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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 1,099 records · Page 61
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Dicarboxylic acid emissions from a GDI engine equipped with a catalytic gasoline particulate filter

Dicarboxylic acids play an important role in atmospheric chemistry, yet their emissions from primary sources, such as internal combustion engines, has not been extensively studied. In this paper, KOH impregnated quartz filters were loaded with exhaust gases from a gasoline direct injection (GDI) engine equipped with a catalytic gasoline particulate filter (GPF). All filters were analyzed for carboxylic and dicarboxylic acids using a derivatized gas chromatography-mass spectroscopy method. Exhaust gas was sampled from pre-GPF and post-GPF locations to determine the performance of the GPF regarding acid conversion. Lean and stoichiometric engine modes were considered with non-oxygenated gasoline and 10% splash blended ethanol in gasoline (E10) to examine the impact of stoichiometry and fuel type. Acid emissions represented as much as 0.51% of total unburned hydrocarbon emissions for total monocarboxylic acids and as much as 0.40% for total dicarboxylic acids. Individual acid concentrations were as high as 38 mg/kg-fuel for monocarboxylic acids and as high as 29 mg/kg-fuel for dicarboxylic acids. Overall, the study found that fuel oxygenates had mixed impact on the acid emissions. Engine-out monocarboxylic acids were reduced when using the E10 fuel by approximately 30–45% for the stoichiometric condition and increased marginally for the lean condition. Dicarboxylic acid emissions were generally insensitive to ethanol content. However, the engine condition significantly affected the acid emissions. Lean operation produced a factor of two to an order of magnitude higher emissions rates of both monocarboxylic and dicarboxylic acids than the stoichiometric condition. The catalytic GPF eliminated between 80 and 92% of the acids emitted from the engine, allowing some acids to be emitted into the environment.

42 ENGINEERING↗
DOE OSTI2021

Effects of knock intensity measurement technique and fuel chemical composition on the research octane number (RON) of FACE gasolines: Part 1 – Lambda and knock characterization

The Research and Motor Octane Number (RON and MON) rate the knock propensity of gasoline in the Cooperative Fuel Research (CFR) engine by comparing the knock intensity of sample fuels relative to that of primary reference fuels (PRF), a binary blend of iso-octane and n-heptane. Important differences exist between standard octane testing and automotive spark ignition (SI) engine knock testing including speed, load, air-to-fuel equivalence ratio (lambda), and knock characterization, which lead to a discrepancy between a fuel’s RON rating and its knock resistance characterized on an automotive SI engine based on knock-limited spark advance. This publication is the first of a set of three publications which modify operating parameters of the RON test method (ASTM D2699) to investigate the effects of these differences with automotive SI engine knock-limited spark advance testing. A fuel’s standard RON is evaluated at the lambda of the highest knock intensity, whereas automotive SI engines typically operate at stoichiometry. Here, we analyze the effects of a stoichiometric RON rating methodology. Additionally, the knock intensity response from the standard CFR knockmeter system is compared to a cylinder pressure oscillation-based knock intensity at several lambda settings. All experiments were performed with a set of seven Coordinating Research Council (CRC) Fuels for Advanced Combustion Engines (FACE) gasolines with approximately 95 RON. The fuel chemical composition impacted the lambda of the highest knock intensity, which resulted in fuel-specific offsets between the standard and stoichiometric RON ratings. The knock system comparison showed significant offsets between cylinder pressure-based and knockmeter-based knock intensity levels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Hydrothermal atomic force microscopy observations of barite step growth rates as a function of the aqueous barium-to-sulfate ratio

