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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 541 records · Page 30
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Biophysical analysis of the plant-specific GIPC sphingolipids reveals multiple modes of membrane regulation

The plant plasma membrane (PM) is an essential barrier between the cell and the external environment, controlling signal perception and transmission. It consists of an asymmetrical lipid bilayer made up of three different lipid classes: sphingolipids, sterols, and phospholipids. The glycosyl inositol phosphoryl ceramides (GIPCs), representing up to 40% of total sphingolipids, are assumed to be almost exclusively in the outer leaflet of the PM. However, their biological role and properties are poorly defined. In this study, we investigated the role of GIPCs in membrane organization. Because GIPCs are not commercially available, we developed a protocol to extract and isolate GIPC-enriched fractions from eudicots (cauliflower and tobacco) and monocots (leek and rice). Lipidomic analysis confirmed the presence of trihydroxylated long chain bases and 2-hydroxylated very long-chain fatty acids up to 26 carbon atoms. The glycan head groups of the GIPCs from monocots and dicots were analyzed by gas chromatograph-mass spectrometry, revealing different sugar moieties. Multiple biophysics tools, namely Langmuir monolayer, ζ-Potential, light scattering, neutron reflectivity, solid state 2H-NMR, and molecular modeling, were used to investigate the physical properties of the GIPCs, as well as their interaction with free and conjugated phytosterols. We showed that GIPCs increase the thickness and electronegativity of model membranes, interact differentially with the different phytosterols species, and regulate the gel-to-fluid phase transition during temperature variations. These results unveil the multiple roles played by GIPCs in the plant PM.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Influence of support on Rh-Co bimetallic catalysts for ethylene hydroformylation

Bimetallic Rh- and Co-based catalysts are promising materials for the heterogenous ethylene hydroformylation reaction. Here, in this study, the influence of a mesoporous silica (SBA-15) support on Rh and Co bimetallic interactions was investigated through a comparison with silica gel and alumina supports. The bimetallic catalyst supported on mesoporous silica (RhCo 3 /SBA-15) showed the best C 3 oxygenate yield among the three bimetallic catalysts. In-situ vibrational studies suggested moderate binding of the gem-dicarbonyl and Rh(CO)(C 2 H 4 ) intermediates due to this bimetallic interaction that led to improved hydroformylation performance. Kinetic studies revealed a lower hydroformylation barrier for the bimetallic compared to a Rh monometallic catalyst, and in-situ X-ray absorption spectroscopy investigations showed clear Rh-Co alloy formation on RhCo 3 /SBA-15. The bimetallic enhancement effect from the interaction with the mesoporous silica support shown here can be further optimized to design olefin hydroformylation catalysts.

58 GEOSCIENCES↗
DOE OSTI2025

Identification and evolution of active sites in isomorphously substituted Fe-ZSM-5 catalysts for methane dehydroaromatization (MDA)

Methane dehydroaromatization (MDA) enables the catalytic conversion of methane into aromatics, mainly benzene, along with hydrogen, in a single-step process under non-oxidative conditions. In this study, we prepared a series of isomorphously substituted Fe-ZSM-5 catalysts with exclusively isolated or low-oligomerized sites up to 3.2% Fe weight loading by adding ethylenediaminetetraacetic acid (EDTA) to the crystallization gel. These catalysts exhibit no induction/activation period and a significantly higher maximum product yield compared to Fe/ZSM-5 catalysts prepared by the incipient wetness impregnation method and containing extensively aggregated FeOx. This investigation focuses on the evolution of Fe sites during the post-synthetic treatments. Most importantly, we demonstrate the quantitative relation between Fe site isolation and catalytic activity, proving that isolated or low-oligomerized Fe species at the exchange sites formed during post-synthetic retreatment are the active sites for methane activation.

02 PETROLEUM↗
DOE OSTI2021

Mesoporous Fe-doped MgO nanoparticles as a heterogeneous photo-Fenton-like catalyst for degradation of salicylic acid in wastewater

Mesoporous Fe-doped MgO nanoparticles were synthesized using a facile sol-gel method and utilized for photo-Fenton-like degradation of salicylic acid (SA). The MgO surface dissolution facilitated an increase in the pH under the reaction conditions that allowed the Fe-MgO catalyst to be active without detectable iron leaching. Under simulated solar radiation, SA was completely degraded with an initial rate constant of 0.048 min -1 at the optimal reaction conditions of 500 ppm loading of 5% Fe-MgO, 20 mM H 2 O 2 concentration, and 50 ppm SA concentration. The catalyst was stable over 5 reaction cycles. The Fe-MgO catalyst was shown to have a surface area up to 171 m 2 /g and contain hematite (Fe 2 O 3 ) nanoparticles with octahedrally coordinated iron catalytic centers, as inferred from diffuse reflectance UV–vis measurements. Post-reaction catalyst characterization showed that some Fe 2+ was present in the catalyst due to the redox cycle during the chain initiation and propagation steps of the reaction.

