Multi-scale chemo-mechanical evolution during crystallization of mixed conducting SrTi[subscript 0.6
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Buckner, Haley B.↗
SEARCH · Engineering Papers
Results for “Oxygen evolution”
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Hydration structure of flat and stepped MgO surfaces
We investigate the solvation structure of flat and stepped MgO(001) in neutral liquid water using ab initio molecular dynamics based on a hybrid density functional with dispersion corrections. Our simulations show that the MgO surface is covered by a densely packed layer of mixed intact and dissociated adsorbed water molecules in a planar arrangement with strong intermolecular H-bonds. The water dissociation fractions in this layer are >20% and >30% on the flat and stepped surfaces, respectively. Slightly above the first water layer, we observe metastable OH groups perpendicular to the interface, similar to those reported in low temperature studies of water monolayers on MgO. Here, these species receive hydrogen bonds from four nearby water molecules in the first layer and have their hydrophobic H end directed toward bulk water, while their associated protons are bound to surface oxygens. The formation of these OH species is attributed to the strong basicity of the MgO surface and can be relevant for understanding various phenomena from morphology evolution and growth of (nano)crystalline MgO particles to heterogeneous catalysis.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Virtual Growth of SRF Materials
Niobium's native surface oxide affects SRF cavity and superconducting qubit performance, motivating interest in controlling its crystalline structure. We combine a literature-derived machine-learning analysis with temperature-dependent XRD to study crystalline ordering in Nb2O5. Random Forest models, trained on 74 processing conditions from 17 papers and validated by leave-one-group-out cross-validation, predicted broad crystallinity outcomes well (balanced accuracy 0.809), but struggled with specific polymorph identity (0.577). Annealing temperature was the dominant predictor across all targets; oxygen partial pressure showed negligible importance, reflecting narrow literature coverage rather than physical irrelevance. Temperature-dependent XRD on anodized and H2O2-treated Niobium showed structural evolution consistent with the machine learning predictions. Our model and overall approach provide a data-driven framework for identifying and optimizing conditions that promote crystallization in initially amorphous oxides. This framework can guide the selection of growth and post-annealing conditions for Nb surfaces by narrowing the experimental parameter space, thereby reducing trial-and-error efforts in developing oxide structures relevant to SRF applications.
Tilkin, Anthony [Fermilab]↗
Chemical models of volcanic outgassing on Mars
During the MSATT workshop in Boulder, CO, several participants emphasized the importance of constraints on the composition and temporal evolution of outgassed volatiles on Mars. I present the results of some preliminary calculations that model the composition of volcanic gases as a function of temperature, pressure, oxygen fugacity, and quench function of temperature. These results can be used in combination with cosmochemical models for the accretion of Mars to assess the plausibility of different atmospheric compositions during the planet's early history.
Fegley, Bruce, Jr.↗
Virtual Growth of SRF Materials: A Machine Learning Approach to Predict the Crystalline Structural Ordering in Nb Surface Oxides
Niobium's native surface oxide affects SRF cavity and superconducting qubit performance, motivating interest in controlling its crystalline structure. We combine a literature-derived machine-learning analysis with temperature-dependent XRD to study crystalline ordering in Nb2O5. Random Forest models, trained on 74 processing conditions from 17 papers and validated by leave-one-group-out cross-validation, predicted broad crystallinity outcomes well (balanced accuracy 0.809), but struggled with specific polymorph identity (0.577). Annealing temperature was the dominant predictor across all targets; oxygen partial pressure showed negligible importance, reflecting narrow literature coverage rather than physical irrelevance. Temperature-dependent XRD on anodized and H2O2-treated Niobium showed structural evolution consistent with the machine learning predictions. Our model and overall approach provide a data-driven framework for identifying and optimizing conditions that promote crystallization in initially amorphous oxides. This framework can guide the selection of growth and post-annealing conditions for Nb surfaces by narrowing the experimental parameter space, thereby reducing trial-and-error efforts in developing oxide structures relevant to SRF applications.
