Na_2S-SiO_2系ガラス中の硫黄の状態分析

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The structure and electronic states of Na_2S-SiO_2 oxysulfide glasses were investigated and the role of sulfur in the glasses is discussed. Na_2S formed stable glass with SiO_2 at an alkali concentration range similar to that of Na_2O-SiO_2 systems by the conventional melt-quench method. The obtained glasses were reddish brown in color and a remaining of sulfur was confirmed. X-ray photoelectron spectroscopy(XPS)was used to study the chemical bonding state of bridging and nonbridging anionic species in Na_2S-SiO_2 glass. The S2p binding energy of the glass was observed to be approximately 161 eV. This value is lower than that of orthorhombic crystalline sulfur and almost the same as the value of Na_2S. From the results, the electron density around sulfur was near to that of S^<2->. Furthermore, by ^<29>Si magic angle spinning(MAS)and unclear magnetic resonance(NMR)measurement, three clear-cut peaks were detected between 0 and -120 ppm. It was assumed that a sulfur atom was joined to silicon via substitution for an oxygen atom, and was present as nonbridging sulfur in Na_2S-SiO_2 glass with low alkali ion concentration. On the other hand, it was revealed that a portion of the sulfur ions existed in an isolated state from the glass-network structure at high alkali content. The glass composition changed to a chemical composition that was more silica rich than predicted. The sulfur ions made sulfide clusters with the sodium ions isolated from the glass-network.
社団法人日本セラミックス協会の論文
1998-02-01

Na_2S-SiO_2系ガラス中の硫黄の状態分析

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