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At least 973 records · Page 54

Surface Plasmon Resonance and Aggregate Stability of Silver Nanoparticle Complexes with Chemotripsin

Extinction spectra, effective sizes, and aggregate stability of silver nanoparticles and nanocomplexes of silver nanoparticles with chymotrypsin obtained by the reactions of chemical reduction of silver nitrate using sodium borohydride as a reducing agent are studied. It is shown that silver nanoparticles obtained in the absence of chymotrypsin are aggregatively stable only at pH values immediately after synthesis. The placement of the synthesized silver nanoparticles in buffer solutions with pH values from 3.0 to 12.0 resulted in the appearance of a wide absorption band in the visible region of the spectrum, which is due to the agglomeration of silver nanoparticles, which appears to be the result of the destruction of the double electric layer formed by the ions making up sodium borohydride. The presence of chymotrypsin in the reaction medium resulted in significant spectral changes. Unlike silver nanoparticles synthesized in the absence of chymotrypsin, for nanocomplexes of silver nanoparticles with chymotrypsin with a change in pH, the shape of the extinction spectra and the position of the surface plasmon resonance band were preserved, while nanocomplexes of silver nanoparticles with chymotrypsin retained the aggregative stability in solutions in the pH range from 3.0 to 12.0 within a month. The observed stabilization effect of silver nanoparticles over a wide pH range induced by the presence of chymotrypsin in the reaction medium can be used further to develop methods for immobilizing enzymes on nanoparticles of biogenic elements and for creating polyfunctional pharmaceuticals, in which the components of nanocomplexes have different biological activity.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Hierarchical Tactile Sensation Integration from Prosthetic Fingertips Enables Multi-Texture Surface Recognition

Multifunctional flexible tactile sensors could be useful to improve the control of prosthetic hands. To that end, highly stretchable liquid metal tactile sensors (LMS) were designed, manufactured via photolithography, and incorporated into the fingertips of a prosthetic hand. Three novel contributions were made with the LMS. First, individual fingertips were used to distinguish between different speeds of sliding contact with different surfaces. Second, differences in surface textures were reliably detected during sliding contact. Third, the capacity for hierarchical tactile sensor integration was demonstrated by using four LMS signals simultaneously to distinguish between ten complex multi-textured surfaces. Four different machine learning algorithms were compared for their successful classification capabilities: K-nearest neighbor (KNN), support vector machine (SVM), random forest (RF), and neural network (NN). The time-frequency features of the LMSs were extracted to train and test the machine learning algorithms. The NN generally performed the best at the speed and texture detection with a single finger and had a 99.2 ± 0.8% accuracy to distinguish between ten different multi-textured surfaces using four LMSs from four fingers simultaneously. The capability for hierarchical multi-finger tactile sensation integration could be useful to provide a higher level of intelligence for artificial hands.

Abd, Moaed A. (ORCID:0000000284954244)↗

Automated inspection of solder joints for surface mount technology

Researchers at NASA/GSFC evaluated various automated inspection systems (AIS) technologies using test boards with known defects in surface mount solder joints. These boards were complex and included almost every type of surface mount device typical of critical assemblies used for space flight applications: X-ray radiography; X-ray laminography; Ultrasonic Imaging; Optical Imaging; Laser Imaging; and Infrared Inspection. Vendors, representative of the different technologies, inspected the test boards with their particular machine. The results of the evaluation showed limitations of AIS. Furthermore, none of the AIS technologies evaluated proved to meet all of the inspection criteria for use in high-reliability applications. It was found that certain inspection systems could supplement but not replace manual inspection for low-volume, high-reliability, surface mount solder joints.

