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At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Cobalt Dissolution from Metal Oxides and Battery Cathode Materials with Acetic Acid-Based Deep Eutectic Solvents

Recovery of critical metals with alternative solvents beyond those in traditional pyrometallurgy and hydrometallurgy is needed in consideration of environmental challenges and the growing demand for metals in energy technologies. Deep eutectic solvents (DESs) have emerged as sustainable alternatives for solvometallurgy in metal separation and recovery. In this study, DESs based on hydrogen bond acceptors (HBAs) including choline chloride (ChCl), acetylcholine chloride (AChCl), and betaine (Bet) were investigated for their effectiveness when paired with acetic acid (AA) as the hydrogen bond donor (HBD) for the dissolution of cobalt from cobalt oxide (CoO), lithium cobalt oxide (LiCoO 2 ), and lithium nickel manganese cobalt oxide (LNMC). Based on the spectroscopic analysis of the metal dissolution and coordination, Bet:AA was found to provide the highest solubility for CoO (0.33 M) in the form of an octahedral complex. On the other hand, ChCl:AA solvent was more effective at dissolving LiCoO 2 with 0.04 M Co 2+ corresponding to 17% dissolution efficiency and LNMC with 0.06 M Co 2+ corresponding to 72% dissolution efficiency at 50 °C, compared to Bet:AA (9% for LiCoO 2 and 31% for LNMC). Although the solubilities of LiCoO 2 and LNMC have not significantly improved in ChCl:AA, this difference in effectiveness between the solvents clearly reveals the role of the HBA in solubilization. The coordination synergy between the chloride and the –OH moiety facilitates the breakdown of the LiCoO 2 driven by the alteration of the solvent polarity. Cobalt in these solutions was found dominantly as a tetrahedral [CoCl 4 ] 2– complex. A chemical separation of cobalt oxalate from a mixed-metal oxide system based on Co, Fe, and Ni was also demonstrated, confirming the potential of these solvents for practical metal recovery.

Cobalt separation↗
DOE OSTI2024

Mark-18A Cold Runs

The Savannah River National Laboratory (SRNL) is tasked by the National Nuclear Security Administration (NNSA) to recover highly valued isotopes from irradiated Mark-18A (Mk-18A) targets. The Savannah River Site (SRS) has sixty-five Mk-18A targets available for the recovery of the high valued materials. The sixty-five Mk-18A targets are currently stored in the L-Area Basin and will be removed one at a time and individually transported to SRNL. Upon receipt at SRNL, the Mk-18A target material will be removed from the confinement, dissolved, chemically separated, and calcined to a stable oxide. The flowsheet is designed to recover the plutonium as well as the trivalent actinides. The remaining unrecovered material will be discarded to the high activity drain (HAD) system in SRNL. A specially designed cask was procured for transport of the targets from L-Area to SRNL. Once received at SRNL, the targets will be loaded into the back of Cell 7 and resized as they enter the cell. The resized targets (1/4 lengths) will then be processed one at a time through the following processes: caustic dissolution and filtration; acidic dissolution and filtration, Reillex anion exchange, diglycolamide (DGA) cation exchange; and DGA calcination. This processing will result in two product streams. The first is an aqueous plutonium solution which will be removed from the shielded cells and taken to a glovebox for further purification and conversion to an oxide. The second is a calcined oxide containing the Am and Cm as well as other lanthanide fission products which will be removed from the shielded cells using a bagless transfer system. Both materials will be packaged for shipment to Oak Ridge National Laboratory (ORNL). All equipment to carry out this process was designed, procured or fabricated, and installed in a mock-up facility (716-4A) at SRS to allow for simulation testing in a non-radioactive area. This equipment was then dismantled and transferred from 716-4A to 773-A and installed in the SRNL Shielded Cells. After installation in the shielded cells facility testing was performed using water followed by surrogates and cold chemicals. Issues were identified during these evaluations, including equipment issues as well as technical challenges. Many of the issues were rectified during performance of the cold runs, and the remaining have a resolution identified. Table ES-1 provides a summary of all issues identified during the cold run operations, as well as the status and identified resolutions to outstanding issues.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2021

