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  4. Energetics of halogen impurities in thorium dioxide
 
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Energetics of halogen impurities in thorium dioxide
File(s)
1-s2.0-S0022311517305731-main.pdf (2.31 MB)
Published version
OA Location
https://doi.org/10.1016/j.jnucmat.2017.08.023
Author(s)
Kuganathan, N
Ghosh, PS
Arya, AK
Dey, GK
Grimes, RW
Type
Journal Article
Abstract
Defect energies for halogen impurity atoms (Cl, Br and I) in thoria are calculated using the generalized gradient approximation and projector augmented plane wave potentials under the framework of density functional theory. The energy to place a halogen atom at a pre-existing lattice site is the incorporation energy. Seven sites are considered: octahedral interstitial, O vacancy, Th vacancy, Th-O di-vacancy cluster (DV) and the three O-Th-O tri-vacancy cluster (NTV) configurations. For point defects and vacancy clusters, neutral and all possible defect charge states up to full formal charge are considered. The most favourable incorporation site for Cl is the singly charged positive oxygen vacancy while for Br and I it is the NTV1 cluster. By considering the energy to form the defect sites, solution energies are generated. These show that in both ThO 2-x and ThO 2 the most favourable solution equilibrium site for halides is the single positively charged oxygen vacancy (although in ThO 2 , I demonstrates the same solubility in the NTV1 and DV clusters). Solution energies are much lower in ThO 2-x than in ThO 2 indicating that stoichiometry is a significant factor in determining solubility. In ThO 2 , all three halogens are highly insoluble and in ThO 2-x Br and I remain insoluble. Although ½Cl 2 is soluble in ThO 2-x alternative phases such as ZrCl 4 exist which are of lower energy.
Date Issued
2017-08-17
Date Acceptance
2017-08-14
Citation
Journal of Nuclear Materials, 2017, 495, pp.192-201
URI
http://hdl.handle.net/10044/1/53631
DOI
https://www.dx.doi.org/10.1016/j.jnucmat.2017.08.023
ISSN
0022-3115
Publisher
Elsevier
Start Page
192
End Page
201
Journal / Book Title
Journal of Nuclear Materials
Volume
495
Copyright Statement
© 2017 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/
).
Sponsor
Engineering & Physical Science Research Council (EPSRC)
Grant Number
EP/K00817X/1
Subjects
Science & Technology
Technology
Materials Science, Multidisciplinary
Nuclear Science & Technology
Materials Science
Thoria
DFT
Defects
Halogen
Nuclear fuel
AUGMENTED-WAVE METHOD
FISSION-PRODUCTS
URANIUM-DIOXIDE
THERMAL-DIFFUSION
NUCLEAR-FUEL
IODINE
ENERGY
UO2
APPROXIMATION
XE
0912 Materials Engineering
Energy
Publication Status
Published online
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