Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “oxygen evolution”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,009 records · Page 56
All sourcesNASA NTRSDOE OSTI
NASA NTRS2010

High C/O Chemistry and Weak Thermal Inversion in the Extremely Irradiated Atmosphere of Exoplanet WASP-12b

The carbon-to-oxygen ratio (C/O) in a planet provides critical information about its primordial origins and subsequent evolution. A primordial C/O greater than 0.8 causes a carbide-dominated interior as opposed to the silicate-dominated composition as found on Earth; the solar C/O is 0.54. Theory, shows that high C/O leads to a diversity of carbon-rich planets that can have very different interiors and atmospheres from those in the solar system. Here we report the detection of C/O greater than or equal to 1 in a planetary atmosphere. The transiting hot Jupiter WASP-12b has a dayside atmosphere depleted in water vapour and enhanced in methane by over two orders of magnitude compared to a solar-abundance chemical equilibrium model at the expected temperatures. The observed concentrations of the prominent molecules CO, CH4, and H2O are consistent with theoretical expectations for an atmosphere with the observed C/O = 1. The C/O ratios are not known for giant planets in the solar system, although they are expected to equal the solar value. If high C/O ratios are common, then extrasolar planets are likely very different in interior composition, and formed very differently, from expectations based on solar composition, potentially explaining the large diversity in observed radii. We also find that the extremely irradiated atmosphere (greater than 2500 K) of WASP-12b lacks a prominent thermal inversion, or a stratosphere, and has very efficient day-night energy circulation. The absence of a strong thermal inversion is in stark contrast to theoretical predictions for the most highly irradiated hot-Jupiter atmospheres.

Madhusudhan, Nikku↗
NASA NTRS2016

Agricultural Fires in the Southeastern U.S. During SEAC4RS: Emissions of Trace Gases and Particles and Evolution of Ozone, Reactive Nitrogen, and Organic Aerosol

Emissions from 15 agricultural fires in the southeastern U.S. were measured from the NASA DC-8 research aircraft during the summer 2013 Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) campaign. This study reports a detailed set of emission factors (EFs) for 25 trace gases and 6 fine particle species. The chemical evolution of the primary emissions in seven plumes was examined in detail for ~1.2 h. A Lagrangian plume cross-section model was used to simulate the evolution of ozone (O3), reactive nitrogen species, and organic aerosol (OA). Observed EFs are generally consistent with previous measurements of crop residue burning, but the fires studied here emitted high amounts of SO2 and fine particles, especially primary OA and chloride. Filter-based measurements of aerosol light absorption implied that brown carbon (BrC) was ubiquitous in the plumes. In aged plumes, rapid production of O3, peroxyacetyl nitrate (PAN), and nitrate was observed with (Delta)O3/(Delta)CO, (Delta)PAN/(Delta)NOy, and (Delta)nitrate/(Delta)NOy reaching approx. 0.1, approx. 0.3, and approx.0.3. For five selected cases, the model reasonably simulated O3 formation but underestimated PAN formation. No significant evolution of OA mass or BrC absorption was observed. However, a consistent increase in oxygen-to-carbon (O/C) ratios of OA indicated that OA oxidation in the agricultural fire plumes was much faster than in urban and forest fire plumes. Finally, total annual SO2, NOx, and CO emissions from agricultural fires in Arkansas, Louisiana, Mississippi, and Missouri were estimated (within a factor of approx. 2) to be equivalent to approx. 2% SO2 from coal combustion and approx. 1% NOx and approx. 9% CO from mobile sources.

OA mass or BrC absorption↗
NASA NTRS2019

Experimental Insights into the Geochemistry of Mercury

With the recent estimate of Mercury's surface composition from the X-Ray Spectrometer and Gamma-Ray Spectrometer that were onboard NASA's MErcury Surface, Space ENvironment, Geochemistry and Ranging (MESSENGER) spacecraft, we now have our first opportunity to directly investigate the compositions of lavas from the planet Mercury and indirectly investigate the chemical make-up of its interior. Results from MESSENGER showed exotic surface compositions with more than 3 wt% sulfur in some lavas and relatively low amounts of iron (less than 3 wt%) across the surface. These striking features are consistent with magmatism occurring under highly reducing conditions which has an impact on the thermal and chemical evolution of a planetary body. Here we'll explore the geochemical evolution of Mercury through a series of experimental studies and discuss the implications of low oxygen fugacity on elemental behavior and magmatic processes.

