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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 811 records · Page 45
All sourcesNASA NTRSDOE OSTI
NASA NTRS1992

Numerical simulation of shock-induced combustion/detonation

A numerical study is conducted to simulate the shock-induced combustion in premixed H2-air mixtures. Two types of bodies, blunt (spherical projectile) and sharp (wedge), are considered in the study. A nine-species, 18-step finite-rate H2-air chemical reaction mechanism coupled with the Navier-Stokes equations is solved. The flow field over the blunt body is found to be unsteady, when the projectile velocity is same as the Chapman-Jouget velocity of the mixture. The unsteadiness is caused by the periodic instabilities originating in the stagnation zone. Numerical results show good qualitative agreement with the ballistic range shadowgraph. In addition, the frequency of oscillations, determined by using the Fourier power spectrum, is found to be in good agreement with the experiment. The flow field over the wedge is found to be stable for the conditions considered in this study. The oblique detonation wave structure is investigated and the important flow features are discussed.

Singh, D. J.↗
DOE OSTI2025

Reliable and Efficient Machine Learning (Final Technical Report)

Modern scientific experiments generate massive amounts of data at a pace much faster than humans can manually analyze. While machine learning has revolutionized commercial data analysis (such as recommending movies or recognizing faces), applying these tools to complex scientific discovery is challenging because scientific answers must be precise, interpretable, and adhere to physical laws. The research under this project aims to develop new mathematical tools and computer algorithms specifically designed for scientific applications. Major progress has been made in automatically cleaning and deconstructing messy experimental data, analyzing the visual information of physical phenomena, determining the underlying physical variables, and providing rig orous mathematical analysis of interesting algorithms and concepts widely used in machine learning. This project addressed the critical gap between our ability to generate massive scientific data and our ability to extract interpretable information from it. We established mathematical foundations for Scientific Machine Learning (SciML) aimed at effective data analytics and automated discovery. Our work focused on three core objectives: (1) developing reliable feature extraction methods for dynamic high-dimensional data, (2) establishing mathematical foundations for discovering dynamics via neural networks, and (3) creating rigorous optimization techniques for these models. Key outcomes come from two fronts. On the practical side, they include the development of algorithms that significantly enhance the extraction of signals from field data, as well as the capability to handle situations that exhibit smooth variations or physical stretching due to temperature changes. They also include the creation of an automated framework for discovering fundamental state variables from raw experimental data, demonstrating the ability to identify intrinsic physical dimensions without prior knowledge of the governing laws. On the theoretical front, the research results in theoretical advances in Optimal Transport, a widely used notion in SciML, specifically regarding functions with fixed-size nodal sets, provide sharp bounds relevant to uncertainty quantification. Meanwhile, the outcomes also include the establishment of convergence theories for nonlocal gradient descent methods, enabling robust optimization with noisy data in high-dimensional settings commonly encountered in scientific modeling. The project also helps creating opportunities to train the next generation of researchers, equipping them with the necessary technical skills for today’s workplace and preparing them for future advances.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2013

He I D3 OBSERVATIONS OF THE 1984 MAY 22 M6.3 SOLAR FLARE

The He I D3 line has a unique response to a flare impact on the low solar atmosphere and can be a powerful diagnostic tool for energy transport processes. Using images obtained from the recently digitized films of the Big Bear Solar Observatory, we report D3 observations of the M6.3 flare on 1984 May 22, which occurred in an active region with a circular magnetic polarity inversion line (PIL). The impulsive phase of the flare starts with a main elongated source that darkens in D3, inside of which bright emission kernels appear at the time of the initial small peak in hard X-rays (HXRs). These flare cores subsequently evolve into a sharp emission strand lying within the dark halo; this evolution occurs at the same time as the main peak in HXRs, reversing the overall source contrast from -5% to 5%. The radiated energy in D3 during the main peak is estimated to be about 10{sup 30} erg, which is comparable to that carried by nonthermal electrons above 20 keV. Afterward, the flare proceeds along the circular PIL in the counterclockwise direction to form a dark circular ribbon in D3, which apparently mirrors the bright ribbons in H{alpha} and He I 10830 A. All of these ribbons last for over one hour in the late gradual phase. We suggest that the present event resembles the so-called black-light flare that was proposed based on continuum images, and that D3 darkening and brightening features herein may be due to thermal conduction heating and the direct precipitation of high-energy electrons, respectively.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2019