Tilkin, Anthony [Unlisted, US, IL; Fermilab]↗
Internal Heterogeneous Processes in Aluminum Combustion
This paper discusses the aluminum particle combustion mechanism which has been expanded by inclusion of gas dissolution processes and ensuing internal phase transformations. This mechanism is proposed based on recent normal and microgravity experiments with particles formed and ignited in a pulsed micro-arc. Recent experimental findings on the three stages observed in Al particle combustion in air and shows the burning particle radiation, trajectory (streak), smoke cloud shapes, and quenched particle interiors are summarized. During stage I, the radiation trace is smooth and the particle flame is spherically symmetric. The temperature measured using a three-color pyrometer is close to 3000 K. Because it exceeds the aluminum boiling point (2730 K), this temperature most likely characterizes the vapor phase flame zone rather than the aluminum surface. The dissolved oxygen content within particles quenched during stage I was below the detection sensitivity (about 1 atomic %) for Wavelength Dispersive Spectroscopy (WDS). After an increase in the radiation intensity (and simultaneous decrease in the measured color temperature from about 3000 to 2800 K) indicative of the transition to stage II combustion, the internal compositions of the quenched particles change. Both oxygen-rich (approx. 10 atomic %) and oxygen-lean (< 1 %) regions are identified within the particles using back-scattered electron imaging and WDS. During stage II, oscillations are observed in particle radiation and the flame and smoke cloud are distorted from their original spherically-symmetric shape. In stage III, particle radiation continues to exhibit oscillations, but its radiation intensity drops and remains at a nearly constant level. The measured temperature decreases to about 2300 K. Also, larger changes in particle velocities are observed, and oxide caps are found on quenched particle surfaces. While these results showed the correlation between the aluminum particle combustion behavior and the evolution of its internal composition, the change from the spherically symmetric to asymmetric flame shape occurring upon the transition from stage I to stage II combustion could not be understood based only on the fact that dissolved oxygen is detected in the particles. The connection between the two phenomena appeared even less significant because in earlier aluminum combustion studies carried in O2/Ar mixtures, flame asymmetry was not observed as opposed to experiments in air or O2/CO mixtures. It has been proposed that the presence of other gases, i.e., hydrogen, or nitrogen causes the change in the combustion regime.
Dreizin, E. L.↗
Domesticating the green alga Scenedesmus obliquus
Microalgae cultivation processes exist only for a few species used in commercial applications. Their domestication is still in its infancy, with major advances required, specifically to overcome limiting factors in microalgae production. The goal is to develop superior strains without the need of genetic technologies that would require lengthy regulatory permits, and often limit consumer acceptance. Adaptive Laboratory Evolution techniques, alone or in conjunction with sexual recombination, can allow for rapid develop of improved strains and their industrial production. Approaches include increased photon utilization efficiency by cultures operating under full sunlight conditions due to higher light saturation levels, allowing for higher productivities under outdoor conditions. Decades of research yielded some promising results under controlled conditions with a few specific mutant strains. However, these failed to achieve the anticipated higher productivities in actual algal mass cultures, in part due to the inability of mutations to overcome photoinhibition, reactive oxygen species, and other pleiotropic impacts on photosynthesis.
09 BIOMASS FUELS↗
Self-Adhesive Ionomers for Alkaline Electrolysis: Optimized Hydrogen Evolution Electrode
Hydrogen produced through low-temperature water electrolysis using anion exchange membranes (AEM) combines the benefits of liquid-electrolyte alkaline electrolysis and solid-polymer proton exchange membrane electrolysis. The anion conductive ionomers in the oxygen-producing anode and hydrogen-producing cathode are a critical part of the three-dimensional electrodes. The ionomer in the hydrogen-producing cathode facilitates hydroxide ion conduction from the cathode catalyst to the anode catalyst, and water transport from the anode to the cathode catalyst through the AEM. This ionomer also binds the catalyst particles to the porous transport layer. Here in this study, the cathode durability was improved by use of a self-adhesive cathode ionomer to chemically bond the cathode catalyst particles to the porous transport layer. It was found that the cathode ionomers with high ion exchange capacity (IEC) were more effective than low IEC ionomers because of the need to transport water to the cathode catalyst and transport hydroxide away from the cathode. The cathode durability was improved by using ionomers which were soluble in the spray-coated cathode ink. Optimization of the catalyst and ionomer content within the cathode led to electrolysis cells which were both mechanically durable and operated at low voltage.
