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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Comparison of Ce( iv )/Th( iv )-alkynyl complexes and observation of a trans -influence ligand series for Ce( iv )

Organometallic cerium(iv) complexes have been challenging to isolate and characterize due to the strongly oxidizing nature of the cerium(iv) cation. Herein, we report two cerium(iv) alkynyl complexes, [Ce(TriNOx)(C[triple bond, length as m-dash]C-SiMe3)] (1-CeTMS) and [Ce(TriNOx)(C[triple bond, length as m-dash]C-Ph)] (1-CePh) (TriNOx3- = tris(2-tert-butylhydroxylaminato)benzylamine), that include terminal alkyne moieties. The isostructural thorium analogue [Th(TriNOx)(C[triple bond, length as m-dash]C-SiMe3)] (1-ThTMS) was also synthesized and compared with 1-CeTMS in bond distance, 13C-NMR spectra, vibrational spectra and electronic structure. The Ce-C bond distances were 2.501(3) Å for 1-CePh and 2.513(5) Å for 1-CeTMS on the shorter end of the few reported CeIV-C single bonds (2.478(3)-2.705(2) Å), possibly indicating significant Ce 5d- and 4f-orbital involvement. 13C-NMR spectroscopy was also consistent with Ce-C covalency, with significantly deshielded resonances ranging from 185-213 ppm. Such 13C-NMR shifts demonstrate a strong influence from spin-orbit coupling (SOC) effects, corroborated by computational studies. Raman analysis showed ν C[triple bond, length as m-dash]C stretching frequencies of 2000 cm-1 (1-CeTMS) and 2052 cm-1 (1-CePh), indicating the cerium(iv)-alkynyl interaction, compared to the parent HC[triple bond, length as m-dash]CPh (IR = 2105 cm-1 and Raman = 2104 cm-1). L3-edge X-ray absorption measurements revealed a predominant Ce(iv) electronic configuration, and magnetic measurements revealed temperature-independent paramagnetism. Electrochemical studies similarly revealed the electron donating ability of the alkynyl ligands, stronger than either fluoride or imido ligands for the Ce(iv)(TriNOx)-framework, with a cerium(iv/iii) reduction potential of E pc = -1.58 to -1.66 V vs. Fc/Fc+. Evidence for a trans-influence has been observed by evaluating a series including previously reported [CeIV(TriNOx)X]+/0 complexes with axial ligands X = THF, I-, Br-, Cl-, F-, -C[triple bond, length as m-dash]C-Ph, -C[triple bond, length as m-dash]C-SiMe3, -NH(3,5-(CF3)2-Ar), -OSiPh3, -N(M(L))(3,5-(CF3)2-Ar) [M(L) = Li(TMEDA), K(DME)2 or Cs(2,2,2-crypt)]. These data stand in contrast with previous reports of an inverse trans-influence at cerium(iv) and point to differences in involvement of cerium 4f- versus 5d-orbitals in the electronic structures of the complexes.

Yang, Qiaomu↗
DOE OSTI2024

Godiva IV central cavity neutron environment characterization with threshold neutron detectors

Godiva IV is a cylindrical fast burst reactor comprised of approximately 65 kg of highly enriched uranium that is operated by Los Alamos National Laboratory and sited at the National Criticality Experiments Research Center at the Nevada National Security Site in Nevada in the United States. Godiva IV is typically operated at delayed critical and in the regime spanning from sub-prompt to super-prompt bursts. Godiva IV is used for sample irradiations, criticality safety demonstrations, dosimetry studies, and for studying super-prompt behavior. In preparation for both an upcoming experiment to reduce uncertainties in the prompt fission spectrum for 235U using threshold neutron detectors, and for future research using Godiva IV, it was desired to exercise the process of the selection of threshold neutron detectors/activation foils, radiation metrology, and the subsequent adjustment of the neutron spectrum. For this exercise, nine high purity threshold neutron detectors/activation foils were irradiated in a Godiva IV burst. The foils were then analyzed using a high-purity germanium detector in the NCERC counting laboratory to determine end of irradiation specific activities for available IRDFF-II reactions. This work summarizes the Godiva IV foil irradiation, radiation metrology results, and adjusted neutron spectrum. The results of this exercise ultimately characterized the neutron environment inside the sample irradiation cavity inside Godiva IV to a higher degree than previously performed, informed decisions for the upcoming larger scale experiment, and will inform future neutron spectrum characterizations at NCERC.