ProbabilisticRecalibration of Forecasts

In this work, we present a scheme by which a probabilistic forecasting system whose predictions have a poor probabilistic calibration may be recalibrated through the incorporation of past performance information in order to produce a new forecasting system that is demonstrably superior to the original, inasmuch as one may use it to win wagers consistently against someone who is using the original system. The scheme utilizes Gaussian process (GP) modeling to estimate a probability distribution over the probability integral transform (PIT) of a scalar predictand. The GP density estimate gives closed-form access to information entropy measures that are associated with the estimated distribution, which allows the prediction of winnings in wagers against the base forecasting system. A separate consequence of the procedure is that the recalibrated forecast has a uniform expected PIT distribution. One distinguishing feature of the procedure is that it is appropriate even if the PIT values are not i.i.d. The recalibration scheme is formulated in a framework that exploits the deep connections among information theory, forecasting, and betting. We demonstrate the effectiveness of the scheme in two case studies: a laboratory experiment with a nonlinear circuit and seasonal forecasts of the intensity of the El Nino-Southern Oscillation phenomenon.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Adsorption and reaction of methanol on Fe 3 O 4 (001)

The interaction of methanol with iron oxide surfaces is of interest due to its potential in hydrogen storage, and from a fundamental perspective as a chemical probe of the reactivity. We present here a study examining the adsorption and reaction of methanol on magnetite Fe 3 O 4 (001) at cryogenic temperatures using a combination of temperature programmed desorption, x-ray photoelectron spectroscopy, and scanning tunneling microscopy. We report the methanol desorption profile from Fe 3 O 4 (001) is complex, exhibiting peaks at 145, 175, 238, and 273 K, corresponding to the desorption of intact methanol, as well as peaks at 350 and 500 K due to the reaction of methoxy intermediates. The saturation of a monolayer of methanol corresponds to ~5 molecules/unit cell (u.c.), which is slightly higher than the number of surface octahedral iron atoms of 4/u.c. We probe the kinetics and thermodynamics of the desorption of molecular methanol using inversion analysis. The deconvolution of the complex desorption profile into individual peaks allows for calculations of both the desorption energy and the prefactor of each feature. The initial 0.7 methanol/u.c. reacts to form a methoxy and hydroxy intermediates by 180 K, which remains on the surface above room temperature after intact methanol has desorbed. The methoxy species react via one of two channels, a recombination reaction with surface hydroxyls to form additional methanol at ~350 K, and a disproportionation reaction to form methanol and formaldehyde at ~500 K. Only 20% of the methoxy species undergo the disproportionation reaction, with most of them reacting via the 350 K pathway.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1997

Characterizing the Relationships Among Lightning and Storm Parameters: Lightning as a Proxy Variable

We have gained important insights from prior studies that have suggested relationships between lightning and storm growth, decay, convective rain flux, vertical distribution of storm mass and echo volume in the region, and storm energetics. A study was initiated in the Summer of 1996 to determine how total (in-cloud plus ground) lightning observations might provide added knowledge to the forecaster in the determination and identification of severe thunderstorms and weather hazards in real-time. The Melbourne Weather Office was selected as a primary site to conduct this study because Melbourne is the only site in the world with continuous and open access to total lightning (LDAR) data and a Doppler (WSR-88D) radar. A Lightning Imaging Sensor Data Applications Demonstration (LISDAD) system was integrated into the forecaster's workstation during the Summer 1996 to allow the forecaster to interact in real-time with the multi-sensor data being displayed. LISDAD currently ingests LDAR data, the cloud-to-ground National Lightning Detection Network (NLDN) data, and the Melbourne radar data in f real-time. The interactive features provide the duty forecaster the ability to perform quick diagnostics on storm cells of interest. Upon selection of a storm cell, a pop-up box appears displaying the time-history of various storm parameters (e.g., maximum radar reflectivity, height of maximum reflectivity, echo-top height, NLDN and LDAR lightning flash rates, storm-based vertically integrated liquid water content). This product is archived to aid on detailed post-analysis.

