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At least 1,117 records · Page 62

Janus Nanocages of Platinum-Group Metals and Their Use as Effective Dual-Electrocatalysts

Janus nanocages with distinctive platinum-group metals on the outer and inner surfaces can naturally catalyze at least two different reactions. In this work, we report a general method based on successive deposition and then selective etching for the facile synthesis of such nanocages. Herein, we have fabricated 11 different types of Janus nanocages characterized by a uniform size and well-defined {100} facets, together with porous, ultrathin, asymmetric walls up to 1.6 nm thick. When tested as dual-electrocatalysts toward oxygen reduction and evolution reactions, the Janus nanocages based on Pt and Ir exhibited superior activities depending on the thickness and relative position of the metal layer. Density functional theory studies suggest that the alloy composition and surface structure of the nanocages both play important roles in enhancing the electrocatalytic activities by modulating the stability of key reaction intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental study of thin-walled composite beams

Thin-walled rectangular section composite beams are built out of graphite-epoxy prepreg tape using an autoclave molding technique. Cantilevered beams are tested under static loads using a specially-built apparatus and bending slope and elastic twist at a station are measured using a laser system. Measured bending slope and bending-induced twist distributions are correlated with predicted results obtained using a simple beam analysis as well as a refined finite element analysis. Natural vibration characteristics at different rotational speeds are determined experimentally by testing beams in a specially built 10 ft diameter vacuum chamber. The rotor is excited by piezo-electric crystals and response is determined from strain gages mounted on the surface. For composite beams with bending-twisting couplings (symmetric layup), effects of section warping and transverse shear on structural response are found to be substantial. These results were substantiated by the analyses.

Chandra, Ramesh↗

A Machine Learning Framework for Modeling Ensemble Properties of Atomically Disordered Materials

Atomic disorder can strongly influence material properties such as charge transport, optical response, and catalytic activity. However, efficiently modeling these disorder effects remains challenging for first-principles methods due to the cost of sampling large configurational spaces and computing complex physical quantities. Recent advances of machine learning techniques, particularly graph neural networks (GNNs), has enabled the efficient and accurate predictions of complex material properties, offering promising tools for studying disordered systems. In this work, we present a general machine-learning-assisted computational framework that integrates equivariant GNNs with Monte Carlo simulations to compute the thermodynamic and ensemble-averaged functional properties of disordered materials. Using the surface-termination-disordered MXene monolayer Ti 3 C 2 T 2–x as a representative system, we find that electrical conductivity exhibits an emergent peak near the order–disorder phase transition temperature due to the interplay between electron scattering and doping. In contrast, optical conductivity remains largely insensitive to local atomic disorder and reflects the global surface chemical composition. These results highlight the role of atomic disorder in affecting material properties and demonstrate the potential of our approach for statistically modeling disorder effects in a wide range of materials such as high-entropy alloys and spin liquids.

MXene↗

Elemental Composition Variations for Large Dusty and Rocky Regions on Mars Using Gamma-Ray Data from the Mars Odyssey Gamma-Ray Spectrometer

The Gamma-Ray Spectrometer (GRS) on the Mars Odyssey spacecraft has been mapping the elemental composition of the surface materials since June 2002. To study elemental composition variations on the martian surface, seven large regions of Mars were selected: three very dusty ones and four mainly rocky ones. Large regions were used to get good counting statistics on as many gamma-ray peaks as possible from spectrum accumulated by the GRS experiment on Mars Odyssey, including elements with poor counting statistics. Data from TES were used to help select these regions. Gamma-ray peaks for several elements were analyzed. Some results and trends are reported.

Evans, L. G.↗

Air maintenance tire

A self-inflating tire assembly includes an air tube mounted within a tire sidewall groove. The air tube is in contacting engagement with opposite angled groove surfaces surrounding the air tube. A segment of the air tube is flattened from an expanded diameter to a flat diameter by bending and compression of the groove in a rolling tire footprint to force air evacuated from the flattened segment along a tube air passageway. The sidewall groove extends into an annular, axially extending, sidewall surface such as an axially oriented surface of a tire chafer protrusion located in non-contacting relationship with the rim. The opposite groove surfaces comprise a rubber composition, the rubber composition comprising: a diene based rubber; from 0.25 to 5 parts by weight, per 100 parts by weight of rubber (phr), of a self-lubrication agent capable of migrating from the rubber composition to the groove surface and disposing on the groove surface as a liquid; and from 1 to 15 parts by weight, per 100 parts by weight of rubber (phr), of a vulcanization modifier for use in the second rubber composition include α,ω-bis(N,N′-dihydrocarbylthiocarbamamoyldithio)alkanes, bismaleimides, and biscitraconimides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Air maintenance tire

