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At least 901 records · Page 50

Characterization of natural titanomagnetites (Fe3-xTixO4) for studying heterogeneous electron transfer to Tc(VII) in the Hanford subsurface

Sediments with basaltic provenance, such as those at the Hanford nuclear reservation, Washington, USA, are rich in Fe-bearing minerals of mixed valence. These minerals are redox reactive with aqueous O2 or Fe(II), and have the potential to react with important environmental contaminants including Tc. Here we isolate, identify and characterize natural Fe(II)/Fe(III)-bearing microparticles from Hanford sediments, develop synthetic analogues and investigate their batch redox reactivity with aqueous Tc(VII). Natural Fe-rich mineral samples were isolated by magnetic separation from sediments collected at several locations on Hanford’s central plateau. This magnetic mineral fraction was found to represent up to 1 wt% of the total sediment, and be composed of 90% magnetite with minor ilmenite and hematite, as determined by X-ray diffraction. The magnetite contained variable amounts of transition metalsconsistent with alio- and isovalent metal substitutions for Fe. X-ray microprobe analysis showed that Ti was the most significant substituent, and that these grains could be described with the titanomagnetite formula Fe3_xTixO4, which falls between endmember magnetite (x = 0) and ulvo¨ spinel (x = 1). The dominant composition was determined to be x = 0.15 by chemical analysis and electron probe microanalysis in the bulk, and by L-edge X-ray absorption spectroscopy and X-ray photoelectron spectroscopy at the surface. Site-level characterization of the titanomagnetites by X-ray magnetic circular dichroism showed that despite native oxidation, octahedral Fe(II) was detectable within 5 nm of the mineral surface. By testing the effect of contact with oxic Hanford and Ringold groundwaters to reduced Ringold groundwater, it was found that the concentration of this near-surface structural Fe(II) was strongly dependent on aqueous redox condition. This highlights the potential for restoring reducing equivalents and thus reduction capacity to oxidized Fe-mineral surfaces through redox cycling in the natural environment. Reaction of these magnetically-separated natural phases from Hanford sediments with a solution containing 10 lmol L_1 Tc(VII) showed that they were able to reductively immobilize Tc(VII) with concurrent oxidation of Fe(II) to Fe(III) at the mineral surface, as were synthetic x = 0.15 microparticle and nanoparticle analogue phases. When differences in the particle surface area to solution volume ratio were taken into consideration, measured Tc(VII) reduction rates for Fe3_xTixO4(x = 0.15) natural material, synthetic bulk powder and nanoparticles scaled systematically, suggesting possible utility for comprehensive batch and flow reactivity studies.

Environmental Molecular Sciences Laboratory↗

Analysis of structure and deformation behavior of AISI 316L tensile specimens from the second operational target module at the Spallation Neutron Source

In an earlier publication, tensile testing was performed on specimens removed from the first two operational targets of the Spallation Neutron Source (SNS). There were several anomalous features in the results. First, some specimens had very large elongations (up to 57%) while others had significantly smaller values. Second, there was a larger than the usual amount of data scatter in the elongation results. Third, the stress-strain diagrams of nominally similar specimens spanned a wide range of behavior ranging from expected irradiation-induced hardening to varying levels of force drop after yield point and indirect signs of "traveling deformation wave" behavior associated with strain-induced martensite formation. To investigate the cause(s) of such variable tensile behavior, several specimens from Target 2, spanning the range of observed tensile behavior, were chosen for detailed microstructural examination using electron backscattering analysis (EBSD). It was also shown that the steel employed in the construction of the target contained an unexpected bimodal grain size distribution, containing very large out-of-specification grains surrounded by necklaces of grains of within-specification sizes. The large grains were frequently comparable to the width of the gauge section of the tensile specimen. Moreover, the propensity to form martensite during deformation was shown to be accelerated by radiation but also to be very sensitive to the relative orientation of the grains with respect to the tensile axis. Specimens having large grains in the gauge that were most favorably oriented for production of martensite strongly exhibited the traveling deformation wave phenomenon, while those specimens with less favorably oriented grains had lesser or no degree of the wave effect, thereby accounting for the larger than expected data scatter.