Whitman, Nicholas H.↗
DOE OSTI2025

Generation and Study of Am(IV) by Temperature-Controlled Electron Pulse Radiolysis

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.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

M IV /Co –I (M = Zr, Hf) Bis(phosphinoamide) Complexes with η 6 - and η 4 -Arenes

Despite their relevance to catalysis, low-/subvalent cobalt complexes are difficult to synthesize and isolate. Consequently, very few “cobaltate” complexes are known and there is a lack of architectural diversity in this field. Lewis acidic d 0 group IV metals have been demonstrated to stabilize Co –I centers via metal–metal bonds. Herein, we report the synthesis of bis(phosphinoamide) heterobimetallic M IV /Co –I arene complexes (M = Zr, Hf). The driving force to maintain the aromaticity of the arenes dictates the hapticity of the Co-bound arene ligands and influences the binding arrangement of the phosphinoamide ligands. Benzene and toluene were observed to bind η 6 to the Co –I center, forcing dissociation of one of the phosphinoamide ligands, whereas η 4 -coordination of anthracene allows both phosphinoamide ligands to remain bound to the Co center. The identity of both the arene and the group IV metal ion starkly influence the lability of the arene. For instance, the Co-bound benzene ligand in the Zr IV /Co –I benzene complex rapidly exchanges with C 6 D 6 in solution, whereas toluene/C 6 D 6 exchange is much slower and appreciable C 6 H 6 /C 6 D 6 exchange is not observed for the Hf analogue. The Zr IV /Co –I benzene complex loses benzene upon repeated exposure to vacuum to form an arene-free tetrametallic dimer.

aromatic compounds↗
DOE OSTI2024

Thermal Activation of Zirconium(IV) Acetylacetonate Catalysts to Enhance Polyurethane Synthesis and Reprocessing

Carbamate formation and exchange catalysts enable efficient polyurethane (PU) manufacturing, as well as emerging recycling and reprocessing methods for PU thermosets. Zirconium β-diketonate complexes, such as Zr acetylacetonate [Zr(acac) 4 ], are effective alternatives to toxic organotin catalysts that have been used for PU reprocessing. Here, we report that Zr(acac) 4 undergoes a thermally activated process in the PU network during reprocessing that transforms it into a more active carbamate exchange catalyst. This process is associated with the irreversible loss of acetylacetonate ligands and is not observed for the more sterically hindered Zr 2,2,6,6-tetramethyl-3,5-heptanedione [Zr(tmhd) 4 ] complex. Crossover experiments between PU thermoplastics indicated enhanced carbamate exchange after the thermal activation of Zr(acac) 4 in the presence of one of the PUs, whereas a sample of Zr(acac) 4 activated in the absence of the PU had no catalytic activity. Thermal gravimetric analysis suggested that this process is associated with the loss of one protonated acac ligand. Stress relaxation analysis of PU thermosets indicated a distinct change in the characteristic relaxation time associated with the thermal activation of Zr(acac) 4 at temperatures above 140 °C; no such change was observed for samples reprocessed using Zr(tmhd) 4 . Density functional theory and molecular experiments suggest that irreversible ligand exchange of acac with alkoxide or carbamate reduces the activation energy for urethane formation and reversion. Furthermore, the Zr(acac) 4 catalyst activated in the presence of a PU’s polyol precursor provided more porous and less dense PU foams compared to those made using the unactivated Zr(acac) 4 catalyst. Furthermore, these findings are important for developing improved PU synthesis and recycling processes. Thermally activating a catalyst during reprocessing may provide more nuanced control of the in-use and reprocessing characteristics of PU thermosets.

