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At least 343 records · Page 19

Strain‐Enhanced Metallic Intermixing in Shape‐Controlled Multilayered Core–Shell Nanostructures: Toward Shaped Intermetallics

Abstract Controlling the surface composition of shaped bimetallic nanoparticles could offer precise tunability of geometric and electronic surface structure for new nanocatalysts. To achieve this goal, a platform for studying the intermixing process in a shaped nanoparticle was designed, using multilayered Pd‐Ni‐Pt core–shell nanocubes as precursors. Under mild conditions, the intermixing between Ni and Pt could be tuned by changing layer thickness and number, triggering intermixing while preserving nanoparticle shape. Intermixing of the two metals is monitored using transmission electron microscopy. The surface structure evolution is characterized using electrochemical methanol oxidation. DFT calculations suggest that the low‐temperature mixing is enhanced by shorter diffusion lengths and strain introduced by the layered structure. The platform and insights presented are an advance toward the realization of shape‐controlled multimetallic nanoparticles tailored to each potential application.

Williams, Benjamin P.↗

Strain-Enhanced Metallic Intermixing in Shape-Controlled Multilayered Core–Shell Nanostructures: Toward Shaped Intermetallics

Controlling the surface composition of shaped bimetallic nanoparticles could offer precise tunability of geometric and electronic surface structure for new nanocatalysts. To achieve this goal, a platform for studying the intermixing process in a shaped nanoparticle was designed, using multilayered Pd-Ni-Pt core–shell nanocubes as precursors. Under mild conditions, the intermixing between Ni and Pt could be tuned by changing layer thickness and number, triggering intermixing while preserving nanoparticle shape. Intermixing of the two metals is monitored using transmission electron microscopy. The surface structure evolution is characterized using electrochemical methanol oxidation. DFT calculations suggest that the low-temperature mixing is enhanced by shorter diffusion lengths and strain introduced by the layered structure. The platform and insights presented are an advance toward the realization of shape-controlled multimetallic nanoparticles tailored to each potential application.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhancing Low-Temperature Syngas Production via Surface Tailoring of Supported Intermetallic Nanocatalysts

An active and coke-resistant silica-encapsulated intermetallic Ni 3 Zn nanoparticle catalyst was developed for low-temperature (450 °C) dry reforming of methane (DRM). The catalyst exhibited a remarkable 4-fold increase in activity (4.5 s –1 ) with over 99% CO selectivity and 3 orders of magnitude less carbonaceous species and demonstrated remarkable stability (70 h) compared to that of a monometallic Ni catalyst. Here, the key is the combined effect of surface ensemble structure and electronic interaction modulation through the surface composition tailoring achieved by off-stoichiometric Ni and Zn loading in controlling surface chemistry for achieving different activities and H 2 /CO ratios. Characterized by ion spectroscopy, X-ray photoelectron spectroscopy, and the neutron pair distribution function, it was revealed that paired Ni δ – –Zn δ+ active sites are crucial for DRM. Transient infrared spectroscopy and isotopic analysis uncovered the synergistic effect of Ni δ – –Zn δ+ sites in activating C–H bonds and dissociating CO 2 to prevent coke formation under low-temperature conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tungsten–carbon surface evolution and erosion modeling for a small angle slot divertor in DIII-D

