In Situ Measurement of Hydrogen Absorption into Copper-Coated Titanium Using Neutron Reflectometry and Electrochemical Impedance Spectroscopy

Abstract

We set out to investigate the possibility that a small amount of hydrogen, generated by sulfide-driven corrosion or radiolytic processes, might be absorbed into the copper coating proposed for use as corrosion protection for the used nuclear fuel containers (UFCs) to be stored in a deep geological repository (DGR) in Canada. Hydrogen absorption may have the potential to alter the mechanical properties of the copper coating. This contribution discusses our initial study, using in situ neutron reflectometry (NR) and electrochemical impedance spectroscopy (EIS), of hydrogen absorption into a 50-nm layer of copper coated onto 4 nm of Ti on a Si single-crystal substrate. In situ NR-EIS experiments detected no increase in the hydrogen content within the copper layer of the copper-titanium thin film following 55 h of polarization in deoxygenated 0.1 M NaCl solution at pH 9, at potentials ranging from −444 mV/SCE to −1300 mV/SCE (detection limit ~2 at.%). However, these NR results showed that hydrogen can be absorbed into copper when the latter is cathodically polarized below about ─900 mV/SCE, which is the experimentally measured potential threshold for the hydrogen evolution reaction (HER) under these conditions. Although hydrogen did not accumulate in the outer Cu layer, our experiments revealed that the absorbed hydrogen quickly traversed the Cu layer to concentrate in the underlying titanium layer, which favours absorbed hydrogen. This observation is consistent with hydrogen uptake measured using inert gas fusion analysis on oxygen-free, phosphorus-doped (OFP) copper, which showed that in the absence of hydrogen recombination inhibitors (e.g., As(III)), only a small increase of 22 wt. ppm hydrogen was absorbed into the copper after 24 h at E = −1300 mV/SCE, and no increase in absorbed hydrogen occurred at potentials of −1100 mV/SCE or more positive. The initial absorption efficiency for electrolytically produced hydrogen atoms at the copper surface was determined to be 3.2%, suggesting that there may be an upper limit for hydrogen uptake by the copper coating of the UFC, although studies on 3 mm copper-coated steel samples representative of UFC materials will be required to confirm that. This result supports the prediction that hydrogen absorption is unlikely to lead to any failure of the copper barrier within a proposed DGR, in which it will not be possible to achieve such negative electrochemical potentials. Intended future research using in situ NR-EIS to study hydrogen absorption during the corrosion of copper thin films by HS⁻ ions and further studies on hydrogen absorption into 3-mm-thick copper-coated steel samples will help to validate these conclusions.