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At least 37 records · Page 2

Optimization of In-Field Alpha Spectrometry for Uranium Enrichment Determination in Uranium Hexafluoride

In response to needs identified by the International Atomic Energy Agency (IAEA) research is underway to develop In-Field Alpha Spectrometry (IFAS) as a method to allow IAEA safeguards inspectors to collect samples of uranium hexafluoride (UF6) at processing facilities to assess and verify uranium enrichment. For sample collection, the IFAS method uses Single-Use Destructive Assay (SUDA) samplers, which contain thin zeolite coatings that trap UF6 gas and convert it to the safer, more stable form uranyl fluoride (UO2F2). For alpha spectrometry, the IFAS instrument employs a large area silicon semiconductor transducer to detect and record alpha particle energy-deposition events. Over the past year optimization work has significantly increased the diameter of useful SUDA samples (from 12.7 mm to 48 mm), improved the manufacturability and reproducibility of SUDA samples, increased the area of the IFAS alpha spectrometer sensor from 1.2 cm to 3.1 cm, and improved source positioning within the IFAS. This paper will report on this optimization work, its impacts on IFAS performance, and future plans for IFAS miniaturization, improvements, and testing.

46 - INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AN↗

In-field alpha spectrometry system for uranium enrichment verification of uranium hexafluoride

A portable In-Field Alpha Spectrometry (IFAS) system was developed to support on-site uranium enrichment determination for samples taken at facilities working with gaseous UF 6 . It consists of a modified commercial alpha spectrometer, a vacuum pump, a laptop computer, and associated connectors and cables. The IFAS uses specially designed Single-Use Destructive Assay (SUDA) samplers to capture gaseous UF 6 and convert and store it as UO 2 F 2 in a thin-film zeolite. To examine the quantitative performance of the IFAS system a large number of replicate SUDA samples was acquired for natural uranium (NU, 0.72 wt%, 23 samples), low enriched uranium 1 (LEU1, 2.33 wt% 235 U, 10 samples), and low enriched uranium 2 (LEU2, 4.62 wt% 235 U, 10 samples). The standard deviation (SD) values for uranium enrichment determination with the IFAS for NU, LEU1, and LEU2, in 20-hour assays, were 0.037 wt% 235 U, 0.063 wt% 235 U, and 0.072 wt% 235 U, respectively. In addition, a separate analysis suggests that comparable SD values can be achieved in less time, approximately 8-10 hours. For context, these SD values are well below the International Atomic Energy Agency’s International Target Values for the determination of uranium enrichment in non-destructive assay measurements.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Direct uranium enrichment assay in gaseous uranium hexafluoride with laser induced breakdown spectroscopy

A set of eleven U atomic emission lines, between 421.099 and 421.460 nm, were characterized for direct enrichment assay of gaseous UF 6 samples with laser induced breakdown spectroscopy (LIBS). Several iterative, multivariate nonlinear spectral-fitting algorithms were evaluated for their efficacies to extract the enrichment information from the measured LIBS spectra. Furthermore, wavelength-dependent weight factors, which take into consideration of the spectral-line position in the fitting model, the determined isotopic ratio, and the isotopic shift of the emission line, are essential for the spectral-fitting model to function adequately. The analytical accuracies and precision were typically within 0.5% in absolute [ 235 U/( 235 U + 238 U)] ratios.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Formation of Aerosol Nanoparticles by Gas-Phase Hydrolysis Reaction of Uranium Hexafluoride

The aerosol physics of uranyl particle formation has been addressed in this research using advanced aerosol instrumentation and an aerosol dynamics model. Based on the research works, we conclude that the formation and growth of aerosol particles by gas-phase UF6 hydrolysis strongly depends on the availability of water molecules in our reactor conditions. The total number concentration of the UO 2 F 2 particulate material that could be produced in the hydrolysis reaction is also regulated primarily by the availability of water molecule concentration. The higher the water molecule concentration, the higher the number and the larger the size of UO 2 F 2 aerosol particles that could be produced in a reactor custom-built at ORNL. Although the aerosol reactor was enabling the study of particle formation kinetics, the instrumentation was still insufficient in characterizing the chemical composition of the produced particles as well as the time-dependent evolution of the particulate species. The temporal evolution could impact the eventual fate of the particles upon release to the environment (i.e., the physio-chemical transformation, transport, and removal). On uranyl particle formation kinetics, we found that the growth rates of aerosol particles appeared to approach a single number in the range of 0.05 ± 0.03 - 0.08 ± 0.04 nm/s, statistically, as the ω value becomes smaller than 1. The size of primary particles from the UF6 hydrolysis at water-deprived condition was estimated to be 3.6 ± 0.4 nm; the higher the availability of water molecules, the larger the primary particles. The ability to precisely control the availability of water molecules in the reaction could lead to the production of nearly monodispersed aerosol particles. In other words, the result suggests that one can precisely manipulate the size of UO 2 F 2 aerosol particles by controlling the water vapor availability and interaction of water molecules with U F6 in the reaction. This finding has significant implications in the engineering manufacturing of fuel powder materials and possibly to future development and deployment of an environmental sampling apparatus.

