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At least 1,405 records · Page 78

Spacecraft Materials Degradation Under Space-Simulated Low Earth Orbit (LEO) Environment

External spacecraft materials play an important role in satellite protection from the harsh space environment. Research has shown that the physical, chemical, and optical properties of matter change continuously as a result of exposure to solar radiation and aggressive chemical species produced in Earth’s upper atmosphere. Thorough knowledge of the material properties evolution throughout a planned mission lifetime helps to improve the reliability of spacecraft. Moreover, the establishment of correlation factors between true space exposure and accelerated space weather experiments at ground facilities enables accurate prediction of on-orbit material performance based on laboratory-based testing. The presented work aims to evaluate the radiation effects of low Earth orbit (LEO) environment, namely, exposure to the high-energy electrons, atomic oxygen (AO), and vacuum ultraviolet (VUV), of several modern spacecraft materials. The studied materials represent the “flight duplicates” of samples that are launched as a part of the 16th Materials International Space Station Experiment Flight Facility (MISSE-FF) mission in 2022.

Elena Plis↗

Heterogeneous Outgassing Regions Identified on Active Centaur 29P/Schwassmann–Wachmann 1

Centaurs are transitional objects between primitive trans-Neptunian objects and Jupiter-family comets. Their compositions and activities provide fundamental clues regarding the processes affecting the evolution of and interplay between these small bodies. Here we report observations of centaur 29P/Schwassmann–Wachmann 1 (29P) with the James Webb Space Telescope (JWST). We identified localized jets with heterogeneous compositions driving the outgassing activity. We employed the NIRSpec mapping spectrometer to study the fluorescence emissions of CO and obtain a definitive detection of CO 2 for this target. The exquisite sensitivity of the instrument also enabled carbon and oxygen isotopic signatures to be probed. Molecular maps reveal complex outgassing distributions, such as jets and anisotropic morphology, which indicate that 29P’s nucleus is dominated by active regions with heterogeneous compositions. These distributions could reflect that it has a bilobate structure with compositionally distinct components or that strong differential erosion takes place on the nucleus. As there are no missions currently planning to visit a centaur, these observations demonstrate JWST’s unique capabilities in characterizing these objects.

Sara Faggi↗

Correlating the phase evolution and anionic redox in Co-Free Ni-Rich layered oxide cathodes

Current trend of high-capacity Ni-rich layered cathode is to develop high-Ni and low-Co or Co-free oxides. The high Ni content layered oxides provide great advantages in capacity, cost and environmental benignity, similar to LiNiO 2 parent compound. But they also inherit drawbacks in structural and chemical instability at high voltages upon cycling. As such, elemental substitution plays a profound role in addressing these challenges. This work elucidates the roles of Al doping in cationic redox and anionic oxygen activity in LiAl x Ni 1-x O 2 using combined X-ray absorption spectroscopy (XAS), resonant inelastic X-ray scattering (RIXS) as well as operando differential electrochemical mass spectrometry (DEMS). Using synchrotron wide-angle X-ray scattering (WAXS), we extrapolate a general principle of phase transition and its coupling with lattice anionic oxygen redox. These findings shed light on the advancement of high-capacity, stable-cycling and safe-operating Ni-rich cathode materials for next generation Li-ion batteries.

25 ENERGY STORAGE↗

Intermittent Defect Fluctuations in Oxide Heterostructures

Abstract The heterogeneous nature, local presence, and dynamic evolution of defects typically govern the ionic and electronic properties of a wide variety of functional materials. While the last 50 years have seen considerable efforts into development of new methods to identify the nature of defects in complex materials, such as the perovskite oxides, very little is known about defect dynamics and their influence on the functionality of a material. Here, the discovery of the intermittent behavior of point defects (oxygen vacancies) in oxide heterostructures employing X‐ray photon correlation spectroscopy is reported. Local fluctuations between two ordered phases in strained SrCoO x with different degrees of stability of the oxygen vacancies are observed. Ab‐initio‐informed phase‐field modeling reveals that fluctuations between the competing ordered phases are modulated by the oxygen ion/vacancy interaction energy and epitaxial strain. The results demonstrate how defect dynamics, evidenced by measurement and modeling of their temporal fluctuations, give rise to stochastic properties that now can be fully characterized using coherent X‐rays, coupled for the first time to multiscale modeling in functional complex oxide heterostructures. The study and its findings open new avenues for engineering the dynamical response of functional materials used in neuromorphic and electrochemical applications.

