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At least 91 records · Page 5

Deciphering the Distribution and Crystal-Chemical Environment of Arsenic, Lead, Silica, Phosphorus, Tin, and Zinc in a Porous Ferrihydrite Grain Using Transmission Electron Microscopy and Atom Probe Tomography

Here the interaction of contaminants and nutrients with soil constituents is controlled by processes in intergranular and intragranular pore spaces of organic matter or/and common secondary minerals such as ferrihydrite, ~Fe 3+ 10 O 14 (OH) 2 . This contribution shows that distribution and clustering of the contaminants As, P, Pb, Si, Sn, and Zn in a porous ferrihydrite grain is greatly affected by the heterogeneous size distribution and chemical composition of the pores as well as the ability of their polyhedra to polymerize with the same type of polyhedron. Transmission electron microscopy (TEM) and atom probe tomography (APT) studies are conducted on focused ion beam (FIB) sections extracted from a porous ferrihydrite grain from the smelter-impacted topsoil in Sudbury, Ontario, Canada. The ferrihydrite grain has pore spaces ranging in diameter from tens to hundreds of nanometers. TEM and scanning-TEM studies indicate that the surfaces of the pore walls are enriched in Si. APT data in conjunction with First Near Neighbor (1NN) analyses indicate different degrees of clustering of Pb, As, Sn, Zn, Si, and P within the sample and selected domains. Careful evaluations of 3D atomic plots and 1NN distances indicates the occurrence of polymerized arsenite-, silica-, Sn-, and Zn-polyhedra within pore spaces of the ferrihydrite. Deciphering adsorption, polymerization, and nucleation processes in porous Fe-(hydr)oxides and other soil constituents requires multianalytical approaches and, in this regard, we discuss the advantages and disadvantages of the combination of TEM and APT for characterizing complex environmental samples at the atomic to nanometer scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dependence of the Element Patterns of HYDROSTAR on Mutual Coupling

HYDROSTAR is a hybrid synthesis radiometer, intended for spaceborne applications, which employs a real aperture (waveguide stick antenna) for resolution along track and employs aperture synthesis to obtain resolution across track. This L-band system is an extension of the successful aircraft prototype, the Electronically Steered Thinned Array Radiometer (ESTAR). A proof-of-concept, full size system was constructed (45 wavelength in the synthesis direction) and subjected to extensive antenna pattern and associated microwave component measurements in an outdoor antenna test facility. HYDROSTAR employs a thinned array of 16 elements each 5.8 inches long in the along track dimension and spanning 9.5 inches across track. Each element is a narrow-wall shunt slot array with 36 slots. The polarization is linear (along-track). In the across track dimension, the antennas are deployed in a minimum redundancy array which has 90 independent baselines spaced in integer multiples of half a wavelength. The closest spacings used are for the first three elements at each end, which are spaced by only one-half wavelength. This study was intended to assess how closely each of 16 stick element patterns compare with their nominal values (as an individual, isolated radiator), when installed in their intended composite thinned array configuration. Extensive pattern measurements of the 16 elements that constitute the HYDROSTAR antenna subsystem were conducted to observe their relative features along the synthesis plane. Data was also collected for the mutual coupling between pairs of selected antennas. All antenna patterns had features different from that of an isolated element indicating some level of interaction among neighboring radiators. Those elements which had nearest neighbors at least five wavelengths away were located near the middle of the array. Their radiation patterns displayed sonic small, symmetric ripple across their full azimuth range. The patterns of elements that lie within 2.5 wavelengths of their neighbors showed stronger and asymmetric features. These are believed to be caused by mutual coupling among these structures. Evidence for this was seen when an antenna position was displaced by 0.05 wavelengths, Its pattern and those of its near neighbors were seen to change. Displacement within the plane of the array were observed to have different effects than displacements out-of-plane. A program of data analysis and theoretical development is in progress to provide a physical interpretation of the properties of these antenna patterns and to develop methods which can optimize the performance of this synthetic aperture imaging system. This includes compensation for pattern asymmetries and element position perturbation.

