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At least 19 records

Progress Towards Synthesis of Uranium Chloride Fuel Salts Using Zinc Chloride

Reliable, scalable methods for producing high-purity actinide chloride salts are needed to support molten salt reactor fuel development and deployment. This report describes the continued development and demonstration of a bench-scale chlorination and purification apparatus using a zinc chloride-based method for synthesizing uranium chloride fuel salts. In this approach, uranium metal is chlorinated by ZnCl2 to produce LiCl-KCl-UCl3. Reaction with three aliquots of added uranium metal was used to generate a target uranium concentration of 30 wt %. While this concentration was chosen for initial testing of the apparatus and method, the final uranium concentration is not limited to 30 wt %. The zinc metal generated in the reaction forms an immiscible layer that was removed by volatilization at moderately high temperatures. Electrochemical measurements confirmed the removal of zinc and applied sensing methods indicated the uranium concentration to be approximately 25 wt %. These initial results demonstrate that the bench-scale chlorination apparatus is an effective platform for the synthesis and purification of uranium chloride salts using ZnCl2. This method shows promise for application to industry-relevant salt systems such as NaCl-UCl3. Further development is recommended to optimize reagent loading, zinc removal, and avoid possible U-Zn alloy formation.

Dulovic, Stephanie

Development of a Chlorine Cathode and Anode Basket Assembly for Production of Uranium Chloride

A chlorine cathode has been developed for in situ chlorination of metals, oxides, and oxychlorides in molten chloride electrolytes that could be used to support synthesis of chloride fuel salts for molten salt reactors. The chlorine cathode is designed to electrochemically reduce chlorine gas to generate chloride ions that, when paired with a metal anode, chlorinate that metal as it is oxidized into the salt. The designed porous carbon electrode effectively distributes Cl 2 to the electrode surface and efficiently generates Clions in the molten chloride electrolyte. This report highlights recent improvements made to the electrode assembly, with a focus on operational control of the anode basket stability. Synthesis tests demonstrated the successful chlorination of uranium metal, resulting in 3.6 wt% uranium generated in the LiCl-KCl base salt in 45 minutes, performed in a bench-scale chlorination apparatus. Higher concentrations could be achieved by applying longer chlorination times or increasing the amount of uranium loaded in the anode basket. Overall, the chlorine cathode can be used with an appropriately designed anode to chlorinate uranium in situ for synthesis of molten salt reactor fuel salts.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS

TEX-Chlorine: Highly Enriched Uranium with Chloride Absorbers to Provide Validation Benchmarks for Y-12 Electrorefining Facility

This report documents the final benchmark of the TEX-Chlorine (IER-499) Thermal Epithermal eXperiments (TEX) with highly enriched uranium with chlorine absorbers and high-density polyethylene reflectors and moderators. TEX-Chlorine is a variation of the TEX-HEU baseline assembly with the addition of sodium chloride absorber plates. This evaluation contains three experimental configurations that were performed on Comet at NCERC between July and August 2024. The three configurations, which were acceptable as benchmark cases, spanned from thermal (first two configurations) to fast (third configuration). All three cases were reviewed and accepted by the ICSBEP TRG in April 2025 and was submitted to the ICSBEP in August 2025 after receiving subgroup approval.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS

Elucidating the corrosion mechanism of Ni-based superalloys in the presence of uranium-containing chloride molten salt

The United States Department of Energy (DOE) is committed to the advancement of nuclear reactor technology through initiatives such as the Advanced Reactor Development Program (ARDP), in an effort to diversify the United States energy portfolio towards more sustainable energy options. The ARDP includes demonstration by industry partners of molten chloride fast reactors (MCFRs). Construction of MCFRs requires qualified nuclear structural materials. Unfortunately, there are no current materials that are fully qualified by the Nuclear Regulatory Commission for the construction of molten salt reactors, including MCFRs. Adapting current structural material qualifications requires expansion of our current knowledgebase on the property-performance relationships regarding corrosion performance. In this investigation, we assess microstructural changes in a Ni-based superalloy after exposure to a UCl3¬-containing chloride salt eutectic mixture through a correlated multi-modal approach combining several advanced characterization techniques, including scanning electron microscopy/focused ion beam (SEM/FIB) and transmission electron microscopy (TEM). SEM/FIB analysis will illustrate changes in elemental composition, microstructure, and isotopic information acquired from energy x-ray dispersive spectroscopy (EDS), electron backscatter diffraction (EBSD), and secondary ion mass spectroscopy (SIMS), respectively. This information will then aid in identifying localized regions to elucidate the corrosion mechanism with TEM through a combination of electron diffraction, electron energy loss spectroscopy (EELS), and additional EDS. The findings from this investigation will further expand our assessment of the corrosion performance of structural materials in molten salt chloride systems, aiding to developing fully qualified materials for construction of MCFRs.

