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Shell effects in quasi-fission: Reactions forming actinide and superheavy compound nuclei

Quasi-fission occurs in fully damped heavy-ion collisions following a significant mass transfer between the fragments, without formation of a compound nucleus. As in fission, quasi-fission is expected to be affected by quantum effects leading to asymmetric mass splits. Quantum shells stabilising fission fragments with octupole shapes have been invoked as a factor determining the distribution of nucleons between the fragments at scission, explaining the fact that the centroid of the heavy fragment charge distribution is found around Z = 54 protons in fission and quasi-fission of actinides. These shell effects are studied in microscopic studies of quasi-fission. In particular, time-dependent Hartree-Fock (TDHF) calculations have been performed for reactions forming actinides.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Actinide 5f Occupations: The Case of PuO 2

In actinide chemistry, the formal number of open-shell 5f electrons, n open , is a well-defined quantity with an integer value. The effective 5f occupation, n f , additionally takes donation and back-donation into account, generally has a non-integer value, and has varying numerical definitions. The present study explores the important distinction between n f and n open in actinide chemistry with the example of PuO2, by using electronic structure methods with a relativistic Hamiltonian in combination with experimental Pu M 5 -edge high-energy-resolution X-ray absorption and emission spectroscopic data. The total donation to the metal in PuO 2 is between 3.1 and 2.4 electrons, depending on the type of calculation, most of which is to the Pu 6d and 5f shells. The donation into 5f is sensitive to the approximations in the electronic structure model but likely amounts to 1.6/0.8 electrons when the diffuse regions of the 5f shell are included/excluded. Valence band resonant inelastic X-ray scattering experiments demonstrate that Pu 5f electron density is present in the valence band; thus, there is a clear experimental signature of covalent bonding in PuO 2 . Pu M 5 -edge and M 3 -edge high-energy-resolution X-ray absorption near-edge structures for Pu 3+ and Pu 4+ in an aqueous solution are compared to PuO 2 , showing that Pu in PuO 2 has an nf closer to Pu 4+ (aq).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Back to Basics: Lanthanide and Heavy Actinide Chelation at High pH by Niobium Polyoxometalates

Niobium polyoxometalates (Nb-POMs) form in alkaline media, which limits their use as ligands for acidic cations, particularly lanthanides and actinides. Metal-Nb-POM moieties have the potential for emergent and enhanced properties, based on strong complexation behavior and high stability of the resultant materials. Here, in this study, we probe interactions of lanthanides (Pr 3+ , Nd 3+ , Sm 3+ , Eu 3+ , Tb 3+ , Dy 3+ ) and actinides (Am 3+ , Cm 3+ ) with a Nb-POM [Nb 6 O 19 ] 8– (Nb 6 ) in alkaline media. Nb 6 , the most charge-dense Nb-POM, enhances f-element luminescence emission by up to × 10 6 , via Nb-POM-mediated sensitization. Lengthened emission lifetimes correlate with the release of the metal-cation hydration sphere, replaced by multidentate Nb-POMs. The Nb 6 –Ln(An) complexes resist carbonate and phosphate displacement, and Nb 6 –Ln(An) complexation is retained upon isolation of the solids from solution. Electrospray ionization mass spectrometry (ESI-MS) and Raman spectroscopy both indicate the formation of the unprecedented Peacock–Weakley Nb-POM ([LnIII(Nb 5 O 18 ) 2 ] 19- ) in addition to simple Nb 6 –Ln coordination complexes. Luminescence emission spectra support the presence of simple Nb 6 –Ln coordination complexes. Small-angle X-ray scattering (SAXS) evidence the formation of Ln-Nb-POM aggregates. This foundational investigation highlights the potential of Nb-POMs as metal–ligands at basic pH, with value-added properties including scaffolding extended materials and controlling light absorption and emission.

organic↗

Expanding on the ability of trivalent actinides to support microbial alcohol metabolism in evolved methylotrophic bacterium