The rate of growth of ionic minerals from solutions with varying aqueous cation:anion ratios may result in significant errors in mineralization rates predicted by commonly-used affinity-based rate equations. To assess the potential influence of solute stoichiometry on barite growth, step velocities on the barite (001) surface have been measured at 108 °C using hydrothermal atomic force microscopy (HAFM) at moderate supersaturation and as a function of the aqueous barium:sulfate ratio (r). Barite growth hillocks at r ~ 1 were bounded by $\langle$120$\rangle$ steps, however at r < 1, kink site densities increased, steps followed a direction vicinal to $\langle$120$\rangle$, and the [010] steps developed. At r > 1, steps roughened and rounded as the kink site density increased. Step velocities peaked at r = 1 and decreased roughly symmetrically as a function of r, indicating the attachment rates of barium and sulfate ions are similar under these conditions. We hypothesize that the differences in our observations at high and low r arise from differences in the attachment rate constants for the obtuse and acute $\langle$120$\rangle$ steps. Based on results at low r, the data suggests the attachment rate constant for barium ions is similar for obtuse and acute steps. Based on results at high r, the data suggests the attachment rate constant for sulfate is greater for obtuse steps than acute steps. In conclusion, utilizing a step growth model developed by Stack and Grantham (2010) the experimental step velocities as a function of r were readily fit while attempts to fit the data using a model developed by Zhang and Nancollas (1998) were less successful.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Theoretical constraints on the effects of added cations on clumped, oxygen, and carbon isotope signatures of dissolved inorganic carbon species and minerals

Carbonate clumped isotope thermometry has emerged as a useful tool for the reconstruction of precipitation temperatures for minerals from surface and subsurface environments. Few studies have examined the impact of variable solution chemistry and mineral chemistry on clumping. Therefore, we used theoretical calculations to predict the impact of the presence of cations in a solution on the equilibrium clumped, oxygen ( 18 O/ 16 O and 17 O/ 16 O, θ and κ), and carbon isotopic ( 13 C/ 12 C) compositions of dissolved inorganic carbon species (DIC), and the impact of cation type and stoichiometry on carbonate mineral composition within the calcite-dolomite-magnesite solid solution. We examined the impact of the presence of Mg 2+ , K + , Na + , and Ca 2+ on equilibrium Δ 63 values of carbonate ion groups in DIC species and the composite DIC pool using the B3LYP/6-311++G(2d, 2p) model. We developed new cluster models for dolomite, magnesite, and high-magnesium calcite (Ca 0.83 Mg 0.17 )CO 3 and (Ca 0.67 Mg 0.33 )CO 3 ) and examined the effect of extraneous cations substituted into the crystal lattices of the carbonate minerals. We find the presence of added cations in the DIC pool increases equilibrium Δ 63 values slightly, depending upon their solution concentrations. For the cations examined, the identity of the added cation does not seem to be significant. Cumulative effects may account for small-scale differences (<0.02‰) but are unlikely to be substantial unless cation/anion association and ion pairing are important in the solution that carbonates are growing from. We also find that at a given temperature, stoichiometric dolomite and magnesite Δ 63 values are similar to calcite and less than aragonite. Surprisingly, substitution of an extraneous cation into a carbonate mineral (e.g., as observed in high-magnesium calcite) generally lowered Δ 63 by a slight amount, which suggests that high and low-magnesian calcites may have resolvable differences in equilibrium clumped isotope signatures, potentially providing an explanation for observations of different Δ 47 values in slow-growing minerals. These results imply the cationic composition of the solution may be a minor factor that should be considered for crystals that rapidly grow from solution, and that cationic substitution into carbonate mineral lattices will influence equilibrium compositions of carbonate minerals. Solution chemistry effects on mineral composition are likely to be observed at high growth rates. In contrast, equilibrium isotope compositions arising from cationic substitution in minerals, such as differences between high-Mg calcite and low-Mg calcite, or high-Mg calcite and dolomite, would likely be observed at slow growth rates.

