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One of the key requirements for the deep geological disposal of high-level nuclear waste is the assessment of its long-term performance and safety. As any other barrier of the disposal system, waste containers must fulfil their respective safety functions for the required duration, which can vary from a few hundreds of years to several hundreds of thousands of years, depending on disposal system requirements. Sufficient corrosion resistance under repository conditions is one key requirement for container material to provide complete waste containment. Copper is an important part of many waste packaging and disposal concepts, e.g. KBS-3 developed in Sweden and Finland and Mark II developed in Canada. Much of the data available regarding its behaviour under repository conditions comes from short-term investigations, such as laboratory experiments at different scales and under controlled conditions. Observations made from copper analogue studies provide additional information on copper behaviour during the assessment time scale and under real geological environments. By this, they can support the argumentation in the safety case.Keweenaw native copper occurrences (Lake Superior, US) reflects more than one billion years of deposit evolution covering various geological (from bedrock to sediments and even anthropogenic mine site remnants) and geochemical environments (e.g., brines to meteoric water, anoxic vs. oxic, sulphur-free vs. sulphur-bearing). These deposits have been mined for a long time and there is a great deal of knowledge related to them as well as samples collected. However, data to be used in process based safety assessments for geological disposal is lacking and no formal review has been made from the geological disposal point of view. The current MICA Project Phase I systematically collect and review the existing literature and data on the Michigan copper analogue sites and available sampling potential. Based on the outcome, MICA Project Phase II will then study and analyse prospective sites and samples to address relevant questions regarding long-term behaviour of copper under disposal conditions. The MICA Project thus will provide a unique complementary data source to estimate processes governing behaviour of metallic copper and to support safety cases.

The internationally accepted plan for nuclear fuel waste disposal is to store used nuclear fuels within a multi barrier system in a deep geological repository (DGR). Similarly, the DGR concept proposed in Canada involves isolating the used nuclear fuel in copper-coated carbon steel vessels surrounded by bentonite clay buffer boxes and gapfill material. The repository environment is anticipated to evolve from early oxic conditions to later anoxic conditions. Likewise, degradation processes of the UFCs should transition from the initial oxygen-driven processes to those governed by the availability of sulfide as oxidant. This transition may involve the conversion of accumulated (hydr)oxide-type corrosion products produced during the oxic phase to copper sulfide compounds. During this conversion, sulfide species could interact with the UFC surface in several ways depending on the type of (hydr)oxide corrosion products present, the nature and concentration of sulfide species, and other factors: Chemical conversion: in this process substitution reactions replace oxy-anions in the corrosion product layers with sulfide anions. This conversion doesn’t involve redox reactions; therefore, until the conversion is complete, the sulfide species would not drive further corrosion of the Cu surface. Over time, the (hydr)oxide corrosion product layer would be replaced by a sulfide layer. Galvanically-coupled process: in this process sulfides react with Cu metal exposed at the base of pores or cracks in the accumulated corrosion product layer, causing the Cu in those locations to oxidize and copper sulfide to form, while simultaneously expelling oxy-anions and causing cupric or cuprous ions to be reduced elsewhere in the corrosion product layer. Although the conservation of charge in these reactions would mean that no net oxidation of the surface would occur, the spatial separation of the sites where copper is oxidized (on the metal surface) and the locations where reduction occurs (in/on the corrosion product layer) would result in further damage to the Cu layer on the UFC surface, possibly localized at the sites where Cu metal is exposed. Eventually the (hydr)oxide corrosion product layer would be replaced by a sulfide layer and any localization should cease. Direct corrosion: in this process, sulfide species react with the Cu exposed at the base of pores or cracks in the accumulated corrosion product layer, causing further corrosion at these locations without the existing (hydr)oxide species being converted (i.e. process a) or galvanically reduced (i.e. process b). These sulfide species would drive further corrosion of the UFC surface, possibly localized at the sites where Cu metal is exposed. Since this process would not contribute to the removal of the (hydr)oxide corrosion product layer, it is possible that localization, if present, could continue. The research work reported here uses electrochemical and surface characterization methods to evaluate the extent to which each of these possible conversion processes take place, and the timescale/rate of conversion of (hydr)oxide layers grown in different ways. Results so far indicate a fairly rapid and quantitative conversion of oxides according to processes a) and/or b), followed by direct corrosion of the Cu surface by sulfide.