08 HYDROGEN↗
Microstructural and Micro-Chemical Evolutions in the Irradiated UCO Fuel Kernels of AGR-1 and AGR-2 TRISO Fuel Particles
AGR-1 and AGR-2 TRISO fuel particles were fabricated with slightly different fuel kernel chemical compositions, modified fabrication processes, different fuel kernel diameters, and changed 235U enrichments. To correlate those differences with the fuel kernel responses to neutron irradiations in terms of irradiated fuel microstructure, fission products chemical and physical states, and fission gas bubble evolutions, extensive microstructural and analytical characterizations were conducted. The studies used a state of art transmission electron microscopy (TEM) equipped with Energy-dispersive X-ray spectroscopy (EDS) of four silicon solid-state detectors which have super sensitivity and fast speed. The TEM specimens were prepared from selected AGR-1 and AGR-2 irradiated fuel kernels exposed to safety testing after irradiation. The particles were chosen to represent a representative irradiation conditions with a fuel burnup within the range from 10.8 to 18.6% FIMA, and the time-average volume-average temperatures vary from 1070 to 1287°C. The 235U enrichment was 19.74 wt.% for the AGR1 fuel kernels and 14.03 wt.% for the AGR-2 fuel kernels. The TEM results show that there were significant microstructural reconstructions in the irradiated fuel kernels for both the AGR-1 and AGR-2 fuels. There are four major phases including fuel matrix of UO2 and UC, U2RuC2, and UMoC2 in the irradiated AGR2 fuel kernel. Zr and Nb form solid solution in the UC phase. UMoC2 phase often shows a detectable concentration of Tc. Pd was found to mainly locate in the buffer layer or to be associated with fission gas bubble within the UMoC2 phase. The EDS maps qualitatively show that the rare-earth fission products (Nb, et al.) preferentially reside in the UO2 phase. In contrast, in the irradiated AGR1 fuel kernel, no U2RuC2 or UMoC2 precipitates were positively identified. Instead, there is a high number of rod-shape precipitates enriched with Ru, Tc, Rh, and Pd observed in the fuel kernel center and edge zone. The difference of microstructural and micro-chemical evolutions in irradiated fuel kernels between the AGR-1 and AGR-2 TRISO fuel particle may result from a combined factor of irradiation temperature, fuel geometry and chemical composition. However, the irradiation temperature probably play a more deterministic role. Limited electron energy loss spectroscopy (EELS) characterizations on the AGR2 fuel kernel show that there is nearly no carbon in the UO2 phase while a small fraction of oxygen was detected in the UC/UMoC2 phase.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Spatial Heterogenous Redox Couples Degradation in Sodium-Ion Battery Cathode Materials and the Mitigation of Voltage Fade by Blocking Oxygen Release
The use of anionic redox has become a new paradigm for improving the energy density of rechargeable batteries, which is essential for improving the market competitiveness of sodium-ion batteries. However, issues such as voltage attenuation and cycling stability degradation persist in layered oxide anion redox cathode materials. Here, in this study, we systematically investigate the classic Na-ion cathode material Na 0.6 Li 0.2 Mn 0.8 O 2 , and the primary causes of voltage decay are identified as the activation of cations and the reduction in anion redox activity. In addition, the activation of cations is closely associated with anion reactions. Through the application of sophisticated multiscale synchrotron absorption spectroscopy and imaging techniques, we have identified a pronounced pattern of spatially dependent degradation in the evolution of redox couples, which is more evident from the material’s surface to its core. With this understanding, we introduced a surface fluorination approach that modulates the local chemical coordination environment. This strategy increases the formation energy of surface oxygen vacancies and locks transition metals oxide state. Consequently, it enables more reversible anionic redox reactions, which block the spatial progression of degradation and mitigates voltage decay.
