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Entropy of Formation of Oxygen Vacancy in Functional Ceramics Determined by Measuring Heat Capacity from Near Absolute Zero

Research Project

Project/Area Number 15360351
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic materials/Physical properties
Research InstitutionUniversity of Hyogo (2004-2006)
Himeji Institute of Technology (2003)

Principal Investigator

MORISHITA Masao  University of Hyogo, Department of Materials Science and Chemistry, Professor, 大学院工学研究科, 教授 (60244696)

Co-Investigator(Kenkyū-buntansha) 香山 滉一郎  兵庫県立大学, 大学院・工学研究科, 教授 (60047595)
Project Period (FY) 2003 – 2006
Project Status Completed (Fiscal Year 2006)
Budget Amount *help
¥9,900,000 (Direct Cost: ¥9,900,000)
Fiscal Year 2006: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 2005: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 2004: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 2003: ¥8,100,000 (Direct Cost: ¥8,100,000)
KeywordsLa_XSr_<1-X>FeO_<3-δ> / La_XSr_<1-X>CoO_<3-δ> / ITO / V^<●●>_O / C_p / C_v / Debye function / Entropy of Formation of OxygenVacancy / La_xSr_<1-x>CoO_<3-δ> / SOFC / カソード / V^¨_o / V^<・・>_o / ITO固溶体 / 熱容量 / 混合のエントロピー / バンドキャップ / 短範囲規則化 / 不純物準位 / 縮退 / 可視光 / バンドギャップ / 規則化 / 吸収
Research Abstract

Oxide functional ceramics are used as conducting materials, and their application for industries has been expanded. Their characteristics drastically changes resulted from doping and formation of oxygen vacancy, V^<●●>_O, and oxygen interstitial, O^<'''>_i, associated with doping. In the present study, Isobaric heat capacities, C_p, of La_XSr_<1-X>MO_<3-δ> (M = Fe and Co) which is used as cathodes of SOFC, and ITO which is used as transparent conducting oxide have been measured from near absolute zero to high temperatures, and change in phase transitions and lattice vibrations were investigated from such C_p values. Also, their Debye temperatures, Θ_D, were determined from the measured C_p values below 10 K and isochoric heat capacities, C_V, were calculated by inserting the Θ_D values into Debye functions, followed by calculating the isochoric entropies of vibration, Δ^T_OS_V. Furthermore, the entropies of vibration of oxygen vacancy, Δ_fS^<vib>_<T_V>, (V^<●●>_O), were estimated by differentiation of Δ^T_OS_V with the V^<●●>_O content at 298 K. The Δ_fS^<vib>_<T_V> (V^<●●>_O) values of La_XSr_<1-X>MO_<3-δ> were found to be very large. Such large Δ_fS^<vib>_<T_V> (V^<●●>_O) are important reason for forming V^<●●>_O. As a result, La_XSr_<1-X>MO_<3-δ> show high conductivity by transporting oxygen ions at high temperature. On the other hand, the Δ_<mix>S_<298> values of ITO were found to be below zero, indicating that short range orderings of Sn^●_<In> and O^<''>_i are caused by a thermodynamic self-assembly to compensate charges. Such a self-assembly makes Sn^●_<In> and O^<''>_i levels in the band gap degenerate, and the degeneracy prevents absorption of visible light, remaining wide band gap over than 3 eV.

Report

(5 results)
  • 2006 Annual Research Report   Final Research Report Summary
  • 2005 Annual Research Report
  • 2004 Annual Research Report
  • 2003 Annual Research Report
  • Research Products

    (29 results)

All 2006 2005 2004 2003 Other

All Journal Article (26 results) Publications (3 results)

  • [Journal Article] La_<1-X>Sr_XFeO<3-δ>の絶対零度付近から高温までの熱容量測定2006

    • Author(s)
      森下政夫, 山本宏明
    • Journal Title

      日本金属学会誌 70

      Pages: 756-763

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Thermodynamics of the Formation Magnesium-Zinc Intermetallic Compounds in the Temperature Range from Absolute Zero to High Temperature2006

    • Author(s)
      M.Morishita, H.Yamamoto, S.Shikada, M.Kusunoto, Y.Matsumoto
    • Journal Title

