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At least 433 records · Page 24

Facet Impact of CuMn 2 O 4 Spinel Nanocatalysts on Enhancement of the Oxygen Reduction Reaction in Alkaline Media

Surface-structure engineering represents an attractive strategy to optimize the energy conversion performance of nanocatalysts using their deliberately controlled exposed facets. To further exploit the potential of non-PGM-based spinel catalysts for alkaline oxygen reduction reaction (ORR), a cathodic fuel cell reaction, we hereby report a strategy of ORR improvement by controlling the crystallographic facets of ultra-small CuMn 2 O 4 spinel nanocatalysts through a developed colloidal synthesis approach. The synthesis of CuMn 2 O 4 nanocrystals with morphological control relies on the design and selection of the Cu-/Mn-precursors with striking discrepancies in reaction kinetics. Following carbon loading and an annealing post-treatment of the as-synthesized nanocatalysts, the exclusively {101} facet-exposed CuMn 2 O 4 spinel nano-octahedra exhibit improved electrocatalytic activity toward ORR in 1 M KOH, when compared to their spherical counterparts, exhibiting a mass activity (MA) of 37.6 A/g at 0.85 V. After 10,000 cycles of ORR durability test, the nano-octahedra still retain an MA of 24.5 A/g, which is twice that of the CuMn 2 O 4 spinel nanospheres. Structural characterizations after durability testing indicate that the MA decay is likely associated with a decrease in the Mn 3+ fraction and the emergence of Cu + on CuMn 2 O 4 nano-octahedral surfaces. Finally, as a paradigm, this synthesis approach could be extended to other Mn-based spinel nanocatalysts with precise shape control, enabling us to understand and establish the relationship between the surface lattice/valence state and electrocatalytic properties.

36 MATERIALS SCIENCE↗

Wetting transition and fluid trapping in a microfluidic fracture

Immiscible fluid–fluid displacement in confined geometries is a fundamental process occurring in many natural phenomena and technological applications, from geological CO 2 sequestration to microfluidics. Due to the interactions between the fluids and the solid walls, fluid invasion undergoes a wetting transition from complete displacement at low displacement rates to leaving a film of the defending fluid on the confining surfaces at high displacement rates. While most real surfaces are rough, fundamental questions remain about the type of fluid–fluid displacement that can emerge in a confined, rough geometry. Here, we study immiscible displacement in a microfluidic device with a precisely controlled structured surface as an analogue for a rough fracture. We analyze the influence of the degree of surface roughness on the wetting transition and the formation of thin films of the defending liquid. We show experimentally, and rationalize theoretically, that roughness affects both the stability and dewetting dynamics of thin films, leading to distinct late-time morphologies of the undisplaced (trapped) fluid. Finally, we discuss the implications of our observations for geologic and technological applications.

42 ENGINEERING↗

Plasma assisted surface coating/modification processes: An emerging technology

A broad understanding of the numerous ion or plasma assisted surface coating/modification processes is sought. An awareness of the principles of these processes is needed before discussing in detail the ion nitriding technology. On the basis of surface modifications arising from ion or plasma energizing and interactions, it can be broadly classified as deposition of distinct overlay coatings (sputtering-dc, radio frequency, magnetron, reactive; ion plating-diode, triode) and surface property modification without forming a discrete coating (ion implantation, ion beam mixing, laser beam irradiation, ion nitriding, ion carburizing, plasma oxidation). These techniques offer a great flexibility and are capable in tailoring desirable chemical and structural surface properties independent of the bulk properties.

Spalvins, T.↗

Plasma assisted surface coating/modification processes - An emerging technology

A broad understanding of the numerous ion or plasma assisted surface coating/modification processes is sought. An awareness of the principles of these processes is needed before discussing in detail the ion nitriding technology. On the basis of surface modifications arising from ion or plasma energizing and interactions, it can be broadly classified as deposition of distinct overlay coatings (sputtering-dc, radio frequency, magnetron, reactive; ion plating-diode, triode) and surface property modification without forming a discrete coating (ion implantation, ion beam mixing, laser beam irradiation, ion nitriding, ion carburizing, plasma oxidation. These techniques offer a great flexibility and are capable in tailoring desirable chemical and structural surface properties independent of the bulk properties.

