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Title: Partitioning and structural role of Mn and Fe ions in ionic sulfophosphate glasses

Abstract

Ionic sulfophosphate liquids of the type ZnO-Na{sub 2}O-Na{sub 2}SO{sub 4}-P{sub 2}O{sub 5} exhibit surprising glass forming ability, even at slow or moderate cooling rate. As a concept, they also provide high solubility of transition metal ions which could act as cross-linking sites between the sulfate and phosphate entities. It is therefore investigated how the replacement of ZnO by MnO and/or FeO affects the glass structure and the glass properties. Increasing manganese levels are found to result in a monotonic increase of the transition temperature T{sub g} and most of the mechanical properties. This trend is attributed to the change of metal-ion coordination from four-fold around Zn{sup 2+} to six-fold around Mn{sup 2+} ions. The higher coordination facilitates cross-linking of the ionic structural entities and subsequently increases T{sub g}. Raman and infrared spectroscopy show that the structure of these glasses involves only SO{sub 4}{sup 2−} and PO{sub 4}{sup 3−} monomers as well as P{sub 2}O{sub 7}{sup 4-} dimers. Replacement of ZnO by MnO is found to favour PO{sub 4}{sup 3−} over P{sub 2}O{sub 7}{sup 4-} species, a trend which is enhanced by co-doping with FeO. Both transition metal ions show, like Zn{sup 2+}, a preference to selectively coordinate to phosphate anionicmore » species, as opposed to sodium ions which coordinate mainly to sulfate anions. EPR spectroscopy finally shows that divalent Mn{sup 2+} ions are present primarily in MnO{sub 6}-clusters, which, in the studied sulfophosphate glasses, convert upon increasing MnO content from corner-sharing to edge-sharing entities.« less

Authors:
;  [1];  [2]; ;  [3]
  1. Otto-Schott-Institute of Materials Research, Friedrich-Schiller-University Jena, Fraunhoferstr. 6, 07743 Jena (Germany)
  2. Institut des Sciences Moléculaires - CNRS UMR 5255, Université de Bordeaux, 33405 Talence (France)
  3. Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vassileos Constaniou Ave., 116 35 Athens (Greece)
Publication Date:
OSTI Identifier:
22413308
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 141; Journal Issue: 22; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTROSCOPY; ANIONS; CROSS-LINKING; ELECTRON SPIN RESONANCE; GLASS; INFRARED SPECTRA; IRON IONS; IRON OXIDES; LIQUIDS; MANGANESE; MANGANESE IONS; MANGANESE OXIDES; MECHANICAL PROPERTIES; PHOSPHATES; PHOSPHORUS OXIDES; SODIUM IONS; SODIUM OXIDES; SODIUM SULFATES; ZINC IONS; ZINC OXIDES

Citation Formats

Möncke, Doris, Wondraczek, Lothar, Sirotkin, Sergey, Stavrou, Elissaios, and Kamitsos, Efstratios I. Partitioning and structural role of Mn and Fe ions in ionic sulfophosphate glasses. United States: N. p., 2014. Web. doi:10.1063/1.4903191.
Möncke, Doris, Wondraczek, Lothar, Sirotkin, Sergey, Stavrou, Elissaios, & Kamitsos, Efstratios I. Partitioning and structural role of Mn and Fe ions in ionic sulfophosphate glasses. United States. https://doi.org/10.1063/1.4903191
Möncke, Doris, Wondraczek, Lothar, Sirotkin, Sergey, Stavrou, Elissaios, and Kamitsos, Efstratios I. 2014. "Partitioning and structural role of Mn and Fe ions in ionic sulfophosphate glasses". United States. https://doi.org/10.1063/1.4903191.
@article{osti_22413308,
title = {Partitioning and structural role of Mn and Fe ions in ionic sulfophosphate glasses},
author = {Möncke, Doris and Wondraczek, Lothar and Sirotkin, Sergey and Stavrou, Elissaios and Kamitsos, Efstratios I.},
abstractNote = {Ionic sulfophosphate liquids of the type ZnO-Na{sub 2}O-Na{sub 2}SO{sub 4}-P{sub 2}O{sub 5} exhibit surprising glass forming ability, even at slow or moderate cooling rate. As a concept, they also provide high solubility of transition metal ions which could act as cross-linking sites between the sulfate and phosphate entities. It is therefore investigated how the replacement of ZnO by MnO and/or FeO affects the glass structure and the glass properties. Increasing manganese levels are found to result in a monotonic increase of the transition temperature T{sub g} and most of the mechanical properties. This trend is attributed to the change of metal-ion coordination from four-fold around Zn{sup 2+} to six-fold around Mn{sup 2+} ions. The higher coordination facilitates cross-linking of the ionic structural entities and subsequently increases T{sub g}. Raman and infrared spectroscopy show that the structure of these glasses involves only SO{sub 4}{sup 2−} and PO{sub 4}{sup 3−} monomers as well as P{sub 2}O{sub 7}{sup 4-} dimers. Replacement of ZnO by MnO is found to favour PO{sub 4}{sup 3−} over P{sub 2}O{sub 7}{sup 4-} species, a trend which is enhanced by co-doping with FeO. Both transition metal ions show, like Zn{sup 2+}, a preference to selectively coordinate to phosphate anionic species, as opposed to sodium ions which coordinate mainly to sulfate anions. EPR spectroscopy finally shows that divalent Mn{sup 2+} ions are present primarily in MnO{sub 6}-clusters, which, in the studied sulfophosphate glasses, convert upon increasing MnO content from corner-sharing to edge-sharing entities.},
doi = {10.1063/1.4903191},
url = {https://www.osti.gov/biblio/22413308}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 22,
volume = 141,
place = {United States},
year = {Sun Dec 14 00:00:00 EST 2014},
month = {Sun Dec 14 00:00:00 EST 2014}
}