SEARCH · Engineering Papers
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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X-ray Raman scattering (XRS) spectroscopy provides access to element-specific core photo-absorption edges of low Z -elements ( e.g. K -edges of C, N, O), using hard X-ray photons enabling bulk and in situ study of green carbons.
Although the two active redox centers in Li-rich cathodes, including the anionic and cationic contributions, can enable Li-ion batteries to achieve outstanding specific energy, their behaviors at different current densities have not been clarified. In this report we provide a comparative study of transition metals (TMs) and oxygen redox activities by directly accessing their oxidation states in Li-rich materials operated at very different current rates. Our data reveal that the oxidation of oxygen in the near-surface region is at the same level for electrodes cycled with a wide range of current rates, indicating a reaction gradient of lattice oxygen redox reactions. The oxidation process of lattice oxygen is found to be dynamically compatible with that of the TMs. Combining the results of first principles calculations and complementary experimental findings, we propose a detailed mechanism of structural distortion from octahedral Li to tetrahedral Li and the role of oxygen vacancy in Li + diffusion. It is found that fast delithiation occurring at high current densities can easily cause local structural transformation, leading to a limited Li + diffusion rate and consequently suppressing rate capability.
In this study, Mn silicate (MnSiO{sub 3}) barrier layers were formed on thermally grown SiO{sub 2} using both metallic Mn and oxidized Mn films, in order to investigate the role of oxygen in determining the extent of the interaction between the deposited Mn and the SiO{sub 2} substrate. Using x-ray photoelectron spectroscopy, it has been shown that a metallic Mn film with an approximate thickness of 1 nm cannot be fully converted to Mn silicate following vacuum annealing to 500 deg. C. Transmission electron microscopy (TEM) analysis suggests the maximum MnSiO{sub 3} layer thickness obtainable using metallic Mn is {approx}1.7 nm. In contrast, a {approx}1 nm partially oxidized Mn film can be fully converted to Mn silicate following thermal annealing to 400 deg. C, forming a MnSiO{sub 3} layer with a measured thickness of 2.6 nm. TEM analysis also clearly shows that MnSiO{sub 3} growth results in a corresponding reduction in the SiO{sub 2} layer thickness. It has also been shown that a fully oxidized Mn oxide thin film can be converted to Mn silicate, in the absence of metallic Mn. Based on these results it is suggested that the presence of Mn oxide species at the Mn/SiO{sub 2} interface facilitates the conversion of SiO{sub 2} to MnSiO{sub 3}, in agreement with previously published studies.
We have reported a combined photoelectron imaging and theoretical study on gaseous mixed-ligand M(I) complexes of [HMSH]{sup −} (M = Cu, Ag, and Au). With the aid of Franck-Condon simulations, vibrationally resolved photoelectron spectra yield accurate electron affinities of 3.269(6), 3.669(10), and 3.591(6) eV for [HCuSH], [HAgSH], and [HAuSH], respectively. And low-frequency modes are observed: 368(12) cm{sup −1} for [HCuSH], 286(12) cm{sup −1} for [HAgSH], and 327(12) cm{sup −1} for [HAuSH], respectively. Extensive theoretical calculations are performed to aid in the spectral assignments and the calculated values agree well with the experimental observations. Although the S and H atoms have little discrepancy in electronegativity (2.20 for H and 2.54 for S), distinct bonding properties are demonstrated between H–M and M–S bond. It is revealed that there exists significant ionic bonding between M–S in [HMSH]{sup −} (M = Cu, Ag, and Au), while a gradual transition from ionic behavior between H–Cu in [HCuSH]{sup −} to quite strong covalent bonding between H–Au in [HAuSH]{sup −}, supported by a variety of chemical bonding analyses.
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Computational and biochemical studies implicate the blue-light sensor cryptochrome (CRY) as an endogenous light-dependent magnetosensor enabling migratory birds to navigate using the Earth’s magnetic field. Validation of such a mechanism has been hampered by the absence of structures of vertebrate CRYs that have functional photochemistry. Here we present crystal structures of Columba livia (pigeon) CRY4 that reveal evolutionarily conserved modifications to a sequence of Trp residues (Trp-triad) required for CRY photoreduction. In ClCRY4, the Trp-triad chain is extended to include a fourth Trp (W369) and a Tyr (Y319) residue at the protein surface that imparts an unusually high quantum yield of photoreduction. These results are consistent with observations of night migratory behavior in animals at low light levels and could have implications for photochemical pathways allowing magnetosensing.
