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At least 1,153 records · Page 64

On the origin and evolution of isotopes of carbon, nitrogen, and oxygen

Calculations of CNO processing in stellar envelopes, based on theoretical nucleosynthesis rather than empirical abundances in evolving stars, are presented and used in two models for the chemical evolution of the solar neighborhood. Seven stable isotopes are considered: C-12, C-13, N-14, N-15, O-16, O-17, and O-18. The two models ('infall' and 'initial-burst') represent extremes of types consistent with general constraints and include theoretical estimates of other nucleosynthesis sites and yields for CNO isotopes. The results obtained are found to predict that all CNO isotopes are produced mainly by stars with lifetimes much less than the age of the Galaxy (even at the present time when low-mass stars have the greatest death rate), so that isotopic ratios evolve very slowly after the first few billion years. Consequences of these slow changes are that the isotopic ratios cannot be employed to test between alternative hypotheses and that galactic evolution does not seem to be able to account for the apparent difference between the C-13/C-12 ratio in the solar system and in molecular clouds. The predicted envelope processing is shown to lead to approximately the solar-system values for the C-13/C-12 and O-17/O-16 abundance ratios but to a N-14/C-12 ratio that is too small by at least a factor of 2.

Dearborn, D.↗

Cost/performance of solar reflective surfaces for parabolic dish concentrators

Materials for highly reflective surfaces for use in parabolic dish solar concentrators are discussed. Some important factors concerning performance of the mirrors are summarized, and typical costs are treated briefly. Capital investment cost/performance ratios for various materials are computed specifically for the double curvature parabolic concentrators using a mathematical model. The results are given in terms of initial investment cost for reflective surfaces per thermal kilowatt delivered to the receiver cavity for various operating temperatures from 400 to 1400 C. Although second surface glass mirrors are emphasized, first surface, chemically brightened and anodized aluminum surfaces as well as second surface, metallized polymeric films are treated. Conventional glass mirrors have the lowest cost/performance ratios, followed closely by aluminum reflectors. Ranges in the data due to uncertainties in cost and mirror reflectance factors are given.

Bouquet, F.↗

Calculated stormtime variations in plasmaspheric thermal ion composition

Model calculations describing stormtime variations in the earth's dayside plasmasphere are used to examine variations in ion composition. The model storm is initiated by high-latitude thermospheric heating that generates meridional winds that carry neutral species, momentum, and energy equatorward. The thermosphere acts on the plasmasphere through collisional transfer of momentum and through chemical reactions between neutral species and ions. Over latitudes near the region of thermospheric heating, the thermosphere-plasmasphere coupling processes cause enhancement in the density of oxygen ions while protons are being lost. Meanwhile, densities of oxygen ions and protons near the equator are increasing together, almost in phase. The largest enhancements in ion density develop at latitudes near 45 deg invariant for both oxygen and hydrogen.

Miller, N. J.↗

Applications of high pressure differential scanning calorimetry to aviation fuel thermal stability research

High pressure differential scanning calorimetry (DSC) was studied as an alternate method for performing high temperature fuel thermal stability research. The DSC was used to measure the heat of reaction versus temperature of a fuel sample heated at a programmed rate in an oxygen pressurized cell. Pure hydrocarbons and model fuels were studied using typical DSC operating conditions of 600 psig of oxygen and a temperature range from ambient to 500 C. The DSC oxidation onset temperature was determined and was used to rate the fuels on thermal stability. Kinetic rate constants were determined for the global initial oxidation reaction. Fuel deposit formation is measured, and the high temperature volatility of some tetralin deposits is studied by thermogravimetric analysis. Gas chromatography and mass spectrometry are used to study the chemical composition of some DSC stressed fuels.

Neveu, M. C.↗

Crystal growth of device quality GaAs in space

The present program has been aimed at solving the fundamental and technological problems associated with Crystal Growth of Device Quality in Space. The initial stage of the program was devoted strictly to ground-based research. The unsolved problems associated with the growth of bulk GaAs in the presence of gravitational forces were explored. Reliable chemical, structural and electronic characterization methods were developed which would permit the direct relation of the salient materials parameters (particularly those affected by zero gravity conditions) to the electronic characteristics of single crystal GaAs, in turn to device performance. These relationships are essential for the development of optimum approaches and techniques. It was concluded that the findings on elemental semiconductors Ge and Si regarding crystal growth, segregation, chemical composition, defect interactions, and materials properties-electronic properties relationships are not necessarily applicable to GaAs (and to other semiconductor compounds). In many instances totally unexpected relationships were found to prevail.

