Molten chloride salts have received considerable research attention as potential nuclear fuel and coolant candidates for molten salt reactors. However, there are several challenges, especially for structural materials due to the selective dissolution of chromium (Cr) in the molten chloride salts environment. Understanding the compatibility of uranium (U), which is used as nuclear fuel in molten salt reactors, with Cr in molten chloride salts is critical for designing the molten salt reactor structure. Therefore, in this study, the cyclic voltammetry (CV) was used to investigate the electrochemical behaviors of U and Cr. The diffusion coefficients and formal potentials were obtained. The electrochemical properties of uranium and chromium were investigated by CV in molten NaCl-MgCl2 salt at 600°C. Tungsten rods for working and counter electrode, and Ag/AgCl for reference electrode were utilized in this experiment. UCl3 made from the chemical dissolution of U rods and CrCl2 (Sigma-Aldrich, 99.99%) were used. Diffusion coefficients (D) of U and Cr were calculated by measuring reduction peak current of U3+/U and Cr2+/Cr from CV curves and using the Berzins-Delahay equation; D (U3+/U) = 3.0×10-5 cm2s-1 and D (Cr2+/Cr) = 3.3×10-5 cm2s-1. The formal potentials were also calculated by using the reduction peak potential obtained from CV results; E0’ (U3+/U) = -1.173 V and E0’ (Cr2+/Cr) = -0.321 V. The ionization tendency was investigated by comparing each reduction peak potential. The reduction peak potential Ep,c was increasing order of Ep,c (U3+/U) < Ep,c (Cr2+/Cr) < Ep,c (U4+/U3+). It can be seen that in the presence of U4+ and Cr metals, the Cr in the alloy can dissolve into Cr2+, but in the presence of U3+ and Cr metals, the Cr in the alloy does not dissolve into Cr2+. By analyzing the CV curve, diffusion coefficients and formal standard potentials were obtained. The result of comparing reduction peak potentials suggests that the nuclear fuel using U4+ should be inhibited to prevent the selective dissolution of Cr.

The density of molten salts is the most important property in the development of molten salt reactor (MSR). The density value measured through the experiment is also very valuable as a gold standard for the validation of the prediction models based on molecular dynamics or other computational methods. To the best of our knowledge, the experimental density data of the ternary NaCl-MgCl2- UCl3 salt system as a MSR candidate fuel salt have never been reported previously. In this study, density measurement experiment of high-temperature molten salt of NaCl-MgCl2 and NaCl-MgCl2- UCl3 was conducted using a previously-developed density measurement system based on the maximum bubble pressure (MPB) method. As a result of the experiment, the density value of 62NaCl- 18MgCl2-20UCl3 molten salt at 873 K was 2.62 g/cm3. A density prediction value of 2.65 g/cm3 at 873 K was derived from the obtained results based on the rule of additivity of molar volume method. The predictred density of 62NaCl-18MgCl2-20UCl3 was consistent with the experimental value within 1%. The density measuring system used in this study is promising for the validation of other multicomponent molten salt systems.

Viscosity of molten salts is an essential property for the thermal hydraulic design and evaluation of molten salt reactor (MSR). Therefore, viscosity data is one of the fundamental physical property data required for safe process operation and countermeasures to severe accidents. In this study, based on our experience of developing a viscosity measurement system for high-temperature LiCl-KCl molten salt system, the viscosity of NaCl-MgCl2 and NaCl-MgCl2-UCl3 molten salts, which are considered promising salts in MSR, was measured. In order to investigate the physical properties of uranium in high-temperature NaCl-MgCl2 molten salt, a viscometer system for high-temperature viscosity measurement was specially designed. As a result of the measurement, the viscosity of the 58NaCl- 42MgCl2 molten salt was 2.73 cP at 838 K, 2.15 cP at 889 K, and 1.68 cP at 940 K. And the viscosity of 73NaCl-21MgCl2-6UCl3 molten salt was 3.79 cP at 877 K, 3.58 cP at 897 K, and 1.63 cP at 941 K. The repeatability of the measurement showed a precision of less than 3%. Although sufficientlyverified starting materials were not used, viscosity data were reported for the first time for NaCl- MgCl2-UCl3 molten salts.

