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At least 55 records · Page 3

p K a of alcohols dictates their reactivity with reduced uranium-substituted thiomolybdate clusters

The uranium-substituted thiomolybdate cluster, (Cp* 3 Mo 3 S 4 )UCp*, has been demonstrated as a model for water reduction by single uranium atoms supported on a molybdenum sulfide surface (U@MoS 2 ). In this study, the scope of O–H bond activation is expanded through the investigation of the reactivity of various alcohols with differing pKa values for the –OH proton. The reaction of (Cp* 3 Mo 3 S 4 )UCp* with stoichiometric amounts of methanol, phenol, 2,6-dichlorophenol, and nonafluoro-tert-butyl alcohol affords the corresponding mono-alkoxide species, (Cp* 3 Mo 3 S 4 )Cp*U(OR), via a uranium-metalloligand cooperative activation of the O–H bond. This observed reactivity is analogous to the O–H bond activation reported by (Cp* 3 Mo 3 S 4 )UCp* in the presence of water. However, addition of tert-butanol induces protonolysis of the Cp* ligand on uranium, resulting in the formation of a uranium tris-tert-butoxide cluster, (Cp* 3 Mo 3 S 4 )U(O t Bu) 3 . Independent synthesis of (Cp* 3 Mo 3 S 4 )Cp*U(O t Bu) was possible via an alternative pathway, eliminating sterics as a justification for the observed discrepancy in reactivity. Furthermore, these results offer insight into the role the –OH proton pKa plays in dictating the mechanism of O–H bond activation of alcohols by the uranium-substituted thiomolybdate cluster.

Patra, Kamaless

Multi-Objective Optimization of Uranium Target Assembly–3: A Comparison of Genetic and Traditional Methods

Commonly produced as a byproduct of uranium fission, 99 Mo is a key medical isotope that is in high demand in the United States. An international goal is to switch from medical isotope production technologies that require highly enriched uranium to medical isotope production technologies that require only low-enriched uranium. Niowave Inc. is contributing to this goal by developing an accelerator-driven subcritical assembly called the Uranium Target Assembly (UTA). This work compares the performance of Dakota’s Multi-Objective Genetic Algorithm (MOGA) against traditional sensitivity analysis in the neutronic optimization of the UTA-3 system. The design objectives are k-eigenvalue (k eff ) and natural uranium fission power, which are directly correlated with the amount of 99 Mo produced. Dakota:MOGA did not perform as well as human engineering ingenuity in optimization studies with high numbers of input parameters, such as fuel rod type selection and fuel rod placement. However, Dakota:MOGA did outperform traditional sensitivity analysis in optimization studies with fewer than 20 parameters and revealed the degree to which each parameter influences the optimal design space for k eff and natural uranium fission power (to a lesser extent). As the design model became more complex in the final stage of design, the computational resources required to calculate the design objective values in the Monte Carlo N-Particle transport code from selected input parameter combinations limited Dakota:MOGA’s performance, and, unfortunately, human intervention was required to discern the optimal design space. In conclusion, future work will attempt to reduce computational resource constraints by incorporating areduced-order neutronics model into the optimization cycle.

Accelerator-driven systems

Stabilization of Tungsten-Uranium Dioxide Composites Under Thermal Cycling Conditions

Uranium losses during thermal cycling of tungsten - uranium dioxide composites to 2500° C in flowing purified hydrogen for specimens initially containing 35 volume percent uranium dioxide were reduced by the use of thorium dioxide, calcium oxide, or yttrium oxide as additives in solid solution with the uranium dioxide. The effectiveness of the additives decreased in the order yttrium oxide, calcium oxide, and thorium dioxide. Stabilization of uranium dioxide by calcium oxide or yttrium oxide can be explained in part on the basis of the introduction of oxygen vacancies into the fluorite lattice and the associated lowered partial molar free energy of oxygen. The difference in the effectiveness of calcium oxide and yttrium oxide is discussed, and a possible explanation of the observed behavior is proposed. Of the concentrations of yttrium oxide tested (i.e., 2. 5, 5, and 10 mole percent), 10 mole percent of yttrium oxide was the most effective in pre­ venting loss of uranium from composities.

Gluyas, Richard E.