The present invention is directed to a pneumatic tire comprising a sidewall component, the sidewall component including an air passageway extending at least partially about the circumference of the tire, the air passageway surrounded by and in fluid communication with a surface comprising a rubber composition, the rubber composition comprising: a diene based rubber; from 0.25 to 5 parts by weight, per 100 parts by weight of rubber (phr), of a self-lubrication agent capable of migrating from the rubber composition to the groove surface and disposing on the groove surface as a liquid; and from 1 to 15 parts by weight, per 100 parts by weight of rubber (phr), of a vulcanization modifier for use in the second rubber composition include α,ω-bis(N,N′-dihydrocarbylthiocarbamamoyldithio)alkanes, bismaleimides, and biscitraconimides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Response of the Quasi-Biennial Oscillation to historical volcanic eruptions

The impact of volcanic eruptions on surface climate is well-appreciated, but their in situ impact on the Quasi-Biennial Oscillation (QBO) has received comparatively little attention. This study examines the QBO responses to Krakatoa and Pinatubo using five configurations of the NASA Goddard Institute for Space Studies (GISS) Model E2.2 and MERRA-2 reanalysis. A dynamically consistent response is found in terms of static stability, zonal wind, and upwelling. Eruptions are found to bias the QBO towards a westerly state, such that the QBO period response depends upon the phase at the time of eruption. The QBO does not have a clear amplitude response to an eruption, based on these simulations. The underlying mechanisms appear not to be influenced to fi rst-order by interactive composition, sea surface temperatures, or long-term trends in CO2 and ozone-depleting substances.

volcanic eruptions↗

Martian and Asteroid Dusts as Toxicological Risks for Human Exploration Missions

As the lunar dust toxicity project winds down, our attention is drawn to the potential toxicity of dust present at the surface of more distant celestial objects. Lunar dust has proven to be surprisingly toxic to the respiratory systems of test animals, so one might expect dust from other celestial bodies to hold toxicological surprises for us. At this point all one can do is consider what should be known about these dusts to characterize their toxicity, and then ask to what extent that information is known. In an ideal world it might be possible to suggest an exposure standard based on the known properties of a celestial dust without direct testing of the dust in laboratory animals. Factors known to affect the toxicity of mineral dusts under some conditions include the following: particle size distribution, particle shape/porosity, mineralogical properties (crystalline vs. amorphous), chemical properties and composition, and surface reactivity. Data from a recent Japanese mission to the S-type asteroid Itokawa revealed some surprises about the dust found there, given that there is only a very week gravitational field to hold the dust on the surface. On Mars the reddish-brown dust is widely distributed by global dust storms and by local clusters of dust devils. Past surface probes have revealed some of the properties of dust found there. Contemporary data from Curiosity and other surface probes will be weighed against the data needed to set a defensible safe exposure limit. Gaps will emerge.

James, John T.↗

Surface and bulk effects of K in Cu 1-x K x In 1-y Ga y Se 2 solar cells

Two strategies for enhancing photovoltaic (PV) performance in chalcopyrite solar cells were investigated: Cu 1-x K x In 1-y Ga y Se 2 absorbers with low K content (K/(K+Cu), or x ~ 0.07) distributed throughout the bulk, and CuIn 1-y Ga y Se 2 absorbers with KIn 1-y Ga y Se 2 grown on their surfaces. Distributing K throughout the bulk absorbers improved power conversion efficiency, open-circuit voltage (VOC) and fill factor (FF) for Ga/(Ga+In) of 0, 0.3 and 0.5. Surface KIn 1-y Ga y Se 2 and bulk x ~ 0.07 Cu 1-x K x In 1-y Ga y Se 2 films with Ga/(Ga+In), or y of 0.3 and 0.5 also had improved efficiency, VOC, and FF, relative to CuIn 1-y Ga y Se 2 baselines. On the other hand, y ~ 1 absorbers did not benefit from K introduction. Similar to Cu 1-x K x InSe 2 , the formation of Cu 1-x K x GaSe 2 alloys was favored at low temperatures and high Na supply by the substrate, relative to the formation of mixed-phase CuGaSe 2 + KGaSe 2 . KIn 1-y Ga y Se 2 alloys were grown for the first time, as evidenced by X-ray diffraction and ultraviolet/visible spectroscopy. For all Ga/(Ga+In) compositions, the surface KIn 1-y Ga y Se 2 absorbers had superior PV performance in buffered and buffer-free devices. However, the bulk x ~ 0.07 absorbers only outperformed the baselines in buffered devices. The data demonstrate that KIn 1-y Ga y Se 2 passivates the surface of CuIn 1-y Ga y Se 2 to increase efficiency, VOC, and FF, while bulk Cu 1-x K x In 1-y Ga y Se 2 absorbers with x ~ 0.07 enhance efficiency, VOC, and FF by some other mechanism.

