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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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50 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

129 I and 247 Cm in meteorites constrain the last astrophysical source of solar r-process elements

The composition of the early Solar System can be inferred from meteorites. Many elements heavier than iron were formed by the rapid neutron capture process (r-process), but the astrophysical sources where this occurred remain poorly understood. We demonstrate that the near-identical half-lives (≃15.6 million years) of the radioactive r-process nuclei iodine-129 and curium-247 preserve their ratio, irrespective of the time between production and incorporation into the Solar System. We constrain the last r-process source by comparing the measured meteoritic ratio 129 I/ 247 Cm = 438 ± 184 with nucleosynthesis calculations based on neutron star merger and magneto-rotational supernova simulations. Moderately neutron-rich conditions, often found in merger disk ejecta simulations, are most consistent with the meteoritic value. Uncertain nuclear physics data limit our confidence in this conclusion.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Separation and Purification of Berkelium-249 and Einsteinium-254

Berkelium-249 ( 249 Bk) and einsteinium-254 ( 254 Es) are isotopes of great importance for the investigation of berkelium and einsteinium chemical properties and super heavy element research. Therefore, it is necessary to be able to isolate acceptable, pure quantities of both isotopes to further research capabilities. These isotopes, along with californium-252 ( 252 Cf), are synthesized through the irradiation of mixed-curium targets in the High Flux Isotope Reactor (HFIR), which has the highest continuous thermal neutron flux in the world. Once irradiated, the targets are transferred to the Radiochemical Engineering Development Center for further chemical processing and final purification to separate 249 Bk and 254 Es from the remainder of isotopes present. Several methods of separation, such as the Berkex batch solvent extraction along with cation-exchange and alpha-hydroxy-isobutyrate (AHIB) columns, are employed to achieve a clean separation of the isotopes. Production Campaigns 74–77 are discussed in depth for 252 Cf, 249 Bk, and 254 Es production and isolation of 249 Bk and 254 Es. An attempt to isolate 257 Fm in Campaign 77 is discussed as well. Table 1 summarizes the total amount of material isolated in each campaign.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

Analysis of a Bulk 237 Np Oxide Sample for Trace Actinides

A neptunium oxide sample was dissolved and trace actinide constituents were measured by isotope dilution ICP-MS (for 239–244 Pu, 233–238 U, 237 Np, 241–243 Am) and alpha spectrometry ( 238 Pu, 242 Cm, 244 Cm). This material contained significant quantities of transuranic elements, notably americium and curium. The isotopic composition of the material will continue to evolve over time due to radioactive decay; the measurements reported here include all isotopes decay corrected to a reference date of 1/1/2022. These factors may be considerations in criticality studies of the related 237 Np sphere.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2020

Countercurrent Actinide Lanthanide Separation Process (ALSEP) Demonstration Test with a Simulated PUREX Raffinate in Centrifugal Contactors on the Laboratory Scale

An Actinide Lanthanide Separation Process (ALSEP) for the separation of trivalent actinides (An(III)) from simulated raffinate solution was successfully demonstrated using a 32-stage 1 cm annular centrifugal contactor setup. The ALSEP solvent was composed of a mixture of 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) and N,N,N',N'-tetra-(2-ethylhexyl)-diglycolamide (T2EHDGA) in n-dodecane. Flowsheet calculations and evaluation of the results were done using the Argonne’s Model for Universal Solvent Extraction (AMUSE) code using single-stage distribution data. The co-extraction of Zr(IV) and Pd(II) was prevented using CDTA (trans-1,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid) as a masking agent in the feed. For the scrubbing of co-extracted Mo; citrate-buffered acetohydroxamic acid was used. The separation of An(III) from the trivalent lanthanides (Ln(III)) was achieved using citrate-buffered diethylene-triamine-N,N,N',N",N"-pentaacetic acid (DTPA), and Ln(III) were efficiently back extracted using N,N,N',N'-tetraethyl-diglycolamide (TEDGA). A clean An(III) product was obtained with a recovery of 95% americium and curium. The Ln(III) were efficiently stripped; but the Ln(III) product contained 5% of the co-stripped An(III). The carryover of Am and Cm into the Ln(III) product is attributed to too few actinide stripping stages, which was constrained by the number of centrifugal contactors available. Improved separation would be achieved by increasing the number of An strip stages. The heavier lanthanides (Pr, Nd, Sm, Eu, and Gd) and yttrium were mainly routed to the Ln product, whereas the lighter lanthanides (La and Ce) were mostly routed to the raffinate.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Assessment of Impurities in Neptunium Metal Using Double-Focusing SF-ICP-MS

