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Title: Beyond the classical kinetic model for chronic graphite oxidation by moisture in high temperature gas-cooled reactors

Abstract

Four grades of nuclear graphite with various microstructures were subjected to accelerated oxidation tests in helium with traces of moisture and hydrogen in order to evaluate the effects of chronic oxidation on graphite components in high temperature gas cooled reactors. Kinetic analysis showed that the Langmuir-Hinshelwood (LH) model cannot consistently reproduce all results. In particular, at high temperatures and water partial pressures oxidation was always faster than the LH model predicts, with stronger deviations for superfine grain graphite than for medium grain grades. It was also found empirically that the apparent reaction order for water has a sigmoid-type variation with temperature which follows the integral Boltzmann distribution function. This suggests that the apparent activation with temperature of graphite reactive sites that causes deviations from the LH model is rooted in specific structural and electronic properties of surface sites on graphite. A semi-global kinetic model was proposed, whereby the classical LH model was modified with a temperature-dependent reaction order for water. The new Boltzmann-enhanced model (BLH) was shown to consistently predict experimental oxidation rates over large ranges of temperature (800-1100 oC) and partial pressures of water (3-1200 Pa) and hydrogen (0-300 Pa), not only for the four grades of graphite butmore » also for the historic grade H-451. The BLH model offers as more reliable input for modeling the chemical environment effects during the life-time operation of new grades of graphite in advanced nuclear reactors operating at high and very high temperatures.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [4];  [4]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Univ. of Tennessee, Knoxville, TN (United States)
  3. (Jo Jo) [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. Idaho National Lab. (INL), Idaho Falls, ID (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Nuclear Energy (NE), Nuclear Reactor Technologies (NE-7)
OSTI Identifier:
1408580
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Carbon
Additional Journal Information:
Journal Volume: 127; Journal Issue: C; Journal ID: ISSN 0008-6223
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Contescu, Cristian I., Mee, Robert W., Lee, Yoonjo, Arregui-Mena, José D., Gallego, Nidia C., Burchell, Timothy D., Kane, Joshua J., and Windes, William E. Beyond the classical kinetic model for chronic graphite oxidation by moisture in high temperature gas-cooled reactors. United States: N. p., 2017. Web. doi:10.1016/j.carbon.2017.11.001.
Contescu, Cristian I., Mee, Robert W., Lee, Yoonjo, Arregui-Mena, José D., Gallego, Nidia C., Burchell, Timothy D., Kane, Joshua J., & Windes, William E. Beyond the classical kinetic model for chronic graphite oxidation by moisture in high temperature gas-cooled reactors. United States. doi:10.1016/j.carbon.2017.11.001.
Contescu, Cristian I., Mee, Robert W., Lee, Yoonjo, Arregui-Mena, José D., Gallego, Nidia C., Burchell, Timothy D., Kane, Joshua J., and Windes, William E. Fri . "Beyond the classical kinetic model for chronic graphite oxidation by moisture in high temperature gas-cooled reactors". United States. doi:10.1016/j.carbon.2017.11.001.
@article{osti_1408580,
title = {Beyond the classical kinetic model for chronic graphite oxidation by moisture in high temperature gas-cooled reactors},
author = {Contescu, Cristian I. and Mee, Robert W. and Lee, Yoonjo and Arregui-Mena, José D. and Gallego, Nidia C. and Burchell, Timothy D. and Kane, Joshua J. and Windes, William E.},
abstractNote = {Four grades of nuclear graphite with various microstructures were subjected to accelerated oxidation tests in helium with traces of moisture and hydrogen in order to evaluate the effects of chronic oxidation on graphite components in high temperature gas cooled reactors. Kinetic analysis showed that the Langmuir-Hinshelwood (LH) model cannot consistently reproduce all results. In particular, at high temperatures and water partial pressures oxidation was always faster than the LH model predicts, with stronger deviations for superfine grain graphite than for medium grain grades. It was also found empirically that the apparent reaction order for water has a sigmoid-type variation with temperature which follows the integral Boltzmann distribution function. This suggests that the apparent activation with temperature of graphite reactive sites that causes deviations from the LH model is rooted in specific structural and electronic properties of surface sites on graphite. A semi-global kinetic model was proposed, whereby the classical LH model was modified with a temperature-dependent reaction order for water. The new Boltzmann-enhanced model (BLH) was shown to consistently predict experimental oxidation rates over large ranges of temperature (800-1100 oC) and partial pressures of water (3-1200 Pa) and hydrogen (0-300 Pa), not only for the four grades of graphite but also for the historic grade H-451. The BLH model offers as more reliable input for modeling the chemical environment effects during the life-time operation of new grades of graphite in advanced nuclear reactors operating at high and very high temperatures.},
doi = {10.1016/j.carbon.2017.11.001},
journal = {Carbon},
number = C,
volume = 127,
place = {United States},
year = {Fri Nov 03 00:00:00 EDT 2017},
month = {Fri Nov 03 00:00:00 EDT 2017}
}

Journal Article:
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