Lars Werme

Anaerobic Corrosion of Steel in Bentonite

In Sweden, spent nuclear fuel will be encapsulated in sealed cylindrical canisters, consisting of a ferrous insert and a copper outer container, for disposal in a geologic repository. Ferrous support structures will also be used in the repository, which will be backfilled with bentonite clay. Once any residual oxygen has been consumed, any ferrous material exposed to anoxic groundwater will undergo anaerobic corrosion, liberating hydrogen, forming a magnetite film, and releasing iron ions into the surrounding matrix. In order to characterise these processes the rate of hydrogen generation of steel in bentonite was measured using a barometric gas cell technique. The initial corrosion rates were found to be higher than measured previously in comparable aqueous solutions, but the long-term corrosion rates were similar. Analysis of the bentonite matrix showed that iron produced by corrosion had penetrated into the bentonite matrix, suggesting that ferrous ion exchange had occurred.

Changes in electronic structure of copper films in aqueous solutions

The possibilities for using x-ray absorption spectroscopy (XAS) and resonant inelastic x-ray scattering (RIXS) to probe the Cu oxidation state and changes in the electronic structure during interaction between copper and ground-water solutions were examined. Surface modifications induced by chemical reactions of oxidized 100 A Cu films with Cl−, SO42− and HCO3− ions in aqueous solutions with various concentrations were studied in situ using liquid cells. Copper corrosion processes in ground water were monitored for up to nine days. By comparing Cu 2p–3d, 4s transitions for a number of reference substances previously measured, changes in electronic structure of the Cu films were analysed. The XAS and RIXS spectral shape at the Cu edge, the chemical shift of the main line for Cu2+, and the energy positions of the observed satellites served as a tool for monitoring the changes during the reaction. It was found that the pH value and the Cl− concentration in solutions strongly affect the speed of the corrosion reaction.

Nuclear waste glass interfaces after one year burial in STRIPA part 1: Glass/glass

Abstract Two simulated nuclear waste glasses were corroded in an in-situ experiment in the STRIPA mine up to one year at 90°C. Changes in compositional in-depth profiles for glass/glass interfaces were measured using SIMS. Both glasses showed a depletion of Na, Cs, and B, but for the more corrosion resistant glass, the lower depletion depth is ascribed to the formation of a thin (2.0 m) coherent and dense outer layer, enriched in Mg, Ca, Sr, Ba, Zn-Al, Fe, and Si, which impedes both the ion exchange and network attack of the bulk glass underneath.

Further Studies of the Anaerobic Corrosion of Steel in Bentonite

In the horizontal emplacement concept (KBS-3H) for the disposal of radioactive waste, which is being developed in Sweden and Finland, copper canisters with cast iron inserts will be surrounded by bentonite buffer and mounted in perforated carbon steel support structures in boreholes within the bedrock. The groundwater will be reducing, leading to anaerobic corrosion of the ferrous material. It is important to understand both the effect of bentonite on the corrosion behaviour of the steel and the effect of the corrosion products on the performance of the bentonite. Previous work on the corrosion of steel in bentonite was extended to investigate a wider range of conditions, including the possible effects of alkaline plumes released from concrete support structures and the effect of chloride concentration and temperature on the corrosion rate of steel in bentonite. Corrosion rates were measured by collecting hydrogen produced by the anaerobic corrosion of iron. In addition, a range of analytical techniques was applied to study the composition and morphology of the corrosion products and the distribution and chemical state of the iron released into the bentonite. Comparison was also made between corrosion in compacted bentonite and artificial bentonite porewater. In the presence of bentonite, the corrosion product layer was relatively thin compared to fully aqueous conditions, probably because the ferrous ions released by corrosion exchanged with the bentonite interlayer or attached to the surface of the bentonite grains, rather than forming a separate iron oxide phase.

On the pH dependence of leaching of nuclear waste glasses

Abstract Two simulated nuclear waste glasses were leached for periods up to one month at 90°C in high-purity water, following standard MCC-1 test procedures. The changes in composition of the surface layers were determined using ESCA and SIMS, which analyses layers of different depths. The results are discussed with reference to the different pH values in the tests performed.