One of the key requirements for the deep geological disposal of high-level nuclear waste is the assessment of its long-term performance and safety (up to 1 Ma). Regarding engineered barrier system materials, such as copper, much of the data available comes from short-term investigations, such as laboratory experiments at different scales. Copper is an important part of many waste packaging and disposal concepts, e.g. KBS-3 developed in Sweden and Finland and Mark II developed in Canada. Natural analogues provide another important way of obtaining understanding on potential repository system behavior. Observations made from the geological systems can be utilized in the safety case, providing information on the assessment time scale. Copper analogue studies (both natural analogues and archaeological analogues) have been reported in the literature and they have been extensively reviewed by various authors (e.g. Miller et al., 2000) and by safety case projects (e.g. Reijonen et al., 2015) within waste management organizations. So far, only a few studies have focussed on the general stability of native copper within its natural media (e.g. Milodowski et al., 2000; Marcos, 2002). Keweenaw native copper occurrences (Lake Superior, USA) have been mentioned as a qualitative source of information (e.g. in Miller et al., 2000); however, data to be used in process-based safety assessments for geological disposal are lacking. These deposits have been mined for a long time and there is a great deal of knowledge related to them as well as samples collected, but no formal review has been made from the geological disposal point of view. The native copper at the Keweenaw area reflects various geological environments from bedrock to sediment and even anthropogenic mine site remnants and geochemical environments (e.g., anoxic vs. oxic, sulphur-free vs. sulphur-bearing). It thus provides a unique complementary data source that will be useful for estimating processes governing behavior of metallic copper. The MICA project phase I systematically collects and reviews the existing literature and data on the Michigan copper analogue sites and available sampling potential. Here, we present the current status of the project.

Copper is considered to react to a very limited extent with oxygen-free water but detection of hydrogen in amounts beyond those predicted by thermodynamic calculations has been reported. It is thus of importance to explore the influence of different factors on the behavior of copper in deoxygenated aqueous solutions. In the present work, we focus on the role of the surface film and associated cuprous species. Electrochemical impedance measurements, in-situ detection of free soluble cupric ion and dissolved hydrogen are employed. The obtained results are quantitatively described by a kinetic model, its main feature being the formation of a CuOH intermediate at the cuprous oxide film/electrolyte interface both by oxidation of Cu and reduction of free soluble Cu2+. This intermediate is assumed to play a pivotal role in a sequential surface reaction generating hydrogen gas by reduction of water. The model is successfully parameterized using regression of the model equations to in-situ experimental data, and conclusions on the effect of oxide films are reached based on the evolution of kinetic parameters with time and temperature.

The long-term anaerobic corrosion rate of copper canisters in a KBS-3 repository is calculated on the basis of sulphide-transport control. The nature of the anodic and cathodic rate-determining ste...

MiniCan is a field test designed to highlight certain aspects of corrosion in a KBS-3 type repository for spent nuclear fuel. Five experimental packages containing miniature copper-cast iron canist...

This paper presents a state-of-the-art analysis of the expected degradation processes of a variety of candidate container materials for the disposal of high-level waste and/or spent nuclear fuel. The work, focusing on the most recent developments, has been performed under the auspices of the Implementing Geological Disposal Technology Platform in the context of an international conference hosted by the Nuclear Waste Management Organisation of Canada (NWMO). The scope of the analysis includes the expected corrosion and environmentally assisted cracking behaviour of copper, carbon steel and titanium in contact with relevant buffer materials (e.g. bentonite, cement) and in conditions expected in an underground disposal facility (long-term anoxic conditions). Considerations relative to the expected evolution of the environmental conditions (especially in the period following backfilling) are also presented. Beyond summarising the current state of knowledge, areas in which opportunities for international collaboration may be present are also highlighted. This paper is part of a supplement on the 6th International Workshop on Long-Term Prediction of Corrosion Damage in Nuclear Waste Systems.

