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At least 397 records · Page 22

In-situ monitoring of atomically dispersed Pt sites supported on OMS-2 during CO 2 activation

Atomically dispersed catalysts have drawn great interest lately, as they showcase a high density of active sites, selectivity, and high turnover frequencies in oxidation chemistry due to labile oxygen activation. In contrast, the applications of these catalysts have lagged in reduction reactions due to the ambiguity caused by the sintering and restructuring of active sites. To bridge this gap, the evolution of Pt 4+ isomorphically substituted into an octahedral molecular sieve structure (OMS-2) under reductive conditions was correlatively characterized using multiple in-situ analytical techniques such as ambient pressure X-ray photoelectron spectroscopy, environmental transmission electron microscopy, and solid-state nuclear magnetic resonance. The surface dynamics of the Pt single atoms were revealed during the Reverse Water Gas Shift (RWGS) reaction, where the active sites were identified as two-coordinated platinum single atoms. Under reaction, we show nonbinding atoms adjacent to the single atoms restructured the motif of the single atoms to Pt 2+ via ion mobility of potassium, increasing the activation energy by 25.6 kJ/mol. Here, this work also highlights the potential for increased stability of the single atom sites via isomorphic substitution of the metal oxide support, since the Pt-OMS-2 catalyst retained activity for about 33 h before deactivation, after which nanoparticles were observed in TEM images. This work offers a new perspective in single atom synthesis using the metal oxide as the host for the single atom site, instead of adatoms on the surface

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pendant-Drop Surface-Tension Measurement On Molten Metal

Method of measuring surface tension of molten metal based on pendant-drop method implemented in quasi-containerless manner and augmented with digital processing of image data. Electrons bombard lower end of sample rod in vacuum, generating hanging drop of molten metal. Surface tension of drop computed from its shape. Technique minimizes effects of contamination.

Man, Kin Fung↗

Etching sharp tips from thin metallic wires for tuning-fork-based scanning probe microscopy

Sharp tips are critical for obtaining high resolution images in scanning probe microscopy (SPM), particularly in samples with large variations in topography. For tuning-fork-based SPM, such tips are commonly obtained by electrochemical etching of metallic wires (e.g., tungsten). Electrochemical etching of metallic wires is the preferred means of preparing tips for scanning tunneling microscopy (STM), and techniques for obtaining sharp tips have been investigated extensively. However, the requirements for STM and tuning-fork-based SPM are different. In particular, the wires used in STM are typically 250-500 μ m in diameter, while the wires used for tuning-fork-based SPM are usually an order of magnitude narrower in order to minimize loading of the tuning fork: 25-50 μ m and sometimes down to a few micrometers in diameter. Consequently, many of the recipes developed for etching thicker metallic wires for STM tips do not give optimal results for smaller diameter wires. The authors describe here a modification of the etching circuit of Ibe et al . that significantly improves the reproducibility and reliability of the etching process for thin wires, and discuss the parameters that affect the aspect ratio of produced tips.

42 ENGINEERING↗

Movement of Cracked Silicon Solar Cells During Module Temperature Changes

Cracks in crystalline silicon solar cells can lead to substantial power loss. While the cells' metal contacts can initially bridge these cracks and maintain electrical connections, the bridges are damaged by mechanical loads, including those due to temperature changes. We investigated the metallization bridges that form over cracks in encapsulated silicon solar cells. Microscopic characterization showed that the crack in the silicon can immediately propagate through the metal grid, but the grid can maintain electrical contact once the load is removed. We also quantified the movement of the cell fragments separated by a crack as a function of temperature. Cell fragments are free to move diagonally and to rotate, so the change in gap across the crack during a temperature change varies along the length of the crack. In one sample, we showed that a 10 degrees C temperature change, causing a 2 um increase in the separation of cell fragments, was sufficient to cause a reversible electrical disconnection of metallization bridging a crack.