Weissman, David E.↗

Enhancing and Archiving the APS Catalog of the POSS I

We have worked on two different projects: 1) Archiving the APS Catalog of the POSS I for distribution to NASA's NED at IPAC, SIMBAD in France, and individual astronomers and 2) The automated morphological classification of galaxies. We have completed archiving the Catalog into easily readable binary files. The database together with the software to read it has been distributed on DVD's to the national and international data centers and to individual astronomers. The archived Catalog contains more than 89 million objects in 632 fields in the first epoch Palomar Observatory Sky Survey. Additional image parameters not available in the original on-line version are also included in the archived version. The archived Catalog is also available and can be queried at the APS web site (URL: http://aps.umn.edu) which has been improved with a much faster and more efficient querying system. The Catalog can be downloaded as binary datafiles with the source code for reading it. It is also being integrated into the SkyQuery system which includes the Sloan Digital Sky Survey, 2MASS, and the FIRST radio sky survey. We experimented with different classification algorithms to automate the morphological classification of galaxies. This is an especially difficult problem because there are not only a large number of attributes or parameters and measurement uncertainties, but also the added complication of human disagreement about the adopted types. To solve this problem we used 837 galaxy images from nine POSS I fields at the North Galactic Pole classified by two independent astronomers for which they agree on the morphological types. The initial goal was to separate the galaxies into the three broad classes relevant to issues of large scale structure and galaxy formation and evolution: early (ellipticals and lenticulars), spirals, and late (irregulars) with an accuracy or success rate that rivals the best astronomer classifiers. We also needed to identify a set of parameters derived from the digitized images that separate the galaxies by type. The human eye can easily recognize complicated patterns in images such as spiral arms which can be spotty, blotchy affairs that are difficult for automated techniques. A galaxy image can potentially be described by hundreds of parameters, all of which may have some relation to the morphological type. In the set of initial experiments we used 624 such parameters, in two colors, blue and red. These parameters include the surface brightness and color measured at different radii, ratios of these parameters at different radii, concentration indices, Fourier transforms and wavelet decomposition coefficients. We experimented with three different classes of classification algorithms; decision trees, k-nearest neighbors, and support vector machines (SVM). A range of experiments were conducted and we eventually narrowed the parameters to 23 selected parameters. SVM consistently outperformed the other algorithms with both sets of features. By combining the results from the different algorithms in a weighted scheme we achieved an overall classification success of 86%.

Humphreys, Roberta M.↗

Taxi-Out Time Prediction for Departures at Charlotte Airport Using Machine Learning Techniques

Predicting the taxi-out times of departures accurately is important for improving airport efficiency and takeoff time predictability. In this paper, we attempt to apply machine learning techniques to actual traffic data at Charlotte Douglas International Airport for taxi-out time prediction. To find the key factors affecting aircraft taxi times, surface surveillance data is first analyzed. From this data analysis, several variables, including terminal concourse, spot, runway, departure fix and weight class, are selected for taxi time prediction. Then, various machine learning methods such as linear regression, support vector machines, k-nearest neighbors, random forest, and neural networks model are applied to actual flight data. Different traffic flow and weather conditions at Charlotte airport are also taken into account for more accurate prediction. The taxi-out time prediction results show that linear regression and random forest techniques can provide the most accurate prediction in terms of root-mean-square errors. We also discuss the operational complexity and uncertainties that make it difficult to predict the taxi times accurately.

Safe and efficient surface operations↗

Crystallizing Kagome Artificial Spin Ice

Artificial spin ices are engineered arrays of dipolarly coupled nanobar magnets. They enable direct investigations of fascinating collective phenomena from their diverse microstates. However, experimental access to ground states in the geometrically frustrated systems has proven difficult, limiting studies and applications of novel properties and functionalities from the low energy states. In this work, we introduce a convenient approach to control the competing diploar interactions between the neighboring nanomagnets, allowing us to tailor the vertex degeneracy of the ground states. We achieve this by tuning the length of selected nanobar magnets in the spin ice lattice. We demonstrate the effectiveness of our method by realizing multiple low energy microstates in a kagome artificial spin ice, particularly the hardly accessible long range ordered ground state—the spin crystal state. Our strategy can be directly applied to other artificial spin systems to achieve exotic phases and explore new emergent collective behaviors.

