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The electrical properties of the entropy stabilized oxides: Zr6Nb2O17, Zr6Ta2O17, Hf6Nb2O17and Hf6Ta2O17were characterized. The results and the electrical properties of the products (i.e. ZrO2, HfO2, Nb2O5and Ta2O5) led us to hypothesize the A6B2O17family is a series of mixed ionic-electronic conductors. Conductivity measurements in varying oxygen partial pressure were performed on A6Nb2O17and A6Ta2O17.The results indicate that electrons are involved in conduction in A6Nb2O17while holes play a role in conduction of A6Ta2O17. Between 900 °C–950 °C, the charge transport in the A6B2O17system increases in Ar atmosphere. A combination of DTA/DSC and in situ high temperature X-ray diffraction was performed to identify a potential mechanism for this increase. In-situ high temperature X-ray diffraction in Ar does not show any phase transformation. Based on this, it is hypothesized that a change in the oxygen sub-lattice is the cause for the shift in high temperature conduction above 900 °C–950 °C. This could be:(i)Nb(Ta)4+- oxygen vacancy associate formation/dissociation,(ii)formation of oxygen/oxygen vacancy complexes(iii)ordering/disordering of oxygen vacancies and/or(iv)oxygen-based superstructure commensurate or incommensurate transitions. In-situ high temperature neutron diffraction up to 1050 °C is required to help elucidate the origins of this large increase in conductivity.
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A Pressure‐Induced Inverse Order–Disorder Transition in Double Perovskites
Abstract Given the consensus that pressure improves cation ordering in most of known materials, a discovery of pressure‐induced disordering could require recognition of an order–disorder transition in solid‐state physics/chemistry and geophysics. Double perovskites Y2CoIrO6and Y2CoRuO6polymorphs synthesized at 0, 6, and 15 GPa show B‐site ordering, partial ordering, and disordering, respectively, accompanied by lattice compression and crystal structure alteration from monoclinic to orthorhombic symmetry. Correspondingly, the long‐range ferrimagnetic ordering in the B‐site ordered samples are gradually overwhelmed by B‐site disorder. Theoretical calculations suggest that unusual unit‐cell compressions under external pressures unexpectedly stabilize the disordered phases of Y2CoIrO6and Y2CoRuO6.
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- Award ID(s):
- 1809931
- PAR ID:
- 10143228
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 59
- Issue:
- 21
- ISSN:
- 1433-7851
- Page Range / eLocation ID:
- p. 8240-8246
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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