14 SOLAR ENERGY↗

Tip-Enhanced Raman Scattering on Both Sides of the Schrödinger Equation

We report historically, molecular spectroscopists have focused their attention to the right-hand side of the Schrödinger equation. Our major goal had and still has to do with determining a (bio)molecular system’s Hamiltonian operator. From a theoretical spectroscopist’s perspective, this entails varying the parameters of a model Hamiltonian until the predicted observables agree with their experimental analogues. In this context, less emphasis has been put on the left-hand side of the equation, where the interplay between a system and its immediate local environment is described. The latter is particularly meaningful and informative in modern applications of optical microscopy and spectroscopy that take advantage of surface plasmons to enhance molecular scattering cross-sections and to increase the attainable spatial resolution that is classically limited by diffraction. Indeed, the manipulation of light near the apex of a metallic nanotip has enabled single molecule detection, identification, and imaging. The distinct advantages of the so-called tip-enhanced optical nanospectroscopy/nanoimaging approaches are self-evident: ultrahigh spatial resolution (nanometer or better) and ultimate sensitivity (down to yoctomolar) are both attainable, all while retaining the ability to chemically fingerprint one molecule at a time (e.g., through Raman scattering). An equally interesting aspect of the same approach stems from using the properties of a single molecule to characterize the local environment in which it resides. This concept of single molecule spectroscopy on the left-hand side of the Schrödinger equation is certainly not novel and has been discussed in pioneering single molecule studies that ultimately led to a Nobel prize in chemistry. That said, local environment mapping through ultrasensitive optical spectroscopy acquires a unique flavor when executed using tip-enhanced Raman scattering (TERS). This is the subject of this Account.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cu Doping Increases Capacity Retention in LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) by Altering the Potential of the Ni-Based Redox Couple and Inhibiting Particle Pulverization

To discern the influence of Cu 2+ as a dopant on both the structural and electrochemical characteristics of LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622), Cu 2+ (aq) was added to the coprecipitation synthesis from the constituent ions. At 5 mol % Cu 2+ , a single-phase Cu-NMC product results, evidenced by an increase in d-spacing along the [003] and [104] directions and a slight increase in the crystal volume of the R–3m hexagonal (rock-salt superstructure) lattice. XRD data and high-resolution TEM imaging support Cu 2+ doping primarily on the transition metal 3b Wyckoff sites. Here, galvanostatic cycling of Cu-NMC shows a reversible gravimetric capacity of 102 mAh/g compared to 136 mAh/g for undoped NMC. Despite the lower capacity, the discharge capacity retention of Cu-NMC is 89% after 100 cycles compared to only 70% for NMC. XPS analysis reveals that this lower capacity is due to an increase in the concentration of Ni 3+ ions at the surface, while XRD data collected at the top and bottom of charge show a smaller decrease in crystalline domain size for Cu-NMC (40.5% decrease) compared to NMC (74.7% decrease), translating to pulverization of the secondary particles.

25 ENERGY STORAGE↗

Compact high repetition rate Thomson parabola ion spectrometer

Here, we present the development of a compact Thomson parabola ion spectrometer capable of characterizing the energy spectra of various ion species of multi-MeV ion beams from >10 20 W/cm 2 laser produced plasmas at rates commensurate with the highest available from any of the current and near-future PW-class laser facilities. This diagnostic makes use of a polyvinyl toluene based fast plastic scintillator (EJ-260), and the emitted light is collected using an optical imaging system coupled to a thermoelectrically cooled scientific complementary metal–oxide–semiconductor camera. This offers a robust solution for data acquisition at a high repetition rate, while avoiding the added complications and nonlinearities of micro-channel plate based systems. Different ion energy ranges can be probed using a modular magnet setup, a variable electric field, and a varying drift-distance. We have demonstrated operation and data collection with this system at up to 0.2 Hz from plasmas created by irradiating a solid target, limited only by the targeting system. With the appropriate software, on-the-fly ion spectral analysis will be possible, enabling real-time experimental control at multi-Hz repetition rates.