Nanoparticle/Polyelectrolyte Complexes for Biomimetic Constructs

Abstract Constructing all‐aqueous systems with tailored geometries can generate a new class of biomimetic materials, a fascinating but challenging goal to achieve. Here, by taking advantage of the interfacial complexation of a polyelectrolyte (PE) and cellulose nanocrystals (CNCs), a unique interfacial PE/CNC complex is demonstrated for the stabilization of aqueous two‐phase systems and for the fabrication of all‐aqueous double emulsions and 3D constructs. The thickness of PE/CNC complex can be effectively adjusted by tuning the osmotic stress imbalance between the two aqueous phases and, during the formation and thickening of PE/CNC complex, individual assemblies can be connected to design hierarchical all‐aqueous structures. This new platform affords tremendous potential for engineering biomimetic constructs with advanced functionality, that can be used for chemical separation, delivery, and biphasic cascading reaction vessels.

Yin, Yixuan↗
DOE OSTI2025

From Molecules to Modules: Advanced Characterization of Membrane Systems

Membrane technologies can enhance the efficiency and selectivity of chemical separations in energy-water systems. Advanced characterization tools are critical for discerning separation mechanisms, revealing degradation processes, and designing novel materials and material systems for new and emerging challenges. The pursuit of next-generation membranes for water and energy applications requires understanding phenomena at the molecular scale, mesoscale, and macroscale. This perspective highlights advanced characterization techniques for elucidating and enhancing membrane performance, while addressing fundamental trade-offs involved in characterizing membranes under realistic conditions.

Zhu, Yaguang [Princeton University, NJ (United Sta↗
DOE OSTI2022

Static and Dynamic Gradient Based Directional Transportation of Neutral Molecules in Swollen Polymer Films

Abstract Materials which selectively transport molecules offer powerful opportunities for concentrating and separating chemical agents. Here, utilizing static and dynamic chemical gradients, transport of molecules within swollen crosslinked polymers is demonstrated. Using an ≈200 μm static hydroxyl to hexyl gradient, the neutral ambipolar nerve agent surrogate diethyl (cyanomethyl)phosphonate (DECP) is directionally transported and concentrated 60‐fold within 4 hours. To accelerate transport kinetics, a dynamic gradient (a “travelling wave”) is utilized. Here, the non‐polar dye pyrene was transported. The dynamic gradient is generated by an ion exchange process triggered by the localized introduction of an aqueous NaCl solution, which converts the gel from hydrophobic to hydrophilic. As the hydrophilic region expands, associated water enters the gel, and pyrene is pushed ahead of the expansion front. The dynamic gradient provides about 10‐fold faster transport kinetics than the static gradient.

Ali, Mohammad A.↗
DOE OSTI2020

Synergistic Self-Assembly of Oxoanions and d-Block Metal Ions with Heteroditopic Receptors into Triple-Stranded Helicates

Cooperativity effects among the interconnected anion and cation binding sites can profoundly alter the performance of heteroditopic receptors in selective ion pair recognition, processes that are oftentimes pertinent to biological systems and chemical separations. In this paper, we report the effect of the linker that connects both binding sites on self-assembly of heteroditopic receptors in the presence of divalent first-row transition metal salts in solution and solid phase. Introduction of backbone flexibility in the receptor results in the formation of triple-stranded ion-pair helicates with an extraordinary selectivity towards CuSO 4 through an anion-induced fit.

