Fe-silicate and -carbonate formations at C-steel- compacted bentonite interface hinders buffer degradation in high-level radioactive waste disposal

菊池 亮佑*; 藤村 竜也*; 佐藤 努*; 大竹 翼*; 大友 陽子*; 後藤 考裕*; 鈴木 覚*; 谷口 直樹 ; 鈴木 宏幸*

Kikuchi, Ryosuke*; Fujimura, Tatsuya*; Sato, Tsutomu*; Otake, Tsubasa*; Otomo, Yoko*; Goto, Takahiro*; Suzuki, Satoru*; Taniguchi, Naoki; Suzuki, Hiroyuki*

In this study, corrosion products in the bentonite in contact with carbon steel coupon under anaerobic artificial seawater at 80 degree for 3 years was investigated using microscopic analysis (SEM, EPMA and FIB-TEM). Corrosion products in compacted bentonite near the interface with carbon steel were identified as Ca-rich siderite, low-crystalline Fe-silicate and montmorillonite with Fe-enriched octahedral sheet. The low-crystalline Fe-silicate was estimated to be a ferrous iron-silicate-hydrate (F-S-H) with an Fe/Si composition of ~1.3 and a structural similarity to a 2:1 type clay with interlayer Na and Ca cations, not the non-swelling 7angstrom phases (greenalite, berthierine and cronstedtite) reported in the literature. The siderite and F-S-H formation were observed over a distance approximately 150 micrometers or less from the interface. The dense formation of siderite and F-S-H at the carbon steel-bentonite interface could suppress the migration of Fe in bentonite and limit the transformation of montmorillonite to 7 angstroms. Unlike previous Fe-clay studies in systems with large reaction surface areas of Fe sources, the experimental system in the present study with a smaller reaction surface area suggests that the decrease in buffer performance is suppressed. Based on thermodynamic calculation, the competition between siderite and F-S-H formation was found to be essentially governed by the pH change near the interface, but an improved database for F-S-H may be needed for more accurate predictions of its formation. The formation of porous F-S-H with large specific surface area in the bentonite interstitial should also be considered in predicting the interaction of electroactive radionuclides such as U and Se, and their migration.