58 GEOSCIENCES↗
DOE OSTI2022

Dynamics and growth rate implications of ribosomes and mRNAs interaction in E. coli

Understanding how cells grow and adapt under various nutrient conditions is pivotal in the study of biological stoichiometry. Recent studies provide empirical evidence that cells use multiple strategies to maintain an optimal protein production rate under different nutrient conditions. Mathematical models can provide a solid theoretical foundation that can explain experimental observations and generate testable hypotheses to further our understanding of the growth process. In this study, we generalize a modeling framework that centers on the translation process and study its asymptotic behaviors to validate algebraic manipulations involving the steady states. Using experimental results on the growth of E. coli under C-, N-, and P-limited environments, we simulate the expected quantitative measurements to show the feasibility of using the model to explain empirical evidence. Our results support the findings that cells employ multiple strategies to maintain a similar protein production rate across different nutrient limitations. Moreover, we find that the previous study underestimates the significance of certain biological rates, such as the binding rate of ribosomes to mRNA and the transition rate between different ribosomal stages. Furthermore, our simulation shows that the strategies used by cells under C- and P-limitations result in a faster overall growth dynamics than under N-limitation. In conclusion, the general modeling framework provides a valuable platform to study cell growth under different nutrient supply conditions, which also allows straightforward extensions to the coupling of transcription, translation, and energetics to deepen our understanding of the growth process.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

A conspicuous 27 Al-NMR signal at 72 ppm during isomerization of Keggin Al 13 ions

A sharp signal at 72 ppm was recently observed in 27 Al-NMR spectra during the isomerization of Keggin-Al 13 ions in the presence of calcium and glycine [1]. It has been proposed that this signal corresponds to one of the Keggin isomers. Conversion of the most common ε-isomer of the Keggin series of molecules, having the stoichiometry [AlO 4 Al 12 (OH) 24 (OH 2 ) 12 ] 7+ , is enhanced by the addition of calcium and glycine [2,3]. Here we show that a 72 ppm signal can also be observed in the absence of calcium or glycine; the magnitude of which depends on aluminum concentration and temperature. Additionally, isomerization of the ε-Keggin-Al 13 to the γ-Keggin-Al 13 isomer was observed in the absence of calcium and glycine at elevated temperatures after several days. Furthermore, calcium and glycine were previously shown to enhance rates of γ-Keggin-Al 13 formation. 2.

27Al-NMR↗
DOE OSTI2020

Parametric study of operating conditions of an SO 2 -depolarized electrolyzer

Large-scale hydrogen generation is needed to satisfy both existing commercial demands and the realization of a hydrogen economy. The hybrid sulfur cycle has the potential to meet this goal without the use of fossil fuels. The ability to model and predict how the electrolyzer step of the cycle is affected by independent and interdependent variables is vital to maximizing the efficiency of the overall cycle. Herein, we report that our parametric study of the SO 2 -depolarized electrolyzer, representing one half of the overall reaction cycle, has identified desirable conditions and will help guide further development for operation that will achieve the benchmarks for economic feasibility. We discuss the interactions among the inlet flow rates, applied current, and cell temperature and pressure, on the resulting cell voltage and acid concentration in the liquid product stream. For example, we find that using a sulfonated polybenzimidazole (s-PBI) membrane and a platinum catalyst, a constant current density of either 0.5 A cm -2 , 0.75 A cm -2 , or 1 A cm -2 with an acid concentration of 65 wt% H 2 SO 4 can be produced at a cell voltage of 0.59 V, 0.63 V, and 0.67 V, respectively, by maintaining a cell temperature of 130 °C, a pressure of 2 bar, and a water-to-SO 2 stoichiometry of 2.77. Finally, we discuss directions for future research based on the findings in this manuscript.

08 HYDROGEN↗
DOE OSTI2022

Cholesterol-induced suppression of Kir2 channels is mediated by decoupling at the inter-subunit interfaces

Cholesterol is a major regulator of multiple types of ion channels. Although there is increasing information about cholesterol binding sites, the molecular mechanisms through which cholesterol binding alters channel function are virtually unknown. In this study, we used a combination of Martini coarse-grained simulations, a network theory-based analysis, and electrophysiology to determine the effect of cholesterol on the dynamic structure of the Kir2.2 channel. We found that increasing membrane cholesterol reduced the likelihood of contact between specific regions of the cytoplasmic and transmembrane domains of the channel, most prominently at the subunit-subunit interfaces of the cytosolic domains. This decrease in contact was mediated by pairwise interactions of specific residues and correlated to the stoichiometry of cholesterol binding events. The predictions of the model were tested by site-directed mutagenesis of two identified residues—V265 and H222—and high throughput electrophysiology.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2013