Savage, Robert M.↗

Sources of Na for the Io atmosphere

The physics and geology of Io have been extensively studied, but there has been little discussion of the chemistry. Relatively little is known about Io chemistry, but there are constraints. Further, it will be a long time before improvements will result from direct observation, given the severe difficulties with the Galileo mission. Via laboratory simulation experiments, plausible thermochemical and photochemical processes which determine the nature and amounts of surface constituents of Io are explored. The well-known density of Io shows that the planet overall is rocky. Because the orbit of Io is well within the magnetosphere of Jupiter and because Io only has a thin, transient SO2 atmosphere, the surface is continually sputtered with magnetospheric ions. Complex processes ionize and accelerate the Io surface atoms to keV and MeV energies. Remarkably, only S, O, and Na ions were found by Voyager. Sputtering also produces an atomic cloud of Na and S (O not observable) with a trace of K. Both gaseous and solid SO2 are known from spectroscopic studies. A trace of H2S and possibly CO2 are present. Geologic features are interpreted in terms of elemental S, but there is no direct evidence for this constituent. We thus have a rocky planet which does not have rocks on the surface. Our general goal is to understand the cycling of Na, S, and O through the crust and atmosphere on present-day Io and to understand how Io evolved to this state. A specific objective was to determine the phases on the surface which are the source of the Na in the atmosphere of Io.

Burnett, D. S.↗

Soil Carbonyl Sulfide (OCS) Fluxes in Terrestrial Ecosystems: An Empirical Model

Measurements of carbonyl sulfide (OCS) enable independent estimates of regional stomatal conductance provided that non-stomatal OCS fluxes are well constrained. OCS is taken up through plant leaves, following the same pathway as CO 2 ; in contrast to CO 2 , OCS is irreversibly destroyed in plant leaves and plants do not typically exhibit OCS emissions. Ecosystem uptake of OCS can indicate changes in stomatal opening. Here we present an empirical model to assess the potential impact of soil OCS exchange, the non-Stomatal OCS exchange Empirical Model (SOCSEM, version 0). We created biome-specific response curves characterizing soil OCS exchange and restricted the model design to require only knowledge of soil moisture and surface temperature because remote sensing observations are available for these two features. Comparing the model to field-based chamber observations reveal deviations that can be attributed to missing complexity of the ground surface (having excluded litter and plants without regulated stomata), shortwave radiation, or the soil environment. For agricultural regions with known net emissions, we use remotely-sensed surface temperature data and demonstrate that data resolution can affect anticipated fluxes. We further investigate the influence of regions with unknown soil OCS responses, for example, Arctic tundra. We compare our model to a process-based and respiration-based soil OCS exchange model that has been implemented in a land surface model. Further field study of tropical and arctic ecosystems in conjunction with studies of non-stomatal surfaces in addition to soil (e.g., bryophytes) will increase confidence in applying OCS as a regional tracer for stomatal conductance.

54 ENVIRONMENTAL SCIENCES↗

Scanning electron microscope investigation of the structural growth in thick sputtered coatings

Sputtered S-Monel, silver, and 304 stainless steel coatings and molybdenum disulfide coatings were deposited on mica and metal substrates with various surface finishes to investigate the structural growth of the coating by scanning electron microscopy. The geometry and the surface morphology of the nodules are characterized. Compositional changes within the coating were analyzed by energy dispersive X-ray analysis. Defects in the surface finish act as preferential nucleation sites and form isolated overlapping and complex nodules and various unusual surface overgrowths on the coating. The nodule boundaries are very vulnerable to chemical etching and these nodules do not disappear after full annealing. Further, they have undesirable effects on mechanical properties; cracks are initiated at the nodules when the coating is stressed by mechanical forces.

Spalvins, T.↗

Surface vs Homogeneous Organo-Hafnium Catalyst Ion-Pairing and Ligand Effects on Ethylene Homo- and Copolymerizations

