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

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
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 22; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
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