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High-Temperature Reference Electrode for Chloride Salts

The unique properties of molten salts enable their use in a wide range of applications, including metal electrodeposition, electrorefining, and as electrolytes in high-temperature batteries. Moreover, molten salts will be used as a coolant in molten salt reactors and as working media in pyrorocessing for nuclear energy applications. As a result, predicting the behavior and properties of the elements involved in the technological processes that employ molten salts is important. The activity of chloride ions in chloride molten salts has a large influence on the behavior of the salts in these applications and one of the key components in measuring the chloride activity is a stable reference electrode. This project aims to develop a reliable and convenient method for measuring chloride ion activity over a wide range of temperatures and salt compositions in chloride salt mixtures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Online and Offline Analytical Techniques to Quantify Chloride Salts

This report serves as the deliverable for Milestone- M3FT-26AN080502017: Summary of Accomplishments for Online and Offline Analytical Qualification of Chloride Fuel Salts. The qualification of chloride fuel salts is a critical challenge for the development and deployment of molten salt reactors (MSRs), requiring precise control and verification of chemical and isotopic composition to ensure predictable neutronics, manageable radiological behavior, and safe plant operation. Currently, there is no universally accepted standard for fuel salt qualification, particularly for chloride-based systems, which underscores the need for robust, science-based analytical methodologies. This report presents a comprehensive evaluation of both online and offline techniques for quantifying chloride fuel salts, including multielectrode array voltammetry, differential thermal analysis (DTA) probes, inert gas fusion (IGF) analyzers, and gamma spectrometry using the Mirion NAIS-2x2 NaI(Tl) detector. The integration of these methods enables real-time monitoring of actinide concentrations, redox state, and thermophysical properties, as well as high-precision measurement of impurities and isotopic composition. The acquisition of advanced instruments such as the Bruker Leonardo G6 for IGF and the Mirion NaI detector enhances analytical capabilities, supporting the establishment of operational envelopes and impurity thresholds. These approaches provide essential data for neutronic impact evaluation, feedstock documentation, and compliance with nuclear safety standards. The methodologies developed and validated in this report lay the groundwork for future standardized protocols, bridging the gap between laboratory research and commercial reactor operation, and advancing the safe and efficient deployment of chloride-fueled MSRs.

Polke, Amber

The Impact of Europium as a Fission Product Surrogate on Chromium Corrosion in Molten Chloride Salt

The rising interest in molten salts, both as thermal energy storage media and as high-temperature solvents for fissile materials in advanced nuclear reactors, has spurred significant growth in research on structural and functional salt-facing materials. Impurities, such as water, play a significant role in the degradation of materials in molten salt environments. Other impurities, such as fission products, are expected to accumulate in molten salts during normal reactor operation and can affect the properties of the salt and salt-facing materials. During normal reactor operation, rare-earth element species are expected to form as byproducts of fission reactions, potentially degrading or altering the performance of both structural and functional materials exposed to salts. Here, in this work, fission product surrogates, europium metal and EuCl 3 , were added to the KCl-MgCl 2 salt while exposing pure Cr specimens in the melt at 600 and 700 °C for 1000 h. Low reactivity was observed with the baseline salt, while both the Eu and EuCl 3 additions to the salt resulted in increased mass loss of Cr specimens. A capillary electrophoresis technique was developed to enable the detection of low parts-per-million (ppm) concentrations of europium (Eu) in chloride salt both before and after exposure of Cr metal. This technique provides a sensitive and reliable method for monitoring trace levels of Eu, which is critical for understanding the interactions and potential contamination effects in salt-facing materials during reactor operation. This quantification technique can be applied to other cationic and anionic contaminants in halide salts.