Alcohols↗
DOE OSTI2026

Oxidation of biogenic U(IV) mediated by iron-bearing clay minerals, iron-reducing bacteria, and organic ligands

Bioreduction of hexavalent uranium (U(VI)) to tetravalent uranium (U(IV)) by dissimilatory metal-reducing bacteria (DMRB) is considered an effective strategy for uranium immobilization in contaminated environments. However, U(IV) can be reoxidized to U(VI) under fluctuating redox conditions and remobilized. This work investigates the oxidation behavior of biogenic U(IV) in the presence of bioreduced iron-bearing clay minerals (rNAu-2), iron-reducing bacteria (Shewanella putrefaciens CN32), and organic ligands (ethylenediaminetetraacetic acid (EDTA) and citrate). Results demonstrate that the presence of CN32 significantly inhibits U(IV) oxidation. rNAu-2 exerted a context-dependent influence on U(IV) oxidation: its effect was masked by bicarbonate-promoted U(VI) mobilization in the absence of active CN32, but became detectable when CN32-mediated microbial protection slowed U(IV) oxidation. EDTA and citrate markedly accelerate U(IV) oxidation via formation of soluble U(IV)-ligand complexes, changing U(IV) redox potentials, and by promoting clay mineral dissolution that enhances Fe(II)/Fe(III) redox cycling. Collectively, our findings constrain the roles that clay minerals, iron-reducing bacteria, and organic ligands play in governing U(IV) stability, emphasizing the need to account for these factors in developing robust bioremediation strategies.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Venturing Past Uranium: Synthesis of a Np(IV) Polyoxomolybdate–Alkoxide Sandwich Complex

The synthesis of a Np(IV) polyoxomolybdate– alkoxide sandwich complex, (TBA) 2 [Np{Mo 5 O 13 (OMe) 4 NO} 2 ] (TBA = tetrabutylammonium), is reported. This compound represents a rare example of a neptunium polyoxometalate cluster isolated outside of water, allowing for characterization of its electrochemical properties in nonaqueous solvents. Complexation of An(IV) cations fine-tunes the redox properties of the cluster, with the observed four reversible reductive events varying slightly both in potential and peak separation depending on the actinide present. The new Np(IV) complex also shows an irreversible event assigned to oxidation of Np(IV) to Np(V). New methodology for facile 17 O enrichment of (TBA) 2 [Mo 5 O 13 (OMe) 4 NO][Na(MeOH)] is presented, which provides a simple pathway to 17 O enriched analogues of the sandwich complexes discussed (Zr(IV), Hf(IV), Th(IV), U(IV), U(V), Np(IV)). 17 O NMR spectroscopy subsequently provides insights into both the nature of metal–oxygen bonding, as well as the influence of unpaired f-electrons on the local environment of the oxygen nuclei.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Ammonolysis with N 2 -diluted NH 3 suppresses Ta( IV ) defects in BaTaO 2 N and enhances photocatalytic water oxidation