25 ENERGY STORAGE↗
Modeling Novel Aqueous Particle and Cloud Chemistry Processes of Biomass Burning Phenols and Their Potential to Form Secondary Organic Aerosols
Phenols emitted from biomass burning contribute significantly to secondary organic aerosol (SOA) formation through the partitioning of semivolatile products formed from gas-phase chemistry and multiphase chemistry in aerosol liquid water and clouds. The aqueous-phase SOA (aqSOA) formed via hydroxyl radical (˙OH), singlet molecular oxygen ( 1 O 2 *), and triplet excited states of organic compounds ( 3 C*), which oxidize dissolved phenols in the aqueous phase, might play a significant role in the evolution of organic aerosol (OA). However, a quantitative and predictive understanding of aqSOA has been challenging. Here, we develop a stand-alone box model to investigate the formation of SOA from gas-phase ˙OH chemistry and aqSOA formed by the dissolution of phenols followed by their aqueous-phase reactions with ˙OH, 1 O 2 *, and 3 C* in cloud droplets and aerosol liquid water. Here, we investigate four phenolic compounds, i.e., phenol, guaiacol, syringol, and guaiacyl acetone (GA), which represent some of the key potential sources of aqSOA from biomass burning in clouds. For the same initial precursor organic gas that dissolves in aerosol/cloud liquid water and subsequently reacts with aqueous phase oxidants, we predict that the aqSOA formation potential (defined as aqSOA formed per unit dissolved organic gas concentration) of these phenols is higher than that of isoprene-epoxydiol (IEPOX), a well-known aqSOA precursor. Cloud droplets can dissolve a broader range of soluble phenols compared to aqueous aerosols, since the liquid water contents of aerosols are orders of magnitude smaller than cloud droplets. Further, our simulations suggest that highly soluble and reactive multifunctional phenols like GA would predominantly undergo cloud chemistry within cloud layers, while gas-phase chemistry is likely to be more important for less soluble phenols. But in the absence of clouds, the condensation of low-volatility products from gas-phase oxidation followed by their reversible partitioning to organic aerosols dominates SOA formation, while the SOA formed through aqueous aerosol chemistry increases with relative humidity (RH), approaching 40% of the sum of gas and aqueous aerosol chemistry at 95% RH for GA. Our model developments of biomass-burning phenols and their aqueous chemistry can be readily implemented in regional and global atmospheric chemistry models to investigate the aqueous aerosol and cloud chemistry of biomass-burning organic gases in the atmosphere.
09 BIOMASS FUELS↗
Flow Development in Radial Plane of Rotating Detonation Engine Integrated with Aerospike
In this study, axial and radial velocity components are measured downstream of a rotating detonation engine (RDE) integrated with an aerospike by using particle image velocimetry (PIV) at 100 kHz. The RDE is operated at high pressures obtained by restricting the RDE exit with a converging nozzle, which also directs the flow radially toward the aerospike. Reactants, methane fuel, and enriched air (67% oxygen and 33% nitrogen) are supplied from separate plenums at ambient temperature. PIV data are presented to investigate how pressure ratios within the RDE channel affect the flow evolution across the aerospike. The RDE is shown to operate stably and consistently in a single wave mode for all six test runs. The study highlights large temporal and spatial variations in both axial and radial flow velocities at the nozzle throat that persist downstream across the aerospike. Each point in the flowfield oscillates at the frequency recorded inside the RDE channel. Overall, the temporally and spatially varying aerospike flowfield is far from the ideal case of a uniform flow at its exit, and it points toward the need to condition the flow within the RDE channel to produce more uniform conditions at the nozzle throat.