316L↗

Examinations of electron temperature calculation methods in Thomson scattering diagnostics

Electron temperature from Thomson scattering diagnostic is derived through indirect calculation based on theoretical model. {chi}-square test is commonly used in the calculation, and the reliability of the calculation method highly depends on the noise level of input signals. In the simulations, noise effects of the {chi}-square test are examined and scale factor test is proposed as an alternative method.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

The transformation of lepidocrocite (γ-FeOOH) with Fe($\tiny{II}$) (aq) in slightly acidic media: intermediate pathways and biomimetic behavior

Lepidocrocite (LP) is commonly found in natural or anthropogenic environments and oxidized alloy steel waste storage containers. Despite its importance, the end products formed and its mineral transformation pathways, including intermediate steps and underlying mechanisms under Fe(II) (aq) catalysis still need to be clarified due to decades of dispersed research. Here, in this work, we investigated LP's catalytic transformation with 10 mM and 0.2 mM Fe(II) (aq) at their natural solution pH's via bulk (X-ray Diffraction/XRD, Raman and Attenuated Total Reflectance Fourier Transform Infrared/ATR-FTIR) and micro/nano-scale (semi in situ Transmission Electron Microscopy/TEM) analysis. In general, we observed that goethite (GT) and LP were the main end products. However, a series of two major distinct intermediate events that were initiated by a dissolution type of reaction along with an “induction period” (lack of dissolution) on LP occurred. Fascinatingly, two of the intermediate steps along its mineral transformation presented novel types of non-classical mechanisms of crystallization via some type of guided oriented particle attachment. Furthermore, one of these intermediate steps is biomimetic in appearance, similar to what is observed during bacterial particle attachment. However, it uses inorganic nano-wire antennas that have a sensory-like function as observed with bacterial fimbriae and/or flagellum through an electron transparent film (similar to a bio-film matrix). Finally, this work leads us to comprehend the evolution of some well documented crystal morphologies for GT commonly observed in natural and anthropogenic settings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Probing the Impact of the EchinT C-Terminal Domain on Structure and Catalysis

Histidine triad nucleotide binding protein (Hint) is considered as the ancestor of the histidine triad protein superfamily and is highly conserved from bacteria to humans. Prokaryote genomes, including a wide array of both Gram-negative bacteria and Gram-positive bacteria, typically encode one Hint gene. The cellular function of Hint and the rationale for its evolutionary conservation in bacteria have remained a mystery. Despite its ubiquity and high sequence similarity to eukaryote Hint1 [Escherichia coli Hint (echinT) is 48% identical with human Hint1], prokaryote Hint has been reported in only a few studies. Here we report the first conformational information on the full-length N-terminal and C-terminal residues of Hint from the E. coli complex with GMP. Structural analysis of the echinT-GMP complex reveals that it crystallizes in the monoclinic space group P2{sub 1} with four homodimers in the asymmetric unit. Analysis of electron density for both the N-terminal residues and the C-terminal residues of the echinT-GMP complex indicates that the loops in some monomers can adopt more than one conformation. The observation of conformational flexibility in terminal loop regions could explain the presence of multiple homodimers in the asymmetric unit of this structure. To explore the impact of the echinT C-terminus on protein structure and catalysis, we conducted a series of catalytic radiolabeling and kinetic experiments on the C-terminal deletion mutants of echinT. In this study, we show that sequential deletion of the C-terminus likely has no effect on homodimerization and a modest effect on the secondary structure of echinT. However, we observed a significant impact on the folding structure, as reflected by a significant lowering of the T{sub m} value. Kinetic analysis reveals that the C-terminal deletion mutants are within an order of magnitude less efficient in catalysis compared to wild type, while the overall kinetic mechanism that proceeds through a fast step, followed by a rate-limiting hydrolysis step, was conserved. Nevertheless, the ability of the C-terminal deletion mutants to hydrolyze lysyl-AMP generated by LysU was greatly impaired. Taken together, our results highlight the emerging role of the C-terminus in governing the catalytic function of Hints.

