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At least 145 records · Page 8

Continuous Particle Monitoring and Removal for Molten Chloride CSP Systems

This report describes the technologies that were developed as part of the Continuous Particle Monitoring and Removal for Molten Chloride CSP Systems project that was funded by the EERE Solar Energy Technologies Office during FY2021. This project consisted of two main tasks: (1) the development electrical resistance tomography (ERT) sensors to provide particle sensing capabilities for CSP-relevant molten chloride salts, and (2) the development of vortex separation technologies to enable efficient removal of particles from the salt. Both of these tasks are crucial because, although the Gen3 CSP chloride heat transfer fluid is inexpensive and can achieve high temperatures, major issues with erosion corrosion and clogging can arise from the presence of MgO particles within the salt. The particle monitoring and removal technologies were both demonstrated over the course of this project. The ERT sensors were able to achieve their performance targets by providing accurate particle concentration measurements over a range from 0.0 to 8.0 wt%. The vortex separators were able to demonstrate separation of particles from molten salt streams, but the separation efficiencies were lower than the targeted level of 90%. With further development and deployment, these technologies will ultimately help to enable successful long-term operations of CSP systems that make use of high-temperature chloride salts.

14 SOLAR ENERGY↗

Accelerated Materials Design for Molten Salt Technologies Using Innovative High-Throughput Methods

The focus of the project is on building an innovative accelerated materials design platform for molten salt technologies using novel high-throughput methods coupled to data analytics. The main objectives is to predict a FeCrMnNi alloy compositional space with better corrosion resistance than stainless steel 316 and identify new molten salt corrosion mechanisms. The project demonstrates the feasibility to use high-throughput methods coupled to data analytics to accelerate alloy design for extreme environments applications. Using a trained and tested machine learning (ML) model, 2000 FeCrMnNi alloy corrosion rate in molten chloride salts were predicted and a compositional field with corrosion rate lower than 316 stainless steel was identified. The ML model interpretability unveiled multiple features of importance in the model prediction. Some features were expected to be of relative significance, such as work function, surface energy and alloy electronegativity, and the ML model interpretability analysis confirmed those. On the other hand, the most important feature is the diffusion coefficient of Ni in the bulk alloy which indicates that a surface diffusion mechanism plays an important role in the overall corrosion mechanism in molten salts.

36 MATERIALS SCIENCE↗

Electrochemical Characterization of Molten Salt Chemistry During Atmospheric Ingressions

This report describes the salt chemistry and sedimentation studies that were completed in FY23 as part of the Pyrochemical Fuel Cycles – ANL project. The primary objective of these activities was to employ electrochemical methods in order to quantify and gain insights into the reaction mechanisms associated with the interaction of O2 and moisture impurities with the molten chloride salts used for the pyrochemical processing of nuclear materials. If not monitored and controlled, the ingression of these atmospheric impurities can lead to changes in the salt redox conditions and initiate the formation of oxide particles, potentially resulting in operational and safeguards challenges. By elucidating the mechanisms underlying the formation of oxide particles, we can effectively monitor the conditions of the salt and design systems to mitigate the influence of atmospheric O2 and H2O. To achieve these goals, we designed a test system that allowed for precisely controlled gas ingressions into the molten salt vessel. This system included on-line monitoring provided by electrochemical probes that enable near real-time measurements of the salt conditions throughout the course of the experiment. Using this system, we systematically varied experimental conditions, including O2/Ar flow rates and O2 concentrations, to comprehensively understand their impact on solid particle formation. We also used a particle size and shape analyzer to characterize the particles that were generated. Tests in FY23 concentrated on the formation of CeO2 particles, but we also prepared a separate apparatus targeting UO2 particles for use in FY24. We additionally conducted extensive modeling activities in support of this work. This included multiphysics simulations of the gas ingressions along with the development of a machine learning workflow to enable accelerated molecular dynamics modeling of the molten salt chemistry of LiCl-KCl-UCl3. The combination of experimental and modeling tools has allowed us to begin to get a more complete understanding of the reactions that occur when atmospheric ingressions occur in pyroprocessing systems.