Abstract We modeled tungsten–carbon mixed surface evolution, sputtering erosion, and transport for the tungsten coated region of a small angle slot (SAS) divertor design for the DIII-D tokamak. This divertor concept aims to achieve a closed slot dissipative plasma to minimize heat load and surface erosion, and to study high- Z material performance. Our advanced simulations use coupled ITMC-DYN material mixing/response and 3D full kinetic REDEP/WBC erosion/redeposition code packages, with divertor plasma solution from the SOLPS-ITER package with 4 MW power input. The SAS design geometry and resulting in-slot plasma parameters cause significant differences in predicted sputter/transport from a conventional divertor. For 2% C/D incident plasma ratio, an equilibrium mixed C/W surface is attained at ∼30 s of discharge, from wall sputtered carbon transported to the 10 cm long tungsten divertor region. Tungsten remains exposed to the plasma, but the evolved surface composition varies with different C/D ratios. Tungsten is primarily sputtered from the mixed surface by impinging carbon ions in the +1 to +4 charge states, with some self-sputtering. Redeposition of sputtered tungsten to the divertor is significant, ∼80% along the higher plasma temperature attached plasma SAS entrance region, but this is less than the typically near-unity values for a conventional divertor. Plasma-incident carbon is highly backscattered (∼50%) from the mixed surface, with little redeposition (<10%); this helps maintain tungsten in the surface sputter zone. Carbon is mainly sputtered from the mixed surface by D + ions, also with low redeposition (∼10%–30%). Finally, the modeling shows non-zero but low sputtered tungsten current from the divertor to the core plasma direction. These results appear favorable for effective testing of a tungsten-containing SAS divertor in DIII-D, and extrapolation of mixed-material evolution/response findings to the analogous low- Z /high- Z , Be/W, ITER plasma facing system.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Global Variations in Regolith Properties on Asteroid Vesta from Dawn's Low-Altitude Mapping Orbit

We investigate the depth, variability, and history of regolith on asteroid Vesta using data from the Dawn spacecraft. High-resolution (15-20 m pixel(sup -1)) Framing Cameraimages are used to assess the presence of morphologic indicators of a shallow regolith,including the presence of blocks in crater ejecta, spur-and-gully-type features in crater walls,and the retention of small (less than 300 m) impact craters. Such features reveal that the broad,regional heterogeneities observed on Vesta in terms of albedo and surface composition extend to the physical properties of the upper approx. 1 km of the surface. Regions of thin regolithare found within the Rheasilvia basin and at equatorial latitudes from approx. 0-90 deg. E and approx.260-360 deg. E. Craters in these areas that appear to excavate material from beneath the regolithhave more diogenitic (Rheasilvia, 090 deg. E) and cumulate eucrite (260-360 deg. E) compositions.A region of especially thick regolith, where depths generally exceed 1 km, is found from approx.100-240 deg. E and corresponds to heavily cratered, low-albedo surface with a basaltic eucritecomposition enriched in carbonaceous chondrite material. The presence of a thick regolithin this area supports the idea that this is an ancient terrain that has accumulated a larger component of exogenic debris. We find evidence for the gardening of crater ejecta towardmore howarditic compositions, consistent with regolith mixing being the dominant form of "weathering" on Vesta.

asteroid↗

Experimental investigations of Critical Heat Flux re-occurrence on post-CHF surfaces

Under the extreme environments of light water reactors, the cladding materials demonstrate evolutionary transformations in terms of material compositions, surface morphologies, and thermal-physical properties. This study investigates how the temperature overshooting of Critical Heat Flux (CHF) affects the re-occurrence of CHF on the post-CHF surfaces. Experimental results reveal that the CHF difference between as-received and post-CHF surfaces can be significant, which depends on materials. CHF is enhanced on post-CHF Stainless Steel (SS 316) specimens while it deteriorates on post-CHF Inconel-600 specimens. In comparison with the as-received surfaces, the post-CHF surface of SS 316 is more hydrophobic, while Inconel 600 is more hydrophilic. The scanning electron microscope micrographs of post-CHF surfaces show that surface morphologies that are structured by oxide crystals are formed on SS 316 samples but not on Inconel 600 samples. The physical rationale behind the CHF difference could be boiling heat transfer conjugated with thermal-physical proprieties of investigated surface materials and surface morphologies features. In conclusion, the results imply that it is indispensable to bookkeep the evolutionary changes of cladding surface materials, especially for cladding candidates of Accident Tolerant Fuel since operation histories can leave footprints on cladding surfaces, thus resulting in CHF re-occurrence differences.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Microscopy of Analogs for Martian Dust and Soil

