Effect of Bentonite Properties on Corrosion Behavior of Carbon Steel
Authors: Sakaeda Yuma , Katayama Hideki , Tsutsumi Yusuke , Kadowaki Mariko , Murase Yoshiharu , Watanabe Hikari , Shitanda Isao , Itagaki Masayuki 
Published: December 2024

Geological disposal is being considered as a disposal method for liquid waste resulting from nuclear power generation. In geological disposal, liquid waste and glass materials are melted together and solidified in an overpack (metal container), and a buffer material is compacted between the overpack and the bedrock. Carbon steel is as a candidate for overpack material and bentonite as a buffer materialin Japan. Overpack materials are required to be safe and reliable over a very long period, and their corrosion behavior and long-term corrosion resistance have been investigated before. However, most of these researches have been conducted in environments where oxygen is fully consumed, and the corrosion behavior and resistance during transient periods have not been fully clarified.
In this study, the effects of bentonite properties on the corrosion behavior of carbon steel in compacted bentonite were investigated by electrochemical methods in order to clarify the corrosion behavior of carbon steel during the transient period.
An iron wire grinded with sandpapers was used as the sample. The amount of bentonite was weighed to achieve the specified compacted density, and firstly approximately one-half of the amount was filled into a titanium compacted vessel. The iron wire was then set on the bentonite and the remaining bentonite was filled into the vessel using a hydraulic press. The properties of the bentonite were adjusted from 0.9 Mg/m3 to 1.8 Mg/m3 with the compaction density when packed. The titanium vessel was then immersed in a 0.1 mol/L NaCl solution and depressurized at room temperature. The solution was supplied to the cell through a filter on the side of the cell.
Polarization and electrochemical impedance measurements were performed in a three-electrode system under open air. The test solution was 0.1 mol/L NaCl solution, a saturated KCl/Ag/AgCl electrode (SSE) was used as the reference electrode, and a platinum wire as the counter electrode. Polarization measurements were conducted by polarizing in the anodic and cathodic directions from the immersion potential at a scanning rate of 0.5 mV/sec. The polarization measurements of an iron wire were also performed in the same solution for comparison. Electrochemical impedance was measured at 24 and 48 hours after immersing the titanium vessel in the test solution.
Polarization curve of iron wire in bentonite with a compressibility density of 1.5 Mg/m3 were compared with that in the solution. A clear diffusion-limiting current of oxygen was observed in the polarization curve of iron wire in the solution, whereas it was unclear for iron wire in bentonite. This result is attributed to the influence of water reduction reaction in a cathodic region. On the other hand, in the anodic region, the anodic current of iron in bentonite was about two orders of magnitude lower than that in the solution. This indicates that electrochemical measurements are possible in bentonite as well as in solution, but the influence of compacted bentonite is not small.
Electrochemical impedance characteristic of the iron wire in bentonite with a compressive density of 1.6 Mg/m3 showed one time constant after 25 hours of immersion and two time constants after 48 hours, respectively.The diameter of the capacitive semicircles decreased with immersion time. The titanium vessel immersed for 48 hours was opened and the surface of the iron wire was visually observed. As a result, corrosion products were observed. These results suggest that the test solution penetrated into the compacted bentonite after at least 25 hours, and that corrosion progressed to form corrosion products on the electrode surface by 48 hours. Curve fitting was performed on the obtained impedance spectra, assuming the two equivalent circuits. As a result, it was confirmed that the polarization resistance at the electrode surface decreases with time.