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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 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
NASA NTRS2011

Metallization for Yb14MnSb11-Based Thermoelectric Materials

Thermoelectric materials provide a means for converting heat into electrical power using a fully solid-state device. Power-generating devices (which include individual couples as well as multicouple modules) require the use of ntype and p-type thermoelectric materials, typically comprising highly doped narrow band-gap semiconductors which are connected to a heat collector and electrodes. To achieve greater device efficiency and greater specific power will require using new thermoelectric materials, in more complex combinations. One such material is the p-type compound semiconductor Yb14MnSb11 (YMS), which has been demonstrated to have one of the highest ZT values at 1,000 C, the desired operational temperature of many space-based radioisotope thermoelectric generators (RTGs). Despite the favorable attributes of the bulk YMS material, it must ultimately be incorporated into a power-generating device using a suitable joining technology. Typically, processes such as diffusion bonding and/or brazing are used to join thermoelectric materials to the heat collector and electrodes, with the goal of providing a stable, ohmic contact with high thermal conductivity at the required operating temperature. Since YMS is an inorganic compound featuring chemical bonds with a mixture of covalent and ionic character, simple metallurgical diffusion bonding is difficult to implement. Furthermore, the Sb within YMS readily reacts with most metals to form antimonide compounds with a wide range of stoichiometries. Although choosing metals that react to form high-melting-point antimonides could be employed to form a stable reaction bond, it is difficult to limit the reactivity of Sb in YMS such that the electrode is not completely consumed at an operating temperature of 1,000 C. Previous attempts to form suitable metallization layers resulted in poor bonding, complete consumption of the metallization layer or fracture within the YMS thermoelement (or leg).

Firdosy, Samad↗
NASA NTRS1973

Spectroscopic and photochemical study of molecules important in chemical evolution

The primary broad goals of this research are to investigate (1) the possible reactions responsible for generation of compounds important in chemical evolution, and (2) reactions of compounds important in chemical evolution. In both cases the interest includes molecules that exist in interstellar space as well as those present on or near other planets and those which were thought to be present on or near the primitive earth.

Becker, R. S.↗
DOE OSTI2025

Probing the Sustainable Reduction of CO 2 , N 2 and NO 3 to Fuels and Chemicals using Non-Traditional Porphyrinoid Catalysts

