Copper corrosion experiments under anoxic conditions

This report gives results from the corrosion experiments with copper under anoxic conditions. The objective was to study whether hydrogen-evolving corrosion reaction could occur. Copper foil samples were exposed in deaerated deionized water in Erlenmeyer flasks in the glove box with inert atmosphere. Four corrosion experiments (Cu1, Cu2, Cu3 and Cu4) were started, as well as a reference test standing in air. Cu1 and Cu2 had gas tight seals, whereas Cu3 and Cu4 had palladium foils as hydrogen permeable enclosure. The test vessels were stored during the experiments in a closed stainless steel vessel to protect them from the trace oxygen of the gas atmosphere and light. After the reaction time of three and a half years, there were no visible changes in the copper surfaces in any of the tests in the glove box, in contrast the Cu surfaces looked shiny and unaltered. The Cu3 test was terminated after the reaction time of 746 days. The analysis of the Pd-membrane showed the presence of H₂ in the test system. If the measured amount of 7.2·10^-5 mol H2 was the result of formation of Cu₂O this would correspond to a 200 nm thick corrosion layer. This was not in agreement with the measured layer thickness with SIMS, which was 6 ± 1 nm. A clear weight loss observed for the Cu3 test vessel throughout the test period suggests the evaporation of water through the epoxy sealing to the closed steel vessel. If this occurred, the anaerobic corrosion of steel surface in humid oxygen-free atmosphere could be a source of hydrogen. A similar weight loss was not observed for the parallel test (Cu4). The reference test standing in air showed visible development of corrosion products.