36 MATERIALS SCIENCE↗
DOE OSTI2023

$In-situ$ synchrotron x-ray diffraction and thermal expansion of TiB2 up to ~3050 °C

There is an increasing interest in understanding the performance and properties of ultra-high temperature ceramics due to their high melting points (<3000 °C) that make them promising for extreme environment applications. In-situ high temperature X-ray diffraction experiments were performed on TiB 2 beads up to ~3050 °C. For these experiments, TiB 2 powders were fabricated into spherical beads via gel casting methods and densified in a high temperature graphite furnace. These sample beads were then levitated in a conical nozzle levitator with reducing atmosphere (3% H 2 -Ar) while being heated using a 400 W CO 2 laser. During levitation a collimated synchrotron X-ray source was used to perform in-situ, temperature-dependent structural characterizations. The anisotropic coefficients of thermal expansion of TiB 2 were characterized as a function of temperature up to ~3050 °C. Elucidation of these properties are critical for the advancement of TiB 2 ceramics and other transition metal di-borides for use in high temperature applications such as hypersonic platforms, nuclear reactors, and atmospheric re-entry.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Rheology characterization of ionic liquids under high pressure and high temperature

Ionic liquids (ILs) are liquid salts that exist at or below ambient temperatures and are composed of ion pairs. They offer promising alternatives to toxic, hazardous, highly flammable, and volatile solvents in various applications such as solution preparation, dispersion, gel formation, composites, and polymer melts. ILs possess unique and interesting characteristics, including excellent chemical and thermal stability and low vapor pressures. Understanding the rheological properties of ILs is essential to optimizing IL performance. This paper presents a comparative analysis of the rheological properties of two ionic liquids, Nsingle bondHexylpyridinium tetrafluoroborate (HPyBF4) and Nsingle bondHexylpyridinium bromide (HPyBr), under different shear rates, temperatures, and pressures. Rheological measurements were performed under varying controlled pressure and temperature conditions. The experimental investigation covered a pressure range of 689–12,411 kPa [100–1800 psi] and a temperature range from room temperature up to 522 kelvin (K) [480°F]. The primary objective is to explore and compare the flow behavior and viscoelastic characteristics of HPyBF4 and HPyBr under high-pressure and high-temperature conditions. The experimental data showed that HPyBF4 and HPyBr exhibited shear-thinning behavior, and pressure had an insignificant effect on rheology compared to the temperature effect. Under the same testing conditions, HPyBr showed higher shear stress and viscosity than HPyBF4. This research significantly contributes to the improved understanding of the rheological behavior of these specific ionic liquids and their suitability for diverse industrial and scientific applications, particularly in high-pressure and high-temperature environments.

15 GEOTHERMAL ENERGY↗
DOE OSTI2021

Pregnancy is accompanied by larger high density lipoprotein particles and compositionally distinct subspecies

Pregnancy is accompanied by significant physiological changes, which can impact the health and development of the fetus and mother. Pregnancy-induced changes in plasma lipoproteins are well documented, with modest to no impact observed on the generic measure of high density lipoprotein (HDL) cholesterol. However, the impact of pregnancy on the concentration and composition of HDL subspecies has not been examined in depth. In this prospective study, we collected plasma from 24 nonpregnant and 19 pregnant women in their second trimester. Using nuclear magnetic resonance (NMR), we quantified 11 different lipoprotein subspecies from plasma by size, including three in the HDL class. We observed an increase in the number of larger HDL particles in pregnant women, which were confirmed by tracking phospholipids across lipoproteins using high-resolution gel-filtration chromatography. Using liquid chromatography-mass spectrometry (LC-MS), we identified 87 lipid-associated proteins across size-speciated fractions. We report drastic shifts in multiple protein clusters across different HDL size fractions in pregnant females compared with nonpregnant controls that have major implications on HDL function. These findings significantly elevate our understanding of how changes in lipoprotein metabolism during pregnancy could impact the health of both the fetus and the mother.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Highly tail-asymmetric lipids interdigitate and cause bidirectional ordering

