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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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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Cyclopentadienyl coordination induces unexpected ionic Am-N bonding in an americium bipyridyl complex

Variations in bonding between trivalent lanthanides and actinides is critical for reprocessing spent nuclear fuel. The ability to tune bonding and the coordination environment in these trivalent systems is a key factor in identifying a solution for separating lanthanides and actinides. Coordination of 4,4'-bipyridine (4,4'-bpy) and trimethylsilylcyclopentadienide (Cp') to americium introduces unexpectedly ionic Am-N bonding character and unique spectroscopic properties. Here we report the structural characterization of (Cp' 3 Am) 2 (μ -4,4'-bpy) and its lanthanide analogue, (Cp' 3 Nd) 2 (μ - 4,4'-bpy), by single-crystal X-ray diffraction. Spectroscopic techniques in both solid and solution phase are performed in conjunction with theoretical calculations to probe the effects the unique coordination environment has on the electronic structure.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Evolution of microscopic heterogeneity and dynamics in choline chloride-based deep eutectic solvents

Deep eutectic solvents (DESs) are an emerging class of non-aqueous solvents that are potentially scalable, easy to prepare and functionalize for many applications ranging from biomass processing to energy storage technologies. Predictive understanding of the fundamental correlations between local structure and macroscopic properties is needed to exploit the large design space and tunability of DESs for specific applications. Here, we employ a range of computational and experimental techniques that span length-scales from molecular to macroscopic and timescales from picoseconds to seconds to study the evolution of structure and dynamics in model DESs, namely Glyceline and Ethaline, starting from the parent compounds. We show that systematic addition of choline chloride leads to microscopic heterogeneities that alter the primary structural relaxation in glycerol and ethylene glycol and result in new dynamic modes that are strongly correlated to the macroscopic properties of the DES formed.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Altering the spectroscopy, electronic structure, and bonding of organometallic curium(III) upon coordination of 4,4'–bipyridine

Structural and electronic characterization of (Cp' 3 Cm) 2 (μ–4,4'–bpy) (Cp' = trimethylsilylcyclopentadienyl, 4,4'–bpy = 4,4'–bipyridine) is reported and provides a rare example of curium–carbon bonding. Cp' 3 Cm displays unexpectedly low energy emission that is quenched upon coordination by 4,4'–bipyridine. Electronic structure calculations on Cp' 3 Cm and (Cp' 3 Cm) 2 (μ–4,4'–bpy) rule out significant differences in the emissive state, rendering 4,4'–bipyridine as the primary quenching agent. Comparisons of (Cp' 3 Cm) 2 (μ–4,4'–bpy) with its samarium and gadolinium analogues reveal atypical bonding patterns and electronic features that offer insights into bonding between carbon with f-block metal ions. Here we show the structural characterization of a curium–carbon bond, in addition to the unique electronic properties never before observed in a curium compound.

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

Non–linear bonding trends in maleonitrile-1,2–dithiolate complexes of the transuranium actinides

The trivalent actinides are produced in the nuclear fuel cycle during power production and provide the largest long-term radiation dose in used nuclear fuel. It is ideal for these elements to be removed from used nuclear fuel for disposal and a necessity for fuel recycling. A key challenge to this is the similarity of chemical behavior of the trivalent actinides to the lanthanides that are also present as fission products in used fuel. Thus far, some of the most effective separations of actinides from lanthanides utilise chelating agents containing sulfur moieties such as dithiophosphinates that selectively bind to actinide ions because of a greater bond covalency relative to lanthanide ions. Typically, greater differences between actinide and lanthanide ions are observable the more ligands and chelators bonds have a covalent character. Here, a series of complexes of the trivalent actinides Np(III) through Cf(III) (excluding Bk(III)) with maleonitrile-1,2-dithiolate (mnt 2– ) are synthesized along with their lanthanide counterparts (La(III) – Nd(III), Sm(III) – Gd(III), Dy(III)), in order to characterize the nature of chemical bonds with these metal ions and a polarizable, non-innocent, sulfur-donor ligand. The metal-sulfur bonds in these complexes trend shorter than measured for lanthanides with equivalent ionic radii. However, particularly large deviations are observed in the neptunium and plutonium complexes in both structure and bonding, resulting in a nonlinear bond length trendline for the actinide series. Density Functional Theory (DFT) calculations with Quantum Theory of Atoms in Molecules (QTAIM) and Natural Bond Order (NBO) analyses indicate that for the neptunium and plutonium complexes, the presence of increased 5f-orbital participation, energy degeneracy of the metal and ligand orbitals, and the structure packing result in shortened M–S bonds. The stabilization of the energy of the 5f-orbitals and the decrease in f-contribution to bonding orbitals in the later actinides results in structural properties more similar to the lanthanide complexes.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2023