Vander Kaaden, Kathleen E.↗
NASA NTRS2020

Structural evolution, electrochemical kinetic properties, and stability of A-site doped perovskite Sr(1-x)Yb(x)CoO(3-δ)

Mixed ionic and electronic conducting (MIEC) perovskite SrCoO(3-δ) is a widely studied (electro)catalyst for the oxygen reduction reaction (ORR) and possesses different crystal structures at different temperatures. These temperature dependent phase transitions significantly impact the ordering of oxygen vacancies and electrochemical kinetic properties as well as the reliability of the related devices. Some of the crystal structures formed, e.g. hexagonal phases, turn out to be almost impermeable to oxygen gas. Therefore, it is important to stabilize the crystal structure of SrCoO(3-δ) that favors the ORR over a wide temperature range. Herein, the partial substitution of the A-site Sr with Yb is systematically studied, including synthesis, characterization and analysis of structural evolution, electrochemical kinetic properties, thermal stability, and stability in a CO2-containing atmosphere. The results indicate that Sr(0.90)Yb(0.10)CoO(3-δ) is able to stabilize the tetragonal crystal structure with less ordered oxygen vacancies, leading to polarization resistances of 0.051, 0.115 and 0.272 U sq.cm at 750, 700 and 650 °C, respectively, on symmetrical cells. Sr(0.90)Yb(0.10)CoO(3-δ) demonstrates a very stable surface oxygen vacancy distribution and electronic structure near oxygen vacancies but dissociation of adsorbed oxygen molecules into atomic oxygen is affected by surface Sr segregation, and polarization resistance degradation is mainly induced by surface Sr segregation. Furthermore, Sr(0.90)Yb(0.10)CoO(3-δ) exhibits excellent thermal stability as well as excellent recovery stability and improved polarization performance after a few pure air/CO2-containing air treatment cycles at 700 °C. However, a hysteresis behavior of polarization performance is observed at 650 °C during gas cycling treatment, which may cause long-term degradation of the Sr(0.90)Yb(0.10)CoO(3-δ) electrode. The different polarization behaviors during gas cycling treatment are induced by different sensitivities of the formed surface strontium carbonate and chemisorbed surface oxo-carbonaceous species to different operating temperatures.

electrochemical kinetic↗
DOE OSTI2024

Stabilization of Catalytically Active Surface Defects on Ga-doped La–Sr–Mn Perovskites for Improved Solar Thermochemical Generation of Hydrogen

Solar thermochemical hydrogen (STCH) production from water splitting typically requires performing redox cycles at temperatures above 1200 °C to reduce and re-oxidize the bulk of a reversible material. Bulk processes such as oxygen vacancy formation and oxygen diffusion energies dictate the viability of a material for STCH. The surface plays an important role in the formation and destruction of vacancies and interacts with gas phase water and surface adsorbed species. These surface processes can lead to surface reconfigurations and even the formation of surface phases with stoichiometry and oxygen content very different from the bulk composition. Understanding in-situ the surface chemical state and its evolution under water splitting is important to design nonstoichiometric oxides capable of longer-lasting STCH generation at lower temperatures. In this work, we describe the water splitting active defect sites in LSM ((La 0.65 Sr 0.35 ) 0.95 MnO 3–δ ) and Ga-doped LSM ((La 0.6 Sr 0.4 ) 0.95 (Mn 0.8 Ga 0.2 )O 3–δ ) perovskites during Operando thermochemical water splitting conditions using ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) experiments at 800 °C under steam. We show that sub-stoichiometric La +3 in the oxygen-vacancy rich surface at operating conditions can be used to correlate surface water splitting activity and the creation of surface hydroxide intermediates. The addition of Ga in LSM is shown to drastically stabilize the surface chemical composition by preventing Sr segregation and stabilizing catalytically active surface defects that promote the binding of adsorbed hydroxides. Here, we use Operando AP-XPS quantification of metastable surface hydroxide intermediates (La(OH) 3 ) to determine the amount of catalytically active surface sites in LSM (2.9%) and in LSMG (7.8–8.1%, depending on the bulk oxidation state).

