導電性バリウム鉄バナジン酸塩ガラス,NTAガラス^<TM>の構造緩和と結晶化(秋季シンポジウム若手研究者論文)

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概要

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• Structure of electrically conductive xBaO・(90-x)V_2O_5・10Fe_2O_3 glasses (x=20, 30 and 40), NTA glass^<TM>, was investigated by ^<57>Fe-Mossbauer spectroscopy, Fourier-transform infrared spectroscopy (FT-IR), X-ray diffractometry (XRD), differential thermal analysis (DTA) and scanning electric micrography (SEM). A remarkable increase in the electric conductivity (σ) was observed from 1.6×10^<-5> to 1.1×10^0 S cm^<-1> after annealing NTA glass^<TM> with 'x' of 20 at 500℃ for 1000min. Precipitation of a small amount of BaFe_2O_4 and BaV_2O_6 phases was confirmed by XRD, indicating that the sample still has a glassy phase even after prolonged isothermal annealing. An activation energy for the crystallization (E_a) was estimated to be 2.3±0.2eV, indicating that the crystallization of the vanadate glasses is involved in a cleavage of Fe-O bond having binding energy of 2.6eV, not of the V-O bond of which binding energy is known to be 3.9-4.9eV. A consistent result was obtained in the FT-IR spectra, showing that the absorption band attributed to a stretching vibration of Fe-O bond of FeO_6 octahedra appeared after the annealing. By applying 'T_g-Δ rule', i.e., a linear relationship between glass transition temperature and quadrupole splitting of the Mossbauer spectra, it proved that Fe^<III> plays a role of a network former (NWF) like V^<IV> and V^V in NTA glass^<TM>. A constant isomer shift of 0.40±0.01mm s^<-1> and a decrease of quadrupole splitting from 0.70±0.02 to 0.53±0.02mm s^<-1> were observed in the Mossbauer spectra after the isothermal annealing. These results suggest that σ of NTA glass^<TM> is enhanced as a result of structural relaxation, i.e., reduced local distortion of the network composed of Fe^<III>O_4, VO_4 and VO_5 units.

• 2007-11-01

著者

• 西田 哲明

  Graduate School Of Advanced Technology Kinki University:department Of Biological And Environmental C

• 西田 哲明

  九州大学理学部

• 久冨木 志郎

  Department Of Chemical And Biological Engineering Ube National College Of Technology

• SAKKA Hiroshi

  Department of Chemical and Biological Engineering, Ube National College of Technology

• TSUGE Kanako

  Department of Chemical and Biological Engineering, Ube National College of Technology

• HOMONNAY Zoltan

  Laboratory of Nuclear Chemistry, Eotvos Lorand University

• SINKO Katalin

  Institute of Chemistry, Eotvos Lorand University

• KUZMANN Erno

  Laboratory of Nuclear Chemistry, HAS CRC, Eotvos Lorand University

• YASUMITSU Hiroki

  Graduate School of Advanced Technology, Kinki University

• Kuzmann Erno

  Laboratory Of Nuclear Chemistry Has Crc Eotvos Lorand University

• Sakka Hiroshi

  Department Of Chemical And Biological Engineering Ube National College Of Technology

• Sinko Katalin

  Institute Of Chemistry Eotvos Lorand University

• Homonnay Zoltan

  Laboratory Of Nuclear Chemistry Eotvos Lorand University

• Yasumitsu Hiroki

  Graduate School Of Advanced Technology Kinki University

• Tsuge Kanako

  Department Of Chemical And Biological Engineering Ube National College Of Technology

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