Isolation of a californium(II) crown–ether complex

The actinides, from californium to nobelium (Z = 98–102), are known to have an accessible +2 oxidation state. Understanding the origin of this chemical behaviour requires characterizing Cf II materials, but investigations are hampered by the fact that they have remained dificult to isolate. This partly arises from the intrinsic challenges of manipulating this unstable element, as well as a lack of suitable reductants that do not reduce Cf III to Cf°. Here we show that a Cf II crown–ether complex, Cf(18-crown-6)I 2 , can be prepared using an Al/Hg amalgam as a reductant. Spectroscopic evidence shows that Cf III can be quantitatively reduced to Cf II , and rapid radiolytic re-oxidation in solution yields co-crystallized mixtures of Cf II and Cf III complexes without the Al/Hg amalgam. Furthermore, quantum-chemical calculations show that the Cf– ligand interactions are highly ionic and that 5f/6d mixing is absent, resulting in weak 5f→5f transitions and an absorption spectrum dominated by 5f→6d transitions.

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

Machine learning predictions of diffusion in bulk and confined ionic liquids using simple descriptors

Ionic liquids have many intriguing properties and widespread applications such as separations and energy storage. However, ionic liquids are complex fluids and predicting their behavior is difficult, particularly in confined environments. We introduce fast and computationally efficient machine learning (ML) models that can predict diffusion coefficients and ionic conductivity of bulk and nanoconfined ionic liquids over a wide temperature range (350–500 K). The ML models are trained on molecular dynamics simulation data for 29 unique ionic liquids as bulk fluids and confined in graphite slit pores. This model is based on simple physical descriptors of the cations and anions such as molecular weight and surface area. Here, we also demonstrate that accurate results can be obtained using only descriptors derived from SMILES (simplified molecular-input line-entry system) codes for the ions with minimal computational effort. This offers a fast and efficient method for estimating diffusion and conductivity of nanoconfined ionic liquids at various temperatures without the need for expensive molecular dynamics simulations.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2024

Insights into water extraction and aggregation mechanisms of malonamide-alkane mixtures

Structure at the nanoscale in the organic phase of liquid–liquid extraction systems is often tied to separation performance. However, the weak interactions that drive extractant assembly lead to poorly defined structures that are challenging to identify. Here, in this work, we investigate the mechanism of water extraction for a malonamide extractant commonly applied to f-element separations. We measure extractant concentration fluctuations in the organic phase with small angle X-ray scattering (SAXS) before and after contact with water at fine increments of extractant concentration, finding no qualitative changes upon water uptake that might suggest significant nanoscopic reorganization of the solution. The critical composition for maximum fluctuation intensity is consistent with small water–extractant adducts. The extractant concentration dependence of water extraction is consistent with a power law close to unity in the low concentration regime, suggesting the formation of 1 : 1 water–extractant adducts as the primary extraction mechanism at low concentration. At higher extractant concentrations, the power law slope increases slightly, which we find is consistent with activity effects modeled using Flory–Huggins theory without introduction of additional extractant–water species. Molecular dynamics simulations are consistent with these findings. The decrease in interfacial tension with increasing extractant concentration shows a narrow plateau region, but it is not correlated with any change in fluctuation or water extraction trends, further suggesting no supramolecular organization such as reverse micellization. This study suggests that water extraction in this system is particularly simple: it relies on a single mechanism at all extractant concentrations, and only slightly enhances the concentration fluctuations characteristic of the dry binary extractant/diluent mixture.