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

Atomic Dynamics of Multi‐Interfacial Migration and Transformations

Redox-induced interconversions of metal oxidation states typically result in multiple phase boundaries that separate chemically and structurally distinct oxides and suboxides. Directly probing such multi-interfacial reactions is challenging because of the difficulty in simultaneously resolving the multiple reaction fronts at the atomic scale. Using the example of CuO reduction in H 2 gas, a reaction pathway of CuO → monoclinic m-Cu 4 O 3 → Cu 2 O is demonstrated and identifies interfacial reaction fronts at the atomic scale, where the Cu 2 O/m-Cu 4 O 3 interface shows a diffuse-type interfacial transformation; while the lateral flow of interfacial ledges appears to control the m-Cu 4 O 3 /CuO transformation. Together with atomistic modeling, it is shown that such a multi-interface transformation results from the surface-reaction-induced formation of oxygen vacancies that diffuse into deeper atomic layers, thereby resulting in the formation of the lower oxides of Cu 2 O and m-Cu 4 O 3 , and activate the interfacial transformations. In conclusion, these results demonstrate the lively dynamics at the reaction fronts of the multiple interfaces and have substantial implications for controlling the microstructure and interphase boundaries by coupling the interplay between the surface reaction dynamics and the resulting mass transport and phase evolution in the subsurface and bulk.

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

Gamma-ray spectrometry analysis methods for radioisotope dissolution and mixing for nuclear forensics applications

We report the production of surrogate nuclear explosive debris involves the dissolution of irradiated fissile material, elemental isolation, and recombination based on required fission product ratios. Gamma-ray spectrometry is used following each step to assess the radioactive fission product inventory. A high-purity germanium detector is used to measure each sample, and the detector efficiencies are determined prior to sample measurements. Through radiochemical techniques, elements are isolated and recombined into samples with specific fission product ratios. As a result, a matrix-based approach can account for imperfect chemical separations to calculate the proper mixture volumes to obtain intended volatile-to-refractory fission product ratios, or R-values.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2022

Inorganic resins enable the increased purification efficiency of 82 Sr from rubidium targets for use in PET imaging isotope production

The 82 Sr/ 82 Rb generator system has found use in positron emission tomography (PET) imaging of myocardial perfusion. 82 Sr is produced by proton irradiation of Rb metal/RbCl salt followed by chemical separation. Inorganic ion-exchangers were synthesized by hydrothermal methods and evaluated for the purification of accelerator-produced 82Sr from a RbCl target and co-produced impurities like 75 Se, Fe, Cr, and Ni. A process consisting of removal of bulk RbCl using sodium nonatitanate (SNT), then removal of remaining tracers of Rb and Se using poorly crystalline silicotitanate (pCST) is suitable for 82 Sr separation and achieves higher purity of 82 Sr vs. commonly used organic resins.

43 PARTICLE ACCELERATORS↗
DOE OSTI2025

Photonuclear production of 225 Ac from 226 Ra targets

Herein we report proof of principal production of 225 Ac via 226 Ra(γ , n) 225 Ra $\overset{^-β}{\rightarrow}$ 225 Ac and subsequent chemical separation via extraction chromatography using BDGA and Ln resins. Irradiation of 0.35 µg 226 Ra with 39 MeV bremsstrahlung end-point energy photons produced 225 Ra and 224 Ra at a rate of 754 and 2215 kBq/g 226 Ra/mA/h, respectively. The production rate of 225 Ac determined at its peak radioactivity was 335 kBq/g 226 Ra/mA/h. Radiochemically pure 225 Ac was isolated with a minimum separation factor of 125,000 for 225 Ac: 226 Ra. In conclusion, these results are promising and lay the foundation for future studies to scale-up production for preclinical quantities of high purity 225 Ac using the 226 Ra(γ , n) 225 Ra $\overset{^-β}{\rightarrow}$ 225 Ac approach.

38 - RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCL↗
DOE OSTI2023

Controlled electron transfer by molecular wires embedded in ultrathin insulating membranes for driving redox catalysis

Organic bilayers or amorphous silica films of a few nanometer thickness featuring embedded molecular wires offer opportunities for chemically separating while at the same time electronically connecting photo- or electrocatalytic components. Such ultrathin membranes enable the integration of components for which direct coupling is not sufficiently efficient or stable. Photoelectrocatalytic systems for the generation or utilization of renewable energy are among the most prominent ones for which ultrathin separation layers open up new approaches for component integration for improving efficiency. Recent advances in the assembly and spectroscopic, microscopic, and photoelectrochemical characterization have enabled the systematic optimization of the structure, energetics, and density of embedded molecular wires for maximum charge transfer efficiency. The progress enables interfacial designs for the nanoscale integration of the incompatible oxidation and reduction catalysis environments of artificial photosystems and of microbial (or biomolecular)-abiotic systems for renewable energy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Cross-sections for 43 Sc, 44 m Sc, and 44 g Sc from two heavy ion reactions