Uranium concentration and distribution in six peridotite inclusions of probable mantle origin

Fission-track activation was used to investigate uranium concentration and distribution in peridotite inclusions in alkali basalt from six localities. Whole-rock uranium concentrations range from 24 to 82 ng/g. Most of the uranium is uniformly distributed in the major silicate phases - olivine, orthopyroxene, and clinopyroxene. Chromian spinels may be classified into two groups on the basis of their uranium content - those which have less than 10 ng/g and those which have 100 to 150 ng/g U. In one sample accessory hydrous phases, phlogopite and hornblende, contain 130 and 300 ng/g U, respectively. The contact between the inclusion and the host basalt is usually quite sharp. Glassy or microcrystalline veinlets found in some samples contain more than 1 microgram/g. Very little uranium is associated with microcrystals of apatite. These results agree with some earlier investigators, who have concluded that suboceanic peridotites contain too little uranium to account for normal oceanic heat flow by conduction alone.

Haines, E. L.

Laboratory-scale uranium RF plasma confinement experiments

An experimental investigation was conducted using 80 kW and 1.2 MW RF induction heater facilities to aid in developing the technology necessary for designing a self-critical fissioning uranium plasma core reactor. Pure uranium hexafluoride (UF6) was injected into argon-confined, steady-state, RF-heated plasmas in different uranium plasma confinement tests to investigate the characteristics of plamas core nuclear reactors. The objectives were: (1) to confine as high a density of uranium vapor as possible within the plasma while simultaneously minimizing the uranium compound wall deposition; (2) to develop and test materials and handling techniques suitable for use with high-temperature, high-pressure gaseous UF6; and (3) to develop complementary diagnostic instrumentation and measurement techniques to characterize the uranium plasma and residue deposited on the test chamber components. In all tests, the plasma was a fluid-mechanically-confined vortex-type contained within a fused-silica cylindrical test chamber. The test chamber peripheral wall was 5.7 cm ID by 10 cm long.

Roman, W. C.

Measurements of uranium mass confined in high density plasmas

An X-ray absorption method for measuring the amount of uranium confined in high density, rf-heated uranium plasmas is described. A comparison of measured absorption of 8 keV X-rays with absorption calculated using Beer Law indicated that the method could be used to measure uranium densities from 3 times 10 to the 16th power atoms/cu cm to 5 times 10 to the 18th power atoms/cu cm. Tests were conducted to measure the density of uranium in an rf-heated argon plasma with UF6 infection and with the power to maintain the discharge supplied by a 1.2 MW rf induction heater facility. The uranium density was measured as the flow rate through the test chamber was varied. A maximum uranium density of 3.85 times 10 to the 17th power atoms/cu cm was measured.

Stoeffler, R. C.

Preliminary Insights Into the Feasibility of Determining the Purification Date of Enriched Uranium by Direct Measurement of the 230 Th/ 234 U Ratio Using an All-Faraday Detector Configuration on the Neoma MC-ICP-MS

Rationale: Mass spectrometric measurement of the 230 Th/ 234 U ratio to calculate the purification age of enriched uranium is typically conducted via a combination of ion counters and faraday detectors, thus requiring an inter-detector calibration scheme. Here, our aim is to understand whether the pursuit of a simplified measurement scheme involving only faraday detectors is feasible. Methods: We investigate the possibility of determining U-Th model ages for two enriched uranium standards (NBL U630 and U850) by direct measurement of the 230 Th/ 234 U ratio (without chromatographic separation or isotope dilution) on a ThermoFisher Scientific Neoma MC-ICP-MS utilizing both solution and laser ablation (LA)-based sampling techniques and an all-faraday detector configuration. Results: For the solution mode analyses conducted on aliquots containing sub μg/mL total U, we produce composite average 230 Th/ 234 U model dates of May 19, 1988 (± 351 days), and March 26, 1961 (± 2.5 years) using the directly measured 230 Th/ 234 U ratios for the NBL U630 and U850 uranium standards, which have certified purification dates of June 6, 1988 (± 190 days), and December 31, 1957 (± 36.5 days), respectively. The ages produced by LA-based sampling of dried residues of the same standards deposited onto cotton TexWipes are less accurate and of poorer precision (June 23, 2004 ± 8.7 years for U630 and December 21, 1965 ± 7.9 years for U850) but still yield meaningful information in regards to the purification date. Conclusions: We believe that further refinement of the all faraday detector measurement approach to include development of a more robust Th/U relative sensitivity factor determination, signal cutoff selection, and data processing protocols will allow for this approach to be confidently applied to enriched uranium materials with unknown purification histories. Potential advantages of the method include the reduced sample handling and infrastructure requirements as well as the ability to simultaneously generate a broad picture of the uranium isotopic composition in tandem with the U-Th age determination.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Oxygen stable isotopes in the nuclear fuel cycle: Assessment of the potential for determining the fabrication and provenance history of anhydrous and hydrous uranium oxides