08 HYDROGEN↗
DOE OSTI2021

Reaction paths of methane activation and oxidation of surface intermediates over NiO on Ceria-Zirconia catalysts studied by In-situ FTIR spectroscopy

Methane activation over NiO/Ce 0.82 Zr 0.18 O 2 catalysts synthesized by combustion synthesis is studied by in-situ IR spectroscopy and correlated to the properties and oxygen speciation of the catalyst. Through XRD, H 2 -TPR, and pyridine adsorption followed by FTIR spectroscopy, the reducibility and Lewis acidity of the catalysts are assessed. In-situ FTIR spectroscopy is used to monitor the methane activation on catalyst surfaces. Complex IR features of methane-derived surface species are observed and are attributed to the formation of surface alkyl/alkoxy, aldehyde, formate/carbonate, and aromatic species. A data analysis algorithm is developed to evaluate the evolution of different surface species over time. The formation of formate and carbonate species is driven by adsorbed surface oxygen, while less reactive oxygen species associated with NiO allow for the production of aromatics and alkoxy intermediates. Finally, by tuning the reducibility and Lewis acidity of the catalyst, the selectivity to alkoxy intermediates can be improved.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Effect of Propagating Dopant Reactivity on Lattice Oxygen Loss in LLZO Solid Electrolyte Contacted with Lithium Metal

Lithium lanthanum zirconium oxide (LLZO) is widely known as the most stable solid electrolyte against lithium metal electrodes. This thermodynamic stability can be lost by the presence of dopants which are required to stabilize the cubic phase of LLZO and can be reduced by lithium metal. However, the role of oxygen in such reactions is taken for granted. In this work, the reduction of Nb-substituted LLZO (Nb-LLZO) is explored by Li metal and shows that interfacial reactions propagate and lead to the decomposition with substantial Nb 5+ reduction deep into the bulk electrolyte. Scanning Transmission Electron Microscopy with Energy Dispersive X-ray Spectroscopy and thermogravimetric analyses show much of the reduction is due to oxygen vacancies formed, leading to increased electronic conductivity mapped with conductive Atomic Force Microscopy. Density functional theory calculations indicate oxygen release is favored by increased excess lithiation of Nb-LLZO. Electrochemical impedance of polycrystalline Nb-LLZO shows the continuous evolution of ionically resistive interphases near the lithium metal interface with Nb-LLZO while single crystals show little reactivity at room temperature and self-limiting reduction at 60°C. This work underlines the role of grain boundaries in propagating destructive solid electrolyte reactions and highlights previously unseen mechanisms involving lattice oxygen in LLZO.

Li metal, solid-state electrolytes↗
DOE OSTI2019

Evolution Pathway from Iron Compunds to Fe 1 (II)-N 4 Sites through Gas-Phase Iron during Pyrolysis

Pyrolysis is indispensable for synthesizing highly active Fe–N–C catalysts for the oxygen reduction reaction (ORR) in acid, but how Fe, N, and C precursors transform to ORR-active sites during pyrolysis remains unclear. This knowledge gap obscures the connections between the input precursors and the output products, clouding the pathway toward Fe–N–C catalyst improvement. Here, we unravel the evolution pathway of precursors to ORR-active catalyst comprised exclusively of single-atom Fe 1 (II)–N 4 sites via in-temperature X-ray absorption spectroscopy. The Fe precursor transforms to Fe oxides below 300 °C and then to tetrahedral Fe 1 (II)–O 4 via a crystal-to-melt-like transformation below 600 °C. The Fe 1 (II)–O 4 releases a single Fe atom that diffuses into the N-doped carbon defect forming Fe 1 (II)–N 4 above 600 °C. This vapor-phase single Fe atom transport mechanism is verified by synthesizing Fe 1 (II)–N 4 sites via “noncontact pyrolysis” wherein the Fe precursor is not in physical contact with the N and C precursors during pyrolysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2003

