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Effects of modifier additions on the thermal properties, chemical durability, oxidation state and structure of iron phosphate glasses

Bingham, P.A., Hand, R.J., Hannant, O.M., Forder, S.D. and Kilcoyne, Susan H. (2009) Effects of modifier additions on the thermal properties, chemical durability, oxidation state and structure of iron phosphate glasses. Journal of Non-Cystalline Solids, 355. pp. 1526-1538. ISSN 0022-3093

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      Abstract

      Modified iron phosphate glasses have been prepared with nominal molar compositions [(1�x)�(0.6P2O5–
      0.4Fe2O3)]�xRySO4, where x = 0–0.5 in increments of 0.1 and R = Li, Na, K, Mg, Ca, Ba, or Pb and y = 1 or 2. In
      most cases the vast majority or all of the sulfate volatalizes and quarternary P2O5–Fe2O3–FeO–RyOz
      glasses or partially crystalline materials are formed. Here we have characterized the structure, thermal
      properties, chemical durability and redox state of these materials. Raman spectroscopy indicates that
      increasing modifier oxide additions result in depolymerization of the phosphate network such that the
      average value of i, the number of bridging oxygens per –(PO4)– tetrahedron, and expressed as Qi,
      decreases. Differences have been observed between the structural effects of different modifier types
      but these are secondary to the amount of modifier added. Alkali additions have little effect on density;
      slightly increasing Tg and Td; increasing a and Tliq; and promoting bulk crystallization at temperatures
      of 600–700 �C. Additions of divalent cations increase density, a, Tg, Td, Tliq and promote bulk crystallization
      at temperatures of 700–800 �C. Overall the addition of divalent cations has a less deleterious effect
      on glass stability than alkali additions. 57Fe Mössbauer spectroscopy confirms that iron is present as Fe2+
      and Fe3+ ions which primarily occupy distorted octahedral sites. This is consistent with accepted structural
      models for iron phosphate glasses. The iron redox ratio, Fe2+/RFe, has a value of 0.13–0.29 for the
      glasses studied. The base glass exhibits a very low aqueous leach rate when measured by Product Consistency
      Test B, a standard durability test for nuclear waste glasses. The addition of high quantities of
      alkali oxide (30–40 mol% R2O) to the base glass increases leach rates, but only to levels comparable with
      those measured for a commercial soda-lime-silica glass and for a surrogate nuclear waste-loaded borosilicate
      glass. Divalent cation additions decrease aqueous leach rates and large additions (30–50 mol%
      RO) provide exceptionally low leach rates that are 2–3 orders of magnitude lower than have been measured
      for the surrogate waste-loaded borosilicate glass. The P2O5–Fe2O3–FeO–BaO glasses reported here
      show particular promise as they are ultra-durable, thermally stable, low-melting glasses with a large
      glass-forming compositional range.

      Item Type: Article
      Subjects: Q Science > QC Physics
      Schools: School of Applied Sciences
      Related URLs:
      Depositing User: Susan Kilcoyne
      Date Deposited: 06 Dec 2011 11:45
      Last Modified: 08 Dec 2011 08:57
      URI: http://eprints.hud.ac.uk/id/eprint/11949

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