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At least 757 records · Page 42

Seasonal Variations in Atmospheric Composition as Measured in Gale Crater, Mars

The Sample Analysis at Mars (SAM) instrument onboard the Mars Science Laboratory Curiosity rover measures the chemical composition of major atmospheric species (CO2, N2, 40Ar,O2, and CO) through a dedicated atmospheric inlet. We report here measurements of volume mixing ratios in Gale Crater using the SAM quadrupole mass spectrometer, obtained over a period of nearly 5 years (3 Mars years) from landing. The observation period spans the northern summer of MY31 and solar longitude (L(sub S)) of 175° through spring of MY 34, L(sub S) = 12°. This work expands upon prior reports of the mixing ratios measured by SAM QMS in the first 105 sols of the mission. The SAM QMS atmospheric measurements were taken periodically, with a cumulative coverage of four or five experiments per season on Mars. Major observations include the seasonal cycle of CO2, N2, and Ar, which lags approximately 20–40° of L(sub S) behind the pressure cycle driven by CO2 condensation and sublimation from the winter poles. This seasonal cycle indicates that transport occurs on faster timescales than mixing. The mixing ratio of O2 shows significant seasonal and interannual variability, suggesting an unknown atmospheric or surface process at work. The O2 measurements are compared to several parameters, including dust optical depth and trace CH4 measurements by Curiosity. We derive annual mean volume mixing ratios for the atmosphere in Gale Crater: CO2 = 0.951 (±0.003), N2 = 0.0259 (±0.0006), 40Ar = 0.0194 (±0.0004), O2 = 1.61 (±0.09) x 10(exp ‐3), and CO = 5.8 (±0.8) x 10(exp ‐4).

Gale Crater↗

Thermal and Chemical Characterization of Composite Materials. MSFC Center Director's Discretionary Fund Final Report, Project No. ED36-18

The purpose of this research effort was to: (1) provide a concise and well-defined property profile of current and developing composite materials using thermal and chemical characterization techniques and (2) optimize analytical testing requirements of materials. This effort applied a diverse array of methodologies to ascertain composite material properties. Often, a single method of technique will provide useful, but nonetheless incomplete, information on material composition and/or behavior. To more completely understand and predict material properties, a broad-based analytical approach is required. By developing a database of information comprised of both thermal and chemical properties, material behavior under varying conditions may be better understood. THis is even more important in the aerospace community, where new composite materials and those in the development stage have little reference data. For example, Fourier transform infrared (FTIR) spectroscopy spectral databases available for identification of vapor phase spectra, such as those generated during experiments, generally refer to well-defined chemical compounds. Because this method renders a unique thermal decomposition spectral pattern, even larger, more diverse databases, such as those found in solid and liquid phase FTIR spectroscopy libraries, cannot be used. By combining this and other available methodologies, a database specifically for new materials and materials being developed at Marshall Space Flight Center can be generated . In addition, characterizing materials using this approach will be extremely useful in the verification of materials and identification of anomalies in NASA-wide investigations.

Stanley, D. C.↗

Quantitative Low-Field 19 F Nuclear Magnetic Resonance Analysis of Carbonyl Groups in Pyrolysis Oils

Pyrolysis bio-oils, one of the products of lignocellulosic biomass pyrolysis, have the potential to be widely used as fuels. The chemical composition of bio-oils is very complicated as they contain hundreds, if not thousands, of different, mostly oxygen-containing, compounds with a wide distribution of physical properties, chemical structures, and concentrations. Detailed knowledge of bio-oil composition is crucial for optimizing both the pyrolysis processes and for any subsequent upgrading into a more viable fuel resource. Here we report the successful use of low-field, or benchtop, nuclear magnetic resonance (NMR) spectrometers in the analysis of pyrolysis oils. Pyrolysis oils from four different feedstocks were derivatized and analyzed using 19 F NMR techniques. The NMR results compare favorably with titrations for total carbonyl content. In addition, the benchtop NMR spectrometer proves able to reveal key spectral features, thus allowing the quantification of different carbonyl groups, such as aldehydes, ketones and quinones. Benchtop NMR spectrometers are typically compact, cheaper than their superconducting counterparts and do not require cryogens. Their use will make NMR analysis of pyrolysis oils easier and more accessible to a wide range of different potential users.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