The upcoming Mars 2001 lander will carry an atomic force microscope (AFM) as part of the Mars Environmental Compatibility Assessment (MECA) payload. By operating in a tapping mode, the AFM is capable of sub-nanometer resolution in three dimensions and can distinguish between substances of different compositions by employing phase-contrast imaging. Phase imaging is an extension of tapping-mode AFM that provides nanometer-scale information about surface composition not revealed in the topography. Phase imaging maps the phase of the cantilever oscillation during the tapping mode scan, hence detecting variations in composition, adhesion, friction, and viscoelasticity. Because phase imaging highlights edges and is not affected by large-scale height differences, it provides for clearer observation of fine features, such as grain edges, which can be obscured by rough topography. To prepare for the Mars 01 mission, we are testing the AFM on a lunar soil and terrestrial basaltic glasses to determine the AFMOs ability to define particle shapes and sizes and grain-surface textures. The test materials include the Apollo 17 soil 79221, which is a mixture of agglutinates, impact and volcanic beads, and mare and highland rock and mineral fragments. The majority of the lunar soil particles are less than 100 microns in size, comparable to the sizes estimated for Martian dust. The terrestrial samples are millimeter size basaltic glasses collected on Black Pointe at Mono Lake, just north of the Long Valley caldera in California. The basaltic glass formed by a phreatomagmatic eruption 13,000 years ago beneath a glacier that covered the Mono Lake region. Because basaltic glass formed by reworking of pyroclastic deposits may represent a likely source for Martian dunes, these basaltic glass samples represent plausible analogs to the types of particles that may be studied in sand dunes by the 01 lander and rover. We have used the AFM to examine several different soil particles at various resolutions. The instrument has demonstrated the ability to identify parallel ridges characteristic of twinning on a 150-micron plagioclase feldspar particle. Extremely small (10-100 nanometer) adhering particles are visible on the surface of the feldspar grain, and appear elongate with smooth surfaces. Phase contrast imaging of the nanometer particles shows several compositions to be present. When the AFM was applied to a 100-micron glass spherule, it was possible to define an extremely smooth surface.E Also visible on the surface of the glass spherule were chains of 100-nanometer- and-smaller impact melt droplets. Additional information is contained in the original extended abstract.

Anderson, M. A.↗

Basalt Alteration in a CO 2 -SO 2 Atmosphere: Implications for Surface Processes on Venus

Venus’ surface and interior dynamics remain largely unconstrained, due in great part to the major obstacles to exploration imposed by its 470°C, 90 bar surface conditions and its thick, opaque atmosphere. Orbiter-based thermal emission data provide opportunities to characterize the surface composition of Venus. However, interpretations of such spectra depend on understanding interactions between the planet’s surface basaltic rocks and its caustic, sulfur dioxide (SO 2 )-bearing carbon dioxide (CO 2 ) atmosphere. Several studies, using remote sensing, thermodynamic modeling, and laboratory experiments, have placed constraints on basaltic alteration mineralogies and rates. Yet constraint with respect to SO 2 -mediated reactions with basalts of contrasting compositions remains incomplete. Here, we present new data from a series of gas-solid reaction experiments, in which samples of two basalt compositions were reacted in an SO 2 -bearing CO 2 atmosphere, at relevant Venus temperatures, pressure, and oxygen fugacity. We subjected reacted specimens to scanning electron microscopy (SEM) and scanning transmission electron microscopy (STEM) analyses using sample cross-sections produced with focused ion beam (FIB) milling. Surface alteration products were characterized, and their abundances estimated; subsurface cation concentrations were mapped to show depth of alteration. We demonstrate that the initial rate of reaction in our experiments is very rapid. Alkaline basalt samples are coated by (meta)thenardite (Na 2 SO 4 ) and amorphous calcium carbonate (CaCO 3 ) alteration products, and tholeiitic basalt samples are primarily covered by anhydrite (CaSO 4 ), Fe-oxide (Fe x O y : likely magnetite, Fe 3 O 4 ), and other minor phases.

