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At least 631 records · Page 35

Simulation of a Periodic Jet in a Crossflow with a RANS Solver Using an Unstructured Grid

A second-order unstructured-grid code, developed and used primarily for steady aerodynamic simulations, is applied to the synthetic jet in a cross flow. The code, FUN3D, is a vertex-centered finite-volume method originally developed by Anderson[1, 2], and is currently supported by members of the Fast Adaptive Aerospace Tools team at NASA Langley. Used primarily for design[3] and analysis[4] of steady aerodynamic configurations, FUN3D incorporates a discrete adjoint capability, and supports parallel computations using MPI. A detailed description of the FUN3D code can be found in the references given above. The code is under continuous development and contains a variety of flux splitting algorithms for the inviscid terms, two methods for computing gradients, several turbulence models, and several solution methodologies; all in varying states of development. Only the most robust and reliable components, based on experiences with steady aerodynamic simulations, were employed in this work. As applied in this work, FUN3D solves the Reynolds averaged Navier-Stokes equations using the one equation turbulence model of Spalart and Allmaras[5]. The spatial discretization is formed on unstructured meshes using a vertex-centered approach. The inviscid terms are evaluated by a flux-difference splitting formulation using least-squares reconstruction and Roe-type approximate Riemann fluxes. Green-Gauss gradient evaluations are used for viscous and turbulence modeling terms. The discrete spatial operator is combined with a backward time operator which is then solved iteratively using point or line Gauss-Seidel and local time stepping in a pseudo time. For steady flows, the physical time step is set to infinity and the pseudo time step is ramped up with the iteration count. A second-order backward in time operator is used for time accurate flows with 20 to 50 steps in the pseudo time applied at each physical time step. For this effort, FUN3D was modified to support spatially varying boundary and initial conditions, and unsteady boundary conditions. Also, a specialized in/out flow boundary condition was implemented to model the action of the diaphragm. This boundary condition is described below in more detail. The grids were generated using the internally developed codes GridEX[6] for meshing the surfaces and inviscid regions of the domain, and for CAD access; and MesherX[7] for meshing the viscous regions. Grid spacing in on the surfaces and in the inviscid regions are indirectly controlled by specifying sources. The viscous layers are generated using an advancing layer technique. MeshersX allows the user to control the spatial variation of the first step off the surface, growth rates, and the termination criterion by providing small problem dependent subroutines.

Atkins, H. L.↗

Flight Crew Workload, Acceptability, and Performance When Using Data Comm in a High-Density Terminal Area Simulation

This document describes a collaborative FAA/NASA experiment using 22 commercial airline pilots to determine the effect of using Data Comm to issue messages during busy, terminal area operations. Four conditions were defined that span current day to future flight deck equipage: Voice communication only, Data Comm only, Data Comm with Moving Map Display, and Data Comm with Moving Map displaying taxi route. Each condition was used in an arrival and a departure scenario at Boston Logan Airport. Of particular interest was the flight crew response to D-TAXI, the use of Data Comm by Air Traffic Control (ATC) to send taxi instructions. Quantitative data was collected on subject reaction time, flight technical error, operational errors, and eye tracking information. Questionnaires collected subjective feedback on workload, situation awareness, and acceptability to the flight crew for using Data Comm in a busy terminal area. Results showed that 95% of the Data Comm messages were responded to by the flight crew within one minute and 97% of the messages within two minutes. However, post experiment debrief comments revealed almost unanimous consensus that two minutes was a reasonable expectation for crew response. Flight crews reported that Expected D-TAXI messages were useful, and employment of these messages acceptable at all altitude bands evaluated during arrival scenarios. Results also indicate that the use of Data Comm for all evaluated message types in the terminal area was acceptable during surface operations, and during arrivals at any altitude above the Final Approach Fix, in terms of response time, workload, situation awareness, and flight technical performance. The flight crew reported the use of Data Comm as implemented in this experiment as unacceptable in two instances: in clearances to cross an active runway, and D-TAXI messages between the Final Approach Fix and 80 knots during landing roll. Critical cockpit tasks and the urgency of out-the window scan made the additional head down time to respond to Data Comm messages undesirable during these events. However, most crews also stated that Data Comm messages without an accompanying audio chime and no expectation of an immediate response could be acceptable even during these events.

