Insights into the sonochemical synthesis and properties of salt-free intrinsic plutonium colloids

Elodie Dalodière (1) , Matthieu Virot (1) , Vincent Morosini (1) , Tony Chave (1) , Thomas Dumas (2) , Christoph Hennig (3) , Thierry Wiss (4) , Oliver Dieste Blanco (4) , David Shuh (5) , Tolek Tyliszcak (6) , Laurent Venault (7) , Philippe Moisy (7) , Sergey I. Nikitenko (1)

1 LSFC - Sonochimie dans les Fluides Complexes
2 AGM - UMR 8088 - Analyse, Géométrie et Modélisation
3 ESRF - European Synchrotron Radiation Facility
4 JRC - European Commission - Joint Research Centre [Karlsruhe]
5 LBNL - Lawrence Berkeley National Laboratory [Berkeley]
6 ALS - Advanced Light Source [LBNL Berkeley]
7 DMRC - Département de recherche sur les procédés pour la mine et le recyclage du combustible

Fundamental knowledge on intrinsic plutonium colloids is important for the prediction of plutonium behaviour in the geosphere and in engineered systems. The first synthetic route to obtain salt-free intrinsic plutonium colloids by ultrasonic treatment of PuO 2 suspensions in pure water is reported. Kinetics showed that both chemical and mechanical effects of ultrasound contribute to the mechanism of Pu colloid formation. In the first stage, fragmentation of initial PuO 2 particles provides larger surface contact between cavitation bubbles and solids. Furthermore, hydrogen formed during sonochemical water splitting enables reduction of Pu(IV) to more soluble Pu(III), which then re-oxidizes yielding Pu(IV) colloid. A comparative study of nanostructured PuO 2 and Pu colloids produced by sonochemical and hydrolytic methods, has been conducted using HRTEM, Pu L III-edge XAS, and O K-edge NEXAFS/ STXM. Characterization of Pu colloids revealed a correlation between the number of Pu-O and Pu-Pu contacts and the atomic surface-to-volume ratio of the PuO 2 nanoparticles. NEXAFS indicated that oxygen state in hydrolytic Pu colloid is influenced by hydrolysed Pu(IV) species to a greater extent than in sonochemical PuO 2 nanoparticles. In general, hydrolytic and sonochemical Pu colloids can be described as core-shell nanoparticles composed of quasi-stoichiometric PuO 2 cores and hydrolyzed Pu(IV) moieties at the surface shell.

Domaines: Matériaux

Elodie Dalodière, Matthieu Virot, Vincent Morosini, Tony Chave, Thomas Dumas, et al.. Insights into the sonochemical synthesis and properties of salt-free intrinsic plutonium colloids. Scientific Reports, 2017, 7, pp.43514. ⟨10.1038/srep43514⟩. ⟨hal-02075390⟩