Science Rationale for Jupiter Entry Probe as Part of JIMO

A Jupiter atmospheric entry probe as part of JIMO is a cost effective way to address fundamental science questions identified in the National Research Council Solar System Exploration Decadal Survey (SSEDS): New Frontiers in the Solar System, An Integrated Ex- ploration Strategy. Compared to either the cost of an entirely separate Jupiter mission, or the cost of JIMO itself, inclusion of such a probe on JIMO would be cost advantageous. The probe itself could be relatively simple, and could build on the Galileo Probe heritage. The SSEDS specifically identified the distribution of water across the Solar System as a Key Scientific Question. Correspondingly, knowing the water abun dance on Jupiter is fundamental to understanding almost every aspect of the evolution of the early solar nebula. The Galileo Probe obtained the abundance of several key elements in Jupiter's atmosphere, which data have already caused major rethinking of theories of how Jupiter formed and how the early solar nebula evolved. However, because of a combination of circumstances, the global abundance of the key element oxygen, in the form of water, was not obtained. Without knowledge of the jovian water abundance, further progress in understanding Solar System evolution and planet formation will be greatly inhibited. Therefore, quantifying jovian water abundance should be a goal of the very next mission to the jovian system. Such a measurement would be impossible via remote sensing from the JIMO orbiter because of the large distances the JIMO orbiter maintains from Jupiter. A Jupiter atmospheric entry probe as part of JIMO could achieve the fundamental water measurement. In order that a probe avoid repeating the Galileo probe's experience of failing to obtain the jovian water abundance, the probe should go deep, to at least 100 bars pressure. Probes to 100 bars have been accomplished many times in descending to the surface of Venus, and at 100 bars the temperature of the jovian atmosphere is 60-70 K less than the surface temperature of Venus.

Young, R. E.↗
DOE OSTI2021

An Analysis of the Impact of Particle Growth on Transport Losses in Polymer-Electrolyte Fuel Cells

Voltage cycling causes catalyst nanoparticles in polymer-electrolyte fuel cells to grow. The concomitant loss of interfacial area results in larger kinetic, transport, and possibly ohmic overpotentials. This paper uses recently published experimental data and mathematical models to investigate the evolutions of transport and ohmic resistances to platinum nanoparticles located on the surface and inside the micropores of carbon black supports. Resistance to oxygen transport rises as surface area declines primarily because the flux to each remaining larger platinum particle increases. The path lengths governing oxygen diffusion to surface and buried platinum sites also increase as nanoparticles grow. Platinum nanoparticles on the surface become relatively less favorable as voltage cycling proceeds because they grow faster than platinum in micropores. Because voltage cycling causes total interfacial area to decline, and the fraction located inside micropores to increase, nanoscale ohmic losses increase as a catalyst layer decays. The practical importance of this effect is difficult to discern because proton conductivity in carbon micropores is not well characterized.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2024