For the last several decades, numerous strategies have been proposed to be able to interconvert electricity and commodity fuels for transportation and other applications. Even as solar and wind energy become more widely available, these renewable energy sources are not always available where the population is most dense or during peak times of energy demand. One plausible solution to the issue of electricity storage and transport is to use electricity to drive the formation of high-energy compounds and chemical fuels. As a result, the electrochemical conversion of CO 2 into chemical fuels has received major attention as a multi-pronged approach for electricity coversion, storage, and transport. Similar strategies are also attractive for conversion of N 2 and NO x into value added compounds such as ammonia. Metalloporphyrin and metallocorrole complexes are comprised of aromatic tetrapyrrole scaffolds and have been extensively studied as homogeneous catalysts for critical catalytic processes like the electrochemical CO 2 reduction reaction (eCO 2 RR) to generate CO as feedstock for the Fischer–Tropsch process to generate a variety of hydrocarbons as chemical fuels. Despite their significance and impact, efficiently driving such catalytic reduction processes is challenging for multiple reasons. Such processes require multiple-electron transfer events, as opposed to single-electron redox chemistry that forms high-energy singly-reduced intermediates. In addition, these electron transfer events must be coupled to proton-transfer steps and avoid application of high overpotentials where proton (H + ) reduction to generate H 2 (as well as other side-reactions) can lower the selectivity and energy efficiency of the eCO 2 RR process. Certain Fe(III) aromatic tetrapyrroles (e.g., porphyrins and corroles) have been reported to overcome these challenges, but are often difficult to synthesize and modify, and have a tendency to support single-electron redox chemistry at the metal as opposed to multielectron redox involving the ligand and metal in concert. Other families of tetrapyrroles in which all four meso-carbons are reduced (i.e., sp 3 -hybridized) are also known in the literature. These non-aromatic tetrapyrroles are known as porphyrinogens and support multi-electron redox chemistry which has been elaborated by several groups, prompting researchers to consider whether these scaffolds may improve the kinetics and efficiencies of multi-electron steps attendant to activation of thermodynamically stable small-molecule substrates such as CO 2 , N 2 , NO 3 − , and NO 2 − . Although porphyrinogens support multi-electron redox properties, the four sp 3 -hybridized meso-carbons inherent to the tetrapyrrole core completely disrupt π-conjugation between pyrrolic units, which compromises the photochemical properties of porphyrinogens in comparison to that of traditional porphyrinoids. Moreover, the highly reducing nature of porphyrinogens predisposes these platforms to extreme air and water sensitivity. Accordingly, such metalated porphyrinogens are often pyrophoric and/or incompatible with many common organic solvents (CH 2 Cl 2 , CHCl 3 , CH 3 CN, EtOAc, etc.). Hence, reports of efficient small-molecule activation or catalysis supported by porphyrinogens have been limited. To overcome the instability of porphyrinogens while retaining the scaffold’s attractive multi-electron redox properties, we have directed attention to establishing less-well studied groups of non-aromatic tetrapyrroles (i.e., phlorins, biladienes, and isocorroles). These non-traditional tetrapyrroles each contain just a single sp 3 -hybridized meso-carbon, which ablates the platforms aromaticity but still provides an extended π-framework. In addition to developing innovative platforms that may be used to sustainably generate value-added chemicals, fuels, and ammonia via either photo- or electrocatalytic approaches our work also has significantly broadened our understanding of how to prepare and modulate the properties of non-aromatic tetrapyrroles for other applications. Our efforts entailed a synergistic partnership and active collaborations with Drs. David C. Grills and Mehmed Z. Ertem (both of Brookhaven National Lab) to better characterize isocorroles (and related non-aromatic tetrapyrroles) using a variety of advanced spectroscopic and theoretical methods. Our combined efforts have shown that the combination of properties that isocorroles (and related tetrapyrroles) provide results in good chemical stability paired with unique redox and photochemical characteristics that are not typically supported by simple and/or unadorned aromatic tetrapyrroles. Beside redox chemistry, the photochemistry of isocorroles and other non-aromatic tetrapyrroles containing one sp 3 -hybridized meso-carbon is also appealing due to their absorption in the long-visible to near-IR regions, which are essential for photocatalysis and related applications that benefit from direct excitation at these wavelengths. The results reported vastly improve our understanding of non-aromatic tetrapyrrole synthesis, properties and utility for activation of small molecule substrates such as O 2 and CO 2 in the presence of weak cationic organic acids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1999

Seal Materials Compatible with the Electroplating Solvent Used in Constellation-X Mirrors

The existing gasket seals used in electroplating of the Constellation-X mirrors are difficult to assemble, and the current seal material is hydrophobic and too thick. The combination of the above problems result in: 1) non-uniform plating; 2) defect sites such as pits on the mirror edges; 3) "bear claws" on the edges of the mandrels and mirrors causing difficulties in shell-mirror separations; and 4) leakage of the plating solution past the seals into the mandrel causing chemical etching of the mandrel interior. This paper reports the results of this summer study in searching for alternate seal materials chemically compatible with the electroplating solvent. Fifteen common elastomeric rubber seal materials made-by Parker Seals were investigated including butyl, ethylene propylene, fluorosilicone, nitrile, Viton fluorocarbon, and silicone. Test results showed that Viton fluorocarbon compounds as a group were superior to the other tested compounds for chemical compatibility with the plating bath.

