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At least 721 records · Page 40

Understanding the nanoscale redox-behavior of iron-anodes for rechargeable iron-air batteries

Iron-air cells provide a promising and resource-efficient alternative battery concept with superior area specific power density characteristics compared to state-of-the-art Li-air batteries and potentially superior energy density characteristics compared to present Li-ion batteries. Understanding charge-transfer reactions at the anode-electrolyte interface is the key to develop high-performance cells. By employing in-situ electrochemical atomic force microscopy (in-situ EC-AFM), in-depth insight into the electrochemically induced surface reaction processes on iron in concentrated alkaline electrolyte is obtained. The results highlight the formation and growth of the redox-layer on iron over the course of several oxidation/reduction cycles. By this means, a direct correlation between topography changes and the corresponding electrochemical reactions at the nanoscale could unambiguously be established. Here in this paper, the twofold character of the nanoparticulate redox-layer in terms of its passivating character and its contribution to the electrochemical reactions is elucidated. Furthermore, the evolution of single nanoparticles on the iron electrode surface is evaluated in unprecedented and artifact-free detail. Based on the dedicated topography analysis, a detailed structural model for the evolution of the redox-layer which is likewise elementary for corrosion science and battery research is derived.

25 ENERGY STORAGE↗

In-situ hydrogen microstructural characterization of Si heterojunction passivation: Addressing V OC degradation and mitigation pathways

Si heterojunction (SHJ) solar cells have demonstrated record efficiency >27%, approaching the theoretical limit of ≈ 29%, primarily due to best surface/interface defect passivation provided by deposited thin layers of hydrogenated amorphous silicon (a-Si:H). Such excellent surface/interface passivation reduces recombination loss and result in >100 mV improvement of cell open circuit voltage (V OC ) to ≈ 750 mV, thus the cell efficiency. However, fielded SHJ modules exhibit loss of V OC and hence efficiency over time in years, presumably due to degradation related to a-Si:H layers. This adversely affects the technology’s market acceptance, and levelized cost of energy (LCOE). It is hypothesized that the origin of a-Si:H degradation is somehow related to the presence of weak Si–Si bonds and hydrogen in a-Si:H films. The objective of this project is to test this hypothesis by directly measuring chemical and structural changes occurring within SHJ component layers and solar cells. This is achieved by developing an innovative in-situ Fourier transform infrared (FTIR) spectrometry apparatus to monitor hydrogen microstructural changes occurring within amorphous silicon and decipher hydrogen evolution kinetics over time when samples are exposed to heat and/or light stress. These in-situ measured hydrogen microstructural changes are correlated to the changes in effective minority carrier lifetime (τ eff ), implied V OC (iV OC ), surface recombination velocity (S), and cell V OC . These mechanistic understandings will provide critical guidance to mitigate the V OC -driven degradation of SHJ solar cell performance. Passivation optimization and degradation analysis of individual SHJ component structures were achieved through systematic deposition of three symmetric structures and the completed SHJ solar cell structure. The three symmetric structures used were intrinsic a-Si:H [(i)a-Si:H] layers in a bilayer structure, intrinsic and p-type doped stacked layers [(i-p)a-Si:H] representing the front heterojunction in the SHJ cell, and intrinsic and n-typed doped stacked layers [(i-n)a-Si:H] representing the back-side back surface field (BSF) in the SHJ cell. State-of-the-art passivation qualities are demonstrated by a champion iV OC of 740 mV for the (i)a-Si:H layers, and the (i-n)a-Si:H symmetric structure. A 725 mV iV OC is observed for the (i-p)a-Si:H symmetric structure. These symmetric passivated SHJ component structures were subsequently subjected to different accelerated lifetime (ALT) stressors to identify which conditions contribute the most to iV OC degradation. Degradation of the thin (10 nm) (i)a-Si:H passivation layers without any additional overlying layers is minimal; complexity of this study arises due to unavoidable surface oxidation of (i)a-Si:H layer during most of the stress application, which is likely irrelevant for a full SHJ cell configuration with overlying protective layers. The iV OC degradation of symmetric structures is found to occur primarily at the (i-p)a-Si:H passivation stack under dark heat stress with associated hydrogen loss from the (p)a-Si:H layer. An activation energy for increase in S (defect creation) of 0.65 eV can be correlated to the activation energy of ≈ 0.4 eV for hydrogen loss from the (i-p)a-Si:H stack. This also suggests the presence of weakly bonded hydrogen in the (p)a-Si:H films, which effuses out of the film stack at such low activation energy. When light and heat stress are applied together, similar hydrogen loss from (i-p)a-Si:H stack is observed, however, does not appreciably degrade iV OC or increase S. This is an important result and departure from direct correlation between hydrogen loss and defect creation. This perhaps indicates additional defect chemistries or annealing that might be occurring in the presence of light requiring further detailed defect measurements. The full SHJ cell structure used for this project is depicted in Fig.1(d). SHJ cells with an initial V OC ≈ 700 mV were fabricated and subjected to similar ALT stress conditions. Cell V OC is found to degrade the most under dark heat stress and is confirmed by observed hydrogen migration out of the (i-p)a-Si:H stack. However, hydrogen cannot escape from the cell stack, it accumulates near the (p)a-Si:H/ITO contact interface, where ITO acts as a barrier preventing hydrogen loss. Furthermore, light-heat combined stress does not degrade V OC appreciably, confirming the occurrence of a defect annealing process.