Carbon- and Oxygen-rich stars in MaStar: identification and classification

ABSTRACT Carbon- and Oxygen-rich stars populating the Thermally Pulsing Asymptotic Giant Branch (TP-AGB) phase of stellar evolution are relevant contributors to the spectra of ∼1 Gyr old populations. Atmosphere models for these types are uncertain, due to complex molecules and mass-loss effects. Empirical spectra are then crucial, but samples are small due to the short (∼3 Myr) TP-AGB lifetime. Here we exploit the vastness of the MaNGA Stellar library MaStar (∼60 000 spectra) to identify C and O-rich type stars. We define an optical colour selection with cuts of (g − r) > 2 and (g − i) < 1.55(g − r) − 0.07, calibrated with known C- and O-rich spectra. This identifies C- and O-rich stars along clean, separated sequences. An analogue selection is found in V, R, I bands. Our equation identifies C-rich and O-rich spectra with predictive performance metric F1-scores of 0.72 and 0.74 (over 1), respectively. We finally identify 41 C- and 87 O-rich type AGB stars in MaStar, 5 and 49 of which do not have a SIMBAD counterpart. We also detect a sample of non-AGB, dwarf C-stars. We further design a fitting procedure to classify the spectra into broad spectral types, by using as fitting templates empirical C- and O-rich spectra. We find remarkably good fits for the majority of candidates and categorize them into C- and O-rich bins following existing classifications, which correlate to effective temperature. Our selection models can be applied to large photometric surveys (e.g. Euclid, Rubin). The classified spectra will facilitate future evolutionary population synthesis models.

Hill, Lewis (ORCID:0000000180528080)↗
DOE OSTI2023

Origin of age softening in the refractory high-entropy alloys

Refractory high-entropy alloys (RHEAs) are emerging materials with potential for use under extreme conditions. As a newly developed material system, a comprehensive understanding of their long-term stability under potential service temperatures remains to be established. This study examined a titanium-vanadium-niobium-tantalum alloy, a promising RHEA known for its superior high-temperature strength and room-temperature ductility. Using a combination of advanced analytical microscopies, Calculation of Phase Diagrams (CALPHAD) software, and nanoindentation, we investigated the evolution of its microstructure and mechanical properties upon aging at 700°C. Trace interstitials such as oxygen and nitrogen, initially contributing to solid solution strengthening, promote phase segregation during thermal aging. As a result of the depletion of solute interstitials within the metal matrix, a progressive softening is observed in the alloy as a function of aging time. This study, therefore, underscores the need for a better control of impurities in future development and application of RHEAs.

36 MATERIALS SCIENCE↗
NASA NTRS1976

Evolution of the ionosphere

Studies were made of the electron density profiles at various stages of atmospheric evolution, with the assumption that the atmospheric composition has changed due to the gradual increase of oxygen while the nitrogen level has remained constant. The result of model calculations indicates that when the oxygen content is less than about 1% of the present earth's atmosphere level, the major ions in the F2 region will change from O(+) to N(+). The maximum number density of N(+) ions reaches approximately 10 million per cu cm because of the absence of a rapid loss mechanism for N(+). The height of the N(+) ion density peak is much lower than the height of the F2 layer peak of the current ionosphere.

Shimizu, M.↗
NASA NTRS1995

The Local Variability of Interstellar Abundances: Observations of C 17O and C 18O in Three Dark Clouds

The abundance ratios of carbon monoxide with isotopes 17 and 18 were mapped in three nearby molecular clouds (B335, L134, and rho Oph), two of which are active star-forming regions. It is suggested that there may be a spatial variability of the two oxygen isotopes resulting from local enrichment and that this may have major implications for galactic nuclear evolution.

dark clouds isotopic abundances interstellar abund↗
NASA NTRS2014

Minerology and Crystallography of Some Itokawa Particles Returned by the Hayabusa Mission

JAXA Hayabusa mission success-fully returned particles of the asteroid Itokawa to the earth in 2010. The recovered particles were carefully studied by the preliminary examination (PE) team and the obtained results are providing significant and unique information about the formation and evolution of meteorite parent bodies [1-6]. These particles further revealed that their mineral compositions and oxygen isotopes are close to those of equilibrated LL chon-drites [1,2], which matches with the observation at the orbit [7]. After the PE, JAXA distributed the samples as international AO study and we received 4 new and 3 PE particles. The new samples may contain some exot-ic components that have not been found by the PE study, and are of special interest. We have performed a detailed mineralogical and crystallographic study on these particles and here report the results.

Mikouchi, T.↗
NASA NTRSDate not supplied

Discovery of hydrated Clasts with Very High Abundance of Ferromagnesian 160-Rich Olivine: Inner or Outer Solar System origin?