Gatos, H. C.↗

Emissions of nitrous oxide from biomass burning

A study has been conducted which compared N2O results obtained over large prescribed fires or wildfires, in which 'grab-sampling' with storage had been used with N2O measurements made in near-real time. CO2-normalized emission ratios obtained initially from the laboratory fires are substantially lower than those obtained over large-scale biomass fires. Combustion may not be the only source of N2O in large fire smoke plumes; physical, chemical, and biochemical processes in the soil may be altered by large biomass fires, leading to large N2O releases.

Winstead, Edward L.↗

A model for the evolution of CO2 on Mars

Our MSATT work has focused on the evolution of CO2 on Mars. We have constructed a model that predicts the evolution of CO2 on Mars from a specified initial amount at the end of the heavy bombardment to the present. The model draws on published estimates of the main process believed to affect the fate of CO2 during this period: chemical weathering, regolith uptake, polar cap formation, and atmospheric escape. Except for escape, the rate at which these processes act is controlled by surface temperatures that we calculate using a modified version of the Gierasch and Toon energy balance model. Various aspects of this work are covered.

Haberle, Robert M.↗

Microbial Anomalies Encountered on the International Space Station

Microorganisms in our living environments are unavoidable. A community of microbes arrived in space with the delivery of the first element of the International Space Station (ISS), attached to hardware and on the bodies of the humans tasked with the initial assembly missions. The risk that microorganisms could cause adverse effects in the health of both the human occupants of the ISS as well as the physical integrity of the station environment and life support systems has been both a driver and a function of engineering and operational controls. Scientists and engineers at NASA have gone to extensive measures to control microbial growth at levels safe for the crewmembers and the spacecraft environment. Many of these measures were initiated with the design of the spacecraft and its systems. Materials used in the ISS were tested for resistance to fungi, such as mold and a paint with a fungus-killing chemical was also used. Controlling the humidity of the air in the Station is also an effective way of discouraging microbe growth. The breathing air is reconditioned by the Environmental Control Life Support System (ECLSS) prior to distribution, utilizing High Efficiency Particulate Air (HEPA) filtration. Requirements restricting the accumulation of water condensate in the air handlers and habitable volume of the ISS were other safeguards added. Water for drinking and food rehydration is disinfected or filtered. A robust in-flight housekeeping regimen for the ISS significantly reduces inappropriate growth of microorganisms and includes a regular cleaning of accessible surfaces with disinfectant wipes. Most of these requirements were suggested by microbiologists to mitigate and possibly prevent many microbiological risks. In addition to these controls, before flight monitoring and analyses of the cabin air, exposed surfaces, water and food, consumables, and crew members are conducted to mitigate microbial risk to the crew and spacecraft. Many microbial risks are much easier to identify and resolve before launch than during space flight. Although the focus has been on prevention of microbiologically related, not all problems can be anticipated. A number of microbial anomalies have occurred on ISS. This paper will discuss the occurrences, root-cause investigations, and mitigation steps taken to remediate the contamination.

Bruce, Rebekah J.↗

Utilizing ARC EMCS Seedling Cassettes as Highly Versatile Miniature Growth Chambers for Model Organism Experiments

The aim of our ground testing was to demonstrate the capability of safely putting specific model organisms into dehydrated stasis, and to later rehydrate and successfully grow them inside flight proven ARC EMCS seedling cassettes. The ARC EMCS seedling cassettes were originally developed to support seedling growth during space flight. The seeds are attached to a solid substrate, launched dry, and then rehydrated in a small volume of media on orbit to initiate the experiment. We hypothesized that the same seedling cassettes should be capable of acting as culture chambers for a wide range of organisms with minimal or no modification. The ability to safely preserve live organisms in a dehydrated state allows for on orbit experiments to be conducted at the best time for crew operations and more importantly provides a tightly controlled physiologically relevant growth experiment with specific environmental parameters. Thus, we performed a series of ground tests that involved growing the organisms, preparing them for dehydration on gridded Polyether Sulfone (PES) membranes, dry storage at ambient temperatures for varying periods of time, followed by rehydration. Inside the culture cassettes, the PES membranes were mounted above blotters containing dehydrated growth media. These were mounted on stainless steel bases and sealed with plastic covers that have permeable membrane covered ports for gas exchange. The results showed we were able to demonstrate acceptable normal growth of C.elegans (nematodes), E.coli (bacteria), S.cerevisiae (yeast), Polytrichum (moss) spores and protonemata, C.thalictroides (fern), D.discoideum (amoeba), and H.dujardini (tardigrades). All organisms showed acceptable growth and rehydration in both petri dishes and culture cassettes initially, and after various time lengths of dehydration. At the end of on orbit ISS European Modular Cultivation System experiments the cassettes could be frozen at ultra-low temperatures, refrigerated, or chemically preserved before being returned to Earth for analyses. Our results suggest that with protocol modifications and future verification testing we can utilize the versatile EMCS to conduct tightly controlled experiments inside our culture cassettes for a wide variety of organisms. These physiological experiments would be designed to answer questions at the molecular level about the specific stress responses of space flight.