Guo, Jicheng↗

Tribological behavior of ceramic-alloy bearing contacts in molten salt lubrication for concentrating solar power

Molten salts are considered as candidate heat transfer fluids and thermal energy storage media for next generation concentrating solar power (CSP). A molten salt circulates inside the piping and heat exchanger and also functions as a lubricant for the sleeve bearings of the CSP pump. Furthermore, wear- and corrosion-resistant high-temperature bearing materials are critical for the pump efficiency and durability. This study evaluated the tribological performance of candidate bearing materials in lubrication of a molten chloride salt mixture (20% NaCl + 40% MgCl 2 + 40% KCl) at 750 °C in an inert argon gas (a simulative CSP pump environment). Six ceramic-alloy pairs were tested, zirconia and silicon nitride against Haynes 244, Hastelloy C276, and Tribaloy T900 alloy, and ranked by the friction coefficient and wear loss. Characterization of worn surfaces suggested the wear mechanism as a combination of abrasion, adhesion, and tribocorrosion. Results from this study provide fundamental insight for the development and selection of bearing materials for molten salt powered CSP pumps.

14 SOLAR ENERGY↗

Atomistic Simulations for Thermophysical Properties of Uranium-Containing Halide Molten Salts

Characterizing the thermophysical properties in both fuel and coolant salts are critical in modeling, developing, process optimizing and utilizing molten salt reactors (MSRs), as these properties directly relate to operation metrics and can inform on the selection of candidate salts. The demand for consistent, accurate and publicly available thermophysical property data has become more apparent in recent years as interests have increased from molten salt reactor developers. There are a number of challenges in experimentally measuring properties such as thermal conductivity, viscosity, density and heat capacity , which have led to sparse and often times conflicting data points or molten salts in general. Additionally, there are a number of hazards to consider when synthesizing, storing, using, treating and disposing of molten salts. With the advances in computational capabilities over the last 10 years, the use of atomistic simulations can be implemented to support these efforts. The primary objective of this work is characterize the thermophysical transport properties in a number of molten chloride salts, and in particular NaCl-UCl 3 using ab-initio molecular dynamic (AIMD) simulations. In this binary salt the UCl 3 acts as the primary fissile material and NaCl acts as a carrier salt due with its’ high solubility for actinides A number of studies on the thermophysical properties of NaCl-UCl 3 have been published but there is not a vast amount of viscosity data for this system. In 1975, Desyatnik, et al published a study reporting dynamic viscosities that were calculated from kinematic viscosity measurements, and using the coefficients provided the viscosity in a 70:30 NaCl:UCl 3 mixture is 2.29 cP and 2.88 for a 60:40 mixture. Termini et al. recently reported viscosities in the range of 2.75 – 3 cP for the 63:37 NaCl-UCl 3 mixture in the same temperature range using rolling ball viscosity measurements. Computational viscosity of a similar mixture (64:36) can be obtained from the work Andersson et al. using the reported diffusion coefficients, and the hydrodynamic radius from the pair-radial distribution functions (RDFs). Using Eq (1) (vida infra), the viscosity would be 2.50 cP at 1100K. This is not to say that these values are incorrect due to the varying reported values, but aims to highlight the necessity of this work. The data reported in this ongoing work are computations on a 64:36 mixture of NaCl-UCl 3 at 987K. This work is likely to be expanded into varying concentrations of this mixture along with the inclusion of other salt candidate mixtures.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Potential of electrolytic processes for recovery of molybdenum from molten salts for 99 Mo production

