SEARCH · Engineering Papers
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.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
The heterobimetallic actinide nitride [(NR 2 ) 3 U V (μ-N)Th IV (NR 2 ) 3 ] (R = SiMe 3 ) has an m J = 5/2 ground state and its highest energy 5f excited state is primarily 5f-N nitride σ-antibonding in character.
The THermally Evaporated Spray for Engineered Uniform particulateS (THESEUS) production platform was developed to generate highly uniform mixed actinide oxide particles.
The diverse coordination modes and electronic features of actinide complexes of porphyrins and related oligopyrrolic systems (referred to as “porpyrinoids”) have been the subject of interest since the 1960s.
The separation of minor actinides in their dioxocation (i.e., actinyl) form in high-valence oxidation states requires efficient ligands for their complexation. Here, in this work, we evaluate the complexation properties of actinyls including americyl, curyl, berkelyl, and californyl in their pentavalent and hexavalent oxidation states with the dipyriamethyrin ligand (L) using density functional theory calculations. The calculated bond parameters show shorter An═O yl bonds with covalent character and longer An–N bonds with ionic character. The bonding between the actinyl cation and the ligand anion shows a flow of charges from the ligand to actinyl in all [An V/VI O 2 –L] 1–/0 complexes. However, across the series, backdonation of charges from the metal to the ligand becomes prominent and stabilizes the complexes. The thermodynamic parameters in the gas phase and solution suggest that the complex formation reaction is spontaneous for [Cf V/VI O 2 –L] 1–/0 complexes and spontaneous at elevated temperatures (>298.15 K) for all other complexes. Spin–orbit corrections have a quantitative impact while the overall trend remains the same. Energy decomposition analysis (EDA) reveals that the interaction between actinyl and the ligand is mainly due to electrostatic contributions that decrease from Am to Cf along with an increase in orbital contributions due to the backdonation of charges from the actinyl metal center to the ligand that greatly stabilizes the Cf complex. The repulsive Pauli energy contribution is observed to increase in the case of [An V O 2 –L] 1– complexes from Am to Cf while a decrease is observed among [An VI O 2 –L] 0 complexes, showing minimum repulsion in [Cf VI O 2 –L] 0 complex formation. Overall, the hexavalent actinyl complexes show greater stability (increasing from Am to Cf) than their pentavalent counterparts.
Uranium- and thorium-iridium multimetallic species with unprecedented actinide–iridium interactions are prepared via salt-elimination reactions between U/Th halides and K[IrCp*H 3 ].
A bis(yldiide) mercury complex [Hg{C(PPh 3 )(SPPh 2 )} 2 ] has been isolated and used as a mild transmetalation reagent to form the first substituted actinide yldiide complexes, which exhibit highly polar metal carbon interactions.
Differences in synthetic conditions and structural systematics in a series of actinide–oxo clusters reflect trends in the hydrolysis behavior of the tetravalent metal ions, Th–Pu.
The total kinetic energy (TKE) release in the fast neutron-induced fission of various actinide nuclei was measured for neutron energies for E n =2.6-100 MeV at the Weapons Neutron Research facility of the Los Alamos National Laboratory. The data are compared to the GEF model of the fission process. The variances of the TKE distributions appear to decrease with increasing Z and A of the fissioning systems.
An alternative to dissolving used nuclear fuel (UNF) in an acidic solution during reprocessing is direct dissolution in an organic solution, which would eliminate an aqueous dissolution step, decrease the amount of nitrate needed, and reduce the facility size. The flowsheet for this potentially less expensive alternative is first to voloxidize the UNF to remove fission product gases and form an oxide. After voloxidation, the UNF is then dissolved in an organic solution containing an extractant mixed with an aliphatic diluent and pre-equilibrated with nitric acid. The organic solution then goes through a solvent extraction process to recover the uranium and/or other desired radionuclides. This work qualitatively studied the dissolution of actinide oxides (UO2, NpO2, and PuO2) in tributyl phosphate using UV-Vis-NIR absorbance spectroscopy to ascertain dissolution behavior. Initial studies included material that is otherwise difficult to dissolve in only nitric acid, specifically CeO2, that is sometimes used as a dissolution surrogate for PuO2. This work confirmed that CeO2, NpO2, and PuO2 are difficult to dissolve in 30 vol% TBP-dodecane pre-equilibrated with 10 M HNO3 and will readily dissolve when co-precipitated with U (i.e., the mixed oxides U-Ce, U-Np, and U-Pu), surrogates for voloxidized nuclear fuel.
The extraction of hexavalent actinides An(VI) by tri-butyl phosphate (TBP) was investigated by electronic absorption and vibrational spectroscopies. Through a series of spectral subtractions, vibrational spectra associated with TBP, TBP–HNO3 adducts, and An(VI)–TBP complexes could be isolated. Investigation of U(VI) extracts indicated spectral features consistent with the formation of the expected [UO2(NO3)2(TBP)2] complex, but spectral features of other species were clearly evident. Likewise, multiple species were evident in the electronic absorption and vibrational spectra of TBP phases generated by extraction of Pu(VI). Although definitive characterization of the additional species formed could not be achieved in this work, it is hypothesized that they contain 3:1 TBP-to-An(VI) stoichiometry.