36 MATERIALS SCIENCE↗

Analysis of stratocumulus cloud fields using LANDSAT imagery: Size distributions and spatial separations

Stratocumulus cloud fields in the FIRE IFO region are analyzed using LANDSAT Thematic Mapper imagery. Structural properties such as cloud cell size distribution, cell horizontal aspect ratio, fractional coverage and fractal dimension are determined. It is found that stratocumulus cloud number densities are represented by a power law. Cell horizontal aspect ratio has a tendency to increase at large cell sizes, and cells are bi-fractal in nature. Using LANDSAT Multispectral Scanner imagery for twelve selected stratocumulus scenes acquired during previous years, similar structural characteristics are obtained. Cloud field spatial organization also is analyzed. Nearest-neighbor spacings are fit with a number of functions, with Weibull and Gamma distributions providing the best fits. Poisson tests show that the spatial separations are not random. Second order statistics are used to examine clustering.

Welch, R. M.↗

Modified cubic convolution resampling for Landsat

An overview is given of Landsat Thematic Mapper resampling technique, including a modification of the well-known cubic convolution interpolator (nearest neighbor interpolation) used to provide geometric correction for TM data. Post launch study has shown that the modified cubic convolution interpolator can selectively enhance or suppress frequency bands in the output image. This selectivity is demonstrated on TM Band 3 imagery.

Prakash, A.↗

The white-light flare of 1982 June 15 - Observations

This paper presents spectral observations of the continuum as well as the profiles of 29 selected atomic lines for the two continuum-emitting kernels of the June 15 1982 white-light flare, and for the neighboring quiet sun. It is found that one of the kernels does not show enhanced emission in chromospheric lines, particularly in H-alpha, although it presents the same level of white-light emission as the other kernel. This suggests that both kernels have the same thermal structure in the continuum-emitting region, but a different structure in the chromosphere, thus supporting the hypothesis that the continuum emission is of photospheric origin, and due to H(-).

Mauas, Pablo J. D.↗

Achieving Ultra-High Selectivity to Hydrogen Production from Formic Acid on Pd–Ag Alloys

Palladium-silver based alloy catalysts have a great potential for CO-free hydrogen production from formic acid for fuel cell applications. However, the structural factors affecting the selectivity of formic acid decomposition is still debated. Herein, the decomposition pathways of formic acid on Pd-Ag alloys with different atomic configurations have been investigated to identify the alloy structures yielding high H 2 selectively. Several Pd x Ag 1-x surface alloys with various compositions were generated on a Pd(111) single crystal; their atomic distribution and electronic structure were determined by a combination of infrared reflection absorption spectroscopy (IRAS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT). It was established that the Ag atoms with Pd neighbors are electronically altered, and the degree of alteration correlates with the number of nearest Pd. Temperature programmed reaction spectroscopy (TPRS) and DFT demonstrated that the electronically altered Ag domains create a new reaction pathway that selectively dehydrogenates formic acid. In contrast, Pd monomers surrounded by Ag are demonstrated to have a similar reactivity compared to pristine Pd(111), yielding CO and H 2 O in addition to the dehydrogenation products. Furthermore, they bind to the produced CO weaker than pristine Pd, demonstrating an enhancement in resistance to CO poisoning. This work therefore shows that surface Ag domains modified by interaction with subsurface Pd are the key active sites for selective decomposition of formic acid, while surface Pd atoms are detrimental for selectivity. Hence the decomposition pathways can be tailored for CO-free H 2 production on Pd-Ag alloy systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanistic Insights into Nonoxidative Ethanol Dehydrogenation on NiCu Single-Atom Alloys