Molten salt reactor (MSR) technologies are receiving significant interest for commercialization because of their potential safety features and efficient energy production. In addition to producing reliable and clean energy, high-value radioisotopes could be harvested from MSRs as an additional revenue stream. Although significant quantities of 99 Mo will be produced in MSRs through fission, how accessible 99 Mo will be for direct recovery from a fuel salt is unclear. Electrolytic processes in fused salts have been used extensively for processing molten salts and have the potential to enable the extraction of 99 Mo directly from the fuel salt. This paper reviews the behavior of 99 Mo in the molten salt reactor experiment and summarizes theoretical aspects of the electrolytic process in high-temperature fused salt and the published experimental results on Mo extraction through electrolytic processes. Here, the general principle of fused-salt electrolytic processes is described, by electrodeposition of Mo with the following aspects: electrowinning, electrorefining, electroplating, and electroextraction with several experimental considerations. Finally, important considerations for recovery of 99 Mo from MSR relevant molten salts via electrodeposition are discussed.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Kinetics of Radiation-induced Cr( II ) and Cr( III ) Redox Chemistry in Molten LiCl-KCl Eutectic

Chromium (Cr) is a frequent constituent of the metal alloys proposed for molten salt nuclear reactor (MSR) applications, and is typically the least noble metal ion present. Consequently, chromium is preferentially corroded into molten salt solutions. Here, the redox poise and redox cycling of chromium ions in the salt can greatly influence its corrosivity towards structural alloys, ultimately impacting the longevity of MSR systems. Radiation-induced chemistry is expected to play a significant role in determining the chromium oxidation state distribution during MSR operations. In the present research, electron pulse radiolysis techniques were employed to characterize the reactivity of Cr(II) and Cr(III) ions with primary radiolysis products in molten lithium chloride–potassium chloride (LiCl–KCl) eutectic over a temperature range of 400–600 °C. Both chromium oxidation states were found to rapidly react with the primary products of molten chloride salt radiolysis, i.e., the solvated electron (e S - ) and the dichlorine radical anion (Cl 2 ˙ - ). For reactions with the e S - , second-order rate coefficients (k) of k = (4.1 ± 0.2) and (6.1 ± 0.3) × 10 10 M -1 s -1 at 400 °C for Cr(II) and Cr(III), respectively, were determined. Temperature-dependent measurements allowed for the derivation of activation parameters for electron capture by Cr(II) and Cr(III). Both chromium ions also react with Cl 2 ˙ - , k = (7.2 ± 0.3) and (1.4 ± 0.1) × 10 9 M -1 s -1 at 400 °C for Cr(II) and Cr(III), respectively.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗

Local Coordination Environment of 3d and 4d Transition Metal Ions in LiCl-KCl Eutectic Mixture

In this study, the structure and coordination environment of two 3d transition elements (Ni and Cr) is investigated in a molten chloride salt system. Electronic absorption spectroscopy was employed to elucidate their coordination environment in 3LiCl-2KCl eutectic salt, as a function of temperature. Density functional theory (DFT) modeling was used to determine the coordination environment of the transition metal species in the eutectic composition as well as the optical spectra computationally. The Ni 2+ and Cr 3+ exist in a tetrahedral and octahedral coordination environment, respectively, in eutectic salt. The spectra thus obtained were compared with the experimental data; a reasonable qualitative agreement was obtained between experimental and computational Ni 2+ and Cr 3+ spectra, and the coordination of both elements in the eutectic composition were in excellent agreement with the experimentally determined results. Computational results were also obtained for two 4d elements, Mo 3+ and Nb 3+ , with both quantum molecular dynamics (QMD) and hybrid functional optical spectra indicating octahedral coordination.