Norman, R. Michael↗

Fundamental Interactions of Bimetallic Cu x Pd y ( x + y = 4) Clusters Supported on the α-WC(0001) Surface and Their Performance for CO 2 Adsorption and Dissociation

The tungsten carbide α-WC(0001) surface, an active system for the activation of H 2 and important hydrogenation processes involving unsaturated hydrocarbons, can serve as a support of bimetallic clusters to produce materials with unique catalytic properties, opening routes for a wide range of technical applications. In particular, Cu x Pd y clusters are of particular interest because they combine metals with different properties. A stochastic method was applied to obtain the geometry of Cu x Pd y (x + y = 4) bare clusters, evaluating thousands of possibilities to obtain stable structures, yielding one isomer for Cu 4 , Cu 2 Pd 2 , Cu 1 Pd 3 , and Pd 4 and two isomers for Cu 3 Pd 1 . These clusters were supported on C and W terminations of the tungsten carbide (0001) surface, exploring all of the binding possibilities. The adsorption energies on the C and W terminations are in the ranges from −2.51 to −3.02 eV and from −2.26 to −3.30 eV, respectively. The strongest and weakest binding was seen for monometallic Cu 4 and Pd 4 clusters on both C and W terminations, while the Cu-Pd bimetallics have intermediate adsorption energies but lack a clear trend in terms of composition. The location of Cu x Pd y clusters over the (0001) surface induces a decrease in the work function relative to the pristine surface, while the cluster-surface Bader charge transfer and variations in the partial density of states point to changes in the electronic structure of the carbide atoms upon binding of the metallic clusters. The d-band center of the Cu x Pd y deposited on WC(0001) indicates an intermediate reactivity among Cu(111) and Pd(111) surfaces, modulating the reactivity with small numbers of Cu and Pd atoms, i.e., atom economy in catalyst design. The likelihood of existence of the most stable Cu x Pd y (x + y = 4) clusters in the temperature range of 298-400 K is 100%. The composite Cu x Pd y /α-WC(0001) (x + y = 4), is a nontrivial system since 22 isomers are needed to completely describe its structural properties. Among the isomers, seven structures are necessary to represent Cu 3 Pd 1 /α-WC(0001), five for Pd 4 /α-WC(0001), two for Cu 4 /α-WC(0001), and four for Cu 2 Pd 2 /α-WC(0001) and Cu 1 Pd 3 /α-WC(0001). The large number of cluster isomers supported on the tungsten carbide surface opens the door for several applications in the heterogeneous catalysis of the Cu x Pd y /α-WC(0001) composite, with the possibility of modulating the geometric, electronic, and chemical properties according to a desired application. Test studies for the adsorption of CO 2 indicate that the Cu x Pd y /α-WC(0001) composites are highly active for the adsorption and decomposition of the molecule, with bimetallic and admetal-carbide interactions playing a key role in the binding performance. In conclusion, this high activity indicates that these systems should be useful as catalysts for the conversion of CO 2 to oxygenates or light alkanes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dusty plasma sheath-like structure in the region of lunar terminator

The main properties of the dusty plasma layer near the surface over the illuminated and dark parts of the Moon are described. They are used to realize dusty plasma behaviour and to determine electric fields over the terminator region. Possibility of the existence of a dusty plasma sheath-like structure in the region of lunar terminator is shown. The electric fields excited in the terminator region are demonstrated to be on the order of 300 V/m. These electric fields can result in rise of dust particles of the size of 2–3 μm up to an altitude of about 30 cm over the lunar surface that explains the effect of “horizon glow” observed at the terminator by Surveyor lunar lander.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Noncollinear Relativistic DFT + U Calculations of Actinide Dioxide Surfaces

