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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 1,063 records · Page 59
All sourcesNASA NTRSDOE OSTI
NASA NTRS2012

Aqueously Dispersed Silver Nanoparticle-Decorated Boron Nitride Nanosheets for Reusable, Thermal Oxidation-Resistant Surface Enhanced Raman Spectroscopy (SERS) Devices

The impurity-free aqueous dispersions of boron nitride nanosheets (BNNS) allowed the facile preparation of silver (Ag) nanoparticle-decorated BNNS by chemical reduction of an Ag salt with hydrazine in the presence of BNNS. The resultant Ag-BNNS nanohybrids remained dispersed in water, allowing convenient subsequent solution processing. By using substrate transfer techniques, Ag-BNNS nanohybrid thin film coatings on quartz substrates were prepared and evaluated as reusable surface enhanced Raman spectroscopy (SERS) sensors that were robust against repeated solvent washing. In addition, because of the unique thermal oxidation-resistant properties of the BNNS, the sensor devices may be readily recycled by short-duration high temperature air oxidation to remove residual analyte molecules in repeated runs. The limiting factor associated with the thermal oxidation recycling process was the Ostwald ripening effect of Ag nanostructures.

Lin, Yi↗
DOE OSTI2015

Supported liquid inorganic membranes for nuclear waste separation

A system and method for the extraction of americium from radioactive waste solutions. The method includes the transfer of highly oxidized americium from an acidic aqueous feed solution through an immobilized liquid membrane to an organic receiving solvent, for example tributyl phosphate. The immobilized liquid membrane includes porous support and separating layers loaded with tributyl phosphate. The extracted solution is subsequently stripped of americium and recycled at the immobilized liquid membrane as neat tributyl phosphate for the continuous extraction of americium. The sequestered americium can be used as a nuclear fuel, a nuclear fuel component or a radiation source, and the remaining constituent elements in the aqueous feed solution can be stored in glassified waste forms substantially free of americium.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS1997

The Use of HFC (CFC Free) Processes at the NASA Stennis Space Center

The search for ozone depleting alternative chemicals was heightened when, in 1990, the more than 65 countries that had signed the Montreal Protocol agreed to phase out completely by the year 2000. In 1992, then-president Bush advanced this date for the United States to January l, 1996. In 1991, it was realized that the planned phase out and eventual elimination of ozone depleting chemicals imposed by the Montreal Protocol and the resulting Clean Air Act (CAA) amendments would impact the cleaning and testing of aerospace hardware at the NASA Stennis Space Center. Because of this regulation, the Test & Engineering Sciences Laboratory has been working on solvent conversion studies to replace CFC-113. Aerospace hardware and test equipment used in rocket propulsion systems require extreme cleanliness levels to function and maintain their integrity. Because the cleanliness of aerospace hardware will be affected by the elimination of CFC-113; alternate cleaning technologies, including the use of fluoridated solvents have been studied as potential replacements. Several aqueous processes have been identified for cleaning moderately sized components. However, no known aqueous alternative exists for cleaning and validating T&ME and complex geometry based hardware. This paper discusses the choices and the methodologies that were used to screen potential alternatives to CFC-113.

