223085)
Project Period (FY) 1996 – 1997
Project Status Completed (Fiscal Year 1997)
Budget Amount *help
¥1,900,000 (Direct Cost: ¥1,900,000)
Fiscal Year 1997: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1996: ¥1,400,000 (Direct Cost: ¥1,400,000)
Keywordssemiconducting glass / structural relaxation / crystallization / electrical conductivity / cleavage of chemical bonds / Mossbauer spectroscopy / DTA / magnetic susceptibility / 電子ホッピング / メスバウアー効果
Research Abstract

Heat treatment of glass causes a structural change from glass to glass-ceramics, in which several crystalline particles with 'nanometer size' are precipitated. This structural change, I.e., crystallization of glass, brings about a drastic change of electrical conductivity, magnetism, optical transparency, etc. The present study was carried out in order to elucidate the mechanism of crystallization and the correlation between the structure and physical prperties of glass-ceramics by means of Mossbauer effect, FT-IR,magnetic susceptibility, XRD,and DTA.As a result, following conclusions could be obtained :
1) Heat treatment of semiconducting 25K_2O・65V_2O_5・10Fe_2O_3 glass at around the crystallization temperature (Tc) for a short time (10-30 min) results in a jump of the electrical conductivity from the order of 10^<-8> S・cm^<-1> to the order of 10^<-4> S・cm^<-1>, owing to the structural relaxation. After a prolonged heat treatment, the electrical conductivity decreases owing to the prec … More ipitation of an insulating crystalline phase.
2) Heat treatment of IR-transmitting aluminate glasses, 60CaO・27Al_2O_3・13Fe_2O_3 and 60CaO・10BaO・17Al_2O_3・13Fe_2O_3, at around the Tc causes a decrease in the IR-transmittance and that of magnetic susceptibility owing to the precipitation of 'nanoparticles' of antiferromagnetic Ca_2Fe_2O_5.
3) Activation energy (Ea) required for the crystallization is equal to the bond energies of the structural units (e.g., Ca-O and Al-O bonds), indicating that cleavage of the chemical bonds triggers the crystallization. The value of Ea is reduced to 2.6 eV in the case of vanadate and tungstate glsses containing iron (Fe (III), being equal to the Fe-O bond energy.
4) Glass transition temperature (Tg) is in proportion to the magnitude of quadrupole splitting (DELTA), one of the Mossbauer parameters, as discovered by Nishida et a1. ("Tg-DELTA rule", 1990). Heat treatment of silicate glass at around the Tg results in a concordant decrease of Tg with the DELTA of Fe (IlI), owing to the structural relaxation associated with a decrease in the distortion of SiO_4 and FeO_4 tetrahedra.
5) The " Tg-DELTA rule", originally discovered for several inorganic glasses containing several mol% of Fe_2O_3, holds for the 'ferrate glasses containing a large amount (-30 mol%) of Fe_2O_3. Less

Report

(3 results)
  • 1997 Annual Research Report   Final Research Report Summary
  • 1996 Annual Research Report
  • Research Products

    (19 results)

All Other

All Publications (19 results)

  • [Publications] T.Nishida: "Verification of the "Tg-Δ Rule"in Sodium Tungstate and Potassium Silicate Glasses" Zeitschrift fur Naturforschung. 51a. 620-626 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Kubuki: "Application of the IR Transmission Method and the Mossbauer Effect to the Crystallization of Calcium Gallate Glass" Journal of Non-Crystalline Solids. 209. 87-95 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Nishida: "Crystallization Mechanism of Aluminoferrate Glass Accompanying a Precipitation of Nanocrystals of Dicalcium Ferrite(Ca_2Fe_2O_5)・・・" Journal of Materials Chemistry. 7. 1801-1806 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Kubuki: "Mossbauer Study on the Crystallization of IR-Transmitting Aluminate Glasses" Journal of Radioanalytical and Nuclear Chemistry. (in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Nishida: "Application of the 'Tg-Δ Rule'to the Local Structural Study of Ferrate Glasses" Journal of Radioanalytical and Nuclear Chemistry. (in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Nishida: ""Mossbauer Spectroscopy of Sophisticated Oxides"" Akademiai Kiado(Budapest), 340 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Nishida: "Verification of the "Tg-DELTA Rule in Sodiun Tungstate and Potassium Silicate Glasses" Zeitschrift fur Naturforschung. 51a. 620-626 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Kubuki, T.Nishida, P.Kaung, T.Yagi, and Y.Maeda: "Application of the IR Transmission Method and the Mossbauer Effect to the Crystallization of Calcium" Journal of Non-Crystalline Solids. 209. 87-95 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Nishida, S.Kubuki, M.Shibata, Y.Maeda, and T.Tamaki: "Crystallization Mechanism of Aluminoferrate Glass Accompanying a Precipitation of Nanocrystals of Dicalcium Ferrite (Ca_2Fe_2O_5)and Maynite (12CaO・7Al_2O_3)" Journal of Materials Chemistry. 7(9). 1801-1806 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Kubuki, T.Nishida, and Y.Maeda: "Mossbauer Study on the Crystallization of IR-Transmitting Aluminate Glasses" Journal of Radioanalytical and Nuclear Chemistry. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Nishida, S.Kubuki, and Y.Maeda: "Application of the Tg-DELTA Rule to the Local Structural Study of Ferrate Glasses" Journal of Radioalytica and Nuclear Chemistry. (in oress).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Nishida: Mossbauer Spectroscopy of Sophisticated Oxides. Akademiai Kiado (Budapes), 340 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Nishida: "Verification of the ″Tg-Δ Rule″in Sodium Tungstate and Potassium Silicate Glasses" Zeitschrift fur Naturforschung. 51a巻. 620-626 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] S.Kubuki: "Application of the IR Transmission Method and the Mossbauer Effect to the Crystallization of Calcium Gallate Glass" Journal of Non-Crystalline Solids. 209. 87-95 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Nishida: "Crystallization Mechanism of Aluminoferrate Glass Accompanying a Precipitation of Nanocrystals of Dicalcium Ferrite (Ca2Fe2O5) ・・・" Journal of Materials Chemistry. 7巻9号. 1801-1806 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] S.Kubuki: "Mossbauer Study on the Crystallization of IR-Transmitting Aluminate Glasses" Journal of Radioanalytical and Nuclear Chemistry. (in press).

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Nishida: "Application of the ′Tg-Δ Rule′to the Local Structural Study of Ferrate Glasses" Journal of Radioanalytical and Nuclear Chemistry. (in press).

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Nishida: "″Mossbauer Spectroscopy of Sophisticated Oxides″" Akademiai Kiado(Budapest), 340 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Nishida: "Structural PRelaxation and Crystallization of Semiconducting Vanadate Glass Accompanying a Jump of the Electrical Conductivity" Journal of Materials Chemistry. 6巻12号. 1889-1896 (1996)

    • Related Report
      1996 Annual Research Report

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Published: 1996-04-01   Modified: 2016-04-21  

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