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At least 91 records · Page 5

Hydrated doped-BaZrO 3 proton conductors studied by positron annihilation lifetime spectroscopy

The study of defect chemistry for doped BaZrO 3 proton conductors is of particular interest because of defect interactions that can affect the proton conductivity of the material. Protons incorporated due to the material's hydration can be trapped by negatively charged immobile dopants, reducing proton mobility. The reduction of the proton conduction impedes using BaZrO 3 materials in energy conversion applications at intermediate temperatures (300°C – 600°C). The probing of proton trapping in doped BaZrO 3 is hindered by the limited availability of techniques sensitive to defect chemistries. In this work, we used positron annihilation lifetime spectroscopy (PALS) to study the defect chemistry of Y-doped and Sc-doped BaZrO 3 . Using a two-state positron trapping model we showed that PALS can be used to study the defect chemistry of hydrated dense proton conductors. Positron trapping rates and lifetimes were correlated with doping levels of the materials. Probability significance t-tests were carried out for PALS parameters to verify whether there are differences/similarities for various populations: non-doped/doped, level and type of doping, high temperature, and surface effects. Further, the results revealed that the initial doping generates a significant number of traps available for positrons. Doping in yttrium increased the positron trapping rate, while this effect was not observed with scandium. Low-temperature hydration affects specimens significantly inhibiting positron trapping at undoped BaZrO 3 material and highly doped specimens. Positronium formation in rough surface layers, and highly doped specimens was detected but does not exceed 1%.

36 MATERIALS SCIENCE↗

Photo-Brook rearrangement of acyl silanes as a strategy for photoaffinity probe design

Photoaffinity labeling (PAL) is a powerful tool for the identification of non-covalent small molecule–protein interactions that are critical to drug discovery and medicinal chemistry, but this approach is limited to only a small subset of robust photocrosslinkers. The identification of new photoreactive motifs capable of covalent target capture is therefore highly desirable. Herein, we report the design, synthesis, and evaluation of a new class of PAL warheads based on the UV-triggered 1,2-photo-Brook rearrangement of acyl silanes, which hitherto have not been explored for PAL workflows. Irradiation of a series of probes in cell lysate revealed an iPr-substituted acyl silane with superior photolabeling and minimal thermal background labeling compared to other substituted acyl silanes. Further, small molecule (+)-JQ1- and rapamycin-derived iPr acyl silanes were shown to selectively label recombinant BRD4-BD1 and FKBP12, respectively, with minimal background. Together, these data highlight the untapped potential of acyl silanes as a novel, tunable scaffold for photoaffinity labeling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lattice distortion mechanism study of TiO{sub 2} nanoparticles during photocatalysis degradation and reactivation

In this paper, the photocatalytic process of TiO{sub 2} (P25) is directly characterized by using a positron annihilation lifetime spectroscopy (PALS), high-resolution transmission electron microscopy (HRTEM), Photoluminescence spectroscopy (PL) and UV Raman spectroscopy (Raman). The experimental results reveal that: 1) From PALS measurements, because τ{sub 1} and τ{sub 2} values and their intensity (I{sub 1} and I{sub 2}) assigned to the different size and amounts of defects, respectively, their variations indicate the formation of different types and amounts of defects during the absorption and degradation. 2) HRTEM observations show that the lattice images become partly blurring when the methylene blue is fully degradated, and clear again after exposed in the air for 30 days. According to the results, we propose a mechanism that the lattice distortion induces the defects as electron capture sites and provides energy for improving photocatalytic process. Meanwhile, the lattice distortion relaxation after exposing in the air for 30 days perfectly explains the gradual deactivation of TiO{sub 2}, because the smaller vacancy defects grow and agglomerate through the several photocatalytic processes. The instrumental PL and Raman are also used to analyze the samples and approved the results of PALS and HRTEM.

