Self-healing ThSiO4-ZrSiO4 system under conditions relevant to underground nuclear waste repositories

Abstract

Two series of Th1-xZrxSiO4 phases were synthesized hydrothermally under weakly basic (pH = 8) and strongly acidic (pH = 1) conditions. Changes in pH were found to have a significant effect on experimental phase diagrams. Synthesis at pH = 8 favors the formation of Th-rich phases with resulting Th1-xZrxSiO4 solid solution for x = 0 – 0.5. Contrary, synthesis at pH = 1 results in the formation of pure end-members of the ThSiO4-ZrSiO4 pseudo-binary system separated by multiple miscibility gaps. Phases formed both under basic and acidic conditions were found to retain water, which can be discharged from the structure upon heating. A different high-pressure (HP) behaviour was found for Th-rich and Zr-rich solid solutions. While Th-rich Th0.9Zr0.1SiO4 and Th0.6Zr0.4SiO4 phases retain their stoichiometry and crystal structure upon compression at HP, a significant reduction of the Th occupancy related to a decrease of the Th-O distances is observed for the Th-poor Th0.26Zr0.74SiO4 phase at P > 8 GPa, with the subsequent formation of a Th-rich amorphous phase. The Th diffusion between the crystalline and amorphous phases was found to be fully reversible. This unique self-healing property makes these phases promising candidates for nuclear applications under extreme pressure and temperature conditions, in particular those found in underground repositories.