(Cu,K)GaSe2↗

Spacecraft thermal control coatings

The Experiment AO 138-6 was located on the trailing edge of the Long Duration Exposure Facility as part of the French Cooperative Payload (FRECOPA) Experiment. It was purely passive in nature: material specimens 2 x 2 cm, independently mounted in sample-holders, with their surface in the same reference plane, were exposed to space. Thirty samples were set in a vacuum-tight canister which was opened in space a few days after LDEF deployment and closed while still in orbit ten months later; twenty-four samples were directly exposed to space for the total flight duration (preflight handling, shuttle bay environment, separation from shuttle, shuttle environment, LEO environment, docking, descent, transfer to KSC). Materials included paints (conductive or nonconductive), SSM's, polymeric films, surface coatings, composite materials, and metals. After sample retrieving, inspection and measurements were carried out in atmospheric laboratory conditions on each sample: observation with binocular lenses and scanning electron microscopy, spectral relectance and transmittance using an integrating sphere in the wavelength range 280-2300 nm, emissivity by the means of a Gier & Dunkle portable reflectometer, electron spectroscopy for chemical analysis-x-ray photoelectron spectroscopy (ESCA-XPS), and Rutherford backscattering spectroscopy (RBS) measurements on some selected samples. The results obtained from flight were compared to laboratory data obtained in UV-irradiation tests when these data were available. As a general statement a good spectral concordance is observed for all samples not in the canister so long as air recoveries are taken into account. For one material, the degradation is more important for the sample in the canister than for those of the same material mounted at the surface of the tray; for most samples in the canister the degradation is slightly higher than the one which can be predicted from laboratory standard irradiations. Contamination problems having been ruled out, the higher temperature experience by the samples on the inside of canister probably explains these phenomena.

Guillaumon, Jean-Claude↗

Sublacustrine geomorphology and modern sedimentation in a glacial scour basin, June Lake, eastern Sierra Nevada, U.S.A.

Small sub-alpine glacial lakes are often targeted as Holocene paleoclimate archives, but their evolution as landforms and depositional basins is understudied. At June Lake in the eastern Sierra Nevada of California (USA), bathymetry, surface sediment composition, and seismic stratigraphy are studied to assess the modern sedimentary system and gain insight into the basin's origins. A basin-wide seismic survey reveals sublacustrine morphological features that attest to the role of ice in scouring the June Lake basin, including a prominent abraded bedrock shoal and an adjacent overdeepened depression. The seismic survey reveals four acoustically distinct stratigraphic units that reflect the history of sedimentation following glacial scouring. The youngest of these is represented in the recovered lacustrine core records as hemipelagically deposited, organic-rich, laminated diatomaceous oozes alternating with coarse tephra beds. The organic-rich oozes are characterized by low carbon and nitrogen stable-isotope values and occur in profundal areas of the modern lake floor. These sediments suggest an algae-dominated productivity regime and preservation of organic matter at depth. With no perennial streams entering June Lake, surface-sediment grain-size distribution and geochemistry are controlled by water depth and basin morphology. Additional modern facies types include poorly sorted coarse detrital landslide deposits below steep basin walls and volcaniclastic sandy gravel in windward littoral areas. Here, these data provide a modern facies model for sedimentation in ice-scoured, hydrologically closed sub-alpine lakes and a baseline for future paleoclimate studies using June Lake sediment cores.