36 MATERIALS SCIENCE↗

Binder jet additive manufacturing of ceramic heat exchangers for concentrating solar power applications with thermal energy storage in molten chlorides

Triply periodic minimal surface (TPMS) geometries can only be fabricated by additive manufacturing methods and are of interest for heat exchangers. Ceramic TPMS heat exchangers can operate at higher temperatures and pressures with superior performance and increased operating efficiencies compared to metal heat exchangers. The properties of ultra-high temperature ceramic (UHTC) materials are also favorable for heat exchangers and potentially suited to concentrated solar power (CSP) systems, such as those based on a molten chloride salt thermal energy storage (TES) medium used to heat CO 2 in a closed-loop Brayton power cycle. We intended to demonstrate binder jet additive manufacturing feasibility of a UHTC-TPMS structure by printing and sintering a null candidate. We aimed to achieve parts with a relative density ≥ 92 % of theoretical and to provide a TPMS part demonstration. The target density indicates the transition from intermediate to final stage sintering, a requirement to inhibit gas permeability and for sintering complex near net shapes to full density with sinter-HIP technology. The goal of the TPMS part demonstration was to determine if printing and sintering parameters developed from test coupons apply to the complex geometries that will eventually be used in a heat exchanger design. Our objective was to print cubic TPMS parts with a 9 cm 3 volume and sinter it without distorting and cracking. We report we were able to sinter ZrB 2 -MoSi 2 composite parts based on the Schwarz-D TPMS and achieve isotropic shrinkage up to 60 % by volume, resulting in densities ranging from 92 % to 96 % of theoretical.

36 MATERIALS SCIENCE↗

Flow and Heat Transfer Experimental Study for 3D-Printed Solar Receiving Tubes With Helical Fins at Internal Surface

3D-printing technology was applied to fabricate novel solar thermal collection tubes that have internal heat transfer enhancement fins and external surfaces with high solar absorptivity and low emissivity due to the ability to use different materials in one tube. Helical fins were selected to introduce circumferential flow and thus minimize the circumferential temperature difference of the tube that receives sunlight on one side. The structures of the helical fins were previously optimized from computational fluid dynamics (CFD) analysis with the objective of low entropy production rate by looking for high heat transfer coefficient and relatively lower pressure loss. High-temperature alloy, Inconel-718, was used to 3D print the tubes, which can resist corrosion for the potential application of molten chloride salts as heat transfer fluid. Experimental tests were carried out using water as the heat transfer fluid with the high heat flux provided by a tubular furnace heater. The tested Reynolds number ranges from 3.9 × 10 3 to 6.1 × 10 4 . Heat transfer coefficients of up to 2.8 times that of the smooth tube could be obtained with the expense of increased pressure loss compared to that of the smooth tube. The total system entropy generation can be significantly reduced due to the benefit of heat transfer enhancement that is greater than the expenses of the increased pressure loss. The experimental results of the 3D-printed heat transfer tubes confirmed the CFD-based results of fin optimization. Furthermore, the novel heat transfer tube is recommended for application in concentrating solar power systems.

14 SOLAR ENERGY↗

Compositional Exploration of Additively Manufactured Ultra-High-Temperature Ceramic Composites for Use in Concentrated Solar Power Plant Heat Exchangers

The DOE has research interest in new technologies for high temperature concentrated solar power plants. Our project this summer was to explore the use of additively manufactured ultra-high-temperature ceramics in a heat exchanger. The heat exchanger would transfer heat between a molten chloride salt and supercritical CO 2 . We selected 22 compositions to test and were able to mix 14 of these compositions. We sintered these compositions using pressureless sintering and direct current sintering. We also conducted high temperature TGA on some ceramic samples. We also performed preliminary binder jet additive manufacturing trials with tungsten carbide powder. Our work so far points towards one of our titanium diboride samples being promising, but much more research needs to be done.

14 SOLAR ENERGY↗

Thermomechanical Behavior of Advanced Manufactured Parts, Subcomponents, and Their Weldments for Gen3 CSP