Electronic structure of Cu3N films studied by soft x-ray spectroscopy

Soft x-ray emission spectroscopy was used to characterize the electronic structure of seven copper nitride films, one synthesized with atomic layer deposition (ALD) and six grown with chemical vapor deposition (CVD) at different preparation temperatures. Interpretation of the x-ray emission spectra was supported by calculations of the electronic structure for bulk pure Cu(3)N and Cu(3)N with: an excess of Cu atoms, oxygen or carbon impurities, and N vacancies. The calculations are shown to describe the experimental spectra quite well. Analysis of the x-ray spectra suggests that films grown in copper rich environments and above a cut-off temperature of approximately 360 °C have a growing fraction of copper enriched areas, while films prepared below this temperature do not have these areas with excess copper.

Resonant inelastic soft X-ray scattering studies of U(VI) reduction on iron surfaces

We report on the spectroscopic analysis of several samples relevant to the processes governing the behavior of oxidized uranium species in groundwater solutions under anoxic conditions. Both Fe samples with different times of exposure to the U(IV) solution and Fe metal-solution inetrfaces in the liquid cell ex-situ and in-situ , respectively. Resonant inelastic soft x-ray scattering is shown to be sensitive to the chemical state of uranium. The measurements were performed at a number of energies of the primary photon beam across the U 5d absorption edge. The results unambiguously indicate the reduction of U(VI) to U(IV) on the Fe surface.

Near Field Performance of the Advanced Cold Process Canister

A near-field performance evaluation of an advanced cold process canister for spent nuclear fuel has been performed jointly by TVO, Finland and SKB, Sweden. The canister consists of a carbon steel canister as a load bearing element, with an outer corrosion shield of copper. The canister design was originally designed by TVO. In the analysis, internal (ie corrosion processes from the inside of the canister) as well as external processes (mechanical and chemical) have been considered both prior to and after canister breach. Throughout the analysis, present day underground conditions have been assumed to persist during the service life of the canister.

5 f -shell correlation effects in dioxides of light actinides studied by O 1s x-ray absorption and emission spectroscopies and first-principles calculations.

Soft x-ray emission and absorption spectroscopic data are reported for the O 1s region of a single crystal of UO2, a polycrystalline NpO2 sample, and a single crystal of PuO2. The experimental data are interpreted using first-principles correlated-electron calculations within the framework of the density functional theory with added Coulomb U interaction (DFT+U). A detailed analysis regarding the origin of different structures in the x-ray emission and x-ray absorption spectra is given and the effect of varying the intra-atomic Coulomb interaction-U for the 5 f electrons is investigated. Our data indicate that O 1s x-ray absorption and emission spectroscopies can, in combination with DFT+U calculations, successfully be used to study 5 f -shell Coulomb correlation effects in dioxides of light actinides. The values for the Coulomb U parameter in these dioxides are derived to be in the range of 4-5 eV.

Chemical reduction of actinides probed by resonant inelastic X-ray scattering.

The study addresses the possibilities of immobilizing the mobile species of actinides in the geosphere using metallic iron. Sorption on corroding iron is well-known, but there have been uncertainties with regard to the possibilities of reducing the actinyl species to sparingly soluble oxides and, thereby, permanently immobilizing them. Resonant inelastic X-ray scattering (RIXS) measurements at the actinide 5d edges on Fe foils exposed to uranium(VI) and neptunium(V) solutions in groundwater unambigiously indicate reduction of actinides to, respectively, uranium(IV) and neptunium(IV) on iron surfaces. The reduction manifests itself in an appearance of distinct specific signatures of uranium(IV) and neptunium(IV) in the RIXS profile of 5f-5f excitations. Such signatures and RIXS intensity/cross-section behavior with varying energy of incident photons can be reproduced by model atomic-multiplet calculations of the RIXS spectra. By normalizing the RIXS signal of corresponding 5f-5f excitations to core-to-core 6p-to-5d characteristic fluorescence transitions of actinides, their reduction rates on Fe samples with different exposure to actinide solutions can be estimated. Observed reduction implies similar processes in the nuclear waste canister thus suggesting reduced probability of nuclear waste release with ground waters from the canister.