Ross, Richard H.↗
DOE OSTI2019

Structural basis of ligand recognition at the human MT1 melatonin receptor

Melatonin (N-acetyl-5-methoxytryptamine) is a neurohormone that maintains circadian rhythms by synchronization to environmental cues and is involved in diverse physiological processes such as the regulation of blood pressure and core body temperature, oncogenesis, and immune function. Melatonin is formed in the pineal gland in a light-regulated manner by enzymatic conversion from 5-hydroxytryptamine (5-HT or serotonin), and modulates sleep and wakefulness5 by activating two high-affinity G-protein-coupled receptors, type 1A (MT 1 ) and type 1B (MT 2 ). Shift work, travel, and ubiquitous artificial lighting can disrupt natural circadian rhythms; as a result, sleep disorders affect a substantial population in modern society and pose a considerable economic burden. Over-the-counter melatonin is widely used to alleviate jet lag and as a safer alternative to benzodiazepines and other sleeping aids and is one of the most popular supplements in the United States. Here in this paper, we present high-resolution room-temperature X-ray free electron laser (XFEL) structures of MT 1 in complex with four agonists: the insomnia drug ramelteon, two melatonin analogues, and the mixed melatonin–serotonin antidepressant agomelatine. The structure of MT 2 is described in an accompanying paper. Although the MT 1 and 5-HT receptors have similar endogenous ligands, and agomelatine acts on both receptors, the receptors differ markedly in the structure and composition of their ligand pockets; in MT 1 , access to the ligand pocket is tightly sealed from solvent by extracellular loop 2, leaving only a narrow channel between transmembrane helices IV and V that connects it to the lipid bilayer. The binding site is extremely compact, and ligands interact with MT 1 mainly by strong aromatic stacking with Phe179 and auxiliary hydrogen bonds with Asn162 and Gln181. Our structures provide an unexpected example of atypical ligand entry for a non-lipid receptor, lay the molecular foundation of ligand recognition by melatonin receptors, and will facilitate the design of future tool compounds and therapeutic agents, while their comparison to 5-HT receptors yields insights into the evolution and polypharmacology of G-protein-coupled receptors.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2016

Concentrated Electrolyte for the Sodium-Oxygen Battery: Solvation Structure and Improved Cycle Life

Alkali metal-oxygen batteries are of great interests for energy storage because of their unparalleled theoretical energy densities. Particularly attractive is the emerging Na-O 2 battery because of the formation of superoxide as the discharge product. Dimethyl sulfoxide (DMSO) is a promising solvent for this battery but its instability towards Na makes it impractical in the Na-O 2 battery. Here in this paper, we report the enhanced stability of Na in DMSO solutions containing concentrated sodium trifluoromethanesulfonimide (NaTFSI) salts (>3molkg -1 ). Raman spectra of NaTFSI/DMSO electrolytes and abinitio molecular dynamics simulation reveal the Na + solvation number in DMSO and the formation of Na(DMSO) 3 (TFSI)-like solvation structure. The majority of DMSO molecules solvating Na + in concentrated solutions reduces the available free DMSO molecules that can react with Na and renders the TFSI anion decomposition, which protects Na from reacting with the electrolyte. Using these concentrated electrolytes, Na-O 2 batteries can be cycled forming sodium superoxide (NaO 2 ) as the sole discharge product with improved long cycle life, highlighting the beneficial role of concentrated electrolytes for Na-based batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

Development of 225Ac-doped biocompatible nanoparticles for targeted alpha therapy

Abstract Targeted alpha therapy (TAT) relies on chemical affinity or active targeting using radioimmunoconjugates as strategies to deliver α-emitting radionuclides to cancerous tissue. These strategies can be affected by transmetalation of the parent radionuclide by competing ions in vivo and the bond-breaking recoil energy of decay daughters. The retention of α-emitting radionuclides and the dose delivered to cancer cells are influenced by these processes. Encapsulating α-emitting radionuclides within nanoparticles can help overcome many of these challenges. Poly(lactic- co -glycolic acid) (PLGA) nanoparticles are a biodegradable and biocompatible delivery platform that has been used for drug delivery. In this study, PLGA nanoparticles are utilized for encapsulation and retention of actinium-225 ([ 225 Ac]Ac 3+ ). Encapsulation of [ 225 Ac]Ac 3+ within PLGA nanoparticles (Z ave = 155.3 nm) was achieved by adapting a double-emulsion solvent evaporation method. The encapsulation efficiency was affected by both the solvent conditions and the chelation of [ 225 Ac]Ac 3+ . Chelation of [ 225 Ac]Ac 3+ to a lipophilic 2,9-bis-lactam-1,10-phenanthroline ligand ([ 225 Ac]AcBLPhen) significantly decreased its release (< 2%) and that of its decay daughters (< 50%) from PLGA nanoparticles. PLGA nanoparticles encapsulating [ 225 Ac]AcBLPhen significantly increased the delivery of [ 225 Ac]Ac 3+ to murine (E0771) and human (MCF-7 and MDA-MB-231) breast cancer cells with a concomitant increase in cell death over free [ 225 Ac]Ac 3+ in solution. These results demonstrate that PLGA nanoparticles have potential as radionuclide delivery platforms for TAT to advance precision radiotherapy for cancer. In addition, this technology offers an alternative use for ligands with poor aqueous solubility, low stability, or low affinity, allowing them to be repurposed for TAT by encapsulation within PLGA nanoparticles. Graphical Abstract

