The nuclide management process for reducing the environmental burden being developed by the Korea Atomic Energy Research Institute is performed in molten salts, resulting in contaminated salt wastes containing fission products such as Cs, Sr, Ba, and rare-earth nuclides. In addition, the spent fuel of a molten salt reactor (MSR) contains a variety of fission products, and a purification process may be required for the reuse of the salt and the separation and disposal of the fission products in the spent nuclear fuel. The melt-crystallization method is a technique used for the purification and separation of chemicals or metals based on the different melting points of the different substances. In a recent study, our group developed a reactive-crystallization method using Li2CO3 precipitation agent to precipitate metal corrosion from the reactor through a chlorination reaction by HCl and Cl2, which may occur in chloride molten salt, and successfully precipitated the metal precipitate and purified and recovered LiCl salt. In this study, reactive-crystallization method has been established for removing fission products and corrosive materials. Using the reactive crystallization method, white LiCl-KCl salt that was not discolored by metal corrosion was recovered through the crystallization plates, and fission products and metal elements were shown to be suppressed to several ppm in the purified salt. Consequently, high-purity salts were recovered with high nuclide and corrosive separation efficiencies. The reactive crystallization procedure can also be applied to other salt waste systems, such as MSR nuclear fuel treatment and molten salt chemistry for the elimination of corrosive substances.

It has been investigated on the management of Strontium-90 in KAERI. It is needed to separate the solute from the salt solution for the recovery of strontium after the chlorination of the strontium oxide in molten salt. A vacuum distillation technology was used for the separation of strontium from the molten salt in our previous study. Strontium chloride was successfully carbonated by reactive distillation of SrCl2 – K2CO3 – LiCl – KCl system. In this study, it was tried to develop another route to recover strontium from the salt solution by a solid-solid reaction for avoiding the entrainment of product and the salt-K2CO3 reaction. Reactive distillation experiments were carried out for SrCl2 - K2CO3 – LiCl – KCl system. The carbonation temperature and pressure were 520°C and 0.8 bar. After the carbonation reaction, the temperature was elevated to 820°C to remove KCl from the reaction product. SrCO3 and KCl peaks were found in the XRD analysis of the residual product. It could be concluded that SrCl2 can be successfully carbonated after salt removal by the solid-solid reaction.

Corrosion-related challenges remain a significant research topic in developing next-generation Molten Salt Reactors (MSRs). To gain a deeper understanding of preventing corrosion in MSRs, previous studies have attempted to improve the corrosion resistance of structural alloys by coating surfaces such as alumina coating. To conduct a corrosion test of coating alloys fully immersed in molten salt, it’s important to ensure that the coating application process is carefully carried out. Ideally, coating all sides of the alloy is necessary to avoid gaps like corners of the alloy, while only applying a one-sided coating alloy can lead to galvanic corrosion with the base metals. Using the droplet shape of eutectic salt applied to only one side of the coating alloy would avoid these problems in conventional corrosion immersion tests, as corrosion would occur solely on the coating surface. Although the droplet method for corrosion tests cannot fully replicate corrosion in the MSRs environment, it offers a valuable tool for comparing and evaluating the corrosion resistance of different coating surfaces of alloys. However, the surface area is important due to the effect of diffusion in the corrosion of alloy in molten salt environments, but it is difficult to unify in the case of droplet tests. Therefore, understanding the droplet-alloy properties and corrosion mechanism is needed to accurately predict and analyze these test systems’ behavior highlighting unity for corrosion tests of different coating surfaces of alloys. To analyze the molten salt droplet behavior on various samples, pelletized eutectic NaCl-MgCl2 was prepared as salt and W-, Mo-coating, and base SS316 as samples. At room temperature, the same mass of pelletized eutectic NaCl-MgCl2 was placed on different samples under an argon atmosphere and heated to a eutectic point of 500°C in a furnace. After every hour, the molten droplets were hardened by rapid cooling at room temperature outside the furnace. The mass loss of salts and the contact area of the samples were measured by mass balance and SEM. The shape, surface area to volume ratio, and evaporation of the droplets of NaCl-MgCl2 per each coating sample and hour were analyzed to identify the optimal mass to equalize the contact coating surface of alloys with salts. Furthermore, We also analyzed whether their results reached saturation of corrosion products through ICP-MS. This will be significant research for the uniformity of the liquid-drop shape corrosion test of the coating sample in molten eutectic salts.