Spalvins, T.↗

Estimation of effective aerodynamic roughness with altimeter measurements

A new method is presented for estimating the aerodynamic roughness length of heterogeneous land surfaces and complex landscapes using elevation measurements performed with an airborne laser altimeter and the Seasat radar altimeter. Land surface structure is characterized at increasing length scales by considering three basic landscape elements: (1) partial to complete canopies of herbaceous vegetation; (2) sparse obstacles (e.g., shrubs and trees); and (3) local relief. Measured parameters of land surface geometry are combined to obtain an effective aerodynamic roughness length which parameterizes the total atmosphere-land surface stress.

Menenti, M.↗

Return Echoes from Medium-Large Footprint Laser Altimeters

For just over 10 years, NASA Goddard Space Flight Center has been at the forefront of developing return echo laser altimeters and analysis techniques for a variety of both space and airborne applications. In 1991, the Laser Remote Sensing Branch began investigating the use of medium-large diameter footprint return waveforms for measuring vegetation height and structure and sub-canopy topography. Over the last 8 years, using a variety of profiling and scanning laser altimeters (i.e. ATLAS, SLICER, SLA, and LVIS), we have collected return waveforms over a variety of terrestrial surface types. We describe the effects of instrument characteristics and within-footprint surface structure on the shape of the return waveform and suggest several techniques for extracting this information. Specifically for vegetation returns, we describe the effects of canopy parameters such as architecture and closure on the shape of the return waveform. Density profiles, statistics, and examples from a variety of vegetation types will be presented, as well as comparisons with small-footprint laser altimeter data.

Blair, J. Bryan↗

Surface Monitoring of CFRP Structures for Adhesive Bonding

Adhesive bonding of composite materials requires reliable monitoring and detection of surface contaminants to assure robust and durable bonded structures. Surface treatment and effective monitoring prior to bonding is essential in order to obtain a surface free from contaminants that may degrade structural performance. Two techniques which monitor the effectiveness of the laser surface treatment of carbon fiber reinforced polymer (CFRP) materials are being investigated: laser induced breakdown spectroscopy (LIBS) and optically stimulated electron emission (OSEE). The applicability of LIBS to detect silicone contaminants on CFRP composites is studied using ~35 ns Nd:YAG laser pulses at 355 nm with a pulse energy of 45 mJ. The LIBS regime in which pulse energies are < 100 mJ is referred to as mLIBS. CFRP surfaces were contaminated with polydimethylsiloxane (PDMS), a major component of silicone based mold release agents. The presence of PDMS is found by inspecting the Si I emission line at 288.2 nm. Untreated CFRP samples and CFRP contaminated with PDMS were tested. The PDMS areal density ranged from 0.36 Â+/- 0.04 to 0.51 Â+/- 0.16 mg/cm2. The results demonstrate the successful detection of PDMS on CFRP using mLIBS. In addition, OSEE was used to measure CFRP surface cleanliness pre- and post-treatment by laser ablation on specimens contaminated with PDMS coatings from 8 nm to 1311 nm in thickness. The results showed a significant increase in the OSEE photocurrent after laser surface treatment.

Ledesma, Rodolfo↗

Vacancy-Mediated Increases in Brine–Salt Surface Energies

Salt formations have been explored for the permanent isolation of spent nuclear fuel based on their high thermal conductivity, self-healing nature, and low hydraulic permeability to brine flow. Vacancy defect concentrations in salt complicate fracture mechanics not driven by dislocation dynamics and can influence the resulting surface structure. Classical molecular dynamic simulations were used to simulate tensile testing of salt crystals (halite) with vacancy defect concentrations of up to 0.5 defects/nm 3 . Increasing defect concentrations resulted in a decrease in ultimate tensile strength and fracture surface energies, driven by increased surface roughness rather than changes in the amount of surface area. Brine–salt surface energies of the fractured surfaces were 0.22 to 0.26 J/m 2 , significantly higher than values reported for atomically flat (100) surfaces at the same brine composition. This change in surface energy increased the brine–salt dihedral angle by ~27°. The dihedral angle threshold for percolation in salt is 60°, and a 27° increase due to rough fracture surfaces identifies a reduction in porosity percolation and a decrease in salt permeability. Therefore, bedded salt and salt domes may be even more stable than those previously predicted from dihedral angle calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mapping of lithologic and structural units using multispectral imagery

The author has identified the following significant results. ERTS-1 MSS imagery covering the Afar-Triangle/Ethiopia and adjacent regions (Ethiopian Plateau, Somali Plateau, and parts of Yemen and Saudi Arabi) was applied to the mapping of lithologic and structural units of the test area at a scale 1:1,000,000. Results of the geological evaluation of the ERTS-1 imagery of the Afar have proven the usefullness of this type of satellite data for regional geological mapping. Evaluation of the ERTS images also resulted in new aspects of the structural setting and tectonic development of the Afar-Triangle, where three large rift systems, the oceanic rifts of the Red Sea and Gulf of Aden and the continental East African rift system, seem to meet each other. Surface structures mapped by ERTS do not indicate that the oceanic rift of the Gulf of Aden (Sheba Ridge) continues into the area of continental crust west of the Gulf of Tadjura. ERTS data show that the Wonji fault belt of the African rift system does not enter or cut through the central Afar. The Aysha-Horst is not a Horst but an autochthonous spur of the Somali Plateau.