36 MATERIALS SCIENCE↗

Mechanistic understanding of speciated oxide growth in high entropy alloys

Abstract Complex multi-element alloys are gaining prominence for structural applications, supplementing steels, and superalloys. Understanding the impact of each element on alloy surfaces due to oxidation is vital in maintaining material integrity. This study investigates oxidation mechanisms in these alloys using a model five-element equiatomic CoCrFeNiMn alloy, in a controlled oxygen environment. The oxidation-induced surface changes correlate with each element’s interactive tendencies with the environment, guided by thermodynamics. Initial oxidation stages follow atomic size and redox potential, with the latter becoming dominant over time, causing composition inversion. The study employs in-situ atom probe tomography, transmission electron microscopy, and X-ray absorption near-edge structure techniques to elucidate the oxidation process and surface oxide structure evolution. Our findings deconvolute the mechanism for compositional and structural changes in the oxide film and will pave the way for a predictive design of complex alloys with improved resistance to oxidation under extreme conditions.

36 MATERIALS SCIENCE↗

RESOLVE 2010 Field Test

This slide presentation reviews the field tests conducted in 2010 of the Regolith Environment Science & Oxygen & Lunar Volatile Extraction (RESOLVE). The Resolve program consist of several mechanism: (1) Excavation and Bulk Regolith Characterization (EBRC) which is designed to act as a drill and crusher, (2) Regolith Volatiles Characterization (RVC) which is a reactor and does gas analysis,(3) Lunar Water Resources Demonstration (LWRD) which is a fluid system, water and hydrogen capture device and (4) the Rover. The scientific goal of this test is to demonstrate evolution of low levels of hydrogen and water as a function of temperature. The Engineering goals of this test are to demonstrate:(1) Integration onto new rover (2) Miniaturization of electronics rack (3) Operation from battery packs (elimination of generator) (4) Remote command/control and (5) Operation while roving. Views of the 2008 and the 2010 mechanisms, a overhead view of the mission path, a view of the terrain, the two drill sites, and a graphic of the Master Events Controller Graphical User Interface (MEC GUI) are shown. There are descriptions of the Gas chromatography (GC), the operational procedure, water and hydrogen doping of tephra. There is also a review of some of the results, and future direction for research and tests.

Captain, J.↗

Ground Testing of the MISSE-16 Materials

External spacecraft materials play an important role in satellite protection from the harsh space environment. Research has shown that the physical, chemical, and optical properties of matter change continuously as a result of exposure to solar radiation and aggressive chemical species produced in Earth’s upper atmosphere. Thorough knowledge of the material properties evolution throughout a planned mission lifetime helps to improve the reliability of spacecraft. Moreover, the establishment of correlation factors between true space exposure and accelerated space weather experiments at ground facilities enables accurate prediction of on-orbit material performance based on laboratory-based testing. The presented work aims to evaluate the radiation effects of low Earth orbit (LEO) environment, namely, exposure to the high-energy electrons and atomic oxygen (AO), of heritage and novel spacecraft materials selection. The studied materials represent the “flight duplicates” of samples that are launched as a part of the 16th Materials International Space Station Experiment Flight Facility (MISSE-FF) mission in 2022.

Elena A. Plis↗

Biochemical Process Modeling and Simulation (BPMS)

The Biochemical Process Modeling and Simulation project aims to reduce the cost and time of research by applying theory, modeling, and simulation to the most relevant bottlenecks in the biochemical process. We use molecular modeling, quantum mechanics, metabolic modeling, fluid dynamics, and reaction-diffusion methods in close collaboration with pretreatment, hydrolysis, upgrading, and TEA. The project's outcomes are increased yields and efficiency of the biochemical process, added value to products, and reduced price of fuels by specifically targeting catalytic efficiency, reactor design, enzyme efficiency, and microbial design. We work closely with experimental projects to identify problems and iterate with experiments to find and refine solutions. By working with experimentalists, we decide on problems that can be solved with simulation that could otherwise not be solved or would take too long with experiment alone to reach BETO's targets. Over the years, we have produced solutions that have resulted in determining the most likely fatty-acid derivative for passive transport out of bacteria that upgrade biomass, and we have also designed enzyme mutations for enhanced lignin upgrading. Metabolic models have been developed to tune the activity of 2,3 butanediol production for the 2030 target. A computational method to deliver understanding of how complex omics data can be interpreted in the metabolic pathways of organisms used in the Agile Biofoundry. We have found methods to overcome specific barriers and continue to develop those methods. Our reactor studies have guided the design of both the microbes and reactors for aerobic and micro-aerobic production at all scales and have been instrumental in improving the accuracy of techno-economic analysis models. This project is essential in the process of selecting the final processes for 2030 SAF production targets. More specifically, recently, we have: 1) Predicted the strength of the basic structural interactions in commodity plastics to provide guidance for plastics upcycling strategies. 2) Developed computational tool to improve the characterization of lignin-derived compounds 3) Developed new methodologies to enable Machine Learning-based Directed Evolution for protein engineering. 4) Developed Machine Learning methods to predict protein promiscuity and mutations to further improve microbial and enzymatic driven processes and demonstrated the utility of ML approaches to engineering proteins from sparse experimental datasets. 5) Developed new methods to enable high-fidelity simulation of aerobic fermentation at industrial scale and resolving mismatch of time scales through subcycling/operator splitting 7) Identified the difficulty in preventing local high-oxygen conditions in industrial bubble columns, which leads to less-desirable acetoin production, suggesting future research directions in alternative reactor configurations (e.g loop reactors, shallow-channel reactors).