59 BASIC BIOLOGICAL SCIENCES↗

The spectrum and morphology of the Fermi bubbles

The Fermi bubbles are two large structures in the gamma-ray sky extending to 55° above and below the Galactic center. We analyze 50 months of Fermi Large Area Telescope data between 100 MeV and 500 GeV above 10° in Galactic latitude to derive the spectrum and morphology of the Fermi bubbles. We thoroughly explore the systematic uncertainties that arise when modeling the Galactic diffuse emission through two separate approaches. The gamma-ray spectrum is well described by either a log parabola or a power law with an exponential cutoff. We exclude a simple power law with more than 7σ significance. The power law with an exponential cutoff has an index of 1.9 ± 0.2 and a cutoff energy of 110 ± 50 GeV. We find that the gamma-ray luminosity of the bubbles is 4.4{sub −0.9}{sup +2.4}×10{sup 37} erg s{sup –1}. We confirm a significant enhancement of gamma-ray emission in the southeastern part of the bubbles, but we do not find significant evidence for a jet. No significant variation of the spectrum across the bubbles is detected. The width of the boundary of the bubbles is estimated to be 3.4{sub −2.6}{sup +3.7} deg. Both inverse Compton (IC) models and hadronic models including IC emission from secondary leptons fit the gamma-ray data well. In the IC scenario, synchrotron emission from the same population of electrons can also explain the WMAP and Planck microwave haze with a magnetic field between 5 and 20 μG.

79 ASTRONOMY AND ASTROPHYSICS↗

Study of Scanning Micro-arc Oxidation and Coating Development

Micro-arc oxidation (MAO) continues to be the focus of numerous investigations, whereas relatively few studies have considered scanning micro-arc oxidation (SMAO). In the present work, an experimental study was performed using stationary and moving electrodes to investigate coating development in SMAO and discern the effect of key process parameters. Examination of oxide deposits made on A356 aluminum show that coating thickness and growth rate are inversely related to inter-electrode spacing and travel speed. An evaluation of SMAO deposits made by stationary and moving nozzles revealed that coating thickness profiles follow a Gaussian distribution due to the electrolyte flow field in the impingement zone. Hardness surveys and scanning electron microscope analysis of SMAO coatings revealed that micro-hardness distributions and cross-sectional morphology are similar to MAO for a stationary nozzle but that a denser outer layer develops when a moving nozzle is used. This is attributed to a high density of discharge occurring in micropores of the oxide film and remelting which results from the moving electrolyte column. Analysis of voltage–current characteristic curves shows that the resistance of the electrolyte column is essentially linear over the range considered and results indicate that it can be modeled as a variable length resistor. While further testing is needed, results confirm that SMAO is suitable for coating large, planar parts and for repairing worn surfaces.

36 MATERIALS SCIENCE↗

Application of Al-2La-1B Grain Refiner to Al-10Si-0.3Mg Casting Alloy

This paper reports the application and microstructure refining effect of an Al-2La-1B grain refiner in Al-10Si-0.3Mg casting alloy. Compared with the traditional Al-5Ti-1B refiner, Al-2La-1B refiner shows better performances on the grain refinement of Al-10Si-0.3Mg alloy. Transmission electron microscopy analysis suggests that the crystallite structure features of LaB6 are beneficial to the heterogeneous nucleation of α-Al grains. Regarding the mechanical performances, tensile properties of Al-10Si-0.3Mg casting alloy are prominently improved, due to the refined microstructures.

