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At least 883 records · Page 49

Vertical ascent from earth to geosynchronous orbit

The concept of ascending vertically from the equator on earth to the point in geosynchronous orbit directly above was investigated. The gravity losses were found to be so great that vertical ascent is not practical with only chemical-rocket propulsion. With laser propulsion, propellant requirements with vertical ascent are reduced and might allow the use of single-stage vehicles from earth to geosynchronous orbit. Combined or composite chemical and laser propulsion is shown to be useful. A gravity ladder suspended from geosynchronous orbit part of the distance to earth is shown to reduce the vehicle propulsion requirements.

Martin, J. A.↗

Stillwater anorthosites - A lunar analog?

Samples of anorthosite from Stillwater complex units AN-I and AN-II have been studied by instrumental neutron activation analysis for FeO, CaO, Na2O, REE, and other trace elements, and the results are discussed. No systematic variations of chemical composition with stratigraphic position were observed. The major and trace compositions of both units appear to be identical, with plagioclase compositions virtually constant throughout both. Thus, there is almost no evidence for evolution of parent magma composition during the genesis of these units. The bulk of the anorthosites appear to consist of cumulus-adcumulus plagioclase and pyroxene. Very little trapped liquid component was found. The chemical elements are not normally or lognormally distributed among samples taken from either anorthosite unit. The irregular distribution of pyroxene oikocrysts indicates that interstitial melt migrated substantially prior to final consolidation of the rock.

Salpas, P. A.↗

Aqueous Alteration and Hydrogen Generation on Parent Bodies of Unequilibrated Ordinary Chondrites: Thermodynamic Modeling for the Semarkona Composition

Ordinary chondrites are the most abundant class of meteorites that could represent rocky parts of solar system bodies. However, even the most primitive unequilibrated ordinary chondrites (UOC) reveal signs of mild alteration that affected the matrix and peripheral zones of chondrules. Major chemical changes include oxidation of kamacite, alteration of glass, removal of alkalis, Al, and Si from chondrules, and formation of phases enriched in halogens, alkalis, and hydrogen. Secondary mineralogical changes include formation of magnetite, ferrous olivine, fayalite, pentlandite, awaruite, smectites, phosphates, carbonates, and carbides. Aqueous alteration is consistent with the oxygen isotope data for magnetite. The presence of secondary magnetite, Ni-rich metal alloys, and ferrous silicates in UOC implies that H2O was the oxidizing agent. However, oxidation by H2O means that H2 is produced in each oxidative pathway. In turn, production of H2, and its redistribution and possible escape should have affected total pressure, as well as the oxidation state of gas, aqueous and mineral phases in the parent body. Here we use equilibrium thermodynamic modeling to explore water-rock reactions in UOC. The chemical composition of gas, aqueous, and mineral phases is considered.

Zolotov, M. Y.↗

Electronic structure manipulation via composition tuning for the development of highly conductive and acid-stable oxides

Exploring materials that simultaneously possess high conductivity and electrochemical stability is critical for various energy-conversion applications. In this study, our combined computations and experiments suggest the Mg–Ti–O chemical space for novel ternary oxide compounds offering high electrical conductivity and corrosion stability in acidic conditions to be potentially used as catalyst supporter of polymer electrolyte membrane fuel cells. High electrical conductivity (6.09 × 10 -1 S cm -1 ) is achieved at room temperature by tuning the chemical composition of Mg 1-x Ti 2+x O 5 while still maintaining good corrosion stability (1.2 × 10 -4 mA cm -2 after six days) in acidic conditions. Furthermore, we discover that a reducing gas environment during the synthesis increases the Ti solubility in Mg 1-x Ti 2+x O 5 with a reduced valence state of Ti, thus resulting in high conductivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Sensitivity of Joint Inversions of Seismic and Geodynamic Data to Mantle Viscosity