Anisotropic magnetization and resistivity of single crystalline RNi1-xBi2±y (R=La–Nd, Sm, Gd–Dy)

We present a detailed study of RNi1-xBi2±y (R = La–Nd, Sm, Gd–Dy) single crystals by measurements of stoichiometry and temperature dependent magnetic susceptibility, magnetization, and electrical resistivity. This series forms with partial Ni occupancy, 0.72 ≤ (1-x) ≤ 0.84, as well as a variable Bi occupancy, 1.76 ≤ (2±y) ≤ 2.14. For R = Ce–Nd, Gd–Dy, the RNi1-xBi2±y compounds show local-moment like behavior and order antiferromagnetically at low temperatures. Determination of anisotropies as well as antiferromagnetic ordering temperatures for RNi1-xBi2±y (R = Ce–Nd, Sm, Gd–Dy) have been made. Crystalline samples from this family exhibit minority, second phase superconductivity at low temperatures, which can be associated with Ni–Bi and Bi contamination. No evidence of bulk superconductivity has been observed.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Indium segregation in Gd 5 (Si, Ge) 4 magnetocaloric materials

Chemical substitution is one of the most efficient tools to tune and optimize magnetic and magnetocaloric properties of the giant magnetocaloric materials. In particular, Indium substitutions could be useful both for tuning properties of these interesting intermetallic materials and to unveil their local-scale behavior across the magnetostructural transition via hyperfine techniques. Hence, in order to investigate the effect of Indium additions on the crystal structure, micro-structure, magnetic and magnetocaloric properties, a series of In-containing samples derived from the base Gd 5 Si 1.2 Ge 2.8 stoichiometry were prepared. Here, the major findings are that while In is insoluble in the 5:4 phase, it will instead promote the emergence of the impurity 5:3 phase and segregates into this phase. Hence, In leads to major crystallographic changes, which enhance atomic disorder and disrupt the Si to Ge ratio in the 5:4 phase. Subsequently, a higher 5:4 unit cell volume and a lower magnetic ordering temperature are found in the In-substituted samples. Finally, the magnetocaloric properties of the In-substituted samples reveal a detrimental effect on the maximum magnetic entropy change.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Phase equilibria in iron-rich Sm–Fe–Ti and Sm–(Fe,Co)–Ti alloys at 1100–1200 °C

Iron-rich corners of ternary Sm–Fe–Ti phase diagram at 1100 °C and quasi-ternary Sm–Fe 0.8 Co 0.2 –Ti phase diagrams at 1100 and 1200 °C are constructed based on experimental investigation of equilibrated alloys with electron probe microanalysis, X-ray diffraction and thermomagnetic analysis. In addition, the upper boundaries of the temperature ranges of Sm(Fe,[Co,]Ti) 12 and Sm 3 (Fe,[Co,]Ti) 29 phases are determined with differential thermal analysis to update earlier rough estimates. The existence of a high-temperature phase of the Th 2 Ni 17 type, originally reported by Ivanova et al. [J. Alloys Compd. 224 (1995) 29], is confirmed. In the Sm–Fe 0.8 Co 0.2 –Ti system, the composition and equilibria of this hexagonal phase are established for 1200 °C; it is Sm-depleted (≈9.8 at.% Sm) compared to the 2:17 stoichiometry and it coexists with the rhombohedral 2:17 phase. The magnetic anisotropy of the cobalt-substituted Th 2 Ni 17 -type phase is planar, with the easy magnetization direction parallel to [100]. Equilibrium between a Sm-rich liquid phase and the 1:12 phase, which is important for the development of new high-performance permanent magnets, is absent up to 1000 °C, but does exist at 1100 °C (for the 1:12 phase with at least 8.7–8.9 at.% Ti) and at 1200 °C (for the 1:12 phase with as little as 7.4 at.% Ti). The development of magnets may be complicated, however, by an observed tendency of the high-temperature liquid to solidify into ferromagnetic phases including the Th 2 Ni 17 -type phase. The Curie temperatures of the α-(Fe,Ti), Sm(Fe,Ti) 12 , Sm 3 (Fe,Ti) 29 and rhombohedral Sm 2 (Fe,Ti) 17 phases are not only increased by the partial Co substitution for Fe, but their dependence on the Ti concentration is changed by this Co substitution from positive (or, for the 1:12 phase, zero) to negative values.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Structural delineation and phase-dependent activation of the costimulatory CD27:CD70 complex