36 MATERIALS SCIENCE↗

High-heat-flux testing of irradiated tungsten-based materials for fusion applications using infrared plasma arc lamps

Testing of advanced materials and component mock-ups under prototypical fusion high-heat-flux conditions, while historically a mainstay of fusion research, has proved to be quite challenging, especially for irradiated materials. A new high-heat-flux–testing (HHFT) facility based on water-wall plasma arc lamps (PALs) is now introduced for materials and small-component testing. Two PAL systems, utilizing a 12 000°C plasma arc contained in a quartz tube cooled by a spiral water flow over the inside tube surface, provide maximum incident heat fluxes of 4.2 and 27 MW/m 2 over areas of 9×12 and 1×10 cm 2 , respectively. This paper will present the overall design and implementation of a PAL-based irradiated material target station (IMTS). The IMTS is primarily designed for testing the effects of heat flux or thermal cycling on material coupons of interest, such as those for plasma-facing components. Temperature results are shown for thermal cycling under HHFT of tungsten coupon specimens that were neutron irradiated in HFIR. Finally, radiological surveys indicated minimal contamination of the 36×36×18 cm test section, demonstrating the capability of the new facility to handle irradiated specimens at high temperature.

36 MATERIALS SCIENCE↗

Monte Carlo Modeling and Design of Photon Energy Attenuation Layers for >10× Quantum Yield Enhancement in Si-Based Hard X-ray Detectors

High-energy (>20 keV) X-ray photon detection at high quantum yield, high spatial resolution, and short response time has long been an important area of study in physics. Scintillation is a prevalent method but limited in various ways. Directly detecting high-energy X-ray photons has been a challenge to this day, mainly due to low photon-to-photoelectron conversion efficiencies. Commercially available state-of-the-art Si direct detection products such as the Si charge-coupled device (CCD) are inefficient for >10 keV photons. Here, we present Monte Carlo simulation results and analyses to introduce a highly effective yet simple high-energy X-ray detection concept with significantly enhanced photon-to-electron conversion efficiencies composed of two layers: a top high-Z photon energy attenuation layer (PAL) and a bottom Si detector. We use the principle of photon energy down conversion, where high-energy X-ray photon energies are attenuated down to ≤10 keV via inelastic scattering suitable for efficient photoelectric absorption by Si. Our Monte Carlo simulation results demonstrate that a 10–30× increase in quantum yield can be achieved using PbTe PAL on Si, potentially advancing high-resolution, high-efficiency X-ray detection using PAL-enhanced Si CMOS image sensors.

47 OTHER INSTRUMENTATION↗

Line-of-sight velocity and metallicity measurements of the palomar 5 tidal stream

We present Subaru/Faint Object Camera and Spectrograph and Keck/Deep Imaging Multi-Object Spectrometer medium-resolution spectroscopy of a tidally disrupting Milky Way (MW) globular cluster Palomar 5 (Pal 5) and its tidal stream. The observed fields are located to cover an angular extent of ∼17° along the stream, providing an opportunity to investigate a trend in line-of-sight velocities (V {sub los}) along the stream, which is essential to constrain its orbit and underlying gravitational potential of the MW’s dark matter halo. A spectral fitting technique is applied to the observed spectra to obtain stellar parameters and metallicities ([Fe/H]) of the target stars. The 19 stars most likely belonging to the central Pal 5 cluster have a mean V {sub los} of −58.1 ± 0.7 km s{sup −1} and metallicity [Fe/H] = −1.35 ± 0.06 dex, both of which are in good agreement with those derived in previous high-resolution spectroscopic studies. Assuming that the stream stars have the same [Fe/H] as the progenitor cluster, the derived [Fe/H] and V{sub los} values are used to estimate the possible V {sub los} range of the member stars at each location along the stream. Because of the heavy contamination of the field MW stars, the estimated V {sub los} range depends on prior assumptions about the stream’s V{sub los}, which highlights the importance of more definitely identifying the member stars using proper motion and chemical abundances to obtain unbiased information of V {sub los} in the outer part of the Pal 5 stream. The models for the gravitational potential of the MW’s dark matter halo that are compatible with the estimated V {sub los} range are discussed.

