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At least 757 records · Page 42

Structural Evaluation of Radially Expandable Cardiovascular Stents Encased in a Polyurethane Film

A method of encasing cardiovascular stents with an expandable polyurethane coating has been developed to provide a smooth homogeneous inner wall allowing for a confluent growth of endothelial cells. In this design, the metal wire stent structure is completely covered by the polyurethane film minimizing biocorrosion of the metal (stainless steel or nitinol), and providing a homogeneous surface for surface treatment and incorporation of various eluting drugs to prevent platelet aggregation while supporting endothelialization. The polyurethane surface was treated with a helium plasma for sterilization and promotes growth of cells. The paper details the performance of the coated film to expand with the metal stent up to 225 % during deployment. We present stress/strain behavior of polyurethane films, and subsequent plasma treatment of the surface and the adhesion of the coating to the stent structure upon expansion. A film of less than 25 tm was found to be sufficient for corrosion resistance and flexibility without producing any excess stress on the stent structure. Straining the film to 225 % and plasma modification did not affect the mechanical and surface properties while allowing for improved biocompatibility as determined by the critical surface tension, surface chemistry, and roughness.

Trigwell, Steve↗

Construction of Lattice Strain in Bimetallic Nanostructures and Its Effectiveness in Electrochemical Applications

Bimetallic nanocrystals (NCs), associated with various surface functions such as ligand effect, ensemble effect, and strain effect, exhibit superior electrocatalytic properties. The stress-induced surface strain effect can alter binding strength between the surface active sites and reactants as well as their intermediates, and the electrochemical performance of bimetallic NCs can be significantly facilitated by the lattice-strain modification via their morphologies, sizes, shell-thickness, surface defectiveness as well as compositions. Here in this review, an overview of fundamental principles, characterization techniques, and quantitative determination of the surface lattice strain is provided. Various strategies and synthesis efforts on creating lattice-strain-engineered bimetallic NCs, including the de-alloying process, atomic layer-by-layer deposition, thermal treatment evolution, one-pot synthesis, and other efforts are also discussed. It is further outlined how the lattice strain effect promotes electrochemical catalysis through the selected case studies. The reactions on oxygen reduction reaction, small molecular oxidation, water splitting reaction, and electrochemical carbon dioxide reduction reactions are focused. In particular, studies of lattice strain arisen from core–shell nanostructure and defectiveness are highlighted. Lastly, the potential challenges are summarized and the prospects of lattice-strain-based engineering on bimetallic nanocatalysts with suggestion and guidance of the future electrocatalyst design are envisioned.

36 MATERIALS SCIENCE↗

Development of electronically passivating surfaces to enhance battery performance

For many decades, lithium metal batteries (LMBs) have been studied for their high energy density, though they suffer from high reactivity, which safety concerns such as explosions and fires. These events can occur as a result of degradation due to redox reactions and lithium morphology that evolve during cycling. Mostly, the failure is caused by the electrolyte degradation leading to the creation of a solid electrolyte interphase (SEI), which tends to induce electron leakage, lithium dendrite growth, and capacity decay. SEI formation is practically inevitable. This work investigated the minimization of degradation events by modifying different battery configurations. Modifications were made by exchanging electrolytes, electrode surfaces, and even annexing innovative components. Our goal is to achieve a configuration where Li-ion transfer is facilitated, and electron transfer is limited which would enable a longer lithium metal battery life cycle. When performing these modifications and testing their electrochemical performance, a current reduction was observed when the electrodes were spontaneously coated with preformed SEI. Herein several classes of artificial SEI layers are explored for their ability to form passivating layers through use of a redox active molecule.

25 ENERGY STORAGE↗

High-Strength Polylactic Acid (PLA) Biocomposites Reinforced by Epoxy-Modified Pine Fibers

The stiffness and tensile strength of biopolymers (e.g., polylactic acid (PLA)) are less than desirable for load-bearing applications in their neat form. The use of natural fibers as reinforcements for composites (for large-scale three-dimensional (3D) printing) has expanded rapidly, attributable to their low weight, low cost, high stiffness, and renewable nature. Silane and acid/alkali are typically used to modify the surface of natural fibers to improve the fiber/polymer interfacial adhesion. In this study, a simple method of impregnation was developed to modify pine fibers (loblolly, mesh size of 90–180 μm, 30 wt %) with a solvent-borne epoxy to reinforce PLA. As a benefit of the epoxy modification (0.5–10 wt %), the tensile strengths and Young’s moduli of the epoxy-modified pine/PLA composites increased by up to 20 and 82%, respectively, as compared to that of neat PLA. Furthermore, the epoxy-modified pine/PLA composites, with an optimum epoxy modification (1.0 wt %), had fewer voids on the fracture surface as compared with pine/PLA composites without the modification of pine fibers via epoxy. Finally, results confirmed that epoxy partially penetrated the pore/hollow inner structures of pine fibers and improved the fiber/matrix interfacial adhesion. Epoxy modification is found to be a simple and effective technique to improve the properties of biocomposites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Importance of standard terminology in surface chemical analysis: ISO 18115-1:2023, general terms and terms used in spectroscopy