Pei, Xiong-Skiba↗
DOE OSTI2021

Nonadiabatic couplings from a variational excited state method based on constrained DFT

Excited Costrained Density Functional Theory (XCDFT) is a variational excited state method that extends ground state DFT to the computation of low-lying excited states. It borrows much of the machinery of Constrained DFT (CDFT) with a crucial difference: the constraint imposes a population of one electron in the Hilbert space spanned by the virtuals of a reference ground state. Here, we present theory and implementation for evaluating nonadiabatic coupling vectors (NACVs) between the first excited state computed with XCDFT and the ground state. Our NACVs are computed analytically using density functional perturbation theory with a formalism that is general enough that could be applied to CDFT diabatic states. We showcase the new method with pilot NACV calculations for the conical intersection in H 3 , the avoided crossing in selenoacrolein, and the NACV magnitudes in azobenzene. Despite complications from the nonorthogonality of the wavefunctions, XCDFT’s energy surfaces and NACVs reproduce benchmark values and respect known sum rules within a reasonable degree. This shows that XCDFT is a viable method for nonadiabatic dynamics simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1992

Experiments with the low melting indium-bismuth alloy system

The following is a laboratory experiment designed to create an interest in and to further understanding of materials science. The primary audience for this material is the junior high school or middle school science student having no previous familiarity with the material, other than some knowledge of temperature and the concepts of atoms, elements, compounds, and chemical reactions. The objective of the experiment is to investigate the indium-bismuth alloy system. Near the eutectic composition, the liquidus is well below the boiling point of water, allowing simple, minimal hazard casting experiments. Such phenomena as metal oxidation, formation of intermetallic compound crystals, and an unusual volume increase during solidification could all be directly observed. A key concept for students to absorb is that properties of an alloy (melting point, mechanical behavior) may not correlate with simple interpolation of properties of the pure components. Discussion of other low melting metals and alloys leads to consideration of environmental and toxicity issues, as well as providing some historical context. Wetting behavior can also be explored.

Krepski, Richard P.↗
DOE OSTI2026

Position-Specific Carbon Isotope Fingerprinting of Fluorinated Organics and Degradation Products

Fluorinated organic compounds are of growing environmental and forensic relevance due to their widespread use in pharmaceuticals, agrochemicals, and consumer products, their environmental persistence, and potential ecological and human health impacts. Elucidating their sources and transformation pathways is therefore a major focus of current research. Stable carbon isotope analysis provides a powerful approach for tracing molecular origins and linking parent compounds to degradation products. Recent isotope measurements have largely relied on mass-spectrometry techniques, which provide only an average isotope ratio across a compound. In this work, we employ a novel nuclear magnetic resonance (NMR) spectroscopy tool to determine position-specific carbon isotope ratios ( 13 C/ 12 C) in organofluorine compounds and their degradation products. This approach enables isotope measurements without combustion or extensive purification and, crucially, resolves ratios at individual carbon positions rather than bulk averages. The resulting intramolecular isotope fingerprints are unique to a molecule’s source. Applied to selected pharmaceuticals and pesticides, these fingerprints allow discrimination of chemically identical compounds. Moreover, we show that the 13 C/ 12 C signature at the fluorinated carbon persists through degradation, demonstrated for lansoprazole and fipronil. The 19 F NMR data produced for the 13 C/ 12 C analyses are also well suited for impurity profiling, providing an additional dimension for fingerprinting fluorinated organics. These findings suggest that position-specific isotope analysis can serve as part of a broader suite of tools for source characterization of organofluorine compounds and their breakdown derivatives, with potential applications in product validation, forensics, and linking these compounds to their breakdown products.

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

Oxygenated Molecules measured with a Nitrate Chemical Ionization Mass Spectrometer

