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Combined computational and experimental investigation of high temperature thermodynamics and structure of cubic ZrO₂ and HfO₂

Hong, Qi-Jun and Ushakov, Sergey V. and Kapush, Denys and Benmore, Chris J. and Weber, Richard J. K. and van de Walle, Axel and Navrotsky, Alexandra (2018) Combined computational and experimental investigation of high temperature thermodynamics and structure of cubic ZrO₂ and HfO₂. Scientific Reports, 8 . Art. No. 14962. ISSN 2045-2322. PMCID PMC6175917.

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Structure and thermodynamics of pure cubic ZrO₂ and HfO₂ were studied computationally and experimentally from their tetragonal to cubic transition temperatures (2311 and 2530 °C) to their melting points (2710 and 2800 °C). Computations were performed using automated ab initio molecular dynamics techniques. High temperature synchrotron X-ray diffraction on laser heated aerodynamically levitated samples provided experimental data on volume change during tetragonal-to-cubic phase transformation (0.55 ± 0.09% for ZrO₂ and 0.87 ± 0.08% for HfO₂), density and thermal expansion. Fusion enthalpies were measured using drop and catch calorimetry on laser heated levitated samples as 55 ± 7 kJ/mol for ZrO₂ and 61 ± 10 kJ/mol for HfO₂, compared with 54 ± 2 and 52 ± 2 kJ/mol from computation. Volumetric thermal expansion for cubic ZrO₂ and HfO₂ are similar and reach (4 ± 1)·10^(−5)/K from experiment and (5 ± 1)·10^(−5)/K from computation. An agreement with experiment renders confidence in values obtained exclusively from computation: namely heat capacity of cubic HfO₂ and ZrO₂, volume change on melting, and thermal expansion of the liquid to 3127 °C. Computed oxygen diffusion coefficients indicate that above 2400 °C pure ZrO₂ is an excellent oxygen conductor, perhaps even better than YSZ.

Item Type:Article
Related URLs:
URLURL TypeDescription CentralArticle
Hong, Qi-Jun0000-0002-5970-0605
Ushakov, Sergey V.0000-0002-8184-8884
Kapush, Denys0000-0003-3179-6163
Benmore, Chris J.0000-0001-7007-7749
Weber, Richard J. K.0000-0002-2145-1279
van de Walle, Axel0000-0002-3415-1494
Navrotsky, Alexandra0000-0002-3260-0364
Alternate Title:Combined computational and experimental investigation of high temperature thermodynamics and structure of cubic ZrO2 and HfO2
Additional Information:© 2018 The Author(s). This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit Received 08 May 2018; Accepted 11 September 2018; Published 08 October 2018. The work was supported by the National Science Foundation under Collaborative Research Awards DMR-1505657,1835939 (Brown University) and DMR-1506229, 1835848 (UC Davis) and by Brown University through the use of the facilities at its Center for Computation and Visualization. This work uses the Extreme Science and Engineering Discovery Environment (XSEDE) resource Stampede 2 at the Texas Advanced Computing Center through allocation TG-DMR050013N, which is supported by National Science Foundation grant number ACI-1548562. Use of the Advanced Photon Source (APS, beamline 6-ID-D), an Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory, was supported by the DOE under Contract No. DE-ACO2-06CH11357. The authors are grateful to Alfred Pavlik, Matthew Fyhrie and Anthony Tamalonis for the help with data collection at APS.
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Brown UniversityUNSPECIFIED
Department of Energy (DOE)DE-AC-02-06CH11357
PubMed Central ID:PMC6175917
Record Number:CaltechAUTHORS:20181023-095115434
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:90353
Deposited By: Tony Diaz
Deposited On:23 Oct 2018 19:56
Last Modified:06 Jul 2020 22:05

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