Crystallization behavior and microstructure characterization of zirconolite glass-ceramic synthesized via controlled cooling.

Zirconolite (CaZrTi 2 O 7) glass-ceramic is considered as a potential stable matrix for the immobilization of Pu or minor actinides (Np, Am, Cm). In this work, the phase combination and evolution of glass (SiO 2 –Al 2 O 3 –Na 2 O–CaO–ZrO 2 –TiO 2 –B 2 O 3) with La as an actinide surrogate were investigated during the process of heating and cooling. By employing controlled cooling process, the zirconolite glass-ceramic with a controllable crystal size was successfully fabricated in borosilicate glass. The results demonstrate that heating and cooling exhibit distinct phase combinations. Both crystallization temperature and duration exert a significant influence on the composition of crystalline phases and microstructure. During the cooling of the melt, an increased degree of supercooling leads to an enhanced crystallization of zirconolite and a significant reduction in crystal size. The experimental results demonstrate that the optimal condition for preparing zirconolite glass-ceramic is held at 950 °C, for 4 h by one-step method, at which time the crystal exhibits a slender acicular morphology with a size of about 30 μm. Most of the simulated nuclides are enriched in crystals, and the rest are dissolved in glass. Zirconolite exhibits thermodynamic instability at elevated temperatures (1000 °C–1100 °C). Following the phase transformation, a proportion of Zr sequestered by titanite, while any excess Zr is either remain dissolved in the glass or gets precipitated as baddeleyite. For La, Al and other elements previously fixed in zirconolite, they are re-released to the glass and partially fixed by titanite, which may be detrimental to the long-term release behavior of the waste forms. In the aqueous durability test, both zirconolite glass-ceramic and phase transformation samples exhibited a low leaching rate, with LR Si , LR Zr , and LR La values of approximately 5 × 10−3, 4 × 10−6, and 6 × 10−6 g·m−2·d−1, respectively, after 28 days of leaching. By controlling the cooling process (one-step method), this paper provides useful information on the preparation of zirconolite glass-ceramic. [ABSTRACT FROM AUTHOR]