BaTaO 2 N stands out among oxynitride photocatalysts because of its ability to capture visible light and to drive the photoelectrochemical water oxidation reaction. However, its solar energy conversion performance is limited by electron–hole recombination at Ta( IV ) defects in the material. These defects are formed by overreduction of the Ta(v) oxide precursor by excess ammonia under the high temperature conditions during ammonolysis. Here we show for the first time that Ta( IV ) defect concentrations can be lowered by conducting the ammonolysis reaction in mixed NH 3 /N 2 gas. The obtained BaTaO 2 N samples crystallize in the cubic CaTiO 3 structure type and form 200–300 nm faceted nanocrystals, based on X-ray diffraction, scanning electron microscopy, and HRTEM. Electron paramagnetic resonance spectra observe the Ta( IV ) defects at g = 1.999 and confirm an 11-fold reduction for the product synthesized in mixed (0.13 : 1.0 vol) NH 3 /N 2 gas, equivalent to 1.14 × 10 16 cm −3 Ta( IV ) ions. This optimized BaTaO 2 N has nearly twice the photocatalytic oxygen evolution activity (AQE of 6.78% at 400 nm) of a reference material made with 1.0 atm ammonia and 78% higher photoelectrochemical water oxidation photocurrent (0.9 mA cm −2 at 1.23 V vs. RHE) under simulated sunlight. According to X-ray photoelectron spectroscopy, remaining Ta( IV ) defects are concentrated in the surface region of the BaTaO 2 N particles, where >50% of all Ta ions are found in the +4 oxidation state. This surface Ta( IV ) population can be directly observed in Vibrating Kelvin Probe Surface Photovoltage Spectra (VK-SPV) via its 1.2–1.4 eV photovoltage onset. Here, it suggests that the surface Ta( IV ) ions contribute empty d-states 0.5–0.7 eV below the BaTaO 2 N conduction band edge. These findings highlight how the energetics and concentrations of Ta( IV ) defects influence the photoelectrochemical water oxidation ability of BaTaO 2 N. Additionally, the work establishes ammonolysis with diluted NH 3 as a new tool to minimize defects in BaTaO 2 N and to raise its solar energy conversion efficiency toward its theoretical limit. Because of its simplicity, the reduced ammonia pressure strategy will likely be applicable to other oxynitrides, which generally suffer from overreduction problems during ammonolysis.

Salmanion, Mahya [University of California, Davis,↗
DOE OSTI2025

Experimental electronic structures of the Fe IV =O bond in S=1 heme vs. nonheme sites: Effect of the porphyrin ligand

High-valent Fe IV =O species are common intermediates in biological and artificial catalysts. Heme and nonheme S=1 Fe IV =O sites have been synthesized and studied for decades but little quantitative experimental comparison of their electronic structures has been available, due to the lack of direct methods focused on the iron. This study allows a rigorous determination of the electronic structure of a nonheme Fe IV =O center and its comparison to an Fe IV =O heme site using 1s2p resonant inelastic X-ray scattering (RIXS) and Fe L-edge X-ray absorption spectroscopy (XAS). Further, variable temperature magnetic circular dichroism (VT-MCD) of the ligand field transitions, combined with nuclear resonance vibrational spectroscopy of the two S=1 Fe IV =O systems show that the equatorial ligand field decreases from a nonheme to a heme Fe IV =O site. Alternatively, RIXS and Fe L-edge XAS combined with MCD show that the Fe dπ orbitals are unperturbed in the Fe IV =O heme relative to the nonheme site because the strong axial Fe-O bond uncouples the Fe dπ orbitals from the porphyrin π-system. As a consequence, the thermodynamics and kinetics of the H-atom abstraction reactions are actually very similar for heme compound II and nonheme Fe IV =O active sites.

bioinorganic chemistry↗
DOE OSTI2025

Isolation of Ce( IV ) centered polyoxoalkoxide sandwich-type complexes allows comparison of metal–oxygen bond covalency

The new Ce III centered sandwich-type complex (TBA) 3 [Ce{W 4 O 13 (OMe) 4 MoNO} 2 ] is reported. The redox properties of this molecule, and its all-molybdenum analogue, (TBA) 3 [Ce{Mo 5 O 13 (OMe) 4 NO} 2 ], were investigated using cyclic voltammetry. The data reveals the presence of reversible Ce IV /Ce III redox couples at modest potentials. One electron oxidation of the complexes provides facile access to the corresponding Ce IV derivatives, which were fully characterized. 17 O NMR spectroscopy reveals that the chemical shifts of the oxygen nuclei directly bound to Ce IV are much higher than the corresponding signals in isostructural, diamagnetic, Zr IV , Hf IV , or Th IV centered complexes. Density functional theory (DFT) calculations indicate that the increase in chemical shift correlates with an increase in the covalency of the M IV –O bonds, illustrating that 17 O NMR spectroscopy is a powerful experimental tool for interrogating the nature of metal oxygen bonding in diamagnetic complexes.