These files contain selected oxygenated compounds detected by chemical ionization mass spectrometry with nitrate reagent ion. Detected compounds were grouped by volatility and the time series of the most intense ions in each volatility class are provided here. Volatility (C*) in units of μg m^-3 was calculated using log_10(C*)=(n_ref -n_C)*b_C - (n_O - 3*n_N)*b_O - 2*(((n_O - 3n_N)*n_C) / (n_C + n_O - 3*n_N))*b_CO - n_N* b_N where n_ref = 25, b_c = 0.475m b_O = 0.2, b_N = -0.5, b_CO = 0.9, n_C is the number of carbon atoms in the ion formula, n_O is the number of oxygen atoms in the ion formula, and n_N is the number of nitrogen atoms in the ion formula. Volatility was calculated for each formula (with the nitrate anion excluded) and compounds were assigned into extremely low volatility (ELVOCs, C* < 10^−4.5 μg m^-3), low volatility (LVOCs, 10^−4.5 μg m^-3 ≤ C* < 10^−0.5 μg m^-3), or semi-volatile (SVOCs, 10^−0.5 μg m^-3 ≤ C* < 10^2.5 μg m^-3) bins. All ions were assumed to be detected with a collision-limited sensitivity and thus represent lower bound values. Values are reported as parts per trillion by volume mixing ratio.

Extremely low-volatility organic compounds↗
NASA NTRS1990

Synthesis of Y1Ba2Cu3O(sub x) superconducting powders by intermediate phase reaction

One of the more striking problems for the synthesis of the Y1Ba2Cu3Ox compound is the high-temperature decomposition of the BaCO3. This compound is present as raw material or as an intermediate compound in chemical processes such as amorphous citrate, coprecipitation oxalate, sol-gel process, acetate pyrolisis, etc. This fact makes difficult the total formation reaction of the Y1Ba2Cu3Ox phase and leads to the presence of undesirable phases such as the BaCuO2 phase, the 'green phase', Y2BaCuO5 and others. Here, a new procedure to overcome this difficulty is studied. The barium cation is previously combined with yttrium and/or copper to form intermediate compounds which can react between them to give Y1Ba2Cu3Ox. BaY2O4 and BaCu2O3 react according to the equation BaY2O4+3BaCu2O3 yields 2Y1Ba2Cu3Ox. BaY2O4 is a stable compound of the Y2O3-BaO system; BaCu2O3 is an intimate mixture of BaCuO2 and uncombined CuO. The reaction kinetics of these phases have been established between 860 and 920 C. The phase evolution has been determined. The crystal structure of the Y1Ba2Cu3Ox obtained powder was studied. According to the results obtained from the kinetics study the Y1Ba2Cu3Ox the synthesis was performed at temperatures of 910 to 920 C for short treatment times (1 to 2 hours). Pure Y1Ba2Cu3Ox was prepared, which develops orthorombic type I structure despite of the cooling cycle. Superconducting transition took place at 91 K. The sintering behavior and the superconducting properties of sintered samples were studied. Density, microstructure and electrical conductivity were measured. Sintering densities higher than 95 percent D(sub th) were attained at temperatures below 940 C. Relatively fine grained microstructure was observed, and little or no-liquid phase was detected.

Moore, C.↗
DOE OSTI2020

Critical Design Elements for an On-Site Mercury Concentration and Holding Facility - 20175

Administrative changes and funding issues have delayed the Department of Energy (DOE) from establishing and commissioning a National Repository for mercury as required under the Mercury Export Ban Act (MEBA) of 2008. In the interim, a few hazardous waste Treatment, Storage, and Disposal Facilities (TSDFs) have been authorized to accept mercury classified as a hazardous waste as under Subtitle C of the Resource Conservation and Recovery Act (RCRA). Waste generators are charged (either by weight or by volume) for the waste they manifest to these TSDFs. In many cases, mercury and mercury compounds have chemically sorbed to (or physically lodged into) the interstitial spaces of a substrate material. This almost always causes the amount of waste generated to be unnecessarily large, due to the extra volume (or weight) of the accompanying, non-mercury materials. Depending on a multitude of factors, it could be financially beneficial for waste generators to take greater control of their mercury affairs by separating these substrate materials from the mercury and mercury compounds that have become associated with them. Building and operating an on-site mercury Concentration and Holding Facility (CHF) could help relieve a waste generator's overall cost burden. The purpose of such CHFs is not to treat or dispose of mercury, but to recover and concentrate mercury from bulky mercury-laden materials to the extent that the host substrate to which the mercury may have previously been sorbed could pass a Toxicity Characteristic Leaching Procedure (TCLP) test and either be disposed of at a conventional landfill, or be disposed of at a hazardous waste landfill, but absent additional restrictions specifically for mercury. A CHF represents a way for waste generators to save money by separating mercury from common host materials, concentrating it, and then safely storing it until transportation to an authorized TSDF takes place This paper focuses on the critical design elements waste generators should consider when designing and operating a mercury CHF. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Chemical Vapor Deposition of Zirconium Compounds: A Review

