Sulfur speciation and network structural changes in sodium silicate glasses: Constraints from NMR and Raman spectroscopy

Tomoyuki Tsujimura, Xianyu Xue, Masami Kanzaki, Michael J. Walter

Research output: Contribution to journalArticle

38 Citations (Scopus)

Abstract

Information about the state of sulfur in silicate melts and glasses is important in both earth sciences and materials sciences. Because of its variety of valence states from S2- (sulfide) to S6+ (sulfate), the speciation of sulfur dissolved in silicate melts and glasses is expected to be highly dependent on the oxygen fugacity. To place new constraint on this issue, we have synthesized sulfur-bearing sodium silicate glasses (quenched melts) from starting materials containing sulfur of different valence states (Na2SO4, Na2SO3, Na2S2O3 and native S) using an internally heated gas pressure vessel, and have applied electron-induced SKα X-ray fluorescence, micro-Raman and NMR spectroscopic techniques to probe their structure. The wavelength shift of SKα X-rays revealed that the differences in the valence state of sulfur in the starting compounds are largely retained in the synthesized sulfur-bearing glasses, with a small reduction for more oxidized samples. The 29Si MAS NMR spectra of all the glasses contain no peaks attributable to the SiO4-nSn (with n > 0) linkages. The Raman spectra are consistent with the coexistence of sodium sulfate (Na2SO4) species and one or more types of more reduced sulfur species containing S-S linkages in all the sulfur-bearing silicate glasses, with the former dominant in glasses produced from Na2SO4-doped starting materials, and the latter more abundant in more reduced glasses. The 29Si MAS NMR and Raman spectra also revealed changes in the silicate network structure of the sulfur-bearing glasses, which can be interpreted in terms of changes in the chemical composition and sulfur speciation.

Original languageEnglish
Pages (from-to)5081-5101
Number of pages21
JournalGeochimica et Cosmochimica Acta
Volume68
Issue number24
DOIs
Publication statusPublished - Dec 15 2004

Fingerprint

Raman spectroscopy
Sulfur
structural change
Nuclear magnetic resonance spectroscopy
nuclear magnetic resonance
silicate
glass
sulfur
sodium
Bearings (structural)
Glass
Silicates
MAS
silicate melt
Nuclear magnetic resonance
Raman scattering
sodium silicate
sulfate
Earth sciences
X rays

ASJC Scopus subject areas

  • Geochemistry and Petrology

Cite this

Sulfur speciation and network structural changes in sodium silicate glasses : Constraints from NMR and Raman spectroscopy. / Tsujimura, Tomoyuki; Xue, Xianyu; Kanzaki, Masami; Walter, Michael J.

In: Geochimica et Cosmochimica Acta, Vol. 68, No. 24, 15.12.2004, p. 5081-5101.

Research output: Contribution to journalArticle

@article{37d4faa4a93a41e9be72a4a357da1758,
title = "Sulfur speciation and network structural changes in sodium silicate glasses: Constraints from NMR and Raman spectroscopy",
abstract = "Information about the state of sulfur in silicate melts and glasses is important in both earth sciences and materials sciences. Because of its variety of valence states from S2- (sulfide) to S6+ (sulfate), the speciation of sulfur dissolved in silicate melts and glasses is expected to be highly dependent on the oxygen fugacity. To place new constraint on this issue, we have synthesized sulfur-bearing sodium silicate glasses (quenched melts) from starting materials containing sulfur of different valence states (Na2SO4, Na2SO3, Na2S2O3 and native S) using an internally heated gas pressure vessel, and have applied electron-induced SKα X-ray fluorescence, micro-Raman and NMR spectroscopic techniques to probe their structure. The wavelength shift of SKα X-rays revealed that the differences in the valence state of sulfur in the starting compounds are largely retained in the synthesized sulfur-bearing glasses, with a small reduction for more oxidized samples. The 29Si MAS NMR spectra of all the glasses contain no peaks attributable to the SiO4-nSn (with n > 0) linkages. The Raman spectra are consistent with the coexistence of sodium sulfate (Na2SO4) species and one or more types of more reduced sulfur species containing S-S linkages in all the sulfur-bearing silicate glasses, with the former dominant in glasses produced from Na2SO4-doped starting materials, and the latter more abundant in more reduced glasses. The 29Si MAS NMR and Raman spectra also revealed changes in the silicate network structure of the sulfur-bearing glasses, which can be interpreted in terms of changes in the chemical composition and sulfur speciation.",
author = "Tomoyuki Tsujimura and Xianyu Xue and Masami Kanzaki and Walter, {Michael J.}",
year = "2004",
month = "12",
day = "15",
doi = "10.1016/j.gca.2004.08.029",
language = "English",
volume = "68",
pages = "5081--5101",
journal = "Geochmica et Cosmochimica Acta",
issn = "0016-7037",
publisher = "Elsevier Limited",
number = "24",