Measuring the concentration of corrosion products or nuclear fission products (FPs) in molten salts is crucial for pyroprocessing and molten salt reactors. Electrochemical analysis methods that can be performed in situ offer significant advantages for monitoring the concentration of corrosion products or FPs in molten salts. A microelectrode is an electrode with a length of several tens of micrometers on one side. The use of a microelectrode for electrochemical analysis has several advantages due to its small size, including rapidly reaching the limiting current regardless of the scan rate, immediate attainment of the limiting current upon applying an overpotential for instant monitoring within milliseconds, accurate measurement even in low convection systems, a small iR drop resulting from low flowing current and high signal accuracy, and high current density resulting in a high signal-tonoise ratio (SNR). Among various methods for making microelectrodes, techniques involving cutting a thin wire or using capillaries (such as the dual-bore capillary and pulled glass capillary methods) require precise manual skills and experience. Therefore, the results may vary depending on the maker’s skill level, and it can be difficult to control the electrode’s area, thickness, and surface uniformly. Recent research has focused on using semiconductor processes to fabricate microelectrodes, where CVD, metal sputtering, photolithography, and etching processes work together to deposit, refine, and shape the required material on a silicon wafer to create microelectrodes. However, the durability of microelectrodes produced this way is still low (usable for about 15-30 minutes), and there is no clear research on the degradation mechanism over time. To verify the proper operation of the fabricated microelectrodes, cyclic voltammetry (CV) is performed at various scan rates (from 10 mVs-1 to 2 Vs-1), and chronoamperometry (CA) is also examined to confirm whether the electrodes rapidly reach a steady-state current. After confirming their proper operation, CV is continuously measured until the microelectrodes are destroyed in a LiCl-KCl solution containing a small amount of FPs (Sm 340 mM) at 450°C. By observing changes in the electrical signal of the microelectrodes over time, the durability is evaluated, and the mechanism of performance degradation of the electrode is discovered. The experiment is then repeated by gradually increasing the temperature by 30°C from 450°C up to 600°C to observe the changes with temperature. This study provides basic information for future microelectrode experiments, and by diagnosing the cause of destruction, a more durable microelectrode structure can be manufactured.

Aluminum’s exceptional properties, such as its high strength-to-weight ratio, excellent thermal conductivity, corrosion resistance, and low neutron absorption cross-section, make it an ideal material for diverse nuclear industry applications, including aluminum plating for the building envelope of nuclear power plants. However, plating aluminum presents challenges due to its high reactivity with oxygen and moisture, thus, complicating the process in the absence of controlled environments. Plating under an inert atmosphere is often used as an alternative. However, maintaining an inert atmosphere can be expensive and presents an economic challenge. To address these challenges, an innovative approach is introduced by using deep eutectic solvents (DES) as a substitute for traditional aqueous electrolytes due to the high solubility of metal salts, and wide electrochemical window. In addition, DESs offer the benefits of low toxicity, low flammability, and environmentally friendly, which makes DESs candidates for industrial-scale applications. In this study, we employed an AlCl3-Urea DES as the electrolyte and investigated its potential for producing aluminum coatings on copper substrates under controlled conditions, for example, current density, deposition duration, and temperature. A decane protective layer, non-polar molecular, has been used to shield the AlCl3-Urea electrolyte from the air during the electrodeposition process. The electrodeposition was successful after being left in the air for two weeks. This study presents a promising and innovative approach to optimizing aluminum electrodeposition using deep eutectic solvents, with potential applications in various areas of the nuclear industry, including fuel cladding, waste encapsulation, and radiation shielding.