Heterogeneous catalysts have long dominated polyethylene and polypropylene production, but understanding their catalysis is challenged by uncertainties in active site structures and percentages. Surface-bound organometallic catalysts are an emerging strategy to combine successful homogeneous catalysts having well-understood structures, relatively high percentages of active sites, and exceptional control of selectivity, with the attractions of surface catalysts, to transition promising homogeneous systems to large-scale heterogeneous ones. Nevertheless, surface-bound olefin polymerization catalysts typically produce ultrahigh M w ’s but with low activity and comonomer selectivity. Here, we report the systematic synthesis and characterization of a series of pyridylamido–Hf complexes and their corresponding surface catalysts chemisorbed on sulfated alumina (AlS) and zirconia (ZrS). Comparative ethylene homo- and 1-octene copolymerizations reveal similar activity and 1-octene selectivity trends in the homogeneous and heterogeneous systems. For the surface pyridylamido–Hf catalyst series, large variations in activity (up to 10×) and 1-octene incorporation (up to 28×) are achieved by ligand and support manipulation. Interestingly, while the homogeneous catalysts exhibit positive comonomer effects in ethylene/1-octene copolymerization, the surface catalysts behave oppositely. Extended X-ray absorption fine structure (EXAFS) reveals significantly elongated Hf···O bond distances vs typical Hf–O covalent bonds (2.06 vs 1.97 Å). Furthermore, density functional theory (DFT) analysis of the heterolytic ion pair separation enthalpies, olefin insertion energetics, and NBO/Bader charges also suggest electrostatic Hf cation–anionic support binding and catalytic patterns, which are modulated by the ion-pairing energetics and ligand architecture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unraveling pH-Dependent Changes in Adsorption Structure of Uranyl on Alumina (012)

Mitigating uranium transport in groundwater is imperative for ensuring access to clean water across the globe. Here, in situ resonant anomalous X-ray reflectivity is used to investigate the adsorption of uranyl on alumina (012) in acidic aqueous solutions, representing typical U VI concentrations of contaminated water near mining sites. The analyses reveal that U VI adsorbs at two distinct heights of 2.4-3.2 and 5-5.3 angstrom from the surface terminal oxygens. The former is interpreted as the mixture of inner-sphere and outer-sphere complexes that adsorb closest to the surface. The latter is interpreted as an outer-sphere complex that shares one equatorial H 2 O with the terminal surface oxygen. With increasing pH, we observe an increasing prevalence of these outer-sphere complexes, indicating the enhanced role of the hydrogen bond that stabilizes adsorbed uranyl species. Finally, the presented work provides a molecular-scale understanding of sorption of uranyl on Al-based-oxide surfaces that has implications for environmental chemistry and materials science.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tailoring Corrosion Resistance of Additively Manufactured Metals with Atomic Layer Deposition

The goal of this work is to develop a scalable post-manufacturing capability at LANL that utilizes atomic layer deposition (ALD) for corrosion-resistant coatings onto additively manufactured (AM) metals. This will provide fundamentally new and essential capabilities towards the interchangeability of AM metals with traditionally wrought or machined material. This will be accomplished by (1) formulating novel ALD precursor doses and film thicknesses onto as-printed coupons of AM metals and (2) providing electrochemical characterization of corrosion susceptibility as a function of deposited film thickness. While ALD is well-established, the unique aspect (risk) of this work is application to rough AM surfaces. This risk is mitigated by repeating ALD deposition cycles, where thicker coatings laterally branch, resulting in a uniform coating. This risk will be assessed in the phase 1 feasibility study, wherein the application of ALD coatings to small AM coupon surfaces will be demonstrated using existing hardware and characterization tools at Sigma. This study alone will provide ground-breaking insight on the compatibility of ALD coating techniques with AM metals. Going beyond the phase 1 study, a standalone deposition chamber will be built, so full AM components can be coated and tested. While this MFR investment is focused on corrosion mitigation, it is critical to highlight external benefits of this technique outside the scope of this proposed study. ALD has extraordinary universality, whereby almost any material can be given almost any coating or graded density coating with atomic precision; and, the only limiting factors to scalability is the size of the dosing chamber. The self-limiting reactions intrinsic to ALD offers high conformity to part geometry and tolerance, even for internal surfaces where electroplating or conventional chemical vapor deposition falls short due to differential diffusion. This uniquely positions ALD at the forefront of post-manufacturing strategies for AM components, especially for those with complex geometry and internal surfaces.

