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At least 955 records · Page 53

Perspectives on high temperature superconducting electronics

The major challenges in making high temperature superconducting (HTSC) electronics viable are predominantly materials problems. Unlike their predecessors, the metal oxide-based superconductors are integratable with other advanced technologies such as opto-electronics and micro-electronics. The materials problems to be addressed relate to the epitaxial growth of high quality films, highly oriented films on non-lattice matched substrates, heterostructures with atomically sharp interfaces of junctions and other novel devices, and the processing of these films with negligible deterioration of the superconducting properties. These issues are illustrated with results based on films prepared in-situ by a pulsed laser deposition process. Films with zero-transition temperatures of 90 K and critical current densities of 5 x 10(exp 6) A/sq cm at 77 K have been prepared by this technique. Ultra-thin films, less than 100 A show T(sub c) is greater than 80 K, supporting the idea of two-dimensional transport in these materials. By the use of appropriate buffer layers, films with T(sub c) of 87 K and J(sub c) of 6 x 10(exp 4) A/sq cm were fabricated on silicon substrates. Submicron structures with J(sub c) is greater than 2 x 10(exp 7) at 10 K were fabricated. Results on nonlinear switching elements, IR detectors, and microwave studies will be briefly summarized.

Venkatesan, T.↗

Revealing particle-scale powder spreading dynamics in powder-bed-based additive manufacturing process by high-speed x-ray imaging

Powder spreading is a key step in the powder-bed-based additive manufacturing process, which determines the quality of the powder bed and, consequently, affects the quality of the manufactured part. However, powder spreading behavior under additive manufacturing condition is still not clear, largely because of the lack of particle-scale experimental study. Here, we studied particle-scale powder dynamics during the powder spreading process by using in-situ high-speed high-energy x-ray imaging. Evolution of the repose angle, slope surface speed, slope surface roughness, and the dynamics of powder clusters at the powder front were revealed and quantified. Interactions of the individual metal powders, with boundaries (substrate and container wall), were characterized, and coefficients of friction between the powders and boundaries were calculated. The effects of particle size on powder flow dynamics were revealed. Here, the particle scale powder spreading dynamics, reported here, are important for a thorough understanding of powder spreading behavior in the powder-bed-based additive manufacturing process, and are critical to the development and validation of models that can more accurately predict powder spreading behavior.

42 ENGINEERING↗

Satellite-Derived Sea Surface Temperature: Workshop 3

This is the third of a series of three workshops, sponsored by the National Aeronautics and Space Administration, to investigate the state of the art in global sea surface temperature measurements from space. Three workshops were necessary to process and analyze sufficient data from which to draw conclusions on the accuracy and reliability of the satellite measurements. In this workshop, the final two (out of a total of four) months of satellite and in situ data chosen for study were processed and evaluated. Results from the AVHRR, HIRS, SMMR, and VAS sensors, in comparison with in situ data from ships, XBTs, and buoys, confirmed satellite rms accuracies in the 0.5 to 1.0 C range, but with variable biases. These accuracies may degrade under adverse conditions for specific sensors. A variety of color maps, plots, and statistical tables are provided for detailed study of the individual sensor SST measurements.

Source record↗

Three-dimensional imaging of dislocation dynamics during the hydriding phase transformation

Crystallographic imperfections can significantly alter material properties and responses to external stimuli, including solute induced phase transformations and crystal growth and dissolution . Despite recent progress in imaging defects using both electron and x-ray techniques, in situ three-dimensional imaging studies of defect dynamics, necessary to understand and engineer nanoscale processes, remains challenging. Here, we report in situ three-dimensional imaging of defect dynamics during the hydriding phase transformation of individual palladium nanocrystals by Bragg Coherent Diffractive Imaging (BCDI) . During constant pressure experiments, we observed that the phase transformation begins after the nucleation of dislocations in large (300 nm) particles. The 3D dislocation network shows that dislocations are close to the phase boundary. The 3D phase morphology resolved by BCDI suggests that the hydrogen-rich phase is more similar to a spherical cap on the hydrogen-poor phase than the core-shell model commonly assumed. We substantiate this conclusion using 3D phase field modeling and demonstrate how phase morphology affects the critical size for dislocation nucleation. We determine the size dependence of the transformation pressure for large (150-300 nm) palladium nanocrystals using variable pressure experiments. Our results reveal a pathway for solute induced structural phase transformations in nanocrystals and demonstrate BCDI as a novel method for understanding dislocation dynamics in phase transforming systems at the nanoscale.

