Enthalpies of formation of Ce-pyrochlore, Ca0.93Ce1.00Ti2.035O7.00, U-pyrochlore, Ca1.46U4+0.23U6+0.46Ti1.85O7.00 and Gd-pyrochlore, Gd2Ti2O7: three materials relevant to the proposed waste form for excess weapons plutonium

Abstract High temperature oxide melt solution calorimetry was used to derive standard enthalpies of formation, ΔH0f (kJ/mol), for three pyrochlore phases: Ca0.93Ce1.00Ti2.035O7.00 (−3656.0±5.6), Ca1.46U4+0.23U6+0.46Ti1.85O7.00 (−3610.6±4.1) and Gd2Ti2O7 (−3822.5±4.9). Enthalpy of drop solution data, ΔHds, were used to calculate enthalpies of formation with respect to an oxide phase assemblage, ΔH0f−ox: CaO+MO2+2TiO2=CaMTi2O7 or Gd2O3+2TiO2=Gd2Ti2O7, and an oxide/perovskite phase assemblage, ΔH0f−pv+ox: CaTiO3+MO2+TiO2=CaMTi2O7, where M=Ce or U. All three pyrochlore samples were stable in enthalpy relative to an oxide assemblage with ΔH0f−ox (kJ/mol) (Gd2Ti2O7)=−113.4±2.8; ΔH0f−ox(Ca1.46U4+0.23U6+0.46Ti1.85O7.00)=−123.1±3.4; ΔH0f−ox(Ca0.93Ce1.00Ti2.035O7.00)=−54.1±5.2. U-pyrochlore was stable in enthalpy relative to an oxide/perovskite assemblage (ΔH0f−pv+ox=−5.1±4.0 kJ/mol). Ce-pyrochlore was metastable in enthalpy relative to the oxide/perovskite phase assemblage (ΔH0f−pv+ox=+21.0±5.5 kJ/mol). A significant metastability field was defined with respect to an oxide/perovskite phase assemblage. However, the proposed waste form baseline composition lies in the stable regions of the phase diagrams.