14 SOLAR ENERGY↗

On-matrix Derivatization for Dynamic Headspace Sampling of Nonvolatile Surface Residues

The goal of this study is to extend sampling by the field and laboratory emission cell (FLEC) purge-and-trap technique to applications that target nonvolatile residues. On-matrix derivatization of residues to render analytes stable and more volatile is explored to achieve this goal. Results show that on-matrix derivatizations of nerve agent hydrolysis products (monoalkyl methylphosphonic acids and methylphosphonic acid [MPA]) with diazomethane were successful on glass and painted wallboard (at the 10-µg level). It also was successful on the more difficult concrete (at the 500-µg level) and carpet (at the 20-µg level) substrates that cannot be successfully sampled using swipe techniques. Analysis of additional chemical warfare (CW)-associated residues can be approached by on-matrix derivatization with trifluoroacetic anhydride (TFAA). For example, amines (used as stabilizers or present as decomposition products of the nerve agent VX) or thiodiglycol (hydrolysis product of sulfur mustard) could be sampled as their TFAA derivatives from glass, painted wallboard, and concrete (at the 40-µg level), as well as carpet (at the 80-µg level) surfaces. Although the amine and thiodiglycol are semi-volatile and could be sampled directly, derivatization improves the recovery and chromatographic behavior of these analytes.

On-matrix derivatization, in-situ derivatization, ↗

In Situ Observation of the Precipitation, Aggregation, and Dissolution Behaviors of TiN Inclusion on the Surface of Liquid GCr15 Bearing Steel

In this study, the precipitation, aggregation, and dissolution behaviors of TiN inclusions on the surface of liquid GCr15 bearing steel have been investigated by combining the observations of confocal laser scanning microscope (CLSM) and field emission scanning electron microscope (FE-SEM) with those obtained from energy dispersive spectrometer (EDS) and theoretical analysis. The kinetic results show that the initial concentration of Ti and N are 0.0078 and 0.0049, respectively, the precipitation temperature is between 1640 K and 1680 K (1367 °C and 1407 °C), and the local cooling rate is between 0.5 and 10 K/s; TiN inclusion can precipitate only when the solid fraction is higher than 0.847 and its precipitation radius is between 1 and 6 μm. The precipitation radius of a TiN inclusion in the GCr15 bearing steel sheet can be reduced by decreasing the N content and increasing the cooling strength. The aggregation and densification of multi-particle aggregated TiN inclusions are verified by CLSM observation and theoretical analysis. The inclusions are aggregated by the cavity bridge force (CBF), and the aggregated TiN is formed by solid-phase sintering. The results of force analysis show that CBF plays a dominant role in the aggregation process of the inclusions. The atomic ratio of Ti and V obtained by EDS is 18:1, which may melt TiN and form the liquid inclusion at 1688 K (1415 °C) observed by CLSM. The theoretical analysis is conducted for the dissolution of the TiN inclusions observed by CLSM, which shows that the dissolution of the TiN inclusions is related to the size of the inclusions; the larger the size, the greater the dissolution rate. The long-strip TiN inclusion may be formed by the Ostwald ripening of two TiN inclusions. The TiN inclusions smaller than 3 μm in the GCr15 bearing steel may be formed by the dissolved Ti and N generated by the dissolution of TiN.