Kronberg, P.↗

The GaAs solar cells with V-grooved emitters

Geometrically structured surfaces have become increasingly important to solar cell efficiency improvements and radiation tolerance. Gallium arsenide solar cells with a V-grooved front surface which demonstrate improved optical coupling and higher short-circuit current compared to planar cells were fabricated. GaAs homojunction cells were fabricated by organometallic chemical vapor deposition (OMCVD) on an n+ substrate. The V-grooves were formed on the surface with an anisotropic etch, and an n-type buffer and p-type emitter were grown by OMCVD, followed by ohmic contacts. Reflectivity measurements show significantly lower reflectance for the microgrooved cell compared to the planar structure. The short circuit current of the V-grooved solar cell is consistently higher than that of the planar controls.

Bailey, Sheila G.↗

Ion beam textured and coated surfaces experiment (IBEX)

The IBEX, with 36 samples of various materials, was placed aboard the LDEF. Twenty-seven of the samples had surfaces modified using ion beam technology, and nine were made up of commercially available materials. The materials are in some way useful in space power systems. The various types of materials tested included six categories: (1) ion beam structured surfaces suitable for solar thermal (concentrator) or space radiators; (2) ion beam sputtered conductive coatings for thermal and space charge control; (3) solar reflector surfaces; (4) flexible thin film coatings and solar array blanket material for protection of spacecraft polymers; (5) painted and/or state-of-the-art solar thermal materials; and (6) micrometeoroid sensitive detector. Data analysis presented include the optical properties of each surface before and after exposure to the space environment and the respective backup surfaces.

Mirtich, Michael J.↗

Purification of Lithium-Ion Battery Black Mass through Tailored Alkaline Corrosion

Obtaining high-purity material outputs is crucial to the viability of novel process aimed at direct recycling of lithium-ion batteries. Metallic impurities in recycled cathodes have been shown to inhibit performance, thereby threatening mainstream acceptance of recycled battery products. Thus, shredded black mass (BM) must be purified to remove metallic contaminants, and specifically Al and Cu originating from the electrode current collectors. We herein explore a process to ionize solid copper and aluminum to ionic form based on tailored alkaline chemistry, without incurring damage to the target cathode material (Li(NixMnyCo1-x-y)O2; NMC). Al and Cu corrosion may be enhanced through the addition of chloride salt, elevated temperatures, and the use of ultrasonication - all of which disrupt the formation of passivating films on the metallic surface, and thereby increase corrosion rate. We demonstrate optimized parameters for Al and Cu corrosion both from a kinetic and overall process cost perspective. Further, we analyze the impact of these conditions on the structural (XRD, SEM), chemical (EDS, ICP), and electrochemical (impedance, cycling, dQ/dV) properties of NMC, and suggest that the present purification method does not significantly disrupt NMC performance. Finally, we present preliminary results from a promising bench-scale demonstration of this purification process applied to a simulated black mass.

ADVANCED PROPULSION SYSTEMS,ENERGY STORAGE↗

Radar mapping of lunar surface roughness.

Comparison of anomalous behavior at infrared and radar wavelengths provides an estimation of lunar surface structure at centimeter-to-meter sizes. Although a simple classification is used, it is shown that the combination of the infrared and radar data contains more information than any of the sets by themselves. The infrared data indicate that bare surface rocks are the source of the roughness which generates enhanced radar backscatter. The different radar maps indicate the size of surface rocks, as was demonstrated for the strewn fields of centimeter-sized rubble (the Type II anomaly). As craters age, they have a rim-bright appearance in the radar maps, and eventually lose their anomalous-behavior at infrared and 3.8-cm radar wavelengths.