CD27 is a tumor necrosis factor (TNF) receptor, which stimulates lymphocytes and promotes their differentiation upon activation by TNF ligand CD70. Activation of the CD27 receptor provides a costimulatory signal to promote T cell, B cell, and NK cell activity to facilitate antitumor and anti-infection immunity. Aberrant increased and focused expression of CD70 on many tumor cells renders CD70 an attractive therapeutic target for direct tumor killing. However, despite their use as drug targets to treat cancers, the molecular basis and atomic details of CD27 and CD70 interaction remain elusive. Here we report the crystal structure of human CD27 in complex with human CD70. Analysis of our structure shows that CD70 adopts a classical TNF ligand homotrimeric assembly to engage CD27 receptors in a 3:3 stoichiometry. By combining structural and rational mutagenesis data with reported disease-correlated mutations, we identified the key amino acid residues of CD27 and CD70 that control this interaction. We also report increased potency for plate-bound CD70 constructs compared with solution-phase ligand in a functional activity to stimulate T-cells in vitro. These findings offer new mechanistic insight into this critical costimulatory interaction.

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

Evolution of Rev7 interactions in eukaryotic TLS DNA polymerase Polζ

Translesion synthesis (TLS) DNA polymerase Polζ is crucial for the bypass replication over sites of DNA damage. The Rev7 subunit of Polζ is a HORMA (Hop1, Rev7, Mad2) protein that facilitates recruitment of Polζ to the replication fork via interactions with the catalytic subunit Rev3 and the translesion synthesis scaffold protein Rev1. Human Rev7 (hRev7) interacts with two Rev7-binding motifs (RBMs) of hRev3 by a mechanism conserved among HORMA proteins whereby the safety-belt loop of hRev7 closes on the top of the ligand. The two copies of hRev7 tethered by the two hRev3-RBMs form a symmetric head-to-head dimer through the canonical HORMA dimerization interface. Recent cryo-EM structures reveal that Saccharomyces cerevisiae Polζ (scPolζ) also includes two copies of scRev7 bound to distinct regions of scRev3. Surprisingly, the HORMA dimerization interface is not conserved in scRev7, with the two scRev7 protomers forming an asymmetric head-to-tail dimer with a much smaller interface than the hRev7 dimer. Here, we validated the two adjacent RBM motifs in scRev3, which bind scRev7 with affinities that differ by two orders of magnitude and confirmed the 2:1 stoichiometry of the scRev7:Rev3 complex in solution. However, our biophysical studies reveal that scRev7 does not form dimers in solution either on its own accord or when tethered by the two RBMs in scRev3. These findings imply that the scRev7 dimer observed in the cryo-EM structures is induced by scRev7 interactions with other Polζ subunits and that Rev7 homodimerization via the HORMA interface is a mechanism that emerged later in evolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2010

Hydrodesulfurization Properties of Rhodium Phosphide: Comparison with Rhodium Metal and Sulfide Catalysts

