高バナジウムガラスの電気伝導度に対する単原子価陽イオンの影響

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The relation between the specific resistance ρ (at 40°C) and V4+ content of the vanadate glasses of composition, 60 V2O5⋅xRO⋅(40-x)P2O5; (x=0-25mol%), in which RO represents the oxides of the mono- or bi- valent metal elements, was investigated. It was found that the concentration of V4+ ion decreased monotonously with the increase of the ratio RO/P2O5, and that ρ showed a minimum at V4+/Vtotal=10-20% for all R. These facts indicate that the electrical conduction of these glasses may be attributed to the valency exchange btween V4+ and V5+. The curves, of ρ v.s. V4+/Vtotal do not coincide with each other, which indicates that the decrease of ρ with increasing RO can not be attributed simply to the reduction of V4+ content, but the characteristic nature of R ion would be playing some important role in the mechanism of conduction. It was found that there is a certain relation between the minimum value ρm of resistance and the cationic field strength (c. f. s.) of R ion.In the region c. f. s.<0.35, ρm was increasing with the increase of c. f. s., because R ion, being a network modifier in nature, would have the trend of approaching to the central ion of V4+-O-V5+, and the smaller the polarizing power of R ion the smaller disturbance they would made to the valency exchange.In the region c. f. s.>0.35, ρm decreased with the increase of c. f. s., because, in this case, R ion would act as a network former, and R-O bond, having the nature of mixed bond, would not be able to coordinate to the central oxygen of V4+-O-V5+.
社団法人日本セラミックス協会の論文
1960-05-01

高バナジウムガラスの電気伝導度に対する単原子価陽イオンの影響

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