The variation of the kinematical properties of the Galactic thick disk with Galactic height Z is studied by means of 412 red giants observed in the direction of the south Galactic pole up to 4.5 kpc from the plane. We confirm the non-null mean radial motion toward the Galactic anticenter found by other authors, but we find that it changes sign at |Z| = 3 kpc, and the proposed inward motion of the local standard of rest alone cannot explain these observations. The rotational velocity decreases with |Z| by -30 km s{sup -1} kpc{sup -1}, but the data are better represented by a power law with index 1.25, similar to that proposed from the analysis of Sloan Digital Sky Survey data. All the velocity dispersions increase with |Z|, but the vertical gradients are small. The dispersions grow proportionally, with no significant variation of the anisotropy. The ratio {sigma}{sub U}/{sigma}{sub W} = 2 suggests that the thick disk could have formed from a low-latitude merging event. The vertex deviation increases with Galactic height, reaching {approx}20 Degree-Sign at |Z| = 3.5 kpc. The tilt angle also increases, and the orientation of the ellipsoid in the radial-vertical plane is constantly intermediate between the alignment with the cylindrical and the spherical coordinate systems. The tilt angle at |Z| = 2 kpc coincides with the expectations of MOdified Newtonian Dynamics, but an extension of the calculations to higher |Z| is required to perform a conclusive test. Finally, between 2.5 and 3.5 kpc we detect deviations from the linear trend of many kinematical quantities, suggesting that some kinematical substructure could be present.
We investigate the impact of photochemistry and X-ray ionization on the molecular composition of, and ionization fraction in, a protoplanetary disk surrounding a typical T Tauri star. We use a sophisticated physical model, which includes a robust treatment of the radiative transfer of UV and X-ray radiation, and calculate the time-dependent chemical structure using a comprehensive chemical network. In previous work, we approximated the photochemistry and X-ray ionization; here, we recalculate the photoreaction rates using the explicit UV wavelength spectrum and wavelength-dependent reaction cross sections. We recalculate the X-ray ionization rate using our explicit elemental composition and X-ray energy spectrum. We find that photochemistry has a larger influence on the molecular composition than X-ray ionization. Observable molecules sensitive to the photorates include OH, HCO{sup +}, N{sub 2}H{sup +}, H{sub 2}O, CO{sub 2}, and CH{sub 3}OH. The only molecule significantly affected by the X-ray ionization is N{sub 2}H{sup +}, indicating that it is safe to adopt existing approximations of the X-ray ionization rate in typical T Tauri star-disk systems. The recalculation of the photorates increases the abundances of neutral molecules in the outer disk, highlighting the importance of taking into account the shape of the UV spectrum in protoplanetary disks. A recalculation of the photoreaction rates also affects the gas-phase chemistry due to the adjustment of the H/H{sub 2} and C{sup +}/C ratios. The disk ionization fraction is not significantly affected by the methods adopted to calculate the photochemistry and X-ray ionization. We determine that there is a probable 'dead zone' where accretion is suppressed, present in a layer, Z/R {approx}< 0.1-0.2, in the disk midplane, within R Almost-Equal-To 200 AU.
We estimated the dynamical surface mass density {Sigma} at the solar position between Z = 1.5 and 4 kpc from the Galactic plane, as inferred from the kinematics of thick disk stars. The formulation is exact within the limit of validity of a few basic assumptions. The resulting trend of {Sigma}(Z) matches the expectations of visible mass alone, and no dark component is required to account for the observations. We extrapolate a dark matter (DM) density in the solar neighborhood of 0 {+-} 1 mM{sub Sun} pc{sup -3}, and all the current models of a spherical DM halo are excluded at a confidence level higher than 4{sigma}. A detailed analysis reveals that a small amount of DM is allowed in the volume under study by the change of some input parameter or hypothesis, but not enough to match the expectations of the models, except under an exotic combination of non-standard assumptions. Identical results are obtained when repeating the calculation with kinematical measurements available in the literature. We demonstrate that a DM halo would be detected by our method, and therefore the results have no straightforward interpretation. Only the presence of a highly prolate (flattening q > 2) DM halo can be reconciled with the observations, but this is highly unlikely in {Lambda}CDM models. The results challenge the current understanding of the spatial distribution and nature of the Galactic DM. In particular, our results may indicate that any direct DM detection experiment is doomed to fail if the local density of the target particles is negligible.