36 MATERIALS SCIENCE

Raman spectroscopic investigation of UCl 4

Uranium chloride salts are a proposed fuel source for molten salt reactors (MSRs). However, despite their relevance to nuclear energy, they remain understudied, in part because of their air and moisture sensitivity. Here, this work provides the first Raman spectra of UCl 4 from 45 to 3200 cm −1 collected with 532 and 785 nm excitation sources as well as the assignment of 10 identified peaks to their respective vibrational modes. These Raman bands are compared to those for isostructural ThCl 4 , the compositionally related UCl 3 , and the computed Raman bands for UCl 4 from local vibrational mode analysis. The observed spectrum of UCl 4 is in accord with that of ThCl 4 and the computed spectra of UCl 4 . We posit that the observed differences between the spectra of UCl 4 and UCl 3 are useful in differentiating these species for applications such as in situ monitoring of MSR operations.

Anoxic spectroscopy

Benchmark Gap Assessment for the Manufacturing of High-Assay Low-Enriched Uranium Fuels

This document develops basic critical conditions for spheres—moderated and unmoderated, as well as reflected and unreflected—in consideration of nuclear criticality safety of a potential fuel production facility producing high-assay low-enriched uranium (HALEU) fuel of several different types like tristructural-isotropic (TRISO), uranium metal and alloys, oxide and non-metallic forms. In addition to spherical arrangements, TRISO particle manufacturing process–specific equipment is modeled as it would be for the criticality safety analysis. The objective is to develop representative systems that can then be used for comparison with existing benchmarks. SCALE/TSUNAMI is used to assess the similarity index between these systems to assess validation gaps for possible fuel production applications of proposed advanced reactors. Several different fuel types were evaluated, including TRISO, uranium metal, uranium molybdenum, uranium zirconium, uranium dioxide, uranium nitride, uranium hydride, U-ZrH, and uranium chloride. This selection of fuel types covers a breadth of proposed reactor types, as well as intermediate steps in the production and fabrication of the fuel

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS

TEX-Chlorine Assemblies: Highly Enriched Uranium Plates with Sodium Chloride Absorbers Using Polyethylene Moderator and Polyethylene Reflector

This evaluation documents highly enriched uranium (HEU) experimental critical configurations with polyethylene moderators and sodium chloride absorbers conducted as part of the United States Nuclear Criticality Safety Program’s Thermal/Epithermal eXperiments (TEX) program. HEU-MET-MIXED-021 provides the benchmark evaluation of five TEX experiments designed to establish baseline configurations with HEU Jemima plates moderated by high density polyethylene (HDPE). The TEX-HEU experiments were designed to cover five different fission energy regimes by varying the thickness of the interstitial HDPE moderator, with varying fractions of thermal, intermediate, and fast fissions, and to be easily modified to accommodate test materials of interest. HEU-MET-INTER-013 documents the first TEX-HEU variation, incorporating hafnium in seven different experimental configurations. This evaluation covers an additional variant that incorporates absorber plates of compacted high-purity sodium chloride salt. These experiments were motivated by a criticality safety need for validation data for uranium purification by means of electrorefining with chloride salts, especially thermal and intermediate energy configurations resulting from moderator upset conditions, and their design was optimized by matching sensitivity profiles from application cases. All three experimental configurations are judged to be acceptable as benchmark cases. The main parameter varied between the configurations is the thickness of the polyethylene moderators and the sodium chloride absorbers between the HEU plates. Varying the thickness of the polyethylene tunes the neutron energy spectrum between majority thermal (Case 1 and 2) and intermediate (Case 3). The fission fractions, presented in Table 1, are determined calculationally. Case 3 is cross listed as HEU-MET-INTER-014.