BIOMASS FUELS↗

Paleosols and the chemical evolution of the atmosphere

The chemistry and mineralogy of soils reflects the chemistry of the atmosphere below which they develop. Today the presence of a cover of land plants can obscure the signature of a highly oxidizing atmosphere. Prior to the advent of higher land plants ca. 400 m.y. ago the obscuring effect of a biological interface should have been minor. It can be shown that under such conditions the behavior of ferrous iron during weathering depends on the relationship between the ratio of the net concentration of oxidants to the concentration of acids in rainwater, and on the ratio of the oxygen demand to the acid demand for complete weathering of the parent rock. An analysis of the behavior of iron in some 15 paleosols between 1.0 and 2.9 b.y. in age showed some time ago that iron was retained, or largely retained, in paleosols developed on rocks with a low ratio of oxidant demand to acid demand (R value) and was lost from paleosols with a high R value. The results indicate that between 1.1 and 2.9 b.y.b.p. the ratio of the net concentration of oxidants to CO2 in rainwater was less than ca. 1/600 of the present-day value. Work during the past year has sought to extend the data base for paleosols and to define more precisely the relationships between the composition of paleosols and the chemistry of the atmosphere below which they developed.

Holland, H. D.↗

Oxygen Isotope Compositions of the Kaidun Meteorite - Indications for Aqeuous Alteration of E-Chondrites

The Kaidun microbreccia is a unique meteorite due to the diversity of its constituent clasts. Fragments of various types of carbonaceous (CI, CM, CV, CR), enstatite (EH, EL), and ordinary chondrites, basaltic achondrites, and impact melt products have been described, and also several unknown clasts [1, and references therein]. The small mm-sized clasts represent material from different places and times in the early solar system, involving a large variety of parent bodies [2]; meteorites are of key importance to the study of the origin and evolution of the solar system, and Kaidun is a collection of a range of bodies evidently representing samples from across the asteroid belt. The parent-body on which Kaidun was assembled is believed to be a C-type asteroid, and 1-Ceres and the martian moon Phobos have been proposed [1-4]. Both carbonaceous (most oxidized) and enstatite (most reduced) chondrite clasts in Kaidun show signs of aqueous alterations that vary in type and degree and are most likely of pre-Kaidun origin [1, 4].

Ziegler, K.↗

X-ray Diffraction of Water in Polyvinylpyrrolidone

PVP is a hydrophilic polymer commonly used as an excipient in pharmaceutical formulations. Here we have performed time-resolved high-energy X-ray scattering experiments on pellets of PVP at different humidity conditions for 1-2 days. A two-phase exponential decay in water sorption is found with a peak in the differential pair distribution function at 2.85 Å, which is attributed to the average (hydrogen bonded) carbonyl oxygen-water oxygen distance. Additional scattering measurements on powders with fixed compositions ranging from 2 to 12.3 wt % H 2 O were modeled with Empirical Potential Structure Refinement (EPSR). Further, the models reveal approximately linear relations between the carbonyl oxygen-water oxygen coordination number (nO C - O W ) and the water oxygen-water oxygen coordination number (nO W - O W ) versus water content in PVP. A stronger preference for water-water hydrogen bonding over carbonyl-water bonding is found. At all the concentrations studied the majority of water molecules were found to be randomly isolated, but a wide distribution of coordination environments of water molecules is found within the PVP polymer strands at the highest concentrations. Overall, the EPSR models indicate a continuous evolution in structure versus water content with nO W - O W =1 occurring at similar to 12 wt % H 2 O, i.e., the composition where, on average, each watermolecule is surrounded by one other water molecule.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A new model for plasma transport and chemistry at Saturn