A noncollinear relativistic PBEsol + U study of low-index actinide dioxides (AnO 2 , An = U, Np, or Pu) surfaces has been conducted. The importance of magnetic vector reorientation relative to the plane of the surface is highlighted; this has often been ignored in collinear nonrelativistic models. The use of noncollinear relativistic methods is key to the design of reliable computational models. The ionic relaxation of each surface is shown to be confined to the first three monolayers, and we have explored the configurations of the terminal oxygen ions on the reconstructed (001) surface. The reconstructed (001) surfaces are ordered as (001)αβ < (001)α < (001)β in terms of energetics. Electrostatic potential isosurface and scanning tunneling microscopy images have also been calculated. In conclusion, by considering the energetics of the low-index AnO 2 surfaces, an octahedral Wulff crystal morphology has been calculated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Surface Transfer Doping in MoO 3– x /Hydrogenated Diamond Heterostructure

Surface transfer doping is proposed to be a potential solution for doping diamond, which is hard to dope for applications in high-power electronics. While MoO 3 is found to be an effective surface electron acceptor for hydrogen-terminated diamond with a negative electron affinity, the effects of commonly existing oxygen vacancies remain elusive. We have performed reactive molecular dynamics simulations to study the deposition of MoO 3–x on a hydrogenated diamond (111) surface and used first-principles calculations based on density functional theory to investigate the electronic structures and charge transfer mechanisms. We find that MoO 3–x is an effective surface electron acceptor and the spatial extent of doped holes in hydrogenated diamond is extended, promoting excellent transport properties. Charge transfer is found to monotonically decrease with the level of oxygen vacancy, providing guidance for engineering of the surface transfer doping process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Swelling-Assisted Sequential Infiltration Synthesis of Nanoporous ZnO Films with Highly Accessible Pores and Their Sensing Potential for Ethanol

Here, we report a swelling-assisted sequential infiltration synthesis (SIS) approach for the design of highly porous zinc oxide (ZnO) films by infiltration of block copolymer templates such as polystyrene-block- polyvinyl pyridine with inorganic precursors followed by UV ozone-assisted removal of the polymer template. We show that porous ZnO coatings with the thickness in the range between 140 and 420 nm can be obtained using only five cycles of SIS. The pores in ZnO fabricated via swelling-assisted SIS are highly accessible, and up to 98% of pores are available for solvent penetration. The XPS data indicate that the surface of nanoporous ZnO films is terminated with -OH groups. Density functional theory calculations show a lower energy barrier for ethanol-induced release of the oxygen restricted depletion layer in the case of the presence of -OH groups at the ZnO surface, and hence, it can lead to higher sensitivity in sensing of ethanol. We monitored the response of ZnO porous coatings with different thicknesses and porosities to ethanol vapors using combined mass-based and chemiresistive approaches at room temperature and 90 °C. The porous ZnO conformal coatings reveal a promising sensitivity toward detection of ethanol at low temperatures. In conclusion our results suggest the excellent potential of the SIS approach for the design of conformal ZnO coatings with controlled porosity, thickness, and composition that can be adapted for sensing applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Exploring New Diamond Surfaces with Precision Chemistry and Quantum Spectroscopy

Point defects in diamond known as color centers are a promising platform for quantum sensing. As atom-like systems, they can exhibit excellent spin coherence and can be manipulated with light. As solid-state defects, they can be produced at high densities and be incorporated into scalable devices. Diamond is a uniquely excellent host; it has a large band gap, can be synthesized with sub-ppb impurity concentrations, and can be isotopically purified to eliminate magnetic noise from nuclear spins. Specifically, the nitrogen vacancy (NV) center has been demonstrated to be a highly sensitive, non-invasive magnetic probe capable of resolving the magnetic field of a single electron spin with nanometer spatial resolution. However, the development of NV centers and other color centers in diamond as a quantum platform crucially relies on developing methods to functionalize and process diamond surfaces. Diamond is the hardest material, making polishing and processing challenging, and diamond surfaces are inert and sterically hindered, making them notoriously difficult to chemically terminate and functionalize. Our approach is to discover new surface chemistries for diamond by combining multimodal surface spectroscopy with NV-based quantum spectroscopy to carefully characterize the diamond surface. We have developed a suite of techniques for characterizing the diamond surface using rapid tools for reaction screening and detailed surface spectroscopy tools for definitive identification of the surface bonding.

