Corrosion of carbon steel in compacted bentonite and its effect on neptunium diffusion under reducing condition

Abstract

The corrosion of carbon steel and its effect on neptunium diffusion were studied by corrosion tests of carbon steel and neptunium diffusion tests under conditions designed with consideration of constituents of a repository for High-level Radioactive Waste disposal. The major constituents of the conditions were carbon steel, corrosion products pre-formed under aerobic conditions, compacted bentonite, reductant and a low-oxygen glove box. The corrosion tests were performed in the presence of water-saturated compacted bentonite. The neptunium diffusion tests were performed with and without carbon steel. The carbon steel and the bentonite were observed by taking photographs and analyzed by X-ray diffraction. The color of the corroded surface of the carbon steel changed from red/orange/black under aerobic conditions to a dark-green under reducing conditions. Portions of the bentonite changed their original color, pale-gray, to a brownish color after the test. Gas-induced cracks were also observed in some bentonite specimens. These changes were discussed combining thermodynamic predictions under the present experimental conditions. The results revealed that anaerobic corrosion of carbon steel occurred in the bentonite. The corrosion processes were also discussed. The corrosion rate of carbon steel was estimated to be ∼0.1 μm/year from iron profiles in the bentonite. This value was much lower than the conservative setting value 20 μm/year in the current performance assessment. The significant restriction in corrosion could be attributed to the presence of bentonite and corrosion products. Oxidation states of neptunium in the bentonite were investigated by thenoyltrifluoroacetone in xylene extraction technique. It was found that tetravalent neptunium accounted for 99% of the total neptunium in the presence of carbon steel and only 63% without. The results revealed that anaerobic corrosion of carbon steel could maintain strong reducing conditions to keep most tetravalent neptunium from being oxidized to pentavalent neptunium, thus effectively restraining migration of neptunium in the bentonite. The apparent diffusions were estimated to be in the order of 10 −15–10 −14 m 2/s for tetravalent neptunium and 10 −13–10 −12 m 2/s for the pentavalent. No significant effect of the corrosion products on neptunium sorption was found through comparing the apparent diffusion coefficients obtained in the diffusion with and without carbon steel. Corrosion of carbon steel under conditions relevant to the repository is essential for further studies, providing a confident and defensible value of corrosion rate for repository design. The effects of corrosion on radionuclide migration, especially redox-sensitive radionuclides in the buffer, should be considered for a reliable safety assessment of geological disposal.