The 4 f elements, known as the lanthanides, have only recently been recognized as biologically essential metals. These elements can be found in the active site of certain alcohol dehydrogenase (ADH) enzymes, which are used by methylotrophic bacteria to metabolize simple alcohols such as methanol and ethanol. The 5 f elements, known as the actinides, often show similar chemical behaviour to the lanthanides and recent reports demonstrated that americium (Am) and curium (Cm) can replace lanthanides in certain ADHs to yield a catalytically competent enzyme and support bacterial life. In this work, we expand on these results to show the trivalent ions actinium (Ac3+), americium (Am3+), curium (Cm3+), berkelium (Bk3+), and californium (Cf3+) all support growth of an evolved strain of the model methylotroph Methylobacterium extorquens AM1. Further in vitro experiments using a reconstituted ethanol dehydrogenase enzyme confirm the ability of this enzyme to utilize trivalent actinide ions.

Woods, Joshua J↗

Actinide complexes with Wells–Dawson polyoxometalates (part 1): americium and curium

We report the first trivalent actinide complexes with a Wells–Dawson polyoxometalate. Americium(III) forms two distinct phases: triclinic K 17 Am(P 2 W 17 O 61 ) 2 ·42.5H 2 O and monoclinic K 17 Am(P 2 W 17 O 61 ) 2 ·12H 2 O. Curium(III) crystallizes as monoclinic K 17 Cm(P 2 W 17 O 61 ) 2 ·8H 2 O. XRD-quality single crystals were obtained from just ∼330 nanograms of actinides. This work establishes clear structure–property relationships that will guide investigations on scarce f-elements.

and nuclear chemistry↗

Muon-induced fission of actinide nuclei

A negative muon captured by an actinide cascades down through the muonic atomic levels; deeply bound transitions can proceed via inverse internal conversion, depositing the muonic transition energy directly into the nucleus and, when the deposited energy exceeds the fission barrier, inducing prompt fission. Because the muon mean lifetime exceeds the saddle-to-scission timescale by orders of magnitude, the muon can survive the entire fission event as a 1⁢𝑠 spectator and ultimately attach to one or both of the emerging fragments. Its postscission attachment probability to the light fragment, 𝑃 𝐿 , can be used as a direct electromagnetic probe of fission dynamics on a timescale of 10 −21 s. In previous work, we introduced a three-dimensional lattice solution of the time-dependent Dirac equation coupled to the electromagnetic field generated by a fissioning nucleus and reported 𝑃 𝐿 for several actinides at a single dissipation strength. In this work, we extend that framework to a systematic survey of 232 Th , 238 U , and 240 Pu and implement a more realistic fission model which incorporates dynamic pairing correlations. We find that 𝑃 𝐿 falls steeply with the fragment charge asymmetry, a robust structural fingerprint of the fissioning system, while its dependence on nuclear dissipation is secondary and sensitive to the phenomenological friction prescription. These results establish 𝑃 𝐿 as a clean electromagnetic probe of fragment charge asymmetry and motivate a self-consistent, coordinate- and time-dependent treatment of nuclear dissipation as the natural next step.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Adaptation of Wallace's approach to the specific heat of elemental solids with significant intrinsic anharmonicity, particularly the light actinide metals

The quasiharmonic approximation is the most common method for modeling the specific heat of solids; however, it fails to capture the effects of intrinsic anharmonicity. In this study, we introduce the “elastic softening approximation,” an alternative approach to modeling intrinsic anharmonic effects on thermodynamic quantities, which is grounded in Wallace's thermodynamic framework that tracks entropy changes resulting from the continuous change (e.g., softening) of phonons as a function of temperature. A key finding of our study is a correlation between Poisson's ratio and the differential rate of phonon softening at finite frequencies, compared to lower frequencies relevant to elastic moduli measurements. We observe that elemental solids such as α -Be, diamond, Al, Cu, In, W, Au, and Pb, which span a wide range of Poisson's ratios and exhibit varying degrees of intrinsic anharmonicity, consistently follow this trend. When applied to α -U, α -Pu, and δ -Pu, our method reveals unusually large anharmonic phonon contributions at elevated temperatures across all three light actinide metals. These findings are attributed to the unique combination of enhanced covalency and softer elastic moduli inherent in the actinides, potentially influenced by their 5 f -electron bonding. Published by the American Physical Society 2025

