%0 Journal Article
%A Murphy, Gabriel L.
%A Wang, Chun-Hai
%A Beridze, George
%A Zhang, Zhaoming
%A Kimpton, Justin A.
%A Avdeev, Maxim
%A Kowalski, Piotr
%A Kennedy, Brendan J.
%T Unexpected Crystallographic Phase Transformation in Nonstoichiometric SrUO 4– x : Reversible Oxygen Defect Ordering and Symmetry Lowering with Increasing Temperature
%J Inorganic chemistry
%V 57
%N 10
%@ 1520-510X
%C Washington, DC
%I American Chemical Society
%M FZJ-2018-03395
%P 5948 - 5958
%D 2018
%X In situ synchrotron powder X-ray diffraction measurements have demonstrated that SrUO4 undergoes a reversible phase transformation under reducing conditions at high temperatures, associated with the ordering of oxygen defects resulting in a lowering of crystallographic symmetry. When substoichiometric rhombohedral α-SrUO4–x, in space group R3̅m with disordered in-plane oxygen defects, is heated above 200 °C in a hydrogen atmosphere it undergoes a first order phase transformation to a (disordered) triclinic polymorph, δ-SrUO4–x, in space group P1̅. Continued heating to above 450 °C results in the appearance of superlattice reflections, due to oxygen-vacancy ordering forming an ordered structure δ-SrUO4–x. Cooling δ-SrUO4–x toward room temperature results in the reformation of the rhombohedral phase α-SrUO4–x with disordered defects, confirming the reversibility of the transformation. This suggests that the transformation, resulting from oxygen vacancy ordering, is not a consequence of sample reduction or decomposition, but rather represents a change in the energetics of the system. A strong reducing atmosphere is required to generate a critical amount of oxygen defects in α-SrUO4–x to enable the transformation to δ-SrUO4–x but once formed the transformation between these two phases can be induced by thermal cycling. The structure of δ-SrUO4–x at 1000 °C was determined using symmetry representation analysis, with the additional reflections indexed to a commensurate distortion vector k = ⟨1/4 1/4 3/4⟩. The ordered 2D layered triclinic structure of δ-SrUO4–x can be considered a structural distortion of the disordered 2D layered rhombohedral α-SrUO4–x structure through the preferential rearrangement of the in-plane oxygen vacancies. Ab initio calculations using density functional theory with self-consistently derived Hubbard U parameter support the assigned ordered defect superstructure model. Entropy changes associated with the temperature dependent short-range ordering of the reduced U species are believed to be important and these are discussed with respect to the results of the ab initio calculations.
%F PUB:(DE-HGF)16
%9 Journal Article
%$ pmid:29714481
%U <Go to ISI:>//WOS:000433013600026
%R 10.1021/acs.inorgchem.8b00463
%U https://juser.fz-juelich.de/record/848119