Seismic tomography has revealed the existence of large-scale velocity heterogeneities in the mantle. The interpretation of seismic velocity anomalies in terms of temperature and chemical composition is nonunique. We use geodynamic observations including gravity, plate motions, dynamic topography, and excess ellipticity of the core-mantle boundary combined with seismic observations to investigate the thermo-chemical structure of the mantle through joint inversions. An outstanding issue, however, is the physical connection between mantle density anomalies and the surface geodynamic observations, which requires knowledge of the mantle viscosity structure. Here we perform joint inversions assuming different viscosity profiles and examine the dependence of the results on the viscosity. We first assume that mantle heterogeneity is due to thermal variations, which places a constraint on the relation between seismic velocity and density, and we subsequently relax the constraint to allow for potential nonthermal effects. In all of our joint inversions, a nonthermal origin of density anomalies is required to explain the geodynamic data, though the amount varies with the assumed viscosity structure. A common observation is a high-density chemical signal in the center of the large low-shear-velocity provinces at the base of the mantle resulting in a near neutral or slightly dense overall buoyancy there. Using the derived density models and their corresponding viscosity profiles, we also calculate instantaneous mantle flow fields. The predicted flow fields derived from joint inversions are generally similar but are quite different from flow fields using density models derived from a posteriori scaling of pure seismic tomography models.

58 GEOSCIENCES↗

Effects of transparent conducting electrodes and hole transport layers on the performance of MAPbI 3 solar cells fabricated on PET substrates

Abstract This study investigates how the performance of perovskite solar cells (PSCs) made on polyethylene terephthalate (PET) substrates depends on transparent conducting electrodes (TCEs) and hole transport layers (HTLs). We fabricated PSCs using commercially available PET/TCEs and compared their performance with PSCs manufactured on Glass/indium tin oxide (ITO) substrates. Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) with varying levels of acidity and NiO nanoparticles were used as HTLs. The current density-voltage characteristics of PSCs made on PET/TCEs were found to be significantly lower when highly acidic PEDOT:PSS was used as the HTL. However, this was not observed for PSCs made on Glass/ITO. To investigate the interaction between HTL and TCE, atomic force microscopy was carried out after dipping the TCEs in PEDOT:PSS solutions of different acidity. X-ray photoelectron spectroscopy measurements further revealed differences in the chemical composition between ITO film on PET vs. on glass. Our results indicate that the performance of PSCs depends both on the TCE substrates and HTLs, which can be explained by their chemical interaction.

14 SOLAR ENERGY↗

The use of airborne imaging spectrometer data to determine experimentally induced variation in coniferous canopy chemistry

It was experimentally determined whether induced differences in forest canopy chemical composition can be detected using data from the Airborne Imaging Spectrometer (AIS). Treatments were applied to an even-aged forest of Douglas fir trees. Work to date has stressed wet chemical analysis of foilage samples and correction of AIS data. Plot treatments were successful in providing a range of foliar N2 concentrations. Much time was spent investigating and correcting problems with the raw AIS data. Initial problems with groups of drop out lines in the AIS data were traced to the tape recorder and the tape drive. Custom adjustment of the tape drive led to recovery of most missing lines. Remaining individual drop out lines were replaced using average of adjacent lines. Application of a notch filter to the Fourier transform of the image in each band satisfactorily removed vertical striping. The aspect ratio was corrected by resampling the image in the line direction using nearest neighbor interpolation.

Swanberg, Nancy A.↗

Heterogeneous Chemistry Related to Stratospheric Aircraft

Emissions from stratospheric aircraft that may directly or indirectly affect ozone include NO(y), H2O, soot and sulfuric acid. To fully assess the impact of such emissions, it is necessary to have a full understanding of both the homogeneous and heterogeneous transformations that may occur in the stratosphere. Heterogeneous reactions on stratospheric particles play a key role in partitioning ozone-destroying species between their active and reservoir forms. In particular, heterogeneous reactions tend to activate odd chlorine while deactivating odd nitrogen. Accurate modeling of the net atmospheric effects of stratospheric aircraft requires a thorough understanding of the competing effects of this activation/deactivation. In addition, a full understanding of the potential aircraft impacts requires that the abundance, composition and formation mechanisms of the particles themselves be established. Over the last three years with support from the High Speed Research Program, we have performed laboratory experiments to determine the chemical composition, formation mechanism, and reactivity of stratospheric aerosols.

