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At least 127 records · Page 7

Polar Rain Gradients and Field-Aligned Polar Cap Potentials

ACE SWEPAM measurements of solar wind field-aligned electrons have been compared with simultaneous measurements of polar rain electrons precipitating over the polar cap and detected by DMSP spacecraft. Such comparisons allow investigation of cross-polarcap gradients in the intensity of otherwise-steady polar rain. The generally good agreement of the distribution functions, f, from the two data sources confirms that direct entry of solar electrons along open field lines is indeed the cause of polar rain. The agreement between the data sets is typically best on the side of the polar cap with most intense polar rain but the DMSP f's in less intense regions can be brought into agreement with ACE measurements by shifting all energies by a fixed amounts that range from tens to several hundred eV. In most cases these shifts are positive which implies that field-aligned potentials of these amounts exist on polar cap field lines which tend to retard the entry of electrons and produce the observed gradients. These retarding potentials undoubtedly appear in order to prevent the entry of low-energy electrons and maintain charge quasi-neutrality that would otherwise be violated since most tailward flowing magnetosheath ions are unable to follow polar rain electrons down to the polar cap. In more limited regions near the boundary of the polar cap there is sometimes evidence for field-aligned potentials of the opposite sign that accelerate polar rain electrons. A solar electron burst is also studied and it is concluded that electrons from such bursts can enter the magnetotail and precipitate in the same manner as polar rain.

Fairfield, D. H.↗

Gamma-Ray Pulsar Light Curves in Offset Polar Cap Geometry

Recent studies have shown that gamma-ray pulsar light curves are very sensitive to the geometry of the pulsar magnetic field. Pulsar magnetic field geometries, such as the retarded vacuum dipole and force-free magnetospheres, used to model high-energy light curves have distorted polar caps that are offset from the magnetic axis in the direction opposite to rotation. Since this effect is due to the sweepback of field lines near the light cylinder, offset polar caps are a generic property of pulsar magnetospheres and their effects should be included in gamma-ray pulsar light curve modeling. In slot gap models (having two-pole caustic geometry), the offset polar caps cause a strong azimuthal asymmetry of the particle acceleration around the magnetic axis. We have studied the effect of the offset polar caps in both retarded vacuum dipole and force-free geometry on the model high-energy pulse profile~. We find that. corn pared to the profile:-; derived from :-;ymmetric caps, the flux in the pulse peaks, which are caustics formed along the trailing magnetic field lines. increases significantly relative to the off-peak emission. formed along leading field lines. The enhanced contrast produces greatly improved slot gap model fits to Fermi pulsar light curves like Vela, which show very little off-peak emIssIon.

Harding, Alice K.↗

Structure of the poxvirus decapping enzyme D9 reveals its mechanism of cap recognition and catalysis

Poxviruses encode decapping enzymes that remove the protective 5' cap from both host and viral mRNAs to commit transcripts for decay by the cellular exonuclease Xrn1. Decapping by these enzymes is critical for poxvirus pathogenicity by means of simultaneously suppressing host protein synthesis and limiting the accumulation of viral double-stranded RNA (dsRNA), a trigger for antiviral responses. Here we present a high-resolution structural view of the vaccinia virus decapping enzyme D9. This Nudix enzyme contains a domain organization different from other decapping enzymes in which a three-helix bundle is inserted into the catalytic Nudix domain. The 5' mRNA cap is positioned in a bipartite active site at the interface of the two domains. Specificity for the methylated guanosine cap is achieved by stacking between conserved aromatic residues in a manner similar to that observed in canonical cap-binding proteins VP39, eIF4E, and CBP20, and distinct from eukaryotic decapping enzyme Dcp2.

59 BASIC BIOLOGICAL SCIENCES↗

Combining Sub-nanometer Adhesion and Capping Layers for Thermally Stable Nanometer-Thick Au Films

Improving the thermal stability of Au thin films is critical if thermo-plasmonic applications such as heat-assisted magnetic recording are to become commercially viable. In this work, Al capping layers are deposited on M/Au films, where adhesion metal M = Ti or Ta, and are investigated for their utility in stabilizing Au thin films against dewetting. Therefore, contrary to previous investigations, it was found that thinner capping layers (0.5 nm) result in a greater stability than that conferred by thicker (1-5 nm) layers. Deposition of 0.5 nm of Al, which subsequently oxidizes when exposed to air, resulted in up to 10x stability enhancement. Similarly, capping with 0.5 nm Al resulted in less damping of the plasmonic response than with thicker capping layers. Finally, based on this work and previous work on metallic adhesion layers, optimally stable systems for thermo-plasmonic applications are proposed.