Studying the local moment and 5 f -electron occupations sheds insight into the electronic behavior in actinide materials. X-ray absorption spectroscopy (XAS) has been a powerful tool to reveal the valence electronic structure when assisted with theoretical calculations. However, the analysis currently taken in the community on the branching ratio of the XAS spectra generally does not account for the hybridization effects between local f orbitals and conduction states. In this paper, we discuss an approach which employs the density functional theory plus Gutzwiller rotationally invariant slave boson method to obtain a local Hamiltonian for the single-impurity Anderson model, and calculates the XAS spectra by the exact diagonalization (ED) method. A customized numerical routine was implemented for the ED XAS part of the calculation. By applying this technique to the recently discovered 5 f -electron topological Kondo insulator Pu B 4 , we determined the signature of 5 f -electronic correlation effects in the theoretical x-ray spectra. Furthermore, we found that the Pu 5 f - 6 d hybridization effect provides an extra channel to mix the j = 5 / 2 and 7 / 2 orbitals in the 5 f valence. As a consequence, the resulting electron occupation number and spin-orbit coupling strength deviate from the intermediate-coupling regime.
A systematic investigation of the ground-state and fission properties of even-even actinides and superheavy nuclei with Z = 90–120 from the two-proton up to two-neutron drip lines with proper assessment of systematic theoretical uncertainties has been performed for the first time in the framework of covariant density functional theory (CDFT). Furthermore, these results provide a necessary theoretical input for the r-process modeling in heavy nuclei and, in particular, for the study of fission cycling. Four state-of-the-art globally tested covariant energy density functionals (CEDFs), namely, DD-PC1, DD-ME2, NL3*, and PC-PK1, representing the major classes of the CDFT models are employed in the present paper. Ground-state deformations, binding energies, two-neutron separation energies, α-decay Q α values and half-lives, and the heights of fission barriers have been calculated for all these nuclei. Theoretical uncertainties in these physical observables and their evolution as a function of proton and neutron numbers have been quantified and their major sources have been identified. Spherical shell closures at Z = 120, N = 184, and N = 258 and the structure of the single-particle (especially, high-j) states in their vicinities as well as nuclear matter properties of employed CEDFs are two major factors contributing to theoretical uncertainties. However, different physical observables are affected in a different way by these two factors. For example, theoretical uncertainties in calculated ground-state deformations are affected mostly by the former factor, while theoretical uncertainties in fission barriers depend on both of these factors.
In this paper, the strengths and limitations of FEFF simulations, as applied to actinide systems, are discussed. While the impact of total angular momentum coupling in the 5f manifold is not addressed within the usual FEFF approach, the utility of FEFF is demonstrated.
Abstract Manifestations of electron scattering in X-ray spectroscopy have been evident for decades. Here, it will be shown that the proper interpretation of variants of X-ray Absorption Spectroscopy (XAS) of actinide materials must include an accurate treatment of features caused by electron scattering, i.e., EXAFS or Extended X-ray Absorption Fine Structure. These EXAFS features can be of such low energy that they are within ten to twenty electron volts of the Unoccupied Density of States (UDOS), immediately above the Fermi Energy or Band Gap. The adaption of simple models using the FEFF simulation program will be presented, including the demonstration of the robust nature of the results from different models. Graphical abstract
This is a final close-out report for DOE contract DE-FG02-99ER45761 entitled “Correlation Effects and Magnetism in Actinides: Elements and Compounds” at Rutgers University in New Jersey. It funded condensed matter physics basic energy science research from 04/15/1999 through 02/14/2020. A list of postdocs that received support from this grant are presented below, along with an overview of the research accomplishments of the grant with highlights of research results from the last funding period and a list of original papers published thru the duration of the grant with impact factor metrics are presented.
One of the key systems required for the Joint Actinide Shock Physics Experimental Research (JASPER) facility is the timely triggering of the Prompt System (PS). The Trigger Unit (TU) is the critical component that determines when the PS is to be triggered. There are two redundant TUs within the JASPER system, and each TU creates three redundant triggers for the PS. In this fashion, the Prompt Trigger System (PTS) can suffer the loss of one sensor, as well as the loss of one TU, and still function correctly. The TU is designed to receive signals from five separate sensors along the flight of the projectile on its way to the target. The TU uses three pairs of these detectors to create a trigger pulse at the appropriate time, based on the actual velocity of the projectile as it passes between the two sensors.
Molten Salt Reactors are described and more detail is given about actinide molten salts in particular, as well as molten chloride salts. Instead of micro-structure evolution, the challenge for MSRs is chemical evolution due to fission and corrosion products and their impact on chemistry, corrosion, phase equilibria, and thermophysical properties.
A new evaluation of the ENDL cross section set for Thorium (Z=90) is developed using the TALYS statistical model cross section code. The primary goal of this effort is to produce an evaluation that attempts to match as closely as possible fission cross sections developed through surrogate reaction techniques on actinide targets 230 Th and 231 Th. This evaluation effort and the processing needed to render its results into data libraries is a necessary step in making the efforts of nuclear experimentalists useful to the broad community of researchers engaged in simulations of nuclear fusion for basic and applied science. Another aspect, verification and validation against various AGEX experiments, is also presented. The end-product is an updated library that includes the latest measurements of fission cross sections for comparison against those measured via traditional techniques. All the steps in the evaluation, processing, validation and verification, and library release are described in the following sections. For completeness, the appendix contains all the parameters used in the TALYS cross section evaluation for neutrons incident on 230 Th and 231 Th.