Engineering↗
Temporal features of the outflow of heavy ionospheric ions in response to a high altitude plasma cavity
Using a hydrodynamic model for the plasma, it is demonstrated that the auroral plasma cavity is capable of drawing an appreciably large flux of oxygen ions, which are normally gravitationally bound. This escape mechanism of O(+) does not involve any additional heating or acceleration of the plasma in the ionosphere. The temporal evolution of the outflow shows that it starts near the cavity and penetrates into the ionosphere with a flux front moving down with the ion-acoustic speed. A steady outflow is reached in a few hours for a cavity at a height of one R(e) if the cavity is maintained. This time reduces to less than 1 hour for cavity heights less than 3000 km. During the transient state the outflux can appreciably exceed that in the steady state. In view of the horizontal convection, the transient outflow is of special significance. As the cavity descends, the ionospheric flux of O(+) increases; for the lower edge of the cavity in the altitude range 3000-10,000 km, the steady flux is found to be in the range 10 to the 7th to 10 to the 9th. An analysis for the steady state shows that outflow is controlled by the density scale height in the cavity.
Singh, Nagendra↗
The early evolution of eukaryotes - A geological perspective
This paper examines the goodness of fit between patterns of biological and environmental history implied by molecular phylogenies of eukaryotic organisms and the geological records of early eukaryote evolution. It was found that Precambrian geological records show evidence that episodic increases in biological diversity roughly coincided with episodic environmental changes and by sharp increases in atmospheric oxygen concentrations which significantly changed the earth surface environments. Although the goodness of fit among physical and biological changes is gratifyingly high, the records of these changes do not always coincide in time. The additional information in these fields that is needed for complete integration of geological and phylogenic records is suggested.
Knoll, Andrew H.↗
Oxygen-enhanced models for globular cluster stars. III - Horizontal-branch sequences
A large grid of horizontal-branch (HB) evolutionary sequences which have been calculated with core expansion and semiconvection and with enhanced oxygen composition are presented and described. Tracks for 10 different metallicities are computed; they range from (Fe/H) = -0.47 to -2.26 and comprise a total of 115 sequences. The evolution is traced from the zero-age horizontal-branch (ZAHB) to the lower AGB at a point where log L/solar luminosity = 2.25. All of the sequences are illustrated on both the theoretical H-R diagram and on the B, V color-magnitude diagram. A complete set of tables for the ZAHB models and a representative sample of tabulations of the track parameters are provided. The phenomena which control HB evolution morphology, and existing certainties in theoretical HB models are discussed.
Dorman, Ben↗
Characterization of Novel Spacecraft Materials aboard the Materials International Space Station Experiment-Flight Facility (Preliminary Results)
This work will encompass the preflight characterization of 15 novel and heritage materials currently under observation on the Materials International Space Station Experiment-Flight Facility (MISSE-FF). MISSE-FF has been upgraded to perform active reflectance measurements of the materials. Images taken in RGB/IR colors are compared to results from an extensive ground testing campaign to obtain quantitative on-orbit material evolution data. Identical materials samples are to be flown on the ram, wake, and zenith faces of MISSE-FF, enabling deconvolution of the energetic electron, proton, atomic oxygen, and ultraviolet damage pathways. Energy deposition from the space environment leads to chemical changes in the material that in turn alter the optical properties. The same chemical damage that manifests as changes in optical reflectance and absorptance also leads to changes in myriad physical properties such as mechanical strength, electrical conductivity, and chemical reactivity. Therefore, flight materials are able to be characterized based on their unique reflectance spectra by comparing on-orbit measurements of optical reflectance with extensive terrestrial experiments, which help to correlate changes in reflectance with respect to changes in other material properties. The MISSE program has been a part of the International Space Station National Laboratory for many years and has been instrumental in understanding space weather modification of material properties. However, MISSE-FF has been limited to passive experiments with only pre/post flight material studies possible. In advance of the MISSE-16 experiment, the flight facility has received a major upgrade to provide daily spectral observations by way of a RGB/IR camera and a tunable light source. The MISSE-16 mission launched in February 2022 and carries 15 material samples for 6 months of the low Earth orbital exposure. Identical materials samples are to be flown on the ram, wake, and zenith faces of MISSE-FF, enabling deconvolution of the energetic electron, proton, atomic oxygen, and ultraviolet damage pathways. This paper discusses the MISSE-16 experiment, highlights the first use of the facility upgrades, and presents results from the extensive preflight material characterization that includes directional hemispherical reflectance, bidirectional reflectance, AFM, SEM, and electrical conductivity. Additionally, data showing the modification of these properties by ground-based exposure to space-like electron and atomic oxygen flux will be discussed. Finally, updates on deployment and initial check-out of the experiment on MISSE-FF will be presented. It is the ultimate goal of this program to provide validation for the development of ground based space weather simulation facilities and techniques.