58 GEOSCIENCES↗

Radiolytic Cryovolcanism Revisited

Location of Enceladus within the inner magnetosphere of Saturn makes it likely that energetic electron irradiation, ion-neutral chemistry of the emergent cryovolcanic plume gas, and resultant radiolytic modification of surface ice composition could impact long-term evolution of molecular composition in the global ice crust. Thermally-driven convection of ice in the south polar terrain would bring radiolytic oxidant products into contact with subsurface reservoirs of primordial organics on million-year time scales. The chemical reactions leading to CO2 gas production as a primary gas-piston driver of cryovolcanic activity would be exponentially elevated in the warm-ice margins of a heated fluid. The fluid temperature is typically assumed to be below 273 K but could be much higher in a gas-pressurized deep subsurface environment. The Perrier Ocean model has demonstrated how a CO2-loaded fluid could account for the observed jets, while the heat content of the fluid arising from the moon's deeper interior could support high levels of chemical reactivity in the thermal margins. Since mass loss and tidal dissipation arguments do not support continuous activity over billions of years, the activity is likely very episodic so that even low-level energy sources including irradiation-driven radiolysis of surface ices could substantially contribute to the chemical dynamics of the activity apparently now in high phase. A multi-phase thermochemical model, and supporting laboratory measurements of temperature-dependent reaction rates, are needed to investigate these potentially complex processes.

Cooper, John F.↗

Geochemical and mineralogical interpretation of the Viking inorganic chemical results

The current status of geochemical, mineralogical, petrological interpretation of refined Viking Lander data is reviewed, and inferences that can be drawn from data on the composition of Martian surface materials are presented. The materials are dominantly fine silicate particles admixed with, or including, iron oxide particles. Both major element and trace element abundances in all samples are indicative of mafic source rocks (rather than more highly differentiated salic materials). The surface fines are nearly identical in composition at the two widely separated Lander sites, except for some lithologic diversity at the 100-m scale. This implies that some agency (presumably aeolian processes) has thoroughly homogenized them on a planetary scale. The most plausible model for the mineralogical constitution of the fine-grained surface materials at the two Lander sites is a fine-grained mixture dominated by iron-rich smectites, or their degradation products, with ferric oxides, probably including maghemite and carbonates (such as calcite), but not such less stable phases as magnesite or siderite.

Toulmin, P., III↗

A new perspective on the initial hydrogenation of $\mathrm{TiFe_{0.9}M_{0.1}}$ ($\mathrm{M = V, Cr, Fe, Co, Ni}$) gained from surface oxide analysis and nucleation thermodynamics

Despite the promise of TiFe-based alloys as low-cost solid-state hydrogen storage materials with mild operating conditions and reasonable hydrogen capacity, their initial hydrogenation process is difficult, hindering broad utilization. The effect of alloying element on the initial hydrogenation kinetics of TiFe alloys, TiFe 0.9 M 0.1 (M = V, Cr, Fe, Co and Ni), was evaluated by analyzing changes to the passivating surface oxide layer that inhibits hydrogen permeation, as well as the ease of initial-stage hydrogen absorption into the underlying matrix. X-ray photoelectron spectroscopy and atom probe tomography revealed key variations in surface oxide compositions and thinning of the passivating oxide layer compared to pure TiFe, which suggests suppressed oxide growth by alloying-induced elemental redistribution. At the same time, density functional theory calculations predicted exothermic formation of hydride nuclei when alloying with V or Cr, as well as a reduced nucleation barrier when alloying with Co or Ni. Overall, these results are consistent with the observed experimental trend of the activation kinetics. We propose that improvements in activation kinetics of TiFe with alloying arises from the combined effect of reduced passivating oxide thickness and easier hydride nucleation, offering a starting point for alloy design strategies towards further improvement.

25 ENERGY STORAGE↗

The Effects of Fiber Surface Modification and Thermal Aging on Composite Toughness and Its Measurement

A detailed experimental study was conducted to establish the structure-property relationships between elevated temperature aging and fiber-matrix bonding, Mode 2 interlaminar fracture toughness, and failure modes of carbon fiber/PMR-15 composites. The fiber-matrix adhesion was varied by using carbon fibers with different surface treatments. Short beam shear tests were used to quantify the interfacial shear strength afforded by the use of the different fiber surface treatments. The results of the short beam shear tests showed that, for times up to 1000 hr, the aging process caused no changes in the bulk of the three composite materials that would degrade the shear properties of the material. Comparisons between the interlaminar shear strengths (ILSS) measured by the short beam shear tests and the GIIC test results, as measured by the ENF test, indicated that the differences in the surface treatments significantly affected the fracture properties while the effect of the aging process was probably limited to changes at the starter crack tip. The fracture properties changed due to a shift in the fracture from an interfacial failure to a failure within the matrix when the fiber was changed from AU-4 to AS-4 or AS-4G. There appears to be an effect of the fiber/matrix bonding on the thermo-oxidative stability of the composites that were tested. The low bonding afforded by the AU 1 fiber resulted in weight losses about twice those experienced by the AS 1 reinforced composites, the ones with the best TOS.