Interests in molten salt reactor (MSR) using a fast spectrum (FS) have been increased not only for having a high power density but for burning the high-level waste generated from nuclear power plants. For developing the FS-MSR technologies, chloride-based fuels are considered due to the advantage of higher solubility of actinides and lanthanides over fluoride-based salts. Despite significant progress in development of MSR technology, the manufacturing technology for production of the fuel is still insufficiently understood. One of the option to prepare the MSR fuel is to use products from pyroprocessing where oxide form of spent nuclear fuel is reduced into metal form and useful elements can be collected via electrochemical methods in molten salt system at high temperature. In order to chlorinate the products into chloride form, previous study used NH4Cl to chlorinate U metal into UCl3 in an airtight reactor. It was found that the U metal was completely chlorinated into chloride forms; however, impurities generated by the reaction of NH4Cl and reactor wall were found in the product. Therefore, in this work, the air tight reactor was re-deigned to avoid the reaction of reactor wall by insertion of Al2O3 crucible inside of the reactor. In addition, the reactor size was increased to produce UCl3 over 100 g. Using the newly designed reactor, U metal chlorination experiments using NH4Cl chlorinating agent were performed to confirm the optimal experimental conditions. The detailed results will be further discussed.

The effect of Li2O addition on precipitation behavior of uranium in LiCl-KCl-UCl3 has been investigated in this study. 99.99% LiCl-KCl eutectic salt is mixed with 10wt% UCl3 chips at 550°C in the Pyrex tube in argon atmosphere glove box, with 10 ppm O2 and 1 ppm H2O. Then, Li2O chunks are added in mixed LiCl-KCl-UCl3 and the system has been cooled down to room temperature for 10 hours to form enough UO2 particles in the salt. The solid salt has been taken out from the glove box, and cut into three sections (top, middle and bottom) by low-speed saw for further microscopic analysis. Three pieces of solid salt are dissolved in deionized water at room temperature and the solution is filtered by a filter paper to collect non-dissolved particles. The filter paper with particles is baked in vacuum oven at 120°C for 6 hours to evaporate remaining moisture from the filter paper. Further analysis was performed for the powder remaining on the filter paper, and periphery of the powder (cake) on the filter paper. Scanning electron microscopy (SEM), electron diffraction spectroscopy (EDS), and X-ray powder diffraction (XRD) are adopted to analysis the characteristic of the particles. From SEM analysis, the powders are consisted of small particles which have 5 to 10 m diameter, and EDS analysis shows they are likely UO2 with 23 at. % of uranium and 77 at. % oxygen. Cake is also analyzed by SEM and EDS, and needle like structures are widely observed on the particle. The length of needle is distributed from 5 to 20 m, and it has 6 to 10 at. % of chlorine, which are not fully dissolved into deionized water at room temperature. From XRD analysis, the particles show the peak position of UO2, and the result is well matched with the SEM-EDS results. We are planning to add more Li2O in the system for fully reacting uranium in UCl3, and compare the results to find the effect of Li2O concentration on UO2 precipitation.

A molten salt reactor (MSR) that uses molten salt mixtures as nuclear liquid fuel has recently received much attention due to its inherent safety. Various fluoride and chloride salt mixtures are considered as fluid fuel for MSRs. Among those, NaCl-MgCl2-UCl3 system is the one of the most promising candidates for molten salt fast reactor. The comprehensive information on thermo-physical properties such as density, viscosity, heat capacity and thermal conductivity are fundamental to MSR design development, but experimental data for NaCl-MgCl2-UCl3 system are unknown to the best of our knowledge. In this study, we estimated the thermophysical properties of NaCl-MgCl2-UCl3 system. The properties were calculated by mole fraction additive method using reliable experimental data from pure salt system. Other methods, such as rule of additivity of molar volume for density, modified Dulong-Petit method for heat capacity, and Rao-Turnbull prediction and Ignatieve-Khokolve correlation for thermal conductivity, have also been applied. Estimated values for the properties were compared with each other as well as available binary experimental data.