36 MATERIALS SCIENCE↗

Design, Construction, and Installation of In-Glovebox Pumped Actinide Molten Salt Loops

This report summarizes the work conducted in FY25 to construct and install pumped actinide-bearing molten salt loopsin a radiological glovebox. The establishment of such a capability will provide a platform in which technologies developed for Gen. IV molten salt reactors may be tested under relevant operating conditions. A review of convective molten salt systems is provided to frame Argonne’s pumped actinide loop relative to contemporary and historical systems. Moreover, the infrastructure needed to operate the system is detailed to provide additional context as to design metrics of the loops and supporting equipment. The pumps’ performance in water testing is outlined and used to inform operational activities planned in FY26. Finally, electrochemical experiments investigating fundamental reaction mechanisms governing reactive oxygen species that promote corrosion of molten salt media is also reported. In total, these combined loop installation and sensor development tasks will serve to aid in the future commercial deployment of molten salt reactors in the U.S.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Biologically Influenced Transport of the +3 Actinide Oxidation State from the WIPP Environment, Using Neodymium as an Analog

This report provides an update to a previously issued report on the bioassociation of the +3 actinide analog, neodymium, with Waste Isolation Pilot Plant (WIPP) microbial isolates (LCO ACP-32, Biologically Influenced Transport of the +3 Actinide Oxidation State from the WIPP Environment, Using Neodymium as an Analog ). Results contribute to updates for the biocolloid parameters for the 2026 Compliance Recertification Application (CRA-2026).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Synthesis Roadmap for Actinide Chloride Salts

Molten salt reactors (MSRs) are among the main advanced nuclear reactor types at the forefront of development by industry, with the support of the US government, for the next fleet of nuclear reactors to support the demand for energy in the coming decades. MSRs are highly unique because they are cooled and typically also fueled by molten salt. This quality brings about safety benefits such as low-pressure operation and self-stabilization of the neutron flux, operational benefits such as high-temperature operation and the ability for online refueling, and fuel and waste management benefits thanks to the flexibility of post-processing of molten salts and reprocessing options that involve removal of fission products and actinide separation. In fact, domestic deployment of molten salt (or molten salt–cooled) reactors is an approaching reality: a handful of molten salt reactor developers are planning to operate demonstration-scale reactors, as a step toward commercial-scale power reactors, within the decade. For example, Natura Resources received a construction permit in September 2024 for the deployment of MSR-1, which is a graphite-moderated thermal spectrum reactor, at Abilene Christian University. Also, TerraPower, in a collaborative effort with Southern Company and Idaho National Laboratory (INL), received approval from DOE in 2023 to proceed with the construction of the Molten Chloride Reactor Experiment (MCRE), a homogeneous chloride fast reactor at INL, and has begun assembly of system components. There are several other examples of developers at different stages of development of their own unique MSR designs (Jenet et al., 2025). As developers are in the process of obtaining approvals for their designs, deploying demonstration-scale reactors, and planning for their commercial-scale power reactors, there is a critical supply chain need for the synthesis of fuel for these reactors that must be addressed. The challenge generally is three-fold: (1) the quantity of fueled salt needed for these reactors is extraordinarily high (>100s of kilograms), but demonstrations of scaled-up techniques for fueled salt synthesis are significantly more limited than demonstrations of lab-scale syntheses; (2) each developer has a unique reactor design, which means different actinide halide elements in different carrier salts must be synthesized; and (3) there is a need for particularly high-purity salt so as to ensure the long-term operability of these reactors with minimal degradation to salt-wetted components, which necessitates synthesis techniques with high levels of quality control, repeatability, and well-characterized precursor and reactant materials. It is crucial that this supply chain challenge be addressed by demonstrating synthesis techniques that are scalable, de-risked, and well-documented so that these technologies may be adopted and utilized by industry to support the fueling needs of MSRs that are to come online within the next 10 years. With this supply chain challenge clearly defined for the developing MSR industry, it is important to consider that addressing such a challenge is oftentimes complex and context-dependent. There is not necessarily a single synthesis technique that can be scaled up and adopted to address the needs of all MSR developers; the synthesis approach that may be viable for producing a desired fuel salt will be entirely dependent on the exact salt composition needed, the quantity needed, purity needed, the refueling and waste plans, and the availability of a carrier salt for the fuel. Therefore, it is important to consider more broadly what synthesis techniques are available and have been demonstrated to understand the benefits, challenges, and general nuances that should be considered when evaluating a particular route for efficient production of high-purity fuel salts at scale.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Transmission Electron Microscopy Characterization of Fuel Cladding Chemical Interaction between Minor Actinides bearing U-Pu-Zr Fuel and AIM1 Cladding