60 APPLIED LIFE SCIENCES↗
DOE OSTI2026

Hydrated Metal and Metal-Nitrate Complexes in Water: Full Lanthanide(III) Series plus Miscellaneous Metal Ions

This is a dataset of hydrated metal complexes and metal–nitrate hydrated complexes intended for public use, reproducibility, and downstream structural analysis. A key feature is coverage across the full lanthanide(III) series (La–Lu), enabling systematic comparisons of coordination motifs and bonding trends across the entire lanthanide sequence. In addition to the lanthanides, the dataset also includes other metal ions such as UO2(VI), Fe(II), and Fe(III). The dataset provides optimized geometries for hydrated and nitrate-containing hydrated complexes, together with representative ab initio molecular dynamics (AIMD) trajectories saved in standard XYZ formats. The accompanying NWChem input decks enable reproduction of the reported calculations and provide a starting point for extending the simulations to related coordination environments. Computationally, DFT calculations employ the B3LYP functional with DFT-D3BJ dispersion corrections and a COSMO continuum solvent model (dielectric constant 78.4) to represent solvation beyond the explicitly treated first hydration shell. AIMD simulations are performed with the NWChem qmd module at 298 K, integrating nuclear motion with the velocity-Verlet algorithm and controlling temperature using a Nosé–Hoover thermostat. Trajectories are approximately 4.8 ps in length and are used primarily to assess short-time stability of candidate coordination motifs, including (for lanthanides) differences between 8- versus 9-water coordination and comparisons between nitrate-bound and nitrate-free hydrated complexes.

Dinpajooh, Mohammadhasan [Pacific Northwest Nation↗
DOE OSTI2015

Electric Double-Layer Structure in Primitive Model Electrolytes. Comparing Molecular Dynamics with Local-Density Approximations

We evaluate the accuracy of local-density approximations (LDAs) using explicit molecular dynamics simulations of binary electrolytes comprised of equisized ions in an implicit solvent. The Bikerman LDA, which considers ions to occupy a lattice, poorly captures excluded volume interactions between primitive model ions. Instead, LDAs based on the Carnahan–Starling (CS) hard-sphere equation of state capture simulated values of ideal and excess chemical potential profiles extremely well, as is the relationship between surface charge density and electrostatic potential. Excellent agreement between the EDL capacitances predicted by CS-LDAs and computed in molecular simulations is found even in systems where ion correlations drive strong density and free charge oscillations within the EDL, despite the inability of LDAs to capture the oscillations in the detailed EDL profiles.

25 ENERGY STORAGE↗
DOE OSTI2016

Condensed phase QM/MM simulations utilizing the exchange core functions to describe exchange repulsions at the QM boundary region

In a recent work, we developed a method [H. Takahashi et al., J. Chem. Phys. 143, 084104 (2015)] referred to as exchange-core function (ECF) approach, to compute exchange repulsion E{sub ex} between solute and solvent in the framework of the quantum mechanical (QM)/molecular mechanical (MM) method. The ECF, represented with a Slater function, plays an essential role in determining E{sub ex} on the basis of the overlap model. In the work of Takahashi et al. [J. Chem. Phys. 143, 084104 (2015)], it was demonstrated that our approach is successful in computing the hydrogen bond energies of minimal QM/MM systems including a cationic QM solute. We provide in this paper the extension of the ECF approach to the free energy calculation in condensed phase QM/MM systems by combining the ECF and the QM/MM-ER approach [H. Takahashi et al., J. Chem. Phys. 121, 3989 (2004)]. By virtue of the theory of solutions in energy representation, the free energy contribution δμ{sub ex} from the exchange repulsion was naturally formulated. We found that the ECF approach in combination with QM/MM-ER gives a substantial improvement on the calculation of the hydration free energy of a hydronium ion. This can be attributed to the fact that the ECF reasonably realizes the contraction of the electron density of the cation due to the deficit of an electron.

