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1 PublicationSynthesis, characterisation, and crystal structure of a novel U(V) brannerite UTi1.23Al0.77O6 and the UTi2-xAlxO6 system
Dixon Wilkins, M. C.; Mottram, L. M.; Maddrell, E. R.; Stennett, M. C.; Corkhill, C. L.; Kvashnina, K. O.; Hyatt, N. C.
Abstract
The synthesis, characterisation and crystal structure of a novel U5+ (dominant) brannerite of composition U1.09(6)Ti1.29(3)Al0.71(3)O6 is reported, as determined from Rietveld analysis of high resolution powder neutron diffraction data. Examination of the UTi2-xAlxO6 system demonstrated the formation of brannerite structured compounds with varying Al3+ and U5+ content, from U0.93(6)Ti1.64(3)Al0.36(3)O6 to U0.89(6)Ti1.00(3)Al1.00(3)O6. Substitution of Al3+for Ti4+, with U5+ charge compensation, resulted in near-linear changes in the b and c unit cell parameters and the overall unit cell volume, as expected from ionic radii considerations. The presence of U5+ as the dominant oxidation state in near single phase brannerite compositions was evidenced by complementary laboratory U L3 edge and high energy resolution fluorescence detected (HERFD) U M4 edge X-ray Absorption Near Edge Spectroscopy. No brannerite phase was found for compositions with Al3+ / Ti4+ > 1, which would require U6+ contribution for charge compensation. These data expand the crystal chemistry of uranium brannerites to the stabilisation of dominant U5+ brannerites by substitution of trivalent cations, such as Al3+, on the Ti4+ site
Involved research facilities
- Rossendorf Beamline at ESRF DOI: 10.1107/S1600577520014265
Related publications
- DOI: 10.1107/S1600577520014265 is cited by this (Id 33069) publication
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Inorganic Chemistry 60(2021)23, 18112-18121
DOI: 10.1021/acs.inorgchem.1c02733
Cited 8 times in Scopus
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