Generation 3 (Gen3) concentrating solar power (CSP) plants may require the use of molten chloride salt storage systems, solar receivers, and supercritical-CO 2 primary heat exchangers (PHX). The temperatures that would be expected in these parts and subcomponents could approach 760°C for hot side and 500°C for cold side at peak operating conditions. With the design limitations, highly corrosion- and creep-resistant alloys are needed for maximizing component lives. This report presents the results for the project "Thermomechanical Behavior of Advanced Manufactured Parts, Subcomponents, and their Weldments for Gen3 CSP", award number DE-EE00036334. In this project, creep enhanced ferritic alloy Grade 91, austenitic stainless-steel (SS) 304H, Ni claddings Ni201 and C22, and nickel-based superalloys Inconel 740H and Haynes 282 and 230 were evaluated for potential applications in Gen3 CSP systems. Advanced manufacturing of these parts, subcomponents and their welds, was investigated and a full technoeconomic analysis was made in comparison to conventional manufacturing techniques. The manufacturing techniques explored are explosion clad welding and combustion synthesis/combustion reaction for transfer pipes, additive manufacturing (AM) including laser-powder bed fusion (L-PBF) and electron beam AM (EBAM) with wire feedstock for PHX and solar receivers, and conventional fusion welding for similar and dissimilar joining of these various parts and subcomponents.

14 SOLAR ENERGY↗

Demonstration of Electroreduction Technology to Convert GNF Uranium Oxide Powder to Metal

Global Nuclear Fuel – Americas LLC (GNF) has partnered with Argonne National Laboratory to demonstrate electroreduction of uranium oxides produced by deconversion of UF 6 to uranium metal through the Gateway for Accelerated Innovation in Nuclear (GAIN) program under the U.S. Department of Energy to accelerate the domestic production of metallic advanced reactor fuels. Electroreduction of uranium oxide was first demonstrated and patented by Argonne in the early 2000s as a technology to convert used oxide nuclear fuel from light water reactors to metal for further fuel reprocessing. More recently, electroreduction has been proposed as a front-end technology for metallization of uranium oxides produced by deconversion of UF 6 and for scrap recovery of oxide materials. During the electroreduction process, UO 2 powder is contained in a stainless-steel mesh basket with a cathode lead located in the center of the UO 2 bed. The basket is immersed in lithium chloride molten salt electrolyte containing 1 wt% lithium oxide along with a platinum anode and a nickel/nickel oxide (Ni/NiO) reference electrode. Current is applied to the cell between the cathode and anode to reduce the UO 2 to metallic uranium via a solid-state reduction reaction. Oxide ions released from the UO 2 during reduction are transported through the salt to the anode where oxygen gas is evolved. Once reduction is complete, the basket containing the metallicized uranium is removed from the salt and can be processed to remove the salt and consolidate the uranium into an ingot for use in metallic fuel fabrication. This project was performed to provide evidence of the electroreduction technology readiness level for metallization of UO 2 powder, identify and retire technical risks for industrialization of electroreduction, and accelerate the path to commercialization for metallic fast reactor fuel production. To that end, five electroreduction tests were performed with UO 2 provided by GNF and the resulting product was analyzed for the extent of conversion to metal and for impurity contents of the metal product to verify that electroreduction does not introduce impurities that would prevent use of the product in metallic fuel fabrication.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Development of a Representative Molten Chloride Fast Reactor Model to Assess the Impact of Nuclear Data

The SCALE code system was employed to conduct a preliminary investigation of nuclear data impacts for a fast spectrum molten chloride salt reactor. A computationally effective depletion model that is representative of the reactor system was successfully developed and used to conduct fuel depletion simulations. Development of this model draws from the SLICE method that was developed at Oak Ridge National Laboratory to enable generation of fuel compositions for an advanced reactor core at equilibrium operation. Eigenvalue uncertainty calculations using the ENDF/B-VII.1 nuclear data library were performed for the reactor in the fresh fuel state and an irradiated fuel state. It was determined that the primary driver of eigenvalue uncertainty was the uncertainty in the 235U (n, 𝛾) cross section. Uncertainty calculation results from this study were compared to results available for a different fast system, a sodium-cooled fast reactor, to confirm similarities and identify differences with respect to nuclear data impacts between the two fast advanced reactor systems.