Venus↗

Resolving Chemical and Spatial Heterogeneities at Complex Electrochemical Interfaces in Li-Ion Batteries

The high specific capacities of Ni-rich transition metal oxides have garnered immense interest for improving the energy density of Li-ion batteries (LIBs). Despite the potential of these materials, Ni-rich cathodes suffer from interfacial instabilities that lead to crystallographic rearrangement of the active material surface as well as the formation of a cathode electrolyte interphase (CEI) layer on the composite during electrochemical cycling. While changes in crystallographic structure can be detected with diffraction-based methods, probing the chemistry of the disordered, heterogeneous CEI layer is challenging. In this work, we use a combination of ex situ solid-state nuclear magnetic resonance (SSNMR) spectroscopy and X-ray photoemission electron microscopy (XPEEM) to provide chemical and spatial information, on the nanometer length scale, on the CEI deposited on LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) composite cathode films. XPEEM elemental maps offer insight into the lateral arrangement of the electrolyte decomposition products that comprise the CEI and paramagnetic interactions (assessed with electron paramagnetic resonance (EPR) and relaxation measurements) in 13 C SSNMR provide information on the radial arrangement of the CEI from the NMC811 particles outward. Using this approach, here we find that LiF, Li 2 CO 3 , and carboxy-containing structures are directly appended to NMC811 active particles, whereas soluble species detected during in situ 1 H and 19 F solution NMR experiments (e.g., alkyl carbonates, HF, and vinyl compounds) are randomly deposited on the composite surface. We show that the combined approach of ex situ SSNMR and XPEEM, in conjunction with in situ solution NMR, allows spatially-resolved, molecular-level characterization of paramagnetic surfaces and new insights into electrolyte oxidation mechanisms in porous electrode films.

36 MATERIALS SCIENCE↗

NASA's surface biology and geology designated observable: A perspective on surface imaging algorithms

The 2017-2027 National Academies' Decadal Survey, Thriving on Our Changing Planet, recommended Surface Biology and Geology (SBG) as a "Designated Targeted Observable" (DO). The SBG DO is based on the need for capabilities to acquire global, high spatial resolution, visible to shortwave infrared (VSWIR; 380 - 2500 nm; ~30 m pixel resolution) hyperspectral (imaging spectroscopy) and multispectral midwave and thermal infrared (MWIR: 3-5 µm; TIR: 8-12 µm; ~60 m pixel resolution) measurements with sub-monthly temporal revisits over terrestrial, freshwater, and coastal marine habitats. To address the various mission design needs, an SBG Algorithms Working Group of multidisciplinary researchers has been formed to review and evaluate the algorithms applicable to the SBG DO across a wide range of Earth science disciplines, including terrestrial and aquatic ecology, atmospheric science, geology, and hydrology. Here, we summarize current state-of-the-practice VSWIR and TIR algorithms that use airborne or orbital spectral imaging observations to address the SBG DO priorities identified by the Decadal Survey: (i) terrestrial vegetation physiology, functional traits, and health; (ii) inland and coastal aquatic ecosystems physiology, functional traits, and health; (iii) snow and ice accumulation, melting, and albedo; (iv) active surface composition (eruptions, landslides, evolving landscapes, hazard risks); (v) effects of changing land use on surface energy, water, momentum, and carbon fluxes; and (vi) managing agriculture, natural habitats, water use/quality, and urban development. We review existing algorithms in the following categories: snow/ice, aquatic environments, geology, and terrestrial vegetation, and summarize the community-state-of-practice in each category. Finally, this effort synthesizes the findings of more than 130 scientists.

54 ENVIRONMENTAL SCIENCES↗

Direct visualization of radiation-induced transformations at alkali halide–air interfaces

Radiation driven reactions at mineral/air interfaces are important to the chemistry of the atmosphere, but experimental constraints (e.g. simultaneous irradiation, in situ observation, and environmental control) leave process understanding incomplete. Using a custom atomic force microscope equipped with an integrated X-ray source, transformation of potassium bromide surfaces to potassium nitrate by air radiolysis species was followed directly in situ at the nanoscale. Radiolysis initiates dynamic step edge dissolution, surface composition evolution, and ultimately nucleation and heteroepitaxial growth of potassium nitrate crystallites mediated by surface diffusion at rates controlled by adsorbed water. Finally, in contrast to in situ electron microscopy and synchrotron-based imaging techniques where high radiation doses are intrinsic, our approach illustrates the value of decoupling irradiation and the basis of observation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reduced Graphene Oxide Aerogels with Functionalization-Mediated Disordered Stacking for Sodium-Ion Batteries

