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Title: Nature of the chemical bond and prediction of radiation tolerance in pyrochlore and defect fluorite compounds

Abstract

The radiation tolerance of synthetic pyrochlore and defect fluorite compounds has been studied using ion irradiation. We show that the results can be quantified in terms of the critical temperature for amorphization, structural parameters, classical Pauling electronegativity difference, and disorder energies. Our results demonstrate that radiation tolerance is correlated with a change in the structure from pyrochlore to defect fluorite, a smaller unit cell dimension, and lower cation-anion disorder energy. Radiation tolerance is promoted by an increase in the Pauling cation-anion electronegativity difference or, in other words, an increase in the ionicity of the chemical bonds. A further analysis of the data indicates that, of the two possible cation sites in ideal pyrochlore, the smaller B-site cation appears to play the major role in bonding. This result is supported by ab initio calculations of the structure and bonding, showing a correlation between the Mulliken overlap populations of the B-site cation and the critical temperature. - Graphical abstract: Three-dimensional representation of the predicted critical amorphization temperature in pyrochlores.

Authors:
 [1];  [2];  [1];  [1];  [3];  [1];  [1];  [4];  [5]
  1. Cambridge Centre for Ceramic Immobilisation, Department of Earth Sciences, University of Cambridge, Downing Street, Cambridge CB2 3EQ (United Kingdom)
  2. (Australia), E-mail: grl@ansto.gov.au
  3. Institute of Materials and Engineering Science, Australian Nuclear Science and Technology Organisation, Private Mail Bag 1, Menai, NSW 2234 (Australia)
  4. (United Kingdom)
  5. Materials Science Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439 (United States)
Publication Date:
OSTI Identifier:
21015802
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 180; Journal Issue: 4; Other Information: DOI: 10.1016/j.jssc.2007.01.028; PII: S0022-4596(07)00061-8; Copyright (c) 2007 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CATIONS; CHEMICAL BONDS; CRITICAL TEMPERATURE; CRYSTAL DEFECTS; FLUORITE; IRRADIATION; LATTICE PARAMETERS; PYROCHLORE; RADIATION EFFECTS

Citation Formats

Lumpkin, Gregory R., Institute of Materials and Engineering Science, Australian Nuclear Science and Technology Organisation, Private Mail Bag 1, Menai, NSW 2234, Pruneda, Miguel, Rios, Susana, Smith, Katherine L., Trachenko, Kostya, Whittle, Karl R., Department of Engineering Materials, University of Sheffield, Sir Robert Hadfield Building, Mappin Street, Sheffield S1 3JD, and Zaluzec, Nestor J. Nature of the chemical bond and prediction of radiation tolerance in pyrochlore and defect fluorite compounds. United States: N. p., 2007. Web. doi:10.1016/j.jssc.2007.01.028.
Lumpkin, Gregory R., Institute of Materials and Engineering Science, Australian Nuclear Science and Technology Organisation, Private Mail Bag 1, Menai, NSW 2234, Pruneda, Miguel, Rios, Susana, Smith, Katherine L., Trachenko, Kostya, Whittle, Karl R., Department of Engineering Materials, University of Sheffield, Sir Robert Hadfield Building, Mappin Street, Sheffield S1 3JD, & Zaluzec, Nestor J. Nature of the chemical bond and prediction of radiation tolerance in pyrochlore and defect fluorite compounds. United States. doi:10.1016/j.jssc.2007.01.028.
Lumpkin, Gregory R., Institute of Materials and Engineering Science, Australian Nuclear Science and Technology Organisation, Private Mail Bag 1, Menai, NSW 2234, Pruneda, Miguel, Rios, Susana, Smith, Katherine L., Trachenko, Kostya, Whittle, Karl R., Department of Engineering Materials, University of Sheffield, Sir Robert Hadfield Building, Mappin Street, Sheffield S1 3JD, and Zaluzec, Nestor J. Sun . "Nature of the chemical bond and prediction of radiation tolerance in pyrochlore and defect fluorite compounds". United States. doi:10.1016/j.jssc.2007.01.028.
@article{osti_21015802,
title = {Nature of the chemical bond and prediction of radiation tolerance in pyrochlore and defect fluorite compounds},
author = {Lumpkin, Gregory R. and Institute of Materials and Engineering Science, Australian Nuclear Science and Technology Organisation, Private Mail Bag 1, Menai, NSW 2234 and Pruneda, Miguel and Rios, Susana and Smith, Katherine L. and Trachenko, Kostya and Whittle, Karl R. and Department of Engineering Materials, University of Sheffield, Sir Robert Hadfield Building, Mappin Street, Sheffield S1 3JD and Zaluzec, Nestor J.},
abstractNote = {The radiation tolerance of synthetic pyrochlore and defect fluorite compounds has been studied using ion irradiation. We show that the results can be quantified in terms of the critical temperature for amorphization, structural parameters, classical Pauling electronegativity difference, and disorder energies. Our results demonstrate that radiation tolerance is correlated with a change in the structure from pyrochlore to defect fluorite, a smaller unit cell dimension, and lower cation-anion disorder energy. Radiation tolerance is promoted by an increase in the Pauling cation-anion electronegativity difference or, in other words, an increase in the ionicity of the chemical bonds. A further analysis of the data indicates that, of the two possible cation sites in ideal pyrochlore, the smaller B-site cation appears to play the major role in bonding. This result is supported by ab initio calculations of the structure and bonding, showing a correlation between the Mulliken overlap populations of the B-site cation and the critical temperature. - Graphical abstract: Three-dimensional representation of the predicted critical amorphization temperature in pyrochlores.},
doi = {10.1016/j.jssc.2007.01.028},
journal = {Journal of Solid State Chemistry},
number = 4,
volume = 180,
place = {United States},
year = {Sun Apr 15 00:00:00 EDT 2007},
month = {Sun Apr 15 00:00:00 EDT 2007}
}