47 OTHER INSTRUMENTATION↗

A Comparative Study on Representativeness and Stochastic Efficacy of Miniature Tensile Specimen Testing

Here, in this article, a miniature dog bone tensile coupon design was tested against the existing ASTM standard specimen design. Specimens were prepared from commercially sourced austenitic stainless steel 304 alloy, and a defect-ridden additively manufactured 304L alloy was studied. By utilizing a tensile specimen design that is 1/230th volume of the smallest ASTM E8-04(2016), Standard Test Methods for Tension Testing of Metallic Materials, dog bone specimen, coupled to a digital image correlation (DIC) setup, case studies were performed to compare tensile property measurements and strain field evolution. Whereas yield strength measurements were observed to be similar, post-yield, the ultimate strength measurements and ductility measurements from the miniature specimens were observed to be higher than the ASTM specimen design. Although the strength measurements were comparable, the strain evolution was found to differ in the miniature specimens. Studies to assess effects of varying thickness and defect population were also pursued on the miniature tensile specimen. From the DIC strain field estimations, the peak local strain values at ultimate tensile strength were observed to be increasing with reducing specimen thickness. Testing of defect ridden stainless steel revealed the sensitivity to failure through strain localization and the influence of defect size was captured in the strength measurements.

36 MATERIALS SCIENCE↗

Nitric Oxide Enhances Charge-Coupled Device

Simple treatment increases and stabilizes quantum efficiency of charge-coupled-device photodetector illuminated on back surface at wavelengths less than 4,500 Angstrom. Must be biased in strong accumulation mode. Physical principle of enhancement explained more fully in "Metal Film Increases CCD Output" (NPO-16815). Useful for imaging at wavelengths from ultraviolet to blue; for example, in astronomical observations.

Hecht, Michael H.↗

Melt Infiltration Studies of 2D Tyranno SA3(R) Ceramic Matrix Composite Preforms with CrSi2 Intermetallic Alloy

The present paper reports the results of melt infiltrating 2D Tyranno SA3@ fiber woven preforms with molten CrSi2 between 1768 and 1896 K under a vacuum of 1.3 x 10-4 Pa (10-6 torr). The infiltration times varied between 1800 and 7200 s, which did not have any significant effect on the volume fraction of voids filled with the metal. Optical and scanning electron microscopy, back scattered electron imaging, energy dispersion spectroscopy and Raman spectroscopy were used to characterize the infiltrated preforms. A plot of the volume fraction of open voids infiltrated against the absolute melt infiltration temperature showed a sharp peak at 1773 K with almost complete infiltration of the voids at this temperature. The extent of silicide infiltration of the preforms dropped steeply above 1773 K with increasing melt infiltration temperature irrespective of the amount of infiltration time. Above 1805 K, the volume fraction of voids infiltrated with the melt was nearly 0%. It is demonstrated that CrSi2 did not show evidence of a reaction with the SiC fibers. The possibility that a resisting force due to contact angle hysteresis (CAH) may have influenced the diminishing amount of voids filled with increasing temperature above 1773 K was examined. The resistance force was estimated to be extremely small to be consequential. Another possibility that the CrSi2 may have decomposed into Cr(g) and Si(g) in the vacuum melt infiltration furnace appeared to be more plausible based on thermodynamic analyses. An empirical equation is proposed to calculate the amount of remaining charge left to infiltrate the preforms at the infiltration temperature. It is shown that an initial charge of 10 g would rationalize the present observations. While the decomposition of the CrSi2 appeared to mostly explain the present results, some discrepancies were observed, which were inconsistent with the decomposition model.

CrSi2, chromium silicide, ceramic matrix composite↗

Project Description and Publications List for UAH CMMR

This research combines a state of the art X-ray Transmission Microscope, XTM, with a specially designed x-ray transparent horizontal Bridgman furnace to image (with resolutions up to 3 micrometers) the solidification of metal alloys in real-time. The objective is to obtain real-time dynamic data to provide direct measure of the solute profile in the liquid, phase coalescence and growth in the liquid, and the detailed interface morphology (e,g., dendrites and cells) during solidification. We are also enhancing the XTM data with precise solid-liquid interfacial temperature and the thermal gradient measurement techniques, and working on the application of this technology to the study of the fundamentals of solidification in microgravity. Over the last several years we have successfully imaged in real-time: interfacial-morphologies, phase growth, coalescence, incorporation of phases into the growing interface, and the solute boundary layer in the liquid at the solid-liquid interface. We have also measured true local growth rates and can evaluate segregation structures in the solid. Interfacial undercoolings are being measured either with a special Seebeck furnace or with micro-thermocouple arrays we are developing. These later techniques are presently being incorporated with the XTM furnace. This last year emphasized the investigation of the solute layer in the melt during solidification. Methods were developed to quantify the solute concentrations using x-ray absorption and to compare to predictions from simulations. In addition, work is being completed on a brass-board portable XTM that incorporates a vertical Bridgman furnace.

