Order-disorder structural transition and thermal expansion properties in Ce-substituted Y2Zr2O7 system

Abstract

In the pursuit of advancing inert matrix fuel (IMF) applications, zirconate pyrochlores have emerged as promising candidates for the incorporation of minor actinides and plutonium. This study employs CeO2 as a nonradioactive surrogate for PuO2 and focuses on the synthesis of cerium-substituted Y2Zr2O7 samples (Y2-xCexZr2O7, 0.0 ≤ x ≤ 2.0) through a solid-state route under both reducing and oxidizing conditions to mimic plutonium incorporation. The impact of cerium content and its valence state, which in turn is influenced by synthesis conditions, on crystal structure and phase stability has been investigated through X-ray diffraction and Raman spectroscopic studies. Samples synthesized under reduced conditions undergo a defect fluorite to pyrochlore phase transition through a biphasic mixture consisting of these two phases upon increasing Ce-substitution. Conversely, the high temperature oxidizing synthesis conditions yield a defect fluorite phase field over a wide composition range (0.0 ≤ x ≤ 1.6) and a tetragonal phase at x = 2.0. Intriguingly, pyrochlore-type phases obtained under reducing conditions transform into the metastable kappa-phases upon mild oxidation at a relatively low temperature (1073 K), as confirmed by Raman spectroscopic studies. A combination of thermo-gravimetric and Raman spectroscopic investigations confirms the complete reduction of Ce4+ to Ce3+ under reducing conditions. The lattice thermal expansion behavior has also been investigated for the defect fluorite phases, synthesized under oxidizing conditions, by means of high temperature XRD spanning the temperature range 298–1273 K. Notably, the thermal expansion of compositions exhibits an increasing trend with increasing cerium content.