42 ENGINEERING

Synthesis and characterization of uranium trichloride in alkali-metal chloride media

Given a growing interest in uranium salts for pyrochemical processing of used fuel and uranium-fueled molten salt reactors, the synthesis of uranium trichloride in alkali-metal chloride media was investigated in a series of four experiments. Specifically, uranium metal powder and uranium hydride powder were prepared and separately blended with ammonium chloride and lithium chloride – potassium chloride eutectic in two runs, while the same powders were separately blended with ammonium chloride and sodium chloride in two additional runs. Each of the lithium chloride – potassium chloride containing blends was slowly heated to 923 K, while those containing sodium chloride were heated to 1123 K. During each heat up, the ammonium chloride sublimed into gaseous ammonia and hydrogen chloride, leading to the chlorination of uranium metal or uranium hydride and the formation of molten salt solutions of the respective chlorides. Experimental conditions were incorporated in the runs to promote formation of uranium trichloride over uranium tetrachloride in the respective media. Molten samples of each run product were taken and characterized via chemical analyses, diffractometry, and microscopy. The final products from each run were dark dense ingots of the respective salt systems with uranium concentrations ranging from 44 to 51 wt%. Chemical analyses and diffractometry identified the predominant presence of uranium trichloride in these systems; however, a possible minor presence of uranium tetrachloride could not be conclusively dismissed.

D Herrmann, Steven

Flow Enhanced Electrochemical Sensor Performance in Complex Salt Systems

To advance MSR MC&A practices, Argonne National Laboratory developed and optimized robust flow enhanced electrochemical sensors (FEES) and multielectrode array voltammetry sensors (MAVS) which provide accurate near-real time measurements of actinides in molten salts. Flow-enhanced electrochemical sensors are installed directly into MSR flow conduits for inline salt chemistry measurement, while MAVS are deployed in quiescent salt conditions enabling online species concentration determination in stationary salt vessels. This report summarizes efforts to improve electrochemical sensor technological readiness through (1) sensor testing in complex, high concentration molten salt systems to demonstrate low uncertainty actinide measurements in MSR-representative solutions and (2) demonstrations of sensor performance in challenging real-world conditions in collaboration with partner MSR institutions.

22 GENERAL STUDIES OF NUCLEAR REACTORS

Elucidating the corrosion mechanism of commercial Ni-based Superalloys in UCl3 containing-chloride Molten Salt Systems

Molten salt reactors (MSRs) have gained renewed interest, providing several advantages over their predecessors, including the capability to consume spent fuels, enhancing the environmental sustainability of the uranium fuel cycle. For example, molten chloride fast reactors (MCFRs) can reach criticality with molten chloride spent fuel containing high concentrations of impurities, such as actinide products like uranium chloride (UCl3). However, the redox potential of chloride molten salt fuels may change in the presence of these impurities, dictating their corrosivity and in turn the corrosion performance of structural components, such as those constructed from nickel (Ni)-based alloys. The purpose of this investigation is to assess the extent of corrosion of Ni-based alloy, Inconel 617, when exposed to UCl3-LiCl-KCl eutectic salt. Inconel 617 one of only six structural materials that are fully qualified by the American Society for Mechanical Engineers (ASME) Boiler and Pressure Vessel Code for high-temperature nuclear reactor components, making it a technologically mature material to consider for constructing MCFRs. Inconel 617 specimens were submerged in a static LiCl-KCl-UCl3 eutectic salt mixture heated at 700 C for 1000 h under an inert atmosphere. Upon completion, the extent of corrosion was analyzed through a multi-modal characterization approach spanning the engineering to nanoscale, employing computed tomography, focused-ion beam, and transmission electron microscopy techniques. Results from this investigation will enhance our understanding of property-to-performance relationships of candidate structural materials for MSRs with respect to corrosion resistance and interactions between the salt and alloy interface.

