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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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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Characterizing the Chemical Behavior of Uranium Compounds for Nuclear Forensics

Better characterization of uranium compounds related to the nuclear fuel cycle is a key goal of the nuclear forensics community. Understanding the chemical behavior of these compounds in various environmental conditions and the effect on observable properties is crucial to the identification of unknown materials. Uranyl fluoride, the hydrolysis product of uranium hexafluoride, is a material of particular interest. Previous studies have suggested that uranyl fluoride may degrade upon exposure to high humidity, but the chemical pathway of degradation was previously not well understood. Our work demonstrates that uranyl fluoride undergoes a chemical reaction with water vapor to form uranyl hydroxide and peroxide species. This understanding will help guide forensic analysis in the future.

Kirkegaard, Marie↗
DOE OSTI2019

Isotopic spectroscopy of uranium atomic beams produced by thermal reduction of uranium compounds

We present a method for producing atomic beams of uranium from molecular uranium precursors in a micro-crucible. In previous work, we have shown that uranium in an atomic beam can be analyzed for isotopic abundances down to enrichment levels of 0.7%. Here in this paper, we show that the same method can be utilized to analyze samples of any of the most common uranium-containing compounds to obtain the same quality of analytical results. This technique relies only on the addition of a metal species capable of reducing the uranium compound of interest. This work presents a brief discussion of the necessary criteria for thermal reduction, development and proof-of-principle of the technique using Er 2 O 3 as a non-radioactive surrogate material, and application to samples of the uranium compounds UO 2 , U 3 O 8 , UO 2 (NO 3 ) 2 , UO 2 F 2 , and UF 4 , to obtain isotope-resolved absorption spectra from an atomic beam produced from these molecular precursors.

Bartlett, Joshua H.↗
DOE OSTI2016

Water Solubility of Plutonium and Uranium Compounds and Residues at TA-55

Understanding the water solubility of plutonium and uranium compounds and residues at TA-55 is necessary to provide a technical basis for appropriate criticality safety, safety basis and accountability controls. Individual compound solubility was determined using published solubility data and solution thermodynamic modeling. Residue solubility was estimated using a combination of published technical reports and process knowledge of constituent compounds. The scope of materials considered includes all compounds and residues at TA-55 as of March 2016 that contain Pu-239 or U-235 where any single item in the facility has more than 500 g of nuclear material. This analysis indicates that the following materials are not appreciably soluble in water: plutonium dioxide (IDC=C21), plutonium phosphate (IDC=C66), plutonium tetrafluoride (IDC=C80), plutonium filter residue (IDC=R26), plutonium hydroxide precipitate (IDC=R41), plutonium DOR salt (IDC=R42), plutonium incinerator ash (IDC=R47), uranium carbide (IDC=C13), uranium dioxide (IDC=C21), U 3 O 8 (IDC=C88), and uranium filter residue (IDC=R26). This analysis also indicates that the following materials are soluble in water: plutonium chloride (IDC=C19) and uranium nitrate (IDC=C52). Equilibrium calculations suggest that PuOCl is water soluble under certain conditions, but some plutonium processing reports indicate that it is insoluble when present in electrorefining residues (R65). Plutonium molten salt extraction residues (IDC=R83) contain significant quantities of PuCl 3 , and are expected to be soluble in water. The solubility of the following plutonium residues is indeterminate due to conflicting reports, insufficient process knowledge or process-dependent composition: calcium salt (IDC=R09), electrorefining salt (IDC=R65), salt (IDC=R71), silica (IDC=R73) and sweepings/screenings (IDC=R78). Solution thermodynamic modeling also indicates that fire suppression water buffered with a commercially-available phosphate buffer would significantly reduce the solubility of PuCl 3 by the precipitation of PuPO 4 .

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2016

Nano-scale mechanical behavior of uranium silicide compounds

Uranium silicide compounds exhibit a range of attractive material properties for nuclear fuel applications, but little is known regarding their mechanical behavior. The structure of nuclear fuels at high burnup can prove to be especially difficult given the significant changes in both chemistry and microstructure caused by fission products. Nano-indentation appears to be a valuable addition to post irradiation examination. The present focus is assessment of the room temperature modulus and hardness of U{sub 3}Si{sub 2}, U{sub 3}Si{sub 5} and USi materials. Each of the compositions under investigation was synthesized via arc melting of the pure metals in an Ar atmosphere using a titanium getter to remove O{sub 2} contamination. The resulting pellets following milling and sintering of the arc melted material were between 96 and 98% of density. Coupling different techniques (SEM and Chemical Analysis), microstructural investigations of the samples has been performed. Preliminary nano-mechanical response of U-Si fuel materials has been demonstrated, on a Hysitron Tribo-indenter which will impact the ability to design advanced fuel materials for enhanced high temperature performance.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2019