Surface modified reduced graphene oxide (rGO) aerogels were synthesized using the hydrothermal method. Ethylene diamine (EDA) and α-cyclodextrin (CD) were used to functionalize the surface of the graphene oxide layers. The oxygen reduction and surface modification occurred in-situ during the hydrothermal self-assembly process. The chemical functionality and structure of the resulting ethylene diamine modified (rGO-EDA) and cyclodextrin modified (rGO-CD) aerogels as well as of the pristine unmodified rGO aerogel were studied using XPS, SEM, XRD, and SANS techniques. The overall surface composition showed a significant decrease in the oxygen content for all synthesized aerogels. The surface modified aerogels were characterized by a disordered stacking of the assembled rGO layers. The surface functionalities resulted in a broad distribution of the interlayer spacing and introduced structural heterogeneities. Such disordered structures can enable a better adsorption mechanism of the sodium ions. Coin cells based on the synthesized aerogels and sodium metal were assembled and tested at several charge and discharge rates. The correlation between the surface functionality of the rGO, the induced structural heterogeneities due to the disordered stacking, and the electrochemical performance of sodium-ion batteries were investigated. Operando XRD measurements were carried out during the battery cycling to investigate the adsorption or intercalation nature of the sodiation mechanism.

25 ENERGY STORAGE↗

The application of surface analysis to polymer/metal adhesion

The use of scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) in the analysis of Ti 6-4 adherend surfaces is described. Differences in Ti 6-4 surface composition as determined by XPS after different chemical pretreatments are detailed. Analysis of fractured surfaces by SEM/XPS is used to establish the failure mode. The surface acidity of Ti 6-4 coupons can be established by reflectance visible spectroscopy using indicator dyes.

Wightman, J. P.↗

Space Weathering Impact on Solar System Surfaces and Planetary Mission Science

We often look "through a glass, darkly" at solar system bodies with tenuous atmospheres and direct surface exposure to the local space environment. Space weathering exposure acts via universal space-surface interaction processes to produce a thin patina of outer material covering, potentially obscuring endogenic surface materials of greatest interest for understanding origins and interior evolution. Examples of obscuring exogenic layers are radiation crusts on cometary nuclei and iogenic components of sulfate hydrate deposits on the trailing hemisphere of Europa. Weathering processes include plasma ion implantation into surfaces, sputtering by charged particles and solar ultraviolet photons, photolytic chemistry driven by UV irradiation, and radiolytic chemistry evolving from products of charged particle irradiation. Regolith structure from impacts, and underlying deeper structures from internal evolution, affects efficacy of certain surface interactions, e.g. sputtering as affected by porosity and surface irradiation dosage as partly attenuated by local topographic shielding. These processes should be regarded for mission science planning as potentially enabling, e.g. since direct surface sputtering, and resultant surface-bound exospheres, can provide in-situ samples of surface composition to ion and neutral mass spectrometers on orbital spacecraft. Sample return for highest sensitivity compOSitional and structural analyses at Earth will usually be precluded by limited range of surface sampling, long times for return, and high cost. Targeted advancements in instrument technology would be more cost efficient for local remote and in-situ sample analysis. More realistic laboratory simulations, e.g. for bulk samples, are needed to interpret mission science observations of weathered surfaces. Space environment effects on mission spacecraft and science operations must also be specified and mitigated from the hourly to monthly changes in space weather and from longer term (e.g., solar cycle) evolution of space climate. Capable instrumentation on planetary missions can and should be planned to contribute to knowledge of interplanetary space environments. Evolving data system technologies such as virtual observatories should be explored for more interdisciplinary application to the science of planetary surface, atmospheric, magnetospheric, and interplanetary interactions.