36 MATERIALS SCIENCE↗

Satellite Analyses of Cirrus Cloud Properties During the FIRE Phase 2 Cirrus Intensive Field Observations over Kansas

The First ISCCP (International Satellite Cloud Climatology Project) Regional Experiment (FIRE) Phase II Intensive Field Observations (IFO) were taken over southeastern Kansas between November 13 and December 7,1991, to determine cirrus cloud properties. The observations include in situ microphysical data; surface, aircraft, and satellite remote sensing; and measurements of divergence over meso- and smaller-scale areas using wind profilers. Satellite remote sensing of cloud characteristics is an essential aspect for understanding and predicting the role of clouds in climate variations. The objectives of the satellite cloud analysis during FIRE are to validate cloud property retrievals, develop advanced methods for extracting cloud information from satellite-measured radiances, and provide multiscale cloud data for cloud process studies and for verification of cloud generation models. This paper presents the initial results of cloud property analyses during FIRE-II using Geostationary Operational Environmental Satellite (GOES) data and NOAA Advanced Very High Resolution Radiometer (AVHRR) radiances.

Minnis, Patrick↗

Surface Emissivity Effects on Thermodynamic Retrieval of IR Spectral Radiance

The surface emissivity effect on the thermodynamic parameters (e.g., the surface skin temperature, atmospheric temperature, and moisture) retrieved from satellite infrared (IR) spectral radiance is studied. Simulation analysis demonstrates that surface emissivity plays an important role in retrieval of surface skin temperature and terrestrial boundary layer (TBL) moisture. NAST-I ultraspectral data collected during the CLAMS field campaign are used to retrieve thermodynamic properties of the atmosphere and surface. The retrievals are then validated by coincident in-situ measurements, such as sea surface temperature, radiosonde temperature and moisture profiles. Retrieved surface emissivity is also validated by that computed from the observed radiance and calculated emissions based on the retrievals of surface temperature and atmospheric profiles. In addition, retrieved surface skin temperature and emissivity are validated together by radiance comparison between the observation and retrieval-based calculation in the window region where atmospheric contribution is minimized. Both simulation and validation results have lead to the conclusion that variable surface emissivity in the inversion process is needed to obtain accurate retrievals from satellite IR spectral radiance measurements. Retrieval examples are presented to reveal that surface emissivity plays a significant role in retrieving accurate surface skin temperature and TBL thermodynamic parameters.

Zhou, Daniel K.↗

X-Ray-induced Deuterium Enrichment of N-rich Organics in Protoplanetary Disks: An Experimental Investigation Using Synchrotron Light