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

Molecular structures of residual solvent in polyacrylonitrile based electrolytes: Implications for conductivity and stability

Lithium-ion batteries increasingly play significant roles in modern technologies; however, increased energy density also raises concerns about electrolyte safety. Traditional electrolytes that use volatile organic solvents face risks of thermal runaways and fires from electrode shorting. In response, polymer-based solid electrolytes have been developed for replacement. Polyacrylonitrile (PAN) is a promising fire-resistant component for electrolyte fabrication, but its limited solubility necessitates using low-volatility solvents, which are notoriously difficult to remove in subsequent drying processes. Here, we use femtosecond two-dimensional infrared spectroscopy to provide an in-depth understanding of how residual solvent from processing affects the molecular structures and dynamics within a polymer electrolyte. To this end, linear and nonlinear infrared spectroscopies are employed to interrogate the molecular interactions in PAN-based electrolytes containing various contents of N,N-dimethylformamide (DMF). We show that the amount of DMF within the PAN electrolyte affects the Li+ structure. Further, the coordination can proceed through the carbonyl group and/or the amide nitrogen to form antiparallel structures with the nitrile groups of PAN through dipole–dipole interactions. The free motion of DMF is drastically inhibited upon interaction with Li+ and PAN, which decreases the ionic conductivity and potentially affects the stability (resistance toward removal and chemical decomposition). These findings have implications for the design and processing of solid polymer electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Solution and Interface Structure and Dynamics in Geochemistry: Gateway to Link Elementary Processes to Mineral Nucleation and Growth

Our understanding of the process of mineral nucleation is starting to evolve from the solely thermodynamical aspects in classical nucleation theory toward a mechanistic study of reactions influenced by solvation structures of ions and their dynamics. A knowledge of how these atomic and molecular interactions respond to changing solution composition and/or the nature of an interface will form a fundamental foundation to understand rate-limiting reactions and processes for nucleation and growth. Here, we review recent advances from multidisciplinary experimental and computational approaches of the structure and dynamics of aqueous solutions and mineral–liquid interfaces that will influence rates of nucleation (and growth behavior) both homogeneously in aqueous solutions and heterogeneously at mineral–liquid interfaces. Furthermore, these processes include structure (and extent) of solute clustering, solvent degrees of freedom, and the presence of noninnocent charge-balancing ions, all of which can drive the selectivity and exert control over nucleation mechanisms. Similar controlling reactions can also occur at interfaces with the added complexities of how solute ions interact with and assemble on surface sites and use different mechanisms from bulk solutes, such as lateral solvent exchanges between distinct surface sites. To gain a predictive understanding of nucleation chemistry, we emphasize several key knowledge gaps that will need to be addressed in this field and highlight the importance of combining computations and experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Interplay of physically different properties leading to challenges in separating lanthanide cations – an ab initio molecular dynamics and experimental study

Lanthanide elements have well-documented similarities in their chemical behavior, which make the valuable trivalent lanthanide cations (Ln 3+ ) particularly difficult to separate from each other in water. Here, we apply ab initio molecular dynamics simulations to compare the free energies (Δ G ads ) associated with the adsorption of lanthanide cations to silica surfaces at a pH condition where SiO – groups are present. The predicted Δ G ads for lutetium (Lu 3+ ) and europium (Eu 3+ ) are similar within statistical uncertainties; this is in qualitative agreement with our batch adsorption measurements on silica. This finding is remarkable because the two cations exhibit hydration free energies (Δ G hyd ) that differ by >2 eV, different hydration numbers, and different hydrolysis behavior far from silica surfaces. We observe that the similarity in Lu 3+ and Eu 3+ Δ G ads is the result of a delicate cancellation between the difference in Eu 3+ and Lu 3+ hydration (Δ G hyd ), and their difference in binding energies to silica. We propose that disrupting this cancellation at the two end points, either for adsorbed or completely desorbed lanthanides ( e.g. , via nanoconfinment or mixed solvents), will lead to effective Ln 3+ separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Enthalpies of formation of polyhalite: A mineral relevant to salt repository

