ChemInform Abstract: Neutron Diffraction Study of the in situ Oxidation of UO2.
This paper discusses uranium oxide crystal structure modifications that are observed during the low-temperature oxidation which transforms UO2 into U3O8. The symmetries and the structural parameters of UO2, β-U4O9, β-U3O7, and U3O8 were determined by refining neutron diffraction patterns on pure single-phase samples. Neutron diffraction patterns were also collected during the in situ oxidation of powder samples at 483 K. The lattice parameters and relative ratios of the four pure phases were measured during the progression of the isothermal oxidation. The transformation of UO2 into U3O8 involves a complex modification of the oxygen sublattice and the onset of complex superstructures for U4O…
Synthesis and characterization of nanometric powders of UO2+x, (Th,U)O2+x and (La,U)O2+x
This paper describes a new way of preparing nanometric powders of uranium oxide, to fit the needs of studies on UO{sub 2} oxidation, through the electrochemical reduction of U(VI) into U(IV). These powders can also be doped with radionuclides if necessary. The precipitation of oxides occurs in reducing and anoxic conditions. This original method makes it possible to synthesize nanometric UO{sub 2} powders with a calibrated size, as well as the Th- and La-doped UO{sub 2} powders with a predefined composition. The powder characterization by the X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron Microscopy shows the formation of spherical crystallites of UO{sub 2+x},…
On the origin of the sigmoid shape in the UO2 oxidation weight gain curves
International audience; Cracking and spalling are known to occur during the oxidation of UO2. However, these phenomena are not considered by the existing kinetic models of the oxidation of UO2 into U3O8. In this study the oxidation of UO2 samples of various sizes from the single crystal to nanopowders, has been followed by isothermal and isobaric thermogravimetry, environmental scanning electron microscopy and in situ X-ray diffraction at temperatures ranging from 250 to 370°C in air. It has been shown that cracking occurs once a critical layer thickness of intermediate oxide has been reached, which corresponds to the beginning of the sigmoid kinetic curve. Cracking contribution to the sigm…
Synchrotron diffraction study of the isothermal oxidation of uranium dioxide at 250°C
ABSTRACTThe structural evolution of UO2 during its oxidation to U3O8 at 250°C in air was studied by in-situ synchrotron X-ray diffraction on the D2AM-CRG beamline at ESRF. The aim of this study is to determine the phases that are likely to appear during the long-term storage of spent nuclear fuel. Our results are in disagreement with the literature in which the existence of an intermediate cubic phase is not reported. Instead, an α-U3O7 tetragonal phase (c/a < 1) was mentioned but not definitively observed. These previous interpretations may have been the result of poor instrumental resolution.
Inelastic neutron scattering study of proton dynamics in Ca(OH)2 at 20 K
Abstract Inelastic neutron scattering (INS) spectra of Ca(OH) 2 at 20 K are presented from 30 to 4000 cm −1 for a powder sample, from 30 to 12000 cm −1 for an oriented single-crystal. INS band splitting due to the lattice density-of-states is observed. Polarization effects reveal the orientation of atomic displacements for each mode and a new band assignment scheme is proposed. For the single-crystal, the v OH mode and overtones are observed. This oscillator shows only moderate anharmonicity. Spectrum simulation reveals that INS spectral intensities are not consistent with simple normal coordinates and harmonic force-fields for Ca(OH) 2 entities. A new dynamical model is proposed, including…
Contribution of the synchrotron diffraction study of the oxidation of uranium dioxide at 250○C
The structural evolution of UO 2 during its oxidation into U 3 O 8 at 250°C in air was studied by in-situ synchrotron X-ray diffraction on the D2AM-CRG beamline at ESRF. The aim of this study is to determine the phases which are likely to appear during a long term storage of used nuclear fuel. Our results are in disagreement with the literature where the existence of the secondary cubic phase is not reported, and an α-U 3 O 7 tetragonal phase (c/a < 1) is also mentioned but definitely not observed. These previous interpretations are possibly due to a poor instrumental resolution, inducing a sensible broadening of the diffraction peaks. Particularly, the fact that the instrumental resolution…
Neutron Diffraction Study of the in Situ Oxidation of UO2
This paper discusses uranium oxide crystal structure modifications that are observed during the low-temperature oxidation which transforms UO(2) into U(3)O(8). The symmetries and the structural parameters of UO(2), beta-U(4)O(9), beta-U(3)O(7), and U(3)O(8) were determined by refining neutron diffraction patterns on pure single-phase samples. Neutron diffraction patterns were also collected during the in situ oxidation of powder samples at 483 K. The lattice parameters and relative ratios of the four pure phases were measured during the progression of the isothermal oxidation. The transformation of UO(2) into U(3)O(8) involves a complex modification of the oxygen sublattice and the onset of…
Influence of the U3O7 domain structure on cracking during the oxidation of UO2
Abstract Cracking is observed when a UO 2 single crystal is oxidised in air. Previous studies led to the hypothesis that cracking occurs once a critical depth of U 3 O 7 oxidised layer is reached. We present some μ-Laue X-ray diffraction results, which evidence that the U 3 O 7 layer, grown by topotaxy on UO 2 , is made of domains with different crystalline orientations. This observation was used to perform a modelling of oxidation coupling chemical and mechanical parameters, which showed that the domain patterning induces stress localisation. This result is discussed in comparison with stress localisation observed in thin layer deposited on a substrate and used to propose an interpretation…
High magnification SEM observations for two types of granularity in a high burnup PWR fuel rim
Abstract Rim microstructure of an UO2 pellet irradiated up to 61 GWd/tU, observed with high magnification scanning electron microscopy, presented two types of subgrains: polyhedral and round subgrains. Round subgrains were also observed on the surface of fabrication pores along the pellet radius. These round-shaped subgrains seem to be associated to free surface rearrangement. This new type of round subgrains was proved to be independent of the rim effect. Observations of the fuel structure in the vicinity of rim area evidenced two types of defects specific to rim effect: planar defects and small intergranular pores. Hypothesis is made that the accumulation of planar defects could generate …