chloride salt

Quality Ranking of Unary Chloride Salt Property Data Included in MSTDB-TP

Molten salt reactor developers rely on thermal property data to design, license and operate the reactors. The Molten Salt Thermal Database-Thermophysical Properties (MSTDB-TP) was established under the DOE Nuclear Energy Advanced Modeling and Simulation (NEAMS) program and is managed by Oak Ridge National Laboratory to serve as a single source of thermophysical property values measured for a wide variety of molten salt systems for use by researchers, molten salt reactor developers, and regulators. These properties include density, viscosity and thermal diffusivity and conductivity. Published measurements of molten salt properties are lacking for many salts of interest and the data that are available are often inconsistent. This creates a challenge for MSR developers when determining which property values to use when designing their reactors. It is the purpose of this work to apply a consistent ranking system to all data entries that indicates the quality of property values listed in the database. These rankings will be the technical basis for down-selections by the database developers and alert users about the quality of the available property values. MSTDB-TP collects all available property data and indicates preferred data sets or correlations. However, all available data sets are included in the database. Quality assessments and rankings are being applied to data in MSTDB-TP to provide an indication of the quality of each data set independent of consistency with other data. Previous reports detailed the ranking system that was followed and assessments of unary fluoride data sets. Documentation of the quality of data in MSTDB-TP was continued by reviewing and assessing all available sources of density, viscosity and thermal diffusivity or conductivity values for unary chloride salts in MSTDB-TP V3.0 using the same criteria.

22 GENERAL STUDIES OF NUCLEAR REACTORS

Corrosion of Wrought and LPBF 316H in Molten Eutectic Na-Mg Chloride Salt

This presentation shows experimental work at INL evaluating the corrosion behavior of wrought and laser powder bed fusion (LPBF) 316H stainless steel (SS) in chloride molten salt systems. This evaluation focuses on understanding the relationship between the material’s as-built characteristics and its corrosion performance, the effects of acid cleaning and descaling before corrosion.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Quantitative Analysis of Fission-Product Surrogates in Molten Salt Chloride Aerosols

This work demonstrates laser-induced breakdown spectroscopy (LIBS) applied to a stream of aerosolized salt from molten eutectic LiCl-KCl. We demonstrate analytical capabilities to track fission-product surrogates of Cs, Sr, Pr, and Nd simultaneously, with application to monitor salts in pyroprocessing schemes and molten salt reactors. This work demonstrates limits of detection using LIBS on the order of 100 μg/g, which proves potentially applicable to monitoring fission-product concentrations in pyroprocessing applications. Additionally, this work explores fundamental aspects of plasma temperature and plasma electron density of the aerosolized species during LIBS with a specific focus on potential non-uniform plasma conditions in the aerosol.

74 - ATOMIC AND MOLECULAR PHYSICS

Synthesis Roadmap for Actinide Chloride Salts

Molten salt reactors (MSRs) are among the main advanced nuclear reactor types at the forefront of development by industry, with the support of the US government, for the next fleet of nuclear reactors to support the demand for energy in the coming decades. MSRs are highly unique because they are cooled and typically also fueled by molten salt. This quality brings about safety benefits such as low-pressure operation and self-stabilization of the neutron flux, operational benefits such as high-temperature operation and the ability for online refueling, and fuel and waste management benefits thanks to the flexibility of post-processing of molten salts and reprocessing options that involve removal of fission products and actinide separation. In fact, domestic deployment of molten salt (or molten salt–cooled) reactors is an approaching reality: a handful of molten salt reactor developers are planning to operate demonstration-scale reactors, as a step toward commercial-scale power reactors, within the decade. For example, Natura Resources received a construction permit in September 2024 for the deployment of MSR-1, which is a graphite-moderated thermal spectrum reactor, at Abilene Christian University. Also, TerraPower, in a collaborative effort with Southern Company and Idaho National Laboratory (INL), received approval from DOE in 2023 to proceed with the construction of the Molten Chloride Reactor Experiment (MCRE), a homogeneous chloride fast reactor at INL, and has begun assembly of system components. There are several other examples of developers at different stages of development of their own unique MSR designs (Jenet et al., 2025). As developers are in the process of obtaining approvals for their designs, deploying demonstration-scale reactors, and planning for their commercial-scale power reactors, there is a critical supply chain need for the synthesis of fuel for these reactors that must be addressed. The challenge generally is three-fold: (1) the quantity of fueled salt needed for these reactors is extraordinarily high (>100s of kilograms), but demonstrations of scaled-up techniques for fueled salt synthesis are significantly more limited than demonstrations of lab-scale syntheses; (2) each developer has a unique reactor design, which means different actinide halide elements in different carrier salts must be synthesized; and (3) there is a need for particularly high-purity salt so as to ensure the long-term operability of these reactors with minimal degradation to salt-wetted components, which necessitates synthesis techniques with high levels of quality control, repeatability, and well-characterized precursor and reactant materials. It is crucial that this supply chain challenge be addressed by demonstrating synthesis techniques that are scalable, de-risked, and well-documented so that these technologies may be adopted and utilized by industry to support the fueling needs of MSRs that are to come online within the next 10 years. With this supply chain challenge clearly defined for the developing MSR industry, it is important to consider that addressing such a challenge is oftentimes complex and context-dependent. There is not necessarily a single synthesis technique that can be scaled up and adopted to address the needs of all MSR developers; the synthesis approach that may be viable for producing a desired fuel salt will be entirely dependent on the exact salt composition needed, the quantity needed, purity needed, the refueling and waste plans, and the availability of a carrier salt for the fuel. Therefore, it is important to consider more broadly what synthesis techniques are available and have been demonstrated to understand the benefits, challenges, and general nuances that should be considered when evaluating a particular route for efficient production of high-purity fuel salts at scale.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Thermodynamics and transport in molten chloride salts and their mixtures