36 MATERIALS SCIENCE↗

Probing the External Surface Chemistry of Imine-Based Covalent Organic Frameworks Using Reactive Organic Dyes

The external surfaces of covalent organic frameworks (COFs) are presumably composed of free terminal functional groups from their constituent monomers. These terminal groups have been utilized to immobilize molecules onto COF surfaces for a variety of studies and potential applications. Despite the utility of these latent functional groups for COF functionalization and composite formation, the surface chemistry of the COFs has not been quantitatively investigated and is not well understood. In this work, fluorescent organic dyes bearing reactive amine and aldehyde functional groups are used to probe the surface chemistry of representative two-dimensional (2D) imine-based COFs. Furthermore, systematic dye binding and displacement experiments provide new insights into the characteristics of COF surfaces and the reactivity of different molecules with the surface groups on the COF crystallites.

COFs↗

Spontaneous dynamical disordering of borophenes in MgB2 and related metal borides

Abstract Layered boron compounds have attracted significant interest in applications from energy storage to electronic materials to device applications, owing in part to a diversity of surface properties tied to specific arrangements of boron atoms. Here we report the energy landscape for surface atomic configurations of MgB 2 by combining first-principles calculations, global optimization, material synthesis and characterization. We demonstrate that contrary to previous assumptions, multiple disordered reconstructions are thermodynamically preferred and kinetically accessible within exposed B surfaces in MgB 2 and other layered metal diborides at low boron chemical potentials. Such a dynamic environment and intrinsic disordering of the B surface atoms present new opportunities to realize a diverse set of 2D boron structures. We validated the predicted surface disorder by characterizing exfoliated boron-terminated MgB 2 nanosheets. We further discuss application-relevant implications, with a particular view towards understanding the impact of boron surface heterogeneity on hydrogen storage performance.

36 MATERIALS SCIENCE↗

Atomic-scale investigations of Ti 3 C 2 T x MXene surfaces

The family of two-dimensional (2D) carbides and/or nitrides, also known as MXenes, has generated great excitement within the scientific community and has been proposed for a wide variety of applications since its discovery. Despite this attention, there have been only limited studies of the atomically resolved local electronic and physical structure of MXene surfaces strongly affecting the physicochemical properties of these materials. Here, in this study, we report local structural, spectroscopic, and chemical investigations of the surfaces of Ti 3 C 2 T x flakes using scanning tunneling microscopy and spectroscopy, closely coupled to theoretical studies. Terminal groups are visualized and characterized, along with surface TiO 2 clusters formed upon exposure to air. Fundamental insight into the local electronic and chemical properties associated with different terminal groups on MXenes and their oxidation products is presented.

36 MATERIALS SCIENCE↗

Searching for topological Fermi arcs via quasiparticle interference on a type-II Weyl semimetal MoTe2

Abstract Weyl semimetals display a novel topological phase of matter where the Weyl nodes emerge in pairs of opposite chirality and can be seen as either a source or a sink of Berry curvature. The exotic effects in Weyl semimetals, such as surface Fermi arcs and the chiral anomaly, make them a new playground for exploring novel functionalities. Further exploiting their potential applications requires clear understanding of their topological electronic properties. Here we report a Fourier transform scanning tunneling spectroscopy (FT-STS) study on a type-II Weyl semimetal candidate MoTe 2 whose Weyl points are predicated to be located above Fermi level. Although its electronic structure below the Fermi level has been identified by angle resolved photo emission spectroscopy, by comparing our experimental data with first-principles calculations, we are able to identify the origins of multiple scattering channels both below and above Fermi level. Our calculations also show the existence of both trivial and topological arc-like states above the Fermi energy. In the FT-STS experiments, we have observed strong signals from intra-arc scatterings as well as from the scattering between the arc-like surface states and the projected bulk states. A detailed comparison between our experimental observations and calculated results reveals the trivial and non-trivial scattering channels are difficult to distinguish in this compound. Interestingly, we find that the broken inversion symmetry changes the terminating states on the two inequivalent surfaces, which in turn changes the relative strength of the scattering channels observed in the FT-STS images on the two surfaces.