The deuterium enrichment of organics in the interstellar medium, protoplanetary disks, and meteorites has been proposed to be the result of ionizing radiation. The goal of this study is to simulate and quantify the effects of soft X-rays (0.1–2 keV), an important component of stellar radiation fields illuminating protoplanetary disks, on the refractory organics present in the disks. We prepared tholins, nitrogen-rich organic analogs to solids found in several astrophysical environments, e.g., Titan’s atmosphere, cometary surfaces, and protoplanetary disks, via plasma deposition. Controlled irradiation experiments with soft X-rays at 0.5 and 1.3 keV were performed at the SEXTANTS beamline of the SOLEIL synchrotron, and were immediately followed by ex-situ infrared, Raman, and isotopic diagnostics. Infrared spectroscopy revealed the preferential loss of singly bonded groups (N–H, C–H, and R–N≡C) and the formation of sp{sup 3} carbon defects with signatures at ∼1250–1300 cm{sup −1}. Raman analysis revealed that, while the length of polyaromatic units is only slightly modified, the introduction of defects leads to structural amorphization. Finally, tholins were measured via secondary ion mass spectrometry to quantify the D, H, and C elemental abundances in the irradiated versus non-irradiated areas. Isotopic analysis revealed that significant D-enrichment is induced by X-ray irradiation. Our results are compared to previous experimental studies involving the thermal degradation and electron irradiation of organics. The penetration depth of soft X-rays in μ m-sized tholins leads to volume rather than surface modifications: lower-energy X-rays (0.5 keV) induce a larger D-enrichment than 1.3 keV X-rays, reaching a plateau for doses larger than 5 × 10{sup 27} eV cm{sup −3}. Synchrotron fluences fall within the expected soft X-ray fluences in protoplanetary disks, and thus provide evidence of a new non-thermal pathway to deuterium fractionation of organic matter.

79 ASTRONOMY AND ASTROPHYSICS↗

NASA Tech Briefs, January 2013

Topics include: Single-Photon-Sensitive HgCdTe Avalanche Photodiode Detector; Surface-Enhanced Raman Scattering Using Silica Whispering-Gallery Mode Resonators; 3D Hail Size Distribution Interpolation/Extrapolation Algorithm; Color-Changing Sensors for Detecting the Presence of Hypergolic Fuels; Artificial Intelligence Software for Assessing Postural Stability; Transformers: Shape-Changing Space Systems Built with Robotic Textiles; Fibrillar Adhesive for Climbing Robots; Using Pre-Melted Phase Change Material to Keep Payloads in Space Warm for Hours without Power; Development of a Centrifugal Technique for the Microbial Bioburden Analysis of Freon (CFC-11); Microwave Sinterator Freeform Additive Construction System (MS-FACS); DSP/FPGA Design for a High-Speed Programmable S-Band Space Transceiver; On-Chip Power-Combining for High-Power Schottky Diode-Based Frequency Multipliers; FPGA Vision Data Architecture; Memory Circuit Fault Simulator; Ultra-Compact Transputer-Based Controller for High-Level, Multi-Axis Coordination; Regolith Advanced Surface Systems Operations Robot Excavator; Magnetically Actuated Seal; Hybrid Electrostatic/Flextensional Mirror for Lightweight, Large-Aperture, and Cryogenic Space Telescopes; System for Contributing and Discovering Derived Mission and Science Data; Remote Viewer for Maritime Robotics Software; Stackfile Database; Reachability Maps for In Situ Operations; JPL Space Telecommunications Radio System Operating Environment; RFI-SIM: RFI Simulation Package; ION Configuration Editor; Dtest Testing Software; IMPaCT - Integration of Missions, Programs, and Core Technologies; Integrated Systems Health Management (ISHM) Toolkit; Wind-Driven Wireless Networked System of Mobile Sensors for Mars Exploration; In Situ Solid Particle Generator; Analysis of the Effects of Streamwise Lift Distribution on Sonic Boom Signature; Rad-Tolerant, Thermally Stable, High-Speed Fiber-Optic Network for Harsh Environments; Towed Subsurface Optical Communications Buoy; High-Collection-Efficiency Fluorescence Detection Cell; Ultra-Compact, Superconducting Spectrometer-on-a-Chip at Submillimeter Wavelengths; UV Resonant Raman Spectrometer with Multi-Line Laser Excitation; Medicine Delivery Device with Integrated Sterilization and Detection; Ionospheric Simulation System for Satellite Observations and Global Assimilative Model Experiments - ISOGAME; Airborne Tomographic Swath Ice Sounding Processing System; flexplan: Mission Planning System for the Lunar Reconnaissance Orbiter; Estimating Torque Imparted on Spacecraft Using Telemetry; PowderSim: Lagrangian Discrete and Mesh-Free Continuum Simulation Code for Cohesive Soils; Multiple-Frame Detection of Subpixel Targets in Thermal Image Sequences; Metric Learning to Enhance Hyperspectral Image Segmentation; Basic Operational Robotics Instructional System; Sheet Membrane Spacesuit Water Membrane Evaporator; Advanced Materials and Manufacturing for Low-Cost, High-Performance Liquid Rocket Combustion Chambers; Motor Qualification for Long-Duration Mars Missions.