MXene-Derived Potassium-Preintercalated Bilayered Vanadium Oxide Nanostructures for Cathodes in Nonaqueous K-Ion Batteries

Bilayered vanadium oxides (BVOs) are promising cathode materials for beyond-Li-ion batteries due to their tunable chemistries and high theoretical capacities. However, the large size of beyond-Li + ions limits electrochemical cycling and rate capability of BVO electrodes. Recent reports of MXene-derived BVOs with nanoscale flower-like morphology have shown improved electrochemical stability at high rates up to 5C in nonaqueous lithium-ion batteries. Here, we report how morphological stabilization can lead to improved rate capability in potassium-ion batteries (PIBs) through the synthesis and electrochemical characterization of MXene-derived K-preintercalated BVOs (MD-KVOs), which were derived from two V 2 CT x precursor materials prepared using two different etching protocols. We show that the etching conditions affect the surface chemistry of the MXene, which plays a role in the MXene-to-oxide transformation process. MXene derived from a milder etchant transformed into a nanoflower MD-KVO with two-dimensional (2D) nanosheet petals (KVO-DMAE) while a more aggressive etchant produced a MXene that transformed into a MD-KVO with one-dimensional (1D) nanorod morphology (KVO-CMAE). Electrochemical cycling of the produced MD-KVOs after drying at 200 °C under vacuum (KVO-DMAE-200 and KVO-CMAE-200) in PIBs showed that electrochemical stability of MD-KVO at high rates improved through the morphological stabilization of 2D particles combined with the control of interlayer water and K + ion content. Structure refinement of KVO-DMAE-200 further corroborates the behavior observed during K + ion cycling, connecting structural and compositional characteristics to the improved rate capability. This work demonstrates how proper synthetic methodology can cause downstream effects in the control of structure, chemical composition, and morphology of nanostructured layered oxide materials, which is necessary for development of future materials for beyond-Li-ion battery technologies.

25 ENERGY STORAGE↗

A Swing of the Pendulum: The Chemodynamics of the Local Stellar Halo Indicate Contributions from Several Radial Merger Events

We find that the chemical abundances and dynamics of APOGEE and GALAH stars in the local stellar halo are inconsistent with a scenario in which the inner halo is primarily composed of debris from a single massive, ancient merger event, as has been proposed to explain the Gaia-Enceladus/Gaia Sausage (GSE) structure. The data contain trends of chemical composition with energy that are opposite to expectations for a single massive, ancient merger event, and multiple chemical evolution paths with distinct dynamics are present. We use a Bayesian Gaussian mixture model regression algorithm to characterize the local stellar halo, and find that the data are fit best by a model with four components. We interpret these components as the Virgo Radial Merger (VRM), Cronus, Nereus, and Thamnos; however, Nereus and Thamnos likely represent more than one accretion event because the chemical abundance distributions of their member stars contain many peaks. Although the Cronus and Thamnos components have different dynamics, their chemical abundances suggest they may be related. We show that the distinct low- and high-α halo populations from Nissen & Schuster are explained by VRM and Cronus stars, as well as some in situ stars. Because the local stellar halo contains multiple substructures, different popular methods of selecting GSE stars will actually select different mixtures of these substructures, which may change the apparent chemodynamic properties of the selected stars. We also find that the Splash stars in the Solar region are shifted to higher v $\phi$ and slightly lower [Fe/H] than previously reported.

79 ASTRONOMY AND ASTROPHYSICS↗

Chemistry and Petrology of Chondrules from the Mokoia CV Chondrite

Bulk chemical compositions of 94 chondrules from Mokoia have been obtained by INAA. Elemental abundances are correlated with petrology. Chemical and petrological properties are very similar to chondrules from Allende and do not show strong alteration signatures.