Iaia, Davide↗

ERAP1 enzyme-mediated trimming and structural analyses of MHC I–bound precursor peptides yield novel insights into antigen processing and presentation

Endoplasmic reticulum aminopeptidase 1 (ERAP1) and ERAP2 critically shape the major histocompatibility complex I (MHC I) immunopeptidome. The ERAPs remove N-terminal residues from antigenic precursor peptides and generate optimal-length peptides (i.e. 8–10-mers) to fit into the MHC class I groove. It is therefore intriguing that MHC class I molecules can present N-terminally extended peptides on the cell surface that can elicit CD8+ T-cell responses. This observation likely reflects gaps in our understanding of how antigens are processed by the ERAP enzymes. To better understand ERAPs' function in antigen processing, here we generated a nested set of N-terminally extended 10–20-mer peptides (RA)nAAKKKYCL covalently bound to the human leukocyte antigen (HLA)-B*0801. We used X-ray crystallography, thermostability assessments, and an ERAP1-trimming assay to characterize these complexes. The X-ray structures determined at 1.40–1.65 Å resolutions revealed that the residue extensions (RA)n unexpectedly protrude out of the A pocket of HLA-B*0801, whereas the AAKKKYCL core of all peptides adopts similar, bound conformations. HLA-B*0801 residue 62 was critical to open the A pocket. We also show that HLA-B*0801 and antigenic precursor peptides form stable complexes. Finally, ERAP1-mediated trimming of the MHC I–bound peptides required a minimal length of 14 amino acids. We propose a mechanistic model explaining how ERAP1-mediated trimming of MHC I–bound peptides in cells can generate peptides of canonical as well as noncanonical lengths that still serve as stable MHC I ligands. Our results provide a framework to better understand how the ERAP enzymes influence the MHC I immunopeptidome.

59 BASIC BIOLOGICAL SCIENCES↗

Plasma Observations During the Mars Atmospheric Plume Event of March-April 2012

We present initial analysis and conclusions from plasma observations made during the reported Mars Dust plume event of March - April 2012. During this period, multiple independent amateur observers detected a localized, high-altitude plume over the Martian dawn terminator [Sanchez-Lavega7 et al., Nature, 2015, doi:10.1038nature14162], the origin of which remains to be explained. We report on in-situ measurements of ionospheric plasma density and solar wind parameters throughout this interval made by Mars Express, obtained over the surface region, but at the opposing terminator. We tentatively conclude that the formation and/or transport of this plume to the altitudes where it was observed could be due in part the result of a large interplanetary coronal mass ejection (ICME) encountering the Martian system. Interestingly, we note that a similar plume detection in May 1997 may also have been associated with a large ICME impact at Mars.

Plumes↗

Expression, purification, crystallization and structure determination of the N terminal domain of Fhb, a factor H binding protein from Streptococcus suis

Fhb is a surface virulence protein from Streptococcus suis, which could aid bacterial evasion of host innate immune defense by recruiting complement regulator factor H to inactivate C3b deposited on bacterial surface in blood. Here we successfully expressed and purified the N terminal domain of Fhb (N-Fhb) and obtained crystals of the N-Fhb by sitting-drop vapor diffusion method with a resolution of 1.50 Å. The crystals belong to space group C2 with unit cell parameters a = 127.1 Å, b = 77.3 Å, c = 131.6 Å, α = 90°, β = 115.9°, γ = 90°. The structure of N-Fhb was determined by SAD method and the core structure of N-Fhb is a β sandwich. We speculated that binding of Fhb to human factor H may be mainly mediated by surface amino acids with negative charges. - Highlights: • We expressed N-Fhb as the soluble protein in Escherichia coli. • Crystals of N-Fhb were grown by sitting drop vapor diffusion method. • Crystals of N-Fhb could diffracted to 1.5 Å. • The core structure of N-Fhb was a β sandwich. • A part of the surface of N-Fhb was rich with negative charges.