Source record↗

Extended hierarchical solvent perturbations from curved surfaces of mesoporous silica particles in a deep eutectic solvent

Here, many applications of deep eutectic solvents (DES) rely on exploitation of their unique yet complex liquid structures. Due to the ionic nature of the DES components, their diffuse structures are perturbed in the presence of a charged surface. We hypothesize that it is possible to perturb the bulk DES structure far (> 100 nm) from a curved, charged surface with mesoscopic dimensions. We performed in situ, synchrotron-based ultra-small angle X-ray scattering (USAXS) experiments to study the solvent distribution near the surface of charged mesoporous silica particles (MPS) (≈ 0.5 µm in diameter) suspended in both water and a common type of DES (1:2 choline Cl-:ethylene glycol). A careful USAXS analysis reveals that the perturbation of electron density distribution within the DES extends ≈ 1 μm beyond the particle surface, and that this perturbation can be manipulated by the addition of salt ions (AgCl). The concentration of the pore-filling fluid is greatly reduced in the DES. Notably, we extracted the real-space structures of these fluctuations from the USAXS data using a simulated annealing approach that does not require a priori knowledge about the scattering form factor, and can be generalized to a wide range of complex small-angle scattering problems.

36 MATERIALS SCIENCE↗

Organometallic Polymeric Conductors

For aerospace applications, the use of polymers can result in tremendous weight savings over metals. Suitable polymeric materials for some applications like EMI shielding, spacecraft grounding, and charge dissipation must combine high electrical conductivity with long-term environmental stability, good processability, and good mechanical properties. Recently, other investigators have reported hybrid films made from an electrically conductive polymer combined with insulating polymers. In all of these instances, the films were prepared by infiltrating an insulating polymer with a precursor for a conductive polymer (either polypyrrole or polythiophene), and oxidatively polymerizing the precursor in situ. The resulting composite films have good electrical conductivity, while overcoming the brittleness inherent in most conductive polymers. Many aerospace applications require a combination of properties. Thus, hybrid films made from polyimides or other engineering resins are of primary interest, but only if conductivities on the same order as those obtained with a polystyrene base could be obtained. Hence, a series of experiments was performed to optimize the conductivity of polyimide-based composite films. The polyimide base chosen for this study was Kapton. 3-MethylThiophene (3MT) was used for the conductive phase. Three processing variables were identified for producing these composite films, namely time, temperature, and oxidant concentration for the in situ oxidation. Statistically designed experiments were used to examine the effects of these variables and synergistic/interactive effects among variables on the electrical conductivity and mechanical strength of the films. Multiple linear regression analysis of the tensile data revealed that temperature and time have the greatest effect on maximum stress. The response surface of maximum stress vs. temperature and time (for oxidant concentration at 1.2 M) is shown. Conductivity of the composite films was measured for over 150 days in air at ambient temperature. The conductivity of the films dropped only half an order of magnitude in that time. Films aged under vacuum at ambient temperature diminished slightly in conductivity in the first day, but did not change thereafter. An experimental design approach will be applied to maximize the efficiency of the laboratory effort. The material properties (initial and long term) will also be monitored and assessed. The experimental results will add to the existing database for electrically conductive polymer materials. Attachments: 1) Synthesis Crystal Structure, and Polymerization of 1,2:5,6:9,10-Tribenzo-3,7,11,13-tetradehydro(14) annulene. 2) Reinvestigation of the Photocyclization of 1,4-Phenylene Bis(phenylmaleic anhydride): Preparation and Structure of (5)Helicene 5,6:9,10-Dianhydride. 3) Preparation and Structure Charecterization of a Platinum Catecholate Complex Containing Two 3-Ethynyltheophone Groups. and 4) Rigid-Rod Polymers Based on Noncoplanar 4,4'-Biphenyldiamines: A Review of Polymer Properties vs Configuration of Diamines.