Cooper, John F.↗

Widespread Weathered Glass on the Surface of Mars

Low albedo sediments cover >10(exp 7) sq km in the northern lowlands of Mars, but the composition and origin of these widespread deposits have remained ambiguous despite many previous investigations. Here we use near-infrared spectra acquired by the Mars Express OMEGA (Observatoire pour la Mineralogie, l'Eau, les Glaces, et l'Activite') imaging spectrometer to show that these sediments exhibit spectral characteristics that are consistent with both high abundances of iron-bearing glass and silica-enriched leached rinds on glass. This interpretation is supported by observations of low-albedo soil grains with possible rinds at the Phoenix Mars Lander landing site in the northern lowlands. By comparison with the extensive glass-rich dune fields and sand sheets of Iceland, we propose an explosive volcanic origin for these glass-rich sediments. We also propose that the glassy remnant rinds on the sediments are the result of post-depositional alteration, as these rinds are commonly formed in arid terrestrial volcanic environments during water-limited, moderately acidic leaching. These weathered, glass-rich deposits in the northern lowlands are also colocated with the strongest concentrations of a major global compositional surface type previously identified in mid-infrared spectra, suggesting that they may be representative of global processes. Our results provide potential confirmation of models suggesting that explosive volcanism has been widespread on Mars, and also raise the possibilities that glass-rich volcaniclastics are a major source of eolian sand on Mars and that widespread surficial aqueous alteration has occurred under Amazonian climatic conditions.

Horgan, Briony↗

Lotus Dust Mitigation Coating and Molecular Adsorber Coating

NASA Goddard Space Flight Center has developed two unique coating formulations that will keep surfaces clean and sanitary and contain contaminants.The Lotus Dust Mitigation Coating, modeled after the self-cleaning, water-repellant lotus leaf, disallows buildup of dust, dirt, water, and more on surfaces. This coating, has been successfully tested on painted, aluminum, glass, silica, and some composite surfaces, could aid in keeping medical assets clean.The Molecular Adsorber Coating is a zeolite-based, sprayable molecular adsorber coating, designed to prevent outgassing in materials in vacuums. The coating works well to adsorb volatiles and contaminates in manufacturing and processing, such as in pharmaceutical production. The addition of a biocide would also aid in controlling bacteria levels.

protective coatings↗

NASA's Surface Biology and Geology Designated Observable: A Perspective on Surface Imaging Algorithms

The 2017–2027 National Academies’ Decadal Survey, Thriving on Our Changing Planet, recommended Surface Biology and Geology (SBG) as a “Designated Targeted Observable” (DO). The SBG DO is based on the need for capabilities to acquire global, high spatial resolution, visible to shortwave infrared (VSWIR; 380–2500 nm; ~30 m pixel resolution) hyperspectral (imaging spectroscopy) and multispectral midwave and thermal infrared (MWIR: 3–5 μm; TIR: 8–12 μm; ~60 m pixel resolution) measurements with sub-monthly temporal revisits over terrestrial, freshwater, and coastal marine habitats. To address the various mission design needs, an SBG Algo-rithms Working Group of multidisciplinary researchers has been formed to review and evaluate the algorithms applicable to the SBG DO across a wide range of Earth science disciplines, including terrestrial and aquatic ecology, atmospheric science, geology, and hydrology. Here, we summarize current state-of-the-practice VSWIR and TIR algorithms that use airborne or orbital spectral imaging observations to address the SBG DO priorities identified by the Decadal Survey: (i) terrestrial vegetation physiology, functional traits, and health; (ii) inland and coastal aquatic ecosystems physiology, functional traits, and health; (iii) snow and ice accumulation, melting, and albedo; (iv) active surface composition (eruptions, landslides, evolving landscapes, hazard risks); (v) effects of changing land use on surface energy, water, momentum, and carbon fluxes; and (vi) managing agriculture, natural habitats, water use/quality, and urban development. We review existing algorithms in the following categories: snow/ice, aquatic environments, geology, and terrestrial vegetation, and summarize the community-state-of-practice in each category. This effort synthesizes the findings of more than 130 scientists.

Aquatic↗

Enhancement and Analysis of Real-Time Radiography Images

Shuttle Redesigned Solid Rocket Motor (RSRM) nozzle interiors fabricated from carbon phenolic composite exhibit "ply lift" when hot fired. The composite surface is smooth when fabricated, but the individual plies separate and lift away from the surface when exposed to high temperature and high-pressure exhaust gas. It shows a cross section of a post-fired composite in which ply lift is evident as dark fissures. Surface charring is also visible as a darker band about 0.2 inches thick. Charring is normal, but ply lift is not desirable since the fissures could possibly initiate an abnormal exhaust path from the RSRM. The underlying mechanisms of ply lift are under investigation as part of the Shuttle Return-To-Flight Program.

Doering, Edward R.↗