Polyhalite is an important coexisting mineral with halite in salt repositories for nuclear waste disposal, such as Waste Isolation Pilot Plant (WIPP) in Carlsbad, New Mexico. The thermal stability of this mineral is a key knowledge in evaluating the integrity of a salt repository in the long term, as water may release due to thermal decomposition of polyhalite. Previous studies on structural evolution of polyhalite at elevated temperatures laid the basis for detailed calorimetric measurements. Using high-temperature oxide-melt drop-solution calorimetry at 975 K with sodium molybdate as the solvent, we have determined the standard enthalpies of formation from constituent sulfates (ΔH° f,sul ), oxides (ΔH° f,ox ) and elements (ΔH° f,ele ) of a polyhalite sample with the composition of K 2 Ca 2 Mg(SO 4 ) 4 ·1.95H 2 O from the Salado formation at the WIPP site. The obtained results are: ΔH° f,sul = -152.5 ± 5.3 kJ/mol, ΔH° f,ox = -1926.1 ± 10.5 kJ/mol, and ΔH° f,ele = -6301.2 ± 9.9 kJ/mol. Furthermore, based on the estimated formation entropies of polyhalite, its standard Gibbs free energy of formation has been derived to be in the range of -5715.3 ± 9.9 kJ/mol to -5739.3 ± 9.9 kJ/mol. In conclusion, these determined thermodynamic properties provide fundamental parameters for modeling the stability behavior of polyhalite in salt repositories.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2013

Silicon Solid Electrolyte Interphase (SEI) of Lithium Ion Battery Characterized by Microscopy and Spectroscopy

The surface reactions of electrolytes with a silicon anode in lithium ion cells have been investigated. The investigation utilizes two novel techniques that are enabled by the use of binder-free silicon (BF-Si) nanoparticle anodes. The first method, transmission electron microscopy with energy dispersive X-ray spectroscopy, allows straightforward analysis of the BF-Si solid electrolyte interphase (SEI). The second method utilizes multi-nuclear magnetic resonance spectroscopy of D2O extracts from the cycled anodes. The TEM and NMR data are complemented by XPS and FTIR data, which are routinely used for SEI studies. Coin cells (BF-Si/Li) were cycled in electrolytes containing LiPF6 salt and ethylene carbonate or fluoroethylene carbonate solvent. Capacity retention was significantly better for cells cycled with LiPF6/FEC electrolyte than for cells cycled with LiPF6/EC electrolyte. Our unique combination of techniques establishes that for LiPF6/EC electrolyte the BF-Si SEI continuously grows during the first 20 cycles and the SEI becomes integrated with the BF-Si nanoparticles. The SEI predominantly contains lithium ethylene dicarbonate, LiF, and LixSiOy. BF-Si electrodes cycled with LiPF6/FEC electrolyte have a different behavior; the BF-Si nanoparticles remain relatively distinct from the SEI. The SEI predominantly contains LiF, LixSiOy, and an insoluble polymeric species.