Model Organism Experiments↗

Numerical Simulation of Lean Blowout of Alternative Fuels in 7-element Lean Direct Injector

This research presents the result of numerically simulating 7-element swirl-venturi Lean Direct Injector (SV-LDI) lean blowout (LBO) experiments conducted at NASA Glenn Research Center in May of 2019. After simulating a cold flow case to confirm the pressure drop agrees well with the experiment, additional cases with two different fuels (an average jet fuel and a Gevo alcohol-to-jet fuel) from the National Jet Fuels Combustion Program (NJFCP) were computed to numerically determine the LBO condition. The procedure to approach the LBO follows the method used in the experiment where the air mass flow rate is gradually increased while the fuel supply is maintained. Transient history of global heat release rate as a function of air flow rate is presented, as well as temperature contours at different conditions to give a visual representation of the flame state. The Open National Combustion Code (OpenNCC) used in this research adopted reduced HyChem (Hybrid Chemistry) models along with k-LES turbulence model and a Lagrangian spray model that takes into account droplet internal temperature distribution affected by the shear force on the droplet surface. The transport equations and chemical reaction terms are integrated together to enhance conservation of chemical species that are especially important in the near LBO conditions. After showing the computed range of LBO agrees well with the experimental measurements, time averaged solutions of both fuels at their initial condition and at their limiting condition just before LBO are compared in detail to facilitate the understanding of LBO mechanism.

combustion↗

Microstructural and infiltration properties of woven preforms during chemical vapor infiltration

Interface-resolved direct numerical simulations (DNSs) of chemical vapor infiltration (CVI) have been performed over a range of furnace-operating conditions (Thiele moduli) and for practical woven preform geometries. A level-set method is used to resolve the geometry of the initial preform at tow scale. The interface between the vapor and solid phase is then evolved in time through the entire CVI densification cycle, fully resolving the time-varying topology between the two phases. In contrast to previous level-set methods for CVI simulation, the physical reaction and diffusion processes govern the level-set movement in the current approach. The surface deposition kinetics is described by the usual one-step model. In this paper, the DNS data are used to study the evolving porosity, surface-to-volume ratio, and flow infiltration properties (permeability and effective diffusivities). Additionally, comparisons are made to popularly-assumed structure functions and the standard, Kozeny–Carmen porous media model commonly employed in modeled CFD simulations of CVI. The virtual DNS experiments reveal a Thiele modulus and preform geometry (fabric layup) dependence which the existing microstructural and infiltration models are not able to describe throughout the entire densification process. The DNS-based, woven geometry-specific correlations can be applied directly to mean-field, furnace-scale CFD simulations.

36 MATERIALS SCIENCE↗

An experimental and chemical kinetic modeling study of 4-butoxyheptane combustion

Here, the combustion kinetics of a novel oxygenated bioblendstock for diesel, 4-butoxyheptane (4-BH), was investigated experimentally using a flow reactor and a heated, high-pressure shock tube. The flow reactor experiments employed oxygen as the oxidizer and helium as the diluent with oxidation conducted at atmospheric pressure and 10 bar for temperatures from 400 to 1000 K at 20-K intervals. The fuel, oxidizer, and diluent flow rates were varied at different temperatures to maintain a constant initial fuel mole fraction of 1000 ppm, with stoichiometric equivalence ratio, and a residence time of 2.0 s. The reacted gas was fed to two separate GC systems that could qualitatively and quantitatively detect product species. Additionally, real fuel-air ignition delay time (IDT) data were collected using a heated, high-pressure shock-tube facility. Fuel lean (φ = 0.5) and stoichiometric (φ = 1.0) mixtures were investigated at 10 atm as well as at 30 atm for the fuel lean case for temperatures between 847 and 1259 K. A detailed chemical kinetics mechanism was developed to model the product distribution from the flow reactor and IDTs from the shock tube. The proposed model was able to predict the double NTC behavior in flow reactor experiments reasonably well. Model predictions at low temperatures were observed to be highly sensitive to the rate constants of ketohydroperoxide (KHP) decomposition in the case of the OOH group in α position which were modeled based on existing literature studies on ethers. It was noted that in the absence of theoretical or experimental studies, the rate constants for KHP decomposition used in the literature were empirically set. Additional studies are required to address the gap in model prediction obtained in this study and to reduce the uncertainty in kinetics models for ether oxidation. Predicted product concentrations and IDTs showed some quantitative agreement with experimental data, but the overall reactivity of the IDTs is underpredicted. Additionally, significant deviation is observed for the IDT results at 10 atm for the stoichiometric case with minor deviations for the other cases. The reaction pathways to the missing products were then further analyzed theoretically through quantum-mechanical calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Processing lunar soils for oxygen and other materials