Jones, R. H.↗

Metallographic Preparation of Space Shuttle Reaction Control System Thruster Electron Beam Welds for Electron Backscatter Diffraction

A Space Shuttle Reaction Control System (RCS) thruster failed during a firing test at the NASA White Sands Test Facility (WSTF), Las Cruces, New Mexico. The firing test was being conducted to investigate a previous electrical malfunction. A number of cracks were found associated with the fuel closure plate/injector assembly (Fig 1). The firing test failure generated a flight constraint to the launch of STS-133. A team comprised of several NASA centers and other research institutes was assembled to investigate and determine the root cause of the failure. The JSC Materials Evaluation Laboratory was asked to compare and characterize the outboard circumferential electron beam (EB) weld between the fuel closure plate (Titanium 6Al-4V) and the injector (Niobium C-103 alloy) of four different RCS thrusters, including the failed RCS thruster. Several metallographic challenges in grinding/polishing, and particularly in etching were encountered because of the differences in hardness, ductility, and chemical resistance between the two alloys and the bimetallic weld. Segments from each thruster were sectioned from the outboard weld. The segments were hot-compression mounted using a conductive, carbon-filled epoxy. A grinding/polishing procedure for titanium alloys was used [1]. This procedure worked well on the titanium; but a thin, disturbed layer was visible on the niobium surface by means of polarized light. Once polished, each sample was micrographed using bright field, differential interference contrast optical microscopy, and scanning electron microscopy (SEM) using a backscatter electron (BSE) detector. No typical weld anomalies were observed in any of the cross sections. However, areas of large atomic contrast were clearly visible in the weld nugget, particularly along fusion line interfaces between the titanium and the niobium. This prompted the need to better understand the chemistry and microstructure of the weld (Fig 2). Energy Dispersive X-Ray Spectroscopy (EDS) was used to confirm the chemical composition of the variations in contrast in these areas. Niobium alloys generally require exposure to more aggressive chemical reagents than titanium alloys for etching because of niobium s chemical resistance; therefore, the titanium portion of the sample was etched first. A five second immersion in Kroll s reagent revealed a general microstructure on the titanium portion of the sample; however, the titanium heat affected zone closest to the weld, was over-etched due to higher concentrations of refined grains and an increase in eta-phase. The Kroll s etchant also revealed some microstructure in the weld nugget itself; the niobium portion of the sample remained unetched.

Martinez, James↗

Mineralogy versus bulk composition of the carbonaceous chondrite clast Kaidun 2

Kaidun is an unusual chondritic meteorite. Its main mass is of CR-type (Kaidun I) and contains CI-like (Kaidun II), EL, and EH clasts. The classification of Kaidun II based on mineralogy and bulk chemical criteria does not allow an unambigious assignment to CI. Here we report on the bulk chemical composition and the mineralogy of the Kaidun II clasts. The results of our investigation show that Kaidun II has some characteristics of both CI and CM chondrites. A possible relationship to the texture and composition of micrometeorites is indicated. The Kaidun II clast shows some conflicting mineralogical and chemical characteristics that do not allow an unambigious assignment to the well established carbonaceous chondrite classes. The overall texture of the matrix-rich clast and morphology of opaques are typical for CI's. Bulk matrix and bulk sample compositions reveal similarities with CM's. In addition, the presence of low-Fe Mn-enriched olivines and the relatively high abundance of enstatite resembles some micrometeorites.