      Acta Materialia 54

      Pages: 3151-3159

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] The Entropy of Vibration of Oxygen Vacancies in La_XSr<1-X>FeO<3-δ>2006

    • Author(s)
      M.Morishita, H.Yamamoto
    • Journal Title

      Delegate Manual of Fifth International Conference on Inorganic Materials, Ljubljana 1

      Pages: 197-198

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Heat Capacity of La_XSr_<1-X>FeO_<3-δ> From Near Absolute Zero Kelvin to High Temperature2006

    • Author(s)
      M.Morishita, H.Yamamoto
    • Journal Title

      Journal of Japan Institute of Metals 70

      Pages: 756-763

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] The Entropy of Vibration of Oxygen Vacancies in La_XSr_<1-X>FeO_<3-δ>2006

    • Author(s)
      M.Morishita, H.Yamamoto
    • Journal Title

      Delegate Manual of Fifth International Conference on Inorganic Materials, Ljubljana 1

      Pages: 197-198

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] La_xSr_<1-X>FeO_<3-δ>の絶対零度付近から高温までの熱容量測定2006

    • Author(s)
      森下政夫, 山本宏明
    • Journal Title

      日本金属学会誌 70

      Pages: 756-763

    • Related Report
      2006 Annual Research Report
  • [Journal Article] The Entropy of Vibration of Oxygen Vacancies in La_xSr_<1-X>FeO_<3-δ>2006

    • Author(s)
      M.Morishita, H.Yamamoto
    • Journal Title

      Delegate Manual of Fifth International Conference on Inorganic Materials 1

      Pages: 197-198

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Thermodynamics of Formation of Magnesium-Zinc Intermetallic Compounds in ihe Temperature Range from Absolute Zero to High Temperature2006

    • Author(s)
      M.Morishita, H.Yamamoto, S.Shikada, M.Kusumoto, Y.Matsumoto
    • Journal Title

      Acta Materialia 54

      Pages: 3151-3159

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Standard Gibbs Energy of Formation of Zn_8La Determined by Solution Calorimetry and Measurement of Heat Capacity from Near Absolute Zero Kelvin2006

    • Author(s)
      M.Morishita, H.Yamamoto, K.Tsuboki, Y.Matsumoto
    • Journal Title

      Materials Transactions 47

      Pages: 1555-1559

    • NAID

      10018160630

    • Related Report
      2006 Annual Research Report
  • [Journal Article] 熱力学踏量の測定とその結果を用いた化学熱力学計算によるNi-Mo-BおよびNi-W-B3成分系状態図の決定2006

    • Author(s)
      香山滉一郎, 森下政夫, 張 国鋒
    • Journal Title

      粉体および粉末冶金 53

      Pages: 419-429

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Determinationof Standard Gibbs Energy of Formation of AlaNd by Solution Calorimetry and Heat Capacity Measurement from Near Absolute Zero Kelvin2006

    • Author(s)
      H.Yamamoto, M Moroshita, M.Kusumoto
    • Journal Title

      Materials Transactions 47

      Pages: 2044-2048

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Thermodynamic Study of Self-Assembly of Ions in the ITO Solid Solution2005

    • Author(s)
      M.Morishita, K.Koyama, T.Shiraga
    • Journal Title

      Microelectronic Engineering 81

      Pages: 382-388

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Thermodynamics of Self-Assembly of Ions in the ITO Solid Solution2005

    • Author(s)
      M.Moroshita, K.Koyama, T.Shiraga
    • Journal Title

      Microelectronic Engineering Vol.81

      Pages: 382-388

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Calorimetric Study of Mg_2Zn_32005

    • Author(s)
      M.Morishita, K.Koyama, S.Shikata, M.Kusumoto
    • Journal Title

      Zeitschrift fur Metallkunde Vol.96

      Pages: 32-67

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Standard Entropy of Formation of SnMg_2 at 298 K2005

    • Author(s)
      M.Morishita, K.Koyama
    • Journal Title

      Journal of Alloys and Compounds Vol.398

      Pages: 12-15

    • Related Report
      2005 Annual Research Report
  • [Journal Article] 絶対零度付近から1380Kまでの熱容量測定と溶解熱カロリメトリーによるNiMoO_4の標準生成ギブズエネルギーの決定2005