Kaukler, William F.↗

COOL-LAMPS. I. An Extraordinarily Bright Lensed Galaxy at Redshift 5.04

In this paper, we report the discovery of COOL J1241+2219, a strongly lensed galaxy at redshift z = 5.043 ± 0.002 with observed magnitude z AB = 20.47, lensed by a moderate-mass galaxy cluster at z = 1.001 ± 0.001. COOL J1241+2219 is the brightest lensed galaxy currently known at optical and near-infrared wavelengths at z $\gtrsim$ 5; it is ~5 times brighter than the prior record-holder lensed galaxy, and several magnitudes brighter than the brightest unlensed galaxies known at these redshifts. It was discovered as part of COOL-LAMPS, a collaboration initiated to find strongly lensed systems in recent public optical imaging data. We characterize the lensed galaxy, as well as the central galaxy of the lensing cluster using ground-based grizJH imaging and optical spectroscopy. We report model-based magnitudes, and derive stellar masses, dust content, metallicity, and star-formation rates via stellar-population synthesis modeling. Our lens mass modeling, based on ground-based imaging, implies a median source magnification of ~30, which puts the stellar mass and star-formation rate (in the youngest age bin, closest to the epoch of observation) at logM* = ${10.11}_{-0.26}^{+0.21}$ and SFR = ${27}_{-9}^{+13} M_⊙$ yr –1 , respectively. We constrain a star-formation history for COOL J1241+2219 consistent with constant star formation across ~1 Gyr of cosmic time, and that places this galaxy on the high-mass end of the star-forming main sequence. COOL J1241+2219 is two to four times more luminous than a galaxy with the characteristic UV luminosity at these redshifts. The UV continuum slope β = –2.2 ± 0.2 places this galaxy on the blue side of the observed distribution of galaxies at z = 5, although the lack of Lyα emission indicates dust sufficient to suppress this emission.

79 ASTRONOMY AND ASTROPHYSICS↗

Interactions between atmospheric pressure plasmas and metallic catalyst particles in packed bed reactors

Atmospheric-pressure plasmas sustained in packed bed reactors (PBRs) are being investigated for chemical conversion of gases and pollution control. Metallic catalysts added to the surfaces of the dielectric beads of PBRs can increase the energy efficiency and selectivity of chemical processes by reducing operating temperature and providing additional reaction pathways. In this paper, results from a computational investigation of plasma surface interactions between micron-scale metallic catalysts and humid-air plasmas in PBRs are discussed. Here we found that high plasma density regions form in the proximity of the metallic catalysts. These higher-density plasma regions were confirmed experimentally using ICCD imaging. The intense plasmas result from geometrical electric field enhancement and redistribution of charges within the conductive particles, leading to further enhancement. The high electric field at the triple points of the catalysts can produce electric field emission of electrons, which provides a pre-ionization source or additional source of electrons. These regions of high electric field and sources of electrons guide discharges towards the catalysts and increases fluxes of excited species, ions, electrons and photons to their surfaces. These fluxes are focused primarily at the triple points between the metal, dielectric and gas. As a result, the catalyst is locally heated, which could lead to further increased rates of thermocatalytic reactions on the surface. Surface roughness of the metal inclusions can lead to additional electric field enhancement, which changes the character of the discharges in the vicinity of the catalysts while reducing breakdown voltage.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Material Characterization of Grade 91 Steel Welds using, Micro-resolution Ultrasonic Imaging System

Grade 91 (9Cr-1Mo-V) steel is a common structural material for fossil-fuel fired and nuclear power plants because of its creep strength and oxidation resistance at high temperatures. In this research, we studied the feasibility of correlating the high-resolution images obtained from the immersion ultrasonic imaging technique to microstructure regions in Grade 91 steel plate weldments. The high-resolution ultrasonic images presented in this paper were generated using a 20-MHz focused transducer as the transmitter, and a laser vibrometer as the receiver in the through transmission configuration to produce longitudinal and shear waves. This nondestructive evaluation (NDE) method was used to identify the Fusion Zone (FZ), Heat-Affected Zone (HAZ), and Base Metal (BM) regions of Grade 91 cold metal transfer (CMT) and flux core arc welds (FCAW). The ultrasonic imaging results were analyzed using beam propagation amplitudes and homogeneity, which in turn were used to relate the different microstructure regions of the FCAW and CMT welded samples. With this study, we were able to identify highly susceptible microstructures in the weld that could potentially promote creep type failures.