Silica-supported rhodium phosphide (Rh2P/SiO2) catalysts were prepared and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), 31P solid-state NMR spectroscopy, X-ray photoelectron spectroscopy (XPS), and chemisorption measurements. XRD and TEM analysis of a 5 wt.% Rh2P/SiO2 catalyst confirmed the presence of well-dispersed Rh2P crystallites on the silica support having an average crystallite size of 10 nm. NMR spectroscopy showed unsupported and silica-supported Rh2P to be metallic and XPS spectroscopy yielded a surface composition of Rh1.94P1.00 that is similar to that expected from the bulk stoichiometry. The 5 wt.% Rh2P/SiO2 catalyst exhibited a higher dibenzothiophene (DBT) hydrodesulfurization (HDS) activity than did Rh/SiO2 and sulfided Rh/SiO2 catalysts having a similar Rh loading and was also more active than a commercial NiAMo/Al2O3 catalyst. The Rh2P/SiO2 catalyst showed excellent stability over a 100 h DBT HDS activity measurement and was more S tolerant than the Rh/SiO2 catalyst. The Rh2P/SiO2 catalyst strongly favored the hydrogenation pathway for DBT HDS, while the Rh/SiO2 and sulfided Rh/SiO2 catalysts favored the direct desulfurization pathway.

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

Vertical gradient freeze growth of detector grade CdZnTeSe single crystals

Here, we report the growth of detector grade Cd 0.9 Zn 0.1 Te 0.97 Se 0.03 (CZTS) single crystals, a recently discovered quaternary semiconductor for room temperature radiation detection, by a vertical gradient freeze (VGF) method. VGF is a comparatively low-temperature growth method and avoids relative motion between the heater and the ampoule containing the precursor materials which minimizes any thermal drift or temperature fluctuations. As a result, CZTS single crystals with superior charge transport properties has been obtained. Growth of detector-grade CZTS single crystals using VGF method has not been reported yet. X-ray spectroscopy based elemental analysis showed that the grown crystals demonstrated the desired stoichiometry required for high resolution radiation detection. Planar detectors fabricated by deposition of gold contacts (~0.07 cm 2 ) demonstrated high bulk resistivity ~10 10 Ω-cm and a very low leakage current density of 2.8 × 10 –8 A/cm 2 at a bias of 100 V when measured at room temperature. The detectors showed excellent radiation response with 100 % charge collection efficiency when exposed to 5486 keV alpha particles. The electron mobility-lifetime (μτ) product was measured to be 3 × 10 –3 cm 2 /V using a single polarity Hecht analysis which is at par with the recently reported values measured in CZTS grown using conventional Bridgman or travelling heater method. The electron mobility has been calculated to be 964 cm 2 V –1 s –1 using a time-of-flight (TOF) method, a substantial improvement over that obtained from conventionally grown CZTS single crystals.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Epitaxial columnar growth of strain-free antiferromagnetic Weyl semimetal Mn 3 Sn on wurtzite c -plane GaN/Al 2 O 3 (0001)

Weyl semimetal thin films with excellent crystalline quality are of great interest for antiferromagnetic spintronics. Mn 3 Sn is one Weyl semimetal with great properties and promise for exciting science and applications. It has proven very challenging, however, to grow Mn 3 Sn thin films with smooth surfaces, negligible strain, and excellent crystallinity. In this work, we discuss the successful preparation of epitaxial Mn 3 Sn (0001)-oriented thin films via molecular beam epitaxial growth on c -plane wurtzite GaN which was grown by MBE on Al 2 O 3 (0001). We present the reflection high energy electron diffraction analysis along with x-ray diffraction in order to demonstrate the crystalline quality of the film, and we give atomic models to explain the epitaxial orientation relationships between the crystal lattices of the substrate, GaN layer, and Mn 3 Sn layer. Importantly, we discuss the film lattice parameters as compared to expected values, demonstrating negligible strain both in-plane and out-of-plane . Atomic force microscopy reveals an epitaxial columnar growth mode characterized by flat-top-mesa islands, while scanning tunneling microscopy shows the atomically smooth surfaces of the mesa-top structures. Finally, Rutherford backscattering informs the stoichiometry of the film as well as the layer thicknesses.

Chiral antiferromagnetic material↗