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Title: Phase transformations in oxides above 2000°C: experimental technique development

Abstract

Here, the oxidation of boride and carbide-based ultra-high-temperature ceramics is the primary limiting factor for their use as aerodynamic surfaces. Understanding the behaviour of the oxides that can result from oxidation of metal borides and carbides at very high temperatures is essential to optimise and tailor the performance of these materials; yet experimental thermodynamic and structural data for refractory oxides above 2000°C are mostly absent. The following techniques that can be applied to fill this gap are discussed: (i) commercial ultra-high-temperature differential thermal analysis for investigation of phase transformations and melting in inert environments to 2500°C, (ii) a combination of laser heating with a splittable nozzle aerodynamic levitator for splat quenching and drop calorimetry from temperatures limited only by sample evaporation, (iii) synchrotron X-ray and neutron diffraction on laser-heated aerodynamically levitated oxide samples for in situ observation of phase transformations in variable atmospheres, refinement of high-temperature structures and thermal expansion. Recent experimental findings include anomalous thermal expansion of the defect fluorite phase of YSZ, thermodynamics of pyrochlore–fluorite transformation from high-temperature structure refinements, and measurement of thermal expansion to the melting temperatures and fusion enthalpies of Zr, Hf, La, Yb and Lu oxides. These methods provide temperatures, enthalpies and volume changemore » for phase transformations above 2000°C, which are required for thermodynamic assessments and calculation of phase diagrams of multicomponent systems.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [4]; ORCiD logo [1]
  1. Univ. of California, Davis, CA (United States)
  2. Argonne National Lab. (ANL), Lemont, IL (United States)
  3. Argonne National Lab. (ANL), Lemont, IL (United States); Materials Development Inc., Arlington Heights, IL (United States)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1492158
Alternate Identifier(s):
OSTI ID: 1496229
Grant/Contract Number:  
AC05-00OR22725; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Advances in Applied Ceramics
Additional Journal Information:
Journal Volume: 117; Journal Issue: sup1; Journal ID: ISSN 1743-6753
Publisher:
Taylor & Francis
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; thermal analysis; X-ray diffraction; oxides; phase diagrams; calorimetry; neutron diffraction; thermal expansion

Citation Formats

Ushakov, Sergey V., Maram, Pardha S., Kapush, Denys, Pavlik, III, Alfred J., Fyhrie, Matthew, Gallington, Leighanne C., Benmore, Chris J., Weber, Richard, Neuefeind, Joerg C., McMurray, Jake W., and Navrotsky, Alexandra. Phase transformations in oxides above 2000°C: experimental technique development. United States: N. p., 2018. Web. doi:10.1080/17436753.2018.1516267.
Ushakov, Sergey V., Maram, Pardha S., Kapush, Denys, Pavlik, III, Alfred J., Fyhrie, Matthew, Gallington, Leighanne C., Benmore, Chris J., Weber, Richard, Neuefeind, Joerg C., McMurray, Jake W., & Navrotsky, Alexandra. Phase transformations in oxides above 2000°C: experimental technique development. United States. doi:10.1080/17436753.2018.1516267.
Ushakov, Sergey V., Maram, Pardha S., Kapush, Denys, Pavlik, III, Alfred J., Fyhrie, Matthew, Gallington, Leighanne C., Benmore, Chris J., Weber, Richard, Neuefeind, Joerg C., McMurray, Jake W., and Navrotsky, Alexandra. Mon . "Phase transformations in oxides above 2000°C: experimental technique development". United States. doi:10.1080/17436753.2018.1516267. https://www.osti.gov/servlets/purl/1492158.
@article{osti_1492158,
title = {Phase transformations in oxides above 2000°C: experimental technique development},
author = {Ushakov, Sergey V. and Maram, Pardha S. and Kapush, Denys and Pavlik, III, Alfred J. and Fyhrie, Matthew and Gallington, Leighanne C. and Benmore, Chris J. and Weber, Richard and Neuefeind, Joerg C. and McMurray, Jake W. and Navrotsky, Alexandra},
abstractNote = {Here, the oxidation of boride and carbide-based ultra-high-temperature ceramics is the primary limiting factor for their use as aerodynamic surfaces. Understanding the behaviour of the oxides that can result from oxidation of metal borides and carbides at very high temperatures is essential to optimise and tailor the performance of these materials; yet experimental thermodynamic and structural data for refractory oxides above 2000°C are mostly absent. The following techniques that can be applied to fill this gap are discussed: (i) commercial ultra-high-temperature differential thermal analysis for investigation of phase transformations and melting in inert environments to 2500°C, (ii) a combination of laser heating with a splittable nozzle aerodynamic levitator for splat quenching and drop calorimetry from temperatures limited only by sample evaporation, (iii) synchrotron X-ray and neutron diffraction on laser-heated aerodynamically levitated oxide samples for in situ observation of phase transformations in variable atmospheres, refinement of high-temperature structures and thermal expansion. Recent experimental findings include anomalous thermal expansion of the defect fluorite phase of YSZ, thermodynamics of pyrochlore–fluorite transformation from high-temperature structure refinements, and measurement of thermal expansion to the melting temperatures and fusion enthalpies of Zr, Hf, La, Yb and Lu oxides. These methods provide temperatures, enthalpies and volume change for phase transformations above 2000°C, which are required for thermodynamic assessments and calculation of phase diagrams of multicomponent systems.},
doi = {10.1080/17436753.2018.1516267},
journal = {Advances in Applied Ceramics},
number = sup1,
volume = 117,
place = {United States},
year = {2018},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Figures / Tables:

Figure 1 Figure 1: DTA of melting and crystallisation of Y2O3 and instrument schematics. Experiments performed in Ar flow at 10°C/min heating and cooling rates on 87.34 mg Y2O3, laser melted and sealed in W crucible. No corrections or baseline subtractions applied. Cooling and heating segments were recorded with different sensors –more » note the difference between sample thermocouple and pyrometer readings as a function of temperature and between two sensors.« less

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.