74 ATOMIC AND MOLECULAR PHYSICS↗

Controlled Reaction Dynamics of Binary Hexafluorides to Explore New Chemical Signatures

Conclusions • Successfully halted the UF6 hydrolysis reaction and trapped intermediate complexes • Simple alcohol instead of water leads to shifting of bands in UF6 likely from change in matrix effects • MoF6 reaction shows some potential for methyl group being present in structure of intermediates • Future work with bulkier R-groups will hopefully reveal further information as to the reaction pathway and intermediate structure via kinetics and peak shifting

Dorris, Austin L. [Savannah River National Laborat↗

Radiation hot spot formation on UF 6 30B cylinders

The accurate material accountancy of a country's enriched uranium hexafluoride (UF 6 ) stockpiles is imperative to the International Atomic Energy Agency (IAEA) for determining appropriate material safeguards. Uranium hexafluoride is typically stored in large cylinders with enrichment verification typically performed with a NaI gamma detector using the enrichment meter method. This approach for calculating enrichment assumes that the UF 6 is homogeneous inside the cylinder. Here, the measurements and tests presented in this manuscript show that the UF 6 in cylinders left outside in the elements can experience fractionation, leading to inhomogeneity, and subsequent development of radiation hot spots. These hot spot locations can produce errant enrichment measurements. In dark-colored cylinders that experience significant surface heating from the sun, UF 6 sublimates off the cylinder walls, leaving only the uranium daughter products in a horizontal patch (stripe) along the cylinder's midline. This daughter patch is hypothesized to be the source of the radiation hot spots. The patch forms during the summer and tends to decay away during the winter, when solar intensity and temperatures are reduced.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Reactions of Atomic Thorium and Uranium Cations with SF 6 Studied by Guided Ion Beam Tandem Mass Spectrometry

The fundamental chemistry of the thorium and uranium fluorides continues to be an area of interest because of the use of thorium and uranium fluoride compounds in nuclear fuel systems. Here, we study the reaction of thorium cations with sulfur hexafluoride for the first time and revisit the reaction of uranium cations with sulfur hexafluoride. By using guided ion beam tandem mass spectrometry, we explore the reaction pathways that become accessible well above thermal energies (E ~ 0.04 eV). Overall, we find that both Th + and U + react very efficiently with SF 6 , approaching the collision limit at both thermal and elevated energies. Here, the primary products observed at low energies include Th 1–3 + , UF 1–4 + , and SF 1–4 + , all of which are formed in barrierless, exothermic processes. SF 5 + was also observed, although the pressure dependence of this channel reveals that SF 5 + forms exothermically through secondary reactions, which the energy dependences suggest result from reactions between ThF 2 + and UF 3 + with SF 6 . At higher energies, both AnF 3 + products are observed to decay to AnF + + F 2 and both SF 4 + and SF 2 + exhibit cross sections with endothermic features. For both systems, the rise in SF 4 + can be attributed to a secondary collision between AnF + with SF 6 on the basis of the pressure dependence of the SF 4 + channel at higher energies and the rise in SF 2 + appears to result from the decomposition of SF 3 + to SF 2 + + F.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

LiPF 6 under pressure: a symmetry-mode-based structural analysis

The lithium salt LiPF 6 is a key component in commercial lithium-ion battery (LIB) electrolytes. However, its structural properties under pressure remain unexplored, despite increasing interest in the effect of pressure on electrolyte behaviour, and a growing interest in high pressure synthesis of new Li-hexafluoride cathode materials. Here, we present the first high pressure neutron diffraction study of solid LiPF 6 up to 7.4 GPa. Refinements reveal that the ambient rhombohedral structure (space group R$\overline{3}$) remains stable throughout, with pressure accommodated primarily by tilting of the corner-shared LiF 6 and PF 6 octahedra and contraction of the LiF 6 units. In conclusion, this study establishes a foundation for understanding the phase behaviour of Li-based hexafluorides under extreme conditions.

25 ENERGY STORAGE↗

Heterogeneity effects on nondestructive assay measurements of enrichment in UF 6 cylinders

A set of measurements were performed using multiple mechanically cooled HPGe detectors at six positions around a cylinder uranium hexafluoride to assess if matrix inhomogeneity is detectible and effects the determined apparent uranium enrichment. These measurements were performed on nine 30B cylinders of uranium hexafluoride. Six of the cylinders appeared to be homogeneous and had similar apparent measured uranium enrichment, as calculated by the FRAM software, at all positions. However, three cylinders appeared to have local inhomogeneity based on the observed results. This was manifested as very low apparent enrichments, often <10% of the declared enrichment, on select positions. The side with a low apparent enrichment shows elevated daughter isotope activity (e.g., elevated 1001 keV and 766 keV peak count rate) and slightly reduced 235 U activity (lower 185.7 keV count rate). We hypothesize that these heterogenous cylinders may have experienced asymmetric solar heating, which caused volatile UF 6 to sublime preferentially away from the warmed side. A similar phenomenon was observed at a second facility where dose rate measurements confirm that the “low-enriched side” of cylinders show elevated gamma ray dose rates, likely from the removal of UF 6 attenuation and concentration of daughter-products. Care should be taken during uranium enrichment verification when applying methods that include gamma-rays associated with daughter nuclides to the determination of uranium enrichment on cylinders that are stored in sunlight and have asymmetric dose readings around the cylinder.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