Glass–ceramic nuclear waste forms obtained from SiO 2–Al 2O 3–CaO–ZrO 2–TiO 2 glasses containing lanthanides (Ce, Nd, Eu, Gd, Yb) and actinides (Th): study of internal crystallization

Abstract

Glass–ceramic waste forms such as zirconolite (nominally CaZrTi 2O 7) based ones can be envisaged as good candidates for minor actinides or Pu immobilization. Such materials, in which the actinides (or lanthanides used as actinide surrogates) would be preferentially incorporated into zirconolite crystals homogeneously dispersed in a durable glassy matrix, can be prepared by controlled crystallization (nucleation + crystal growth) of parent glasses belonging to the SiO 2–Al 2O 3–CaO–ZrO 2–TiO 2 system. In this work we present the effects of the nature of the minor actinide surrogate (Ce, Nd, Eu, Gd, Yb, Th) on the structure, the microstructure and the composition of the zirconolite crystals formed in the bulk of the glass–ceramics. The amount of lanthanides and thorium incorporated into zirconolite crystals is discussed in relation with the capacity of the glass to accommodate these elements and of the crystals to incorporate them in the calcium and zirconium sites of their structure.