79 ASTRONOMY AND ASTROPHYSICS↗

A PARC system for terminal docking

A Panoramic viewing system for Automated Rendezvous and Capture (PARC) has been proposed as a visual information feedback system for terminal docking/berthing. The system relies on a unique Panoramic Annular Lens (PAL) which captures an image of its surroundings in real time. This paper describes the evolution of the PAL along with technical details of its imaging capabilities. Several examples are given of radial metrology, where PAL imaging systems are used to perform visual inspections and measurements. Digital image acquisition and processing techniques, used to interpret various features appearing in the images and to transform images for improved human viewing, are also included. These discussions are followed by a potential application for PARC involving berthing of active and passive mechanical assemblies associated with Space Station Freedom.

Gilbert, John A.↗

Nitrogen recycling during phenylpropanoid metabolism in sweet potato tubers

In the first step of the phenylpropanoid metabolic pathway, L-phenylalanine (L-Phe) is deaminated to form E-cinnamate, in a conversion catalyzed by phenylalanine ammonia-lyase (PAL; EC 4.3.1.5). The metabolic fate of the ammonium ion (NH4+) produced in this reaction was investigated in sweet potato (Ipomoea batatas) tuber discs. [15N]-Labeled substrates including L-Phe, in the presence or absence of specific enzyme inhibitors, were administered to sweet potato discs in light under aseptic conditions. 15N-Nuclear magnetic resonance spectroscopic analyses revealed that the 15NH4+ liberated during the PAL reaction is first incorporated into the amide nitrogen of L-glutamine (L-Gln) and then into L-glutamate (L-Glu). These results extend our previous observations in pine and potato that PAL-generated NH4+ is assimilated by the glutamine synthetase (GS; EC 6.3.1.2)/glutamate synthase (GOGAT; EC 1.4.1.13) pathway, with the NH4+ so formed ultimately being recycled back to L-Phe via L-Glu as aminoreceptor and donor.

Non-NASA Center↗

Utilization of Airborne and in Situ Data Obtained in SGP99, SMEX02, CLASIC and SMAPVEX08 Field Campaigns for SMAP Soil Moisture Algorithm Development and Validation

Field experiment data sets that include coincident remote sensing measurements and in situ sampling will be valuable in the development and validation of the soil moisture algorithms of the NASA's future SMAP (Soil Moisture Active and Passive) mission. This paper presents an overview of the field experiment data collected from SGP99, SMEX02, CLASIC and SMAPVEX08 campaigns. Common in these campaigns were observations of the airborne PALS (Passive and Active L- and S-band) instrument, which was developed to acquire radar and radiometer measurements at low frequencies. The combined set of the PALS measurements and ground truth obtained from all these campaigns was under study. The investigation shows that the data set contains a range of soil moisture values collected under a limited number of conditions. The quality of both PALS and ground truth data meets the needs of the SMAP algorithm development and validation. The data set has already made significant impact on the science behind SMAP mission. The areas where complementing of the data would be most beneficial are also discussed.