Youngs, Wiley J.↗

Verification of the SMAP Level-4 Soil Moisture Analysis Using Rainfall Observations in Australia

Global, 3-hourly, 9-km resolution soil moisture estimates are available with a mean latency of ~2.5 days from the NASA Soil Moisture Active Passive (SMAP) mission Level-4 Soil Moisture (L4_SM) product. These estimates are based on the assimilation of SMAP radiometer brightness temperature (Tb) observations into the NASA Catchment land surface model using a spatially distributed ensemble Kalman filter. Routine monitoring of the L4_SM system's assimilation diagnostics revealed occasionally large observation-minus-forecast Tb differences across eastern central Australia that resulted in large analysis increments (or adjustments) of the model forecast soil moisture. Because this region lacks in situ soil moisture measurements, we developed an alternative approach to assess the veracity of the soil moisture analysis increments in the L4_SM system. Using regional gauge-based precipitation data, we demonstrate that the L4_SM soil moisture increments are correlated with errors in the L4_SM precipitation forcing, suggesting that the SMAP Tb observations contribute valuable information to the L4_SM soil moisture estimates.

Reichle, R.↗

Comprehensive study of carbon dioxide adsorption in the metal–organic frameworks M 2 (dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn)

Analysis of the CO 2 adsorption properties of a well-known series of metal–organic frameworks M 2 (dobdc) (dobdc 4– = 2,5-dioxido-1,4-benzenedicarboxylate; M = Mg, Mn, Fe, Co, Ni, Cu, and Zn) is carried out in tandem with in situ structural studies to identify the host–guest interactions that lead to significant differences in isosteric heats of CO 2 adsorption. Neutron and X-ray powder diffraction and single crystal X-ray diffraction experiments are used to unveil the site-specific binding properties of CO 2 within many of these materials while systematically varying both the amount of CO 2 and the temperature. Unlike previous studies, we show that CO 2 adsorbed at the metal cations exhibits intramolecular angles with minimal deviations from 180°, a finding that indicates a strongly electrostatic and physisorptive interaction with the framework surface and sheds more light on the ongoing discussion regarding whether CO 2 adsorbs in a linear or nonlinear geometry. This has important implications for proposals that have been made to utilize these materials for the activation and chemical conversion of CO 2 . For the weaker CO 2 adsorbents, significant elongation of the metal–O(CO 2 ) distances are observed and diffraction experiments additionally reveal that secondary CO 2 adsorption sites, while likely stabilized by the population of the primary adsorption sites, significantly contribute to adsorption behavior at ambient temperature. In conclusion, density functional theory calculations including van der Waals dispersion quantitatively corroborate and rationalize observations regarding intramolecular CO 2 angles and trends in relative geometric properties and heats of adsorption in the M 2 (dobdc)–CO 2 adducts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

From thermal catalysis to plasma catalysis: a review of surface processes and their characterizations

The use of atmospheric pressure plasma to enhance catalytic chemical reactions involves complex surface processes induced by the interactions of plasma-generated fluxes with catalyst surfaces. Industrial implementation of plasma catalysis necessitates optimizing the design and realization of plasma catalytic reactors that enable chemical reactions that are superior to conventional thermal catalysis approaches. This requires the fundamental understanding of essential plasma-surface interaction mechanisms of plasma catalysis from the aspect of experimental investigation and theoretical analysis or computational modeling. In addition, experimental results are essential to validate the relative theoretical models and hypotheses of plasma catalysis that was rarely understood so far, compared to conventional thermal catalysis. This overview focuses on two important application areas, nitrogen fixation and methane reforming, and presents a comparison of important aspects of the state of knowledge of these applications when performed using either plasma-catalysis or conventional thermal catalysis. We discuss the potential advantage of plasma catalysis over thermal catalysis from the aspects of plasma induced synergistic effect and in situ catalyst regeneration. In-situ/operando surface characterization of catalysts in plasma catalytic reactors is a significant challenge since the high pressure of realistic plasma catalysis systems preclude the application of many standard surface characterization techniques that operate in a low-pressure environment. Here, we present a review of the status of experimental approaches to probe gas-surface interaction mechanisms of plasma catalysis, including an appraisal of demonstrated approaches for integrating surface diagnostic tools into plasma catalytic reactors.

