A Multi-spectroscopic Investigation of Sulphur Speciation in Silicate Glasses and Slags
A Multi-spectroscopic Investigation of Sulphur Speciation in Silicate Glasses and Slags
复制标题
硅酸盐玻璃和炉渣中硫形态的多光谱研究
DOI：
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发表时间：
2010
期刊：
影响因子：
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通讯作者：
R. Edge
中科院分区：
文献类型：
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作者：
P. Bingham;A. Connelly;R. Hand;N. Hyatt;P. Northrup;R. A. Mori;P. Glatzel;M. Kavčič;M. Zitnik;K. Bučar;R. Edge
Sulphur K-edge x-ray absorption near-edge structure (XANES), sulphur K{sub {alpha}} and K{sub {beta}} high resolution x-ray emission spectroscopies (XES), electron paramagnetic resonance (EPR) and optical absorption spectroscopies have been used to study the speciation of sulphur in a range of soda-lime-silica glasses and silicate slags. Several inorganic standards with known sulphur oxidation states and structural environments have also been analysed. Results confirm that the average oxidation state of sulphur in glasses decreases, as expected, in the order (colourless>light olive>dark olive>light amber>dark amber). This behaviour is consistent with decreasing S{sup 6+}/{Sigma}S ratio, which has been quantified by linear combination fitting of XES S K{alpha} spectra, and with analysed sulphur contents which exhibit a characteristic relationship with oxygen partial pressure, pO{sub 2}. A combination of S{sup 6+}, S{sup 5+}, S{sup 4+} and more reduced sulphur species has been detected in olive and amber glasses. The S{sup 4+} and S{sup 5+} species are most evident in olive-coloured glasses produced under moderately reducing conditions that coincide with minimum sulphur solubilities. The reduced form of sulphur, present in all reduced glasses, is interpreted as being present as S{sup 2-} on the basis of XANES, XES, EPR and optical measurements. An alternative interpretation of the datamore » is that there is a continuum of less strongly reduced species, primarily S{sup +} and S{sup 2+}; this interpretation has less merit. In this paper we show that the established relationship that describes sulphur redox only in terms of S{sup 6+} and S{sup 2-}, and which states that only these two species co-exist over a narrow, moderately reducing range of pO{sub 2}, does not fully describe the behaviour of S in the industrial, non-equilibrated glasses studied. Hence this relationship requires slight modification for non-equilibrated systems to explain the existence of intermediate sulphur oxidation states such as S{sup 4+} and S{sup 5+}, particularly within the intermediate pO{sub 2} range that corresponds with sulphur solubility minima.« less
Sulphur K-edge x-ray absorption near-edge structure (XANES), sulphur K{sub {alpha}} and K{sub {beta}} high resolution x-ray emission spectroscopies (XES), electron paramagnetic resonance (EPR) and optical absorption spectroscopies have been used to study the speciation of sulphur in a range of soda-lime-silica glasses and silicate slags. Several inorganic standards with known sulphur oxidation states and structural environments have also been analysed. Results confirm that the average oxidation state of sulphur in glasses decreases, as expected, in the order (colourless>light olive>dark olive>light amber>dark amber). This behaviour is consistent with decreasing S{sup 6+}/{Sigma}S ratio, which has been quantified by linear combination fitting of XES S K{alpha} spectra, and with analysed sulphur contents which exhibit a characteristic relationship with oxygen partial pressure, pO{sub 2}. A combination of S{sup 6+}, S{sup 5+}, S{sup 4+} and more reduced sulphur species has been detected in olive and amber glasses. The S{sup 4+} and S{sup 5+} species are most evident in olive-coloured glasses produced under moderately reducing conditions that coincide with minimum sulphur solubilities. The reduced form of sulphur, present in all reduced glasses, is interpreted as being present as S{sup 2-} on the basis of XANES, XES, EPR and optical measurements. An alternative interpretation of the datamore » is that there is a continuum of less strongly reduced species, primarily S{sup +} and S{sup 2+}; this interpretation has less merit. In this paper we show that the established relationship that describes sulphur redox only in terms of S{sup 6+} and S{sup 2-}, and which states that only these two species co-exist over a narrow, moderately reducing range of pO{sub 2}, does not fully describe the behaviour of S in the industrial, non-equilibrated glasses studied. Hence this relationship requires slight modification for non-equilibrated systems to explain the existence of intermediate sulphur oxidation states such as S{sup 4+} and S{sup 5+}, particularly within the intermediate pO{sub 2} range that corresponds with sulphur solubility minima.« less