Molten salt reactor (MSR) is one of the non-pressurized-water fourth-generation reactors that uses liquid nuclear fuel that integrates coolant and nuclear fuel, so it is a safe reactor that can fundamentally prevent severe accidents caused by coolant loss. MSR uses NaCl-MgCl2 as a coolant salt, which is considered a promising diluent that can dissolve the fuel salt by forming an eutectic mixture. In this study, a zone-melting system was used to remove impurities from the NaCl-MgCl2 used in MSR. The system was designed in detail to control eutectic salt impurities by traversing long charges into a small molten zone.

Molten salt consisting primarily of eutectic LiCl-KCl is currently being used in electrorefiners in the Fuel Conditioning Facility at Idaho National Laboratory. Options are currently being evaluated for storing this salt outside of the argon atmosphere hot cell. The hygroscopic nature of eutectic LiCl-KCl makes is susceptible to deliquescence in air followed by extreme corrosion of metallic cannisters. In this study, the effect of occluding the salt into a zeolite on water sorption/desorption was tested. Two zeolites were investigated: Na-Y and zeolite 4A. Na-Y was ineffective at occluding a high percentage of the salt at either 10 or 20wt% loading. Zeolite-4A was effective at occluding the salt with high efficiency at both loading levels. Weight gain in salt occluded zeolite-4A (SOZ) from water sorption at 20% relative humidity and 40℃ was 17wt% for 10% SOZ and 10wt% for 20% SOZ. In both cases, neither deliquescence nor corrosion occurred over a period of 31 days. After hydration, most of the water could be driven off by heating the hydrated salt occluded zeolite to 530℃. However, some HCl forms during dehydration due to salt hydrolysis. Over a wide range of temperatures (320–700℃) and ramp rates (5, 10, and 20℃ min−1), HCl formation was no more than 0.6% of the Cl− in the original salt.

Decontamination of spent nuclear fuel from decommissioned nuclear reactors is crucial to reduce the volume of intermediate-level waste. Fuel cladding hulls are one of the important parts due to high radioactivity. Their decontamination could possibly enable reclassification as low-level waste. Fuel cladding hulls used in research reactors and being developed for conventional light water reactors are Al-Mg and Fe-Cr-Al alloys, respectively. Therefore, the recovery of these component metals after decontamination is necessary to reduce the volume of highly radioactive waste. Electrochemical approach is often chosen due to its simplicity and effectiveness. Non-aqueous solvents, such as molten salts (MSs) and ionic liquids (ILs), are preferred to aqueous solvents due to the absence of hydrogen evolution. However, MSs and ILs are limited by high temperature and high synthesis cost, along with toxicity issues. Deep eutectic solvents (DESs) are synthesized from a hydrogen bond acceptor (HBA) and donor (HBD) and exhibit outstanding metal salt solubility, wide electrochemical window, good biocompatibility, and economic production process. These characteristics make DES an attractive candidate solvent for economic, green, and efficient electrodeposition compared with aqueous solvents such acids or nonaqueous solvents such as MSs or ILs. In this research, the feasibility of electrodeposition of Al-Mg and Fe-Cr-Al alloys in ChCl:EG, the most common DES synthesized from choline chloride (ChCl) and ethylene glycol (EG), will be tested. A standard three-electrode electrochemical cell with an Au plated working electrode and Al wires for counter and reference electrodes is utilized. Two electrolyte solutions (Al-Mg and Fe-Cr-Al) are prepared by dissolving 100 mM of each anhydrous metal chloride salts (AlCl3, MgCl2, CrCl3, and FeCl2) in ChCl:EG. Cyclic voltammogram (CV) is measured at 5, 10, 15, and 20 mV·s−1 to observe the redox reactions occurring in the solutions. Electrodeposition of each alloy is performed via chronoamperometry at observed reduction potentials from CV measurements. The deposited surfaces and cross-sections are examined by scanning electron microscopy and energy dispersive spectroscopy (SEM-EDS) to analyze the surface morphology, cross-section composition, and thickness. Authors anticipate that the presence of different metals will greatly affect the possibility of electrodeposition. It is expected that although all metals are distributed throughout the surface, the morphology, in terms of particle size and shape, would differ depending on metals. Different metals will be deposited by layers of an approximate thickness of a few μm each. This research will illustrate a potential for recovery and electrodeposition of other precious radioactive metals from DES.