36 MATERIALS SCIENCE↗

NASA atmospheric effects of aviation projects: Status and plans

NASA's Atmospheric Effects of Aviation Project is developing a scientific basis for assessment of the atmospheric impact of subsonic and supersonic aviation. Issues addressed include predicted ozone changes and climatic impact, and related uncertainties. A primary goal is to assist assessments of United Nations scientific organizations and, hence, consideration of emission standards by the International Civil Aviation Organization. Project focus is on simulation of atmospheric processes by computer models, but studies of aircraft operations, laboratory studies, and remote and in situ observations of chemical, dynamic, and radiative processes are also included.

Wesoky, Howard L.↗

Pulsed Laser-Assisted Focused Electron-Beam-Induced Etching of Titanium with XeF 2 : Enhanced Reaction Rate and Precursor Transport

We introduce a laser-assisted focused electron-beam-induced etching (LA-FEBIE) process which is a versatile, direct write nanofabrication method that allows nanoscale patterning and editing; we do this in order to enhance the etch rate of electron-beam-induced etching. The results demonstrate that the titanium electron stimulated etch rate via the XeF2 precursor can be enhanced up to a factor of 6 times with an intermittent pulsed laser assist. Moreover, the evolution of the etching process is correlated to in situ stage current measurements and scanning electron micrographs as a function of time. Finally, the increased etch rate is attributed to photothermally enhanced Ti–F reaction and TiF4 desorption and in some regimes enhanced XeF2 surface diffusion to the reaction zone.

36 MATERIALS SCIENCE↗

Surface Engineering of Electrospun Fibers to Optimize Ion and Electron Transport in Li + Battery Cathodes

This report documents research into the fabrication of Lithium Manganese Oxide (Spinel) (LMO) cathode material in the form of fibrous mats, the degradation process of this material in a battery electrolyte, the formation of core-shell coated fibers and the electrochemical properties of the active cathode core fiber. In practice, LMO experiences several degradation mechanisms ranging from capacity fading, the Jahn-Teller distortion phenomenon leading to dissolution in the electrolyte phase, and the formation of surface films by degradation of the electrolyte, and/or phase transitions at the surface to form Mn 2 O 3 . Density Functional Theory (DFT) was applied to model from first principles the interactions between the electrolyte and the surface leading to Mn ion dissolution. Thermodynamic values of solvation energy were calculated and related to the applied potential on the material during electrochemical cycling. Direct in situ observation of the degradation process was conducted on fiber structures using AFM and coin cell measurements, showing the rapid formation of theorized surface films. This provides the first direct evidence of processes occurring at the interface, such as dissolution of the active material, facet development, decomposition of the electrolyte to form a surface electrolyte interface (SEI) layer, or the formation of Li alcoxides/carboxylates. Methods for fabricating fiber structures of LMO were researched using two techniques; electrospinning and forcespinning. Chemical precursors were evaluated and optimized to lead to polycrystalline, hollow fibers of LMO, as well as tetragonal zirconia fiber mats. Sol-gel chemistries for the synthesis of LMO and zirconia have been implemented to generate these fiber morphologies. Core-shell methods were attempted using both techniques, proving partial success and insight into the physics of coherent core-shell fibers. The knowledge developed in this program has increased understanding of the degradation mechanisms of the active energy storage material, and aided development of a protective interface which resists these processes while permitting rapid Li + transport, good e - conductivity, a stable interface, and prevention of the formation of a solid-electrolyte interphase (SEI) layer.

