Enhanced crevice corrosion of stainless steel 316 by degradation of Cr-containing hollandite crevice former

The disposal of high-level nuclear waste (HLW) is an important societal problem. It is also an extremely challenging corrosion research topic due to the highly complicated waste chemistry, long lasting radiation effect, and inevitable exposure to aqueous environments for hundreds of thousands of years. To safely accommodate some critical radionuclides such as volatile ¹²⁹I and strongly heat generating ¹³⁷Cs, numerous crystalline ceramic waste forms have been created and studied. Among the promising nuclear waste forms, hollandite was developed to isolate Cs waste and the corresponding decay product Ba due to the open tunnel structure capable of accommodating mono- or divalent cations. In this study, the synergistic corrosion interactions between a Cr-containing hollandite (Ba_1.15Cr_2.3Ti_5.7O₁₆) and stainless steel (SS) 316 is explored. This is relevant to the permanent disposal of HLW involving the encasement of glass or crystalline ceramic waste forms containing immobilized radionuclides in a metallic canister made from corrosion resistant alloys such as SS. The experiments performed in this study simulate the potential corrosion interactions occurring at the interface of the SS and ceramic. After corroding the SS316 and Cr-containing hollandite in proximity in 0.6 M NaCl at 90 ^oC for 28 days, severe crevice corrosion was identified on the surface of the SS, as evidenced by the presence of large pits and crevice damage with diameters of hundreds of microns. Similarly, localized damage was also found at matching sites on the Cr-hollandite surface, indicating interactions between the two materials. The synergistic corrosion interaction was likely due to the continuous release of Cr³⁺ cations from both materials, including the passive dissolution of the SS and the heterogenous degradation of the Cr-hollandite. The extra Cr³⁺ cations originated from the hollandite reduces the incubation time required to reach the critical crevice solution condition, thereby accelerating the breakdown of the passive film of SS and the subsequent onset of active dissolution. An adapted crevice corrosion model is applied to quantitively explain the accelerated corrosion of SS observed in this study.