36 MATERIALS SCIENCE↗

Twice upon a time: timelike-separated quantum extremal surfaces

The Python’s Lunch conjecture for the complexity of bulk reconstruction involves two types of nonminimal quantum extremal surfaces (QESs): bulges and throats, which differ by their local properties. The conjecture relies on the connection between bulk spatial geometry and quantum codes: a constricting geometry from bulge to throat encodes the bulk state nonisometrically, and so requires an exponentially complex Grover search to decode. However, thus far, the Python’s Lunch conjecture is only defined for spacetimes where all QESs are spacelike-separated from one another. Here we explicitly construct (time-reflection symmetric) spacetimes featuring both timelike-separated bulges and timelike-separated throats. Interestingly, all our examples also feature a third type of QES, locally resembling a de Sitter bifurcation surface, which we name a bounce. By analyzing the Hessian of generalized entropy at a QES, we argue that this classification into throats, bulges and bounces is exhaustive. We then propose an updated Python’s Lunch conjecture that can accommodate general timelike-separated QESs and bounces. Notably, our proposal suggests that the gravitational analogue of a tensor network is not necessarily the time-reflection symmetric slice, even when one exists.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Hardware-Accelerated Ray Tracing of CAD-Based Geometry for Monte Carlo Radiation Transport

Monte Carlo radiation transport (MCRT) methods have been used to simulate radiation environments for many decades by tracking individual particles through a model to accumulate statistical information. MCRT geometry is historically formed using the constructive solid geometry (CSG). Recently, significant work has been performed to support simulations using computer-aided design (CAD)-based tessellated surfaces to support highly complex geometries. Ray tracing acceleration data structures from the rendering and visualization community are applied to accelerate particle tracking in CAD-based models. Despite these efforts, CSG representations provide the superior performance in surface intersection operations during particle flight. Concurrently, pseudo Monte Carlo methods have become prevalent in rendering applications to support more realistic models for scattering media, motivating innovations that are advantageous for MCRT simulations. Finally, the authors’ work extends these innovations by employing Intel’s Embree ray tracing kernel within a geometry toolkit for Monte Carlo to improve the simulation performance using CAD-based models by factors of 1.5 to 2.

42 ENGINEERING↗

Onboard Radar Processing Development for Rapid Response Applications

We are developing onboard processor (OBP) technology to streamline data acquisition on-demand and explore the potential of the L-band SAR instrument onboard the proposed DESDynI mission and UAVSAR for rapid response applications. The technology would enable the observation and use of surface change data over rapidly evolving natural hazards, both as an aid to scientific understanding and to provide timely data to agencies responsible for the management and mitigation of natural disasters. We are adapting complex science algorithms for surface water extent to detect flooding, snow/water/ice classification to assist in transportation/ shipping forecasts, and repeat-pass change detection to detect disturbances. We are near completion of the development of a custom FPGA board to meet the specific memory and processing needs of L-band SAR processor algorithms and high speed interfaces to reformat and route raw radar data to/from the FPGA processor board. We have also developed a high fidelity Matlab model of the SAR processor that is modularized and parameterized for ease to prototype various SAR processor algorithms targeted for the FPGA. We will be testing the OBP and rapid response algorithms with UAVSAR data to determine the fidelity of the products.

dual polarized data↗

Impact Experiments into Granular Targets Containing Solitary Blocks of Varying Strength and Size