25 ENERGY STORAGE↗

In-situ/operando study of Cu-based nanocatalysts for CO 2 electroreduction using electrochemical liquid cell TEM

The structure of a nanocatalyst during electrocatalytic reactions often deviates from its pristine structure due to intrinsic properties, or physical and chemical adsorption at the catalytic surfaces. Taking Cu-based catalysts for CO 2 electroreduction reactions (CO 2 RR) as an example, they often experience segregation, leaching, and alloying during reactions. With the recent breakthrough development of high-resolution polymer electrochemical liquid cells, in-situ electrochemical liquid cell transmission electron microscopy (EC-TEM) alongside other advanced microscopy techniques, has become a powerful platform for revealing electrocatalysts restructuring at the atomic level. Considering the complex reactions involving electrified solid-liquid interfaces and catalyst structural evolution with intermediates, systematic studies with multimodal approaches are crucial. In this article, we demonstrate a research protocol for the study of electrocatalysts structural evolution during reactions using the in-situ EC-TEM platform. Using Cu and CuAg nanowire catalysts for CO 2 RR as model systems, we describe the experimental procedures and findings. We highlight the platform’s crucial role in elucidating atomic-scale pathways of nanocatalyst restructuring and identifying catalytic active sites, as well as avoiding potential artifacts to ensure unbiased conclusions. Using the multimodal characterization toolbox, we provide the opportunity to correlate the structure of a working catalyst with its performance. Finally, we discuss advancements as well as the remaining gap in elucidating the structural-performance relationship of working catalysts. We expect this article will assist in establishing guidelines for future investigations of complex electrochemical reactions, such as CO 2 RR and other catalytic processes, using the in-situ EC-TEM platform.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In situ monitoring of structure formation in the active layer of polymer solar cells during roll-to-roll coating

The active layer crystallization during roll-to-roll coating of organic solar cells is studied in situ. We developed an X-ray setup where the coater unit is an integrated part of the small angle X-ray scattering instrument, making it possible to control the coating process while recording scattering measurements in situ, enabling us to follow the crystal formation during drying. By varying the distance between the coating head and the point where the X-ray beam hits the film, we obtained measurements of 4 different stages of drying. For each of those stages, the scattering from as long a foil as possible is summed together, with the distance from coating head to scattering point kept constant. The results are average crystallographic properties for the active layer coated on a 30 m long foil. With this insight into the dynamics of crystallization in a roll-coated polymer film, we find that the formation of textured and untextured crystallites seems uncorrelated, and happens at widely different rates. Untextured P3HT crystallites form later in the drying process than expected which may explain previous studies speculating that untextured crystallization depends on concentration. Textured crystallites, however, begin forming much earlier and steadily increases as the film dries, showing a development similar to other in situ studies of these materials.

36 MATERIALS SCIENCE↗

Friction stir processing of an aluminum-magnesium alloy with pre-placing elemental titanium powder: In-situ formation of an Al{sub 3}Ti-reinforced nanocomposite and materials characterization

A fine-grained Al–Mg/Al{sub 3}Ti nanocomposite was fabricated by friction stir processing (FSP) of an aluminum-magnesium (AA5052) alloy with pre-placed titanium powder in the stirred zone. Microstructural evolutions and formation of intermetallic phases were analyzed by optical and electron microscopic techniques across the thickness section of the processed sheets. The microstructure of the nanocomposite consisted of a fine-grained aluminum matrix (1.5 µm), un-reacted titanium particles (<40 µm) and reinforcement particles of Al{sub 3}Ti (<100 nm) and Mg{sub 2}Si (<100 nm). Detailed microstructural analysis indicated solid-state interfacial reactions between the aluminum matrix and micro-sized titanium particles to form Al{sub 3}Ti intermetallic phase. The hard inclusions were then fractured and re-distributed in the metal matrix by the severe thermo-mechanical conditions imposed by FSP. Evaluation of mechanical properties by hardness measurement and uniaxial tensile test determined significant enhancement in the mechanical strength (by 2.5 order of magnetite) with a high ductility (~22%). Based on a dislocation-based model analysis, it was suggested that the strength enhancement was governed by grain refinement and the presence of hard inclusions (4 vol%) in the metal matrix. Fractographic studies also showed a ductile-brittle fracture mode for the nanocomposite compared with fully ductile rupture of the annealed alloy as well as the FSPed specimen without pre-placing titanium particles. - Highlights: • FSP was employed to fabricate in situ nanocomposite. • The AA5052 Al alloy with pre-placed micro-sized Ti particles were utilized. • The structural analysis was revealed that the in situ formation of Al{sub 3}Ti nanophase. • The SZ grain structure was refined by PSN and ZHP mechanisms during DRX. • Hardness and tensile strength were improved up to ~2.5 times with a good ductility.