Ethanol dehydrogenation presents a promising pathway towards the production of acetaldehyde, a valuable building block in chemicals production. Under non-oxidative conditions, the reaction is facilitated by supported Cu nanoparticles which afford reasonable activity and high selectivity. The stability issues associated with Cu nanoparticle sintering can be addressed by the addition of small amounts of Ni, which further boost reactivity while retaining selectivity. Despite the promise of NiCu single-atom alloys for non-oxidative ethanol dehydrogenation, little is known about the role of each component and the pathway of this mechanistically complex process. Herein, kinetic investigations from reactor tests identify C-H bond scission as the rate limiting step, while 1-hydroxyethyl is detected as the intermediate via IR spectroscopy. Temperature program desorption studies are employed to examine the effect of Ni coverage and to demonstrate that Ni atoms activate ethanol selectively at lower temperatures, resulting in higher acetaldehyde yield than pure Cu. Temperature program desorption experiments also reveal the spillover of intermediates from the Ni atom to neighboring Cu sites as a relevant step in the reaction pathway. Density functional theory calculations are used to investigate the 2 reaction energetics and to confirm that C-H bond scission is the initial reaction step, while a clear effect of H 2 partial pressure on the reaction pathway is realized. Further, counter to the expected behavior that all reaction steps take place on the Ni atoms, our degree of rate control analysis reveals that a mechanism involving spillover of the 1-hydroxyethyl intermediate from the Ni atom to the Cu surface, where it will dehydrogenate further, is more likely. Furthermore, our combined kinetic, spectroscopic, and theoretical approach sheds light on this complex reaction mechanism and represents a promising method for the understanding and designing of highly active, selective, and stable single-atom alloys for other multistep catalytic processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dehydrogenation of Propane and n -Butane Catalyzed by Isolated PtZn 4 Sites Supported on Self-Pillared Zeolite Pentasil Nanosheets

Propene and 1,3-butadiene are important building-block chemicals that can be produced by dehydrogenation of propane and butane over Pt catalysts. The challenge is to develop highly active and selective catalysts that are resistant to deactivation by Pt sintering and coke formation. We have recently shown that these objectives can be met for propane dehydrogenation using atomically dispersed Pt atoms anchored to neighboring ≡SiOZn-OH groups bonded to the framework dealuminated zeolite BEA. In the present study, we demonstrate that significantly superior performance can be achieved by using self-pillared pentasil (SPP) zeolite nanosheets. Following catalyst reduction in H 2 , atomic-resolution, scanning transmission electron microscopy (STEM) and X-ray absorption spectroscopy (XAS) indicate that Pt is stabilized in structures well approximated as (≡Si-O-Zn) 4-5 Pt. These species are highly active, selective, and stable for propane dehydrogenation (PDH) to give propene and for n-butane dehydrogenation (BDH) to give 1,3-butadiene. No catalyst deactivation was observed after 12 days of time on stream, and the selectivity remained at nearly 100% for PDH conducted at 823 K and a weight hourly space velocity (WHSV) of 1,350 h -1 . The apparent rate coefficient for PDH over this catalyst is significantly higher than that reported previously for Pt-containing catalysts. For BDH at 823 K and a WHSV of 3560 h -1 , the selectivity to butene isomers and 1,3-butadiene is 98.9%, and the selectivity to 1,3-butadiene is 45%. Here, we propose that the high catalyst stability observed during PDH and BDH is a consequence of a large fraction of the Pt-containing centers being located on the external surface of the zeolite nanosheets, where nascent coke precursors can desorb before condensing to form coke.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Automated System-wide Event Detection and Classification Using Machine Learning on Synchrophasor Data

As the number of phasor measurement units (PMUs) deployed in a power system increases, and their data volume streamed to the control canter intensifies, operators are facing challenges related to the analysis of such data, which need to be observed and responded to as the measurements are displayed in the Control Room. Humans are generally unable to process such large amount of data efficiently and rapidly. There is an apparent need for automated ways to analyze the data, extract actionable information about occurrence of specific events, and characterize the events quickly and cost effectively. This paper discusses the use of machine learning (ML) to facilitate such tasks by providing automated, highly computationally efficient, and cost-effective ways of extracting actionable information from synchrophasor big data in real-time. We developed Big Data Smart (BDSmart) ML-based prototype tool for the Control Room use that automatically analyses data properties from synchrophasor system measurements taken across the three grid Interconnections in the USA (Western, Eastern and ERCOT). The data collected from several hundreds of PMUs located across the Interconnections over a period of two years have been made available for our extensive study. As a result, we were able to identify a number of big data properties that influence how ML methodology is applied to select, develop, train and test the data models that can eventually be used for the tool implementation. The resulting set of candidate algorithms spans unsupervised, supervised, semi-supervised and transfer-learning approaches. Many ML techniques, such as decision trees, multinomial logistic regression, feed-forward neural networks, K-nearest neighbor, multiclass support vector machine, and single and multi-channel convolutional neural networks, are implemented, and their performance is examined. We offer the results from testing the data models. The novelty of our study is in the approaches for bad data detection and mitigation, selection of a simplified feature for event detection, and data label improvements. As a result, we came up with a list of recommendations for the utilities on how to improve the PMU recording practices to cater to the future ML applications aimed at automating the analysis of synchrophasor data.