Crater scaling relationships provide a means to correlate dimensions of laboratory-scale impact experiments to naturally formed craters at planetary scales. For relatively larger impact events, where gravity is the dominant arresting force against crater growth, these scaling relations are comparatively simple. For smaller craters, however, the target properties have increasing influence over the cratering process. Further complexities are easily envisaged when considering realistic surfaces that contain small-scale heterogeneities in cohesive strength, density, porosity, friction, as these properties will each have unequal effects on the resultant crater morphometry. Even when produced under controlled laboratory conditions, understanding (and controlling) the entire relevant parameter space is daunting, and deconvolution of the relevant contributors can be complicated even in the best-case scenario. To this end, we have begun an extensive series of impact experiments that will provide a nascent framework that will aid in the interpretation of craters observed on complex natural surfaces throughout the solar system. To start with the simplest configuration, experiments were performed with cylindrical PVC buckets that were filled with quartz sand and contained a single cubic block of synthetic sandstone. The blocks varied in size (14-33 mm) and unconfined compressive strength (0.5-7.4 MPa) and were placed in/on the sand along the trajectory of the incoming impactor and buried to different depths. All experiments were conducted using the vertical gun located in the Experimental Impact Lab at NASA Johnson Space Center with alumina projectiles that were accelerated to ~1.53 km s^-1 under a vacuum of 1 torr. After the impact, target containers were removed from the chamber are morphometric data were extracted by using a Peel 2 3D-scanner in combination with the open-source software, CloudCompare. Initial results show that block strength is a secondary effect on crater diameter and depth, but when at least one edge of the block is exposed and the surface (partial burial) the strength will dictate the number of surviving block fragments around the crater, as well as how much disrupted block material is retained within the crater walls.

Christopher J. Cline II↗

Acid–base catalysis over perovskites: a review

We present that perovskite catalysts have been extensively studied for reduction–oxidation (redox) reactions; however, their acid–base catalytic properties are still under-explored. This review collects work aiming to study the acid–base catalytic properties of perovskites. Reports regarding combined acid–base/redox catalysis over perovskites lie beyond the scope of the present review. For the characterization of acid–base properties, researchers have studied the interaction of probe molecules with perovskite surfaces by means of multiple techniques that provide information about the density, strength and type of adsorption sites. The top-surface composition of perovskites, which relates to the abundance of the acid–base sites, has been studied by means of low energy ion scattering (LEIS), and, the less surface sensitive, conventional X-ray photoelectron spectroscopy (XPS). Probe reactions, with the conversion of 2-propanol as the common choice, have also been employed for characterizing the acid–base catalytic properties of perovskites. The complex nature of perovskite surfaces, which explains the still absent fundamental relations between the structure of the catalyst and reaction rates/selectivity, encounters a great challenge due to the surface reconstruction of these materials. In this review, we devote a special section to highlight recent publications that report the impact of surface reconstruction and particle shape on acid–base catalysis over perovskites. In addition, we review promising catalytic performances of perovskite catalysts for other reactions of interest. Challenges in acid–base catalysis over perovskites focus on the development of time-resolved monolayer-sensitive characterization of surfaces under operando conditions and the discernment of combined acid–base/redox reaction mechanisms. Finally, opportunities lay on tuning the acid–base characteristics of perovskites with computation-based catalytic descriptors to achieve desired selectivities and enhanced rates.

36 MATERIALS SCIENCE↗

120-GHz HEMT Oscillator With Surface-Wave-Assisted Antenna

Two monolithic microwave integrated circuits (MMICs) have been designed and built to function together as a source of electromagnetic radiation at a frequency of 120 GHz. One of the MMICs is an oscillator and is the highest-power 120-GHz oscillator reported thus far in the literature. The other MMIC is an end-fire antenna that radiates the oscillator signal. Although these MMICs were constructed as separate units and electrically connected with wire bonds, future oscillator/ antenna combinations could readily be fabricated as monolithic integrated units. Such units could be used as relatively high-power solid-state microwave sources in diverse applications that include automotive radar, imaging, scientific instrumentation, communications, and radio astronomy. As such, these units would be attractive alternatives to vacuum-tube oscillators, which are still used to obtain acceptably high power in the frequency range of interest. The oscillator (see figure) includes a high-electron-mobility transistor (HEMT), with gate-periphery dimensions of 4 by 37 m, in a common-source configuration. The series feedback element of the oscillator is a grounded coplanar waveguide (CPW) at the source. The HEMT is biased for class-A operation (meaning that current is conducted throughout the oscillation cycle) to maximize the output power of the oscillator. Input and output impedance-matching circuit elements are designed to maximize output power and to establish the conditions needed for oscillation. The design of the antenna takes advantage of surface waves, which, heretofore, have been regarded as highly disadvantageous because they can leak power and degrade the performances of antennas that have not been designed to exploit them. Measures taken to suppress surface waves have included complex machining of circuit substrates and addition of separate substrates. These measures are difficult to implement in standard MMIC fabrication processes. In contrast, because the design of the present antenna eliminates the need to suppress surface waves, the fabrication of the antenna is fully compatible with standard MMIC fabrication processes.

