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AbstractAbstract
[en] Three copper electrodes have been exposed for eight years in the outer section of the Prototype Repository at Aespoe. The electrodes were installed in the upper bentonite block of deposition hole 5 in May 2003. Most of the time the temperature of the electrodes has been somewhat below 35 deg C. The electrodes were retrieved for post-test examination in September 2011. This report presents results from electrochemical measurements and the post-test examination of one of the electrodes. The corrosion potential of the examined copper electrode was -40 mV SHE (2011-02-04) when part of the concrete plug to the outer section of the repository had been removed and made measurements possible. When the back-fill in the deposition tunnel had been removed it was 25 mV SHE (2011-09-12). Finally, before letting loose the copper electrode from the retrieved bentonite block, the corrosion potential was found to be 165 mV SHE (2011-11-15) being a sign of air ingress to the electrode/ bentonite interface. It was immediately obvious from the appearance of the copper electrode, when part of the surrounding bentonite had been removed, that both Cu(I) and Cu(II) corrosion products existed on the electrode surface. X-ray diffraction measurements also verified the presence of cuprite, Cu2O, and malachite, Cu2(OH)2CO3, on the electrode; however, paratacamite, Cu2(OH)3Cl, was not found. The performed Fourier transform infrared and Raman spectroscopy confirmed these observations. The corrosion product film, of which cuprite is the main part, was quite uneven and porous. No unmistakable signs of pitting have been found. The appearance of the copper electrode reminded of the coupons from the retrieved LOT test parcels, but was different from the appearance of the surface on the full-size canisters. For the latter blue-green Cu(II) corrosion products have not or only rarely been observed from visual examination immediately after removing the surrounding bentonite. Differences that can have a marked influence on the corrosion behaviour between the exposed small samples and the big components exist. The most convincing is that lubricants were used in manufacturing of the full-size bentonite blocks and rings (so available machines could handle the required pressure); lubricants have neither been used for the copper electrodes in the Prototype Repository, nor for the copper coupons in the LOT test parcels. Based upon the performed corrosion potential measurements and the findings from the post-test examination the following scenario of exposure is envisaged: When installed the copper electrode had merely a very thin cuprite film on the surface from exposure in air. After some length of exposure a corrosion potential was reached that allowed formation of Cu(II) corrosion products. Since the chloride activity in the pore water from start of exposure was low (the bentonite had been conditioned with tap water), malachite rather than paratacamite was formed. Later on the corrosion potential has decreased, influenced by changes in the near-field environment and filming of the surface, and obtained a corrosion potential of -40 mV SHE at the time when part of the concrete plug to the outer section had been removed, which indicates a mildly oxidizing environment. Thus, it is anticipated that the copper electrode has been exposed to oxic conditions all through the exposure period
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Apr 2013; 31 p; ISSN 1402-3091;
; Also available from: http://www.skb.se/upload/publications/pdf/R-13-14.pdf; refs., figs., tabs.

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