Soil moisture↗

Simulated Vision-based Approach and Landing System for Advanced Air Mobility

Advanced Air Mobility (AAM) aircraft require precision approach and landing systems (PALS) in several environments, such as urban, suburban, and rural. It is challenging to implement current state-of-the-art methods approved for automated approach and landing for AAM operations with challenges such as GPS degradation in urban environments and visual navigation aids like the glideslope and localizer being narrow and not allowing alternative incoming landing angles at vertiports. However, existing technology and systems, i.e., the instrument landing system (ILS) with glideslope and localizer indicators that use vision, IR, radar, or GPS methods, provide baseline perception and sensing requirements for AAM aircraft approach and landing. This paper focuses on vision-based PAL and computer vision feature correspondence methods to demonstrate a baseline navigation system while adhering to the Federal Aviation Administration requirements and regulations about heliport design (FAA AC 150/5390-2C), which is one of the closest references for vertiport requirements and regulations. The coplanar pose from orthography and scaling with iterations (COPOSIT) algorithm determines pose estimation, which feeds into an Extended Kalman filter that combines IMU with vision to create a vision-based approach and landing (VAL) sensor fusion navigation solution for GPS-denied environments. The VAL navigation solution provides promising simulation results for AAM PALS with Hough circle detection and feature correspondence, which demonstrate robustness to false positives. This paper incorporates moderately high- fidelity simulations with computer graphics rendering to show a distributed sensor network to track an AAM aircraft during approach and landing to compare with the aircraft’s onboard vision-based navigation solution.

distributed sensing↗

T7 Expression Systems for Inducible Production of Proteins from Cloned Genes in E. coli

Inducible T7 expression systems are capable of producing a wide range of proteins in E. coli . Improvements over common practice include: preventing unintended induction by establishing and maintaining expression strains in non-inducing growth media comprised entirely of purified components instead of complex growth media that may variably induce target proteins on approach to saturation; and expressing many target proteins in parallel by convenient and productive auto-induction in BL21(DE3) and other suitable hosts, instead of IPTG induction. From earliest days, basal expression prevented establishment of inducible strains for producing proteins that are stressful to the host. Newly developed pAL vectors now reduce basal expression to levels where coding sequences for even the most stressful proteins can be maintained and induced. In conclusion, asymmetric ligation allows simple and efficient cloning of individual coding sequences or simultaneous cloning of two or three coding sequences for co expression from a single pAL vector.

59 BASIC BIOLOGICAL SCIENCES↗

A position-aware linear solid constitutive model for peridynamics

A position-aware linear solid (PALS) peridynamic constitutive model is proposed for isotropic elastic solids. The PALS model addresses problems that arise, in ordinary peridynamic material models such as the linear peridynamic solid (LPS), due to incomplete neighborhoods near the surface of a body. We improved model behavior in the vicinity of free surfaces through the application of two influence functions that correspond, respectively, to the volumetric and deviatoric parts of the deformation. Furthermore, the model is position-aware in that the influence functions vary over the body and reflect the proximity of each material point to free surfaces. Demonstration calculations on simple benchmark problems show a sharp reduction in error relative to the LPS model.

36 MATERIALS SCIENCE↗

Positron annihilation lifetime spectroscopy study of polyvinylpyrrolidone‐added polyvinylidene fluoride membranes: Investigation of free volume and permeation relationships

ABSTRACT Polyvinylidene fluoride (PVDF) membranes were prepared via the phase inversion method from casting solutions containing PVDF, dimethylformamide (DMF), and polyvinylpyrrolidone (PVP) as pore former. PVP was used in the casting solution in a range of 0–5 wt % and extracted. The effect on membranes of using PVP in the casting process was analyzed by X‐ray diffraction, differential scanning calorimetry, scanning electron microscopy, viscosity, and water permeability techniques. With an increase of PVP from 0 to 5 wt %, the PVDF casting solution viscosities increased from 858 to 1148 cP; the resulting PVDF membrane thickness increased; and the crystallinity of PVDF membranes decreased from 40.0 to 33.3%, which indicates that the addition of PVP inhibits the degree of crystallization in the PVDF membranes. SEM results revealed the shape and size of macropores in the membranes; these macropores changed after PVP addition to the casting solutions. The impact of structural changes on free‐volume properties was evaluated using positron annihilation lifetime spectroscopy (PALS) studies. PALS analysis indicated no effect on the average radius (~3.4 Å) of membrane free‐volume holes from the addition of PVP to the casting solution. However, the percentage of o ‐Ps pick‐off annihilation intensity, I 3 , increased from 1.7 to 5.1% with increased PVP content. Further, increasing the PVP content from 0.5 to 5% resulted in an increased final pure water permeability flux. For instance, the 210 min flux for a 14% PVDF + 0.5% PVP membrane was found to be 3.3 times greater than a control membrane having the same PVDF concentration. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58 , 589–598