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

High-Performance, Hybrid Polymer Membrane for Carbon Dioxide Separation from Ambient Air

The Department of Energy (DOE) seeks to develop carbon capture materials specifically tailored for Direct Air Capture (DAC) processes. Related to this, they require recipients to develop novel DAC materials such as: solvents, membranes, or sorbents that demonstrate high affinities or capacities for carbon dioxide (CO2) at concentrations typically available in air and at near ambient conditions. Toward this, InnoSense LLC (ISL) is developing High-Performance, Hybrid Polymer Membranes (HypoMemTM) for Carbon Dioxide Separation from Ambient Air. HypoMem consists of two major layers. The first layer is the active layer which contains the active ingredients that help to separate CO2 from ambient air. The second is the support layer that provides good mechanical support to have a free-standing membrane without interfering with the properties of the active layer.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2024

Basic Energy Sciences Roundtable: Foundational Science to Accelerate Nuclear Energy Innovation

Energy security, availability, and reliability are among the greatest challenges facing the nation and the planet. An abundant potential source of energy resides in the fundamental atomic building blocks of the universe in the form of nuclear fission and fusion reactions. In fact, energy from nuclear fission currently provides the majority of the world’s zero-carbon electricity, and future fusion energy systems offer great promise; carbon-free nuclear energy technologies can be key to the world’s decarbonized energy future. Although contemporary fission systems use well-established technologies to supply safe and efficient baseload power, they could be more fuel efficient and less costly. Moving beyond massive light-water fission reactors to a variety of advanced nuclear systems—which will vary in size and operate in extremes of temperature, corrosivity, and other parameters—will place stringent conditions on materials and chemical systems. New demands will be placed on the coolants and solvents, the materials, and the monitoring tools used in these reactors. Fusion-based nuclear energy will require superior materials to withstand extremely high temperatures, plasma exposure, radiation damage, and implanted gases. The advantages associated with these new fission and fusion technologies will be realized only through continued advancements in the fundamental science underpinning our knowledge of the physics and chemistry of nuclear systems gained via improved experimental and computational methods. In July 2022, the U.S. Department of Energy’s Office of Basic Energy Sciences—in coordination with the Offices of Nuclear Energy, Fusion Energy Sciences, and Advanced Scientific Computing Research—held a virtual roundtable titled “Foundational Science to Accelerate Nuclear Energy Innovation” to discuss the scientific and technical barriers for advanced nuclear energy systems. Five priority research opportunities were identified to address these scientific and technical challenges and to accelerate progress toward the realization of next-generation fusion and fission energy systems. The foundational science gaps inhibiting the advancement of nuclear energy technologies are identified and tackled in five priority research opportunities. These opportunities pave the way to accelerate the development and ultimately the adoption of new nuclear energy systems. They include the fundamental aspects of ion-electron interactions; novel properties of next-generation coolants and solvents; interfacial dynamics, not only in solids, but in other aspects of nuclear reactors; novel operando and in situ monitoring and sensing; and artificial intelligence to accelerate condensed phases discovery. Building on the foundation established by previous Basic Energy Sciences workshops, these opportunities encompass recent advances in fundamental knowledge and focus on the experimental and computational methods needed to resolve major technical challenges for nuclear energy technologies. Through developing fundamental scientific insight as well as pushing the frontiers of modeling complex systems and probing the operation of materials and chemical systems in extreme environments, research motivated by the priorities identified here will further develop the promise, potential, and utilization of nuclear energy for a clean energy future.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2024

High-Performance AEM LTE with Advanced Membranes, Ionomers and PGM-Free Electrodes

Alkaline low temperature electrolysis (LTE) systems enjoy several potential advantages over acid-based LTE systems including facile oxygen evolution reaction (OER) kinetics and electrodes that can use little to no platinum group metals (PGM). The polymer membranes and membrane electrode assembly (MEA) structures going into alkaline electrochemical systems have seen significant advances in recent years. The objective of this project is to combine state-of-the-art alkaline polymer electrolyzer components into one optimized membrane electrode assembly (MEA) system to achieve DOE low temperature electrolysis (LTE) goals. The benefit of individual component advances cannot be fully appreciated until all aspects and components of the MEA are working at an equally high level of performance. New electrode fabrication methods were developed where solvent cast catalyst/ionomer solutions were used in place of insoluble ionomers to significantly improve adhesion. The membranes were improved in terms of durability and mechanical properties. The OER and HER catalysts were improved and made more durable.

08 HYDROGEN↗