20 FOSSIL-FUELED POWER PLANTS↗

Deep-Learning-Based Segmentation of Keyhole in In-Situ X-ray Imaging of Laser Powder Bed Fusion

In laser powder bed fusion processes, keyholes are the gaseous cavities formed where laser interacts with metal, and their morphologies play an important role in defect formation and the final product quality. The in-situ X-ray imaging technique can monitor the keyhole dynamics from the side and capture keyhole shapes in the X-ray image stream. Keyhole shapes in X-ray images are then often labeled by humans for analysis, which increasingly involves attempting to correlate keyhole shapes with defects using machine learning. However, such labeling is tedious, time-consuming, error-prone, and cannot be scaled to large data sets. To use keyhole shapes more readily as the input to machine learning methods, an automatic tool to identify keyhole regions is desirable. In this paper, a deep-learning-based computer vision tool that can automatically segment keyhole shapes out of X-ray images is presented. The pipeline contains a filtering method and an implementation of the BASNet deep learning model to semantically segment the keyhole morphologies out of X-ray images. The presented tool shows promising average accuracy of 91.24% for keyhole area, and 92.81% for boundary shape, for a range of test dataset conditions in Al6061 (and one AliSi10Mg) alloys, with 300 training images/labels and 100 testing images for each trial. Prospective users may apply the presently trained tool or a retrained version following the approach used here to automatically label keyhole shapes in large image sets.

36 MATERIALS SCIENCE↗

Interaction of Burning Metal Particles

Physical characteristics of the combustion of metal particle groups have been addressed in this research. The combustion behavior and interaction effects of multiple metal particles has been studied using a microgravity environment, which presents a unique opportunity to create an "aerosol" consisting of relatively large particles, i.e., 50-300 m diameter. Combustion behavior of such an aerosol could be examined using methods adopted from well-developed single particle combustion research. The experiment included fluidizing relatively large (order of 100 m diameter) uniform metal particles under microgravity and igniting such an "aerosol" using a hot wire igniter. The flame propagation and details of individual particle combustion and particle interaction have been studied using a high speed movie and video-imaging with cameras coupled with microscope lenses to resolve individual particles. Interference filters were used to separate characteristic metal and metal oxide radiation bands from the thermal black body radiation. Recorded flame images were digitized and various image processing techniques including flame position tracking, color separation, and pixel by pixel image comparison were employed to understand the processes occurring in the burning aerosol. The development of individual particle flames, merging or separation, and extinguishment as well as induced particle motion have been analyzed to identify the mechanisms governing these processes. Size distribution, morphology, and elemental compositions of combustion products were characterized and used to link the observed in this project aerosol combustion phenomena with the recently expanded mechanism of single metal particle combustion.

Dreizin, Edward L.↗

Interaction of Burning Metal Particles

Physical characteristics of the combustion of metal particle groups have been addressed in this research. The combustion behavior and interaction effects of multiple metal particles has been studied using a microgravity environment, which presents a unique opportunity to create an "aerosol" consisting of relatively large particles, i.e., 50-300 micrometer diameter. Combustion behavior of such an aerosol could be examined using methods adopted from well-developed single particle combustion research. The experiment included fluidizing relatively large (order of 100 micrometer diameter) uniform metal particles under microgravity and igniting such an "aerosol" using a hot wire igniter. The flame propagation and details of individual particle combustion and particle interaction have been studied using a high speed movie and video-imaging with cameras coupled with microscope lenses to resolve individual particles. Interference filters were used to separate characteristic metal and metal oxide radiation bands form the thermal black body radiation. Recorded flame images were digitized and employed to understand the processes occurring in the burning aerosol. The development of individual particle flames, merging or separation, and extinguishing as well as induced particle motion have been analyzed to identify the mechanisms governing these processes. Size distribution, morphology, and elemental compositions of combustion products were characterized and used to link the observed in this project aerosol combustion phenomena with the recently expanded mechanism of single metal particle combustion.

Dreizin, Edward L.↗