Two different heavy ion reactions were used to produce 43 Sc (t$_{\frac12}$ = 3.891 h), 44g Sc (t$_{\frac12}$ = 4.042 h), and 44m Sc (t$_{\frac12}$ = 58.61 h) among other stable or long-lived chemically separable products. Production cross sections for 19 F + 27 Al and the reverse kinematic reaction 35 Cl + nat B were measured using an MC-SNICS ion source and the Notre Dame FN Tandem Accelerator. 19 F beams from 35 to 60 MeV were produced with beam currents between 40–80 pnA and 35 Cl beams were produced at six entrance energies with comparable beam currents. This work reports nuclear reaction cross sections 27 Al ( 19 F, x) 43 Sc, 27 Al ( 19 F, pn) 44g Sc, and 27 Al ( 19 F, pn) 44m Sc at six energies between 35 and 60 MeV lab energy. Cross sections within the same energy range were measured for 27 Al ( 19 F, 3pn) 42 K and 27 Al ( 19 F, 3p) 43 K. Comparative measurements were performed for the same compound nucleus produced from nat B( 35 Cl, x) 43 Sc, nat B( 35 Cl, pn) 44g Sc, and nat B( 35 Cl, pn) 44m Sc. The measured thin target cross sections show an overestimation by several statistical models for the scandium radioisotopes. This is corroborated by the measured thick target production rates for both entrance channels. This may be due to angular momentum effects of a heavy ion entrance channel compared to light-ion production, but additional work is required to understand this discrepancy. Finally, these measurements demonstrate that the medically useful 43 Sc, 44g Sc, and 44m Sc radioisotopes can be free of the long-lived contaminant 46 Sc without the use of enriched targets, using heavy ion beams and robust target materials.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2020

Operator inference for non-intrusive model reduction of systems with non-polynomial nonlinear terms

Here in this work we present a non-intrusive model reduction method to learn low-dimensional models of dynamical systems with non-polynomial nonlinear terms that are spatially local and that are given in analytic form. In contrast to state-of-the-art model reduction methods that are intrusive and thus require full knowledge of the governing equations and the operators of a full model of the discretized dynamical system, the proposed approach requires only the non-polynomial terms in analytic form and learns the rest of the dynamics from snapshots computed with a potentially black-box full-model solver. The proposed method learns operators for the linear and polynomially nonlinear dynamics via a least-squares problem, where the given non-polynomial terms are incorporated on the right-hand side. The least-squares problem is linear and thus can be solved efficiently in practice. The proposed method is demonstrated on three problems governed by partial differential equations, namely the diffusion–reaction Chafee–Infante model, a tubular reactor model for reactive flows, and a batch-chromatography model that describes a chemical separation process. The numerical results provide evidence that the proposed approach learns reduced models that achieve comparable accuracy as models constructed with state-of-the-art intrusive model reduction methods that require full knowledge of the governing equations.

42 ENGINEERING↗
DOE OSTI2020

Analytical Determination of Radioactive Strontium and Cesium by Thermal Ionization Mass Spectrometry

Thermal ionization mass spectrometry (TIMS) has been evaluated for the detection of the radioactive isotopes of strontium and cesium. The instrument was investigated for the analysis of isotopic ratios of 89Sr to 90Sr and 135Cs to 137Cs in the presence of atomic isobars (Y and Zr for Sr analysis and Ba for Cs analysis). Signicant discrimination using TIMS was found for both Sr and Cs through evaluation using stable isotopes. Fusion procedures with different flux were evaluated for preparation of sample matrices. Chemical separations were developed and used after fusion to isolate the Sr and Cs from a prepared background matrix (i.e., Montana Soil). A graded approach, increasing in stable background isotopes, was performed to monitor the chemistry and instrument response. A thermal neutron irradiation was performed to produce a sample that contained the radioisotopes of Sr and Cs. Even though the irradiated sample was not a certified standard it does provide accurate expectation values via published, well understood cumulative fission yield data. The results presented in this work correlate extremely well with the published data. Furthermore, a significant decrease in uncertainty (by a factor of 5 { 10) was found for the isotopic ratios measured with TIMS compared to the published values.

