Plutonium oxide melt structure and covalency

Wilke, Stephen K.; Benmore, Chris J.; Alderman, Oliver G.; Sivaraman, Ganesh; Ruehl, Matthew D.; Hawthorne, Krista L.; Tamalonis, Anthony; Andersson, David A.; Williamson, Mark A.; Weber, Richard

doi:10.1038/s41563-024-01883-3

Title: Plutonium oxide melt structure and covalency

Journal Article · Thu Apr 25 20:00:00 EDT 2024 · Nature Materials

DOI: https://doi.org/10.1038/s41563-024-01883-3 · OSTI ID:2472836

;

; Hawthorne, Krista L.; Tamalonis, Anthony;

; Williamson, Mark A.; Weber, Richard

Advances in nuclear power reactors include the use of mixed oxide fuel, containing uranium and plutonium oxides. The high-temperature behaviour and structure of PuO_2-x above 1,800 K remain largely unexplored, and these conditions must be considered for reactor design and planning for the mitigation of severe accidents. Here, in this study, we measure the atomic structure of PuO_2-x through the melting transition up to 3,000 +/- 50 K using X-ray scattering of aerodynamically levitated and laser-beam-heated samples, with O/Pu ranging from 1.57 to 1.76. Liquid structural models consistent with the X-ray data are developed using machine-learned interatomic potentials and density functional theory. Molten PuO_1.76 contains some degree of covalent Pu-O bonding, signalled by the degeneracy of Pu 5f and O 2p orbitals. The liquid is isomorphous with molten CeO_1.75, demonstrating the latter as a non-radioactive, non-toxic, structural surrogate when differences in the oxidation potentials of Pu and Ce are accounted for. These characterizations provide essential constraints for modelling pertinent to reactor safety design. The molten structure of plutonium oxide-a component of mixed oxide nuclear fuels-is measured, showing some degree of covalent bonding. Its atomic structure is similar to that of cerium oxide, which could be a non-radioactive structural surrogate.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Materials Development, Inc., Arlington Heights, IL (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Nuclear Energy (NE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Science (SC), Office of SBIR/STTR Programs (SBIR/STTR)

Grant/Contract Number:: 89233218CNA000001; AC02-06CH11357; SC0015241; SC0018601

OSTI ID:: 2472836

Report Number(s):: LA--UR-24-22906; 183641

Journal Information:: Nature Materials, Journal Name: Nature Materials Journal Issue: 7 Vol. 23; ISSN 1476-1122

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

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