Minor actinides (MA) significantly contribute to the long-term radiotoxicity of spent nuclear fuel (SNF). Separating MA from SNF and incorporating it into metallic fuels for fast reactor transmutation is a potential method to reduce this radiotoxicity. Here, this study focuses on transmission electron microscopy characterization of two samples from the fuel cladding chemical interaction (FCCI) region of an americium (Am) and neptunium (Np)-bearing (MA-bearing) uranium-plutonium-zirconium (U-Pu-Zr) fuel irradiated in the Phenix fast reactor to 9.5 % FIMA burnup at approximately 550 °C cladding temperature. The results show that despite the complex chemical interactions between MA and AIM1 cladding elements, excessive FCCI was not induced, and Am penetration depth in the cladding limited to less than 4 µm. Np remained mostly inside fuel. The Zr-rich compounds layer effectively limited the accumulation of lanthanide on the inner cladding surface. Overall, the FCCI behavior between investigated MA-bearing U-Pu-Zr fuel and AIM1 cladding is benign.

Chemical interaction↗

Elucidating the effect of minor-actinide addition on fuel-cladding chemical interaction in an HT-9 clad U-Pu-Zr metallic fuel irradiated to 6.15 at.% burnup in EBR-II

Scanning and transmission electron microscopy (S/TEM) were used to characterize the local fuel-cladding chemical interaction (FCCI) in one cross-section taken from a HT-9 clad U-20.3Pu-10Zr-1.2Am-1.3Np (in wt.%) fuel irradiated to 6.15 at.% burnup with inner cladding temperatures ranging between 460–490 °C. Results showed that the total interaction thickness between fuel and cladding was <10 µm. Fe infiltrated the fuel to form U-Zr-Fe phases while fuel elements or lanthanides did not infiltrate into the cladding. Np was not involved in the formation of any phases in the examined locations; however, Am played a role by forming a ∼2 µm thick homogeneous Fe-Pu-Am planar front at the inner cladding wall. An oxidized Na layer existed in the fuel-cladding gap with Fe and lanthanide particles dispersed within, suggesting Na could facilitate the transport of fuel and cladding constituents. Secondary phases, including an FCC Zr-rich phase, lanthanide phases, and α’-Cr(Fe) were identified in the outer fuel and FCCI regions. Furthermore, this study suggests that, for the irradiation conditions specific to this cross-section, minor actinides have little impact on FCCI behavior beyond what would be observed in typical HT-9 clad U-Pu-Zr fuel pins systems.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Bond Dissociation Energies and Electronic Calculations on the Actinide Halides ThX and UX (X = Cl, Br, I)

Resonant two-photon ionization spectroscopy has been used to locate predissociation thresholds in the spectra of the actinide halides ThX and UX, where X = Cl, Br, and I. These predissociation thresholds are identified as the bond dissociation energies (BDEs) of the molecules. The resulting values show very similar BDEs for the corresponding ThX and UX species, with the thorium molecules being slightly more strongly bound: D 0 (ThCl) = 5.077(6) eV, D 0 (ThBr) = 4.391(4) eV, D 0 (ThI) = 3.537(8) eV, D 0 (UCl) = 4.989(3) eV, D 0 (UBr) = 4.313(3) eV, and D 0 (UI) = 3.449(8) eV. Here, the estimated error limit is given in parentheses in units of the last reported digit. Spinor-based coupled cluster calculations have also been carried out on the halides of this work, including also ThF and UF. Here, the final D 0 values after including contributions due to basis set incompleteness, outer-core-correlation, picture-change, and QED effects are within 0.04 eV of the present experimental values in each case.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Curious Case of [AnH(NR 2 ) 3 ] (An = Th, U; R = SiMe 3 ): Two Monomeric Actinide Hydrides Revisited