Interaction of copper with deoxygenated solutions is key to quantify corrosion during long-term exposure in a final high-level nuclear waste repository. To evaluate the effect of ionic strength on such interaction, electrochemical measurements in 0.001 - 0.1 mol dm-3 NaClO4 were performed at 22, 50 and 70 °C. An extended model including a homogeneous reaction is proposed to account for the extra features in impedance spectra, and the effect of perchlorate concentration (i. e. ionic strength) on its kinetic parameters is discussed. Using the model predictions, the rates of hydrogen production in pure water are estimated and compared to literature data.

In some countries, spent nuclear fuel is planned to be encapsulated in canisters with a copper shell for corrosion protection, for further disposal in geologic repositories. The possibilities for corrosion after oxygen depletion must be evaluated, even if copper is considered to be immune in oxygen-free water. To follow the interaction of copper with deoxygenated aqueous solution, open-circuit potentiometric and electrochemical impedance measurements have been coupled to in-situ detection of cupric ion, dissolved molecular hydrogen and oxygen concentrations using electrochemical sensors. A kinetic model that considers the production of hydrogen as a catalytic process, the rate of which is proportional to the surface coverage of an intermediate species formed during interaction between copper and the solution is used to interpret the results. Kinetic parameters are estimated by a simultaneous fit of the experimental impedance spectra, the open circuit potential and cupric ion concentration as depending on temperature (22–70 °C) and exposure time (up to 720 h) to the model equations. Using the obtained values and a balance equation of hydrogen production on copper and its diffusion out of the cell through its walls, the kinetic parameters of this process are estimated by fitting dissolved molecular hydrogen concentration vs. time data at the three temperatures.

The formation of sulfide and oxide films on copper has been studied in sulfide solutions containing chloride and buffered to pH = 9 with borate over the temperature range 20 °C to 80 °C. The primary goal was to investigate the susceptibility of copper to pitting corrosion over a range of temperatures expected in a deep geological repository. Films were formed electrochemically and characterized using scanning electron microscopy (SEM), energy dispersive X-ray and Raman spectroscopy and X-ray diffractometry (XRD). Chalcocite (Cu2S) formation was observed to occur under partially transport-controlled conditions in the potential range −0.9 V to −0.3 V vs SCE. At less negative potentials (≥ −0.3 V vs SCE), a transition from active dissolution to partial passivation by a copper oxide film was observed. Temperature had only a minor effect on the formation of the sulfide film, but the onset of active dissolution and oxide film formation shifted to lower potentials as the temperature increased.

Copper canisters in a KBS-3-type underground repository will be subject to general corrosion and minor localised attack. The form of the localised corrosion will depend on the composition of the bentonite pore water in contact with the canister surface and, in particular, the pH and chloride, sulphate, and bicarbonate ion concentrations. The presence of a passive Cu2O/Cu(OH)2 layer is a pre-requisite for film breakdown and pitting. Literature pitting data have been used to determine whether pitting is possible or whether the environmental conditions will favour active dissolution of the canister. It is concluded that the canister surface will corrode generally and will be subject to only minor localised corrosion in the form of surface roughening.

The evolution of open-circuit potential, soluble copper concentration and impedance during immersion of Cu in deoxygenated neutral borate buffer containing 0.01–1.0 mol l−1 NaCl was monitored for up to 3000 h. The open-circuit potential was found to be close to the CuCl2-/Cu equilibrium potential. No corrosion layer was detected by voltammetric scans and the soluble copper concentration reached a steady state. Experimental data were quantitatively interpreted by a kinetic model featuring CuOH and CuCl intermediates. The process through which the system reached steady state is tentatively related to a reaction that could lead to hydrogen evolution.