In the transmutation process, minor actinides such as neptunium, americium and curium obtained from spent nuclear fuel are incorporated into new fuel that can be placed into a fast reactor, where these elements fission into products with shorter half-lives which reduces the health and safety hazards. In order to better understand the all the involved processes, fundamental physical properties of actinides should be investigated, and for that reason, high-purity materials need to be produced. One of the main challenges in characterizing these materials is the lack of pure metal available for study, and lack of analytical methods to determine the purity. Trans-uranic elements are challenging to study because of the need to be handled in specialized facilities, safeguards concerns and they are not easily purchased and/or produced. High-purity Np metal is being produced at the Materials and Fuels Complex (MFC) of Idaho National Laboratory (INL), in a process of direct oxide reduction developed by Squires and Lessing, with a target purity of 99.999%. The goal of this research is to develop methods to determine the impurities in the Np metal, with detection limits low enough to achieve this purity level. In this work, we have used several ICP-MS and ICP OES techniques, but the focus was the method development using a recently acquired Double-Focusing Sector Field Inductively Coupled Plasma Mass Spectrometer (SF-ICP-MS). To produce the Np metal, approximately 20 g of the neptunium oxide powder was calcined at 800 oC for 6 h in a magnesium oxide crucible, which is placed inside a stainless steel crucible, that goes into the Hot Uniaxial Press (HUP) furnace insert. After the calcining step, the Np oxide was mixed with approximately 9 g of calcium metal and 100 g of ultra-dry calcium chloride. The HUP furnace was heated in a ramp rate of 50 oC min -1 up to 1000 oC. When the reaction mixture reached 850 oC, a tantalum stirrer was activated at 100 rpm. After the tantalum stirrer was removed and the mixture cooled overnight, the MgO crucible was opened with a hammer and chisel to retrieve the Np metal button at the bottom of the reaction mixture. Prior to the dissolution process, the surface contaminants of the sample were removed. The Np button was washed in 10 mL of ultra-pure water for 1 min, with a faint reaction observed on the surface, indicating the presence of Ca metal. The water-washed sample was placed in a tube with 2 M HCl for only 3 s, as a vigorous reaction in the button surface was observed. The leachates were saved for further analysis. The sample was then rinsed with ultra-pure water and air-dried prior to dissolution. The cleaned sample was placed in a PTFE beaker and 25 mL of 6 M HCl and 150 µL of 24 M HF were added. After 10 minutes of reaction, the beaker was placed on a hot plate for 1 h and 30 min, followed by the addition of 1 mL of 16 M HNO3 and allowed to react for a further 1 h and 20 min. The sample was removed from heat and 10 mL of HNO3 16 M was added to react with the HCl. The beaker was covered and left for overnight reaction, producing a solution with approximately 20 mL of final volume. A Quadrupole Inductively Coupled Plasma Mass Spectrometer (Q-ICP-MS, Perkin Elmer ELAN DRC II Q-ICP-MS) was used to obtain qualitative mass spectra for the dissolution blank, each of the leachates and the dissolved sample. In the water leachate spectrum mainly Ca and Mg were observed, while the acid wash had a similar peak pattern to the one observed for the Np metal sample, indicating that the process not only removed surface contamination, but also reacted with the sample itself. In the Np material spectrum, Ta and actinides were identified as candidates for major contaminants, as the most intense peaks corresponded to the mass-to-charge ratios of these elements. Minor contaminants included Al, Au, Ca, Cr, Fe, I, Na, Nb, Pb, Sn, Ti, Tl, V, Y. The presence of impurities in the material could have originated from several sources, such as the materials used for the casting process, the use of impure NpO2 or contamination of reagents and materials used for the analysis. Some of the isotopes listed as potential contaminants are susceptible to spectral interferences, so Double-Focusing SF-ICP-MS (Nu Instruments Attom ES HR-ICP-MS) was used for the quantitative analysis. For each isotope determined, several items were evaluated: raw signal of a blank solution, sensitivity and determination coefficient of calibration curves, possibility of interferences and comparison of results obtained for at least two resolving powers (RP): 300 and 4000. The evaluation of the signal in a blank solution can indicate if a spectral interference from the plasma gas and/or the solvent was successfully resolved (commonly observed for 52Cr+/40Ar12C+, for example). It is important to highlight that a signal reduction is expected when a higher RP is used, as the ion beam transmission is decreased by the use of narrower slits

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Impacts of Lanthanide Ion Complexation on the Radiation Robustness of Diglycolamide Extractants