The International Standard ISO 18115-1 on terminology in surface chemical analysis has been revised with clarifications, modifications, and deletions to more than 70 terms and with the addition of more than 50 terms in response to trends, issues, and needs identified by the surface analysis community. This revision adds terminology and concepts associated with emerging methods such as atom probe tomography, near ambient pressure XPS, and hard X-ray photoelectron spectroscopy. It includes 25 new and revised terms to ensure that the description of resolution is consistent across all surface analysis methods. The 630 terms in the document cover words or phrases used in describing the samples, instruments, and concepts involved in surface chemical analysis. Here, the terms have been collated into subject specific sections to ensure that related terms can be found easily.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analysis and testing for rotordynamic coefficients of turbulent annular seals with different, directionally homogeneous surface-roughness treatment for rotor and stator elements

A theory is presented, based on a simple modification of Hirs' turbulent lubrication equations, to account for different but directionally-homogeneous surface roughness treatments for the rotor and stator of annular seals. The theoretical results agree with von Pragenau's predictions that a damper seal which uses a smooth rotor and a rough stator yields more net damping than a conventional seal which has the same roughness for both the rotor and stator. Experimental results for four stators confirm that properly-designed roughened stators yield higher net damping values and substantially less leakage than seals with smooth surfaces. The best seal from both damping and leakage viewpoints uses a round-hole-pattern stator. Initial results for this stator suggest that, within limits, seals can be designed to yield specified ratios of stiffness to damping.

Childs, D. W.↗

Mass Movement and Landform Degradation on the Icy Galilean Satellites: Results of the Galileo Nominal Mission

The Galileo mission has revealed remarkable evidence of mass movement and landform degradation on the icy Galilean satellites of Jupiter. Weakening of surface materials coupled with mass movement reduces the topographic relief of landforms by moving surface materials down-slope. Throughout the Galileo orbiter nominal mission we have studied all known forms of mass movement and landform degradation of the icy galilean satellites, of which Callisto, by far, displays the most degraded surface. Callisto exhibits discrete mass movements that are larger and apparently more common than seen elsewhere. Most degradation on Ganymede appears consistent with sliding or slumping, impact erosion, and regolith evolution. Sliding or slumping is also observed at very small (100 m) scale on Europa. Sputter ablation, while probably playing some role in the evolution of Ganymede's and Callisto's debris layers, appears to be less important than other processes. Sputter ablation might play a significant role on Europa only if that satellite's surface is significantly older than 10(exp 8) years, far older than crater statistics indicate. Impact erosion and regolith formation on Europa are probably minimal, as implied by the low density of small craters there. Impact erosion and regolith formation may be important on the dark terrains of Ganymede, though some surfaces on this satellite may be modified by sublimation-degradation. While impact erosion and regolith formation are expected to operate with the same vigor on Callisto as on Ganymede, most of the areas examined at high resolution on Callisto have an appearance that implies that some additional process is at work, most likely sublimation-driven landform modification and mass wasting. The extent of surface degradation ascribed to sublimation on the outer two Galilean satellites implies that an ice more volatile than H2O is probably involved.

Moore, Jeffrey M.↗

Stability and rheology of dispersions of silicon nitride and silicon carbide

The relationship between the surface and colloid chemistry of commercial ultra-fine silicon carbide and silicon nitride powders was examined by a variety of standard characterization techniques and by methodologies especially developed for ceramic dispersions. These include electrokinetic measurement, surface titration, and surface spectroscopies. The effects of powder pretreatment and modification strategies, which can be utilized to augment control of processing characteristics, were monitored with these technologies. Both silicon carbide and nitride were found to exhibit silica-like surface chemistries, but silicon nitride powders possess an additional amine surface functionality. Colloidal characteristics of the various nitride powders in aqueous suspension is believed to be highly dependent on the relative amounts of the two types of surface groups, which in turn is determined by the powder synthesis route. The differences in the apparent colloidal characteristics for silicon nitride powders cannot be attributed to the specific absorption of ammonium ions. Development of a model for the prediction of double-layer characteristics of materials with a hybrid site interface facilitated understanding and prediction of the behavior of both surface charge and surface potential for these materials. The utility of the model in application to silicon nitride powders was demonstrated.