The reaction of AnCl 4 (DME) x (An = Th, x = 2; An = U, x = 0) with 4 equiv of NaNR 2 (R = SiMe 3 ) in THF at 65 °C results in the formation of [An{N(R)(SiMe 2 CH 2 )}(NR 2 ) 2 ] (An = U, 1; An = Th, 2), and not the reported monomeric actinide hydrides, [AnH(NR 2 ) 3 ], as expected. Furthermore, both complexes 1 and 2 were characterized by X-ray crystallography. Surprisingly, their unit cell parameters are remarkably close to those reported for [AnH(NR 2 ) 3 ], suggesting that the original crystals of [AnH(NR 2 ) 3 ] were, in fact, [An{N(R)(SiMe 2 CH 2 )}(NR 2 ) 2 ], but were misidentified. Reduction of 1 with 1.1 equiv of KC 8 in THF, in the presence of 1 equiv of 2.2.2-cryptand, results in the formation of [K(2.2.2-cryptand)][U{N(R)(SiMe 2 CH 2 )}(NR 2 ) 2 ] (3) in good yield. Likewise, the reaction of 1 with 1 equiv of bis(diisopropylamino)cyclopropenylidene (BAC) results in the formation of the BAC adduct, [(BAC)U{N(R)(SiMe 2 CH 2 )}(NR 2 ) 2 ] (4), in moderate yield. Finally, the addition of H 2 (10 bar) to 2 in C 6 D 6 at room temperature results in the formation of the targeted monomeric hydride, [ThH(NR 2 ) 3 ], in 32% yield, according to integrations against an internal standard. However, removal of the H 2 atmosphere results in rapid reformation of 2. In contrast, the addition of H 2 (10 bar) to 1 in C 6 D 6 at room temperature results in no apparent reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigating Radiation-Induced Actinide Species in Solution

Used nuclear fuel (UNF) separation techniques that strive to separate radiotoxic americium (Am) from trivalent lanthanide fission products through oxidation state control have increased research efforts surrounding Am(V) and Am(VI). However, equivalent knowledge of the tetravalent state, Am(IV), has remained elusive, particularly in conditions more representative of UNF reprocessing, i.e., in concentrated nitric acid (HNO3). With this in mind, we have used electron pulse radiolysis to study the radiation-induced redox reaction of Am(III) with the oxidizing nitrate radical (NO3?) in 6 M HNO3: Am(III) + NO3? ? Am(IV) + NO3? . These experiments enabled us to observe the growth and decay of Am(IV) in a concentrated acidic solution for the first time. The transient Am(IV) species was found to have a lifetime of ~16 µs?sufficiently long-lived to play a critical mechanistic role in UNF reprocessing systems. Additionally, we performed the first-ever temperature-dependent kinetics study of an actinide element, elucidating unprecedented Arrhenius and Eyring activation parameters for the reaction of Am(III) with NO3?. This new knowledge provides much-needed molecular-level insights into the radiation-induced behavior of Am.

actinide↗

Investigating Radiation-Induced Actinide Species in Solution

Our fundamental understanding of actinide radiation-induced redox chemistry is crucial due to their unavoidable exposure to ionizing radiation fields, both inherent and from in-process applications. Plutonium (Pu) and americium (Am) both possess multiple oxidation states, the careful manipulation of which are essential in the study and utilization of their rich chemistry, developing new nuclear technologies, and securing the long-term sustainability of nuclear power. However, knowledge in this area is far from complete. Consequently, we have studied the radiation-induced chemistry of both Pu and Am through a variety of techniques. Temperature-controlled electron pulse radiolysis has been used to study Am for the first time, determining the feasibility of Am redox reactions under used nuclear fuel reprocessing conditions, (e.g. nitric acid, non-ambient temperature). Additionally, we developed an experimentally evaluated multi-scale computer model for the prediction of gamma radiation-induced Pu redox chemistry due to radiolysis and disproportionation reactions in concentrated nitric acid solutions.

actinide↗