Thompson, T. W.↗

Optical and electrical properties of ion beam textured Kapton and Teflon

Results are given for ion beam texturing of polyimide (Kapton) and fluorinated ethylene propylene (Teflon) by means of a 30-cm diam electron bombardment argon ion source. Ion beam-textured Kapton and Teflon surfaces are evaluated for various beam energies, current densities, and exposure times. The optical properties and sheet resistance are measured after each exposure. Provided in the paper are optical spectral data, resistivity measurements, calculated absorptance and emittance measurements, and surface structure SEM micrographs for various exposures to argon ions. It is found that Kapton becomes conducting and Teflon nonconducting when ion beam-textured. Textured Kapton exhibits large changes in the transmittance and solar absorptance, but only slight changes in reflectance. Surface texturing of Teflon may allow better adherence of subsequent sputtered metallic films for a high absorptance value. The results are valuable in spacecraft charging applications.

Mirtich, M. J.↗

Multi-scale roughness spectra of Mount St. Helens debris flows

A roughness spectrum allows surface structure to be interpreted as a sum of sinusoidal components with differing wavelengths. Knowledge of the roughness spectrum gives insight into the mechanisms responsible for electromagnetic scattering at a given wavelength. Measured spectra from 10-year-old primary debris flow surfaces at Mount St. Helens conform to a power-law spectral model, suggesting that these surfaces are scaling over the measured range of spatial frequencies. Measured spectra from water-deposited surfaces deviate from this model.

Austin, Richard T.↗

A direct numerical simulation study for confined non-isothermal jet impingement at moderate nozzle-to-plate distances: Capturing jet-to-ambient density effects

A direct numerical simulation (DNS) campaign is deployed for a series of confined downward oriented, non-isothermal turbulent impinging jet configurations. A baseline Reynolds number of 9960 is obtained through a precursor DNS pipe flow simulation (Re τ = 505). Three jet temperature configurations (confinement height to nozzle diameter of three) enter a cylindrical domain that share ambient and impingement plate temperatures (298.15 K). The range of jet temperatures are crafted such that the ratio of inlet to ambient density varies from unity to 0.52, showcasing the effect of density disparity on flow characteristics such as core collapse, radial mixing of momentum and energy, near-wall stagnation behavior, wall-jet profiles, and large-scale vortical structures. Surface quantities provided include mean radial heat flux and wall-shear stress profiles, and heat flux histograms at select radial stations. Results showcase increased radial normal stresses for higher temperature jets that support increased mixing, resulting in large-scale recirculation structures that are smaller, while retaining similar normalized radial wall profiles for shear stress, heat flux and pressure. Furthermore, radial plots for wall shear stress and Nusselt number showcase strong radial decay as compared to previous configurations that share similar jet and ambient temperatures. For the 373.15 K case, a Gaussian-like histogram for heat fluxes at the impingement plate transitions to a log-normal profile as radial distances increase. In contrast, the 573.15 K configuration displays a bi-modal heat flux characteristic at the impingement plate, and in similar manner to the moderate temperature counterpart, transitions to a log-normal profile at larger radial distances.

33 ADVANCED PROPULSION SYSTEMS↗

Thoughts on the past, present and future of UHV surface chemistry and the birth of Single-Atom Alloys

Throughout its relatively short lifetime, ultra-high vacuum (UHV) surface chemistry has progressed quickly. In the 1960's, pioneers like Ertl and Somorjai started the field using single crystals and gained significant insight into catalytic processes by relating surface structure to reactivity. The more recent proliferation of scanning probes has significantly increased the power of the single crystal approach by enabling the atomic-scale structure of active sites to be correlated with their reactivity. In this perspective we briefly discuss how the field developed, identify some challenges, and highlight Single-Atom Alloys (SAAs), a new class of heterogeneous catalyst that was developed from a fundamental surface science approach. However, despite recent successes, funding for fundamental surface science has declined. Academic hires in the discipline are also declining in part due to the start-up costs. We make the case that fundamental UHV surface chemistry is still too young a field to be in recession.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The role of surfaces in flexoelectricity

We develop the relationship between the strain derivative of the mean-inner potential and surface contributions to flexoelectricity, identifying the true surface-specific component of the flexoelectric response of finite samples. Density functional theory calculations on a range of experimentally observed, low energy SrTiO 3 , MgO, and Si surfaces demonstrate that the mean-inner potential and its contributions to flexoelectricity are sensitive to small differences in surface structure, chemistry, and adsorbates. We also introduce a method to estimate mean-inner potential contributions to flexoelectricity using electron scattering factors and use this approximation to predict total flexoelectric responses for a variety of insulators. Strategies to experimentally disentangle bulk and surface flexoelectric terms are also discussed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