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Abstract Hollandite has been studied as a candidate ceramic waste form for the disposal of high‐level radioactive waste due to its inherent leach resistance and ability to immobilize alkaline‐earth metals such as Cs and Ba at defined lattice sites in the crystallographic structure. The chemical and structural complexity of hollandite‐type phases developed for high‐level waste immobilization limits the systematic experimental research that is required to understand phase development due to the large number of potential additives and compositional ranges that must be evaluated. Modeling the equilibrium behavior of the complex hollandite‐forming oxide waste system would aid in the design and processing of hollandite waste forms by predicting their thermodynamic stability. Thus, a BaO–Cs 2 O–TiO 2 –Cr 2 O 3 –Al 2 O 3 –Fe 2 O 3 –FeO–Ga 2 O 3 thermodynamic database was developed in this work according to the CALPHAD methodology. The compound energy formalism was used to model solid solution phases such as hollandite while the two‐sublattice partially ionic liquid model characterized the oxide melt. Results of model optimizations are presented and discussed including a 1473 K isothermal BaO–Cs 2 O–TiO 2 pseudo‐ternary diagram that extrapolates phase equilibrium behavior to regions not experimentally explored.
Plasma-enhanced atomic layer deposition was utilized to grow aluminum nitride (AlN) films on Si from trimethylaluminum and N{sub 2}:H{sub 2} plasma at 200 °C. Thermal treatments were then applied on the films which caused changes in their chemical composition and nanostructure. These changes were observed to manifest in the refractive indices and densities of the films. The AlN films were identified to contain light element impurities, namely, H, C, and excess N due to nonideal precursor reactions. Oxygen contamination was also identified in the films. Many of the embedded impurities became volatile in the elevated annealing temperatures. Most notably, high amounts of H were observed to desorb from the AlN films. Furthermore, dinitrogen triple bonds were identified with infrared spectroscopy in the films. The triple bonds broke after annealing at 1000 °C for 1 h which likely caused enhanced hydrolysis of the films. The nanostructure of the films was identified to be amorphous in the as-deposited state and to become nanocrystalline after 1 h of annealing at 1000 °C.
Alkaline hydrogen peroxide pretreatment catalyzed by Cu(II) 2,2'-bipyridine complexes has previously been determined to substantially improve the enzymatic hydrolysis of woody plants including hybrid poplar as a consequence of moderate delignification. In the present work, cell wall morphological and lignin structural changes were characterized for this pretreatment approach to gain insights into pretreatment outcomes and, specifically, to identify the extent and nature of lignin modification.
This data package includes leaf traits, canopy traits and sample details for leaves from 71 species sampled from the San Lorenzo forest canopy crane site, Panama (PA-SLZ) during the BNL field campaign in January to March 2020. Each leaf sample is described with species, phenological stage and location within vertical canopy profiles. Leaf area index (LAI) and height is presented for each canopy profile location. Leaf mass per area (LMA), leaf water content (LWC) and leaf carbon and nitrogen content are included for a subset of the samples. This data package includes sample details, processed data for leaf traits and LAI (*.csv), LAI raw data (compressed as *.zip) and digital camera images (*.jpg, compressed as *.zip) of the leaf samples. Metadata files include data descriptions (_dd.csv) for tabular data, a list of all species sampled during the campaign (*.csv) and a detailed description of the field campaign protocol and methods (*.pdf). See related datasets for leaf gas exchange, leaf water potential and leaf spectral measurements made on the samples described here.
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This is a combined experimental and theoretical study of the compound Cs 2 PuO 2 Cl 4 , using X-ray Photoelectron Spectroscopy (XPS) and Relativistic Discrete Variation (RDV) calculations.
The primary objective of this effort is to develop the capability to apply new single molecule imaging methods to the study of plant cell structure and the dynamics of cellulase enzyme activity.