60 APPLIED LIFE SCIENCES↗

Unusual Electrochemical Activity of Thin SiO 2 Layers Leads to Instability of Molecular Attachment in Hybrid Photoelectrodes

Hybrid photoelectrodes, comprised of a light-absorbing semiconductor and a surface-integrated molecular catalyst, are attractive for applications in artificial photosynthesis, since they combine the advantages of broadband semiconductor light absorption with the selectivity of molecular catalysis. A widely used class of hybrid photoelectrodes is based on Si substrates passivated by a thin (<3 nm) layer of silicon oxide, which is commonly prepared by controlled chemical or thermal oxidation, resulting in chemical oxide (ChO) or thermal oxide (ThO) layers, respectively. However, the electrochemical stability of these oxide layers, and the chemical stability of the semiconductor-molecule assembly in hybrid photoelectrodes, are not well understood, with evidence that covalently-bound molecules detach from the oxide surface upon application of cathodic bias. We have examined the intrinsic electrochemical reactivity of silicon oxide layers and how it affects the attachment of molecular monolayers. We determined that the surface of Si|ThO is primarily terminated with hydrophobic siloxane moieties, whereas that of Si|ChO contains a higher concentration of hydrophilic silanol groups. Initial high current densities for Si|ChO under applied bias up to -2 V vs. Ag/AgCl, decrease during repeated cyclic voltammetry scans, due to the consumption of surface-bound water. This is manifested by a reversible wave around -0.5 V in CH 3 CN solution, and a similar pH-dependent wave in water, revealing the pK a of the silanol groups to be ~4. Here, our combined observations support the electrochemically-induced dehydration of the SiO 2 surface, which converts silanol groups to siloxanes and proceeds through an H-atom intermediate that is most likely stabilized by pentavalent Si. We propose that similar reactivity is responsible for the electrochemical loss of alkylsiloxane-attached molecules under cathodic bias, which has important implications for the choice of catalyst attachment strategy in hybrid photoelectrodes.

14 SOLAR ENERGY↗

Integrated Airport Surface Operations

The current air traffic environment in airport terminal areas experiences substantial delays when weather conditions deteriorate to Instrument Meteorological Conditions (IMC). Research activity at NASA has culminated in the development, flight test and demonstration of a prototype Low Visibility Landing and Surface Operations (LVLASO) system. A NASA led industry team and the FAA developed the system which integrated airport surface surveillance systems, aeronautical data links, DGPS navigation, automation systems, and controller and flight deck displays. The LVLASO system was demonstrated at the Hartsfield-Atlanta International Airport using a Boeing 757-200 aircraft during August, 1997. This report documents the contractors role in this testing particularly in the area of data link and DGPS navigation.

Koczo, S.↗

Enhancement of Perfluoropolyether Boundary Lubrication Performance

A ball bearing simulator operating under starved conditions was used to perform screening tests to evaluate the boundary lubrication performance of a branched perfluoropolyether (PFPE), K-143 AB. Several approaches to enhance boundary lubrication were studied. These included: (1) soluble boundary additives, (2) bearing surface modifications, (3) 'run-in' surface films, and (4) ceramic bearing components. In addition, results were compared with two non-perfluorinated liquid lubricant formulations. Based on these tests, the following tentative conclusions can be made: (1) Substantial improvements in boundary lubrication performance were observed with a beta-diketone boundary additive and a tricresyl phosphate (TCP) liquid surface pretreatment, (2) the use of rough Si3N4 balls (R(sub a) = 40 micro-inch) also provided increases in test duration, but with concomitant abrasive wear, (3) moderate improvements were seen with two boundary additives (a phosphine and a phosphatriazine) and a neat (100%) fluid (a carboxylic acid terminated PFPE); and small improvements with surface pretreatments with synthetic hydrocarbons, a polytetrafluoroethylene (PTFE) coating, and TiC coated 440 C and smooth Si3N4 balls (R(sub a) = 1 micro-inch), and (4) two non-PFPE lubricant formulations (a polyalphaolefin (PAO) and synthetic hydrocarbon) yielded substantial improvements.

Jones, W. R., Jr.↗