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The challenge of growing rare-earth (RE) sesquioxide crystals can be overcome by tailoring their structural stability and melting point via composition engineering. This work contributes to the advancement of the field of crystal growth of high-entropy oxides. A compound with only small REs (Lu,Y,Ho,Yb,Er)2O3 maintains a cubic C-type structure upon cooling from the melt, as observed via in-situ high-temperature neutron diffraction on aerodynamically levitated samples. On the other hand, a compound with a mixture of small and large REs (Lu,Y,Ho,Nd,La)2O3 crystallizes as a mixture of a primary C-type phase with an unstable secondary phase. Crystals of compositions (Lu,Y,Ho,Nd,La)2O3 and (Lu,Y,Gd,Nd,La)2O3 were grown by the micro-pulling-down (mPD) method with a single monoclinic B-type phase, while a powder of (Lu,Y,Ho,Yb,Er)2O3 did not melt at the maximum operating temperature of an iridium–rhenium crucible. The minimization of the melting point of the two grown crystals is attributed to the mismatch in cation sizes. The electron probe microanalysis reveals that the general element segregation behavior in the crystals depends on the composition.


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Tuning the melting point and phase stability of rare-earth oxides to facilitate their crystal growth from the melt

Show Author's information Matheus PIANASSOLAa,b( )Kaden L. ANDERSONa,bJoshua SAFINbCan AGCAcJake W. MCMURRAYcBryan C. CHAKOUMAKOSdJöerg C. NEUEFEINDdCharles L. MELCHERa,b,eMariya ZHURAVLEVAa,b
Scintillation Materials Research Center, The University of Tennessee, Knoxville 37996, USA
Department of Materials Science and Engineering, The University of Tennessee, Knoxville 37996, USA
Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge 37831, USA
Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge 37831, USA
Department of Nuclear Engineering, The University of Tennessee, Knoxville 37996, USA

Abstract

The challenge of growing rare-earth (RE) sesquioxide crystals can be overcome by tailoring their structural stability and melting point via composition engineering. This work contributes to the advancement of the field of crystal growth of high-entropy oxides. A compound with only small REs (Lu,Y,Ho,Yb,Er)2O3 maintains a cubic C-type structure upon cooling from the melt, as observed via in-situ high-temperature neutron diffraction on aerodynamically levitated samples. On the other hand, a compound with a mixture of small and large REs (Lu,Y,Ho,Nd,La)2O3 crystallizes as a mixture of a primary C-type phase with an unstable secondary phase. Crystals of compositions (Lu,Y,Ho,Nd,La)2O3 and (Lu,Y,Gd,Nd,La)2O3 were grown by the micro-pulling-down (mPD) method with a single monoclinic B-type phase, while a powder of (Lu,Y,Ho,Yb,Er)2O3 did not melt at the maximum operating temperature of an iridium–rhenium crucible. The minimization of the melting point of the two grown crystals is attributed to the mismatch in cation sizes. The electron probe microanalysis reveals that the general element segregation behavior in the crystals depends on the composition.

Keywords: crystal growth, high-entropy oxides, neutron diffraction, crystallography

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Publication history

Received: 30 April 2022
Revised: 13 June 2022
Accepted: 19 June 2022
Published: 05 September 2022
Issue date: September 2022

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© The Author(s) 2022.

Acknowledgements

This work was supported by the National Science Foundation (DMR 1846935). The authors are grateful for the support from the Center for Materials Processing, The University of Tennessee. The powder XRD was performed at the Institute for Advanced Materials & Manufacturing Diffraction Facility, The University of Tennessee, Knoxville. The electron microprobe measurements were performed at the Electron Microprobe Laboratory in the Department of Earth and Planetary Sciences, The University of Tennessee, Knoxville, with the assistance of Molly MCCANTA and Allan PATCHEN. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory.

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