Nuclear power reactors represent a clean and reliable source of baseload energy. However, nuclear reactors produce used nuclear fuel (UNF), which, if not recycled/reprocessed, must be disposed of as high-level radioactive waste, necessitating long-term storage options. UNF contains approximately a third of the periodic table, including the radioactive minor actinides (MA) americium and curium. Removal of these MA from UNF would greatly reduce the radiotoxic burden, volume, and cost of a storage facility or geological repository. Thus, a significant global effort has been devoted to the design of reprocessing strategies for the clean separation of the MA from UNF. As MA separations are difficult, due to the presence of lanthanide elements in UNF and their remarkably similar chemical properties, many extractants have been studied. The diglycolamide (DGA) class of extractants are promising for this separation as they exhibit high distribution coefficients for the MAs, high metal loading capacities, and are robust in highly acidic radiation environments.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

Nuclear data uncertainty quantification for the nuclide inventory of a Calvert Cliffs spent fuel sample

The impact of nuclear data cross section uncertainties and covariance matrices on the nuclide vector of spent nuclear fuel was investigated; This exercise was carried out for the Calvert Cliffs fuel assembly D047 benchmark available in the SFCOMPO database. Sample P irradiated in rod MKP109 for 4 cycles up to a burnup of approximately 44 GWd/MTU was selected for the analysis. Nuclear data uncertainties were taken from the most recent libraries released by evaluation projects JEFF, ENDF/B and JENDL, and were propagated using the SANDY code via a stochastic sampling approach. This paper provides a quantification of the uncertainty on the concentration of several actinides and fission products relevant for spent fuel management. Uncertainties generally below 5 % were predicted for the concentrations of most of the uranium, neptunium and plutonium isotopes relevant for SNF applications. Curium isotopes carry larger uncertainties that might exceed 10 %. The contribution of cross section uncertainties on the concentrations of fission products was found to be marginal with the exception of a few nuclides. These results can be significantly affected by the lack of evaluated covariance matrices for the capture cross section of several fission products. Burnup tracers such as {sup 148}Nd and {sup 137}Cs have negligible uncertainties because of the power normalisation imposed in every stochastic calculation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Gas-phase stability of large lanthanide:diglycolamide clusters evaluated using collision-induced dissociation

Efficient utilization of long-term deep geologic storage repositories is critical for the large-scale deployment of nuclear energy. As the minor actinides (americium and curium) are the largest contributor to the decay heat of used nuclear fuel after a few hundred years, their removal from used fuel prior to disposal can significantly increase the amount of waste that can be stored in a given volume. The development of ligands that can effectively separate the minor actinides from other components of used nuclear fuel are crucial to efficient utilization of geological storage repositories. N,N,N’,N’-tetraoctyl diglycolamide (TODGA) is a promising extractant for the separation of lanthanides and the minor actinides from other components of used nuclear fuel. While the use of TODGA in f-element separations has been investigated in process-based formulations, gas-phase metal ion cluster experiments enable the study of covalent interactions in reprocessing systems absent from solvent effects. Exploring fundamental differences in lanthanide-ligand covalent interactions can impact the development and implementation of actinide-lanthanide separation systems in nuclear fuels reprocessing. In this study, lanthanide-TODGA clusters were synthesized in the gas-phase and identified using mass spectrometry fragmentation experiments. Large europium and samarium clusters were identified that contained up to 8 and 10 bound TODGA ligands, respectively; this was surprising due to the size and multidentate binding that is normal for TODGA. In addition, while smaller clusters showed evidence of sequential ligand fragmentation, larger clusters displayed the loss of neutral TODGA with applied collision voltage. Interestingly, the voltage required for this removal decreased as more TODGA ligands were bound to the metal, suggesting that the metal coordination sphere was becoming more saturated and TODGA ligands were more weakly bound as the clusters got larger.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Extraction of 88 Y, 152 Eu, 228 Ac, 241 Am, and 244 Cm with 2-thenoyltrifluoroacetone (TTA) resin

In this report the behavior of 88 Y, 152 Eu, 228 Ac, 241 Am, and 244 Cm was studied with 2-thenoyltrifluoroacetone resin with batch uptake, kinetics and column studies. Studies were performed in acetate buffer solutions (pH ~ 2 to ~ 6) and there was high uptake of all isotopes, except 228 Ac, at pH > 4.5. The kinetics of uptake were reasonable, although slower for the actinides, and sufficient for column studies. The retention of 88 Y, 152 Eu, and 241 Am on the resin in column studies was demonstrated as well as a reasonable separation of these isotopes from 228 Ac.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2025