Olivine is one of the major minerals in chondritic meteorites and occurs in all chondritic components, including amoeboid olivine aggregates (AOAs), forsterite-bearing Type B (FoB) Ca, Al-rich inclusions (CAIs), chondrules, and matrices. As a result, olivines could preserve chemical and isotopic characteristics of their formation environments. There are significant variations in oxygen isotopic compositions of chondritic olivine. Forsteritic olivine in AOAs and FoB-CAIs has solar-like 16O-rich compositions (D17O ~ -23±2‰); the former condensed from an 16O-rich gas of ~solar composition, whereas the latter crystallized from remelted condensates in an isotopic similar gaseous reservoir. Olivine phenocrysts in chondrules are significantly 16O-depleted compared to CAIs and AOAs: D17O ranges from ~ -7 to +3‰. Only rare relict olivines in chondrules have CAI/AOA-like 16O-rich compositions; these grains most likely represent fragments of CAIs and AOAs incompletely melted during chondrule formation. Olivine in matrices of weakly metamorphosed meteorites is extremely fine-grained (<100 nm) and has predominantly forsteritic composition. In metamorphosed chondrites, matrix olivines are coarse-grained (up to 10 μm) and enriched in FeO. Due to small grain sizes, oxygen isotopic compositions of matrix olivines are poorly known. Mapping of matrices of Vigarano and Kakangari using isotope microscopes (secondary ion mass-spectrometer (SIMS) plus SCAPS detector) revealed the presence of 16O-rich olivine grains. While most matrix olivines in Vigarano have 16O-poor compositions, nearly half of olivines measured in Kakangari matrix are16O-rich.Here, we present for the first time new lithologies largely composed of 16O-and Fe-rich olivine. We attempt to address the question of whether these 16O-richolivine grains were formed by condensation in the solar nebula or by a secondary process during the evolution of the parent body. Mineralogical characteristics of these unusual olivines, as well as in-situ measured oxygen-isotope compositions of different phases are reported in detail.

I. Kerraouch↗
DOE OSTI2021

In Situ ATR-FTIR Study of the Cathode–Electrolyte Interphase: Electrolyte Solution Structure, Transition Metal Redox, and Surface Layer Evolution

We present a study of the lithium nickel manganese cobalt oxide (LiNi 0.6 Mn 0.2 Co 0.2 O 2 , NMC622) cathode-electrolyte interphase (CEI) during galvanostatic charging and discharging using in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) methods to investigate the voltage dependent electrolyte solution structure changes at the interface, transition metal (TM) redox chemistry, and cathode/electrolyte interfacial layer evolution. Furthermore, our in situ cell design provides both reliable electrochemical device testing and strong FTIR vibrational absorption signals near the cathode surface. Specifically, advanced spectral analysis elucidates changes of near-surface Li+ ion (de)solvation by solvent molecules during galvanostatic cycling. Moreover, cathode metal-oxygen vibrational absorptions, sensitive to TM redox behaviors and subsequent local structural variations, were correlated to cathode de-lithiation (and lithiation) and electrolyte solution structure changes. In addition, we have detected the formation and evolution of a CEI surface layer on the NMC622 cathode that contributes to the cell's capacity fade.

25 ENERGY STORAGE↗
NASA NTRS2005

ISS ECLSS Technology Evolution for Exploration

The baseline environmental control and life support systems (ECLSS) currently deployed on the International Space Station (ISS) and the regenerative oxygen generation and water reclamation systems to be added in 2008 are based on technologies selected during the early 1990's. While they are generally meeting, or exceeding requirements for supporting the ISS crew, lessons learned from hardware development and on orbit experience, together with advances in technology state of the art, and the unique requirements for future manned exploration missions prompt consideration of the next steps to be taken to evolve these technologies to improve robustness and reliability, enhance performance, and reduce resource requirements such as power and logistics upmass. This paper discusses the current state of ISS ECLSS technology and identifies possible areas for evolutionary enhancement or improvement.

Carrasquillo, Robyn L.↗