モリブデンとケイ酸塩ガラス融液との分極下における反応について-Fe_2O_3, NiO, Cr_2O_3およびMnO_2の影響

概要

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The fundamental electrochemical behavior of molybdenum was investigated in a commercially important glass (Na_2O-CaO-SiO_2) with various additives such as Fe_2O_3, NiO, Cr_2O_3 and MnO_2 by means of linear potential sweep voltammetry at 1400℃. The molybdenum-glass interface after polarization was also analysed by EPMA. The cathodic current in the initial applied potential region was larger in the additive-containing glass than in the glass with no additive. The additives were reduced predominantly to the metallic state at the initial potential but reduced together with silicate anions at higher potentials and made alloys with Si and Mo. The additives were more or effective to promote oxidation of molybdenum. Fe^<3+> ions oxidized molybdenum to MoO_2 by the reaction 2Fe_2O_3+Mo=4FeO+MoO_2(ΔG=-35.2kcal/mol). Ni^<2+> ions showed marked oxidizing power by the reactions 2NiO+Mo=2Ni十MoO_2(ΔG=-26.4kcal/mol) and 3NiO+Mo=3Ni+Mo0_3 (ΔG=-10.6kcal/mol). Cr^<6+> and Mn^<3+> ions should also have marked oxidizing power but the respective redox equilibrium in the soda-lime-silica glass seemed to be shifted to the lower valence states. Therefore, the oxidation of molybdenum by Cr and Mn ions was depressed.
社団法人日本材料学会の論文
1986-02-15