Coatings of zirconium compounds are used in a wide variety of fields, yet an understanding and descriptions of deposition mechanisms are scant in the public literature. The mechanisms of deposition for metallic zirconium, ZrC, ZrN, ZrO 2 , ZrB 2 , and zirconium silicides are discussed based on the direct vapor deposition research of those compounds where possible or compared to complementary titanium systems when direct research is lacking. Both inorganic and organometallic deposition systems are discussed. As a class of compounds, an understanding of the vapor deposition mechanisms can be significantly improved by investigations on metallic zirconium deposition by zirconium halides and hydrogen and by in situ analysis techniques such as Fourier-transform infrared (FTIR) spectroscopy or x-ray photoelectron spectroscopy (XPS).

organometallic↗
DOE OSTI2023

Vapor-phase grafting of functional silanes on atomic layer deposited Al 2 O 3

Fundamental studies are needed to advance our understanding of selective adsorption in aqueous environments and develop more effective sorbents and filters for water treatment. Vapor-phase grafting of functional silanes is an effective method to prepare well-defined surfaces to study selective adsorption. In this investigation, we perform vapor phase grafting of five different silane compounds on aluminum oxide (Al2O3) surfaces prepared by atomic layer deposition. These silane compounds have the general formula L3Si–C3H6–X where the ligand, L, controls the reactivity with the hydroxylated Al2O3 surface and the functional moiety, X, dictates the surface properties of the grafted layer. We study the grafting process using in situ Fourier transform infrared spectroscopy and ex situ x-ray photoelectron spectroscopy measurements, and we characterize the surfaces using scanning electron microscopy, atomic force microscopy, and water contact angle measurements. Here, we found that the structure and density of grafted aminosilanes are influenced by their chemical reactivity and steric constraints around the silicon atom as well as by the nature of the anchoring functional groups. Methyl substituted aminosilanes yielded more hydrophobic surfaces with a higher surface density at higher grafting temperatures. Thiol and nitrile terminated silanes were also studied and compared to the aminosilane terminated surfaces. Uniform monolayer coatings were observed for ethoxy-based silanes, but chlorosilanes exhibited nonuniform coatings as verified by atomic force microscopy measurements.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Quantum Chemical Density Matrix Renormalization Group Method Boosted by Machine Learning

The use of machine learning (ML) to refine low-level theoretical calculations to achieve higher accuracy is a promising and actively evolving approach known as Δ-ML. The density matrix renormalization group (DMRG) is a powerful variational approach widely used for studying strongly correlated quantum systems. High computational efficiency can be achieved without compromising accuracy. Here, we demonstrate the potential of a simple ML model to significantly enhance the performance of the quantum chemical DMRG method.

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

Collective states and charge density waves in the group IV transition metal trichalcogenides

It has been nearly a century since the original mechanism for charge density wave (CDW) formation was suggested by Peierls. Since then, the term has come to describe several related concepts in condensed matter physics, having their origin in either the electron–phonon or electron–electron interaction. The vast majority of CDW literature deals with systems that are metallic, where discussions of mechanisms related to the Fermi surface are valid. Recently, it has been suggested that semiconducting systems such as TiS 3 and TiSe 2 exhibit behavior related to CDWs. In such cases, the origin of the behavior is more subtle and intimately tied to electron–electron interactions. We introduce the different classifications of CDW systems that have been proposed and discuss work on the group IV transition metal trichalcogenides (TMTs) (ZrTe 3 , HfTe 3 , TiTe 3 , and TiS 3 ), which are an exciting and emergent material system whose members exhibit quasi-one-dimensional properties. TMTs are van der Waals materials and can be readily studied in the few-layer limit, opening new avenues to manipulating collective states. We emphasize the semiconducting compound TiS 3 and suggest how it can be classified based on available data. Although we can conjecture on the origin of the CDW in TiS 3 , further measurements are required to properly characterize it.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Competing Magnetic Interactions in the Antiferromagnetic Topological Insulator MnBi 2 Te 4