Phospholipids form structurally and compositionally diverse membranes. A less studied type of compositional diversity involves phospholipid tail variety. Some phospholipids contain two acyl tails which differ in length. These tail-asymmetric lipids are shown to contribute to temperature sensitivity, oxygen adaptability, and membrane fluidity. Membranes of a highly virulent intracellular bacterium, Francisella tularensis, contain highly tail-asymmetric 1-lignoceroyl-2-decanoyl-sn-glycero-3-phosphatidylethanolamine (XJPE) lipids which were previously shown to inhibit inflammatory responses in host cells. XJPE tails have unusually high asymmetry, and how they contribute to membrane properties on a molecular level is unknown. Here, we use small angle X-ray scattering and molecular dynamics simulations to investigate how varying XJPE ratios alters properties of simple membranes. Our results demonstrate that at high concentration they promote liquid-to-gel transition in otherwise liquid membranes, while at low concentration they are tolerated well, minimally altering membrane properties. In liquid membranes, XJPE lipids dynamically adopt two main conformations; with the long tail extended into the opposing leaflet or bent-back residing in its own leaflet. When added to both leaflets XJPE primarily adopts an extended confirmation, while asymmetric addition results in more bent-back orientations. The former increases tail ordering and the latter decreases it. XJPE tails adopt different conformations that induce composition- and leaflet-dependent bidirectional effect on membrane fluidity and this suggests that Francisella tularensis could use tail asymmetry to facilitate vesicle fusion and destabilize host cells. The effect of tail-asymmetric lipids on complex membranes should be further investigated to reveal the regulatory roles of high tail asymmetry.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

The congenital APOA1 K107del mutation disrupts the lipid-free conformation of monomeric APOA1 and impairs oligomerization

Apolipoprotein A-I (APOA1) oligomerization is thought to be essential for high-density lipoprotein (HDL) formation and metabolism. Naturally occurring mutations can disrupt normal APOA1 folding and self-association, leading to dysfunctional HDL formation and cardiovascular disease. The congenital APOA1 variant p.K131del (APOA1 K107del ) has been associated with cardiovascular pathologies such as low HDL-cholesterol levels and aortic amyloidosis, and multiple studies indicate structural changes in APOA1 conformation underlie associated dysfunction. In the current study, we confirmed that APOA1 K107del exhibits no notable defect in lipid-binding. However, using polyacrylamide gel electrophoresis (PAGE) and size-exclusion chromatography (SEC), we found that loss of lysine 107 resulted in a remarkable shift in the distribution of APOA1 oligomers with a much higher proportion of monomers present in APOA1 K107del compared to wild-type APOA1. Further investigation using quantitative cross-linking revealed a major disruption of interactions in helical regions reported to participate in domain swaps necessary for proper self-association. This structural disruption appears to impair N- and C-termini interactions and dynamics that lead to non-specific aggregation. In conclusion, these findings support the hypothesis that lysine 107 is critical for proper folding and self-association of lipid-free APOA1 which could impact HDL biogenesis.

APOA1 (p.K131del)↗
DOE OSTI2020

Metamagnetism and kinetic arrest in a long-range ferromagnetically ordered multicaloric double perovskite Y 2 CoMnO 6

A systematic magnetic study of the double perovskite oxide Y 2 CoMnO 6 (YCMO) has been performed. A monoclinic P21/n phase of YCMO was synthesized using a sol-gel method. Neutron diffraction (ND) measurements evidence the onset of long-range ferromagnetic (FM) ordering at TC ~ 76 K, which persists down to 5 K. The presence of 25% antisite disorder, estimated from the ND data, leads to the appearance of short-range antiferromagnetic (AFM) interactions. The existence of thermal hysteresis due to competing interactions between FM and AFM phases is observed in the M vs. T measurements. The pinning of magnetic domain walls at the Co/Mn antiphase boundaries results in a metamagnetic-like behavior. The field dependence of thermomagnetic irreversibility and the nature of virgin curves indicate the occurrence of a kinetic arrest phenomenon, which is further verified via cooling and heating of the system in an unequal fields (CHUF) protocol. In full agreement with the ND data, a detailed analysis of critical exponents near the paramagnetic (PM)-FM phase transition also establishes YCMO as a long-range interacting mean-field system. A close examination of the temperature- and field-dependent magnetic entropy change yields an in-depth understanding of coexisting magnetically ordered and disordered phases in YCMO, leading to a comprehensive magnetic phase diagram of this multifunctional double perovskite system.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Patchy particle model of hydrated amorphous silica