54 ENVIRONMENTAL SCIENCES↗

Epitaxial strontium titanate films grown by atomic layer deposition on SrTiO{sub 3}-buffered Si(001) substrates

Epitaxial strontium titanate (STO) films have been grown by atomic layer deposition (ALD) on Si(001) substrates with a thin STO buffer layer grown by molecular beam epitaxy (MBE). Four unit cells of STO grown by MBE serve as the surface template for ALD growth. The STO films grown by ALD are crystalline as-deposited with minimal, if any, amorphous SiO{sub x} layer at the STO-Si interface. The growth of STO was achieved using bis(triisopropylcyclopentadienyl)-strontium, titanium tetraisopropoxide, and water as the coreactants at a substrate temperature of 250 Degree-Sign C. In situ x-ray photoelectron spectroscopy (XPS) analysis revealed that the ALD process did not induce additional Si-O bonding at the STO-Si interface. Postdeposition XPS analysis also revealed sporadic carbon incorporation in the as-deposited films. However, annealing at a temperature of 250 Degree-Sign C for 30 min in moderate to high vacuum (10{sup -6}-10{sup -9} Torr) removed the carbon species. Higher annealing temperatures (>275 Degree-Sign C) gave rise to a small increase in Si-O bonding, as indicated by XPS, but no reduced Ti species were observed. X-ray diffraction revealed that the as-deposited STO films were c-axis oriented and fully crystalline. A rocking curve around the STO(002) reflection gave a full width at half maximum of 0.30 Degree-Sign {+-} 0.06 Degree-Sign for film thicknesses ranging from 5 to 25 nm. Cross-sectional transmission electron microscopy revealed that the STO films were continuous with conformal growth to the substrate and smooth interfaces between the ALD- and MBE-grown STO. Overall, the results indicate that thick, crystalline STO can be grown on Si(001) substrates by ALD with minimal formation of an amorphous SiO{sub x} layer using a four-unit-cell STO buffer layer grown by MBE to serve as the surface template.

36 MATERIALS SCIENCE↗

Quasi in-situ analysis of geometrically necessary dislocation density in α-fibre and γ-fibre during static recrystallization in cold-rolled low-carbon Ti-V bearing microalloyed steel

Highlights: • Average GND density is higher in gamma fibre than alpha fibre. • Higher drop in average GND density in un-recrystallized portion of gamma fibre • Fine precipitates pin the grain boundary at 700 °C 0 s. • Precipitates are coarse at 800 °C and present inside strain-free grains. - Abstract: In the present study, cold-rolled low-carbon steel is annealed at three different conditions: 700 °C for 0 s, 800 °C for 0 s and 800 °C for 2 min at the heating rate of ~10 °C/s. Recrystallization behaviour on sample surface is studied using a heated stage Scanning Electron Microscopy and Electron Backscattered Diffraction. For the lower annealing temperature of 700 °C with no dwell, almost no recrystallization is observed and microstructure resembles the as-received deformed material with the exception of occasional sub-micron sized nuclei. For the annealing conditions of 800 °C 0 s and 800 °C 2 min, onset and evolution of recrystallization is observed in-situ as a function of the initial as-cold rolled texture. Slower recovery rate of alpha fibre than gamma fibre is observed and confirmed by lower drop in average geometrically necessary dislocation (GND) density for un-recrystallized alpha fibres (1.1E+14 m{sup −2} for 700 °C 0 s, 1.4E+14 m{sup −2} for 800 °C 0 s and 4.5E+14 m{sup −2} for 800 °C 2 min) than for un-recrystallized gamma fibre grains (3.0E+14 m{sup −2} for 700 °C 0 s, 6.2E+14 m{sup −2} for 800 °C 0 s and 9.8E+14 m{sup −2} for 800 °C 2 min) during annealing. Strong gamma texture in recrystallized matrix is found for annealing conditions of 800 °C 0 s and 800 °C 2 min. From TEM characterisation it was shown that sub-grain boundaries are decorated with fine precipitates (diameter d < 15 nm) of titanium‑vanadium carbides (Ti,V)C for the annealing condition of 700 °C 0 s, which suggests that these precipitates play a major overall role in retardation of the recrystallization kinetics.