Brandstaetter, F.↗

Clay minerals in primitive meteorites and interplanetary dust 1

Many meteorites and interplanetary dust particles (IDPs) with primitive compositions contain significant amounts of phyllosilicate minerals, which are generally interpreted as evidence of protoplanetary aqueous alteration at an early period of the solar system. These meteorites are chondrites (near solar composition) of the carbonaceous and ordinary varieties. The former are subdivided (according to bulk composition and petrology) into CI, CM, CV, CO, CR, and ungrouped classes. IDPs are extraterrestrial particulates, collected in stratosphere, which have chemical compositions indicative of a primitive origin; they are typically distinct from the primitive meteorites. Characterization of phyllosilicates in these materials is a high priority because of the important physico-chemical information they hold. The most common phyllosilicates present in chondritic extraterrestrial materials are serpentine-group minerals, smectites, and micas. We discuss these phyllosilicates and describe the interpretation of their occurrence in meteorites and IDPs and what this indicates about history of their parent bodies, which are probably the hydrous asteroids.

Zolensky, M. E.↗

The effects of sequential hydrothermal-mechanical refining pretreatment on cellulose structure changes and sugar recoveries

The recalcitrance of lignocellulosic biomass necessitates an efficient pretreatment protocol for operating a successful cellulosic biorefinery. It is critical to improve cellulose accessibility for hydrolysis and fermentation by altering the plant cell wall’s physical structure and chemical composition. Sequential hydrothermal-mechanical refining pretreatment (HMR) allows efficient recovery of cellulosic sugars without utilizing any hazardous chemicals. HMR has been successfully applied to Liberty switchgrass, a bioenergy cultivar released by the USDA, and now it is being applied to oilcane, a recently developed transgenic sugarcane variety engineered to accumulate lipids in its vegetative tissues. Sugar yields of oilcane bagasse (OCB) and switchgrass (SG) treated with HMR are 96.4% and 75.4%, respectively. This study sought to correlate cellulosic sugar yields with structural changes within the cell wall caused by HMR on two distinct bioenergy crops. Simon’s staining technique for the specific surface area analysis showed that HMR increased the specific surface area of pretreated biomass residues by 80–112%. In addition, ATR-FTIR was performed to determine the effects of HMR on physical structures based on the total crystallinity index (TCI) and hydrogen bonding intensity (HBI). Irrespective of biomass type, HMR decreased the initial crystalline cellulose contents of untreated biomass residues by 3.5% and reduced TCI and HBI by 7–13%. Here, the study found that sugar yields were negatively correlated to reducing values of hydrogen bonding intensity, crystalline cellulose content, and total crystallinity index.

09 BIOMASS FUELS↗

Emerging continuous SiC fibers for high-temperature applications

Silicon carbide (SiC) fibers are responsible for the ultimate strength and toughness of SiC-fiber reinforced composites in harsh environments. The development of a new generation of continuous SiC fibers continues to advance the mechanical properties of composite materials. Tyranno™ SA4 fiber was recently released as a successor of Tyranno™ SA3 fiber. Laser-driven chemical vapor deposition (LCVD) has been adopted as an alternative fiber processing route to synthesizing high-strength SiC fiber with tailorable small diameters and chemical compositions. Both Tyranno™ SA4 and laser-driven CVD fibers show very high tensile strength, about 4 GPa in the as-fabricated condition. The degradation of thermal stability and strength due to annealing in an inert environment were similar for Tyranno™ SA3 and SA4 fibers because of their similar carbon-rich, crystalline microstructure. Silicon-rich fibers produced by LCVD possessed heterogeneous crystallinity, which was attributed to laser power distribution and showed microstructural instability at 1500 °C and above. Finally, the new SiC fibers demonstrated an increase in as-fabricated strength but faced the same challenges in environmental resistance as the traditional SiC fibers do.

36 MATERIALS SCIENCE↗

Squeezed Light Stimulated Raman Scattering (SRS) Microscopy for Bioenergy Applications

Stimulated Raman scattering (SRS) microscopy using picosecond near-IR pulses have provided a great penetration depth with reduced fluorescence interference when imaging biological samples for bioenergy applications. These tools have provided insight into 1) tracking the degradation of chemical composites in biomass feedstocks to investigate the recalcitrant factors during the deconstruction processes, 2) monitoring the production of chemicals in photosynthetic plants and wood-digesting microorganisms, and 3) probing plant-bacteria interactions. However, the above processes are usually slow and require continuous imaging for an extended period. This is challenging for classic SRS because the laser power needed to achieve enough sensitivity causes photodamage in the samples during such long experiments. Quantum-squeezed light with reduced noise in the intensity quadrature can improve the sensitivity of classic SRS microscopy beyond the shot noise limit. The successful squeezing of one of the picosecond pulses in the above SRS will improve sensitivity and reduce photodamage, greatly expanding the range of studies available to SRS microscopy.

