Rights statement: This is the author’s version of a work that was accepted for publication in Journal of Nuclear Materials. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Journal of Nuclear Materials, 464, 2016 DOI: 10.1016/j.jnucmat.2015.04.007
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Research output: Contribution to Journal/Magazine › Journal article › peer-review
Research output: Contribution to Journal/Magazine › Journal article › peer-review
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TY - JOUR
T1 - The effect of hydrogen peroxide on uranium oxide films on 316L stainless steel
AU - Wilbraham, Richard
AU - Boxall, Colin
AU - Goddard, David T.
AU - Taylor, Robin J.
AU - Woodbury, Simon E.
N1 - This is the author’s version of a work that was accepted for publication in Journal of Nuclear Materials. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Journal of Nuclear Materials, 464, 2016 DOI: 10.1016/j.jnucmat.2015.04.007
PY - 2015/9
Y1 - 2015/9
N2 - For the first time the effect of hydrogen peroxide on the dissolution of electrodeposited uranium oxide films on 316L stainless steel planchets (acting as simulant uranium-contaminated metal surfaces) has been studied. Analysis of the H2O2-mediated film dissolution processes via open circuit potentiometry, alpha counting and SEM/EDX imaging has shown that in near-neutral solutions of pH 6.1 and at [H2O2] 0.1 mol dm(-3) the uranium oxide film, again in analogy to common corrosion processes, behaves as if in a transpassive state and begins to dissolve.This transition from passive to transpassive behaviour in the effect of peroxide concentration on UO2 films has not hitherto been observed or explored, either in terms of corrosion processes or otherwise. Through consideration of thermodynamic solubility product and complex formation constant data, we attribute the transition to the formation of soluble uranyl-peroxide complexes under mildly alkaline, high [H2O2] conditions - a conclusion that has implications for the design of both acid minimal, metal ion oxidant-free decontamination strategies with low secondary waste arisings, and single step processes for spent nuclear fuel dissolution such as the Carbonate-based Oxidative Leaching (COL) process. (C) 2015 Elsevier B.V. All rights reserved.
AB - For the first time the effect of hydrogen peroxide on the dissolution of electrodeposited uranium oxide films on 316L stainless steel planchets (acting as simulant uranium-contaminated metal surfaces) has been studied. Analysis of the H2O2-mediated film dissolution processes via open circuit potentiometry, alpha counting and SEM/EDX imaging has shown that in near-neutral solutions of pH 6.1 and at [H2O2] 0.1 mol dm(-3) the uranium oxide film, again in analogy to common corrosion processes, behaves as if in a transpassive state and begins to dissolve.This transition from passive to transpassive behaviour in the effect of peroxide concentration on UO2 films has not hitherto been observed or explored, either in terms of corrosion processes or otherwise. Through consideration of thermodynamic solubility product and complex formation constant data, we attribute the transition to the formation of soluble uranyl-peroxide complexes under mildly alkaline, high [H2O2] conditions - a conclusion that has implications for the design of both acid minimal, metal ion oxidant-free decontamination strategies with low secondary waste arisings, and single step processes for spent nuclear fuel dissolution such as the Carbonate-based Oxidative Leaching (COL) process. (C) 2015 Elsevier B.V. All rights reserved.
KW - CHEMICAL DECONTAMINATION PROCESS
KW - OXIDATIVE DISSOLUTION
KW - NUCLEAR-FUEL
KW - ELECTROCHEMICAL REDUCTION
KW - SURFACE ELECTROCHEMISTRY
KW - ANODIC-DISSOLUTION
KW - AQUEOUS CORROSION
KW - PART II
KW - UO2
KW - DIOXIDE
U2 - 10.1016/j.jnucmat.2015.04.007
DO - 10.1016/j.jnucmat.2015.04.007
M3 - Journal article
VL - 464
SP - 86
EP - 96
JO - Journal of Nuclear Materials
JF - Journal of Nuclear Materials
SN - 0022-3115
ER -