36 MATERIALS SCIENCE↗

Thermoset Blends of an Epoxy Resin and Polydicyclopentadiene

In this work, the mechanical properties of two chemically distinct and complementary thermoset polymers were manipulated through development of thermoset blends. The thermoset blend system was composed of an anhydride-cured diglycidyl ether of bisphenol A (DGEBA)-based epoxy resin, contributing high tensile strength and modulus, and polydicyclopentadiene (PDCPD), which has a higher toughness and impact strength as compared to other thermoset polymers. Ultra-small-angle and small-angle X-ray scattering analysis explored the morphology of concurrently cured thermoset blends, revealing a macroscopically phase separated system with a surface fractal structure across blended systems of varying composition. The epoxy resin rich and PDCPD rich phases exhibited distinct glass transitions (T g ’s): the T g observed at higher temperature was associated with the epoxy resin rich phase and was largely unaffected by the presence of PDCPD, whereas the PDCPD rich phase T g systematically decreased with increasing epoxy resin content due to inhibition of dicyclopentadiene ring-opening metathesis polymerization. The mechanical properties of these phase-separated blends were in reasonable agreement with predictions by the rule of mixtures for the blend tensile strength, modulus, and fracture toughness. Scanning electron microscopy analysis of the tensile and fracture specimen fracture surfaces showed an increase in energy dissipation mechanisms, such as crazing, shear banding, and surface roughness, as the fraction of the more ductile component, PDPCD, increased. These results present a facile method to tune the mechanical properties of a toughened thermoset network, in which the high modulus and tensile strength of the epoxy resin can be largely retained at high epoxy resin content in the blend, while increasing the fracture toughness.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermal Stability of Au Rhombic Dodecahedral Nanocrystals Can Be Greatly Enhanced by Coating Their Surface with an Ultrathin Shell of Pt

Rhombic dodecahedral nanocrystals have been considered particularly difficult to synthesize because they are enclosed by {110}, a low-index facet with the greatest surface energy. Recently, we demonstrated the use of seed-mediated growth for the facile and robust synthesis of Au rhombic dodecahedral nanocrystals (AuRD). While the unique shape and surface structure of AuRD are desirable for potential applications in plasmonics and catalysis, respectively, their high surface energy makes them highly susceptible to thermal degradation. Here we demonstrate that it is feasible to greatly improve the thermal stability with some sacrifice to the plasmonic properties of the original AuRD by coating their surface with an ultrathin shell made of Pt. Our in situ electron microscopy analysis indicates that the ultrathin Pt coating can increase the thermal stability from 60 up to 450 °C, a trend that is also supported by the results from a computational study.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Supplementing zinc oxide nanoparticles to cryopreservation medium minimizes the freeze-thaw-induced damage to spermatozoa

The sperm DNA integrity post cryopreservation of human semen samples is one of the serious concerns in human infertility treatment. In the present study, the beneficial effects of zinc oxide nanoparticles in preserving the functional ability of spermatozoa was explored. Ejaculates of normozoospermic men cryopreserved along with Zinc oxide nanoparticles (ZnONPs) exhibited non-significantly higher percentage of total and progressive motility in frozen-thawed samples compared to control. The sperm chromatin damage and malondialdehyde (MDA) level was significantly lower in ZnONPs group (P P < 0.05 respectively) and the spermatozoa's ability to undergo acrosome reaction was also unaltered. Fluorescence microscopy and High resolution transmission electron microscopy analysis demonstrated that the ZnONPs do not penetrate the membrane of spermatozoa but stay around the spermatozoa. In conclusion, the presence of ZnONPs during cryopreservation appears to be beneficial to the spermatozoa as they withstand freeze-thaw process competently better than control, without any adverse effect shown.