36 MATERIALS SCIENCE↗

Air Dispersion Modeling for the Idaho National Laboratory Permit to Construct P-2020.0045 Facility Emission Cap Revision Request

The U.S. Department of Energy Idaho Operations Office (DOE-ID) is seeking to modify permit to construct (PTC) P-2020.0045 issued to U S Dept. of Energy – Idaho National Laboratory (INL) on January 29, 2021 by the Idaho Department of Environmental Quality (DEQ). This PTC allowed the INL to become a synthetic minor source of air pollutants using a facility emission cap (FEC). Air dispersion modeling was performed as part of the permit revision application process to demonstrate that the modifications will comply with the National Ambient Air Quality Standards (NAAQS). This report documents the modeling methodology and complete results for the air dispersion impact analysis and is supplied as an appendix to the permit revision request, Idaho National Laboratory Permit to Construct P-2020.0045 (INL 2025). All criteria air pollutants (CAPs) regulated under Section 109 of the Clean Air Act were modeled with the exception of lead (Pb) and ozone which are not required to be modeled by DEQ. Consistent with the original permit application, modeling was not performed for toxic air pollutants (TAPs) as uncontrolled emissions did not exceed screening emission levels for carcinogenic and non-carcinogenic TAPs. Acceptable model design values (concentrations) for each CAP and averaging period were summed with average background concentrations and compared to NAAQS. The results demonstrate the impacts of requested FEC limits for CAPs are less than applicable standards and demonstrate emissions up to FEC limits will not cause a violation of ambient air quality standards.

54 ENVIRONMENTAL SCIENCES↗

Flexible‐rate optoelectronic wireless transmission system at 101 GHz using multiband CAP‐PAM modulation and envelope detection

Abstract In this paper, we have experimentally demonstrated the first flexible‐rate optoelectronic terahertz wireless transmission system at 101 GHz based on multiband CAP‐PAM modulation and cost‐efficient envelope detection. Instead of traditional M‐QAM mapping, PAM‐N mapping is used in CAP modulation with low‐computational complexity. The system performances and optimal capacity in both single‐band case and multiband case are intensively investigated. The results show that the highest data rate for single‐band system is 13.35 Gbit/s with CAP‐PAM‐5 modulation, while the optimum aggregate transmission line rate of 8.49 Gbit/s can be obtained with 4‐sub‐bands CAP‐PAM‐{5,3,2,2} modulation under 7% FEC limit of 3.8 × 10 −3 for four‐user access.

Zhang, Jiao↗

Investigations on the electronic properties and effect of chitosan capping on the structural and optical properties of zinc aluminate quantum dots

Quantum confined uncapped and chitosan capped nanoparticles of ZnAl 2 O 4 synthesized by microwave-assisted sol–gel method were investigated by structural analysis and optical techniques. X-ray diffraction studies confirmed the formation of cubic spinels with crystallite size 4.5 nm and 3.4 nm, respectively for uncapped and chitosan capped ZnAl 2 O 4 nanoparticles. Chitosan capping produced a blue shift in bandgap energy (3.84 to 3.94 eV) agreeing with size effects according to the Brus equation. A blue shift in emission peak and enhancement in photoluminescence intensity was also observed upon chitosan capping. The electronic band structure and the density of states of the bulk spinel were also calculated using density functional theory. The effective masses of electrons and holes estimated based on the band structure were used to extract the excitonic Bohr radius.

36 MATERIALS SCIENCE↗

Droplet Evaporation on Hot Micro-Structured Superhydrophobic Surfaces: Analysis of Evaporation from Droplet Cap and Base Surfaces