A model of plasma transport and chemistry is described which calculates the evolution of a plasma population in latitude and radial distance. This model is applied to the magnetosphere of Saturn, where it is used to fit the density profile of the heavy ions assuming both satellite and ring sources of plasma. Use of an extended source region is found to significantly alter the resulting plasma profile. Water ions cannot fit the observed density profile inside L = 6 even with a large ring source. Oxygen ions can fit the density profile throughout the region inside L = 12 given a suitable profile of neutral hydrogen; a suitable profile contains up to 5 H/cu cm outside L = 4 with the number increasing inside this. Preferred values of K are 1-3 x 10 exp -10 R(S)2/s, but any value K less than 10 exp -9 R(S)2/s can be accommodated. The temperature profile is shown to favor models invoking in situ plasma formation and loss as opposed to models where transport is important.

Richardson, John D.↗

Formation and Stability of Radiation Products in Europa's Icy Shell

Spectra of Europa reveal a surface dominated by water-ice along with hydrated materials and minor amounts of SO2, CO2, and H2O2. Jovian magnetospheric ions (protons, sulfur, and oxygen) and electrons produce significant chemical modifications of the surface on time scales of a few years at micrometer depths. Our laboratory studies examine the formation and stability of radiation products in H2O-rich ices relevant to Europa. Infrared (IR) spectra of ices before and after irradiation reveal the radiation destruction of molecules and the formation of products at 86 - 132 K. In addition, spectra of ices during warming track thermal evolution due to chemical changes and sublimation processes. IR-identified radiation products in 86 - 132 K irradiated H2O + SO2 ices are the bisulfate ion, HSO4(-), sulfate ion, SO4(2-) and the hydronium ion, H3O(+). Warming results in the formation of a residual spectrum similar to liquid sulfuric acid, H2SO4, for H2O:SO2 ratios of 30:1, whereas hydrated sulfuric acid, H2SO4 4 H2O, forms for ratios of 30:1. Radiation products identified for irradiated H2O + H2S ices at 86 K are H2S2 and SO2. When irradiated at 110 and 132 K, ices with H2O:H2S ratios if either 3:1 or 30:1 show the formation of H2SO4 4 H2O on warming to 175 K. We have also examined the radiation stability of H2SO4. Addition of CO2 to H2O + SO2 ices results in the formation of CO3 at 2046 cm (sup -1) (4.89 m). This is the strongest band from a carbon-containing product in the mid-IR spectral region, and it is also seen when either pure CO2 or H2O + CO2 ice is irradiated. Experiments with CH4 added to H2O + SO2 + CO2 ices addressed the question of methane's use as a marker of methanogens in an irradiated ice environment. New results on the near-IR spectrum of pure H2O2 will be included in this presentation. Interpretations of near-IR water bands, with H2O2 present, will be discussed. Irradiations of H2O2 and H2O + H2O2 mixtures, to examine the possibility of O2 and O3 formation, are currently under investigation and new results will be discussed.

Moore, M. H.↗

Theoretical constraints on oxygen and carbon dioxide concentrations in the Precambrian atmosphere

Simple (one-dimensional) climate models suggest that carbon dioxide concentrations during the Archean must have been at least 100-1000 times the present level to keep the Earth's surface temperature above freezing in the face of decreased solar luminosity. Such models provide only lower bounds on CO2, so it is possible that CO2 levels were substantially higher than this and that the Archean climate was much warmer than today. Periods of extensive glaciation during the early and late Proterozoic, on the other hand, indicate that the climate at these times was relatively cool. To be consistent with climate models CO2 partial pressures must have declined from approximately 0.03 to 0.3 bar around 2.5 Ga ago to between 10(-3) and 10(-2) bar at 0.8 Ga ago. This steep decrease in carbon dioxide concentrations may be inconsistent with paleosol data, which implies that pCO2 did not change appreciably during that time. Oxygen was essentially absent from the Earth's atmosphere and oceans prior to the emergence of a photosynthetic source, probably during the late Archean. During the early Proterozoic the atmosphere and surface ocean were apparently oxidizing, while the deep ocean remained reducing. An upper limit of 6 x 10(-3) bar for pO2 at this time can be derived by balancing the burial rate of organic carbon with the rate of oxidation of ferrous iron in the deep ocean. The establishment of oxidizing conditions in the deep ocean, marked by the disappearance of banded iron formations approximately 1.7 Ga ago, permitted atmospheric oxygen to climb to its present level. O2 concentrations may have remained substantially lower than today, however, until well into the Phanerozoic.

