Fundamental aspects of creating passivation layers for corrosion resistance in nuclear engineering applications, specifically the ability to form complete layers versus porous ones, are being explored in this study. Utilizing a laser ablation technique, 1,064 nm fire at 10 Hz with 60 pulses per shot and 0.5 mm between impact points, aluminum samples are treated in an attempt to create a fully formed passivation layer that will be tested in a LiCl-KCl eutectic salt. By placing these samples into an electrochemical environment mimicking a pyroprocessing system, corrosion rates, resistances and material characteristics are tested for one week and then compared between treated and untreated samples. In initial testing, linear sweep voltammetry indicates corrosion current density for the untreated sample at −0.038 mA·cm−2 and treated samples at −0.024 mA·cm−2 and −0.016 mA·cm−2, respectively. This correlates to a control sample corrosion rate of −0.205 mm·yr−1 and treated rates of −0.130 mm·yr−1 and −0.086 mm·yr−1 for samples 1 and 2. In addition, electrochemical impedance spectroscopy circuits show application of a longer-lasting porous passivation layer on the treated metal, compared to the naturally forming layer. However, the current technique fails to create a uniform protection layer across the sample.

This work provided a review of three techniques—(1) spectrochemical, (2) electrochemical, and (3) spectroelectrochemical– for molten salt medias. A spectroelectrochemical system was designed by utilizing this information. Here, we designed a spectroelectrochemical cell (SEC) and calibrated temperature controllers, and performed initial tests to explore the system’s capability limit. There were several issues and a redesign of the cell was accomplished. The modification of the design allowed us to assemble, align the system with the light sources, and successfully transferred the setup inside a controlled environment. A preliminary run was executed to obtain transmission and absorption background of NaCl-CaCl2 salt at 600°C. It shows that the quartz cuvette has high transmittance effects across all wavelengths and there were lower transmittance effects at the lower wavelength in the molten salt media. Despite a successful initial run, the quartz vessel was mated to the inner cavity of the SEC body. Moreover, there was shearing in the patch cord which resulted in damage to the fiber optic cable, deterioration of the SEC, corrosion in the connection of the cell body, and fiber optic damage. The next generation of the SEC should attach a high temperature fiber optic patch cords without introducing internal mechanical stress to the patch cord body. In addition, MACOR should be used as the cell body materials to prevent corrosion of the surface and avoid the mating issue and a use of an adapter from a manufacturer that combines the free beam to a fiber optic cable should be incorporated in the future design.

Deionized water, methanol, and ethanol were investigated for their effectiveness at dissolving LiCl-KCl-UCl3 at 25, 35, and 50℃ using inductively coupled plasma mass spectrometry (ICP-MS) to study the concentration evolution of uranium and mass ratio evolutions of lithium and potassium in these solvents. A visualization experiment of the dissolution of the ternary salt in solvents was performed at 25℃ for 2 min to gain further understanding of the reactions. Aforementioned solvents were evaluated for their performance on removing the adhered ternary salt from uranium dendrites that were electrochemically separated in a molten LiCl-KCl-UCl3 electrolyte (500℃) using scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS). Findings indicate that deionized water is best suited for dissolving the ternary salt and removing adhered salt from electrodeposits. The maximum uranium concentrations detected in deionized water, methanol, and ethanol for the different temperature conditions were 8.33, 5.67, 2.79 μg·L-1 for 25℃, 10.62, 5.73, 2.50 μg·L-1 for 35℃, and 11.55, 6.75, and 4.73 μg·L-1 for 50℃. ICP-MS analysis indicates that ethanol did not take up any KCl during dissolutions investigated. SEM-EDS analysis of ethanol washed uranium dendrites confirmed that KCl was still adhered to the surface. Saturation criteria is also proposed and utilized to approximate the state of saturation of the solvents used in the dissolution trials.

This study provides an assessment on a proposed method for separation of cesium, strontium, and barium using electrochemical reduction at a liquid bismuth cathode in LiCl-KCl eutectic salt, investigated via cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and scanning electron microscopy with energy dispersive X-ray spectrometry (SEM-EDS). CV studies were performed at temperatures of 723-823 K and concentrations of the target species up to 4.0wt%. Redox reactions occurring during potential sweeps were observed. Concentration of BaCl2 in the salt did not seem to influence the diffusivity in the studied concentration range up to 4.0wt%. The presence of strontium in the system affected the redox reaction of lithium; however, there were no distinguishable redox peaks that could be measured. Impedance spectra obtained from EIS methods were used to calculate the exchange current densities of the electroactive active redox couple at the bismuth cathode. Results show the rate-controlling step in deposition to be the mass transport of Cs+ ions from the bulk salt to the cathode surface layer. Results from SEM-EDS suggest that Cs-Bi and Sr-Bi intermetallics from LiCl-KCl salt are not thermodynamically favorable.

Molten salt solutions consisting of eutectic LiCl-KCl and concentrations of samarium chloride (0.5 to 3.0 wt%) at 500℃ were analyzed using both cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The CV technique gave the average diffusion coefficient for Sm3+ over the concentration range. Equipped with Sm3+ diffusion coefficient, the Randles-Sevcik equation predicted Sm3+ concentration values that agree with the given experimental values. From CV measurements; the anodic, cathodic, and half-peak potentials were identified and subsequently used as a parameter to acquire EIS spectra. A six-element Voigt model was used to model the EIS data in terms of resistance-time constant pairs. The lowest resistances were observed at the half-peak potential with the associated resistance-time constant pairs characterizing the reversible reaction between Sm3+ and Sm2+. By extrapolation, the Voigt model estimated the polarization resistance and established a polarization resistance-concentration relationship.