}

TY - JOUR

T1 - Sulfur speciation and network structural changes in sodium silicate glasses

T2 - Constraints from NMR and Raman spectroscopy

AU - Tsujimura, Tomoyuki

AU - Xue, Xianyu

AU - Kanzaki, Masami

AU - Walter, Michael J.

PY - 2004/12/15

Y1 - 2004/12/15

N2 - Information about the state of sulfur in silicate melts and glasses is important in both earth sciences and materials sciences. Because of its variety of valence states from S2- (sulfide) to S6+ (sulfate), the speciation of sulfur dissolved in silicate melts and glasses is expected to be highly dependent on the oxygen fugacity. To place new constraint on this issue, we have synthesized sulfur-bearing sodium silicate glasses (quenched melts) from starting materials containing sulfur of different valence states (Na2SO4, Na2SO3, Na2S2O3 and native S) using an internally heated gas pressure vessel, and have applied electron-induced SKα X-ray fluorescence, micro-Raman and NMR spectroscopic techniques to probe their structure. The wavelength shift of SKα X-rays revealed that the differences in the valence state of sulfur in the starting compounds are largely retained in the synthesized sulfur-bearing glasses, with a small reduction for more oxidized samples. The 29Si MAS NMR spectra of all the glasses contain no peaks attributable to the SiO4-nSn (with n > 0) linkages. The Raman spectra are consistent with the coexistence of sodium sulfate (Na2SO4) species and one or more types of more reduced sulfur species containing S-S linkages in all the sulfur-bearing silicate glasses, with the former dominant in glasses produced from Na2SO4-doped starting materials, and the latter more abundant in more reduced glasses. The 29Si MAS NMR and Raman spectra also revealed changes in the silicate network structure of the sulfur-bearing glasses, which can be interpreted in terms of changes in the chemical composition and sulfur speciation.

AB - Information about the state of sulfur in silicate melts and glasses is important in both earth sciences and materials sciences. Because of its variety of valence states from S2- (sulfide) to S6+ (sulfate), the speciation of sulfur dissolved in silicate melts and glasses is expected to be highly dependent on the oxygen fugacity. To place new constraint on this issue, we have synthesized sulfur-bearing sodium silicate glasses (quenched melts) from starting materials containing sulfur of different valence states (Na2SO4, Na2SO3, Na2S2O3 and native S) using an internally heated gas pressure vessel, and have applied electron-induced SKα X-ray fluorescence, micro-Raman and NMR spectroscopic techniques to probe their structure. The wavelength shift of SKα X-rays revealed that the differences in the valence state of sulfur in the starting compounds are largely retained in the synthesized sulfur-bearing glasses, with a small reduction for more oxidized samples. The 29Si MAS NMR spectra of all the glasses contain no peaks attributable to the SiO4-nSn (with n > 0) linkages. The Raman spectra are consistent with the coexistence of sodium sulfate (Na2SO4) species and one or more types of more reduced sulfur species containing S-S linkages in all the sulfur-bearing silicate glasses, with the former dominant in glasses produced from Na2SO4-doped starting materials, and the latter more abundant in more reduced glasses. The 29Si MAS NMR and Raman spectra also revealed changes in the silicate network structure of the sulfur-bearing glasses, which can be interpreted in terms of changes in the chemical composition and sulfur speciation.

UR - http://www.scopus.com/inward/record.url?scp=11044221870&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=11044221870&partnerID=8YFLogxK

U2 - 10.1016/j.gca.2004.08.029

DO - 10.1016/j.gca.2004.08.029

M3 - Article

AN - SCOPUS:11044221870

VL - 68

SP - 5081

EP - 5101

JO - Geochmica et Cosmochimica Acta

JF - Geochmica et Cosmochimica Acta

SN - 0016-7037

IS - 24

ER -