Tolbert, Margaret A.↗

Detailed Studies on the Structure and Dynamics of Reacting Dusty Flows at Normal and Microgravity

Dusty reacting flows are of particular interest for a wide range of applications. Inert particles can alter the flammability and extinction limits of a combustible mixture. Reacting particles can release substantial amount of heat and can be used either for power generation or propulsion. Accumulation of combustible particles in air can result in explosions which, for example, can occur in grain elevators, during lumber milling and in mine galleries. Furthermore, inert particles are used as flow velocity markers in reacting flows, and their velocity is measured by non-intrusive laser diagnostic techniques. Despite their importance, dusty reacting flows have been less studied and understood compared to gas phase as well as sprays. The addition of solid particles in a flowing gas stream can lead to strong couplings between the two phases, which can be of dynamic, thermal, and chemical nature. The dynamic coupling between the two phases is caused by the inertia that causes the phases to move with different velocities. Furthermore, gravitational, thermophoretic, photophoretic, electrophoretic, diffusiophoretic, centrifugal, and magnetic forces can be exerted on the particles. In general, magnetic, electrophoretic, centrifugal, photophoretic, and diffusiophoretic can be neglected. On the other hand, thermophoretic forces, caused by steep temperature gradients, can be important. The gravitational forces are almost always present and can affect the dynamic response of large particles. Understanding and quantifying the chemical coupling between two phases is a challenging task. However, all reacting particles begin this process as inert particles, and they must be heated before they participate in the combustion process. Thus, one must first understand the interactions of inert particles in a combustion environment. The in-detail understanding of the dynamics and structure of dusty flows can be only advanced by considering simple flow geometries such as the opposed-jet, stagnation-type. In such configurations the imposed strain rate is well characterized, and the in-depth understanding of the details of the physico-chemical processes can be systematically obtained. A number of computational and experimental studies on spray and particle flows have been conducted in stagnation-type configurations. Numerically, the need for a hybrid Eulerian-Lagrangian approach has been identified by Continillo and Sirignano, and the use of such approach has allowed for the prediction of the phenomenon of droplet flow reversal. Gomez and Rosner have conducted a detailed study on the particle response in the opposed-jet configuration, and the particle thermophoretic diffusivities were determined experimentally. Sung, Law and co-workers have conducted numerical studies on the effect of strain rate and temperature gradients on the dynamics of inert particles, as a way of understanding potential errors in experimental LDV data that may arise from thermophoretic forces. This investigation is a combined experimental and numerical study on the details of reacting dusty flows. The specific tasks are: (1) Experimental determination of laminar flame speeds, and extinction strain rates of dusty flows at normal- and micro-gravity as functions of the particle type, particle initial diameter, particle initial number density, and gas phase chemical composition; (2) Detailed numerical simulation of the experiments. Results are compared with experiments and the adequacy of theoretical models is assessed; and (3) Provision of enhanced insight into the thermo-chemical coupling between the two phases.

Andac, M. Gurhan↗

Comets, Carbonaceous Meteorites, and the Origin of the Biosphere

The biosphere comprises the Earth s crust, atmosphere, oceans, and ice caps and the living organisms that survive within this habitat. The discoveries of barophilic chemolithoautotrophic thermophiles living deep within the crust and in deep-sea hydrothermal vents, and psychrophiles in permafrost and deep within the Antarctic Ice Sheet indicate the Earth s biosphere is far more extensive than previously recognized. Molecular biomarkers and Bacterial Paleontology provide evidence that life appeared very early on the primitive Earth and the origin of the biosphere is closely linked with the emergence of life. The role of comets, meteorites, and interstellar dust in the delivery of water, organics and prebiotic chemicals has long been recognized. Deuterium enrichment of seawater and comets indicates that comets delivered oceans to the early Earth. Furthermore, the similarity of the D/H ratios and the chemical compositions of CI carbonaceous meteorites and comets indicate that the CI meteorites may be remnants of cometary nuclei with most volatiles removed. Comets, meteorites, and interstellar dust also contain complex organic chemicals, amino acids, macromolecules, and kerogen-like biopolymers and may have played a crucial role in the delivery of complex organics and prebiotic chemicals during the Hadean (4.5-3.8 Gyr) period of heavy bombardment. The existence of indigenous microfossils of morphotypes of cyanobacteria in the CI and CM carbonaceous meteorites suggests that the paradigm that life originated endogenously in the primitive oceans of early Earth may require re-consideration. Recent data on the hot (300-400 K) black crust on comet P/Halley and Stardust images of P/Wild 2 showing depressions, tall cliffs, and pinnacles, indicate the presence of thick, durable, dark crusts on comets. If cavities within the ice and crust sustain vapor pressures in excess of 10 millibar, then localized pools of liquid water and brines could exist within the comet. Since life exists on Earth wherever there is liquid water, it is suggested that comets might also harbour viable and/or cryopreserved microbiota.