Remote quantification of Cm(III) and HNO 3 by fluorescence spectroscopy and chemometrics

A unique approach to remotely quantify Cm(III) (0–100 µg mL −1 ) in HNO 3 (1–12 M) using steady-state laser fluorescence spectroscopy and multivariate regression models was developed. Photoluminescence is amenable to remote measurements using fiber-optic cables and is sensitive to numerous lanthanide and actinide species. In-line measurements can provide feedback to support complex processing in harsh environments (e.g., hot cells) to help guide and optimize radiochemical separations. In this work, Cm(III) spectra were acquired remotely in a glove box as a function of HNO 3 concentration to better understand spectral characteristics and evaluate the utility of multivariate regression models in this system. Furthermore, the Cm(III) fluorescence peak shape, width, position, and intensity changed significantly as a function of HNO 3 concentration, likely because of the displacement of emission quenching inner-sphere water molecules and complexation with nitrate ions. Despite significant covariance and nonlinearity in the data, a D-optimal design strategy successfully minimized training set sample size and was used to build effective partial least squares regression models for Cm(III) and HNO 3 concentrations without a priori knowledge of solution conditions. Chemometrics for modeling complex fluorescence spectra are promising and may find widespread applicability for online analysis in numerous chemical systems found in the nuclear field.

Actinide↗
DOE OSTI2026

Covalency of M–N Bonds in Isomorphous Lanthanide and Actinide 5-(2-Pyridyl)-1H-tetrazolate Complexes

Experimental and computational analyses of [M(pdtz) 3 (H 2 O) 3 ]·3.5H 2 O (M 3+ = Pu 3+ −Cm 3+ , La 3+ −Nd 3+ , and Sm 3+ −Ho 3+ , pdtz− = 5-(2-pyridyl)-1H-tetrazolate) were conducted to understand potential differences in bonding between lanthanide and actinide complexes with a N-donor ligand. Structural analyses show that the An−N bond distances in the Pu 3+ , Am 3+ , and Cm 3+ complexes are within error of one another. Whereas in the lanthanide series, there is a nearly linear decrease in the Ln−N bond lengths from La 3+ to Ho 3+ (excluding Pm 3+ ). The An−N bond lengths are ∼0.015 Å shorter than their similarly-sized lanthanide analogs, in agreement with computational results that suggest greater covalent character in these bonds versus those with lanthanides. QTAIM analysis indicates that the An−N orbital mixing remains essentially unchanged from Pu 3+ to Cm 3+ , consistent with the nearly identical An−N bond lengths. However, upon deconvolution of the NLMOs into orbital compositions, the metal orbital contributions to An−N bonding decreases slightly overall wherein the 6d involvement remains constant, 7s involvement slightly increases, and 5f participation decreases. The molecular orbital energy diagram indicates that energy degeneracy between the 5f metal and 2p ligand orbitals increases from Pu 3+ to Cm 3+ and counteracts the contraction of the 5f orbtials. Together with prior reports of decreasing energy degeneracy between 5f and 3p orbitals from Np 3+ to Cf 3+ , these observations provide guidance on understanding how chemical bonding evolves in the actinide series.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Recent Advances in Radiation-Induced Actinide Redox Chemistry

The actinide series boasts many unique physical and chemical features worthy of both fundamental and applied study. However, the chemical influence of their inherent radiation field is often overlooked, especially as we begin to explore the late actinides in more detail than ever possible before. From the perspective of used nuclear fuel reprocessing, the absorption of ionizing radiation induces the formation of a variety of transient and steady-state excited states, radicals, ions, and molecular degradation products, many of which are highly redox active and can lead to significant changes in a reprocessing solvent system’s physical and chemical properties. For example, radiolysis of the actinides can drive steady-state redox distributions and the formation of non-traditional oxidation states which can complicate their separation and recovery from fission products. This scenario is further exacerbated when complexation is taken into account. Consequently, a molecular-level understanding of radiation effects on the actinides over multiple time, distance, and material domains is essential for supporting innovation in used nuclear fuel reprocessing technologies. Attaining this knowledge necessitates a firm grasp of actinide radiation chemistry to develop predictive, mechanistic, multiscale models to support engineering efforts. Presented here are several recent studies that highlight recent advances in actinide radiation chemistry, in particular, the effect of actinide complexation on ligand reactivity towards radiation-induced transients.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

Recent Advances in Actinide Radiation Chemistry

The attached presentation discusses recent advances in actinide radiation chemistry from the perspective of the INL Center for Radiation Chemistry Research, to be presented virtually at the Los Alamos National Laboratory G. T. Seaborg Institute Seminar Series.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