Modelling oxygen self-diffusion in UO2 under pressure

Access to values for oxygen self-diffusion over a range of temperatures and pressures in UO2 is important to nuclear fuel applications. Here, elastic and expansivity data are used in the framework of a thermodynamic model, the cBΩ model, to derive the oxygen self-diffusion coefficient in UO2 over a range of pressures (0–10 GPa) and temperatures (300–1900 K). The significant reduction in oxygen self-diffusion as a function of increasing hydrostatic pressure, and the associated increase in activation energy, is identified

The defect chemistry of UO2±x from atomistic simulations

Control of the defect chemistry in UO2±x is important for manipulating nuclear fuel properties and fuel performance. For example, the uranium vacancy concentration is critical for fission gas release and sintering, while all oxygen and uranium defects are known to strongly influence thermal conductivity. Here the point defect concentrations in thermal equilibrium are predicted using defect energies from density functional theory (DFT) and vibrational entropies calculated using empirical potentials. Electrons and holes have been treated in a similar fashion to other charged defects allowing for structural relaxation around the localized electronic defects. Predictions are made for the defect concentrations and non-stoichiometry of UO2±x as a function of oxygen partial pressure and temperature. If vibrational entropy is omitted, oxygen interstitials are predicted to be the dominant mechanism of excess oxygen accommodation over only a small temperature range (1265 K–1350 K), in contrast to experimental observation. Conversely, if vibrational entropy is included oxygen interstitials dominate from 1165 K to 1680 K (Busker potential) or from 1275 K to 1630 K (CRG potential). Below these temperature ranges excess oxygen is predicted to be accommodated by uranium vacancies, while above them the system is hypo-stoichiometric with oxygen deficiency accommodated by oxygen vacancies. Our results are discussed in the context of oxygen clustering, formation of U4O9, and issues for fuel behavior. In particular, the variation of the uranium vacancy concentrations as a function of temperature and oxygen partial pressure will underpin future studies into fission gas diffusivity and broaden the understanding of UO2±x sintering

The high-temperature heat capacity of the (Th,U)O 2 and (U,Pu)O 2 solid solutions

International audienceThe enthalpy increment data for the (Th,U)O2 and (U,Pu)O2 solid solutions are reviewed and complemented with new experimental data (400-1773 K) for not yet measured compositions. The results of the review show that from room temperature up to about 2000 K the enthalpy data are in agreement with the additivity rule (Neumann-Kopp) in the whole composition range. Above 2000 K the effect of Oxygen Frenkel Pair (OFP) formation leads to an excess enthalpy (heat capacity) that is modeled using the enthalpy and entropy of OFP formation from the end members derived previously. A good agreement with existing experimental work is observed

Angle- and spin-resolved photoelectron spectroscopy of the Hg 5d10 subshell

Schönhense G, Schäfers F, Heinzmann U, Kessler J. Angle- and spin-resolved photoelectron spectroscopy of the Hg 5d10 subshell. Zeitschrift für Physik A: Hadrons and Nuclei. 1982;304(1):31-40.Parameters describing electron spin polarization in Hg 5d10 subshell photoionization have been measured at rare-gas resonance wavelengths between 73.59 nm and 30.38 nm. The spin parameters as well as asymmetry parameters beta of a recent measurement are discussed in comparison with both nonrelativistic and relativistic ab initio calculations of several authors. The importance of many-electron correlations and spin-orbit coupling effects is considered. We would like to express our thanks to F. Combet Farnoux, N. Cherepkov, W. Johnson and S. Manson for useful correspondence as well as for the communication of unpublished results. This work was supported by the DFG and BMFT. One of us (G.S.) wishes to thank the Studienstiftung des Deutschen Volkes for financial support

Analysis of autoionization resonances in the Hg 6s2-photoionization by measurements of photoelectron polarization

Schäfers F, Schönhense G, Heinzmann U. Analysis of autoionization resonances in the Hg 6s2-photoionization by measurements of photoelectron polarization. Zeitschrift für Physik A: Hadrons and Nuclei. 1982;304(1):41-48.Measurements of the spin polarization of photoelectrons in the autoionization region of the Hg 6s2-subshell using circularly polarized synchrotron radiation and using unpolarized light from rare gas discharge lamps are reported. The results obtained show a pronounced structure across the resonances. Together with data of the cross section and its angular distribution these data from a complete parameter set for the determination of the transition matrix elements and the phase difference of the continuum wavefunctions. Evidences for strong configuration interaction and channel mixing between the open and closed channels were found. The matrix elements and their ratio vary strongly across the resonances and the relative phase shows some changes of sign. A change of the relative phase by Pi across an autoionization resonance, predicted by Fano, has been verified experimentally for the triplet resonance. We would like to express our gratitude to Professors W. Paul, G. Nöldeke and J. Kessler for their continued interest and encouragement. We thank Dr. D. Husmann, Dr. J. Hormes and B. Osterheld for their assistance in performing the experiment in Bonn. We are grateful to Dr. N.A. Cherepkov for helpful discussions and acknowledge support by the DFG and BMFT