Goodman, S. J.↗
DOE OSTI2019

Signatures of low-dimensional magnetism and short-range spin fluctuations in Co-based trirutiles

Features of low dimensional magnetism resulting from a square-net arrangement of Co atoms in trirutile CoTa2O6 is studied in the present work by means of density functional theory and is compared with the experimental results of specific heat and neutron diffraction. The small total energy differences between the ferromagnetic (FM) and antiferromagnetic (AFM) configuration of CoTa2O6 shows that competing magnetic ground states exist, with the possibility of transition from FM to AFM phase at low temperature. Our calculation further suggests the semi-conducting behavior for CoTa2O6 with a band gap of ~0.41 eV. The calculated magnetic anisotropy energy is ~2.5 meV with its easy axis along the [100] (in-plane) direction. Studying the evolution of magnetism in Co1-xMgxTa2O6 (x = 0, 0.1, 0.3, 0.5, 0.7 and 1). it is found that the sharp AFM transition exhibited by CoTa2O6 at TN = 6.2 K in it’s heat capacity vanishes with Mg-dilution, indicating the obvious effect of weakening the superexchange pathways of Co. The current specific heat study reveals the robust nature of TN for CoTa2O6 in applied magnetic fields. Clear indication of short-range magnetism is obtained from the magnetic entropy, however, diffuse components are absent in neutron diffraction data. At TN , CoTa2O6 enters a long-range ordered magnetic state which can be described using a propagation vector, ( 1 1 0). Upon Mg-dilution at x =0.1, the long-range ordered magnetism is destroyed. The present results should motivate an investigation of magnetic excitations in this low-dimensional anisotropic magnet.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2012

THE FERMI BUBBLES: SUPERSONIC ACTIVE GALACTIC NUCLEUS JETS WITH ANISOTROPIC COSMIC-RAY DIFFUSION

The Fermi Gamma-Ray Space Telescope reveals two large bubbles in the Galaxy, which extend nearly symmetrically {approx}50 Degree-Sign above and below the Galactic center. Using three-dimensional (3D) magnetohydrodynamic simulations that self-consistently include the dynamical interaction between cosmic rays (CRs) and thermal gas and anisotropic CR diffusion along the magnetic field lines, we show that the key characteristics of the observed gamma-ray bubbles and the spatially correlated X-ray features in the ROSAT 1.5 keV map can be successfully reproduced by recent jet activity from the central active galactic nucleus. We find that after taking into account the projection of the 3D bubbles onto the sky the physical heights of the bubbles can be much smaller than previously thought, greatly reducing the formation time of the bubbles to about a Myr. This relatively small bubble age is needed to reconcile the simulations with the upper limit of bubble ages estimated from the cooling time of high-energy electrons. No additional physical mechanisms are required to suppress large-scale hydrodynamic instabilities because the evolution time is too short for them to develop. The simulated CR bubbles are edge-brightened, which is consistent with the observed projected flat surface brightness distribution. Furthermore, we demonstrate that the sharp edges of the observed bubbles can be due to anisotropic CR diffusion along magnetic field lines that drape around the bubbles during their supersonic expansion, with suppressed perpendicular diffusion across the bubble surface. Possible causes of the slight bends of the Fermi bubbles to the west are also discussed.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2014