Samoska, Lorene↗

Combined shape and topology optimization for minimization of maximal von Mises stress

Here, this work shows that a combined shape and topology optimization method can produce optimal 2D designs with minimal stress subject to a volume constraint. The method represents the surface explicitly and discretizes the domain into a simplicial complex which adapts both structural shape and topology. By performing repeated topology and shape optimizations and adaptive mesh updates, we can minimize the maximum von Mises stress using the p-norm stress measure with p-values as high as 30, provided that the stress is calculated with sufficient accuracy.

42 ENGINEERING↗

Effect of amine type on acidic toxic gas adsorption at ambient conditions on modified CuBTC

We report two amine-modified copper-based Metal Organic Frameworks (MOF (CuBTC)) of different surface chemical and textural features were synthesized and used as adsorbents of acidic toxic gases (NO 2 and H 2 S) in both moist (71% relative humidity (R.H.)) and dry conditions. The initial and exhausted samples were characterized by nitrogen adsorption, powder X-ray diffraction, scanning electron microscopy, thermal gravimetric analysis and Fourier transform infrared spectroscopy. The addition of melamine prevented full growth of CuBTC crystals and resulted in amorphous-like particles with sizes less than 200 nm. The material was non-porous with a small surface area. When urea was used as an amine source, the resulting particles maintained the overall octahedral shape of the parent CuBTC MOF and the material was more porous than the parent MOF. While the urea-modified CuBTC sample performed well as an NO 2 adsorbent in the presence of moisture, the reactivity of the melamine-modified sample and its physical properties provided a favorable environment for the removal of H 2 S. The incorporation of amines into the MOF structure also resulted in surface defects /open copper sites that favored the removal of toxic gases in dry conditions. The reactivity of the adsorbents with toxic gases was demonstrated by the changes in the adsorbent colors, in texture, and in surface chemistry (organic salts, complexes, sulfides and nitrates were formed).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ice Nucleating Particle Connections to Regional Argentinian Land Surface Emissions and Weather During the Cloud, Aerosol, and Complex Terrain Interactions Experiment

Abstract Here, we present a multi‐season study of ice‐nucleating particles (INPs) active via the immersion freezing mechanism, which took place in north‐central Argentina, a worldwide hotspot for mesoscale convective storms. INPs were measured untreated, after heating to 95°C, and after hydrogen peroxide digestion. No seasonal cycle of INP concentrations was observed. Heat labile INPs, which we define as “biological” herein, dominated the population active at −5 to −20°C, while non‐heat‐labile organic INPs (decomposed by peroxide) dominated at lower temperatures, from −20 to −28°C. Inorganic INPs (remaining after peroxide digestion), were minor contributors to the overall INP activity. Biological INP concentration active around −12°C peaked during rain events and under high relative humidity, reflecting emission mechanisms independent of the background aerosol concentration. The ratio of non‐heat‐labile organic and inorganic INPs was generally constant, suggesting they originated from the same source, presumably from regional arable topsoil based on air mass histories. Single particle mass spectrometry showed that soil particles aerosolized from a regionally common agricultural topsoil contained known mineral INP sources (K‐feldspar and illite) as well as a significant organic component. The INP activity observed in this study correlates well with agricultural soil INP activities from this and other regions of the world, suggesting that the observed INP spectra might be typical of many arable landscapes. These results demonstrate the strong influence of regional continental landscapes, emitting INPs of types that are not yet well represented in global models.

54 ENVIRONMENTAL SCIENCES↗