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

Abstract

Structure and thermodynamics of pure cubic ZrO₂ and HfO₂ were studied computationally and experimentally from their tetragonal to cubic transition temperatures (2311 and 2530 degrees C) to their melting points (2710 and 2800 degrees 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. Finally, 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 degrees C. Computed oxygen diffusion coefficients indicate that above 2400 degrees C pure ZrO₂ is an excellent oxygen conductor, perhaps even better thanmore » YSZ.« less

Authors:

Hong, Qi-Jun  ^[1];

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• Search DOE PAGES for ORCID "0000-0002-5970-0605"

Ushakov, Sergey V.  ^[2];

• Search DOE PAGES for author "Ushakov, Sergey V."
• Search DOE PAGES for ORCID "0000-0002-8184-8884"

Kapush, Denys  ^[2];

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• Search DOE PAGES for ORCID "0000-0003-3179-6163"

Benmore, Chris J.  ^[3];

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• Search DOE PAGES for ORCID "0000-0001-7007-7749"

Weber, Richard J. K.  ^[4];

• Search DOE PAGES for author "Weber, Richard J. K."
• Search DOE PAGES for ORCID "0000-0002-2145-1279"

van de Walle, Axel  ^[5];

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• Search DOE PAGES for ORCID "0000-0002-3415-1494"

Navrotsky, Alexandra  ^[2]

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• Search DOE PAGES for ORCID "0000-0002-3260-0364"

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+ Show Author Affiliations

1. Brown Univ., Providence, RI (United States). School of
2. Univ. of California, Davis, CA (United States). Peter A. Rock Thermochemistry Lab. and NEAT ORU
3. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS), X-Ray Science Division
4. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS), X-Ray Science Division; Materials Development, Inc., Arlington Heights, IL (United States)
5. Brown Univ., Providence, RI (United States). School of Engineering

Publication Date:

Mon Oct 08 00:00:00 EDT 2018

Research Org.:

Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:

National Science Foundation (NSF); Brown University; USDOE Office of Science (SC)

OSTI Identifier:

1480864

Grant/Contract Number:  

AC02-06CH11357

Resource Type:

Accepted Manuscript

Journal Name:

Scientific Reports

Additional Journal Information:

Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 2045-2322

Publisher:

Nature Publishing Group

Country of Publication:

United States

Language:

English

Subject:

97 MATHEMATICS AND COMPUTING; 36 MATERIALS SCIENCE