Understanding the Corrosion of Copper in Nitric Acid By Tuning the Solution Chemistry

Abstract

The used fuel container (UFC) is a key engineered barrier to permanently contain and isolate used nuclear fuels underground in deep geological repositories (DGR) to be implemented in Canada, Sweden and Finland.1,2 Copper is used for corrosion protection in the current design of the UFC. Within a DGR, radiolysis of humid air will result in the formation of nitric acid.3 Recent studies showed that copper corrodes faster in nitric acid when oxygen is present, which will be the case for a short period after the UFC’s emplacement.4 When the oxygen becomes depleted in a DGR, the corrosion of copper will be minimal but can be affected by corrosion products such as Cu+, Cu2+, NO2 - and NO. Previous results suggest that the presence of copper ions in the solution surrounding the copper can activate nitrate as a cathodic reagent.5 A possible mechanism is that Cu+ reacts with nitrate through its oxidation to Cu2+, which then reacts with metallic copper through its comproportionation reaction, accelerating the corrosion process.5 Yet, a precise mechanistic understanding of the role of Cu+, such as the degree to which oxidation of Cu+ occurs in solution, or if Cu+ simply acts as a catalyst for nitrate reduction or decomposition, is missing. As a result, an improved understanding of the influence of solution parameters on the corrosion mechanisms of copper in nitric acid is needed, including the presence of oxidants and Cu+-chelating species such as chloride.Herein, the interplay between the dissolved redox couples, Cu+/Cu2+ and NO3 -/NO2 - and Cl- is explored, and their effect on the corrosion of copper is studied by linear sweep voltammetry and polarization resistance and Tafel analysis. The interpretation of linear polarization resistance measurements in the presence of multivalent ions and the role of corrosion products are discussed.1 P. G. Keech, P. Vo, S. Ramamurthy, J. Chen, R. Jacklin and D. W. Shoesmith, Corrosion Engineering, Science and Technology, 49, 2014, 425-430.2 F. King, L. Ahonen, C. Taxen, U. Vuorinen and L. Werme, Copper corrosion under expected conditions in a deep geologic repository (SKB-TR--01-23), 2001. Sweden.3 R. P. Morco, J. M. Joseph, D. S. Hall, C. Medri, D. W. Shoesmith and J. C. Wren, Corrosion Engineering, Science and Technology, 52, 2017, 141-147.4 J. Turnbull, R. Szukalo, M. Behazin, D. Hall, D. Zagidulin, S. Ramamurthy, J. Wren and D. Shoesmith, Corrosion, 74, 2017, 326-336.5 J. Turnbull, R. Szukalo, D. Zagidulin, M. Biesinger and D. W. Shoesmith, Materials and Corrosion, 72, 2021, 348–360.