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Crystal structure of a high-pressure/high-temperature phase of alumina by in situ X-ray diffraction

Nature Materials volume 3, pages 389–393 (2004)Cite this article

Abstract

Alumina (α-Al2O3) has been widely used as a pressure calibrant in static high-pressure experiments1,2,3,4 and as a window material in dynamic shock-wave experiments5,6,7,8,9,10,11,12,13,14; it is also a model material in ceramic science. So understanding its high-pressure stability and physical properties is crucial for interpreting such experimental data, and for testing theoretical calculations15,16,17,18,19,20,21. Here we report an in situ X-ray diffraction study of alumina (doped with Cr3+) up to 136 GPa and 2,350 K. We observe a phase transformation that occurs above 96 GPa and at high temperatures. Rietveld full-profile refinements show that the high-pressure phase has the Rh2O3 (II) (Pbcn) structure, consistent with theoretical predictions22. This phase is structurally related to corundum, but the AlO6 polyhedra are highly distorted, with the interatomic bond lengths ranging from 1.690 to 1.847 Å at 113 GPa. Ruby luminescence spectra from Cr3+ impurities within the quenched samples under ambient conditions show significant red shifts and broadening, consistent with the different local environments of chromium atoms in the high-pressure structure inferred from diffraction. Our results suggest that the ruby pressure scale needs to be re-examined in the high-pressure phase, and that shock-wave experiments using sapphire windows need to be re-evaluated.

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Figure 1: In situ X-ray diffraction study of Al2O3 under high pressures and high temperatures.
Figure 2: Typical Rietveld full-profile refinement, performed using the GSAS program28, of the X-ray diffraction pattern collected at 113 GPa and 300 K after laser heating.
Figure 3: Interatomic bond lengths (Al–Al, Al–O and O–O bonds) of Al2O3 at 113 GPa and 300 K in the corundum, Rh2O3 (II), and orthorhombic perovskite structure model (Table 1).
Figure 4: Ruby luminescence peaks measured under ambient conditions.

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Acknowledgements

We thank the staff at the BL10XU sector of SPring-8, Japan, and at the HPCAT and GSECARS sectors of the Advanced Photon Source, Argonne National Laboratory, for help with the synchrotron facilities. We also thank G. Shen, V. Prakapenka, M. Yue, O. Yasuo and J. Shu for their assistance in the experiments, and C. Sanloup, R. Hazen, M. Somayazulu, R. Cohen, S. Merkel, Y. Fei and S. Hardy for discussions. This work was supported by the NSF (grant EAR-0217389). Work at Carnegie was supported by DOE/BES, DOE/NNSA (CDAC no. DE-FC03-03NA00144), the NSF and the W.M. Keck Foundation.

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Authors and Affiliations

  1. Geophysical Laboratory, Carnegie Institution of Washington, Washington, 20015, DC, USA

    Jung-Fu Lin, Olga Degtyareva, Przemyslaw Dera, Eugene Gregoryanz, Ho-kwang Mao & Russell J. Hemley

  2. Department of Geosciences, University of Arizona, Tucson, 85721, Arizona, USA

    Charles T. Prewitt

  3. Institute for Frontier Research on Earth Evolution, Japan Marine Science and Technology Center, Kanagawa, 237-0061, Japan

    Nagayoshi Sata

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Lin, JF., Degtyareva, O., Prewitt, C. et al. Crystal structure of a high-pressure/high-temperature phase of alumina by in situ X-ray diffraction. Nature Mater 3, 389–393 (2004). https://doi.org/10.1038/nmat1121

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