Review, Tutorial↗

Investigating the History of Aubrites Using X-Ray Computed Tomography and Bulk Partition Coefficients

The aubrites are a unique group of differentiated meteorites that formed on parent bodies with oxygen fugacities (ƒO2) from ~2 to ~6 log units below the iron-wustite buffer. At these highly reduced condi- tions, elements deviate from the geochemical behavior exhibited at terrestrial ƒO2, and may form FeO-poor silicates, Si-bearing metals, and exotic sulfides. Geochemical examinations of aubrites, such as mineral major-element compositions, bulk-rock compositions, O isotopes, and crystallization ages, are crucial to understand their formation and evolution at extreme ƒO2 conditions. In this study, we determine partitioning relationships of elements between bulk silicate, sulfide, and metal phases within aubrites, and compare the results to partition coefficients determined from petrologic experiments run under mercurian conditions. While previous studies have described the petrology and 2D modal abundances of aubrites, this work provides the first 3D view of aubritic mineralogies, which are com- pared to the available 2D data. Constraints of 3D modal abundances will increase the accuracy of computed bulk distribution coefficients; therefore, 3D scans of aubrite samples are imperative. We utilize X-ray computed tomogra- phy (XCT) to non-destructively analyze the distribution and abundances of mineral phases in aubrites and locate composite clasts of sulfide grains for future analysis.

Wilbur, Z. E.↗

The evolution of water vapor in the atmosphere of Venus.

Examination of the feasibility of loss of water vapor from the Venus atmosphere, assuming H2O as the sole initial constituent. A steady-state model is constructed, and the photochemistry establishes the distribution of important products in the upper atmosphere. Calculations of exospheric temperatures yield values as high as 100,000 K. Such large temperatures result from the large abundance of atomic hydrogen in the exosphere, and imply a dynamic outflow of all constituents from the upper region of the atmosphere. Such an outflow would cause the escape of all hydrogen and some of the oxygen resulting from dissociation of H2O. Little loss of CO2 would result, due to its low abundance in the upper region, permitting its accumulation to the present observed value. It is concluded that if Venus formed from the same mix of materials as the earth, much tectonic activity and fairly rapid outgassing must have occurred during the early phase of its history to account for the loss of water vapor.

Smith, L. L.↗

Origin of structural degradation in Li-rich layered oxide cathode

Li- and Mn-rich (LMR) cathode materials that utilize both cation and anion redox can yield substantial increases in battery energy density 1,2,3 . However, although voltage decay issues cause continuous energy loss and impede commercialization, the prerequisite driving force for this phenomenon remains a mystery 3,4,5,6 In this work, with in situ nanoscale sensitive coherent X-ray diffraction imaging techniques, we reveal that nanostrain and lattice displacement accumulate continuously during operation of the cell. Evidence shows that this effect is the driving force for both structure degradation and oxygen loss, which trigger the well-known rapid voltage decay in LMR cathodes. By carrying out micro- to macro-length characterizations that span atomic structure, the primary particle, multiparticle and electrode levels, we demonstrate that the heterogeneous nature of LMR cathodes inevitably causes pernicious phase displacement/strain, which cannot be eliminated by conventional doping or coating methods. We therefore propose mesostructural design as a strategy to mitigate lattice displacement and inhomogeneous electrochemical/structural evolutions, thereby achieving stable voltage and capacity profiles. These findings highlight the significance of lattice strain/displacement in causing voltage decay and will inspire a wave of efforts to unlock the potential of the broad-scale commercialization of LMR cathode materials.

25 ENERGY STORAGE↗

CO 2 reduction on pure Cu produces only H 2 after subsurface O is depleted: Theory and experiment

Significance Electrochemical reduction of CO 2 to fuels and valuable chemicals is a global imperative to address energy and climate challenges. Despite enormous efforts, there is not yet a commercial process. The best catalyst remains Cu metal, but a great deal of controversy revolves around the role of the presence of oxygen in the material. We combine theory and experiments to show that pure Cu without subsurface oxygen leads to no organic products. Thus, maintaining substantial oxygen at Cu surfaces is essential for long-term reduction of CO 2 to organics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