NONUNIFORM EXPANSION OF THE YOUNGEST GALACTIC SUPERNOVA REMNANT G1.9+0.3

We report measurements of the X-ray expansion of the youngest Galactic supernova remnant, G1.9+0.3, using Chandra observations in 2007, 2009, and 2011. The measured rates strongly deviate from uniform expansion, decreasing radially by about 60% along the X-ray bright SE-NW axis from 0.84% ± 0.06% yr{sup –1} to 0.52% ± 0.03% yr{sup –1}. This corresponds to undecelerated ages of 120-190 yr, confirming the young age of G1.9+0.3 and implying a significant deceleration of the blast wave. The synchrotron-dominated X-ray emission brightens at a rate of 1.9% ± 0.4% yr{sup –1}. We identify bright outer and inner rims with the blast wave and reverse shock, respectively. Sharp density gradients in either the ejecta or ambient medium are required to produce the sudden deceleration of the reverse shock or the blast wave implied by the large spread in expansion ages. The blast wave could have been decelerated recently by an encounter with a modest density discontinuity in the ambient medium, such as may be found at a wind termination shock, requiring strong mass loss in the progenitor. Alternatively, the reverse shock might have encountered an order-of-magnitude density discontinuity within the ejecta, such as may be found in pulsating delayed-detonation Type Ia models. We demonstrate that the blast wave is much more decelerated than the reverse shock in these models for remnants at ages similar to G1.9+0.3. Similar effects may also be produced by dense shells possibly associated with high-velocity features in Type Ia spectra. Accounting for the asymmetry of G1.9+0.3 will require more realistic three-dimensional Type Ia models.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

Low-temperature spin dynamics in the TmFeO 3 orthoferrite with a non-Kramers ion

We investigate the magnetic dynamics of the orthorhombic perovskite TmFeO 3 at low temperatures, below the spin reorientation transition at TSR≈80 K, by means of time-of-flight neutron spectroscopy. We find that the magnetic excitation spectrum combines two emergent collective modes associated with different magnetic sublattices. The Fe subsystem orders below TN~632 K into a canted antiferromagnetic structure and exhibits sharp, high-energy magnon excitations. We describe them using linear spin-wave theory, and reveal a pronounced anisotropy between in- and out-of-plane exchange interactions, which was mainly neglected in previous reports on the spin dynamics in orthoferrites. At lower energies, we find two crystalline electrical field (CEF) excitations of Tm3+ ions at energies of ~2 and 5 meV. In contrast to the sister compound YbFeO 3 , where the Yb 3+ ions form quasi-one-dimensional chains along the c axis, the Tm excitations show dispersion along both directions in the (0KL) scattering plane. Analysis of the neutron scattering polarization factor reveals a longitudinal polarization of the 2 meV excitation. To evaluate the effect of the CEF on the Tm 3+ ions, we perform point-charge model calculations, and their results quantitatively capture the main features of Tm single-ion physics, such as energies, intensities, and polarization of the CEF transitions, and the type of magnetic anisotropy.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS2000

BUNDLE: A Novel Furnace for Performing Controlled Directional Solidification Experiments in a Microgravity Environment