Liquid Bi pool is a candidate electrode for an electrometallurgical process in the molten LiCl-KCl eutectic to treat the spent nuclear fuels from nuclear power plants. The electrochemical behavior of Bi3+ ions and the electrode reaction on liquid Bi pool were investigated with the cyclic voltammetry in an environment with or without BiCl3 in the molten LiCl-KCl eutectic. Experimental results showed that two redox reactions of Bi3+ on inert W electrode and the shift of cathodic peak potentials of Li+ and Bi3+ on liquid Bi pool electrode in molten LiCl-KCl eutectic. It is confirmed that the redox reaction of lithium with respect to the liquid Bi pool electrode would occur in a wide range of potentials in molten LiCl-KCl eutectic. The obtained data will be used to design the electrometallurgical process for treating actinide and lanthanide from the spent nuclear fuels and to understand the electrochemical reactions of actinide and lanthanide at liquid Bi pool electrode in the molten LiCl-KCl eutectic.

In this study, the electrochemical behavior of Sm on the binary liquid Al-Ga cathode in the LiCl-KCl molten salt system is investigated. First, the co-reduction process of Sm(III)-Al(III), Sm(III)-Ga(III), and Sm(III)-Ga(III)-Al(III) on the W electrode (inert) were studied using cyclic voltammetry (CV), square-wave voltammetry (SWV) and open circuit potential (OCP) methods, respectively. It was identified that Sm(III) can be co-reduced with Al(III) or Ga(III) to form AlzSmy or GaxSmy intermetallic compounds. Subsequently, the under-potential deposition of Sm(III) at the Al, Ga, and Al-Ga active cathode was performed to confirm the formation of Sm-based intermetallic compounds. The X-ray diffraction (XRD) and scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) analyses indicated that Ga3Sm and Ga6Sm intermetallic compounds were formed on the Mo grid electrode (inert) during the potentiostatic electrolysis in LiCl-KCl-SmCl3-AlCl3- GaCl3 melt, while only Ga6Sm intermetallic compound was generated on the Al-Ga alloy electrode during the galvanostatic electrolysis in LiCl-KCl-SmCl3 melt. The electrolysis results revealed that the interaction between Sm and Ga was predominant in the Al-Ga alloy electrode, with Al only acting as an additive to lower the melting point.

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.

This study proposes a method of separating uranium (U) and minor actinides from rare earth (RE) elements in the LiCl-KCl salt system. Several RE metals were used to reduce UCl3 and MgCl2 from the eutectic LiCl-KCl salt systems. Five experiments were performed on drawdown U and plutonium (Pu) surrogate elements from RECl3-enriched LiCl-KCl salt systems at 773 K. Via the introduction of RE metals into the salt system, it was observed that the UCl3 concentration can be lowered below 100 ppm. In addition, UCl3 was reduced into a powdery form that easily settled at the bottom and was successfully collected by a salt distillation operation. When the RE metals come into contact with a metallic structure, a galvanic interaction occurs dominantly, seemingly accelerating the U recovery reaction. These results elucidate the development of an effective and simple process that selectively removes actinides from electrorefining salt, thus contributing to the minimization of the influx of actinides into the nuclear fuel waste stream.

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.