Incorporation of uranium in pyrochlore oxides and pressure-induced phase transitions

Uranium-doped gadolinium zirconates with pyrochlore structure were studied at ambient and high-pressure conditions up to 40 GPa. The bonding environment of uranium in the structure was determined by x-ray photoelectron and Raman spectroscopies and x-ray diffraction. The uranium valence for samples prepared in air is mainly U6+, but U4+ is present in pyrochlores fabricated in an argon atmosphere. Rietveld refinement of the XRD pattern suggests that uranium ions in pyrochlores are on the 16d site in 6-fold coordination with oxygen. At pressures greater than 22 GPa, the pyrochlore structure transformed to a cotunnite-type phase. The cotunnite high-pressure phase transformed to a defect fluorite structure on the release of pressure. (C) 2014 Elsevier Inc. All rights reserved.