Hoover, Richard B.↗

Apollo 17 Soil Characterization for Reflectance Spectroscopy

It is the fine fractions that dominate the observed spectral signatures of bulk lunar soil, and the next to the smallest size fractions are the most similar to the overall properties of the bulk soil. Thus, our Lunar Soil Characterization Consortium has concentrated on understanding the inter-relations of compositional, mineralogical, and optical properties of the <45-micron size fraction and its component sizes (20-44 micron, 10-20 micron, and <10 micron size fractions). To be able to generalize our results beyond the particular sample set studied, it is necessary to quantitatively identify the observed effects of space weathering and evaluate the processes involved. For this, it is necessary to know the chemistry of each size fraction, modal abundances of each phase, average compositions of the minerals and glasses, I(sub s)/FeO values, reflectance spectra, and the physical makeup of the individual particles and their patinas. This characterization includes the important dissection of the pyroxene minerals into four separate populations, with data on both modes and average chemical compositions. Armed with such data, it should be possible to effectively isolate spectral effects of space weathering from spectral properties related to mineral and glass chemistry. Four mare soils from the Apollo 17 site were selected for characterization based upon similarities in bulk composition and their contrasting maturities, ranging from immature to submature to mature. The methodology of our characterization has been discussed previously. Results of the Apollo 17 mare soils, outlined herein, are being prepared for publication in MAPS. As shown, with decreasing grain size, the agglutinitic (impact) glass content profoundly increases. This is the most impressive change for the mare soils. In several soils we have examined, there is an over two-fold increase in the agglutinitic glass contents between the 90-150- micron and the 10-20-micron size fractions. Accompanying this increase in agglutinitic glass is a definite decrease in pyroxenes and to lesser extents, the oxides (ilmenite), volcanic glass, and olivine. Unexpectedly, however, the absolute plagioclase abundances stay relatively constant throughout the different grain sizes, although the abundance of plagioclase relative to the mafic minerals increases with decreasing particle size. These soils were chosen for study based upon their similarities in FeO and Ti02 content, allowing for direct comparisons between evolutions of chemistry between size fractions and among different maturities of soils. The bulk chemistry of these fractions was determined by EMP analyses of fused glass beads. In contrast to the systematic variations in bulk chemistry discussed below, the relatively uniform composition of agglutinitic glass with grain size and soil maturity is illustrated. The composition of the bulk fraction of each size fraction becomes more feldspathic with increasing maturity, with the effect being most pronounced for the finest fractions. The composition of the agglutinitic glass, however, is relatively invariant and more feldspathic (i.e., rich in Al2O3) than even the <10-micron fraction. This relation not only strengthens the "fusion of the finest fraction" (F(sup 3)) hypothesis, but also highlights the important role of plagioclase in the formation of agglutinitic glass. With decreasing grain size, FeO, MgO, and TiO2 contents decrease, whereas CaO, Na2O, and Al2O3 (plag components) increase for all soils. These chemical variations would appear to be coupled with the significant increase in agglutinitic glass and decrease in oxide (ilmenite),pyroxene, and volcanic glass. These changes in chemistry do not appear to be due to distinct changes in the compositions of individual phases but to their abundances. Values of I(sub s)/FeO increase with decreasing grain size, even though the bulk FeO contents decrease. That is, the percentage of the total Fe that is present as nanophase Fe(sup O) has increased substantially in the smaller size fraction. Note that the increase in nanophase FeO in smaller size fractions is significantly greater than the increase in agglutinitic glass content, with its single-domain FeO component. This would seem to indicate that at least some of the FeO is surface correlated. To illustrate this effect, if it is assumed that the nanophase FeO is entirely surface correlated, then equal masses of 15-micron and 6-micron spheres should have about 3x as much FeO in the finer fraction. The recent findings of Kelleret al. of the major role of vapor-deposited, nanophase FeO-containing patinas on most soil particles is a major breakthrough in our understanding of the distribution of FeO within agglutinitic glass and upon grain surfaces. Bidirectional reflectance spectra for a representative Apollo 17 soil (70181) are shown. The size separates all have similar albedo in the blue and follow a regular sequence in which the continuum slope increases, ferrous bands weaken, and albedo, increases with decreasing particle size. The bulk <45-micron soil is typically close to the 10-20 micron spectrum. It is important to note that although the finest fraction (<10 micron) is close in composition to the abundant agglutinitic glass in each size fraction, this size fraction is relatively featureless and does not dominate the spectrum of the bulk <45-micron soil. It has long been suspected that agglutinitic glass, to a large extent, is the product of melting of the finest fraction of the soils, with a dominance of plagioclase. Given the low abundance of pyroxene in the finest fractions of each soil the source of the FeO in these Apollo 17 agglutinitic glasses is not fully identified. We suspect the abundant volcanic glass in these samples may be a significant contributor and this hypothesis will be tested with the suite under study from other Apollo sites.