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

Impacts of benchmarking choices on inferred model skill of the Arctic–Boreal terrestrial carbon cycle

Abstract Land surface models require continuous validation against observations to improve and reduce simulation uncertainty. However, inferred model performance can be heavily influenced by subjective choices made in the selection and application of observational data products. A key area often misrepresented by models is the Arctic–Boreal region, which is a potential tipping point region in Earth’s climate system due to large permafrost carbon stocks that are vulnerable to release with climate warming. We use the International Land Model Benchmarking (ILAMB) framework to evaluate how the model skill of TRENDY-v9 models varies based on the choice of observational-based benchmark and how benchmarks are applied in model evaluation. This analysis uses global datasets integrated into ILAMB and new, regionally-specific observational products from the Arctic–Boreal Vulnerability Experiment. Our results cover the overall time period of 1979–2019 and show that model scores can vary substantially depending on the data product applied, with higher model scores indicating better model performance against observations. The lowest model scores occur when benchmarked against regional, compared to global, datasets. We also evaluate observed and modeled functional relationships between ecosystem respiration and air temperature and between gross primary production and precipitation. Here, we find that the magnitude and shape of the responses are strongly impacted by the choice of observational dataset and the approach used to construct the functional relationship benchmark. These results suggest that model evaluation studies could conclude a false sense of model skill if only using a single benchmark data product or if not applying regional data products when performing a regional model analysis. Collectively, our findings highlight the influence of benchmarking choices on model evaluation and point to the need for benchmarking guidelines when assessing model skill.

Poe, Jeralyn (ORCID:0000000318495278)↗
DOE OSTI2021

A Nitroxide Containing Organic Molecule in a Deep Eutectic Solvent for Flow Battery Applications

The nitroxide radical redox organic molecule, 2-phenyl-4,4,5,5-tetrame- thylimidazoline-1-oxyl-3-oxide (PTIO), was investigated for the first time in a deep eutectic solvent (DES)-like system consisting of a 1:4 molar ratio of choline chloride and ethylene glycol(Ch1EG4) as a redox flow battery electrolyte. PTIO is a single molecule with three oxidation states, and can provide both positive and negative redox couples for a flow battery. A flow battery using the PTIO/Ch1EG4 electrolyte demonstrated nearly 50% roundtrip efficiency with an approximately 1 V open circuit potential. Inefficiencies were primarily due to membrane resistance which can be significantly lowered with increased temperature. While PTIO appears stable over short periods (hours), the oxidized form is not stable in the DES-like electrolyte over longer times. Molecular modeling was performed to investigate the relative stability of PTIO in DES as compared to the previously studied 4-hydroxy-TEMPO (4HT). It was found that the oxoammonium cation 4HT + exhibits a noticeably larger nucleophilic reactive cloud as compared to PTIO + , indicating a higher reactivity. This method to predict stability of the oxoammonium cation shows promise to inform the design and synthesis of promising redox systems based on nitroxide radicals in DES electrolytes to identify new chemistries for large scale energy storage.

25 ENERGY STORAGE↗
DOE OSTI2026

Harvesting Isotopically Pure Ac-225 from Ra-225 Produced in Thorium Target Spallation Reaction

A method for isolating Ra-225 from linear accelerator irradiated Th metal chemical processing waste streams has been established. Separating Ra-225 from the complex matrix following proton irradiation of Th metal provides a source of isotopically pure Ac-225 free of the Ac-227 impurity that is present in accelerator-produced Ac-225. Ra isotopes are first separated from the irradiated Th target via cation exchange methods. Importantly, the Ra-containing fraction is cleaned from residual citrate via dilute nitric acid washes (0.5 M) on AG50W-X8 resin. The mixed Ra isotopes are then further purified from Ba-140 impurity using a Sr resin column. Ra elutes through the resin with successive washes of 2.5 M HNO 3 while Ba-140 is retained. Ac-225 is then harvested by loading the Ra content onto an AG50W-X8 cation exchange column where the Ra-225 parent is eluted with 2.5 M HNO 3 before the Ac-225 daughter is eluted with 8 M HNO 3 .

