A model for the oxygen potential of oxide fuels at high burnup

Using Lindemer's analysis as a starting point, a comprehensive description of the chemical state of the fluorite fuel matrix along with the most abundant fission products has been developed. The model was then implemented within the framework of an upgraded version of the SOLGASMIX program known as SAGE. In addition to approximately seventy solid compounds, three different mixture phases are modelled. The first one is the gaseous phase and comprises roughly sixty different compounds. The second is made up of noble metals such as Mo, Ru, Tc, Pd. The third mixture phase is a representation of the fluorite fuel matrix. Since SAGE is a code which calculates chemical equilibria by minimizing the Gibbs energy of the system, it is essential that reliable free energies of formation be used as data. This is relatively straightforward with regard to most compounds and thermochemical data are readily available in the open literature. As regards the fluorite phase however, the basic hypothesis is that it is possible to model the effect of defects such as interstitials (in the hyperstoichiometric phase) and vacancies (in the hypostoichiometric phase) by assuming the existence of hypothetical solute compounds such as U2O4.5 that stabilize the hyperstoichiometric phase. As rare earths (Re) of valence two or three are dissolved in the matrix, the hypothetical compounds Re4/3O2 and URe2O6 are chosen to reflect the behavior of the ternay system. This description accurately predicts the hypostoichiometric region of the phase diagram but underestimate the increase in oxygen potential in the hyperstoichiometric region. 26 refs, 10 figs, 1 tab