Synchrophasors, Machine Learning, System-wide Even↗

Iridium pair sites anchored to Zr 6 O 8 nodes of the metal–organic framework UiO-66 catalyze ethylene hydrogenation

Isolated metal pair sites on metal oxide and zeolite supports are drawing attention as catalysts, because—in contrast to single atomically dispersed metals—they provide neighboring metal centers that can act cooperatively. We now report pairs of iridium atoms anchored to the Zr 6 O 8 nodes of the metal–organic framework (MOF) UiO-66, synthesized by chemisorption of Ir 2 (μ-OCH 3 ) 2 (COD) 2 (COD is cyclooctadienyl) followed by removal of the COD ligands. The supported species were characterized with infrared spectra of adsorbed CO combined with iridium LIII-edge extended X-ray absorption fine structure and high-energy-resolution fluorescence detection X-ray absorption near edge (HERFD XANES) spectra. The HERFD XANES spectra were recorded with the sample in a variety of atmospheres in which the iridium pair sites were stable, including CO, H 2 , and C 2 H 4 + H 2 at temperatures in the range of 35–80 °C. The data provide sensitive measures of the electronic structure of the iridium in the pair sites. The samples were evaluated as catalysts for ethylene hydrogenation, with the pair-sites being more selective for hydrogenation than analogous isolated atomically dispersed iridium, which catalyzes both hydrogenation and isomerization. Metal pair sites on MOFs offer uncharted opportunities for catalysts having reactivities associated with neighboring metal centers.

36 MATERIALS SCIENCE↗

Quenching in the Right Place at the Right Time: Tracing the Shared History of Starbursts, Active Galactic Nuclei, and Poststarburst Galaxies Using Their Structures and Multiscale Environments

This work uses multiscale environments and the structures of galaxies in the Sloan Digital Sky Survey as consistency checks on the evolution from starburst to quiescence at redshift z < 0.2. The environmental indicators include fixed-aperture mass overdensities (δ xMpc , x ϵ {0.5, 1, 2, 4, 8} h –1 Mpc), k-nearest neighbor distances, the tidal parameter, halo mass (M h ), and satellite/central classification. The residuals of the specific star formation rates (Δ SSFRs) are used to select starbursts (ΔSSFR > 0.6 dex, N ≈ 8600). Quenched poststarbursts (QPSBs) are selected using Hα < 3 Å emission and Hδ A > 4 Å absorption (N ≈ 750). The environments of starbursts and QPSBs are compared with those of active galactic nuclei (AGNs) and inactive galaxies of varying ΔSSFR. The environments of starbursts, AGNs, and QPSBs are unlike the environments of most quiescent galaxies (QGs). About 70%–90% of starbursts, AGNs with Hδ A > 4 Å, and QPSBs are centrals; ~80%–90% have M h < 10 13 M ⊙ , and only ~2%–4% have M h > 10 14 M ⊙ or live in clusters. Their M h and satellite fractions are also different from those of QGs. All QPSBs are matched to some SFGs, starbursts, AGNs, and QGs of similar M $\star$ , environments, concentration indices, and velocity dispersions. A significant fraction (~20%–30%) of starbursts cannot be matched to QPSBs or QGs. The implications are that: (1) some starbursts do not quench rapidly; (2) the satellite-quenching mechanisms operating in high-density environments cannot account for most QPSBs; (3) the evolution from starbursts to QPSBs to QGs is not the dominant path at z < 0.2; and (4) starbursts are not mainly triggered by tidal interactions.

