The effect of entropy on the structure and aqueous durability of nanocrystalline rare-earth zirconate ceramics

A series of compositionally complex A₂Zr₂O₇ nanocrystalline ceramics were successfully prepared using sol-gel and co-precipitation methods. The resultant ceramics possess a cubic defect fluorite structure, with the sol-gel method yielding an average grain size of approximately 50–70 nm, while the co-precipitation method result in an average grain size of about 40–60 nm. Leaching tests revealed that the smaller grain sizes are correlated with higher leaching rates. Furthermore, for ceramics with similar grain sizes, those with higher entropy values exhibited higher leaching rates. The increase in grain boundaries was found to reduce the leaching performance of the rare earth zirconate ceramics, and this effect became more pronounced with increasing entropy. This work provides insights into the selection of entropy values and grain sizes for the high-level radioactive waste matrices, which can be considered as a potential substrate for the simultaneous immobilization of multiple radionuclides.