Glasses corroded in static aqueous conditions typically reach a slow, residual rate of dissolution as a result of the complex interplay between multiple processes. While intrinsically suited to address this problem, Monte Carlo (MC) models developed to date have relied on lattices to describe the amorphous structure of glass and are thus unable to reproduce the residual rate of glass corrosion. A recently developed MC approach based on amorphous structures derived from molecular dynamics simulations offers a solution [Kerisit and Du J. Non-Cryst. Solids 522 (2019) 119601], but it requires a simple model that can rapidly relax the glass-water interface upon each dissolution/condensation event to retain the ability of MC simulations to reach large spatial and temporal scales. To this end, a patchy particle model of hydrated amorphous silica was developed and evaluated against atomistic simulations in this work. Models of water and amorphous silica were first developed separately, and cross terms were then defined to enable simulations of hydrated amorphous silica structures with varying water content. While the nature of its interaction potential prevents the patchy particle model from reproducing simultaneously the structure and dynamics of the systems of interest with a single set of parameters, it described well the connectivity of hydrated amorphous silica structures and the local coordination geometry of individual species. Therefore, this model opens the door to MC simulations of the residual rate of glass corrosion and offers an alternative to atomistic models to investigate the evolution of silica gels over large spatial and temporal scales.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Predicting zeolites’ stability during the corrosion of nuclear waste immobilization glasses: Comparison with glass corrosion experiments

During the long-term corrosion of nuclear waste glasses under nuclear waste disposal conditions, the precipitation of zeolitic phases has been linked to a delayed acceleration in glass corrosion (known as “Stage III”). Hence, predicting the thermodynamic propensity for zeolites to form upon the dissolution of nuclear waste glasses is key to ensure their long-term performance. Here, we compile a unified, internally-consistent thermodynamic database “clay20” to estimate the stability of clay and feldspar phases relevant to nuclear waste immobilization glasses, including beidellite(Mg, Ca, Na, K), kaolinite, montmorillonite(Mg, Ca, Na, K), nontronite(Mg, Ca, Na, K), saponite(Ca, Na, K), and albite. Based on this, we report a geochemical modeling method allowing us to predict the stability of secondary phases (including zeolites, calcium–silicate–hydrate gels, and clays) upon the dissolution of nuclear waste immobilization glasses. We show that this approach offers a realistic description of the stability of the secondary phases forming during the dissolution of two archetypical model nuclear glasses (namely, the International Simple Glass, ISG, and WVUTh-203) under conditions relevant to nuclear waste disposal (T = 90°C, p = 1 bar) as a function of pH. We find that the formation of silica and clay secondary phases is thermodynamically favored at low pH (pH < 10), whereas, in contrast, zeolite (analcime) and calcium–silicate–hydrate phases are favored at high pH (pH > 10.5). This suggests that thermodynamics (i.e., not solely kinetics) plays a key role in determining the range of solution pH wherein stage III corrosion may occur, i.e., when zeolite formation is favored.

Zhen-Wu, Bi Yun↗
DOE OSTI2021

Trichloroethylene replacements for the cleaning of silicone oil used in the internal gelation process

Silicone oil continues to be used as a gelation medium for internal gelation process. Typically, the silicone oil has been removed from the gel spheres using trichloroethylene (TCE) washes. However, TCE is no longer a viable option for large-scale operations because of environmental issues, health concerns, and disposal costs. Furthermore, during the development of a large gelation system at the Y-12 National Security Complex, two new TCE wash replacements were identified. NuSolv SOR-C and FluoSolv WS were used in a number of uranium runs and found to effectively remove silicone oil. NuSolv SOR-C was determined to be the best option.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Composite biopolymer electrolytes for high-performance reversible zinc-air batteries

Zinc-air batteries (ZABs) are regarded as one of the most promising candidates for next-generation energy storage systems due to their inherent safety, high energy density, and low cost. In this study, we optimized the composition of gel polymer electrolytes (GPEs), which play a crucial role in enhancing ZAB reversibility due to their water retention capabilities. The GPEs are synthesized using a combination of polyacrylic acid (PAA), polyacrylamide (PAM), and biopolymer kappa-carrageenan (KC), with and without additional additives. Among these, the composite GPE containing KC, PAA, and PAM demonstrated superior ionic conductivity (6.68 mS/cm at 30 °C) and enhanced water retention compared to the PAA–PAM-based GPE. Furthermore, this composite electrolyte operates within a wider electrochemical window of −1.0 V–2.2 V. A bifunctional catalyst, nickel–iron layered double hydroxide (NiFe-LDH), is electrochemically synthesized on a modified activated carbon cloth (CC). The catalyst loading is optimized based on oxygen evolution reaction (OER) performance, showing an overpotential of 555 mV. The oxygen reduction reaction (ORR) occurred at a half-wave potential of 0.620 V, which is lower than that of Pt/C (0.852 V), indicating better catalytic activity. The KC based cell exhibit better cycling stability than PAA–PAM-based GPE. The electrochemical performance of ZAB cells is evaluated under various atmospheres: ambient air and humid conditions and temperatures. Notably, in a humid environment, the cells achieved extended cycling stability, operating for over 500 h—significantly longer than under open-air conditions. Overall, this study highlights the importance of tailored GPE design and efficient bifunctional catalysts to enhance the performance and longevity of zinc-air batteries for long-duration energy storage applications.

