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High-pressure phase behavior and equations of state of ThO2 polymorphs

  • Bethany A. Chidester EMAIL logo , Olivia S. Pardo , Rebecca A. Fischer , Elizabeth C. Thompson , Dion L. Heinz , Clemens Prescher , Vitali B. Prakapenka and Andrew J. Campbell
Published/Copyright: April 30, 2018
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American Mineralogist
From the journal American Mineralogist Volume 103 Issue 5

Abstract

ThO2 is an important material for understanding the heat budget of Earth’s mantle, as well as the stability of nuclear fuels at extreme conditions. We measured the in situ high-pressure, high-temperature phase behavior of ThO2 to ~60 GPa and ~2500 K. It undergoes a transition from the cubic fluorite-type structure (thorianite) to the orthorhombic α-PbCl2 cotunnite-type structure between 20 and 30 GPa at room temperature. Prior to the transition at room temperature, an increase in unit-cell volume is observed, which we interpret as anion sub-lattice disorder or pre-transformation “melting” (Boulfelfel et al. 2006). The thermal equation of state parameters for both thorianite [V0 = 26.379(7), K0 = 204(2), αKT = 0.0035(3)] and the high-pressure cotunnite-type phase [V0 = 24.75(6), K0 = 190(3), αKT = 0.0037(4)] are reported, holding K0′ fixed at 4. The similarity of these parameters suggests that the two phases behave similarly within the deep Earth. The lattice parameter ratios for the cotunnite-type phase change significantly with pressure, suggesting a different structure is stable at higher pressure.

Keywords: XRD data; ThO2; Raman spectroscopy; phase transition; high-pressure studies; diamond-anvil cell; high-temperature studies; laser-heating

* Present address: Earth and Planetary Sciences Department, University of California Davis, Davis, California 95616, U.S.A.

† Present address: Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, California 91125, U.S.A.

‡ Present address: Department of Earth and Planetary Sciences, Harvard University, Cambridge, Massachusetts 02138, U.S.A.

§ Present address: Institut für Geologie und Mineralogie, Universität zu Köln, 50674 Köln, Germany.

Acknowledgments

The authors are grateful to Jinyuan Yan for his assistance with the room-temperature measurements. This study was funded by NSF Graduate Research Fellowship Grant DGE-1144082, NSF Grants EAR-1427123, and EAR-0944298, and the Carnegie/DOE Alliance Center (CDAC). Portions of this work were done at GeoSoilEnviroCARS (The University of Chicago, Sector 13) of the Advanced Photon Source, Argonne National Laboratory, and at Sector 12.2.2 of the Advanced Light Source, Lawrence Berkeley National Laboratory. GeoSoilEnviroCARS is supported by the National Science Foundation—Earth Sciences (EAR-1634415) and Department of Energy, GeoSciences (DE-FG02–94ER14466). This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02–06CH11357. Sector 12.2.2. is funded in part by the Consortium for Materials Properties Research in Earth Sciences (COMPRES) under NSF Cooperative Agreement EAR 10–43050. The Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02–05CH11231.

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Received: 2017-6-13
Accepted: 2018-1-30
Published Online: 2018-4-30
Published in Print: 2018-5-25

© 2018 Walter de Gruyter GmbH, Berlin/Boston

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https://doi.org/10.2138/am-2018-6212
Keywords for this article
XRD data; ThO2; Raman spectroscopy; phase transition; high-pressure studies; diamond-anvil cell; high-temperature studies; laser-heating

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  6. Surface-modified phillipsite-rich tuff from the Campania region (southern Italy) as a promising drug carrier: An ibuprofen sodium salt trial
  8. Structure of low-order hemimorphite produced in a Zn-rich environment by cyanobacterium Leptolingbya frigida
  10. Formation of dolomite catalyzed by sulfate-driven anaerobic oxidation of methane: Mineralogical and geochemical evidence from the northern South China Sea
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