36 MATERIALS SCIENCE↗

Analysis of Cryogenic Propellant Liquefaction Rates in Cooled Constant-Wall-Temperature Tanks

NASA has been focused on developing technology that would allow the production of cryogenic propellants on the Lunar and Martian surfaces. Utilizing Lunar/Martian resources, the produced gaseous propellants must first be liquefied and stored prior to use on the Moon or Mars ascent vehicle. Liquefaction of cryogenic propellants is a necessary technical development to enable NASA’s future spaceflight goals. This paper presents an overview of a proposed model for a propellant liquefaction system, and the effect of tank wall temperatures on cryogenic propellant liquefaction rates. The propellant system was assumed to be a receiver of a gas from an In-Situ Resource Utilization (ISRU) harvester and condensed the gas by cooling the tank walls. First, the heat transfer principles pertinent to condensation are summarized, followed by an overview of the model which performed the analysis, including a summary of the Fortran algorithm implementation. The sensitivity of the condensation rate relative to varying tank wall temperatures is also discussed.

Anson Koch↗

Machine Learning Downscaling of SoilMERGE in the United States Southern Great Plains

SoilMERGE (SMERGE) is a root-zone soil moisture (RZSM) product that covers the entire continental United States and spans 1978 to 2019. Machine learning techniques, Random Forest (RF), eXtreme Gradient Boosting (XGBoost), and Gradient Boost (GBoost) downscaled SMERGE to spatial resolutions straddling the field scale domain (100 to 3000 m). Study area was northern Oklahoma and southern Kansas. The coarse resolution of SMERGE (0.125 degree) limits this product’s utility. To validate downscaled results in situ data from four sources were used that included: United States Department of Energy Atmospheric Radiation Measurement (ARM) observatory, United States Climate Reference Network (USCRN), Soil Climate Analysis Network (SCAN), and Soil moisture Sensing Controller and oPtimal Estimator (SoilSCAPE). In addition, RZSM retrievals from NASA’s Airborne Microwave Observatory of Subcanopy and Surface (AirMOSS) campaign provided a nearly spatially continuous comparison. Three periods were examined: era 1 (2016 to 2019), era 2 (2012 to 2015), and era 3 (2003 to 2007). During eras 1 and 2, RF outperformed XGBoost and GBoost, whereas during era 3 no model dominated. Performance was better during eras 1 and 2 as opposed to the pre-L band era 3. Improvements across all eras, regions, and models realized from downscaling included an increase in correlation from 0.03 to 0.42 and a decrease in ub RMSE from -0.0005 to -0.0118 m 3 /m 3 . This study demonstrates the feasibility of SMERGE downscaling opening the prospect for the development of a long-term RZSM dataset at a more desirable field-scale resolution with the potential to support diverse hydrometeorological and agricultural applications.

54 ENVIRONMENTAL SCIENCES↗

The characterization of an air pollution episode using satellite total ozone measurements

A case study is presented which demonstrates that measurements of total ozone from a space-based platform can be used to study a widespread air pollution episode over the southeastern U.S. In particular, the synoptic-scale distribution of surface-level ozone obtained from an independent analysis of ground-based monitoring stations appears to be captured by the synoptic-scale distribution of total ozone, even though about 90 percent of the total ozone is in the stratosphere. Additional analyses of upper air meteorological data, other satellite imagery, and in situ aircraft measurements of ozone likewise support the fact that synoptic-scale variability of tropospheric ozone is primarily responsible for the observed variability in total ozone under certain conditions. The use of the type of analysis discussed in this study may provide an important technique for understanding the global budget of tropospheric ozone.

Fishman, Jack↗