Determining the origin and history of interdicted nuclear materials is a central challenge in nuclear forensics. The oxygen stable isotope composition of uranium oxide compounds has emerged as a promising forensic signature, attracting increasing attention since the early 2000s. This review examines analytical techniques for measuring oxygen isotope compositions in uranium oxides and evaluates how the nuclear fuel production cycle introduces or modifies these isotopic signatures. The potential for forensic geolocation is explored through workflows that calibrate the relationship between environmental water oxygen isotopes and those found in uranium oxides. Key strengths and limitations of this approach are assessed, including gaps in knowledge related to isotope fractionation during specific stages of the fuel cycle, and processing facility water inputs. The importance of proper sample handling and storage under inert atmospheres, as well as a deeper understanding of both intra-sample oxygen isotope heterogeneity, and hydrous uranium oxide phase formation, is highlighted for improving the reliability of forensic interpretations. In conclusion, the development of uranium oxide standards with well-characterized δ 18 O values and international collaboration toward consensus on their use are identified as essential steps for advancing the field.

Attribution

Uranium Chemistry: Identifying the Next Frontiers

While uranium is the most extensively studied actinide in terms of chemical properties, there remains much to be explored about its fundamental chemistry. Organometallic and organoactinide chemistry first emerged in the 1950s with research that found inspiration from transition-metal chemistry with the synthesis and characterization of uranocene, expanding new opportunities for organoactinide chemistry. Since then, a significant amount of research has pursued many avenues characterizing the fundamental nature of the f orbitals and their modes of bonding as well as their potential in catalysis. Uranium(III/IV) arene complexes dominate much of uranium organometallic chemistry, with bonding interactions stabilized by δ-back-bonding. Recent additions to this area of chemistry include the first UI and new additions of U II organouranium compounds. Uranium–transition metal complexes are still rare and maintain U IV oxidation states, with variable bond lengths determining the transition-metal oxidation state. Resultant reactivities are discussed as synthetic complexes, and unique bonding and coordination motifs are highlighted. In conclusion, this Viewpoint will focus on significant developments in uranium chemistry from the last 15 years while considering key areas for future research.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA

Early-stage uranium-hydrogen corrosion kinetics and mechanism

Research into the early-stage uranium-hydrogen degradation mechanism lacks unified interpretation and understanding due to inadequate temporal and spatial characterization resolution required to unify reaction observations. In this study, white-light interferometry was adapted to characterize the uranium-hydrogen reaction at a temperature of 50 °C and hydrogen pressure of 13.8 kPa. The uranium surface remained unchanged for 62 min during the hydride induction period before the first hydride blister appeared. This blister was monitored from induction through critical spallation and UH₃ powder release during rapid surface hydriding. The critical spallation dimensions measured for height, diameter, area, and perimeter of the first blister were 1.79 µm, 17.58 µm, 187.7 µm 2 and 59.79 µm. Hydriding growth kinetics were assessed by tracking the first hydride site over the reaction time. Analysis shows that the spall-front velocity of the hydride was changing at a rate of 0.91 µm/min which compares favorably with legacy Sievert’s experiments in literature. Total percentage of the surface area hydrided after 242 min was 42.7%, and post-characterization of the UH 3 powders shows both α-UH 3 and β-UH 3 . This work highlights the strength of characterizing the early-stage uranium-hydrogen reaction using white-light interferometry, but more importantly, unifying the understanding and mechanism of the uranium-hydrogen reaction kinetics.

Materials science

Rapid Oxidation of Uranium Steel Alloys: Combustion Synthesis

This project explored the use of combustion synthesis as a rapid, high-temperature method for oxidizing uranium-bearing steel alloys. Traditional laboratory-scale synthesis methods often fail to replicate the thermal and kinetic conditions experienced by real-world particulates, particularly those formed under rapid quenching or high-temperature scenarios. Combustion synthesis offers a promising alternative by enabling fast, localized heating and flexible precursor selection. A series of targeted experiments were conducted using a U 2 NiCrFe 4 alloy as the precursor. The alloy was oxidized using combustion synthesis reactions fueled by uranyl nitrate and glycine, achieving peak temperatures exceeding 1,200 °C. Postreaction analysis using scanning electron microscopy (SEM), elemental mapping, and Raman spectroscopy revealed the formation of iron-based oxides, with limited but detectable evidence of uranium oxide phases such as UO 2 . The results indicate that under the rapid reaction and cooling conditions of combustion synthesis, iron oxides form preferentially, but uranium oxide formation is kinetically limited. These findings validate combustion synthesis as a viable method for simulating the oxidation behavior of uranium steels in extreme environments and lay the groundwork for future studies aimed at enhancing uranium oxide formation through higher temperatures or modified precursor compositions.