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2025

Warming Permafrost Model Intercomparision Project (WrPMIP): Pan-Arctic Perturbation Warming Simulations

Title: Warming Permafrost Model Intercomparision Project (WrPMIP): Pan-Arctic Perturbation Warming Simulations Description: WrPMIP Pan-Arctic simulations including historial baseline and two warming simulations. Models were perturbed similarly to known experimental warming trials that have been implemented across the Pan-Arctic over the last several decades. More information about the dataset can be found at the following links: https://warmingpermafrost.nau.edu/ The dataset is available at: https://esgf-node.ornl.gov/search/project=WrPMIP&mip_era=CMIP6&activity_id=WrPMIP

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Verification of a Modeling Toolkit for the Design of Building Electrical Distribution Systems

DC electrical distribution systems offer many potential advantages over their AC counterparts. They can facilitate easier integration with distributed energy resources, improve system energy efficiency by eliminating AC/DC converters at end-use devices (e.g., laptop chargers), and reduce installation material, time, and cost. However, DC electrical distribution systems present additional design considerations, largely resulting from potentially greater magnitude and variation in cable losses. Modeling and simulation are rarely used to design such systems. However, the greater dependency of DC system energy efficiency on design choices such as distribution voltages, architecture, and integration of PV and BESS suggests that modeling and simulation may be required. Such system performance analysis is currently not a standard practice, in part due to limited availability and validation of capable software tools. This paper characterizes the accuracy of a Modelica-based Building Electrical Efficiency Analysis Model (BEEAM) toolkit, as a precursor for validating its use to perform system performance analysis and inform design decisions. The study builds upon previous verification research by characterizing complete systems comprised of commercially available equipment, and providing a more detailed analysis of simulation results. Five lighting systems with varying electrical distribution architectures were designed using market-available equipment, installed in a laboratory environment, modeled using BEEAM, and simulated using three Modelica integrated development environments (IDEs). Simulated and measured results were compared to characterize toolkit accuracy. Initial results revealed that simulated performance was mostly within ±5% of measured system-level and device-level performance. While simulation results were not found to be dependent on the IDE, some Modelica compiler interoperability issues were identified. Although the BEEAM toolkit showed promise for the targeted use case, further work is needed to determine whether the demonstrated 5% accuracy is sufficient for making real-world design decisions, and for BEEAM to advance from an interesting research tool to one that can impact real-world building projects.

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2020

The Viscosity and Atomic Structure of Volatile-Bearing Melilititic Melts at High Pressure and Temperature and the Transport of Deep Carbon

Understanding the viscosity of mantle-derived magmas is needed to model their migration mechanisms and ascent rate from the source rock to the surface. High pressure–temperature experimental data are now available on the viscosity of synthetic melts, pure carbonatitic to carbonate–silicate compositions, anhydrous basalts, dacites and rhyolites. However, the viscosity of volatile-bearing melilititic melts, among the most plausible carriers of deep carbon, has not been investigated. In this study, we experimentally determined the viscosity of synthetic liquids with ~31 and ~39 wt% SiO 2 , 1.60 and 1.42 wt% CO 2 and 5.7 and 1 wt% H 2 O, respectively, at pressures from 1 to 4.7 GPa and temperatures between 1265 and 1755 °C, using the falling-sphere technique combined with in situ X-ray radiography. Our results show viscosities between 0.1044 and 2.1221 Pa·s, with a clear dependence on temperature and SiO 2 content. The atomic structure of both melt compositions was also determined at high pressure and temperature, using in situ multi-angle energy-dispersive X-ray diffraction supported by ex situ microFTIR and microRaman spectroscopic measurements. Our results yield evidence that the T–T and T–O (T = Si,Al) interatomic distances of ultrabasic melts are higher than those for basaltic melts known from similar recent studies. Based on our experimental data, melilititic melts are expected to migrate at a rate ~from 2 to 57 km·yr -1 in the present-day or the Archaean mantle, respectively.

36 MATERIALS SCIENCE↗