RESUMEN
AISI Type 304 stainless steel coupons have been exposed to a simulant aqueous environment representative of the Magnox Reprocessing Plant (MRP) at Sellafield, UK. The experiments were performed for extended time periods (up to 420 days) at elevated temperatures to develop a comprehensive understanding of the extent, nature, and depth of contamination for pipework and vessels in Magnox spent nuclear fuel reprocessing environments. This will inform upcoming decommissioning work which represents a major post-operational challenge. Previous relevant literature has focused on developing fundamental understanding of contamination mechanisms of stainless steels in simplistic, single-element systems, which lack elements of industrial relevance. Contamination behavior is expected to be drastically different in these more complex environments. A characterization portfolio has been developed to enable detailed assessment of corrosion and contamination behavior in acidic reprocessing environments. Solution, surface, and depth analysis determined that uptake was dominated by the elements present in highest concentrations within the environment, namely, Mg, Nd, and Cs. Most contaminants were incorporated into a relatively thin surface oxide layer (<100 nm) in metal oxide form, although there were some exceptions (Cs and Sr). Grain boundary etching was present despite very low corrosion rates (3 µm year-1). As a result of this lack of corrosion, diffusion of contaminants beyond the immediate surface (10-20 nm) did not occur, evidenced through depth profiling. As a result of these findings, surface-based decontamination techniques minimizing excess secondary waste generation can be further developed in order to reduce the environmental and economic burden associated with decommissioning activities.
RESUMEN
The objective of this study was to investigate and visualize the initiation and propagation of crevice corrosion in grade 2205 duplex stainless steel by means of time-lapse imaging. Transparent Poly-Methyl-Meth-Acrylate washer and disk were coupled with duplex stainless steel to create an artificial crevice, with electrochemical monitoring applied to obtain information about the nucleation and propagation characteristics. All nucleation sites and corroding areas inside crevices were recorded in situ using a digital microscope set-up. Localized corrosion initiated close to the edge of the washer, where the crevice gap was very tight, with active corrosion sites then propagating underneath the disk into areas with wider gaps, towards the crevice mouth. The growth was associated with a rise in anodic current interlaced with sudden current drops, with parallel hydrogen gas evolution also observed within the crevice. The current drops were associated with a sudden change in growth direction, and once corrosion reached the crevice mouth, the propagation continued circumferentially and in depth. This allowed different corrosion regions to develop, showing selective dissolution of austenite, a region with dissolution of both phases, followed by a region where only ferrite dissolved. The effect of applied electrochemical potential, combined with time-lapse imaging, provides a powerful tool for in situ corrosion studies.
RESUMEN
Damage initiation and crack propagation in concrete are associated with localisation of energy dissipation by the concrete meso-structure. Meso-scale models are, therefore, required for realistic analysis of concrete non-linear behaviour. Such models are constructed either from X-ray Computed Tomography images (image-based modelling) or by in silico meso-structure generation (parametric modelling), while both approaches are widely used and their advantages and disadvantages are recognised, little work is done on comparing their performance in predicting measured macroscopic behaviour with equivalent constitutive relations for meso-structural features. This work uses microstructure characterisation and mechanical behaviour data to construct, validate and compare the two modelling approaches. The macroscopic behaviour obtained with both meso-structural models is found to be in good agreement with experimental data. Differences are observed only between the predicted distributions of damage within specimens. These outcomes suggest that the computationally simpler parametric meso-structures are sufficient to derive stress-strain behaviour for engineering-scale models in the absence of other environmental factors. The observed differences in damage distribution could be important for analysis of coupled behaviour, e.g., mass transport and chemical reactions affecting local mechanical properties and being affected by local damage. Establishing the importance of damage distribution is such cases requires further research.
RESUMEN
Controlling corrosion with naturally occurring corrosion scales is potentially a more environmentally sustainable alternative to current approaches, including dosing of organic corrosion inhibitors. We report operando grazing incidence X-ray diffractograms correlated with electrochemical measurements to elucidate the growth and corrosion protection properties of a corrosion scale composed of FeCO3 crystallites, which is encountered in various key energy industry applications. Data, acquired as a function of time from high-purity iron immersed in CO2-saturated deionized H2O at pH 6.8 and T = 80 °C, show that the FeCO3 scale not only prevents corrosion of the covered substrate but also acts as a significant interfacial diffusion barrier for corrosion reagents and/or products once sufficient coverage is achieved. Most notably, from a corrosion engineering perspective, however, it is determined that corrosion occurring in gaps between scale crystallites remains appreciable; this important insight is gained through the analysis of electrochemical impedance spectra to estimate the variation in electrochemically active surface area as scale coverage increases. These results indicate that naturally occurring FeCO3 scales are not a tenable solution for corrosion protection, as even in their intact state they are highly likely to be, at best, semiprotective.
RESUMEN
Stainless steels can become contaminated with radionuclides at nuclear sites. Their disposal as radioactive waste would be costly. If the nature of steel contamination could be understood, effective decontamination strategies could be designed and implemented during nuclear site decommissioning in an effort to release the steels from regulatory control. Here, batch uptake experiments have been used to understand Sr and Cs (fission product radionuclides) uptake onto AISI Type 304 stainless steel under conditions representative of spent nuclear fuel storage (alkaline ponds) and PUREX nuclear fuel reprocessing (HNO3). Solution (ICP-MS) and surface measurements (GD-OES depth profiling, TOF-SIMS, and XPS) and kinetic modeling of Sr and Cs removal from solution were used to characterize their uptake onto the steel and define the chemical composition and structure of the passive layer formed on the steel surfaces. Under passivating conditions (when the steel was exposed to solutions representative of alkaline ponds and 3 and 6 M HNO3), Sr and Cs were maintained at the steel surface by sorption/selective incorporation into the Cr-rich passive film. In 12 M HNO3, corrosion and severe intergranular attack led to Sr diffusion into the passive layer and steel bulk. In HNO3, Sr and Cs accumulation was also commensurate with corrosion product (Fe and Cr) readsorption, and in the 12 M HNO3 system, XPS documented the presence of Sr and Cs chromates.