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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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Hydrochlorination of Uranium Dioxide in a Molten Salt Mixture- Phase 2: Sparged Benchtop Reaction Vessel Experiment

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 Metatomic 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 2 (of 2) experimentation. Though Phase 1 provided evidence of successful hydrochlorination, Phase 2 highlighted the nuances and challenges associated with scaling the reaction. The target UCl 4 species generated by the hydrochlorination of UO 2 generates water, which consumes UCl 4 . Compared to the single datapoint obtained at the end of the Phase 1 experiments, data collected at multiple timepoints during Phase 2 experiments indicated a presumed maximum percent conversion of 23% for this system that is likely influenced by water generation. Engineering improvements might be able to increase the percent conversion, but not likely to the degree needed for successful implementation of the technology. Moisture also presents an issue for the Hastelloy C276 reaction vessel. Eventually, corrosion will compromise the integrity of the reaction vessel, and the corrosion products could potentially affect the hydrochlorination chemistry. The presence of corrosion products, which were not produced in the Phase 1 alumina crucible, can and have created challenges when analyzing samples.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Oak Ridge National Laboratory Fission Product Hydrochlorination

This work supports the recovery of high-assay low-enriched uranium (HALEU, uranium enriched in 235 U to >5% and <20%) from used nuclear fuel through a process based on the zirconium extraction (ZIRCEX) process. The ZIRCEX process starts with the dry head-end removal of zirconium or aluminum cladding from the nuclear fuel via chlorination or hydrochlorination, which results in the separation of cladding from the fuel as the metal chloride (e.g., aluminum trichloride or zirconium tetrachloride). The hydrochlorination process is included in the Material Recovery Pilot Plant (MRPP), a ZIRCEX-based demonstration plant at Idaho National Laboratory (INL). The experiments outlined in this report assessed fission product (FP) volatility and transport under the hydrochlorination conditions used to separate cladding from used nuclear fuel.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Hybrid Zircex Hydrochlorinator

This project was driven by the desire to create easier and faster ways to load Advanced Test Reactor (ATR) Fuel Elements into the Hybrid Zircex hydrochlorinator. The primary requirements for this project were to minimize the potential release of radioactive contamination, minimize maintenance operations to replace or remove the lid seal, and allow for remote usage. Three preliminary designs were made. These designs allow ATR fuel elements to be loaded into the hydrochlorinator more efficiently while fulfilling the requirements.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

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↗

Observations regarding inclusions in the growth of $\mathrm{Cs}$ 2 $\mathrm{HfCl}$ 6 single crystal scintillators

Cs 2 HfCl 6 (CHC) is a promising high density, high-Z, non-hygroscopic, and high energy resolution scintillator. In CHC, many crystals have CsCl inclusions that form during growth. In this paper, we investigate how material synthesis, growth rate, and thermal gradient affect the formation of CsCl inclusions and their effect on scintillation performance. First, precursor material was made through a methanol synthesis process both with and without hydrochlorination. Next, five crystals were grown using Bridgman method, at growth rates of 1 or 0.5 mm/h, and thermal gradients of 21 °C or 34 °C per millimeter. The best overall performance was observed in a 22 mm diameter crystal produced using hydrochlorination which was grown at 1 mm/h in a thermal gradient of 34 °C per millimeter. It had a light yield of 36,000 photons/MeV and an energy resolution of 4.0% at 662 keV. Finally, we have also shown that poorer scintillation performance in the lower quality crystals is most likely due to reduced light collection caused by a higher concentration of inclusions.

36 MATERIALS SCIENCE↗

On-line Measurement of Hydrogen Gas using Raman Spectroscopy for Process Gas Systems

Advanced reprocessing schemes such as the Zircex process are important for continued development of the nuclear fuel cycle. The hydrochlorination reaction of the Zircex process flow sheet for metallic fuels has a known off-gas stream of H 2 (g) and HCl. The flow sheet can be simplified through HCl recycling, which requires detection and quantification of any residual H 2 (g) for safety and purity. In this work, commercially available Raman spectroscopy was applied for low-level, on-line detection of H 2 (g) in process gas streams, and parameters were adjusted to optimize the H 2 (g) Raman signal. Increasing the number of scans and exposure time in the spectrometer increased the signal-to-noise ratio of the H 2 (g) Raman signal, while the gas flow rate was optimized at 2.3 L/min. The limit of detection for H 2 (g) was estimated to be 2,100 ppm H 2 (g) in an N 2 (g) background. This scoping study for the application of Raman spectroscopy for on-line measurements of H 2 (g) shows that H 2 (g) can be detected at low levels (approximately 5% of the lower explosive limit (LEL)) in flowing gas streams.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Demonstration of In Situ Down Blending During ZIRCEX Process

The Material Recovery Pilot Plant has successfully demonstrated in situ down-blending of HEU fuel to support INL’s commitment to HALEU production technologies. Depleted uranium pellets, along with an HEU fuel piece were placed in the hydrochlorinator and subsequently declad and oxidized. UOx product was recovered, analyzed, and demonstrated to have reduced enrichment within the targeted range of 20 – 30 % U-235. This first attempt at in situ down-blending will be followed by continued process refinement over the remaining fuel operations at MRPP.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