In this study, evaporation of sessile water droplets on hot micro-structured superhydrophobic surfaces is experimentally and theoretically investigated. Water droplets of 4 µL are placed on micro-pillared silicon substrates with the substrate temperature heated up to 120°C. A comprehensive thermal circuit model is developed to analyze the effects of substrate roughness and substrate temperature on the sessile droplet evaporation. For the first time, two components of heat and mass transfer, i.e., one from the droplet cap surface and the other from the droplet base surface, during droplet evaporation are distinguished and systematically studied. As such, the evaporation heat transfer rates from both the droplet cap surface and the interstitial liquid-vapor interface between micropillars at the droplet base are calculated in various conditions. For droplet evaporation on the heated substrates in the range of 40°C – 80°C, the predicted droplet cap temperature matches well with the experimental results. Furthermore, during the constant contact radius mode of droplet evaporation, the decrease of evaporation rate from the droplet base contributes most to the continuously decreasing overall evaporation heat transfer rate, whereas the decrease of evaporation rate from the droplet cap surface is dominant in the constant contact angle mode. The influence of internal fluid flow is considered for droplet evaporation on substrates heated above 100°C, and an effective thermal conductivity is adopted as a correction factor to account for the effect of convection heat transfer inside the droplet. Temperature differences between the droplet base and the substrate base are estimated to be about 2°C, 5°C, 8°C, 13°C and 18°C for droplet evaporation on substrates heated at 40°C, 60°C, 80°C, 100°C, and 120°C, respectively, elucidating the delayed or depressed boiling of water droplets on a heated rough surface due to evaporative cooling.

42 ENGINEERING↗

Effect of cold-cap-bottom shear stress on primary foam stability

Here, we analyze the heat transfer between the melt pool and the layer of reacting materials called cold cap, which is the determining factor for the glass production rate in Joule-heated air-bubbled nuclear waste glass melters. We consider the effects of bubbling rate, melt viscosity, melt thermal conductivity, conversion kinetics, and shear rate at the cold-cap bottom, and develop simple relationships for the cold-cap bottom temperature and glass production rate. We show that the melt convection enhances the heat transfer to the cold cap by suppressing the thermal boundary layer and primary foam, while the conversion kinetics opposes these effects. Additionally, we mention how dissolving silica particles affects the primary foam stability and discuss the limitations of the presented approach for vigorously foaming feeds.

36 MATERIALS SCIENCE↗

Formation of Bimetallic Nanoparticles via Exsolution Using a Reducible Metal Oxide Capping Layer

Bimetallic nanoparticles are promising catalysts that can improve performance in heterogeneous catalysis and solid-state electrochemistry. Exsolution is a useful method for forming such nanoparticles; however, it is limited by the elements present within the host oxide lattice. Here, in this work, we develop and demonstrate a strategy to form bimetallic particles from La 0.5 Sr 0.5 Ti 0.94 Ni 0.06 O 3 (LSTN) exsolution and using a reducible SnO 2 capping layer, expanding the range of elements available for bimetallic nanoparticle formation. Using this capping layer strategy, we formed nickel–tin (Ni 0 –Sn 0 ) bimetallic nanoparticles via exsolution. We used in situ near-ambient pressure X-ray photoelectron spectroscopy to monitor surface chemical changes during exsolution, showing that first, SnO 2 volatilized. This SnO 2 loss exposed the perovskite surface of LSTN to reducing conditions, which induced Ni exsolution, and compounded with SnO 2 reduction led to the formation of bimetallic Ni 0 –Sn 0 particles. To evaluate the associated microstructural evolution, we measured grazing incidence small-angle X-ray scattering (GISAXS), which confirmed the loss of the SnO 2 capping layer, and scattering simulations suggested the formation of bimetallic particles. We confirmed the bimetallic nanoparticle composition and morphology by Auger spectroscopy and scanning transmission electron microscopy. The resulting bimetallic nanoparticles were smaller and more thermally stable than the monometallic Ni counterparts on LSTN. This capping layer and exsolution approach allow synthesizing multimetallic nanoparticles and can be applied to other reducible metal oxides and perovskite hosts, broadening the compositional space for advanced catalytic materials.

36 MATERIALS SCIENCE↗

Optical properties of a diamond NV color center from capped embedded multiconfigurational correlated wavefunction theory

Diamond defects are among the most promising qubits. Modeling their properties through accurate quantum mechanical simulations can further their development into robust units of information. We use the recently developed capped density functional embedding theory (capped-DFET) with the multiconfigurational n-electron valence second-order perturbation theory to characterize the electronic excitation energies for different spin manifolds of the well-characterized negatively charged substitutional N defect adjacent to a vacancy (V C ) in diamond (N C V C − ). We successfully reproduce vertical excitation energies for both triplet and singlet states of N C V C − with errors < 0.1 eV. Unlike other embedding methods, capped-DFET exhibits robust predictions that are approximately independent of the embedded cluster size: it only requires a cluster to contain the defect atoms and their nearest neighbors (as small as a 40-atom capped cluster). Furthermore, our method is free from slowly converging Coulomb interactions between charged defects, and thus also only weakly dependent on supercell size.

