Formation, structure and magnetism of the metastable defect fluorite phases AVO3.5+x (A=In, Sc)

  1. Get@NRC: Formation, structure and magnetism of the metastable defect fluorite phases AVO3.5+x (A=In, Sc) (Opens in a new window)
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Journal titleJournal of Solid State Chemistry
Pages33333340; # of pages: 8
SubjectBixbyite structure; Defect fluorite structure; In-situ X-ray diffraction; InVO_(3.5+x); Low temperature magnetism; Powder neutron diffraction; ScVO_(3.5+x); Thermal analysis; Topotactic oxidation
AbstractWe report the preparation and stability of ScVO3.5+x and the novel phase InVO3.5+x. AVO3.5+x (A=Sc, In) defect fluorite structures are formed as metastable intermediates during the topotactic oxidation of AVO3 bixbyites. The oxidation pathway has been studied in detail by means of thermogravimetric/differential thermal analysis and in-situ powder X-ray diffraction. The oxidation of the bixbyite phase follows a topotactic pathway at temperatures between 300 and 400??C in air/carbon dioxide. The range of accessible oxygen stoichiometries for the AVO3.5+x structures following this pathway are 0.00[less-than-or-equals, slant]x[less-than-or-equals, slant]0.22. Rietveld refinements against powder X-ray and neutron data revealed that InVO3.54 and ScVO3.70 crystallize in the defect fluorite structure in space group Fm-3?m (227) with a=4.9863(5) and 4.9697(3)?, respectively with A3+/V4+ disorder on the (4a) cation site. Powder neutron diffraction experiments indicate clustering of oxide defects in all samples. Bulk magnetic measurements showed the presence of V4+ and the absence of magnetic ordering at low temperatures. Powder neutron diffraction experiments confirmed the absence of a long range ordered magnetic ground state.
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AffiliationNational Research Council Canada; NRC Canadian Neutron Beam Centre
Peer reviewedNo
NPARC number12338340
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Record identifier43e48e96-7590-4460-9278-6305e399ef7b
Record created2009-09-10
Record modified2016-05-09
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