36 MATERIALS SCIENCE↗

Self-Flammability of Gases Generated by Hanford Tank Waste and the Potential of Nitrogen Inerting to Eliminate Flammability Safety Concerns

Through radiolytic and thermolytic reactions, Hanford tank wastes generate and retain a variety of gases, including hydrogen, nitrous oxide, methane (and other hydrocarbons), ammonia, and nitrogen. This gas generation can be expected to continue during processing in the Hanford Tank Waste Treatment and Immobilization Plant (WTP). The generation rates in the WTP will change from those for the in-situ tank waste because of different process temperatures, different dose rates produced by in-process changes in the proportions of solid and liquid, and dilution of the waste liquid. The flammability of the generated gas that is continuously released, and of any retained gas that might be released into a vessel headspace in quantity due to a spontaneous release, depends on the concentrations not only of the fuel gases—primarily hydrogen (H2), methane, other hydrocarbons, and ammonia—but of the oxidizer nitrous oxide (N2O). As a result of high concentrations of N2O, some gas mixtures are “self-flammable” (i.e., ignition can occur when no air is present because N2O provides the only oxidizer needed). Self-flammability could potentially reduce the effectiveness of using a nitrogen (N2) purge in the headspace as a flammability control, if its effects are not accounted for. A given amount of inertant gas (N2) can accommodate only a certain amount of a generated self-flammable gas before the mixture with inertant gas becomes flammable.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

In Situ Molecular Imaging of the Biofilm and Its Matrix

Molecular mapping of live biofilms at submicron resolution presents a grand challenge. Here, we present the first chemical mapping results of biofilm extracellular polymeric sub-stance (EPS) components in biofilms using correlative imaging be-tween super resolution florescence microscopy and liquid time-of-flight secondary ion mass spectrometry (ToF-SIMS). Shewanella oneidensis is used as a model organism. Heavy metal anions chro-mate (Cr2O72-) consisting of chromium Cr (VI) was a model envi-ronmental stressor used to treat the biofilms. Of particular interest, biologically relevant water clusters have been first observed in the biofilms. Characteristic fragments of biofilm matrix components such as proteins, polysaccharides, and lipids can be spatially im-aged. Furthermore, characteristic fatty acids (e.g., palmitic acid), quinolone signal, and riboflavin fragments are found to respond af-ter the biofilm is treated with Cr (VI), leading to biofilm dispersion. Significant changes in water clusters and quorum sensing signals indicative of intercellular communication in the aqueous environ-ment are observed, suggesting that they might result in fatty acid synthesis and inhibit riboflavin production. The Cr (VI) reduction seems to follow the Mtr pathway leading to Cr (III) formation. Our approach potentially opens a new avenue for mechanistic insight of microbial community processes and communications using in situ imaging mass spectrometry and superresolution optical micros-copy.

Environmental Molecular Sciences Laboratory↗

A Compact, Solid-State UV (266 nm) Laser System Capable of Burst-Mode Operation for Laser Ablation Desorption Processing

Compared to wet chemistry and pyrolysis techniques, in situ laser-based methods of chemical analysis provide an ideal way to characterize precious planetary materials without requiring extensive sample processing. In particular, laser desorption and ablation techniques allow for rapid, reproducible and robust data acquisition over a wide mass range, plus: Quantitative, spatially-resolved measurements of elemental and molecular (organic and inorganic) abundances; Low analytical blanks and limits-of-detection ( ng g-1); and, the destruction of minimal quantities of sample ( g) compared to traditional solution and/or pyrolysis analyses (mg).