36 MATERIALS SCIENCE

Fuel Retention Improvement at High Temperatures in Tungsten-Uranium Dioxide Dispersion Fuel Elements by Plasma-Spray Cladding

An investigation was undertaken to determine the feasibility of depositing integrally bonded plasma-sprayed tungsten coatings onto 80-volume-percent tungsten - 20-volume-percent uranium dioxide composites. These composites were face clad with thin tungsten foil to inhibit uranium dioxide loss at elevated temperatures, but loss at the unclad edges was still significant. By preheating the composite substrates to approximately 3700 degrees F in a nitrogen environment, metallurgically bonded tungsten coatings could be obtained directly by plasma spraying. Furthermore, even though these coatings were thin and somewhat porous, they greatly inhibited the loss of uranium dioxide. For example, a specimen that was face clad but had no edge cladding lost 5.8 percent uranium dioxide after 2 hours at 4750 dgrees F in flowing hydrogen. A similar specimen with plasma-spray-coated edges, however, lost only 0.75 percent uranium dioxide under the same testing conditions.

Grisaffe, Salvatore J.

Measured and calculated fast neutron spectra in a depleted uranium and lithium hydride shielded reactor

Measurements of MeV neutron were made at the surface of a lithium hydride and depleted uranium shielded reactor. Four shield configurations were considered: these were assembled progressively with cylindrical shells of 5-centimeter-thick depleted uranium, 13-centimeter-thick lithium hydride, 5-centimeter-thick depleted uranium, 13-centimeter-thick lithium hydride, 5-centimeter-thick depleted uranium, and 3-centimeter-thick depleted uranium. Measurements were made with a NE-218 scintillation spectrometer; proton pulse height distributions were differentiated to obtain neutron spectra. Calculations were made using the two-dimensional discrete ordinates code DOT and ENDF/B (version 3) cross sections. Good agreement between measured and calculated spectral shape was observed. Absolute measured and calculated fluxes were within 50 percent of one another; observed discrepancies in absolute flux may be due to cross section errors.

Lahti, G. P.

Production of fissioning uranium plasma to approximate gas-core reactor conditions

The intense burst of neutrons from the d-d reaction in a plasma-focus apparatus is exploited to produce a fissioning uranium plasma. The plasma-focus apparatus consists of a pair of coaxial electrodes and is energized by a 25 kJ capacitor bank. A 15-g rod of 93% enriched U-235 is placed in the end of the center electrode where an intense electron beam impinges during the plasma-focus formation. The resulting uranium plasma is heated to about 5 eV. Fission reactions are induced in the uranium plasma by neutrons from the d-d reaction which were moderated by the polyethylene walls. The fission yield is determined by evaluating the gamma peaks of I-134, Cs-138, and other fission products, and it is found that more than 1,000,000 fissions are induced in the uranium for each focus formation, with at least 1% of these occurring in the uranium plasma.

Lee, J. H.

Electrically Heated Testing of the Kilowatt Reactor Using Stirling Technology (KRUSTY) Experiment Using a Depleted Uranium Core

The Kilopower project aims to develop and demonstrate scalable fission-based power technology for systems capable of delivering 110 kW of electric power with a specific power ranging from 2.5 - 6.5 Wkg. This technology could enable high power science missions or could be used to provide surface power for manned missions to the Moon or Mars. NASA has partnered with the Department of Energys National Nuclear Security Administration, Los Alamos National Labs, and Y-12 National Security Complex to develop and test a prototypic reactor and power system using existing facilities and infrastructure. This technology demonstration, referred to as the Kilowatt Reactor Using Stirling TechnologY (KRUSTY), will undergo nuclear ground testing in the summer of 2017 at the Nevada Test Site. The 1 kWe variation of the Kilopower system was chosen for the KRUSTY demonstration. The concept for the 1 kWe flight system consist of a 4 kWt highly enriched Uranium-Molybdenum reactor operating at 800 degrees Celsius coupled to sodium heat pipes. The heat pipes deliver heat to the hot ends of eight 125 W Stirling convertors producing a net electrical output of 1 kW. Waste heat is rejected using titanium-water heat pipes coupled to carbon composite radiator panels. The KRUSTY test, based on this design, uses a prototypic highly enriched uranium-molybdenum core coupled to prototypic sodium heat pipes. The heat pipes transfer heat to two Advanced Stirling Convertors (ASC-E2s) and six thermal simulators, which simulate the thermal draw of full scale power conversion units. Thermal simulators and Stirling engines are gas cooled. The most recent project milestone was the completion of non-nuclear system level testing using an electrically heated depleted uranium (non-fissioning) reactor core simulator. System level testing at the Glenn Research Center (GRC) has validated performance predictions and has demonstrated system level operation and control in a test configuration that replicates the one to be used at the Device Assembly Facility (DAF) at the Nevada National Security Site. Fabrication, assembly, and testing of the depleted uranium core has allowed for higher fidelity system level testing at GRC, and has validated the fabrication methods to be used on the highly enriched uranium core that will supply heat for the DAF KRUSTY demonstration.