Feke, Donald L.↗

Mercury's Weather-Beaten Surface: Understanding Mercury in the Context of Lunar and Asteroidal Space Weathering Studies

Mercury's regolith, derived from the crustal bedrock, has been altered by a set of space weathering processes. Before we can interpret crustal composition, it is necessary to understand the nature of these surface alterations. The processes that space weather the surface are the same as those that form Mercury's exosphere (micrometeoroid flux and solar wind interactions) and are moderated by the local space environment and the presence of a global magnetic field. To comprehend how space weathering acts on Mercury's regolith, an understanding is needed of how contributing processes act as an interactive system. As no direct information (e.g., from returned samples) is available about how the system of space weathering affects Mercury's regolith, we use as a basis for comparison the current understanding of these same processes on lunar and asteroidal regoliths as well as laboratory simulations. These comparisons suggest that Mercury's regolith is overturned more frequently (though the characteristic surface time for a grain is unknown even relative to the lunar case), more than an order of magnitude more melt and vapor per unit time and unit area is produced by impact processes than on the Moon (creating a higher glass content via grain coatings and agglutinates), the degree of surface irradiation is comparable to or greater than that on the Moon, and photon irradiation is up to an order of magnitude greater (creating amorphous grain rims, chemically reducing the upper layers of grains to produce nanometer scale particles of metallic iron, and depleting surface grains in volatile elements and alkali metals). The processes that chemically reduce the surface and produce nanometer-scale particles on Mercury are suggested to be more effective than similar processes on the Moon. Estimated abundances of nanometer-scale particles can account for Mercury's dark surface relative to that of the Moon without requiring macroscopic grains of opaque minerals. The presence of nanometer-scale particles may also account for Mercury's relatively featureless visible-near-infrared reflectance spectra. Characteristics of material returned from asteroid 25143 Itokawa demonstrate that this nanometer-scale material need not be pure iron, raising the possibility that the nanometer-scale material on Mercury may have a composition different from iron metal [such as (Fe,Mg)S]. The expected depletion of volatiles and particularly alkali metals from solar-wind interaction processes are inconsistent with the detection of sodium, potassium, and sulfur within the regolith. One plausible explanation invokes a larger fine fraction (grain size less than 45 micron) and more radiation-damaged grains than in the lunar surface material to create a regolith that is a more efficient reservoir for these volatiles. By this view the volatile elements detected are present not only within the grain structures, but also as adsorbates within the regolith and deposits on the surfaces of the regolith grains. The comparisons with findings from the Moon and asteroids provide a basis for predicting how compositional modifications induced by space weathering have affected Mercury's surface composition.

Weathering↗

In Situ Tracking of Nonthermal Plasma Etching of ZIF-8 Films

Surface characterization is critical for understanding the processes used for preparing catalysts, sorbents, and membranes. Nonthermal plasma (NTP) is a process that achieves high reactivity at low temperatures and is used to tailor the surface properties of materials. In this work, we combine the capabilities of infrared reflection absorption spectroscopy (IRRAS) with NTP for the in situ interrogation of zeolitic imidazolate framework-8 (ZIF-8) thin films to probe modifications in the material induced by oxygen and nitrogen plasmas. The IRRAS measurements in oxygen plasma reveal etching of organic ligands with sequential removal of the methyl group and imidazole ring and with the formation of carbonyl moieties (C═O). In contrast, nitrogen plasma induces mild etching and grafting of nitrile groups (−C≡N). Scanning electron microscopy imaging shows that oxygen plasma, at prolonged times, significantly degrades the ZIF-8 film at the grain boundaries. Treatment of ZIF-8 membranes using mild plasma conditions yields a fivefold enhancement for H 2 /N 2 and CO 2 /CH 4 ideal selectivities and an eightfold enhancement for CO 2 /N 2 ideal selectivity. Additionally, the new tools described here can be used for spectroscopic in situ tracking of plasma-induced chemistry on thin films in general.

IRRAS↗

Shock-wave-induced turbulent boundary-layer separation at hypersonic speeds

An experiment is described that tests and guides computations of the interaction of a shock wave with a turbulent boundary layer. Numerical solutions of the time-averaged Navier-Stokes equations for the entire flow field employing algebraic eddy viscosity and turbulent Prandtl number models for shear stress and heat flux are presented and used to illustrate the dependence of the computations on the particulars of the turbulence models. To guide modifications in the models, the mean flow profiles and surface measurements of pressure, shear, and heat flux are analyzed critically. The results show that the models of eddy viscosity require substantial modifications in the interaction region. Improved solutions employing the experimentally modified models are presented.