Laser↗

Effects of quartz particle size and water-to-solid ratio on hydrothermal synthesis of tobermorite studied by in-situ time-resolved X-ray diffraction

Hydrothermal synthesis process of tobermorite (5CaO.6SiO{sub 2}.5H{sub 2}O) has been investigated by in-situ X-ray diffraction using high-energy X-rays from a synchrotron radiation source in combination with a purpose-build autoclave cell. Dissolution rates of quartz were largely affected by its particle size distribution in the starting mixtures. However, the composition (Ca/Si) of non-crystalline C-S-H at the start of tobermorite formation was identical regardless of the quartz dissolution rate. An effect of water-to-solid ratio (w/s) was investigated for samples using fine particle quartz. Tobermorite did not occur with w/s of 1.7 but occurred with w/s higher than 3.0. Surprisingly, however, the dissolution curves of quartz were nearly identical for all samples with w/s from 1.7 to 9, indicating that the dissolution rate is predominated by surface area. Possible reaction mechanism for tobermorite formation will be discussed in terms of Ca and/or silicate ion concentration in the liquid phase and distribution of Ca/Si in non-crystalline C-S-H. - Graphical abstract: Time-resolved XRD data set was obtained at up to 190 deg. C under a saturated steam pressure. Tobermorite (5CaO.6SiO{sub 2}.5H{sub 2}O) formation reaction was investigated in detail for several different starting materials. Highlights: > Hydrothermal formation of tobermorite was monitored by in-situ XRD. > Ca/Si of C-S-H at the start time of tobermorite formation was determined. > The Ca/Si value was identical regardless of the quartz particle size in the starting mixture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Accelerated and heterogeneous corrosion of Cr-doped uranium nitride fuel pellets

The steam oxidation of Cr-doped UN fuel pellets is analyzed during sequential isothermal holds up to 720 °C. In situ neutron diffraction results show how Cr is accommodated in a secondary U 2 CrN 3 phase, leading to the formation of a duplex UN/U 2 CrN 3 microstructure. Under corrosion, the oxidation of the two phases begins at 400 °C for UN and 430 °C for U 2 CrN 3 , respectively. Because the UN phase is preferentially oxidized in the presence of U 2 CrN 3 , addition of Cr in UN based nuclear fuel is found to accelerate the corrosion rate. At 430 °C the oxidation of UN in the UN/U 2 CrN 3 microstructure is ~ 5 times faster than pure UN, increasing to ~19 times faster at 460 °C. The oxidation of U 2 CrN 3 produces UO 2 via the formation of two transient intermediate phases. In situ neutron diffraction enables oxidation processes of UN and U 2 CrN 3 components to be followed separately within the two-phase system.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

In situ liquid cell TEM reveals bridge-induced contact and fusion of Au nanocrystals in aqueous solution

During nanoparticle coalescence in aqueous solution, dehydration and initial contact of particles are critically important but poorly understood processes. In this work, we used in situ liquid-cell transmission electron microscopy to directly visualize the coalescence process of Au nanocrystals. It was found that the Au atomic nanobridge forms between adjacent nanocrystals that are separated by a ~0.5 nm hydration layer. The nanobridge structure first induces initial contact of Au nanocrystals over their hydration layers and then surface diffusion and grain boundary migration to rearrange into a single nanocrystal. Classical density functional theory calculations and ab initio molecular dynamics simulations suggest that the formation of the nanobridge can be attributed to the accumulation of auric ions and a higher local supersaturation in the gap, which can promote dehydration, contact, and fusion of Au nanocrystals. The discovery of this multistep process advances our understanding of the nanoparticle coalescence mechanism in aqueous solutions.

Jin, Biao↗