Calorimetric determination of energetics of solid solutions of UO2+x with CaO and Y2O3

Lena Mazeina, Alexandra Navrotsky, Martha Greenblatt

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15 Scopus citations


Quantitative study of thermodynamic properties of solid solutions of UO2+x with divalent and trivalent oxides is important for predicting the behavior of oxide fuel. Although early literature work measured vapor pressure in some of these solid solutions, direct calorimetric measurements of enthalpies of formation have been hampered by the refractory nature of such oxides. First measurements of the enthalpies of formation in the systems UO2+x-CaO and UO2+x-YO1.5, obtained by high-temperature oxide melt solution calorimetry, are reported. Both systems show significantly negative (exothermic) heats of formation from binary oxides (UO2, plus O2 and CaO or YO1.5, as well as from UO2 plus UO3 and CaO or YO1.5), consistent with reported free energy measurements in the urania-yttria system. The energetic contributions of oxygen content (oxidation of U4+) and of charge balanced ionic substitution as well as defect clustering are discussed. Behavior of urania-yttria is compared to that of corresponding systems in which the tetravalent ion is Ce, Zr, or Hf. The substantial additional stability in the solid solutions compared to pure UO2+x may retard, in both thermodynamic and kinetic sense, the oxidation and leaching of spent fuel to form aqueous U6+ and solid uranyl phases.

Original languageEnglish (US)
Pages (from-to)39-43
Number of pages5
JournalJournal of Nuclear Materials
Issue number1-3
StatePublished - Feb 15 2008

All Science Journal Classification (ASJC) codes

  • Nuclear and High Energy Physics
  • General Materials Science
  • Nuclear Energy and Engineering


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