Copper has been proposed as a canister material for the disposal of spent nuclear fuel in a deep geologic repository in a number of countries worldwide. Since it was first proposed for this purpose in 1978, a significant number of studies have been performed to assess the corrosion performance of copper under repository conditions. These studies are critically reviewed and the suitability of copper as a canister material for nuclear waste is re-assessed. Over the past 30–35 years there has been considerable progress in our understanding of the expected corrosion behaviour of copper canisters. Crucial to this progress has been the improvement in the understanding of the nature of the repository environment and how it will evolve over time. With this improved understanding, it has been possible to predict the evolution of the corrosion behaviour from the initial period of warm, aerobic conditions in the repository to the long-term phase of cool, anoxic conditions dominated by the presence of sulphide. An historical review of the treatment of the corrosion behaviour of copper canisters is presented, from the initial corrosion assessment in 1978, through a major review of the corrosion behaviour in 2001, through to the current level of understanding based on the results of on-going studies. Compared with the initial corrosion assessment, there has been considerable progress in the treatment of localised corrosion, stress corrosion cracking, and microbiologically influenced corrosion of the canisters. Progress in the mechanistic modelling of the evolution of the corrosion behaviour of the canister is also reviewed, as is the continuing debate about the thermodynamic stability of copper in pure water. The overall conclusion of this critical review is that copper is a suitable material for the disposal of spent nuclear fuel and offers the prospect of containment of the waste for an extended period of time.

Segregated impurities at grain boundaries can dramatically change the mechanical behavior of metals, while the mechanism is still obscure in some cases. Here, we suggest an unified approach to investigate segregation and its effects on the mechanical properties of polycrystalline alloys using the example of 3$sp$ impurities (Mg, Al, Si, P, or S) at a special type $\Sigma 5(310)[001]$ tilt grain boundary in Cu. We show that for these impurities segregating to the grain boundary the strain contribution to the work of grain boundary decohesion is small and that the chemical contribution correlates with the electronegativity difference between Cu and the impurity. The strain contribution to the work of dislocation emission is calculated to be negative, while the chemical contribution to be always positive. Both the strain and chemical contributions to the work of dislocation emission generally become weaker with the increasing electronegativity from Mg to S. By combining these contributions together we find, in agreement with experimental observations, that a strong segregation of S can reduce the work of grain boundary separation below the work of dislocation emission, thus embrittling Cu, while such an embrittlement cannot be produced by a P segregation because it lowers the energy barrier for dislocation emission relatively more than for work separation.

New important applications of copper metal, e.g., in the areas of hydrogen production, fuel cell operation, and spent nuclear fuel disposal, require accurate knowledge of the physical and chemical properties of stable and metastable copper compounds. Among the copper(I) compounds with oxygen and hydrogen, cuprous oxide Cu 2 O is the only one stable and the best studied. Other such compounds are less known (CuH) or totally unknown (CuOH) due to their instability relative to the oxide. Here we combine quantum-mechanical calculations with experimental studies to search for possible compounds of monovalent copper. Cuprous hydride (CuH) and cuprous hydroxide (CuOH) are proved to exist in solid form. We establish the chemical and physical properties of these compounds, thereby filling the existing gaps in our understanding of hydrogen- and oxygen-related phenomena in Cu metal.

The Swedish Nuclear Fuel and Waste Management Company has developed a method for safely disposing spent nuclear fuel, which involves encapsulation of the waste in copper canisters and burying it deep in the stable crystalline rock of the Fenno-Scandian shield. The design life of the canisters in the so called KBS-3 design is in excess of 100 000 years. These long canister lifetimes are a consequence of a number of factors involving the properties of the material and the nature of the near field environment in the KBS-3 repository. One of these factors, namely the thermodynamic stability of copper in O2 free water in the absence of sulphide, has been questioned. This paper critically reviews the evidence for and against the claim that water oxidises copper, and discusses the implications for canister lifetimes even if the proposed mechanism is correct. Even though the evidence presented in support of the proposed mechanism is not compelling, the Swedish Nuclear Fuel and Waste Management Company is ...

To ensure the safe disposal of spent fuel in Sweden, SKB is planning to use the copper–iron canister in a granitic deep geological repository, surrounded by a compacted bentonite engineered barrier. In order to develop a deeper understanding of the internal corrosion behaviour of the design should a leak occur in the outer copper canister, a set of model canisters was set up in the Aspo underground laboratory in contact with bentonite with a range of densities. The environmental conditions and electrochemical corrosion behaviour were monitored using a range of techniques. Water analysis and electrochemical measurements indicated an increase in the corrosion rate of both iron and copper in contact with low density bentonite, and of iron only in experiments with no bentonite present. This behaviour may be attributable to microbial activity. The measured corrosion rate depends on the technique used and it will be necessary to confirm the measurements by removal and examination of weight loss coupons.