Horstman, C. C.↗

Polyethylene Glycol Propionaldehydes

New class of compounds derived from polyethylene glycol (PEG's) namely, PEG-propionaldehydes, offers two important advantages over other classes of PEG aldehyde derivatives: compounds exhibit selective chemical reactivity toward amino groups and are stable in aqueous environment. PEG's and derivatives used to couple variety of other molecules, such as, to tether protein molecules to surfaces. Biotechnical and biomedical applications include partitioning of two phases in aqueous media; immobilization of such proteins as enzymes, antibodies, and antigens; modification of drugs; and preparation of protein-rejecting surfaces. In addition, surfaces coated with PEG's and derivatives used to control wetting and electroosmosis. Another potential application, coupling to aminated surfaces.

Harris, Joe M.↗

Experimental evidence for modifying the current physical model for ice accretion on aircraft surfaces

Closeup movies, still photographs, and other experimental data suggest that the current physical model for ice accretion needs significant modification. At aircraft airspeeds there was no flow of liquid over the surface of the ice after a short initial flow, even at barely subfreezing temperatures. Instead, there were very large stationary drops on the ice surface that lose water from their bottoms by freezing and replenish their liquid by catching the microscopic cloud droplets. This observation disagrees with the existing physical model, which assumes there is a thin liquid film continuously flowing over the ice surface. With no such flow, the freezing-fraction concept of the model fails when a mass balance is performed on the surface water. Rime ice does, as the model predicts, form when the air temperature is low enough to cause the cloud droplets to freeze almost immediately on impact. However, the characteristic shapes of horn-glaze ice or rime ice are primarily caused by the ice shape affecting the airflow locally and consequently the droplet catch and the resulting ice shape. Ice roughness greatly increases the heat transfer coefficient, stops the movement of drops along the surface, and may also affect the airflow initially and thereby the droplet catch. At high subreezing temperatures the initial flow and shedding of surface drops have a large effect on the ice shape. At the incipient freezing limit, no ice forms.

Olsen, W.↗

The evolution of the clear air convective layer revealed by surface-based remote sensors

Results are reported for simultaneous observations of the growth and decay of the clear-air convective mixing layer near a coastline, which were made with an FM-CW radar, a high-power narrow-beam S-band radar, and an acoustic echo sounder. The main purpose of this study was to determine the relationship between the rise rate of the convective depth and the lapse rate of temperature, particularly in the morning hours. The results indicate that the three remote sensors can provide excellent mutually supporting data on the convective depth. It is found that this depth is well behaved during the day and that its rise rate varies roughly linearly with the inverse square root of the temperature lapse rate during the morning. The data suggest that some models concerning the rise rate require modification, since these models imply that the surface heat flux would have to be unreasonably large to produce the observed relationship.

Noonkester, V. R.↗

Understanding the Stability of Manganese Chromium Antimonate Electrocatalysts through Multimodal In Situ and Operando Measurements

Herein, we utilize an on-line electrochemical flow cell coupled with an inductively coupled plasma-mass spectrometer (ICP-MS) to characterize the impact of composition and reactant gas on the multielement dissolution of Mn(-Cr)-Sb-O electrocatalysts. Compared to Mn 2 O 3 and Cr 2 O 3 oxides, we find that the antimonate framework stabilizes Mn at OER potentials and Cr at both ORR and OER potentials. Furthermore, dissolution of Mn and Cr from Mn(-Cr)-Sb-O is found to be driven by ORR reaction rate, with minimal dissolution under N 2 . We observe preferential dissolution of Cr totaling 13% over 10 minutes at 0.3, 0.6, and 0.9 V vs RHE, with only 1.5% loss of Mn, indicating an enrichment of Mn at the surface of the particles. Despite this asymmetric dissolution, in situ X-ray absorption spectroscopy (XAS) showed no measurable changes in the Mn K-edge at comparable potentials. This lack of change could suggest that modification to the Mn oxidation state in the surface layer is too small or that layer is too thin to be measured with the bulk XAS measurement. Lastly, on-line ICP-MS was used to assess the effects of applied potential, scan rate, and current of Mn-Cr-Sb-O during cyclic voltammetry and accelerated stress tests. With this deeper understanding of the interplay between oxygen reduction and dissolution, testing procedures were identified to maximize both activity and stability. This work highlights the use of multi-modal in situ characterization techniques in tandem to build a more complete model of stability and develop protocols for optimizing catalyst performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Improvements to TOVS retrievals over sea ice and applications to estimating Arctic energy fluxes