Fixed-Angle Reflectance from Uranium Compounds and U-Bearing Minerals: Experimental Challenges to Determine the Optical Constants n and k

Fixed-angle reflectance spectroscopy using a commercial Fourier transform infrared (FTIR) spectrometer was employed to derive the optical constants n and k of several uranium compounds. This technique relies upon measurement of the quantitative reflectance R(?) spectra from a polished surface across a broad spectral range (in this case, the mid- and far-IR covering ca. 7500 to 50 cm-1) followed by application of the Kramers-Kronig transformation (KKT). Near-normal fixed-angle measurements as used in this technique require continuous reflectance spectra to as low a wavenumber value as possible. Here, we discuss some of the many challenges in measuring the far-IR and very far-IR (terahertz) spectra using an interferometric instrument, particularly those stemming from small sample sizes, typically just millimeters on a face for crystalline samples, as well as limitations due to optical components and diffraction. We apply this method to single-crystal UO2 and its mineralogical form uraninite, as well as other U-bearing minerals such as autunite [Ca(UO2)2(PO4)2·8-12H2O] and the dehydrated form of autunite, meta-autunite. In addition to the specular reflectance spectra, x-ray diffractometry was used as a confirmatory technique to analyze the surface composition of the species. Deriving the infrared optical constants for such U-bearing species (as well as other solids) will enable nondestructive detection under a variety of environmental and compositional conditions.

Uranium Minerals, infrared spectroscopy, optical c↗
DOE OSTI2021

Interplay between London Dispersion, Hubbard U , and Metastable States for Uranium Compounds

High-throughput computational studies of lanthanide and actinide chemistry with density-functional theory are complicated by the need for Hubbard U corrections, which ensure localization of the f-electrons, but can lead to metastable states. This work presents a systematic investigation of the effects of both Hubbard U value and metastable states on the predicted structural and thermodynamic properties of four uranium compounds central to the field of nuclear fuels: UC, UN, UO 2 , and UCl 3 . We also assess the impact of the exchange-hole dipole moment (XDM) dispersion correction on the computed properties. Overall, the choice of Hubbard U value and inclusion of a dispersion correction cause larger variations in the computed geometric properties than result from metastable states. Further, the weak dependence of structure optimization on metastable states should simplify future high-throughput calculations on actinides. Conversely, addition of the dispersion correction is found to offset the repulsion introduced by the Hubbard U term and provides greatly improved agreement with experiment for both cell volumes and heats of formation. The XDM dispersion correction is largely invariant to the chosen U value, making it a robust dispersion correction for actinide systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Use of an ion mobility spectrometer for detecting uranium compounds

The safeguards community currently lacks a method to rapidly determine the chemical form of radioactive and non-radioactive compounds in real time during inspection activities. Chemical speciation identification can provide important information on both the types of materials that are collected during environmental sampling and can inform inspectors as to where to focus efforts during inspections or complementary access visits. Ion Mobility Spectrometry (IMS) is an established field technique for the detection of explosives, narcotics, and other organic compounds. More recently, electrospray ionization (ESI) has been used to introduce inorganic compounds to IMS instruments for analysis. These techniques have shown the ability to supply chemical information about the compounds being analyzed. Although these laboratory based instruments use a liquid-based injection system, there is evidence in the literature of unaltered and intact pharmaceutical tablets being volatilized and ionized in open atmosphere using heat and a Ni-63 source. Lastly, this work determined that a commercial-off-the-shelf (COTS) IMS could be used for the identification of solid uranium compounds directly after sampling using a COTS sample swipe.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2025