Eren, Bilge↗

Degradation of Congo Red dye by a Fe 2 O 3 @CeO 2 -ZrO 2 /Palygorskite composite catalyst: Synergetic effects of Fe 2 O 3

A newly designed Fe 2 O 3 @CeO 2 -ZrO 2 /Palygorskite heterogeneous Fenton catalyst with high degradation efficiency toward Congo Red (CR) is reported in this paper. The iron oxide (Fe 2 O 3 ) was used as the originator of hydroxyl radicals ( OH), CeO 2 -ZrO 2 was used as an efficient matrix of Fe 2 O 3 to enhance the oxidation performance, and the Palygorskite (Pal) played the role of substrate and adsorbent. A synergetic effect of the catalyst was realized by enhancing the adsorption capacity and dispersibility of CeO 2 -ZrO 2 and Fe 2 O 3 nanoparticles, and also due to charge transfer between these two species. The products were characterized by XRD, FTIR, SEM, TEM, XPS, VSM and nitrogen adsorption-desorption isotherms. The catalytic activities were evaluated in terms of many reaction parameters. The removal efficiency of CR was up to 95% on Fe 2 O 3 @CeO 2 -ZrO 2 /Pal under optimized conditions (Pal accounted for 30% of the catalyst mass fraction and Ce/Zr atoms molar ratio = 8:2, T = 30 °C, pH = 3.4, 4 g L -1 catalyst, 40 mM H 2 O 2 and 500 mg/L CR), the product also has shown good reusability. Both α-Fe 2 O 3 and CeO 2 -ZrO 2 played important roles in the generation of hydroxyl radicals, which determined the catalytic efficiency of the composite catalyst. Fe 2 O 3 @CeO 2 -ZrO 2 /Pal was proven to be a promising candidate in the field of heterogeneous Fenton catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Organic solution-processible electroluminescent molecular glasses for non-doped standard red OLEDs with electrically stable chromaticity

Highlights: • The D–A–D electroluminescent molecular glasses are synthesized. • Non-doped red electroluminescent film is fabricated by spin-coating. • Red OLED shows stable wavelength, luminous efficiency and chromaticity. • CIE1931 coordinate is in accord with standard red light in PAL system. - Abstract: Organic light-emitting molecular glasses (OEMGs) are synthesized through the introduction of nonplanar donor and branched aliphatic chain into electroluminescent emitters. The target OEMGs are characterized by {sup 1}H NMR, {sup 13}C NMR, IR, UV–vis and fluorescent spectra as well as elemental analysis, TG and DSC. The results indicated that the optical, electrochemical and electroluminescent properties of OEMGs are adjusted successfully by the replacement of electron-donating group. The non-doped OLED device with a standard red electroluminescent emission is achieved by spin-coating the THF solution of OEMG with a triphenylamine moiety. This non-doped red OLED device takes on an electrically stable electroluminescent performance, including the stable maximum electroluminescent wavelength of 640 nm, the stable luminous efficiency of 2.4 cd/A and the stable CIE1931 coordinate of (x, y) = (0.64, 0.35), which is basically in accord with the CIE1931 coordinate (x, y) = (0.64, 0.33) of standard red light in PAL system.