Bowles, Kenneth J.↗

Trace Metal Content and Speciation, Water and Soil Chemistry, and Methane Production for a Wetland in Missouri (September 2015) and in Florida (January 2016)

Data is associated with a manuscript in preparation for submission to explore whether low trace metal availability inhibits methane production in freshwater wetland soils. Reported data are from two field sites, one in Missouri and the second in Florida (see location data). At each site, surface water compositions and properties and soil compositions are reported. Trace metal availability is assessed via sequential chemical extractions, Ni K-edge X-ray absorption near edge structure (XANES) spectroscopy, and X-ray microfluorescence imaging. Soil mineralogy is determined via powder X-ray diffraction. Multi-energy X-ray microfluorescence imaging as well as bulk and microscale S K-edge XANES spectra assess sulfur speciation in the soils. This package also reports data from trace metal amendment experiments, specifically methane (CH4) production versus time in soil incubations, the dissolved trace metal concentrations in these incubations, and the Ni K-edge XANES and extended X-ray absorption fine structure (EXAFS) spectra of soils to which increasing concentrations of Ni were added. A final version of this package will be published upon acceptance of the associated manuscript.

54 ENVIRONMENTAL SCIENCES↗

The Effects of Fiber Surface Modification and Thermal Aging on Composite Toughness And its Measurement

A detailed experimental study was conducted to establish the structure-property relationships between elevated temperature aging and (I) fiber-matrix bonding, (2) Mode II interlaminar fracture toughness, and (3) failure modes of carbon fiber/PMR-15 composites. The fiber-matrix adhesion was varied by using carbon fibers with different surface treatments. Short beam shear tests were used to quantify the interfacial shear strength afforded by the use of the different fiber surface treatments. The results of the short beam shear tests definitely showed that, for aging times up to 1000 hr, the aging process caused no observable changes in the bulk of the three composite materials that---would degrade the shear properties of the material. Comparisons between the interlaminar shear strength (ILSS) measured by the short beam shear tests and the GII c test results, as measured by the ENF test, indicated that the differences in the surface treatments significantly affected the fracture properties while the effect of the aging process was probably limited to changes at the starter crack tip. The fracture properties changed due to a shift in the fracture from an interfacial failure to a failure within the matrix when the fiber was changed from AU-4 to AS-4 or AS-4G. There appears to be an effect of the fiber/matrix bonding on the thermo-oxidative stability of the composites that were tested. The low bonding afforded by the AU-4 fiber resulted in weight losses about twice those experienced by the AS-4 reinforced composites, the ones with the best TOS.

Bowles, Kenneth J.↗

Multifunctional ferrofluid-infused surfaces with reconfigurable multiscale topography

Developing adaptive materials with geometries that change in response to external stimuli provides fundamental insights into the links between the physical forces involved and the resultant morphologies and creates a foundation for technologically relevant dynamic systems. In particular, reconfigurable surface topography as a means to control interfacial properties has recently been explored using responsive gels, shape-memory polymers, liquid crystals and hybrid composites, including magnetically active slippery surfaces. However, these designs exhibit a limited range of topographical changes and thus a restricted scope of function. Here we introduce a hierarchical magneto-responsive composite surface, made by infiltrating a ferrofluid into a microstructured matrix (termed ferrofluid-containing liquid-infused porous surfaces, or FLIPS). We demonstrate various topographical reconfigurations at multiple length scales and a broad range of associated emergent behaviours. An applied magnetic-field gradient induces the movement of magnetic nanoparticles suspended in a viscous fluid, which leads to microscale flow of this ferrofluid first above and then within the microstructured surface. This redistribution changes the initially smooth surface of the ferrofluid (which is immobilized by the porous matrix through capillary forces) into various multiscale hierarchical topographies shaped by the size, arrangement and orientation of the confining microstructures in the magnetic field. We analyse the spatial and temporal dynamics of these reconfigurations theoretically and experimentally as a function of the balance between capillary and magnetic pressures and of the geometric anisotropy of the FLIPS system. Several interesting functions at three different length scales are demonstrated: self-assembly of colloidal particles at the micrometre scale; regulated flow of liquid droplets at the millimetre scale; and switchable adhesion and friction, liquid pumping and removal of biofilms at the centimetre scale. We envision that FLIPS could be used as part of integrated control systems for the manipulation and transport of matter, thermal management, microfluidics and fouling-release materials.

36 MATERIALS SCIENCE↗