Modeling studies suggest that polar regions play a major role in modulating the Earth's climate and that they may be more sensitive than lower latitudes to climate change. Until recently, however, data from meteorological stations poleward of 70 degs have been sparse, and consequently, our understanding of air-sea-ice interaction processes is relatively poor. Satellite-borne sensors now offer a promising opportunity to observe polar regions and ultimately to improve parameterizations of energy transfer processes in climate models. This study focuses on the application of the TIROS-N operational vertical sounder (TOVS) to sea-ice-covered regions in the nonmelt season. TOVS radiances are processed with the improved initialization inversion ('3I') algorithm, providng estimates of layer-average temperature and moisture, cloud conditions, and surface characteristics at a horizontal resolution of approximately 100 km x 100 km. Although TOVS has flown continuously on polar-orbiting satellites since 1978, its potential has not been realized in high latitudes because the quality of retrievals is often significantly lower over sea ice and snow than over the surfaces. The recent availability of three Arctic data sets has provided an opportunity to validate TOVS retrievals: the first from the Coordinated Eastern Arctic Experiment (CEAREX) in winter 1988/1989, the second from the LeadEx field program in spring 1992, and the third from Russian drifting ice stations. Comparisons with these data reveal deficiencies in TOVS retrievals over sea ice during the cold season; e.g., ice surface temperature is often 5 to 15 K too warm, microwave emissivity is approximately 15% too low at large view angles, clear/cloudy scenes are sometimes misidentified, and low-level inversions are often not captured. In this study, methods to reduce these errors are investigated. Improvements to the ice surface temperature retrieval have reduced rms errors from approximately 7 K to 3 K; correction of microwaves (50 GHz) brightness temperatures for view angle dependence now allows the surface type (open water versus sea ice) to be determined; modifications to the clear/cloud tests have improved cloud detection over sea ice, especially where it is inhomogeneous; and improved surface temperature estimates have resulted in more successful diagnoses of low-level stratification. Applications of improved retrievals to studies of the Arctic energy budget are encouraging. Preliminary calculations of air-ice stress vectors, 10-m wind speed, and horizontal advection of heat and moisture are presented.

Francis, Jennifer A.↗

The Deep Structure of Lunar Basins: Clues to the Understanding of Basin Formation and Modification

Basin excavation has played a major role in shaping the surface and subsurface of the Moon. Though photogeologic observations provide estimates for the present volumes of lunar impact basins and their ejecta deposits, there is not sufficient information to describe completely either the geometry of the basins at the time of impact or their modification with time. Determination of the structure of the crust and upper mantle beneath large basins can provide important insight into the thermal and mechanical processes associated with basin formation and modification as well as the differences in these processes as functions of basin age and size. Using observed gravity and topography together with the seismically determined crustal thickness of the central nearside, a model for the structure of the crust and upper mantle of the nearside of the Moon is presented. With this model the deep structure of the largest lunar basins are compared. The implications for the processes of basin formation and modification at different stages in lunar history are explored.

Bratt, S. R.↗

Potential ecological impacts of climate intervention by reflecting sunlight to cool Earth

As the effects of anthropogenic climate change become more severe, several approaches for deliberate climate intervention to reduce or stabilize Earth’s surface temperature have been proposed. Solar radiation modification (SRM) is one potential approach to partially counteract anthropogenic warming by reflecting a small proportion of the incoming solar radiation to increase Earth’s albedo. While climate science research has focused on the predicted climate effects of SRM, almost no studies have investigated the impacts that SRM would have on ecological systems. The impacts and risks posed by SRM would vary by implementation scenario, anthropogenic climate effects, geographic region, and by ecosystem, community, population, and organism. Complex interactions among Earth’s climate system and living systems would further affect SRM impacts and risks. We focus here on stratospheric aerosol intervention (SAI), a well-studied and relatively feasible SRM scheme that is likely to have a large impact on Earth’s surface temperature. We outline current gaps in knowledge about both helpful and harmful predicted effects of SAI on ecological systems. Desired ecological outcomes might also inform development of future SAI implementation scenarios. In addition to filling these knowledge gaps, increased collaboration between ecologists and climate scientists would identify a common set of SAI research goals and improve the communication about potential SAI impacts and risks with the public. Without this collaboration, forecasts of SAI impacts will overlook potential effects on biodiversity and ecosystem services for humanity.

54 ENVIRONMENTAL SCIENCES↗