PNNL

Abstract

The garnet structure has been proposed as a potential crystalline nuclear waste form for accommodation of actinide elements, especially uranium (U). In this study, yttrium iron garnet (YIG) as a model garnet host was studied for the incorporation of U analogs, cerium (Ce), and thorium (Th), incorporated by a charge-coupled substitution with calci-um (Ca) for yttrium (Y) in YIG, namely 2Y3+ = Ca2+ + M4+, where M4+ = Ce4+ or Th4+. Single phase garnets Y3-xCa0.5xM0.5xFe5O12, synthesized by the citrate-nitrate combustion method, were obtained up to x = 0.7. Ce was confirmed to be tetravalent by X-ray absorption spectroscopy and X-ray photoelectron spectroscopy. X-ray diffraction and 57Fe-Mössbauer spectroscopy indicated that the samples are single phase, M4+ and Ca2+ cations are restricted to the c-site, the nature of M4+ has only a minor effect on the structure, and the local environments of both the tetrahedral and octahedral Fe3+ are systematically affected by the extent of substitution, especially on the tetrahedral sublattice. The charge coupled substitution has advantages in incorporating Ce/Th and in stabilizing the substituted phases, compared to a single substitution strategy. Enthalpies of formation of garnets were obtained by high temperature oxide melt solution calorimetry, and the enthalpies of substitution of Ce and Th were determined. The thermodynamic analysis demonstrates that the substituted garnets are entropically rather than energetically stabilized. This suggests that such garnets may form and persist in repositories at high temperature but might decompose near room temperature. These structural and thermodynamic findings shed light on possible incorporation of U in this garnet system.