Ryan Hoffman↗
The evolution of the interstellar medium in elliptical galaxies. I - The early wind phase
The evolving mass loss rates from type I and II SNe, stellar winds, and PN and the associated evolution of the mass-averaged temperature of the stellar ejecta are calculated. At early times, the mass-averaged temperature of the ejecta is found to be much greater than the central escape temperature from even very luminous elliptical galaxies due to the high frequency of type II SNe. The amount of oxygen and iron that can be injected into the intracluster medium from type II SN-driven winds in elliptical galaxies is calculated and the results are compared with observations. The gas ejected during this early wind phase is very hot and can heat the cluster gas to temperatures greater than that produced by gravitational heating alone. Two numerical simulations concerning the evolution of the ISM in an elliptical galaxy model with L(B) = 10 to the 11th solar are presented which confirm the existence of an early type II SN-driven wind phase and reproduce the observed X-ray properties of bright elliptical galaxies in the present epoch.
David, L. P.↗
A genomic timescale of prokaryote evolution: insights into the origin of methanogenesis, phototrophy, and the colonization of land
BACKGROUND: The timescale of prokaryote evolution has been difficult to reconstruct because of a limited fossil record and complexities associated with molecular clocks and deep divergences. However, the relatively large number of genome sequences currently available has provided a better opportunity to control for potential biases such as horizontal gene transfer and rate differences among lineages. We assembled a data set of sequences from 32 proteins (approximately 7600 amino acids) common to 72 species and estimated phylogenetic relationships and divergence times with a local clock method. RESULTS: Our phylogenetic results support most of the currently recognized higher-level groupings of prokaryotes. Of particular interest is a well-supported group of three major lineages of eubacteria (Actinobacteria, Deinococcus, and Cyanobacteria) that we call Terrabacteria and associate with an early colonization of land. Divergence time estimates for the major groups of eubacteria are between 2.5-3.2 billion years ago (Ga) while those for archaebacteria are mostly between 3.1-4.1 Ga. The time estimates suggest a Hadean origin of life (prior to 4.1 Ga), an early origin of methanogenesis (3.8-4.1 Ga), an origin of anaerobic methanotrophy after 3.1 Ga, an origin of phototrophy prior to 3.2 Ga, an early colonization of land 2.8-3.1 Ga, and an origin of aerobic methanotrophy 2.5-2.8 Ga. CONCLUSIONS: Our early time estimates for methanogenesis support the consideration of methane, in addition to carbon dioxide, as a greenhouse gas responsible for the early warming of the Earths' surface. Our divergence times for the origin of anaerobic methanotrophy are compatible with highly depleted carbon isotopic values found in rocks dated 2.8-2.6 Ga. An early origin of phototrophy is consistent with the earliest bacterial mats and structures identified as stromatolites, but a 2.6 Ga origin of cyanobacteria suggests that those Archean structures, if biologically produced, were made by anoxygenic photosynthesizers. The resistance to desiccation of Terrabacteria and their elaboration of photoprotective compounds suggests that the common ancestor of this group inhabited land. If true, then oxygenic photosynthesis may owe its origin to terrestrial adaptations.
Methane/metabolism↗