Shiels, Dominic [Univ. of Rochester, NY (United St↗
DOE OSTI2025

The Cosmic Evolution of C IV Absorbers at 1.4 < z < 4.5: Insights from 100,000 Systems in DESI Quasars

We present the largest catalog to date of triply ionized carbon (C IV ) absorbers detected in quasar spectra from the Dark Energy Spectroscopic Instrument. Using an automated matched-kernel convolution method with adaptive signal-to-noise thresholds, we identify 101,487 C IV systems in the redshift range 1.4 < z < 4.5 from 300,637 quasar spectra. Completeness is estimated via Monte Carlo simulations, and the catalog is 50% complete at EW C IV ≥ 0.4 Å. The differential equivalent width frequency distribution declines exponentially and shows weak redshift evolution. The absorber incidence per unit comoving path increases by a factor of 2–5 from z ≈ 4.5 to z ≈ 1.4, with stronger redshift evolution for strong systems. Using column densities derived from the apparent optical depth method, we constrain the cosmic mass density of C IV , Ω C IV , which increases by a factor of ∼3.8 from (0.82 ± 0.05) × 10 −8 at z ≈ 4.5 to (3.16 ± 0.2) × 10 −8 at z ≈ 1.4. From Ω C IV , we estimate a lower limit on intergalactic medium metallicity ${\mathrm{log}}({Z}_{{\rm{IGM}}}/{Z}_{\odot })\gtrsim -3.25$ at z ∼ 2.3, with a smooth decline at higher redshifts. These trends trace the cosmic star formation history and He II photoheating rate, suggesting a link between C IV enrichment, star formation, and UV background over ∼3 Gyr. The catalog also provides a critical resource for future studies connecting circumgalactic metals to galaxy evolution, especially near cosmic noon.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Godiva IV Simulated Radiation Field Characterization and Variance Reduction

Godiva IV is a system comprised of highly enriched uranium alloyed with molybdenum in the form of fuel plate rings. The reactor, along with its predecessors, was designed with the unique ability to satisfy interests in the super-prompt-critical reactor operation space. Originally, the reactor was part of the Los Alamos Critical Experiments Facility (LACEF) at Technical Area-18 (TA-18). The radiation field around Godiva at this facility was well characterized and understood. As a fast neutron system, the neutron spectrum in and around Godiva was close to a Watt Fission spectrum. The Kiva where Godiva IV was located at LACEF was made of thin, sheet metal walls which did not contribute significantly to the neutron spectrum. Following the transition of LACEF to the National Critical Experiments and Research Center (NCERC) in Nevada, Godiva-IV was moved from TA-18 to the Device Assembly Facility (DAF) at the Nevada National Security Site (NNSS). Part of this move brought renewed interest in radiation field characterization. The new facility introduced significant changes to the environment surrounding Godiva, and preliminary foil irradiation results suggested that the room contribution to the neutron spectrum was significant. Unlike at TA-18, a large thermal neutron signature was added to the fast spectrum from Godiva due to significant room return. A primary goal due to the additional complexity that the room return adds to the Godiva IV radiation emission spectrum was the development of an efficient Monte Carlo N-Particle (MCNP) calculation capable of characterizing the neutron spectrum anywhere in the room around Godiva. A campaign of activation foil irradiations and analysis were completed to support the validation of the MCNP model. The modeling of these foils in MCNP can be easily done with a standard volumetric neutron flux tally. However, given the multitude of locations and reaction rates to be modeled, further steps must be taken to increase the efficiency of these calculations in MCNP. During this study, a benchmark model currently under development for Godiva IV was used. A qualitative assessment of the thermal neutron contributors was performed using spatial neutron distribution plots. Additional detail was added to the model based on the qualitative results showing the thermal spectrum’s large sensitivity to hydrogenous material. Neutron energy spectra was evaluated at discrete locations in the room around Godiva to quantify the relative contribution of various components. It was discovered that the concrete walls are the largest contributor to the thermal signature, with minor contributions from plastic components surrounding Godiva. Following these results, two different variance reduction techniques were implemented to improve the problem efficiency in these calculations. In the first approach, an F5 point detector tally was implemented in the standard Godiva IV criticality problem. The second approach involved a weight-window generator implementation with an F5 point detector tally in a fixed source problem. The weight window implementation reduced the runtime from 42739.55 minutes to 1803.34 minutes (computer time), compared to the F5 KCODE implementation.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2025