Hirji, Rakim [Georgia Institute of Technology]↗

Gamma Irradiation of NaCl-UCl 3 Salt for the Molten Chloride Fast Reactor

This report documents the results of the gamma ray irradiation of NaCl-UCl 3 eutectic salt in the Advanced Test Reactor (ATR) spent fuel pool gamma tube and subsequent analysis of capsules utilizing the Gas Assay Sample and Recharge (GASR) system. NaCl-UCl 3 salt capsules at four different temperatures, 75C, 150C, 300C and 600C, were irradiated shortly after the core internal changeout (CIC) of the ATR, beginning April 28 th of 2021, and ending on August 18 th of 2021. Re-positioning of the fuel elements in the spent fuel pool to move more fresh fuel elements around the gamma tube occurred on May 11 th of 2021, resulting in an approximate 20% increase in the dose rate and consequently the total absorbed dose. In total, the salt-filled capsules underwent 2638 hours of gamma irradiation from the adjacent freshly discharged ATR spent fuel. Capsule internal pressure measurements were taken via the Gas Assay Sample and Recharge (GASR) system in the INL Hot Fuels Examination Facility (HFEF) following completion of the irradiation. Based on the GASR analysis results, the primary conclusion from this experiment to-date is that radiolytic generation of chlorine gas is insignificant for the dose rates and total absorbed dose that these samples experienced. To elucidate more detailed effects of radiolysis on NaCl-UCl 3 eutectic salts and reach a more definitive conclusion, further advanced analyses such as electron microscopy, simultaneous thermal analysis, and electron paramagnetic resonance are recommended to analyze the capsule wall and salt samples.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Mitigation of Molten Salt Corrosion

The desire to increase the peak operational temperature of Concentrated Solar Power (CSP) plants to lower the levelized cost of CSP-derived electricity, has led to consideration of an earth-abundant, low-cost, thermally-stable, molten MgCl 2 -KCl-NaCl (40-40-20 mole%) salt for high-temperature thermal energy storage and heat transfer. The reliable, long-term containment of such a molten salt is challenging, however, due to the corrosion of cost-effective, high-temperature structural metal alloys in this salt (particularly if this salt is contaminated with oxygen-bearing species). This project has been focused on: i) development of equipment for evaluating corrosion kinetics in molten chlorides under well-controlled thermal, fluid dynamic, and atmospheric conditions at CSP-relevant temperatures, ii) use of such equipment to evaluate the influence of forced convection on corrosion kinetics (to determine the role of liquid phase diffusion on such corrosion), and iii) identifying a corrosion-mitigation strategy that can be industrially applied to achieve a projected annual corrosion ≤30 μm at CSP-relevant temperatures. The overall goals of this project have been: i) to understand the rate-limiting step(s) and associated kinetic laws governing corrosion in molten chlorides at 750°C, ii) to determine key operational parameters affecting the corrosion kinetics in molten salts, and iii) to demonstrate the tailoring of such parameters to appreciably reduce such corrosion.

14 SOLAR ENERGY↗

Electrode Blocking Due to Redox Reactions in Aluminum Chloride-Sodium Iodide Molten Salts

Iodide redox reactions in molten NaI/AlCl 3 are shown to generate surface-blocking films, which may limit the useful cycling rates and energy densities of molten sodium batteries below 150 °C. An experimental investigation of electrode interfacial stability at 110 °C reveals the source of the reaction rate limitations. Electrochemical experiments in a 3-electrode configuration confirm an increase of resistance on the electrode surface after oxidation or reduction current is passed. Using chronopotentiometry, chronoamperometry, cyclic voltammetry, and electrochemical impedance spectroscopy, the film formation is shown to depend on the electrode material (W, Mo, Ta, or glassy carbon), as well as the Lewis acidity and molar ratio of I − /I 3 − in the molten salt electrolytes. These factors impact the amount of charge that can be passed at a given current density prior to developing excessive overpotential due to film formation that blocks the electrode surface. The results presented here guide the design and use of iodide-based molten salt electrolytes and electrode materials for grid scale battery applications.

25 ENERGY STORAGE↗