The electrochemical behaviour of Cu exposed to deoxygenated borate buffer for 330 h was characterised by chronopotentiometry, voltammetry, electrochemical impedance spectroscopy and cupric ion-selective electrode measurements. The results were interpreted by a quantitative kinetic model of the copper/electrolyte interface featuring two adsorbed intermediates produced by interaction of Cu with adsorbed water and electrochemical reduction of soluble divalent copper. The model reproduces successfully both the current vs. potential curve and the electrochemical impedance spectra around the open-circuit potential. On the basis of the experimental and calculation results, tentative conclusions for the interplay between hydrogen generation and copper corrosion are drawn.

Hydrogen gas has been detected in a closed system containing copper and pure anoxic water [P. Szakalos, G. Hultquist, and G. Wikmark, Electrochem. Solid-State Lett.10, C63 (2007)10.1149/1.2772085 and G. Hultquist, P. Szakalos, M. Graham, A. Belonoshko, G. Sproule, L. Grasjo, P. Dorogokupets, B. Danilov, T. Aastrup, G. Wikmark, G. Chuah, J. Eriksson, and A. Rosengren, Catal. Lett.132, 311 (2009)10.1007/s10562-009-0113-x]. Although bulk corrosion into any of the known phases of copper is thermodynamically forbidden, the present paper shows how surface reactions lead to the formation of hydrogen gas in limited amounts. While water cleavage on copper has been reported and investigated before, formation of molecular hydrogen at a single-crystal Cu[100] surface is here explored using density functional theory and transition state theory. It is found that although solvent catalysis seems possible, the fastest route to the formation of molecular hydrogen is the direct combination of hydrogen atoms on the coppersurface. The activation free energy (△Gs ‡ f) of hydrogen formation in condensed phase is 0.70 eV, which corresponds to a rate constant of 10 s−1 at 298.15 K, i.e., a relatively rapid process. It is estimated that at least 2.4 ng hydrogen gas could form per cm2 on a perfect coppersurface.

Stress corrosion cracking is a potential failure mechanism of the copper canister proposed to be the main corrosion barrier in the Scandinavian design of the final nuclear waste disposal vault. The main target in SCC-oriented research is to determine the limiting values for the critical concentration of harmful species, the potential range in which these species cause SCC and the threshold stress level required for SCC. The present paper attempts to redefine the criteria for SCC susceptibility of copper in acetate solutions through analysis of potentiodynamic curves using both rotating disc and thin plate electrodes insulated on one side. A potential range in which the current densities at a slow sweep rate are lower than those at a fast sweep rate exists for Cu in 0.001 M - 0.1 M acetate. However, the values of the current densities within this range are significantly smaller than those postulated for active anodic dissolution, implying dissolution mediated by a surface film. New criteria for the SCC susceptibility of pure copper in acetate solutions have been formulated through Stern-Geary analysis of the polarisation curves. Several electrochemical characteristics, such as the current density at the positive crossover potential, the ratio between the corrosion current densities determined from the slow and fast sweeps, as well as the anodic current density in a fast sweep show a clear jump for concentrations between 0.01 M and 0.05 M. This, however, cannot yet be considered as an indication of SCC susceptibility at higher acetate concentrations, as evidenced by complementary SSRT tests.

Electrochemical oxidation of symmetrical dimethylbithiophenes with free α-positions yields electroactive polymers with excellent cycling ability.

Two sensors, an on-line corrosion sensor based on the wire-resistance probe design and a reference electrode which are applicable in repository conditions are introduced. Both sensors have been tested in simulated repository conditions in bentonite saturated with highly saline groundwater at 80 °C temperature and 14 MPa pressure up to 150 h exposure. In addition, it has been demonstrated that after an initial transient period of ca. 5–8 h, Cu corrosion in highly saline groundwater filled with bentonite becomes undetectably low probably because of the anoxic conditions reached in the free groundwater. At the same time, the measured corrosion potential of Cu is still in the active corrosion region. Furthermore, redox potentials in the wetted bentonite remain significantly higher than in the free groundwater. This may mean that the decomposition of oxygen contained in the pores of the bentonite is a process occurring in a time scale larger than that of the present experiments.