The antiferromagnetic (AFM) compound MnBi 2 Te 4 is suggested to be the first realization of an AFM topological insulator. Here, we report on inelastic neutron scattering studies of the magnetic interactions in MnBi 2 Te 4 that possess ferromagnetic triangular layers with AFM interlayer coupling. The spin waves display a large spin gap and pairwise exchange interactions within the triangular layer are long ranged and frustrated by large next-nearest neighbor AFM exchange. The degree of frustration suggests proximity to a variety of magnetic phases, potentially including skyrmion phases, which could be accessed in chemically tuned compounds or upon the application of symmetry-breaking fields.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Applying the core-satellite species concept: Characteristics of rare and common riverine dissolved organic matter

Introduction: Dissolved organic matter (DOM) composition varies over space and time, with a multitude of factors driving the presence or absence of each compound found in the complex DOM mixture. Compounds ubiquitously present across a wide range of river systems (hereafter termed core compounds) may differ in chemical composition and reactivity from compounds present in only a few settings (hereafter termed satellite compounds). Here, we investigated the spatial patterns in DOM molecular formulae presence (occupancy) in surface water and sediments across 97 river corridors at a continental scale using the “Worldwide Hydrobiogeochemical Observation Network for Dynamic River Systems—WHONDRS” research consortium. Methods: We used a novel data-driven approach to identify core and satellite compounds and compared their molecular properties identified with Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Results: In this work, we found that core compounds clustered around intermediate hydrogen/carbon and oxygen/carbon ratios across both sediment and surface water samples, whereas the satellite compounds varied widely in their elemental composition. Within surface water samples, core compounds were dominated by lignin-like formulae, whereas protein-like formulae dominated the core pool in sediment samples. In contrast, satellite molecular formulae were more evenly distributed between compound classes in both sediment and water molecules. Core compounds found in both sediment and water exhibited lower molecular mass, lower oxidation state, and a higher degree of aromaticity, and were inferred to be more persistent than global satellite compounds. Higher putative biochemical transformations were found in core than satellite compounds, suggesting that the core pool was more processed. Discussion: The observed differences in chemical properties of core and satellite compounds point to potential differences in their sources and contribution to DOM processing in river corridors. Overall, our work points to the potential of data-driven approaches separating rare and common compounds to reduce some of the complexity inherent in studying riverine DOM.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1996

Spacecraft Maximum Allowable Concentrations for Selected Airborne Contaminants

The National Aeronautics and Space Administration (NASA) has developed spacecraft maximum allowable concentrations (SMACs) for contaminants that might be found in the atmosphere within spacecraft during space missions to ensure the health and well-being of astronauts traveling and working in this unique environment. In volume 1 of this series, NASA developed SMACs for 11 compounds: acetaldehyde, ammonia, carbon monoxide, formaldehyde, Freon 113, hydrogen, methane, methanol, octamethyltrisiloxane, trimethylsilanol, and vinyl chloride. Volume 2 includes SMACs for 12 more airborne contaminants: acrolein, benzene, carbon dioxide, 2-ethoxyethanol, hydrazine, indole, mercury, methylene chloride, methyl ethyl ketone, nitromethane, 2-propoanol, and toluene. In developing SMACs from the toxicological literature, NASA followed the Guidelines for Developing Spacecraft Maximum Allowable Concentrations for Space Station Contaminants published in 1992 by the National Research Council.

Spacecraft contamination↗