Godiva IV Thermal Neutron Dosimetry Modeling and Variance Reduction

The transfer of the Godiva IV experiment from the Los Alamos Critical Experiments Facility (LACEF) to the National Critical Experiments Research Center (NCERC) introduced a vastly different experiment room return to the neutron flux. The contribution of the background to the burst neutron energy spectrum is significant in the thermal and epithermal neutron energies. Target materials may be placed in various locations in the Godiva room, or outside of the room, for thermal neutron activation. Modeling of this dosimetry problem in Monte Carlo N-Particle (MCNP) presented a novel challenge compared to previous Godiva IV glory hole irradiation simulations. An advanced dosimetry modeling framework for high efficiency calculations in locations far from the Godiva IV fission source was desired. The mesh-based weight windows and point detector advanced variance reduction techniques in MCNP were implemented and tested using adaptations of the critical experiment benchmark model of the Godiva IV problem. The models were validated against measured activations of Nickel, Indium, Scandium, and Cobalt foils at locations 2 meters from the Godiva IV core. Dosimetry measurements were performed in collaboration with Sandia National Laboratory. The weight windows and point detector variance reduction coupled method resulted in the highest problem efficiency.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2026

Pu(IV) quantification via visible–near-infrared absorption spectroscopy: tackling interferences using D-optimal design and partial least squares

Here, this study presents a novel analytical approach for quantifying Pu(IV) in glove box environments using fiber-optic-based visible–near-infrared absorption spectroscopy in combination with partial least squares regression (PLSR) and design of experiments. The method addresses significant challenges posed by overlapping spectral features arising from Nd(III), which is a common fission product impurity, and the speciation variability of Pu(IV) nitrato complexes in HNO 3 concentrations ranging from 2.5 to 11 M. A curated training set consisting of data from 20 samples was developed via D-optimal design to enable robust PLSR model calibration for Pu(IV) using the near-infrared band near 1050 nm. The training set was acquired from samples in cuvettes with a 1-cm path length and was used to build the PLSR model. The robustness of the model was validated with data collected using a dip probe with a 1-cm path length and varying Pu(IV) concentrations. The strong performance of the model indicates good model transfer from cuvette to dip probe and highlights the potential for in situ measurements and online monitoring of reactions in a crystallization reactor vessel. The results demonstrate that this combined spectroscopic and chemometric approach can accurately and simultaneously quantify Pu(IV) and HNO 3 , thereby offering a promising tool for real-time monitoring in process environments.