79 ASTRONOMY AND ASTROPHYSICS↗

Vapor–Fed Electrolyzers for Carbon Dioxide Reduction Using Tandem Electrocatalysts: Cuprous Oxide Coupled with Nickel–Coordinated Nitrogen–Doped Carbon

We report ethylene is particularly attractive due to its major importance as a feedstock for various applications including the polymer industry. As such, catalyst and electrolyzer developments are crucial to achieve industrially relevant ethylene production and efficiency levels. In this work, a tandem electrocatalyst composed of copper nanocubes and nickel-coordinated nitrogen-doped carbon (NiNC) is presented, which is integrated into gas diffusion electrodes (GDEs) for direct conversion of vapor-fed CO 2 into ethylene. Evaluation of tandem GDEs in the vapor-fed flow electrolyzer shows significantly increased ethylene selectivity in terms of faradaic efficiency and C 2 H 4 /CO ratio compared to a non-tandem copper GDE. The enhancements are attributed to the increased local CO availability near the copper surface via effective CO 2 to CO conversion on neighboring NiNC. The experimental results are validated by 3D resolved continuum simulations, which show increased flux of higher-order prod-ucts with the added CO flux from NiNC. The practical viability of Cu/NiNC catalyst is further evaluated in a membrane electrode assembly electrolyzer, achieving 40% FE toward ethylene at 150 mA cm -2 and 3.2 V. These find-ings highlight the high selectivity and formation rate of ethylene achieved by successful device integration of the Cu/NiNC catalyst, demonstrating the potential for implementation in large-scale sustainable CO 2 electrolyzers.

36 MATERIALS SCIENCE↗

Preactivated zeolite nanosheet plate-tiled membrane on porous PVDF film: Synthesis and study of proton-selective ion conduction

Preactivated MFI zeolite nanosheet plates (ZNPs) with large areas (~2.0 × 2.0 μm 2 ) and nanometer thicknesses (~60 nm) were prepared directly in liquid-dispersed state. The individual ZNP was a stack of 4-nm-thick single crystalline zeolite nanosheets (ZNs) interlinked by Si–O–Si bonds between neighboring ZN surfaces. The dispersed open-pore ZNPs allowed formulating suspensions for tiling ZNP membranes on polymer substrates without requiring post-coating activation. A pinhole-free ZNP-tiled (ZNPT) membrane has been achieved on macroporous PVDF film by a self-repairing vacuum-assisted filtration coating method. The resultant ZNPT layer was ~500 nm-thick consisting of about 7 ZNP layers with inter-ZNP width and inter-ZNP entrance porosity around 9 nm and 2%, respectively. The ZNPT-PVDF membrane exhibited high selectivity to proton transport over vanadyl ion and low resistances to proton conduction in aqueous solutions. The membrane also demonstrated to function as an efficient ion separator for the vanadium redox flow battery. The reported synthesis of preactivated ZNP suspension may overcome the major hurdle to realizing polymer-supported ZN membranes, which is the inefficiency of existing methods in obtaining readily dispersible open-pore ZNs. Finally, the ZNPT-PVDF membrane can be a more affordable and sustainable alternative to the Nafion-based ion separation membranes.

36 MATERIALS SCIENCE↗

Beam test of a harmonic kicker cavity

A harmonically resonant kicker cavity designed for beam exchange in a circulator cooler was built and successfully tested at the Upgraded Injector Test Facility (UITF) at Jefferson Lab. This type of cavity is being considered for the injection scheme of the Rapid Cycling Synchrotron at the Electron-Ion Collider, where the spacing of neighboring bunches demands very short kicks. Operating with five transversely deflecting modes simultaneously that resonate at 86.6 MHz and consecutive odd harmonics thereof, the prototype cavity selectively deflects 1 of 11 electron bunches while leaving the others unperturbed. An RF driver was developed to synthesize phase- and amplitude-controlled harmonic signals and combine them to drive the cavity while also separating the modes from a field-probe antenna for RF feedback and dynamic tuning. Beam deflection was measured by sweeping the cavity phase; the deflection waveform agrees with expectations, having sub-nanosecond rise and fall times. No emittance increase is observed. Harmonically resonant cavities like the one described provide a new capability for injection and extraction at circulators and rings.

Bruker, M.W.↗