36 MATERIALS SCIENCE

Evaluation of corrosion coupons exposed to molten-chloride electrorefiner salts long term

Corrosion mitigation has long been considered a challenge in long-term service of both pyrochemical reprocessing and molten salt reactor applications. Corrosion coupons consisting of 2.25Cr 1Mo ASME SA387 Grade 22 Class 2 steel, were installed in a uranium electrorefiner containing molten chloride salt at 500°C. This electrorefiner went into service at Idaho National Laboratory in 1994. Seven of these coupons were removed in 2019 (i.e., submerged in molten salt for 25 years) for analysis and characterization including neutron imaging, optical microscopy, scanning electron microscopy, and wave/energy dispersive x-ray spectroscopy. The results showed that all seven coupons experienced between 30 to 175 µm of surface degradation without evidence of brittle fracture. Meaning there was no evidence of accelerated corrosion or fractures, and the average steel surface loss was of less than 5 µm per year. All indications were that the environmental conditions inside the electrorefiner were favorable for the steel alloy.

36 - MATERIALS SCIENCE

Preparation of a uranium monocarbide anode and electrochemical characterization in molten LiCl-KCl-UCl 3

Porous uranium carbide (UC) pellets possessing moderate electrical conductivity were synthesized by reaction of UO 2 with graphite at temperatures up to 1550°C under rough vacuum. Conversions as high as 98% were achieved at soak times of 2-4 hours. The electrochemistry of the UC pellets in molten LiCl-KCl-6.5 wt% UCl 3 was explored using a variety of techniques including DC polarization methods, cyclic voltammetry, chronopotentiometry and bulk electrolysis. Here, the electrode reaction for anodic dissolution was found to be kinetically controlled by dissociation of UC to a transition state complex that was hypothesized to consist of a uranium atom partially complexed by chloride ions. Precise measurements of current efficiencies using chronopotentiometry indicated upper limits of 90.9 ± 3.4% and 98.3 +1.7/-3.7% for anode and cathode, respectively, when operating at anodic overpotentials near +300 mV. Bulk electrolysis of a UC pellet performed by passing 98% of the theoretical charge resulted in nearly complete recovery of its uranium content as highly pure metal at the cathode.

36 MATERIALS SCIENCE

Characterization of MC&A for the Molten Salt Fuel Cycle

Advanced reactor developers are exploring diverse reactor designs, including molten salt reactors (MSRs). These advanced reactors are considered for wider applications and a range of deployment locations, including supporting the integration of renewable energy sources in the grid. There are three main types of MSRs: (1) reactors in which the fuel salt freely circulates within the core; (2) reactors with the fuel salt contained within vented fuel tubes; and (3) reactors that use molten salt solely as a coolant, with the fuel in a separate, solid form. In this document, the term MSR refers specifically to the first two types, which use fuel salt—special nuclear material (enriched uranium, plutonium, and 233 U) in chloride or fluoride form mixed with chloride- or fluoride-based carrier salt in a peritectic mixture—as the primary medium for fission. The composition of fuel salt, both at startup and for makeup or refueling, varies depending on the MSR design and the chosen fuel cycle approach, which can be either once-through or closed. For MSRs, a variety of fuel cycle approaches (e.g., U, U–Pu, U–Pu–TRU, U–Th, U–Pu–Th) are being considered. Fuel in MSRs is much different than traditional solid fuel, including its preparation. The uniqueness warrants investigation into characterizing fuel preparation processes, known as fuel salt synthesis . This effort characterized major fuel preparation and synthesis processes, identifying temperature, equipment, and environmental requirements for uranium-, plutonium-, and thorium-based fuel preparation and synthesis. Because MSR fuel salt synthesis facilities handle special nuclear material in loose, bulk form, a material control and accounting plan will be required for licensing from the US Nuclear Regulatory Commission or under the US Department of Energy authorization. This effort serves as a foundation to investigate material control and accounting approaches for synthesis facilities, including determining measurement points and techniques. Because several MSR developers are planning demonstration facilities in the coming years, this effort will support stakeholders with preparing or reviewing material control and accounting plans for providing assurance that all special nuclear material is accounted for at fuel salt synthesis facilities. This report was produced for Materials Protection, Accounting, and Control Technologies (MPACT) program under the US Department of Energy (DOE), Office of Nuclear Energy, Nuclear Fuel Cycle and Supply Chain.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Quantitative Voltammetry Measurements of High-Concentration Actinides in Molten Chloride Fuel Salts