NASA Marshall Space Flight Center has developed a novel directional solidification furnace prototype for processing metals and alloys experiments in a microgravity environment. The BUNDLE (Bridgman Unidirectional Dendrite in Liquid Experiment) furnace is intended to accommodate the science requirements of Flight Definition Principle Investigators studying cellular/dendritic growth in aluminum and lead alloys at processing temperatures up to 1200 C. The furnace implements a number of innovative features to achieve high thermal gradients and quench rates in a low-power, light-weight design. These include a pyrolytic boron nitride/graphite composite heating element surrounded by layers of self-supporting refractory metal shielding, and a graphite fiber enhanced cold zone allowing high levels of heat extraction from the sample crucible. Novel to the BUNDLE design is an in-situ helium gas quench capability that ensures rapid freezing of the solidifying region (mushy zone) of the metal sample within the furnace without sample disturbance prior to quenching; this is a stringent requirement for subsequent analysis and understanding of microstructural development. The experiment hardware concept features multiple furnaces that may be "bundled" together so many samples, currently up to eight, can be processed at one time. The design of BUNDLE is flexible enough to be implemented on the Shuttle and Space Station in a number of locations (SpaceHab, Express Rack, MPESS, ISPR, etc). BUNDLE prototype furnaces have directionally solidified and quenched 1cm diameter lead - 5.8 weight percent antimony and aluminum - 4 weight percent copper alloys. Quenching of the mushy zone, as recorded by in-situ thermocouples, occurred on the order of 0.5 seconds or less, a rate within the PI's requirements. Subsequent metallographic examination revealed the solidified microstructure to be, as expected, unidirectional. Both the dendrite tips and the eutectic reaction were planar in nature indicating uniform axial heat flow. Delineation between the growing dendrites and eutectic structure with the "quenched-in" liquid was sharp, attesting to the efficacy of the helium quench. BUNDLE's conception, development, capability, and adaptability are presented (in view of Flight PI's needs and science requirements) through viewgraphs depicting actual hardware, generated thermal analysis, and micrographs prepared from BUNDLE processed, flight-like samples.

Carrasquillo, Edgar J.↗
NASA NTRS2001

BUNDLE - A Novel Furnace for Performing Controlled Directional Solidification Experiments in a Microgravity Environment

NASA Marshall Space Flight Center has developed a novel directional solidification furnace prototype for processing metals and alloys experiments in a microgravity environment. The BUNDLE (Bridgman Unidirectional Dendrite in Liquid Experiment) furnace is intended to accommodate the science requirements of Flight Definition Principle Investigators studying cellular/dendritic growth in aluminum and lead alloys at processing temperatures up to 1200 C. The furnace implements a number of innovative features to achieve high thermal gradients and quench rates in a low-power, light-weight design. These include a pyrolytic boron nitride/graphite composite heating element surrounded by layers of self-supporting refractory metal shielding, and a graphite fiber enhanced cold zone allowing high levels of heat extraction from the sample crucible. Novel to the BUNDLE design is an in-situ helium gas quench capability that ensures rapid freezing of the solidifying region (mushy zone) of the metal sample within the furnace without sample disturbance prior to quenching; this is a stringent requirement for subsequent analysis and understanding of microstructural development. The experiment hardware concept features multiple furnaces that may be "bundled" together so many samples, currently up to eight, can be processed at one time. The design of BUNDLE is flexible enough to be implemented on the Shuttle and Space Station in a number of locations (SpaceHab, Express Rack, MPESS, ISPR, etc). BUNDLE prototype furnaces have directionally solidified and quenched 1cm diameter lead - 5.8 weight percent antimony and aluminum - 4 weight percent copper alloys. Quenching of the mushy zone, as recorded by in-situ thermocouples, occurred on the order of 0.5 seconds or less, a rate within the PI's requirements. Subsequent metallographic examination revealed the solidified microstructure to be, as expected, unidirectional. Both the dendrite tips and the eutectic reaction were planar in nature indicating uniform axial heat flow. Delineation between the growing dendrites and eutectic structure with the "quenched-in" liquid was sharp, attesting to the efficacy of the helium quench. BUNDLE's conception, development, capability, and adaptability are presented (in view of Flight PI's needs and science requirements) through viewgraphs depicting actual hardware, generated thermal analysis, and micrographs prepared from BUNDLE processed, flight-like samples.