Chemistry↗

Adsorption of ethylenediamine on Cu surfaces: attributes of a successful capping molecule using first-principles calculations

The shape-controlled synthesis of Cu nanocrystals can benefit a wide range of applications, though challenges exist in achieving high and selective yields to a particular shape. Capping agents play a pivotal role in controlling shape, but their exact role remains ambiguous. In this study, the adsorption of ethylenediamine (EDA) on Cu(100) and Cu(111) was investigated with quantum density functional theory (DFT) to reveal the complex roles of EDA in promoting penta-twinned Cu nanowire growth. We find EDA has stronger binding on Cu(100) than on Cu(111), which agrees the general expectation that penta-twinned Cu nanowires express facets with stronger capping-molecule binding. Despite this stronger binding, ab initio thermodynamics reveals the surface energy of EDA-covered Cu(111) is lower than that EDA-covered Cu(100) at all solution-phase EDA chemical potentials, so there is no thermodynamic driving force for penta-twinned nanowires. We also investigated the capability of EDA to protect Cu surfaces from oxidation in water by quantifying energy barriers for a water molecule to diffuse through EDA layers on Cu(100) and Cu(111). The energy barrier on Cu(100) is significantly lower, which supports observations of faster oxidation of Cu(100) in electrochemical experiments. Thus, we elucidate another possible function of a capping agent – to enable selective oxidation of crystal facets. This finding adds to the general understanding of successful attributes of capping agents for shape-selective nanocrystal growth.

36 MATERIALS SCIENCE↗

Photoinduced electron transfer across the polymer-capped CsPbBr 3 interface in a polar medium

In-situ polymer capping of cesium lead bromide (CsPbBr 3 ) nanocrystals with polymethyl acrylate is an effective approach to improve the colloidal stability in the polar medium and thus extends their use in photocatalysis. The photoinduced electron transfer properties of polymethyl acrylate (PMA)-capped CsPbBr 3 nanocrystals have been probed using surface-bound viologen molecules with different alkyl chains as electron acceptors. The apparent association constant (K app ) obtained for the binding of viologen molecules with PMA-capped CsPbBr 3 was 2.3 × 10 7 M −1 , which is an order of magnitude greater than that obtained with oleic acid/oleylamine-capped CsPbBr 3 . Although the length of the alkyl chain of the viologen molecule did not show any impact on the electron transfer rate constant, it influenced the charge separation efficiency and net electron transfer quantum yield. Further, viologen moieties with a shorter alkyl chain length exhibited a charge separation efficiency of 72% compared with 50% for the longer chain alkyl chain length viologens. Implications of polymer-capped CsPbBr 3 perovskite nanocrystals for carrying out photocatalytic reduction in the polar medium are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Obtaining bulk-like correlated oxide surfaces with protective caps

Functional oxides exhibit a diverse range of correlated electron phenomena, some of which are highly attractive for novel electronic, magnetic, and optical devices. Despite decades of advancement of our fundamental understanding of these materials, they consistently fall short of realizing their promise in functional devices. We identify a significant bottleneck toward device realization to be surface overoxidation. Protective caps can effectively prevent overoxidation, but their interfaces with functional oxides are not well understood. These interfaces are critical for effectively using functional oxides in field-effect devices, where “the interface is the device.” This work addresses the chemistry and physics of the interface between protective caps and the correlated metal SrVO3, a model functional oxide. Our comparison of five different cap materials reveals effective protection and similar SrVO3 surface chemistry in all cases. Systematic comparisons of surface and bulk-sensitive photoelectron spectra reveal that negligible interface redox takes place, elucidating the cap-SrVO3 interface chemistry. This work demonstrates a robust and simple solution to the surface overoxidation problem in vanadates, paving the way toward effectively using these materials in field-effect devices. Our conclusions are general and can be applied to numerous other systems, thus moving oxide electronics closer to the realization of functional devices.

