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Spinel and post-spinel phase assemblages in Zn2TiO4: an experimental and theoretical study

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Abstract

Zn2TiO4 spinel (Zn2TiO4-Sp) was synthesized by a solid-state reaction method (1573 K, room P and 72 h) and quasi-hydrostatically compressed to ~24 GPa using a DAC coupled with a synchrotron X-ray radiation (ambient T). We found that the Zn2TiO4-Sp was stable up to ~21 GPa and transformed to another phase at higher P. With some theoretical simulations, we revealed that this high-P phase adopted the CaTi2O4-type structure (Zn2TiO4-CT). Additionally, the isothermal bulk modulus (K T) of the Zn2TiO4-Sp was experimentally obtained as 156.0(44) GPa and theoretically obtained as 159.1(4) GPa, with its first pressure derivative \(K_{\text{T}}^{'}\) as 3.8(6) and 4.37(4), respectively. The volumetric and axial isothermal bulk moduli of the Zn2TiO4-CT were theoretically obtained as K T = 150(2) GPa (\(K_{\text{T}}^{'}\) = 5.4(2); for the volume), K T-a  = 173(2) GPa (\(K_{{\text{T-}}a}^{'}\) = 3.9(1); for the a-axis), K T-b  = 74(2) GPa (\(K_{{\text{T-}}b}^{'}\) = 7.0(2); for the b-axis), and K T-c  = 365(8) GPa (\(K_{{\text{T-}}c}^{'}\) = 1.5(4); for the c-axis), indicating a strong elastic anisotropy. The Zn2TiO4-CT was found as ~10.0 % denser than the Zn2TiO4-Sp at ambient conditions. The spinel and post-spinel phase assemblages for the Zn2TiO4 composition at high T have been deduced as Zn2TiO4-Sp, ZnTiO3-ilmenite + ZnO-wurtzite, ZnTiO3-ilmenite + ZnO-rock salt, ZnTiO3-perovskite + ZnO-rock salt, and Zn2TiO4-CT as P increases, which presumably implies a potential stability field for a CT-type Mg2SiO4 at very high P.

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Acknowledgments

We thank two anonymous reviewers for their constructive comments on our manuscript, and Dr T Tsuchiya for processing our paper. The high-P work was performed at GeoSoilEnviroCARS (Sector 13), Advanced Photon Source (APS), Argonne National Laboratory. GeoSoilEnviroCARS is supported by the National Science Foundation-Earth Sciences (EAR-1128799) and Department of Energy-GeoSciences (DE-FG02-94ER14466). Use of the COMPRES-GSECARS gas loading system was supported by COMPRES under NSF Cooperative Agreement EAR 11-57758 and by GSECARS through NSF Grant EAR-1128799 and DOE Grant DE-FG02-94ER14466. This research used resources of the Advanced Photon Source, a US 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. This work is financially supported by the Natural Science Foundation of China (Grant No. 41440015 and 41273072), and by the Natural Sciences and Engineering Research Council of Canada.

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  1. Key Laboratory of Orogenic Belts and Crustal Evolution, MOE, Peking University, Beijing, 100871, People’s Republic of China

    Yanyao Zhang, Xi Liu, Xinjian Bao & Fei Wang

  2. School of Earth and Space Sciences, Peking University, Beijing, 100871, People’s Republic of China

    Yanyao Zhang, Xi Liu, Xinjian Bao & Fei Wang

  3. Department of Earth Sciences, University of Western Ontario, London, ON, N6A 5B7, Canada

    Sean R. Shieh & Tianqi Xie

  4. Key Laboratory of Earth and Planetary Physics, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing, 100029, People’s Republic of China

    Zhigang Zhang

  5. Center for Advanced Radiation Sources, University of Chicago, Chicago, IL, 60439, USA

    Clemens Prescher & Vitali B. Prakapenka

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Zhang, Y., Liu, X., Shieh, S.R. et al. Spinel and post-spinel phase assemblages in Zn2TiO4: an experimental and theoretical study. Phys Chem Minerals 44, 109–123 (2017). https://doi.org/10.1007/s00269-016-0841-6

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