TIMS, environmental contamination, radiostrontium,↗
DOE OSTI2022

Synthesis and characterization of magnetic ionic liquids containing multiple paramagnetic lanthanide and transition metal centers and functionalized diglycolamide ligands

Magnetic ionic liquids (MILs) containing paramagnetic centers have gained widespread recognition as sustainable solvents due to their ability to respond to an external magnetic field. The physico-chemical properties of MILs are dependent on the choice of anion/cation ligands and metal centers; the search for highly tunable ligands and precursors that can confer favorable characteristics, such as low viscosity, is ongoing. Diglycolamides employed as cationic ligands have been previously shown to form hydrophobic MILs that can simultaneously incorporate multiple lanthanide metal centers in both the anion/cation. Despite their enhanced magnetic susceptibility, the effect of diglycolamide chemical structure modifications on the physico-chemical properties of MILs has not been thoroughly studied. Additionally, the possibility of forming diglycolamide-based MILs with popularly employed transition metals has not been investigated and combinations that can simultaneously embed two different types of metal centers in both the anion/cation have not been explored. In this study, thirty (30) MILs comprised of lanthanide and transition metals were synthesized by examining their chelation to both straight-chained and branched diglycolamides. Here, transition metal-based MILs were found to possess high thermal stabilities up to 235 °C compared to 192 °C for those comprised of lanthanides. While MILs comprised of rare-earth metal centers exhibited the lowest viscosities, substituting lanthanides with transition metals in just the anion or cation resulted in enhanced thermal stability and reduced viscosity. The effective magnetic moment for these MILs varied between 4.71 and 21.08 µ B and was much higher compared to all previous classes of MILs prepared using the same metals. Results from this study explore all possible modifications that can be made to these MILs in an effort to demonstrate their structural tunability, which is often highly desirable in various applications, including organic synthesis and chemical separations.

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

U-Pu and Ba-Cs isotopic measurements on Trinitite by laser ablation sampling on the Neoma MC-ICP-MS

In this study we present the results of combined U-Pu and Ba-Cs isotope measurements obtained by laser ablation (LA) sampling of two glassy debris fragments (‘Trinitite’) from the world's first atomic bomb detonation conducted in New Mexico on July 16, 1945. Our primary goal in conducting these measurements was to understand whether examination of the U-Pu and Ba-Cs systematics by direct sampling (e.g. without any chemical separation or purification prior to isotope ratio measurement) could yield meaningful information that would differentiate the Trinitite fragments from glassy material lacking a nuclear fission signature. These measurements were conducted on a ThermoFisher Scientific Neoma multi collector – inductively coupled plasma – mass spectrometer (MC-ICP-MS), which is a relatively new MC-ICP-MS platform, so we also examine the behavior of these isotope systems in standards sampled in solution and via LA. Unsurprisingly, the measurements made on purified solutions of the U, Pu, and Ba isotopic standards produce high precision isotope ratios. Furthermore, this extends to the U-Pu measurements made by LA sampling, with the expected degradation in precision and accuracy related to matrix effects and signal intensity fluctuation. However, the Ba-Cs data acquired by LA is of low precision across all of the matrices examined and bears evidence of complex mass fractionation that will require further investigation to resolve. In total, our results indicate that the observed U-Pu isotope data are of sufficient quality to accurately constrain the U and Pu isotopic composition of glass containing sub-ppm levels of these elements which in turn could be used to differentiate glass containing anthropogenic fission products from natural glass whereas the Ba-Cs LA data cannot be used for this purpose until further methodological refinement is performed.

Ba-Cs↗