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Theoretical and Experimental Evidence for a Post-Cotunnite Phase Transition in Hafnia at High Pressures

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Abstract

Using first-principles density-functional theory (DFT) computations, we have predicted a new post-cotunnite (OII) phase of hafnia (HfO2) at high pressures. Our computations, using the generalized gradient approximation (GGA), predict a phase transition from OII to a Fe2P-type structure at ~ 120 GPa (~ 140 GPa) with a slight volume collapse at the transition pressure of ~ 0.2% (~ 0.1%) between the two phases using the second- (third-) order Birch-Murnaghan equation of state, respectively. The prediction of the new phase is consistent with recent experiments and computations performed on similar dioxides titania (TiO2) and zirconia (ZrO2) at extreme pressure-temperature (p-T) conditions. Importantly, our theoretical prediction for the OII → Fe2P transition in HfO2 is experimentally supported by the re-analysis of X-ray diffraction patterns of HfO2 at extreme pressure-temperature conditions. Additionally, the equation of state and hardness of the predicted phase have been computed and show that Fe2P-type phase while less compressible than the OII phase is nearly identical in hardness, indicating that none of the HfO2 phases qualify as superhard.

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Authors and Affiliations

  1. Department of Basic Sciences, Princess Sumaya University for Technology, Amman, 11941, Jordan

    Yahya Al-Khatatbeh & Khaldoun Tarawneh

  2. School of Basic Sciences and Humanities, German Jordanian University, Amman, 11180, Jordan

    Hussein Al-Taani

  3. Department of Geology and Geophysics, Yale University, New Haven, Connecticut, 06511, USA

    Kanani K. M. Lee

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  1. Yahya Al-Khatatbeh
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  2. Khaldoun Tarawneh
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  3. Hussein Al-Taani
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  4. Kanani K. M. Lee
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Correspondence to Yahya Al-Khatatbeh.

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Al-Khatatbeh, Y., Tarawneh, K., Al-Taani, H. et al. Theoretical and Experimental Evidence for a Post-Cotunnite Phase Transition in Hafnia at High Pressures. J. Superhard Mater. 40, 374–383 (2018). https://doi.org/10.3103/S1063457618060023

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