Molten chloride mixtures containing high concentrations of UCl 3 (i.e., >70 wt%) are candidates for next-generation molten salt reactor (MSR) fuel salts that enable new plant optimization and fuel cycle strategies. MSR licensing, however, is contingent on the development of effective material control and accounting (MC&A) practices for these salts. To close this gap, we have developed an electroanalytical approach that enables accurate in situ measurements of uranium concentrations in these highly loaded fuel salts. This methodology uses a multielectrode array voltammetry sensor combined with digital simulations that account for non-idealities such as uncompensated resistance effects. The theory-based numerical simulations of voltammetry responses yielded correction factors that are agnostic of electrochemical cell geometry and produced consistent voltammetry peak current results when correcting for varying amounts of ohmic resistance. In doing so, we have demonstrated accurate concentration measurements for UCl 3 in LiCl-KCl-UCl 3 across a range of mass fractions between 55 and 72.3 wt% at 550 °C.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Quantifying uncertainty in uranium concentration measurements via K-edge densitometry

This study quantifies the uncertainty in uranium concentration predictions of fluoride and chloride-based salts within a steel pipe using K-edge densitometry. Modeling and simulation was conducted with the Monte Carlo N-Particle Transport (MCNP) code. The quality of of this technique’s prediction in a pipe requires proper characterization of the pipe’s thickness, which is dependent on the source size and axial offset from the pipe centerline. The thickness was determined as either the center-line thickness seen by the X-ray source or an average value determined through random sampling. Generally, the predicted concentrations were slightly better at lower offset with the random sampling thickness and using the center-line thickness for the highest offsets. For a line-beam source and varying axial offsets, the relative error of concentration was within 1% of the true value but uncertainty increased by 2 orders of magnitude. Similarly, for no axial offset, the relative error was significantly less than 1% while no trend for uncertainty was found. However, at the largest possible offset for a given source size, the concentrations become erroneous and greater than the allowable 1% relative error. Furthermore, high offsets tended to increase the variance of the transmission spectra by 3 orders of magnitude.

Characterization and Analytical Technique

Electrolytic Co-deposition Neutron Production Evaluation

Co-deposition electrochemical cells are a simple means to examine novel nuclear reactions. In this study, palladium and deuterium atoms were co-deposited on a cathode at stoichiometric densities, forming dendritic morphologies. Bubble detector neutron dosimeters were used to measure equivalent dose levels during electrolytic deposition. Standard configuration cells expected to produce excess neutrons were denoted as experimental cells and contained an electrolyte consisting of palladium(II) chloride, lithium chloride, and heavy water. The control cells used copper(II) chloride, lithium chloride, and heavy water electrolyte. Experimental and control cells were supplied current, increasing from 0.1 to 100.0 mA over a period of 20 days. For test days 9 through 20, the standard configuration experimental cells exhibited significantly higher average neutron radiation than the controls at a 99% confidence level. Alternative configurations involving more increasing current over a shortened time scale, substitutions of water in place of heavy water or potassium chloride for lithium chloride, as well as inclusion of depleted uranium near the cell cathodes all resulted in inconclusive evidence for promoting neutron production.

neutron

Hydrochlorination of Uranium Dioxide in a Molten Salt Mixture - Phase 1: Tube Furnace Cross Flow Experiments

In 2023, Metatomic® Inc., a South Carolina based company, was awarded a Gateway for Advanced Innovation in Nuclear (GAIN) research voucher for a proposed series of experiments aimed at demonstrating the viability of a spent nuclear fuel (SNF) recycling process patented by Met atomic® Inc. For the GAIN voucher, Metatomic® Inc. selected Savannah River National Laboratory (SRNL) as a partner in executing the proposed proof-of-concept experiments. This report outlines the proof-of-concept experiments performed by SRNL for Metatomic® Inc. during Phase 1 (of 2) experimentation. The Phase 1 hydrochlorination experiments consisted of weighing UO2 into alumina crucibles with a eutectic mixture of NaCl and CsCl, heating the uranium/salt mixture to a varied temperature (550, 650, or 750 °C), and flowing anhydrous hydrogen chloride (AHCl) gas across the surface of the uranium-bearing molten salt mixture. The hydrochlorination process conditions were maintained for 4-5 hours and the percent conversion for each batch of UO2 was determined using a suite of analytical characterization techniques. The degree of UO2 conversion was found to be greatest at the highest tested temperature, ultimately achieving 32.9% conversion of UO2 to water soluble uranium-chloro species (e.g., UO2Cl2, UCl4) after exposure to AHCl for 4.25 hours at 750 °C.

