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Macdonald, Digby D.; Sharifi-Asl, Samin; Engelhardt, George R.; Urquidi-Macdonald, Mirna
Swedish Radiation Safety Authority, Stockholm (Sweden)2012
Swedish Radiation Safety Authority, Stockholm (Sweden)2012
AbstractAbstract
[en] This Phase II report continues to address a central issue of the KBS-2 and KBS-3 plans for the disposal of high level nuclear waste (HLNW) in Sweden; that although copper metal in pure water under anoxic conditions can exist in the thermodynamically-immune state, and hence will not corrode, the environment in the proposed repository is far from being pure water and contains species that activate copper toward corrosion. Thus, SKB recognizes that, in practical repository environments, such as that which exists at Forsmark, copper is no longer immune, because of the presence of sulphide ion, and that the metal will corrode at a rate that is controlled by the rate of transport of sulphide ion to the canister surface. This rate is estimated by SKB to be at a high of about 10 nm/year (corresponding to an average corrosion current density of 4.3x10-8A/cm2), at least for a number of canisters in the envisaged repository, resulting in a loss of copper over a 100 000 year storage period of approximately 1 mm, which is well within the 5-cm corrosion allowance of the current canister design. However, it is important to note that native copper deposits have existed for geological time (presumably, billions of years), which can only be explained if the metal has been thermodynamically more stable than any product that may form via the reaction of the metal with the environment over much of that period and it is of interest to speculate as to whether conditions within the near-field environment might be engineered to render copper thermodynamically immune and hence impossible to corrode. Such conditions would almost certainly require the absence of strongly activating species, such as sulphide ion, as well as the absence of oxygen. Nevertheless, even the assumption of immunity of copper in pure water under anoxic conditions has been recently questioned by Swedish scientists (Hultquist and Szakalos), who report that copper corrodes in oxygen-free, pure water with the release of hydrogen. While this finding is controversial, it is not at odds with thermodynamics, provided that the concentration of Cu+ and the partial pressure of hydrogen are suitably low, as we demonstrated in the Phase I report. Despite the paucity of data for the model parameters, the predicted loss of metal from a canister is predicted to vary between 1.7 nm/y and 100 nm/y, depending upon the dose rate, when averaged over a two thousand year period, with most of the loss occurring at short times, when oxic conditions prevail and when HS- is available close to the canister surface. It has known that the canister temperature will be high enough (around 100 deg C) to evaporate adjacent groundwater and, hence, the canister is expected to be in contact with steam. If this condition exists, then the canister may suffer steam corrosion. In order to assess whether this scenario is likely, it will be necessary to estimate the pressure in the repository, which is located 500m below the surface. Unfortunately, there is a lack of information about steam corrosion of pure copper in the available literature and, therefore, some experimental work needs to be done, in order to address the corrosion mechanism and rate of copper canister corrosion in the earliest time possible. Although a comprehensive and accurate set of model parameter values is not yet available, 'scoping' calculations suggests that at an initial γ-dose rate of 1 Gy/h, radiolysis is not a significant factor in determining the corrosion behavior of the canisters. This same modeling work indicates that, at an initial dose rate of 100 Gy/h, radiolysis has a significant impact on the corrosion behavior of a canister. A full and accurate assessment of water radiolysis must await the experimental acquisition of values for important model parameters. These values are scheduled to be determined in Phase III
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Mar 2012; 160 p; ISSN 2000-0456;
; Also available from: http://www.stralsakerhetsmyndigheten.se/Global/Publikat; refs., figs., tabs.

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