Briggs, Maxwell H.

Understanding neutron capture processes in uranium deposits using combined U-Sm-Nd isotopic compositions

Valuable insights into the history and evolution of a geologic deposit can be found by investigating neutron capture reactions. Thermal neutron capture reactions occur within both the samarium (Sm) and the uranium (U) systems, where 149 Sm and 235 U can capture neutrons to become 150 Sm and 236 U, respectively. Although largely unexplored, paired measurements of 150 Sm and 236 U could be important for understanding neutron capture effects within uranium ore bodies, and such measurements are potentially useful in nuclear forensics for assessing a material's provenance or mineral exploration. In this work, we refined measurement procedures of Sm isotope compositions utilizing MC-ICPMS. While geologic reference materials were found to have indistinguishable Sm isotope compositions, we found significant isotope variations consistent with nuclear field shift among synthetic Sm standards. Here, this observation highlights that future high-precision Sm isotope investigations need to carefully evaluate synthetic standard(s) against geologic reference materials until an unfractionated and agreed-upon standard is identified. Here, we applied this method to a set of nine uranium ores from the South Australian Beverley North uranium deposits. Although 236 U excesses had been previously reported for these U ores, we found no measurable isotopic shifts in 149 Sm- 150 Sm at the current level of precision (±5 parts per million). One possible explanation for this disparity in the observed neutron capture signatures between U and Sm is that the source(s) of the U and Sm in these ores may be decoupled. This is consistent with the finding that these ores have variable 143 Nd/ 144 Nd, thus demonstrating that diverse sources were involved in the formation of the Beverley North deposits. Alternatively, this deposit may be too young (<50Ma) to have accumulated measurable neutron capture effects in Sm to be detected with the methods employed here.

Mineral exploration

Development of the technological process for the IGR reactor's highly-enriched irradiated uranium-graphite fuel immobilization

The immobilization of irradiated highly enriched uranium (HEU) fuel is a critical component of nuclear waste management and non-proliferation efforts. In Kazakhstan, at National Nuclear Center of the Republic of Kazakhstan special attention is given to managing legacy HEU fuel from research reactors. One such case involves the IGR research reactor, whose first core containing irradiated HEU uranium-graphite fuel was operated from 1961 to 1966 and removed following reactor modernization. This fuel now requires a reliable and secure immobilization strategy. Here, this paper presents the development of a technological process for immobilizing this fuel to reduce its enrichment to below 20 % in terms of 235U content. The proposed method involves down-blending irradiated HEU fuel with depleted uranium, followed by encapsulation in a Portland cement matrix. Full-scale experiments were conducted to assess the uniformity of uranium distribution within the matrix. The results confirm the effectiveness of this approach, ensuring reliable immobilization of fuel in accordance with international requirements, including IAEA standards and Kazakhstan's regulatory framework. These findings contribute to the broader effort of adapting immobilization strategies for the safe management of spent fuel from research reactors.

12 - MGMT OF RADIOACTIVE AND NON-RADIOACTIVE WASTE

Chemical speciation correlated with microstructural heterogeneity of interdicted uranium materials

Two uranium powders seized by law enforcement in Victoria, Australia, have been characterized by established nuclear forensic methods in a previously published study. Here, in this work, the results of further characterization by a scanning transmission x-ray microscope (STXM) operating in the soft x-ray regime are reported. STXM images are used to estimate the elemental distribution in micrometer-scale particles of each powder, and oxygen K-edge absorption spectra are used to determine the chemical state of uranium. The results of the current study are consistent with the previous analysis; the first powder is found to be a potassium-uranium hydrate, while the second powder is determined to be a mixture of uranium oxides primarily consisting of UO 3 .

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA