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.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
The accumulation of oxidative charges on atomically dispersed Ir catalytic sites shows dependence on the support. The impact of the hole redistribution on the rate of water oxidation leads to temperature-dependent kinetics of water oxidation.
Metal–support interaction plays a crucial role in governing the stability and activity of atomically dispersed platinum catalysts on ceria support. The migration and aggregation of platinum atoms during the catalytic reaction leads to the redistribution of active sites. In this study, by utilizing a multimodal characterization scheme, we observed the aggregation of platinum atoms at high temperatures under reverse water gas shift reaction conditions and the subsequent fragmentation of platinum clusters, forming “single atoms” upon cooling. Theoretical simulations of both effects uncovered the roles of carbon monoxide binding on perimeter Pt sites in the clusters and hydrogen coverage in the aggregation and fragmentation mechanisms. Finally, this study highlights the complex effects of adsorbate and supports interactions with metal sites in Pt/ceria catalysts that govern their structural transformations under in situ conditions.
The aggregation and onset of gelation of PEGylated gold nanoparticles dispersed in a glycerol–water mixture is studied by small-angle X-ray scattering and X-ray photon correlation spectroscopy.
Maximizing iridium utilization while maintaining high oxygen evolution reaction (OER) performance remains a persistent challenge in acidic water electrolysis. Immobilizing Ir on conductive, acid-stable supports is promising, yet simultaneously achieving sub-nanometer size, high area coverage, and strong electronic coupling is difficult. Here, we report a sequential surface synthesis on titanium nitride (TiN) that yields uniformly distributed sub-nanometer Ir arrays (∼0.7 nm). Our method uses ethylenediaminetetraacetic acid (EDTA) as a temporal scaffold: it chemisorbs to TiN to install dense chelating sites, captures Ir 3+ ions, and confines Ir cluster growth. A subsequent thermal treatment at 500 °C in a reducing atmosphere removes the ligand shell, while preserving ultrasmall particle size and establishing direct Ir–TiN electronic coupling. The optimized catalyst exhibits mixed Ir 0 /Ir x+ coordination with low charge-transfer resistance (R ct = 19.2 Ω), delivering a mass activity of 342 A g Ir −1 at 1.54 V in acidic electrolyte. In situ X-ray absorption spectroscopy reveals irreversible surface oxidation as the primary stability-limiting factor. This stepwise strategy provides a general framework for supported catalysts that maximize precious metal utilization via sub-nanometer dispersion.
The second catalogue of Planck Sunyaev-Zeldovich (SZ) sources, hereafter PSZ2, represents the largest galaxy cluster sample selected by means of their SZ signature in a full-sky survey. For this work, using telescopes at the Canary Island observatories, we conducted the long-term observational program 128- MULTIPLE-16/15B (hereafter LP15), a large and complete optical follow-up campaign of all the unidentified PSZ2 sources in the northern sky, with declinations above –15° and no correspondence in the first Planck catalogue PSZ1. This paper is the third and last in the series of LP15 results, after Streblyanska et al. (2019, A&A, 628, A13) and Aguado-Barahona et al. (2019, A&A, 631, A148), and presents all the spectroscopic observations of the full program. We complement these LP15 spectroscopic results with Sloan Digital Sky Survey archival data and other observations from a previous program (ITP13-08), and present a catalogue of 388 clusters and groups of galaxies including estimates of their velocity dispersion. The majority of them (356) are optical counterparts of PSZ2 sources. A subset of 297 of those clusters are used to construct the M SZ – M dyn scaling relation based on the estimated SZ mass from Planck measurements and our dynamical mass estimates. We discuss and correct for different statistical and physical biases in the estimation of the masses, such as the Eddington bias when estimating M SZ and the aperture and the number of galaxies used to calculate M dyn . The SZ-to-dynamical mass ratio for those 297 PSZ2 clusters is (1 – B) = 0.80 ± 0.04 (stat) ± 0.05 (sys), with only marginal evidence for a possible mass dependence for this factor. Our value is consistent with previous results in the literature, but is associated with a significantly smaller uncertainty due to the use of the largest sample size for this type of study.
Engineering design studies are underway to assess the feasibility of converting the High Flux Isotope Reactor (HFIR) to operate with low-enriched uranium (LEU) silicide dispersion (U3Si2-Al) fuel. These studies are supported by the U.S. Department of Energy National Nuclear Security Administration’s Office of Material Management and Minimization. A systematic approach employing neutronic and thermal-hydraulic analyses have been performed with the ORNL Shift and HFIR Steady State Heat Transfer Code tools, respectively, to predict reactor performance and thermal safety margins for proposed LEU3Si2-Al fuel designs. The design process was initiated by generating an optimized design with fabrication features identified from previous studies that result in excellent performance and safety metrics. The approach continued by substituting a single fabrication feature anticipated to be difficult to manufacture with another feature expected to perform an analogous function to that of the removed feature. Four conceptual fuel element design candidates, with various fabrication features, for conversion of HFIR with 4.8 gU/cm3 LEU3Si2-Al fuel have been generated and shown to meet pre-defined performance and safety metrics. Results to date indicate that HFIR could convert with the subject fuel system and meet performance and safety requirements if, among other considerations, fabrication of the specific design features are demonstrated and qualification of the fuel is complete under HFIR-specific conditions.
A quantitative method to measure the reduction in oxide species on the surface of electrochemically etched tungsten tips during direct current annealing is developed using energy dispersive x-ray spectroscopy. Oxide species are found to decrease with annealing current, with the trend repeatable over many tips and along the length of the tip apex. A linear resistivity approximation finds significant oxide sublimation occurs at 1714 K, but surface melting and tip broadening at 2215 K. This method can be applied to calibrate any similar annealing stage, and to identify the tradeoff regime between required morphological and chemical properties.
Growth of CuO nanowires by annealing method has been studied in-situ by grazing incidence Energy Dispersive X-ray Diffraction (EDXRD) technique on Indus-2. It was observed that Cu slowly oxidized to Cu{sub 2}O and finally to CuO. The data was taken as a function of time at two annealing temperatures 500 Degree-Sign C where nanowires form and 300 Degree-Sign C where nanowires don't form. We found that the strain in the CuO layer may be a principal factor for the spontaneous growth of nanowires in annealing method.
We have designed and fabricated parallel plate ionization chamber detectors and voltage vs. current characteristics (V-I curve) of the detectors were recorded with synchrotron radiation to qualify for use in X-ray Absorption Spectroscopy (XAS) measurements. After qualifying the ionization chambers, the detectors were used in the dispersive EXAFS beamline (BL-08) at INDUS-2 SRS in Turbo-XAS geometry. Using the same setup and under the same setting, XAS spectra were also recorded with a CCD detector and the observation on relative performance of the ionization chamber vis-a-vis the CCD detector is presented in this paper.
Atomic-scale quantification of chemical composition across oxide interfaces is important for understanding physical properties of epitaxial oxide nanostructures. Energy-dispersive X-ray spectroscopy (EDS) in an aberration-corrected scanning transmission electron microscope was used to quantify chemical composition across the interface of ferromagnetic La{sub 0.7}Sr{sub 0.3}MnO{sub 3} and antiferromagnetic BiFeO{sub 3} quantum structure. This research demonstrates that chemical composition at atomic columns can be quantified by Gaussian peak-fitting of EDS compositional profiles across the interface. Cation diffusion was observed at both A- and B-sublattice sites; and asymmetric chemical profiles exist across the interface, consistent with the previous studies.
The use of high resistivity amorphous solids as photodetectors, especially amorphous selenium, is currently of great interest because they are readily produced over large area at substantially lower cost compared to grown crystalline solids. However, amorphous solids have been ruled out as viable radiation detection media for high frame-rate applications, such as single-photon-counting imaging, because of low carrier mobilities, transit-time-limited photoresponse, and consequently, poor time resolution. To circumvent the problem of poor charge transport in amorphous solids, we propose unipolar time-differential charge sensing by establishing a strong near-field effect using an electrostatic shield within the material. For the first time, we have fabricated a true Frisch grid inside a solid-state detector by evaporating amorphous selenium over photolithographically prepared multi-well substrates. The fabricated devices are characterized with optical, x-ray, and gamma-ray impulse-like excitations. Results prove the proposed unipolar time-differential property and show that time resolution in non-dispersive amorphous solids can be improved substantially to reach the theoretical limit set by spatial spreading of the collected Gaussian carrier cloud.
Superhydrophilic graphite surfaces and water-dispersible graphite colloids are obtained by electrochemical exfoliation with hydrophobic graphite electrodes. Such counterintuitive characteristics are caused by partial oxidation and investigated by examining both graphite electrodes and exfoliated particles after electrolysis. The extent of surface oxidation can be explored through contact angle measurement, scanning electron microscope, electrical sheet resistance, x-ray photoelectron spectroscopy, zeta-potential analyzer, thermogravimetric analysis, UV-visible, and Raman spectroscopy. The degree of wettability of the graphite anode can be altered by the electrolytic current and time. The water contact angle declines generally with increasing the electrolytic current or time. After a sufficient time, the graphite anode becomes superhydrophilic and its hydrophobicity can be recovered by peeling with adhesive tape. This consequence reveals that the anodic graphite is oxidized by oxygen bubbles but the oxidation just occurs at the outer layers of the graphite sheet. Moreover, the characteristics of oxidation revealed by UV peak shift, peak ratio between D and G bands, and negative zeta-potential indicate the presence of graphite oxide on the outer shell of the exfoliated colloids. However, thermogravimetric analysis for the extent of decomposition of oxygen functional groups verifies that the amount of oxygen groups is significantly less than that of graphite oxide prepared via Hummer method. The structure of this partially oxidized graphite may consist of a graphite core covered with an oxidized shell. The properties of the exfoliated colloids are also influenced by pH of the electrolytic solution. As pH is increased, the extent of oxidation descends and the thickness of oxidized shell decreases. Those results reveal that the degree of oxidation of exfoliated nanoparticles can be manipulated simply by controlling pH.
Thin poly(methylmethacrylate) films doped by or covalently attached to disperse Red 1 acrylate (DR1) were patterned by laser scanning and simultaneous sample movement in confocal microscope. In both cases, periodical structure due to Marangoni effect is created. Modified polymers surfaces were analyzed by FTIR spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. After first stage of patterning, second stage with sample movement in perpendicular direction was applied. Depending on the method of DR1 dotation fishnet structure is obtained or pattern structure disappears. In the latter case, reversibility of pattern formation and erasure by laser scanning was studied.
The in-situ growth of CuO nanowires was studied by Energy Dispersive X-ray Diffraction (EDXRD) to observe the mechanism of growth. The study was carried out for comparison at two temperatures—at 500 °C, the optimum temperature of the nanowires growth, and at 300 °C just below the temperature range of the growth. The in situ observation revealed the successive oxidation of Cu foil to Cu{sub 2}O layer and finally to CuO layer. Further analysis showed the presence of a compressive stress in CuO layer due to interface at CuO and Cu{sub 2}O layers. The compressive stress was found to increase with the growth of the nanowires at 500 °C while it relaxed with the growth of CuO layer at 300 °C. The present results do not support the existing model of stress relaxation induced growth of nanowires. Based on the detailed Transmission Electron Microscope, Scanning Electron Microscope, and EDXRD results, a microstructure based growth model has been suggested.
Vlasiator is a new hybrid-Vlasov plasma simulation code aimed at simulating the entire magnetosphere of the Earth. The code treats ions (protons) kinetically through Vlasov's equation in the six-dimensional phase space while electrons are a massless charge-neutralizing fluid [M. Palmroth et al., J. Atmos. Sol.-Terr. Phys. 99, 41 (2013); A. Sandroos et al., Parallel Comput. 39, 306 (2013)]. For first global simulations of the magnetosphere, it is critical to verify and validate the model by established methods. Here, as part of the verification of Vlasiator, we characterize the low-β plasma wave modes described by this model and compare with the solution computed by the Waves in Homogeneous, Anisotropic Multicomponent Plasmas (WHAMP) code [K. Rönnmark, Kiruna Geophysical Institute Reports No. 179, 1982], using dispersion curves and surfaces produced with both programs. The match between the two fundamentally different approaches is excellent in the low-frequency, long wavelength range which is of interest in global magnetospheric simulations. The left-hand and right-hand polarized wave modes as well as the Bernstein modes in the Vlasiator simulations agree well with the WHAMP solutions. Vlasiator allows a direct investigation of the importance of the Hall term by including it in or excluding it from Ohm's law in simulations. This is illustrated showing examples of waves obtained using the ideal Ohm's law and Ohm's law including the Hall term. Our analysis emphasizes the role of the Hall term in Ohm's law in obtaining wave modes departing from ideal magnetohydrodynamics in the hybrid-Vlasov model.
Electron Spin Resonance (ESR) spectroscopy and Nuclear Magnetic Relaxation Dispersion (NMRD) experiments are reported for propylene glycol solutions of the nitroxide radical: 4-oxo-TEMPO-d{sub 16} containing {sup 15}N and {sup 14}N isotopes. The NMRD experiments refer to {sup 1}H spin-lattice relaxation measurements in a broad frequency range (10 kHz–20 MHz). A joint analysis of the ESR and NMRD data is performed. The ESR lineshapes give access to the nitrogen hyperfine tensor components and the rotational correlation time of the paramagnetic molecule. The NMRD data are interpreted in terms of the theory of paramagnetic relaxation enhancement in solutions of nitroxide radicals, recently presented by Kruk et al. [J. Chem. Phys. 138, 124506 (2013)]. The theory includes the effect of the electron spin relaxation on the {sup 1}H relaxation of the solvent. The {sup 1}H relaxation is caused by dipole-dipole interactions between the electron spin of the radical and the proton spins of the solvent molecules. These interactions are modulated by three dynamic processes: relative translational dynamics of the involved molecules, molecular rotation, and electron spin relaxation. The sensitivity to rotation originates from the non-central positions of the interacting spin in the molecules. The electronic relaxation is assumed to stem from the electron spin–nitrogen spin hyperfine coupling, modulated by rotation of the radical molecule. For the interpretation of the NMRD data, we use the nitrogen hyperfine coupling tensor obtained from ESR and fit the other relevant parameters. The consistency of the unified analysis of ESR and NMRD, evaluated by the agreement between the rotational correlation times obtained from ESR and NMRD, respectively, and the agreement of the translation diffusion coefficients with literature values obtained for pure propylene glycol, is demonstrated to be satisfactory.
The low repetition rates and possible shot-to-shot variations in laser-plasma studies place a high value on single-shot diagnostics. For example, white-beam scattering methods based on broadband backlighter x-ray sources are used to determine changes in the structure of laser-shocked crystalline materials by the evolution of coincidences of reciprocal lattice vectors and kinematically allowed momentum transfers. Here, we demonstrate that white-beam techniques can be extended to strongly disordered dense plasma and warm dense matter systems where reciprocal space is only weakly structured and spectroscopic detection is consequently needed to determine the static structure factor and thus, the ion-ion radial distribution function. Specifically, we report a photometric study of energy-dispersive x-ray diffraction (ED-XRD) for structural measurement of high energy density systems at large-scale laser facilities such as OMEGA and the National Ignition Facility. We find that structural information can be obtained in single-shot ED-XRD experiments using established backlighter and spectrometer technologies.
We extend the derivation of the time-dependent Hartree-Fock equation recently obtained by Benedikter et al. [“Mean-field evolution of fermionic systems,” Commun. Math. Phys. (to be published)] to fermions with a relativistic dispersion law. The main new ingredient is the propagation of semiclassical commutator bounds along the pseudo-relativistic Hartree-Fock evolution.