Nguyen, Vinh T. [Savannah River National Laborator

Final Design for Thermal/Epithermal eXperiments (TEX) with Lithium Absorbers to Provide Validation Benchmarks for Y-12 Electrorefining Facility

One of the main goals of the Thermal/Epithermal eXperiments (TEX) project is to use existing Nuclear Criticality Safety Program (NCSP) assets to create critical experiment plutonium and uranium test beds for materials important to criticality safety that have insufficient benchmark evaluations. The plutonium test bed experiments were completed in 2018 and are published in the 2020 edition of the International Criticality Safety Benchmark Evaluation Project (ICSBEP) Handbook. The uranium test bed assemblies were completed in 2023 and accepted in the 2024 edition of the ICSBEP Handbook. The Nuclear Criticality Safety (NCS) group at Y-12 National Security Complex has identified programmatic need for validation cases for uranium electrorefining operations at Y-12. The electrorefining operation credits lithium enriched in 6 Li in addition to 35 Cl as absorbers in the design criticality safety evaluation for precluding criticality under upset conditions in the large and geometrically unfavorable electro-refiner. There is, however, inadequate experimental validation for the 6 Li absorbers. As an extension of the TEX uranium test bed, TEX-Cl critical experiments were performed with sodium chloride salt to address the 35 Cl thermal absorption as well as other validation needs at Los Alamos National Laboratory (LANL). These experiments were completed in 2024 and accepted into the 2025 ICSBEP Handbook. To continue the methodology used in TEX-Cl, TEX-Li aims to accomplish the same. The overall design of both experiments was to use commercially available, high purity, salts with polyethylene moderator and HEU plates to configure a critical assembly. Three experiments are planned for TEX-Li using encapsulated lithium carbonate (Li 2 CO 3 ), with natural 6 Li abundance. For all experiments, the highly enriched uranium (HEU) Jemima plates will be used as fissile material. Multiple layers will be stacked together with encapsulated Li 2 CO 3 alternated with polyethylene in standard configurations. Standard stacking was found to be optimal in matching the different sensitivity profiles provided by the Y-12 models. Three configurations are proposed with varying polyethylene moderation and a constant 1/4” absorber thickness. The first uses 11 layers of 5/4” polyethylene, the second uses 9 layers of 3/4” polyethylene, and the third uses 10 layers of 1/2” polyethylene. Calculations showed that some alternative forms of lithium-based materials provided slightly less-optimal sensitivity profiles when compared to lithium carbonate but come with other drawbacks. These alternatives included lithium aluminate (LiAlO 2 ), Aluminum-2050 alloy, Aluminum-8090, Aluminum-2095, lithium hydride (LiH), and lithium fluoride (LiF). Lithium aluminate and aluminum-2050 provided comparable sensitivity profiles when compared to lithium carbonate and can be used instead if lithium carbonate cannot be readily procured. After a broad material study, lithium carbonate outperformed any alternative material with a balance in affordability and workability. The assessment of experimental uncertainties of the non-absorber and absorber components was predicted to be 0.00089 and 0.00093 Δk eff , respectively. The largest uncertainties may be reduced with precision dimensional inspection of the components. Many of the parts and equipment for IER 575 have already been fabricated or procured for previous projects and therefore do not contribute significantly to the overall cost of this experiment. This includes the Jemima plates and Comet critical assembly machine, which are existing NCSP assets, as well as the aluminum platen and polyethylene reflector rings, which were fabricated and authorized for the TEX experiment involving HEU with polyethylene. Lithium carbonate containers will be procured by LANL and will be filled by LLNL. The total material costs for TEX-Li experiments are estimated to be on the order of $\$$47,400. Precision inspection, including dimensional, mass, density, and impurity, is recommended for all components for an estimated cost of $\$$12,000.

35Cl