Resonant x-ray emission across the L 3 edge of uranium compounds

A narrow bandwidth x-ray beamline and a multi-crystal von Hamos spectrometer were used to record x-ray absorption and x-ray emission (XES) across the uranium L 3 edge of UO 2 , UO 3 , Cs 2 UO 2 Cl 4 , and Cs 2 UCl 6 . Measurements were made over 17150–17250 eV with an instrumental resolution of ∼2 eV. This resolution allowed the use of Lorentzian peak fits to the L 3 N 4 and L 3 N 5 characteristic x-ray fluorescence lines that have ∼12–13 eV lifetime widths. The fluorescence yields of the four compounds display strong white lines near threshold and multiple scattering features at higher energies. The XES spectra were fit with three Lorentzians, two for the L 3 N 4 and L 3 N 5 lines and one for inelastic scattering by 2p–6d excitations and 4d–6d final states. The intensities of the white lines were largely due to the inelastic scattering component. To support the measurements, relativistic equation-of-motion coupled-cluster and restricted active space configuration interaction calculations were performed for uranium core-excitation energies in Cs 2 UO 2 Cl 4 and Cs 2 UCl 6 . These calculations with rigorous treatments of relativistic effects are shown to provide accurate uranium L 3 -edge binding energies, L 3 N 5 emission energies, as well as the energy losses in the inelastic scattering process. The measured and calculated results show variations between compounds with U(IV) oxidation states that contain 6d 0 5f 2 electrons in their ground configurations (UO 2 and Cs 2 UCl 6 ) compared with U(VI) compounds (UO 3 and Cs 2 UO 2 Cl 4 ) with empty 5f and 6d configurations.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Probing U 5f Covalency in Uranium Compounds through Oxidant 2p Bonding

Oxidant K (1s) X-ray Emission Spectroscopy (XES) was used to investigate covalency in the Oxidant 2p – Uranium 5f bonds of Uranium Dioxide (UO 2 ) and Uranium Tetrafluoride (UF 4 ). It will be shown that the width of the 2p Occupied Density of States (ODOS), determined from the XES measurements, correlates with the increased 5f covalency of UO 2 and the increased ionicity of UF 4 . Analysis of the XES results includes comparison to spectral simulations, cluster calculations and peak fitting, demonstrating the potential of the oxidant XES measurements as a probe of 5f covalency.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2017

Unraveling 5f-6d hybridization in uranium compounds via spin-resolved L-edge spectroscopy

Here, the multifaceted character of 5f electrons in actinide materials, from localized to itinerant and in between, together with their complex interactions with 6d and other conduction electron states, has thwarted efforts for fully understanding this class of compounds. While theoretical efforts abound, direct experimental probes of relevant electronic states and their hybridization are limited. Here we exploit the presence of sizable quadrupolar and dipolar contributions in the uranium L 3 -edge X-ray absorption cross section to provide unique information on the extent of spin-polarized hybridization between 5f and 6d electronic states by means of X-ray magnetic circular dichroism. As a result, we show how this 5f-6d hybridization regulates the magnetism of each sublattice in UCu 2 Si 2 and UMn 2 Si 2 compounds, demonstrating the potentiality of this methodology to investigate a plethora of magnetic actinide compounds.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2019

U 2 Ni 2 Sn and the origin of magnetic anisotropy in uranium compounds

Here, U 2 Ni 2 Sn is a member of a large family of intermetallic compounds with the tetragonal Mo 2 FeB 2 crystal structure. It orders antiferromagnetically at 25 K with propagation vector $q = (0, 0, \frac{1}{2})$. Magnetization, magnetoacoustic, and neutron-diffraction experiments on a single crystal provide evidence that the uranium moments align parallel to the $c$ axis with the anisotropy energy of ≈170 K, indicating that U 2 Ni 2 Sn can be classified as an Ising system. The results are at variance with previous studies on polycrystals, which indicated different magnetic structure, and which were incompatible with the $5f - 5f$ two-ion anisotropy model dominant in most U band systems. High-field magnetization studies exhibit a weak linear response for fields along the basal plane up to the highest field applied (60 T), while the $c$-axis magnetization curve exhibits three metamagnetic transitions at approximately 30, 39, and 50 T. The U magnetic moments of $0.87 μ_B$, the low magnetic entropy, and the enhanced Sommerfeld coefficient $γ$ = 187 mJ/mol f.u.K 2 suggest that U 2 Ni 2 Sn can be classified as an itinerant antiferromagnet with strong electron-electron correlations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Mathematical simulation of the amplification of 1790-nm laser radiation in a nuclear-excited He – Ar plasma containing nanoclusters of uranium compounds

The possibility of applying dusty active media in nuclearpumped lasers has been considered. The amplification of 1790-nm radiation in a nuclear-excited dusty He – Ar plasma is studied by mathematical simulation. The influence of nanoclusters on the component composition of the medium and the kinetics of the processes occurring in it is analysed using a specially developed kinetic model, including 72 components and more than 400 reactions. An analysis of the results indicates that amplification can in principle be implemented in an active laser He – Ar medium containing 10-nm nanoclusters of metallic uranium and uranium dioxide. (lasers)

74 ATOMIC AND MOLECULAR PHYSICS↗