60 APPLIED LIFE SCIENCES↗

Electrochemical Deposition of Iron Nanoneedles on Titanium Oxide Nanotubes

Iron as a catalyst has wide applications for hydrogen generation from ammonia, photodecomposition of organics, and carbon nanotube growth. Tuning the size and shape of iron is meaningful for improving the catalysis efficiency. It is the objective of this work to prepare nanostructured iron with high surface area via electrochemical deposition. Iron nanoneedles were successfully electrodeposited on Ti supported TiO2 nanotube arrays in a chlorine-based electrolyte containing 0.15 M FeCl2 {center_dot} 4H2O and 2.0 M HCl. Transmission electron microscopic analysis reveals that the average length of the nanoneedles is about 200 nm and the thickness is about 10 nm. It has been found that a high overpotential at the cathode made of Ti/TiO2 nanotube arrays is necessary for the formation of the nanoneedles. Cyclic voltammetry test indicates that the electrodeposition of iron nanoneedles is a concentration-limited process.

36 MATERIALS SCIENCE↗

Symmetry determination on Pb-free piezoceramic 0.5Ba(Zr{sub 0.2}Ti{sub 0.8})O{sub 3}-0.5(Ba{sub 0.7}Ca{sub 0.3})TiO{sub 3} using convergent beam electron diffraction method

(1−x)(Ba(Zr{sub 0.2}Ti{sub 0.8})O{sub 3}-x(Ba{sub 0.7}Ca{sub 0.3})TiO{sub 3} (BZT-xBCT) Pb-free piezoceramic has been reported showing ultrahigh piezoelectric performance in its morphotropic phase boundary (MPB) region. However, the crystal structure characteristic for the MPB composition of BZT-xBCT is still under debate—between single orthorhombic phase and tetragonal + rhombohedral two phase mixture. In the present study, we perform the local symmetry determination on the MPB composition x = 0.5 using convergent beam electron diffraction analysis (CBED). Our CBED results from multiple zone axes suggest that there are two coexisting phases with the point group symmetries of 4 mm (tetragonal) and 3 m (rhombohedral) respectively, which agree with two phase mixture model. The strong piezoelectricity can thus be understood by considering the polarization rotation between tetragonal and rhombohedral phases by external field.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Interfacial bonding and electronic structure of GaN/GaAs interface: A first-principles study

Understanding of GaN interfacing with GaAs is crucial for GaN to be an effective interfacial layer between high-k oxides and III-V materials with the application in high-mobility metal-oxide-semiconductor field effect transistor (MOSFET) devices. Utilizing first principles calculations, here, we investigate the structural and electronic properties of the GaN/GaAs interface with respect to the interfacial nitrogen contents. The decrease of interfacial N contents leads to more Ga dangling bonds and As-As dimers. At the N-rich limit, the interface with N concentration of 87.5% shows the most stability. Furthermore, a strong band offsets dependence on the interfacial N concentration is also observed. The valance band offset of N7 with hybrid functional calculation is 0.51 eV. The electronic structure analysis shows that significant interface states exist in all the GaN/GaAs models with various N contents, which originate from the interfacial dangling bonds and some unsaturated Ga and N atoms. These large amounts of gap states result in Fermi level pinning and essentially degrade the device performance.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Synthesis, characterization and electrochemical studies of nanostructured CaWO{sub 4} as platinum support for oxygen reduction reaction

Highlights: • Nanostructured CaWO{sub 4} was fabricated by co-precipitation method. • Platinum was electrodeposited onto the surface prepared nanostructured CaWO{sub 4}. • Pt/CaWO{sub 4}-graphite demonstrate good oxygen reduction reaction activity. - Abstract: In the present work, we employed nanostructured calcium tungstate as a supporting material for platinum, a well-known electrocatalyst for oxygen reduction. The co-precipitation method has been utilized to synthesize nanostructured calcium tungstate from aqueous solution. The structure and morphology of the obtained CaWO{sub 4} were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Preparation of the Pt/CaWO{sub 4}-graphite catalyst was carried out by electrodeposition of Pt onto the surface of CaWO{sub 4}/graphite electrode. The physical properties of the catalyst were determined by scanning electron microscopy analysis and energy dispersive X-ray (SEM/EDX). The electrochemical activity of the Pt/CaWO{sub 4}-graphite for the oxygen reduction reaction (ORR) was investigated in acid solution by cyclic voltammetry measurements, linear sweep voltammetry, and electrochemical impedance spectroscopy. The results revealed that the Pt/CaWO{sub 4}-graphite has higher electrocatalytic activity for oxygen reduction in comparison with Pt/graphite catalyst.

