Redox Equilibrium of Rare-Earth Ions in Chlorine- and Bromine-Doped Fluoroaluminate Glasses

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  • YANO Tetsuji
    Department of Inorganic Materials, Faculty of Engineering, Tokyo Institute of Technology
  • YAMAZAKI Koji
    Department of Inorganic Materials, Faculty of Engineering, Tokyo Institute of Technology
  • SHIBATA Shuichi
    Department of Inorganic Materials, Faculty of Engineering, Tokyo Institute of Technology
  • YAMANE Masayuki
    Department of Inorganic Materials, Faculty of Engineering, Tokyo Institute of Technology
  • INOUE Satoru
    National Institute for Research in Inorganic Materials

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  • 塩化物イオン及び臭化物イオン添加フッ化アルミニウム系ガラスにおける希土類金属イオンの酸化還元平衡
  • Redox Equilibrium of Rare-Earth Ions in

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Abstract

The effect of chloride and/or bromide ions on the redox equilibrium of rare-earth ions, Sm and Yb, was investigated in an AlF3-based YABC glass system. The large absorption bands of 4f-5d transition of Sm2+ and Yb2+ ions were found in the chlorine-doped samples in the visible and ultra-violet regions, respectively. Their intensities increased with the degree of incorporation. Change in the redox equilibrium of Yb ions was found to be a function of both the quantity and type of non-fluoride halide ions used as dopants. Br- was about 6 times more efficient than Cl- and co-doping resulted in a greater number of divalent Yb2+ ions. X-ray photoelectron spectra of Y3d and the thermodynamics data of various halide compounds and molecules reveal that the direct bond formation between rare-earth ions and non-fluoride ions and the lower free energies of mixed halide molecules would play key roles in the formation of divalent rare-earth ions in the glass melts.

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