Taylor, L. A.↗

The Sturgeon Falls paleosol and the composition of the atmosphere 1.1 Ga BP

A paleosol is exposed along the north bank of the Sturgeon River, some 25 km SW of Baraga, Michigan. The paleosol was developed on hydrothermally altered Keweenawan basalt and is overlain by the Jacobsville sandstone. Textures, mineralogy, and chemical composition change gradually upwards from unweathered metabasalt, through the paleosol, to the contact of the paleosol with the Jacobsville sandstone. Many of these changes are similar to those in modern soils developed on basaltic rocks. However, K has clearly been added to the paleosol, probably by solutions which had equilibrated with K-feldspar in the Jacobsville sandstone. The Keweenawan basalt was oxidized quite extensively during its conversion to greenstone. During weathering, the remaining Fe2+ was oxidized to Fe3+ and was retained in the paleosol. The composition of the parent greenstone and its change during weathering can be used to define an approximate lower limit to the ratio of the O2 pressure to the CO2 pressure in the atmosphere during the formation of the paleosol [formula: see text]. Free O2 must have been present in the atmosphere 1.1 Ga ago, but its partial pressure could have been 10(3) times lower than in the atmosphere today.

NASA Program Exobiology↗

Strengthening the Magnetic Interactions in Pseudobinary First-Row Transition Metal Thiocyanates, M(NCS) 2

Understanding the effect of chemical composition on the strength of magnetic interactions is key to the design of magnets with high operating temperatures. The magnetic divalent first-row transition metal (TM) thiocyanates are a class of chemically simple layered molecular frameworks. Here, we report two new members of the family, manganese(II) thiocyanate, Mn(NCS) 2 , and iron(II) thiocyanate, Fe(NCS) 2 . Using magnetic susceptibility measurements on these materials and on cobalt(II) thiocyanate and nickel(II) thiocyanate, Co(NCS) 2 and Ni(NCS) 2 , respectively, we identify significantly stronger net antiferromagnetic interactions between the earlier TM ions—a decrease in the Weiss constant, θ, from 29 K for Ni(NCS) 2 to -115 K for Mn(NCS) 2 —a consequence of more diffuse 3d orbitals, increased orbital overlap, and increasing numbers of unpaired $t_{2_g}$ electrons. We elucidate the magnetic structures of these materials: Mn(NCS) 2 , Fe(NCS) 2 , and Co(NCS) 2 order into the same antiferromagnetic commensurate ground state, while Ni(NCS) 2 adopts a ground state structure consisting of ferromagnetically ordered layers stacked antiferromagnetically. We show that significantly stronger exchange interactions can be realized in these thiocyanate frameworks by using earlier TMs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Intercalation of Lithium into Graphite: Insights from First-Principles Simulations

Understanding ion intercalation at electrode–electrolyte interfaces is key to the development of energy storage and water desalination. Here, we investigate Li + kinetics at a prototypical interface between graphite anodes and an organic electrolyte, and we elucidate key factors that determine ion transport, using first-principles methodology coupling ab initio molecular dynamics simulations with a solvation model. We show that surface chemical composition significantly influences the kinetics of ion intercalation from the liquid into graphite. We find that this is partly related to the ion desolvation process, which varies notably for different graphite surface chemical terminations. In addition, interfacial polarization is found to play an important role in determining energy barriers for ion transfer. We also discuss the impact of electrode potentials, which is often neglected in conventional first-principles calculations despite being a key factor in device configurations. Our study provides insights into the coupling of electronic and ionic effects of interfacial chemistry on ion transport at complex electrode–electrolyte interfaces.

