Micrometric drilling of (meta-)studtite square platelets formed by pseudomorphic conversion of UO under high-frequency ultrasound.

Pseudomorphic transformations are related to chemical conversions of materials while conserving their shape and structural features. Structuring ceramic shapes this way can be used to tailor the physico-chemical properties of materials that can benefit particular applications. In the context of spent nuclear fuel storage interacting with radiolysis products, the sonochemical behavior of powdered UO was investigated in dilute aqueous solutions saturated with Ar/(20 %)O (20 °C). Optimized parameter settings enabled the complete conversion of UO micrometric platelets into uranyl peroxide precipitates, referred to as (meta-)studtite [(UO(O)(HO))xHO] with x = 2 or 4. While the most acidic conditions yielded elongated crystal shapes in agreement with a dissolution/reprecipitation mechanism, softer conditions allowed the pseudomorphic transformation of the platelet shape oxide suggesting a complex formation mechanism. For specific conditions, this unprecedented morphology was accompanied with the formation of a hole in the platelet center. Investigations revealed that the formation of the drilled polymorphs is related to a perfect blend of H, in-situ generation of HO and high-frequency ultrasound, and is most probably related to the sono-capillary effect. These insights pave the way for new sonochemical approaches dedicated to the preparation of material polymorphs tailoring specific structural properties.