    • Author(s)
      森下政夫
    • Journal Title

      日本学術振興会合金状態図第172委員会報告書 Vol.5,No.1

      Pages: 24-32

    • Related Report
      2005 Annual Research Report
  • [Journal Article] 熱力学諸量の測定とその結果を用いた化学熱力学計算によるNi-Mo-BおよびNi-W-B 3成分状態図の決定2005

    • Author(s)
      香山滉一郎, 森下政夫, 張 国鋒
    • Journal Title

      粉体粉末冶金協会平成17年度秋季大会講演概要集

      Pages: 343-343

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Al_<11>Nd_3の絶対零度付近からの熱容量と電気抵抗測定2005

    • Author(s)
      楠本 稔, 森下政夫
    • Journal Title

      平成17年度日本金属学会秋期大会講演概要集

      Pages: 179-179

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Thermodynamics of Self-Assembly of Ions in the ITO Solid Solution2005

    • Author(s)
      M.Morishita, K.Koyama, T.Shiraga
    • Journal Title

      Microelectronic Engineering 77(掲載決定)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Thermodynamics of Self-Assembly of Ions and Vacancies in the ITO Solid Solution2004

    • Author(s)
      M.Morishita, K.Koyama, T.Shiraga
    • Journal Title

      Abstracts of International Conference of Nano and Giga Challenges in Microelectronics, Cracow 1

      Pages: 172-172

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Thermodynamics of Self-Assembly of Ions and Vacancies in the ITO Solid Solution2004

    • Author(s)
      M.Morishita, K.Koyama, T.Shiraga
    • Journal Title

      Abstracts of International Conference of Nano and Giga Challenges in Microelectronics, Cracow, Poland

      Pages: 172-172

    • Related Report
      2004 Annual Research Report
  • [Journal Article] ITO固溶体のイオンと空孔配置自己組織化の熱力学2004

    • Author(s)
      森下政夫, 香山滉一郎, 白神智広
    • Journal Title

      粉体粉末冶金協会平成16年度春季講演会概要集

      Pages: 57-57

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Direct Measurement of Relative Partial Molar Enthalpy of SiO_2 in SiO_2-M_2O (M=Li, Na, K and Cs) Binary and SiO_2-CaO-Al_2O_3 Ternary Melts2004

    • Author(s)
      M.Morishita, A.Navrotsky, M.C.Wilding
    • Journal Title

      Journal of the American Ceramic Society 87

      Pages: 1550-1555

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Calorimetric Study of Zn_<13>La2004

    • Author(s)
      M.Morishita, K.Koyama, K.Tsuboki
    • Journal Title

      Zeitschrift fur Metallkunde 95

      Pages: 708-712

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Standard Gibbbs Energy of Formation of Mg_<48>Zn_<52> Determined by Solution Calorimetry and Measurement of Heat Capacity from Absolute Zero Kelvin2004

    • Author(s)
      M.Morishita, K.Koyama, S.Shikata, M.Kusumoto
    • Journal Title

      Metallurgical and Materials Transactions B35

      Pages: 891-895

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Calorimetric Study of Nickel Molybdate : Heat Capacity, Enthalpy and Gibbs Energy of Formation2003

    • Author(s)
      M.Morishita, A.Navrotsky
    • Journal Title

      Journal of the American Ceramic Society 86

      Pages: 1927-1932

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Publications] M.Morishita, K.Koyama: "Calorimetric Study of MgZn_2 and Mg_2Zn_<11>"Z.Metallkd.. Vol.94, No.9. 967-971 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Koyama, M.Morishita, T.Harada, N.Maekawa: "Determination of Standard Gibbs Energies of Formation of Fe_2Mo_3O_12, Fe_2Mo_3O_8, Fe_2MoO_4, and FeMoO_4 of the Fe-Mo-O Ternary System"Met.Materials Trans.. Vol.34B, Oct.. 653-659 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] M.Morishita, A.Navrotsky: "Calorimetric Study of Nickel Molybdate : Heat Capacity, Enthalpy, and Gibbs Energy of Formation"J.Am.Cerm.Soc.. Vol.86, No.11. 1927-1932 (2003)

    • Related Report
      2003 Annual Research Report

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Published: 2003-04-01   Modified: 2016-04-21  

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