25 ENERGY STORAGE↗

Advancing Molecular Level Understanding of Aerosol Processes in the Amazon and Integration with Modeling (Final Report)

The Amazon forest is being converted to urban and agricultural uses through land clearing including large scale burning. It is also the dominant source of biogenic hydrocarbons globally, which can chemically transform in the atmosphere to form secondary organic aerosol (SOA). Most aerosols (solid or liquid particles suspended in air) are organic and formed through secondary chemical processes. This means that SOA chemical composition and their physical properties can impact cloud formation, the hydrologic cycle, and radiative balance in this region. The 2014 GoAmazon field campaign at the DOE/ARM facility at T3 afforded study of chemical transformations in the region downwind of Manaus. Local biogenic hydrocarbons emissions are high, and their chemical oxidation can be studied with varying degrees of influence by the urban plume. We collected aerosol filter samples and made time-resolved molecular level measurements by deploying a sequential filter sampler and a Semi-Volatile Thermal desorption Aerosol Gas Chromatograph (SV-TAG) during Jan-Mar 2014 (wet season) and Aug-Oct 2014 (dry season).

54 ENVIRONMENTAL SCIENCES↗

Influence of sequential stimulation practices on geochemical alteration of shale

Water-based hydraulic fracturing fluids (HFFs) can chemically interact with formation shale, resulting in altered porosity and permeability of the host rock. Experimental investigations of spatial and temporal shale-HFF interactions are helpful in interpreting chemical compositions of the injectate, as well as predicting alteration of hydraulic properties in the reservoir due to mineral dissolution and precipitation. Most bench-top experiments designed to study shale-HFF chemical interactions, either using batch reactors or flow-through setups, are carried out assuming that the acid spearhead has already become mixed with neutral HFFs. During operations, however, HFFs are typically injected according to a sequenced pumping schedule, starting with a concentrated acid spearhead, followed by multiple additions of near-neutral pH HFFs containing chemical amendments and proppant. In this study, we use geochemical modeling to consider whether this pre-mixed experimental protocol provides results directly comparable to a sequential discrete fluid-shale interaction protocol. Our results show that for the batch system, the transient evolution in major ion concentrations is faster with the sequential procedure. After 2 h of reaction time, the two protocols converge to the same aqueous concentrations. In a flow-through geometry, the pre-mixed model predicts extensive chemical alteration close to the injection point but negligible alteration downstream. In contrast, the sequential model predicts mineral reactions over hundreds of meters along the flow path. The extent of shale alteration in the sequential model at a given location depends on shale mineralogy and where the acid spearhead resides during the shut-in period. The predictive model developed in this study can help experimentalists to design bench-top tests and operators to better translate the results of laboratory experiments into practical applications.

Li, Qingyun↗

Nitrogen Isotopic Anomalies in a Hydrous Interplanetary Dust Particle

Interplanetary dust particles (IDPs) collected in the stratosphere are the fine-grained end member (5 - 50 microns in size) of the meteoritic material available for investigation in the laboratory. IDPs are derived from either cometary or asteroidal sources. Some IDPs contain cosmically primitive materials with isotopic signatures reflecting presolar origins. Recent detailed studies using the NanoSIMS have shown there is a wide variation of isotopic signatures within individual IDPs; grains with a presolar signature have been observed surrounded by material with a solar isotopic composition. The majority of IDPs studied have been anhydrous. We report here results from integrated NanoSIMS/FIB/TEM/Synchrotron IR studies of a hydrous IDP, focused on understanding the correlations between the isotopic, mineralogical and chemical compositions of IDPs.

Smith, J. B.↗