Roles of Radiolytic and Externally Generated H2 in the Corrosion of Fractured Spent Nuclear Fuel.

A 2-D model for the corrosion of spent nuclear fuel inside a failed nuclear waste container has been modified to determine the influence of various redox processes occurring within fractures in the fuel. The corrosion process is driven by reaction of the fuel with the dominant α radiolysis product, H2O2. A number of reactions are shown to moderate or suppress the corrosion rate, including H2O2 decomposition and a number of reactions involving dissolved H2 produced either by α radiolysis or by the corrosion of the steel container vessel. Both sources of H2 lead to the suppression of fuel corrosion, with their relative importance being determined by the radiation dose rate, the steel corrosion rate, and the dimensions of the fractures in the fuel. The combination of H2 from these two sources can effectively prevent corrosion when only micromolar quantities of H2 are present.

Determination of the local corrosion rate of magnesium alloys using a shear force mounted scanning microcapillary method.

The successful development of scanning probe techniques to characterize corrosion in situ using multifunctional probes is intrinsically tied to surface topography signal decoupling from the measured electrochemical fluxes. One viable strategy is the shear force controlled scanning microcapillary method. Using this method, pulled quartz micropipettes with an aperture of 500 nm diameter were used to resolve small and large variations in topography in order to quantify the local corrosion rate of microgalvanically and galvanically corroded Mg alloys. To achieve topography monitoring of corroded surfaces, shear force feedback was employed to position the micropipette at a reproducible working height above the substrate. We present proof of concept measurements over a galvanic couple of a magnesium alloy (AE44) and mild steel along with a microgalvanically corroded ZEK100 Mg alloy, which illustrates the ability of shear force to track small (1.4 µm) and large (700 µm) topographic variations from high aspect ratio features. Furthermore, we demonstrate the robustness of the technique by acquiring topographic data for 4 mm along the magnesium-steel galvanic couple sample and a 250 × 30 µm topography map over the ZEK100 Mg alloy. All topography results were benchmarked using standard optical microscopies (profilometry and confocal laser scanning microscopy).

The influence of hydrogen peroxide and hydrogen on the corrosion of simulated spent nuclear fuel.

The synergistic influence between H(2)O(2) and H(2) on the corrosion of SIMFUEL (simulated spent nuclear fuel) has been studied in solutions with and without added HCO(3)(-)/CO(3)(2-). The response of the surface to increasing concentrations of added H(2)O(2) was monitored by measuring the corrosion potential in either Ar or Ar/H(2)-purged solutions. Using X-ray photoelectron spectroscopy it was shown that the extent of surface oxidation (U(V) + U(VI) content) was directly related to the corrosion potential. Variations in corrosion potential with time, redox conditions, HCO(3)(-)/CO(3)(2-) concentration, and convective conditions showed that surface oxidation induced by H(2)O(2) could be reversed by reaction with H(2), the latter reaction occurring dominantly on the noble metal particles in the SIMFUEL. For sufficiently large H(2)O(2) concentrations, the influence of H(2) was overwhelmed and irreversible oxidation of the surface to U(VI) occurred. Subsequently, corrosion was controlled by the chemical dissolution rate of this U(VI) layer.

Analyzing the influence of alloying elements and impurities on the localized reactivity of titanium grade-7 by scanning electrochemical microscopy.

Scanning electron microscopy/energy dispersive X-ray analysis (SEM/EDX) was applied to investigate the grain boundaries on ASTM grade-7 titanium (Ti-7) with a freshly polished surface, and the results showed that the alloying element, Pd, and the impurity, Fe, cosegregated to grain boundaries. Scanning electrochemical microscopy (SECM) was used to study the variations in reactivity on Ti-7 exposed to an aerated neutral solution of 0.1 M NaCl. Locations that possessed an enhanced reactivity compared to the oxide-covered (TiO(2)) surface of the grains on SECM images were proposed to be the boundaries. These areas were further activated by the application of a cathodic bias, and interconnection of the active locations allowed the construction of "grain boundary maps". Variations in surface reactivity were quantitatively analyzed by fitting probe approach curves (PACs) to curves simulated with a model based on finite element analyses using the platform of COMSOL multiphysics software. The difference in reactivity between active grain boundaries and oxide-covered grains was up to a factor of 100 on freshly polished surfaces. This difference decreased to a factor of 10-15 after longer-term exposure of the Ti-7 to the aerated solution, indicating partial passivation of the Pd/Fe-stabilized beta-phase in the grain boundaries. PAC analyses of oxide-covered grains showed that the reactivity increased logarithmically as the bias potential to the Ti-7 was decreased, consistent with reduction of the insulating TiO(2) layer to a more conductive TiOOH layer.