Density of chloride molten salts is an essential physical property in the reactor core design and thermal-hydraulic design simulation, especially in molten salt reactor (MSR) design currently under development in Korea. NaCl-MgCl2-UCl3 pseudo-ternary system is one of the various candidate chloride-based salt mixtures because it has relatively-low melting point, very low vapor pressure, high thermal conductivity, etc. However, to the best of our knowledge, the density data of NaCl-MgCl2- UCl3 have not yet been measured or published worldwide, and therefore the ballpark figures of the density should be given for the preliminary reactor design. In our present study, the density estimation of NaCl-MgCl2-UCl3 based on the pseudo-binary data, i.e., NaCl-MgCl2, MgCl2-UCl3, and NaCl- UCl3, reported in the literature previously were performed using the Redlich-Kister model. Binary interaction parameter for MgCl2-UCl3 was higher than that for NaCl-MgCl2 and lower than that for NaCl-UCl3. As an example, calculated density of 0.62 NaCl: 0.18 MgCl2: 0.20 UCl3 at 873 K was 2.578 g·cm−3. In our further study, the methodology using Redlich-Kister model will be applied to more complex multicomponent systems and to other physical properties such as viscosity, thermal conductivity, surface tension, etc.

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.

파이로프로세싱의 전해환원공정에서 생산된 금속전환체의 조성은 전해정련공정 운전의 중요한 운전변수인 용융염 중 UCl3 의 농도변화에 영향을 미친다. 따라서, 본 연구에서는 금속전환체에 함유된 TRU와 RE 원소의 함량 및 금속전환체에 동반 되어 전해정련 전해조에 유입될 수 있는 Li2O 농도가 전해정련 전해조의 UCl3 농도 변화에 미치는 영향을 검토하였다. 금속 전환체의 TRU 원소와 RE 원소의 농도만을 고려하였을 때 전해정련 운전 batch 수 증가에 따라 UCl3 농도가 감소하였다. 전 해정련 1 campaign(20 batch)를 운전하기 위해서는 UCl3를 3회 이상 추가 보충해야 함을 알 수 있었다. 한편, 금속전환체에 동반되어 전해정련 전해조에 유입되는 Li2O의 유입량 증가에 따라 UCl3 농도 감소의 영향이 크게 나타났으며, 이에 따라 운전 가능 batch 수가 급격히 감소하게 되어 전해정련 운전에 중요한 운전 변수임을 보여주었다. 이러한 결과는 전해정련 운전 중 UCl3 농도 유지를 위해 금속전환체에 포함된 TRU 및 RE 원소뿐만 아니라 금속전환체에 동반되어 유입될 가능성이 있는 Li2O의 영향도 고려하여 전해정련 운전모드를 설정하여야 함을 보여주었다.

사용후핵연료을 건식처리하는 파이로프로세싱 중 전해정련 및 제련공정 후 발생되는 우라늄과 초우라늄 및 희토류 등의 염화물을 함유한 LiCl-KCl 공융염에는 특히 희토류 함량이 높기 때문에 유효자원으로 활용이 가능한 형태의 우라늄과 초우라 늄의 분리/회수가 쉽지 않다. 이러한 문제점을 해결하기 위해 본 연구에서는 LiCl-KCl-UCl3-NdCl3 시스템에서 산화제(K2CO3) 를 이용하여 UCl3를 산화물 형태로 전환한 후 전기화학적 방법을 이용하여 NdCl3를 금속형태로 분리하는 실험을 실시하였 다. 실험에 앞서, 이론적 평형계산을 수행하여 우라늄 염화물을 산화물로 전환하기 위한 실험조건을 결정하였다. 상기의 실 험에서 LiCl-KCl 내 UCl3는 첨가제의 주입량이 이론적 반응당량에 근접하였을 때 거의 대부분이 염내에서 염화물 형태로 존 재하지 않는 것으로 나타났다. 이후 액체금속음극을 이용하여 NdCl3를 금속형태로 전착시켰으며, 전착실험 후 투명한 용융 상의 LiCl-KCl 공융염과 갈색의 우라늄 산화침전물이 존재함이 확인되었다. 이러한 결과들을 통해 LiCl-KCl-UCl3-NdCl3 시스 템에서 우라늄 및 희토류를 각각 분리할 수 있는 방안을 수립할 수 있을 것으로 판단된다.

Densities of molten salt mixtures of eutectic LiCl-KCl with UCl3, CeCl3, or LaCl3 at various concentrations (up to 13 wt%) were measured using a liquid surface displacement probe. Linear relationships between the mixture density and the concentration of the added salt were observed. For LaCl3 and CeCl3, the measured densities were significantly higher than those previously reported from Archimedes’ method. In the case of LiCl-KCl-UCl3, the data fit the ideal mixture density model very well. For the other salts, the measured densities exceeded the ideal model prediction by about 2%.