Catalyst↗
DOE OSTI2026

Enhanced electrochemical performance and extended cycling of resorcinol-formaldehyde derived N-doped carbon xerogel for alkali metal-ion (Li/Na/K) batteries

Resorcinol formaldehyde-derived carbon xerogel (RFC) is a versatile material with tuneable properties, synthesized through a simple sol-gel method. This study presents nitrogen-doped RF carbon xerogel (N-RFC) with 11.8 at% nitrogen doping, offering a microporous architecture ideal for alkali metal-ion (Li, Na, K) batteries. The porous N-doped framework enhances electrochemical performance by improving ion transport, increasing active storage sites, and significantly boosting metal-ion adsorption, particularly through pyrrolic nitrogen, as revealed by first-principles calculations supported by XPS analysis. N-RFC anodes showed excellent cycling stability, high-capacity retention, and fast charge/discharge capabilities, rendering them suitable for commercial applications. Notably, the N-RFC anode demonstrates high-rate long-term cycling stability, retaining its capacity of 83.5 % (188 mAh/g at 2 C-rate) and 50 % (133 mAh/g at 1250 mA/g) over 1000 cycles for Li and Na-ion batteries, respectively, favorable for commercial battery applications. Additionally, N-RFC demonstrates a reversible capacity of 120 mAh/g after 394 cycles with a retention of 82 % for K-ion batteries. The ability of the material to accommodate larger ions like Na + and K + further emphasizes its versatility and potential application in diverse alkali metal-ion battery systems.

25 ENERGY STORAGE↗
DOE OSTI2023

Combustion synthesis of Eu 2 O 3 nanomaterials with tunable phase composition and morphology

Combustion reactions in europium nitrate – acetylacetone – 2-methoxyethanol solutions and gels were investigated to produce europium (III) oxide (Eu 2 O 3 ) nanocrystalline materials and thin films. Thermal analyses of solutions indicated that the 2-methoxyethanol solvent also acts as a fuel in the absence of acetylacetone. Adding acetylacetone increases the overall heat of the reaction. Thermal analysis results revealed that the slow oxidation of unburned hydrocarbon residues follows the primary combustion reaction. Time-temperature profile measurements of the bulk combustion synthesis process in air and nitrogen atmospheres enabled the extraction of the maximum reaction temperature and the heating and cooling rates in the combustion zone. Several direct correlations exist between measured combustion parameters and the phase composition of the products. Combustion in air results in mixed-phase cubic and monoclinic nanocrystalline Eu 2 O 3 . Increasing the acetylacetone concentration in solutions increases the synthesis temperature and decreases the quantity of cubic Eu 2 O 3 . Here, the reaction of solutions in a nitrogen atmosphere or diluted with Eu 2 O 3 provides control of the product phase composition and reduces the quantity of the monoclinic phase. Transmission electron microscopy imaging shows that the Eu 2 O 3 end products are highly porous aggregates of nanocrystalline particles. Electrospraying of reactive solutions onto different substrates followed by short annealing makes the preparation of Eu 2 O 3 materials with diverse morphologies possible.

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

Rapid scalable plasma processing of thin-film Li–La–Zr–O solid-state electrolytes

Solid-state electrolytes, such as lithium lanthanum zirconium oxide (LLZO), show promise as technologies for next-generation high-energy-density batteries, but commercial development has been hindered by a lack of scalable processing methods. Current fabrication methods are costly or require long annealing steps to create dense films. We report an atmospheric pressure blown-arc nitrogen plasma jet process to rapidly form sub-micrometer-thick, dense amorphous LLZO (a-LLZO) films from sol-gel precursors. Films are processed in less than 2 min, an order of magnitude faster than what has previously been reported. We demonstrate 500-nm-thick a-LLZO films processed at 350°C with an ionic conductivity of 2 × 10 −6 S/cm at 30°C and 2 × 10 −3 S/cm at 100°C and a conductance of 19 S at 100°C, the highest conductance of any LLZO phase to date. Here, the films exhibit outstanding smooth surface morphology with low defectivity, advancing atmospheric plasma processing as a scalable processing method for solid-state electrolytes.

25 ENERGY STORAGE↗