Crystallization of neodymium-rich phases in silicate glasses developed for nuclear waste immobilization

Glass-ceramics containing neodymium-rich crystalline phases can be obtained by crystallization of silicate glasses (nucleation + crystal growth heat treatments) or by controlled cooling of melts. Such materials could be envisaged as durable matrices for conditioning minor actinides- and Pu-rich nuclear wastes if the partitioning ratio of the wastes between crystalline phase and residual glass is high (principle of double containment barrier). In radioactive waste forms, Nd would be partially substituted by actinides and neutron absorbers (Gd). In this work, two silicate glass compositions leading to efficient nucleation and crystallization of either zirconolite (Ca1−xNdxZrTi2−xAlxO7, x < 1) or apatite (Ca2Nd8Si6O26) in their bulk were studied as potential waste forms. The effect of the method used to prepare glass-ceramics (controlled cooling from the melt or nucleation + crystal growth from the glass) on both the microstructure and the structure of the neodymium-rich crystalline phase was studied. The highest number of zirconolite or apatite crystals in the bulk was obtained using the nucleation + crystal growth method. However, the percentage of neodymium incorporated in zirconolite crystals remained too small to make realistic the use of such materials for the conditioning of actinides in comparison with more durable bulk ceramics.