36 MATERIALS SCIENCE↗

Analysis of governing factors controlling gas transport through fresh and aged triptycene-based polyimide films

In this report the fundamental gas transport properties and physical aging behavior of a series of triptycene-based polyimides with various substitution groups were investigated. Wide-angle x-ray diffraction revealed that the 6FDA-1,4-triptycene polyimides exhibit two chain packing domains with d-spacing values of ~6.7 Å and ~5.3 Å, corresponding to triptycene-induced chain packing disruption and chain segments lacking the triptycene moiety, respectively. Positron annihilation lifetime spectroscopy (PALS) showed a bimodal distribution of microcavity size made up of triptycene cleft cavities that are ~3 Å diameter and larger interchain cavities with an average diameter of ~7 Å. Additionally, PALS confirmed 6FDA-1,4-trip_CH 3 has the lowest fractional free volume, primarily due to smaller contributions from the interchain cavities, and 6FDA-1,4-trip_CF 3 has the largest fractional free volume. It was also found that the addition of substituent groups had a unique and positive effect on the aging properties over nine months, in which the addition of CH 3 and CF 3 groups led to permeability increases of ~20% and ~40%, respectively. This is caused by the combination of the lowered driving force for physical aging, the substituent groups sterically hindering tighter packing with time, and the interconnectivity and/or unblocking of free volume over time through small-scale, local chain motion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Intrinsically Hierarchical Nanoporous Polymers via Polymerization-Induced Microphase Separation

The synthesis of microporous polymers generally requires postpolymerization modification via hyper-cross-linking to trap the polymeric network in a state with high void volume. An alternative approach utilizes rigid, sterically demanding monomers to inhibit efficient packing, thus leading to a high degree of free volume between polymer side groups and main chains. In this work we combine polymers of intrinsic microporosity with polymerization-induced microphase separation (PIMS), a versatile methodology for the synthesis of nanostructured materials that can be rendered mesoporous. Copolymerization of various styrenic monomers with divinylbenzene in the presence of a poly(lactide) terminated with a chain-transfer agent (PLA-CTA) results in kinetic trapping of a microphase-separated state. Subsequent etching of PLA provides a bicontinuous mesoporous network. Using equilibrium and kinetic nitrogen sorption experiments as well as positron annihilation lifetime spectroscopy (PALS), we demonstrate that variations in the steric characteristics of the styrenic monomer impart the network with microporosity, resulting in hierarchically (meso and micro) porous materials. Additionally, structure–property relationships of the styrenic monomer with total surface area and pore volume indicate that the glass transition temperature (T g ) of the corresponding styrenic homopolymers provides a reasonable measure of the steric interactions and resultant microporosity in these systems. Finally, PALS provides insight into micro- and mesoscopic void volume differences between porous monoliths containing either tert-butyl or TMS-modified styrenic monomers compared to the parent, unmodified styrene.

36 MATERIALS SCIENCE↗

Interface effect of Fe and Fe 2 O 3 on the distributions of ion induced defects

The stability of structural materials in extreme nuclear reactor environments—with high temperature, high radiation, and corrosive media—directly affects the lifespan of the reactor. In such extreme environments, an oxide layer on the metal surface acts as a passive layer protecting the metal underneath from corrosion. To predict the irradiation effect on the metal layer in these metal/oxide bilayers, nondestructive depth-resolved positron annihilation lifetime spectroscopy (PALS) and complementary transmission electron microscopy (TEM) were used to investigate small-scale defects created by ion irradiation in an epitaxially grown (100) Fe film capped with a 50 nm Fe 2 O 3 oxide layer. In this study, the evolution of induced vacancies was monitored, from individual vacancy formation at low doses—10 –5 dpa—to larger vacancy cluster formation at increasing doses, showing the sensitivity of positron annihilation spectroscopy technique. Furthermore, PALS measurements reveal how the presence of a metal–oxide interface modifies the distribution of point defects induced by irradiation. TEM measurements show that irradiation induced dislocations at the interface is the mechanism behind the redistribution of point defects causing their accumulation close to the interface. Finally, this work demonstrates that the passive oxide layers formed during corrosion impact the distribution and accumulation of radiation induced defects in the metal underneath and emphasizes that the synergistic impact of radiation and corrosion will differ from their individual impacts.

36 MATERIALS SCIENCE↗