BIOMASS FUELS↗

Improved field assessments of chemicals and explosives using high-resolution gamma-ray spectroscopy with a tagged neutron interrogation system

A field-portable tagged neutron interrogation system is being developed for detection of explosives and chemical warfare agents by prompt γ-ray neutron activation analysis. The system combines an associated particle imaging deuterium-tritium neutron generator with a high-purity germanium γ-ray detector. Fine spatial resolution neutron and α detectors enable precise mapping of characteristic γ-ray emission distributions onto high-clarity neutron radiographic images. A narrow coincidence gate associated with each tagged neutron ensures a large signal-to-background ratio, thus significantly improving sensitivity to the chemical compositions of the items being assessed. Recent experimental results recorded from test objects involving mock explosives and other chemicals are presented.

Bucher, Brian [Idaho National Laboratory (INL)]↗

Data for The Effects of Sequential Hydrothermal-Mechanical Refining Pretreatment on Cellulose Structure Changes and Sugar Recoveries

The recalcitrance of lignocellulosic biomass necessitates an efficient pretreatment protocol for operating a successful cellulosic biorefinery. It is critical to improve cellulose accessibility for hydrolysis and fermentation by altering the plant cell wall’s physical structure and chemical composition. Sequential hydrothermal-mechanical refining pretreatment (HMR) allows efficient recovery of cellulosic sugars without utilizing any hazardous chemicals. HMR has been successfully applied to Liberty switchgrass, a bioenergy cultivar released by the USDA, and now it is being applied to oilcane, a recently developed transgenic sugarcane variety engineered to accumulate lipids in its vegetative tissues. Sugar yields of oilcane bagasse (OCB) and switchgrass (SG) treated with HMR are 96.4% and 75.4%, respectively. This study sought to correlate cellulosic sugar yields with structural changes within the cell wall caused by HMR on two distinct bioenergy crops. Simon’s staining technique for the specific surface area analysis showed that HMR increased the specific surface area of pretreated biomass residues by 80-112%. In addition, ATR-FTIR was performed to determine the effects of HMR on physical structures based on the total crystallinity index (TCI) and hydrogen bonding intensity (HBI). Irrespective of biomass type, HMR decreased the initial crystalline cellulose contents of untreated biomass residues by 3.5% and reduced TCI and HBI by 7-13%. The study found that sugar yields were negatively correlated to reducing values of hydrogen bonding intensity, crystalline cellulose content, and total crystallinity index.

Biomass Analytics↗

An application of artificial intelligence to the interpretation of mass spectra.

Description of the DENDRAL (Dendritic Algorithm) project, the objectives of which were to base the computer program on an alogorithm that generates an exhaustive, nonredundant list of all the structural isomers of a given chemical composition, and to devise a computer program that would perform an organic structure determination, given a molecular formula and a mass spectrum. This program is called 'Heuristic DENDRAL' and it operates by using the known structure/spectrum correlations to constrain the DENDRAL isomer generator to produce a single isomer for that composition. The collaboration of chemists and computer scientists has produced a tool of some practical utility from the chemical viewpoint, and an interesting program from the viewpoint of artificial intelligence.

Buchanan, B. G.↗

Continuous Monitoring of Aerosols

Online spectrometer monitors composition of individual aerosol particles. Single aerosol particles up to about 5 microns in diameter are analyzed for chemical composition, yielding valuable information on nature of pollution source. Tests show system has promise for monitoring oxidation of sulfur dioxide to sulfates important in controlling pollution from coal-fired power plants.

Mahadeva, S. P.↗