TY - JOUR

T1 - Simulated Advanced Gas-Cooled Reactor Spent Nuclear Fuels

T2 - Determination of the O/U Ratio - an XRD, XPS and Raman Study

AU - Wilbraham, Richard J.

AU - Howett, Elizabeth A.

AU - Boxall, Colin

AU - Hambley, David I.

AU - Higgins, Jessica K.

PY - 2022/9/30

Y1 - 2022/9/30

N2 - This paper reports a detailed chemical and materials characterization study of novel Simulated Spent Nuclear Fuels (SIMFuel) which replicate the chemical and microstructural state of Spent Nuclear Fuel (SNF) discharged from a UK Advanced Gas-cooled Reactor (AGR). Recent advances in the analysis of pure UO2 samples by XPS, micro-Raman spectroscopy and XRD, have been assessed for deployment in the characterisation of SIMFuels generally and these AGR SIMFuels in particular. All three analytical methods reveal the extent that the UO2 bulk matrix is defected in the SIMFuels by the presence of lanthanide dopants. XPS, by inspection of the U4f peaks and their satellites, indicates the presence of U(V) in the UO2 matrix as a means to charge compensate for the incorporation of Ln(III) states and presence of a slight hyperstoichiometry in the UO2 solid solution. This was corroborated by detailed Raman analysis of the UO2 matrix of the SIMFuels – wherein the (Ba,Sr)ZrO3 and metallic particle phases, that simulate the precipitated grey phases and ε-particles formed in real spent fuel, were avoided – which indicated the presence of both interstitial oxygens and oxygen vacancies, the latter as a parallel means of charge compensation for the presence of Ln(III). Further confirmation was provided by XRD measurements through observation of a lattice parameter contraction arising from the presence of the smaller U(V) ion in the U(IV)O2 matrix. XPS and Raman allow for the reporting of O/U ratios in the SIMFuels. These XPS and Raman-derived O/U ratios are in good agreement, indicating: (i) that the SIMFuels are near stoichiometric/slightly hyperstoichiometric, concurring with previous analogous studies on real and simulated light water reactor fuels; and (ii) that either technique may find application in the analysis of real fuel analysis, both pre- and post-irradiation.

AB - This paper reports a detailed chemical and materials characterization study of novel Simulated Spent Nuclear Fuels (SIMFuel) which replicate the chemical and microstructural state of Spent Nuclear Fuel (SNF) discharged from a UK Advanced Gas-cooled Reactor (AGR). Recent advances in the analysis of pure UO2 samples by XPS, micro-Raman spectroscopy and XRD, have been assessed for deployment in the characterisation of SIMFuels generally and these AGR SIMFuels in particular. All three analytical methods reveal the extent that the UO2 bulk matrix is defected in the SIMFuels by the presence of lanthanide dopants. XPS, by inspection of the U4f peaks and their satellites, indicates the presence of U(V) in the UO2 matrix as a means to charge compensate for the incorporation of Ln(III) states and presence of a slight hyperstoichiometry in the UO2 solid solution. This was corroborated by detailed Raman analysis of the UO2 matrix of the SIMFuels – wherein the (Ba,Sr)ZrO3 and metallic particle phases, that simulate the precipitated grey phases and ε-particles formed in real spent fuel, were avoided – which indicated the presence of both interstitial oxygens and oxygen vacancies, the latter as a parallel means of charge compensation for the presence of Ln(III). Further confirmation was provided by XRD measurements through observation of a lattice parameter contraction arising from the presence of the smaller U(V) ion in the U(IV)O2 matrix. XPS and Raman allow for the reporting of O/U ratios in the SIMFuels. These XPS and Raman-derived O/U ratios are in good agreement, indicating: (i) that the SIMFuels are near stoichiometric/slightly hyperstoichiometric, concurring with previous analogous studies on real and simulated light water reactor fuels; and (ii) that either technique may find application in the analysis of real fuel analysis, both pre- and post-irradiation.

KW - Nuclear fuel

KW - Uranium dioxide

KW - X-ray photoelectron spectroscopy

KW - Raman

KW - X-ray diffraction

U2 - 10.1016/j.jnucmat.2022.153867

DO - 10.1016/j.jnucmat.2022.153867

M3 - Journal article

VL - 568

JO - Journal of Nuclear Materials

JF - Journal of Nuclear Materials

SN - 0022-3115

M1 - 153867

ER -