Carrasquillo, Edgar J.↗
NASA NTRS1991

Chronology of glaciation in the Hellas region of Mars

The Hellas Impact Basin is one of the oldest features on Mars, as indicated by the high density of large impact craters in parts of the basin. The highly degraded condition of Hellas seems consistent with great antiquity. However, many of the most strikingly modified landscapes in the basin, believed to be glaciogenic, also appear to be geologically youthful. Stratigraphic relations suggest two episodes of glaciation. Chronologic constraints are imposed on glaciation based on the impact cratering record, the focus of which is the southwestern portion of Hellas. Major terrain units are mapped. The lineated terrain and ridged plains form the summit and flanks of a large shield volcano, Amphitrites Patera, which was superimposed over the southwestern rim of Hellas toward the end of heavy bombardment. The ridged plains and lineated terrain are crossed by numerous wrinkle ridges. The lineated terrain is distinguished by a pervasive system of deep erosional troughs and sharp ridges thought to have been glacially sculpted by the Hellas Lobe. It is concluded that glaciation in Hellas occurred during the Middle Amazonian, roughly coeval with glaciation in Argyre.

Johnson, N.↗
DOE OSTI2022

Analysis of ionizing radiation induced DNA damage response in human adult stem cells and differentiated neurons

Findings of neurodegenerative features associated with human radiosensitive syndromes such as Ataxia telangiectasia suggest that DNA repair efficiency is crucial for maintaining the functional integrity of central nervous system. To gain a better understanding of ionizing radiation (IR) induced DNA damage response in undifferentiated and differentiated neural cell types and to evaluate the role of ATM in DNA double strand break (DSB) repair, an in vitro human neural cell differentiation model system was utilized in this study. As compared to adult stem cells, differentiated neurons displayed an attenuated DSB repair response (as judged by the persistence of 53BP1 foci) after IR exposure and the attenuation was even more pronounced in stem cells and neurons after suppression of ATM (Ataxia Telangiectasia Mutated) gene product suggesting the importance of ATM for an optimal DSB repair efficiency in human neural cell types. In corroboration with an attenuated DNA damage response, a sharp decline in the expression levels of several DSB repair genes was observed in neurons. Furthermore, our results suggest that cellular differentiation modulates the expression of several genes thereby compromising the DSB repair fidelity in post mitotic neurons. Further studies are required to verify whether or not ATM mediated exacerbation of DNA repair deficiency in differentiated neurons leads to neurodegeneration.

53 binding protein 1↗
DOE OSTI2020

Organismic materials for beyond von Neumann machines

The elementary basis of intelligence in organisms with a central nervous system includes neurons and synapses and their complex interconnections forming neural circuits. In non-neural organisms such as slime mold with gel-like media, viscosity modulation enables adaptation to changing environments. At a larger scale, collective intelligence emerges via social interactions and feedback in animal colonies. Learning and memory are therefore multi-scale features that evolve as a result of constant interactions with the environment. There is growing interest in emulating such features of intelligence in computing machines and autonomous systems. Materials that can respond to their environment in a manner similar to organisms (referred to as "organismic materials") therefore may be of interest as hardware components in artificial intelligence machines. In this brief review, we present a class of semiconductors called correlated oxides as candidates for learning machines. The term "correlated" refers to the fact that electrons in such lattices strongly interact and the ground state is not what is predicted by classical band theory. Such materials can undergo insulator-metal transitions at near ambient conditions under external stimuli such as thermal or electrical fields, strain, and chemical doping. Depending on the mechanism driving the transition, intermediate states can be metastable with different volatilities, and the time scales of phase change can be controlled over many orders of magnitude. The change in electronic properties can be sharp or gradual, leading to digital or analog behavior. These properties enable the realization of artificial neurons and synapses and emulate the associative and non-associative learning characteristics found in various organisms. We examine microscopic properties concerning electronic and structural transitions leading to collective behavior and theoretical treatments of the ground state and dynamical response, showcasing VO 2 as a model system. Next, we briefly review algorithms designed from the plasticity demonstrated by phase changing systems. Finally, we conclude the brief review with suggestions for future research toward realizing non-von Neumann machines.