Actinide↗
DOE OSTI2026

Quantifying Temperature Dependence of Pu(IV) Absorbance Spectra for Advanced Online Monitoring of Nuclear Processes

This article presents a systematic study of Pu(IV) absorbance spectral features as a function of temperature to develop an understanding of this parameter’s effect on chemometric models that can be used as online monitoring tools to support nuclear processing. The descriptive and predictive models that provide real-time feedback of these processes are usually constructed with data collected in conditions typical of a laboratory environment, which can differ drastically from a processing environment. To assess the impact of temperature on Pu(IV) absorbance spectra, 11 samples of Pu(IV) were synthesized with varying HNO 3 concentrations ranging from 0.6 to 9.5 M and heated between 15 and 45 °C. Ultraviolet (UV)–visible (vis)–near-infrared (NIR) absorption spectra collected at different HNO 3 concentrations and temperatures revealed that features associated with Pu(IV) are sensitive to temperature at all HNO 3 concentrations and that changes in features depend on HNO 3 concentration. The contributions of temperature and HNO 3 concentration to variation in Pu(IV) spectral features were evaluated using the principal component analysis of spectra that were baseline-corrected with an asymmetric least-squares method. Furthermore, predictive modeling for HNO 3 concentration with partial least-squares regression of UV–vis–NIR spectra highlighted the importance of accounting for temperature in the calibration set to optimize model performance. This methodology constitutes a new, systematic approach to account for the effect of temperature on the absorption spectra of metal ions and is useful for process monitoring applications in many industries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Mk-IV Salt Crystallization Hot Finger Apparatus for Partitioning Used Electrorefiner Salt

Electrorefining is a controlled redox process used to regulate the behavior of ionic species. Through this process, metals can be deposited onto a cathode from an electrolyte solution in a controlled manner. The Mk-IV electrorefiner (Mk-IV ER) at Idaho National Laboratory is an engineering-scale, molten salt-based electrorefining cell that has been used for decades to recover metallic uranium from spent fuel. As a result, highly stable fission product chlorides have accumulated in the electrolyte. This accumulation results in changes to the salt’s properties, such as melting temperature, thermal conductivity, and density, as well as elevated product impurity and fissile materials criticality margin. These factors prompt the need for a salt regeneration process, such as melt-crystallization and species drawdown. This work focuses on providing a conceptual design to regenerate ER salt from used Mk-IV-ER salt in-situ, while minimizing salt waste volumes by concentrating the fission products in a final processed salt heal. We propose using a hot-finger crystallization apparatus design to fractionally crystallize salt in the Mk-IV-ER head space (or baffle space), allowing the collection of solid and liquid fractions. By using a cup-drain design, the used salt will be allowed to slowly solidify on the walls of a stainless-steel cup. The apparatus drain plug will then open to allow the liquid salt phase to drain to a lower cup, effectively separating the liquid phase from the solid phase. Under the hypothesis that the liquid phase salt concentrates the fission products, which is under examination in the accompanying work package, this separation allows the recovered solid salt to be reused while minimizing the high-level salt waste volume of used ER salt.

36 - MATERIALS SCIENCE↗
DOE OSTI2026

Oxygen Effects and Selective Oxidation of Group IV Alloying Additions in Group V-Based Refractory Multi-principal Element Alloys

Refractory multi-principal element alloys (RMPEAs) hold significant potential for advancing ultra-high-temperature technologies due to their remarkable strength retention under these conditions. However, the beneficial effects of alloying on microstructural evolution and mechanical properties are often obscured by the presence of interstitial alloying elements. The intricate interactions between substitutional alloying elements of Groups IV, V, and VI and interstitial content, whether intentional or incidental, remain poorly understood. In this study, we investigate the impact of dissolved oxygen on the microstructural evolution and stability of RMPEAs primarily composed of Group V elements, Nb and V, along with Group IV elements Ti, Zr, and Hf. We show that the strong affinity of oxygen for Group IV elements Zr and Hf leads to the internal precipitation of oxides during heat treatment, which competes with the homogenization of the as-cast dendritic microstructure. Here, we demonstrate that careful control and design of oxygen content and Group IV alloying additions are essential to minimize micro-segregation and prevent the detrimental precipitation of internal oxides. To address these challenges, we propose employing non-equilibrium solidification calculations to predict and optimize as-cast solidification structures, thereby reducing the reliance on homogenization processes.

Alloy design↗