Relationship between thermophysical properties and phonon mean free path. Heat capacity, viscosity, and thermal conductivity in ionic liquids decrease as mean free path decreases and dynamics become less “solid-like” and collect motion diminishes.

Cockrell, C. [Nuclear Futures Institute, Bangor Un

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

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

Direct Measurement of Cl − Activity in Metal Chloride Molten Salts using a Cl 2 /Cl − Electrode

Molten metal chloride salts are promising candidates for advanced heat transfer fluids in generation IV nuclear reactors and beyond. The activity of the chloride ion in the salt has a large influence on the redox characteristics of the corresponding molten salt. There exists a knowledge gap for the direct measurement of chlorobasicity (Lewis basicity) in molten-salt mixtures. Here, the focus of this work was to develop a Cl 2 /Cl − electrode for the direct measurement of chloride activity in molten metal-chloride salt mixtures. The LiCl–KCl eutectic system was utilized as the reference melt to determine the change in chloride ion activity as increasing concentrations of MgCl 2 are added to the LiCl–KCl eutectic working electrode. The results of the measurements indicated a reduction in chloride ion activity as the concentration of magnesium chloride increased, consistent with the complexation of free chlorides by Lewis acidic magnesium cationic species. The Temkin model was used to estimate the thermodynamic properties of MgCl 4 2− complex.

Chloride

High-Temperature Ferrofluids Based on Molten Salts

Molten metal chloride salts are promising candidates for advanced heat transfer fluids in generation IV nuclear reactors and beyond. However, research on the magnetic properties of suspended metallic nanoparticles at elevated temperatures is scarce, and there have been no attempts to develop a high-temperature, molten salt based ferrofluid. Such a ferrofluid would enable in situ manipulation of both the physical and thermal properties of the fluid via an external magnetic field. This study examines molten salt based ferrofluids comprised of metallic cobalt nanoparticles dispersed in molten metal chloride salts. High-temperature magnetometry and magneto-thermogalvometric measurements were conducted to evaluate the magnetic characteristics of the ferrofluid. Further analysis was conducted through a combination of microscopy, spectroscopy, solubility tests, and diffraction measurements. Furthermore, the metallic cobalt nanoparticles exhibited a notable degree of chemical stability and sustained magnetism from 25 to 800 °C when suspended in NaCl–MgCl 2 and KCl–ZnCl 2 mixtures.

Cobalt

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

Elucidating the corrosion mechanism of commercial Ni-based superalloys in UCl3 containing-chloride molten salt systems

Elucidating the role of UCl3 in the corrosion mechanism of Ni-based superalloys exposed to chloride molten salts Trishelle Copeland-Johnson1, Michael Woods1, Ruchi Gakhar1, Daniel J. Murray1, Guoping Cao1, Lingfeng He1 1Idaho National Laboratory, Idaho Falls, ID, United States The United States Department of Energy (DOE) aims to diversify the domestic energy portfolio towards more sustainable options, including implementation of molten salt reactor (MSR) technology. Chloride molten salts have been investigated as an appropriate MSR coolant and fuel because their relatively inexpensive, abundant, and exhibit favorable thermophysical properties. However, the corrosivity of chloride molten salts have not been extensively studied, especially with the inclusion of actinide products, such as UCl3. Accordingly, the development of nuclear structural materials with excellent corrosion performance is critical to the successful implementation of MSRs, particularly from a mechanistic perspective. In this investigation, we attempt to elucidate the interfacial corrosion mechanism between Ni-based structural materials, such as Inconel 617, and UCl3-containing salt systems through a multi-modal advanced characterization approach, including electron microscopy techniques. The findings from this investigation will expand the knowledgebase of chloride molten salt corrosion of MSR structural materials for strategic property-to-performance design.

36 - MATERIALS SCIENCE

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