42 ENGINEERING↗
DOE OSTI2022

B/PS bulges in DESI Legacy edge-on galaxies – I. Sample building

ABSTRACT We present the biggest up-to-date sample of edge-on galaxies with boxy/peanut-shaped (B/PS) bulges and X-structures. The sample was prepared using images from the Dark Energy Spectroscopic Instrument (DESI) Legacy catalogue and contains about 2000 galaxies. To find suitable candidates in catalogue, we made the assumption that the residues (original images minus model) of galaxies with B/PS bulges should exhibit a characteristic X-shape. Galaxies with such features were selected by eye and then used as input data for a neural network training, which was applied to a bigger sample of edge-on galaxies. Using the available data and the photometric models from the literature, we investigated the observational and statistical properties of the sample created. Comparing the B/D ratios for galaxies with and without B/PS bulges, we found that the B/D ratio for galaxies from our sample is statistically higher, with typical values in the range ≈0.2–0.5 depending on the decomposition procedure. We studied how the opening angles φ of the X-structure and the length of its rays are distributed in the formed sample and found them to be consistent with previous measurements and predictions from N-body models, e.g. $\varphi \gtrsim 25{^\circ }$, but measured here for a much larger number of galaxies. We found a sharp increase in the B/PS bulge fraction for stellar masses log M⋆ ≳ 10.4, but for edge-on galaxies, which complements the results of previous works. The sample can be used in future work to test various bar models and their relationship with B/PS bulges, as well as to study their stability and evolution.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2017

Understanding the Oxygen Evolution Reaction Mechanism on CoO x using Operando Ambient-Pressure X-ray Photoelectron Spectroscopy

Photoelectrochemical water splitting is a promising approach for renewable production of hydrogen from solar energy and requires interfacing advanced water-splitting catalysts with semiconductors. Understanding the mechanism of function of such electrocatalysts at the atomic scale and under realistic working conditions is a challenging, yet important, task for advancing efficient and stable function. This is particularly true for the case of oxygen evolution catalysts and, here, we study a highly active Co 3 O 4 /Co(OH) 2 biphasic electrocatalyst on Si by means of operando ambient-pressure X-ray photoelectron spectroscopy performed at the solid/liquid electrified interface. Spectral simulation and multiplet fitting reveal that the catalyst undergoes chemical-structural transformations as a function of the applied anodic potential, with complete conversion of the Co(OH) 2 and partial conversion of the spinel Co 3 O 4 phases to CoO(OH) under precatalytic electrochemical conditions. Furthermore, we observe new spectral features in both Co 2p and O 1s core-level regions to emerge under oxygen evolution reaction conditions on CoO(OH). The operando photoelectron spectra support assignment of these newly observed features to highly active Co 4+ centers under catalytic conditions. Comparison of these results to those from a pure phase spinel Co 3 O 4 catalyst supports this interpretation and reveals that the presence of Co(OH) 2 enhances catalytic activity by promoting transformations to CoO(OH). The direct investigation of electrified interfaces presented in this work can be extended to different materials under realistic catalytic conditions, thereby providing a powerful tool for mechanism discovery and an enabling capability for catalyst design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1983

Airborne dual laser excitation and mapping of phytoplankton photopigments in a Gulf Stream Warm Core Ring

Utilization of a two-color airborne lidar system in the systematic study of a major oceanographic feature is reported here for the first time. An excimer pumped dye laser was optically and electronically integrated into the NASA Airborne Oceanographic Lidar for simultaneous use with a frequency doubled Nd:YAG laser. The output beams exit the laser system along parallel paths after being produced on an alternating pulse basis at a combined rate of 12.5 pps. Results are presented for missions flown over a Gulf Stream Warm Core Ring (WCR) as well as over shelf, slope, Gulf Stream, and Sargasso Sea waters. From the airborne data a high coherence is shown between the two-color chlorophyll a data and between the Nd:YAG chlorophyll a and phycoerythrin responses within each of these water masses. However, distinct differences in the response patterns of these photopigments are shown to exist between the differing water masses. At certain of the boundaries separating the water masses a sharp transition is seen to occur, while at others a wider transition zone was observed in which the correlation between the photopigments appears to degrade.

Hoge, F. E.↗