36 MATERIALS SCIENCE↗

Synthesis of AlFeCuCrMg{sub x} (x = 0, 0.5, 1, 1.7) alloy powders by mechanical alloying

Novel AlFeCuCrMg{sub x} (x = 0, 0.5, 1, 1.7 mol) high-entropy alloys (HEAs) were synthesized by mechanical alloying. The effect of Mg content on the phase evolution of HEAs was investigated using X-Ray diffractometry (XRD), transmission electron microscopy (TEM) and selected area electron diffraction (SAED) pattern analysis. The particle morphology and composition of HEAs were investigated by scanning electron microscopy (SEM). Thermodynamic parameters were calculated and analyzed to explain the formation of a solid solution. XRD analysis revealed BCC as major phase and FCC as a minor phase in as-milled AlFeCuCr and AlFeCuCrMg{sub 0.5} HEAs. Also, XRD analysis of as-milled AlFeCuCrMg, AlFeCuCrMg{sub 1.7} confirmed the formation of two BCC phases (BCC 1 and BCC 2). TEM–SAED analysis of AlFeCuCrMg{sub x} HEAs concurred with XRD results. Microstructural features and mechanism for solid solution formation have been conferred in detail. Phase formation of the present HEAs has been correlated with calculated thermodynamic parameters. Differential thermal analysis (TGA-DTA) of these alloys confirmed that there is no substantial phase change up to 500 °C. - Highlights: • Novel AlFeCuCrMg{sub x} (x = 0, 0.5, 1, 1.7) HEAs were prepared by mechanical alloying. • Phase evolution and lattice parameter were studied by X-Ray Diffraction. • Crystallite size and lattice microstrain calculated failed to obey the Williamson–Hall method. • Criterions for formation of simple solid solution were compared to the thermodynamic parameters of the present HEAs. • Increase in the Mg concentration in AlMg{sub x}FeCuCr (x = 0, 0.5, 1, 1.7) HEAs supports the formation of BCC phase.

36 MATERIALS SCIENCE↗

Probing Liquid Surfaces under Vacuum Using SEM and TOF-SIMS

Applying vacuum-based molecular probes of liquid surfaces would aid many environmental, biological, and industrial studies. However the high vapor pressure of water and most organic solvents largely prohibit this use. We report a newly developed versatile and self-contained vacuum interface for high-vapor pressure liquid surfaces, and its application in a time of flight secondary ion mass spectrometer (TOFSIMS) and scanning electron microscope (SEM). The self-contained module requires no wires or tubing connections to the outside of the instrument. It uses a microfluidic channel with a 3 micrometer diameter window into the flowing fluid beneath it. This window supports the liquid against the vacuum by the liquid’s surface tension, while limiting the high-density vapor region traversed by the probe beams to only a few microns. This aperture size also limits temperature and concentration changes due to evaporation of the solvent. The beam damage caused by the probe beams is largely negligible, as the flowing liquid surface self-renews. We demonstrate the performance of this microfluidic interface for in situ liquid surface TOFSIMS (ISLS-TOFSIMS) and SEM (ISLS-SEM) for chemical analysis of liquid surfaces. This device enables in situ liquid (ISL) studies in a wide range of vacuum analytical methods beyond SEM and TOFSIMS.

99 GENERAL AND MISCELLANEOUS↗