Cohen, Amit (ORCID:0009000276477510)↗

Humidified single-scattering albedometer (H-CAPS-PM SSA ): Design, data analysis, and validation

In this work, we report the development and validation of a new humidified aerosol single-scattering albedometer to quantify the effects of water uptake on submicrometer particle optical properties. The instrument simultaneously measures in situ aerosol light extinction ( σ ep ) and scattering ( σ sp ) using a cavity-attenuated phase shift-single scattering albedo particulate matter (PM) monitor (CAPS-PM SSA , Aerodyne Research, Inc., Billerica, MA, USA). It retrieves by difference aerosol light absorption ( σ ap ) and directly quantifies aerosol single-scattering albedo (SSA), the aerosol “brightness.” We custom built a relative humidity (RH) control system using a water vapor-permeable membrane humidifier and coupled it to the CAPS-PM SSA to enable humidified aerosol observations. Our humidified instrument (H-CAPS-PM SSA ) overcomes problems with noise caused by mirror purge-flow humidification, heating, and characterizing cell RH. Careful angular truncation corrections in scattering, particularly for larger particles, were combined with empirical observations. Results show that the optimal operational size to be D p < 400 nm. The H-CAPS-PM SSA was evaluated with several pure single-component aerosols including ammonium sulfate ((NH 4 ) 2 SO 4 ), absorbing nigrosin, and levoglucosan, an organic biomass smoke tracer. The measured σ ep , σ sp , and the derived optical hygroscopicity parameter ( κ ) for size-selected ammonium sulfate are in good agreement with literature values. For dry size-selected nigrosin in the 100 < D p < 400 nm range, SSA values increased from ~0.3 to 0.65 with increasing D p . The enhancement in nigrosin σ ap at RH = 80% was a factor of 1.05–1.20 relative to dry conditions, with the larger particles showing greater enhancement. SSA increased with RH with the largest fractional enhancement measured for the smallest particles. For polydisperse levoglucosan, we measured an optical κ of 0.26 for both light extinction and scattering and negligible absorption. Our new instrument enables reliable observations of the effects of ambient humidity on mixed aerosol optical properties, particularly for light-absorbing aerosols whose climate forcing is uncertain due to measurement gaps.

54 ENVIRONMENTAL SCIENCES↗

Concomitant appearance of conductivity and superconductivity in (111) LaAlO 3 /SrTiO 3 interface with metal capping

In epitaxial polar-oxide interfaces, conductivity sets in beyond a finite number of monolayers (ML). This threshold for conductivity is explained by accumulating sufficient electric potential to initiate charge transfer to the interface. Here we experimentally and theoretically study the LaAlO 3 /SrTiO 3 (111) interface where a critical thickness $t_c$ of nine epitaxial LaAlO 3 ML is required to turn the interface from insulating to conducting and even superconducting. In this work, we show that $t_c$ decreases to 3 ML when depositing a cobalt overlayer (capping) and 6 ML for platinum capping. The latter result contrasts with the (001) interface, where platinum capping increases $t_c$ beyond the bare interface. Our density functional theory calculations with a Hubbard U term confirm the observed threshold for conductivity for the bare and the metal-capped interfaces. Interestingly, conductivity appears concomitantly with superconductivity for metal/LaAlO 3 /SrTiO 3 (111) interfaces, in contrast with the metal/LaAlO 3 /SrTiO 3 (001) interfaces where conductivity appears without superconductivity. We attribute this dissimilarity to the different orbital polarization of eg for the (111) versus dxy for the (001) interface.

36 MATERIALS SCIENCE↗

Effect of capping layers on the near-surface region of SrVO 3 films

Surfaces of correlated-electron oxides are of significant interest both from fundamental and applied perspectives. Many such oxides feature a near-surface region (NSR) which differs from the bulk’s properties. The NSR can significantly affect the interpretation of the material’s electronic structure, especially for those in thin film form, and have detrimental effects for applications such as field effect devices and catalysts. In this work we study the changes in the composition and electronic structure of the NSR of SrVO 3 (SVO) thin films. We employ x-ray photoelectron spectroscopy (XPS) and compare TiOx-capped SVO films to identical uncapped films that were exposed to ambient conditions. The significant over-oxidation of the SVO surface in the bare film, illustrated by a primary V 5+ component, is prevented by the TiO x layer in the capped film. Furthermore, the capped film further exhibits a decrease in Sr surface phases. These results demonstrate the importance and potential of such capping layers in preserving the bulk properties of correlated oxides in their NSR, enabling more accurate probes for their underlying physics and offering a route for their integration into devices.

36 MATERIALS SCIENCE↗