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Oxidation of plutonium dioxide

Nature Materials volume 3, pages 225–228 (2004)Cite this article

Abstract

The physics and chemistry of the actinide elements form the scientific basis for rational handling of nuclear materials1,2,3. In recent experiments4, most unexpectedly, plutonium dioxide has been found to react with water to form higher oxides up to PuO2.27, whereas PuO2 had always been thought to be the highest stable oxide of plutonium2,3. We perform a theoretical analysis of this complicated situation on the basis of total energies calculated within density functional theory5,6 combined with well-established thermodynamic data. The reactions of PuO2 with either O2 or H2O to form PuO2+δ are calculated to be endothermic: that is, in order to occur they require a supply of energy. However, our calculations show that PuO2+δ can be formed, as an intermediate product, by reactions with the products of radiolysis of water, such as H2O2.

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Figure 1: Calculated enthalpies of formation for PuO2±δ solid solutions, as a function of stoichiometry and defect structure.
Figure 2: Calculated and experimental4,24 compositional variation of the lattice parameter in PuO2±δ solid solutions relative to stoichiometric PuO2.

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Acknowledgements

We thank L.R. Morss for providing us with the results of his unpublished work. This work is supported by SKB AB, the Swedish Nuclear Fuel and Waste Management Company, by the Swedish Foundation for Strategic Research (SSF) through the Center of Computational Thermodynamics, and the Inalloy consortia, and by the Swedish Research council (VR). Part of this work is supported by the project OTKA T035043 of the Hungarian Scientific Research Fund, the Hungarian Academy of Science, and the EC Centre of Excellence program (no. ICA1-CT-2000-70029). We thank the Swedish National Infrastructure for Computing for computer resources.

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Authors and Affiliations

  1. Department of Materials Science and Engineering, Applied Materials Physics, Royal Institute of Technology (KTH), Stockholm, SE-100 44, Sweden

    Pavel A. Korzhavyi, Levente Vitos, David A. Andersson & Börje Johansson

  2. Research Institute for Solid State Physics and Optics, Budapest, PO Box 49, H-1525, Hungary

    Levente Vitos

  3. Department of Physics, Condensed Matter Theory Group, Uppsala University, Box 530, Uppsala, SE-751 21, Sweden

    Börje Johansson

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  1. Pavel A. Korzhavyi
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Correspondence to Pavel A. Korzhavyi.

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Korzhavyi, P., Vitos, L., Andersson, D. et al. Oxidation of plutonium dioxide. Nature Mater 3, 225–228 (2004). https://doi.org/10.1038/nmat1095

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