Two types of lunar materials are excellent candidates for lunar oxygen production: ilmenite and silicates such as anorthite. Both are lunar surface minable, occurring in soils, breccias, and basalts. Because silicates are considerably more abundant than ilmenite, they may be preferred as source materials. Depending on the processing method chosen for oxygen production and the feedstock material, various useful metals and bulk materials can be produced as byproducts. Available processing techniques include hydrogen reduction of ilmenite and electrochemical and chemical reductions of silicates. Processes in these categories are generally in preliminary development stages and need significant research and development support to carry them to practical deployment, particularly as a lunar-based operation. The goal of beginning lunar processing operations by 2010 requires that planning and research and development emphasize the simplest processing schemes. However, more complex schemes that now appear to present difficult technical challenges may offer more valuable metal byproducts later. While they require more time and effort to perfect, the more complex or difficult schemes may provide important processing and product improvements with which to extend and elaborate the initial lunar processing facilities. A balanced R&D program should take this into account. The following topics are discussed: (1) ilmenite--semi-continuous process; (2) ilmenite--continuous fluid-bed reduction; (3) utilization of spent ilmenite to produce bulk materials; (4) silicates--electrochemical reduction; and (5) silicates--chemical reduction.

Knudsen, Christian W.↗

A Reductively Stable Electrolyte Realizes Deep Cycling Behavior in Anode‐free Sodium Batteries

For anode‐free sodium batteries to achieve practical consideration, highly reversible chemistries require exceptional ≥99.95% coulombic efficiencies that maintain over prolonged cycling periods. To do so, consumption of this severely limited sodium inventory must be restricted while metal nucleation processes that comprise the in situ formed metal anode are improved. Herein, we describe a fluorine‐free carborane electrolyte that satisfies these criteria by emphasizing reductive stability and weakly coordinating anion behavior as design principles. We find this approach promotes the development of a thin, robust SEI chemistry rich in both organic speciation and boron. The electrolyte described herein exhibits ideal metal nucleation behavior on one‐micron thin carbonaceous current collector surfaces and achieves a metal deposition/stripping efficiency near parity for 400 cycles. This novel anode chemistry is introduced to anode‐free full cell configurations where 87% of the initial discharge capacity is retained after 1000 cycles at 2.0 C. In conclusion, post‐test characterization of deep‐cycled anode‐free cells reveals suppressed capacity fade in these systems is attributed to the chemical stability of the carborane anion.

anode-free↗

Identifying the Catalytic Active Site for Propylene Metathesis by Supported ReO x Catalysts

A series of supported ReO x catalysts were investigated that allowed identifying the unique surface anchoring sites on oxide supports responsible for activating the surface ReO 4 sites for propylene metathesis (the catalytic active site). The catalysts were synthesized by incipient-wetness impregnation of aqueous HReO 4 onto the oxide supports (Al 2 O 3 , ZrO 2 , TiO 2 , SiO 2 and CeO 2 ), characterized under dehydrated and propylene metathesis reaction conditions with in situ spectroscopy (Raman, DRIFTS, UV-Vis and NAP-XPS), and chemically probed (CH 3 CH=CH 2 -TPSR, CH 2 =CH 2 /CH 3 CH=CHCH 3 titration and steady-state self-metathesis of propylene to ethylene and 2-butene). The initially calcined supported rhenia species anchor as isolated surface Re 7+ O 4 sites on the oxide supports by reacting with the surface hydroxyls (terminal S-OH, bridged S-OH-S and tricoordinated S 3 -OH) of the oxide supports. The specific oxide support was found to control the number of activated sites (Al 2 O 3 >> ZrO 2 > CeO 2 > TiO 2 > SiO 2 ) and propylene metathesis activity (Al 2 O 3 >> ZrO 2 >> TiO 2 ~ CeO 2 ~ SiO 2 ) revealing that the oxide support action is a potent ligand for the surface ReO x sites. The activation and specific activity of the surface ReO x sites depend on several factors (nature of surface hydroxyls (S 3 -OH > S-OH-S > S-OH), coordination of the oxide support surface cation (ZrO 7 , AlO 6 , CeO 4 ) and electronegativity of the oxide support cation (SiO 2 > Al 2 O 3 > TiO 2 > ZrO 2 > CeO 2 ). No relationships exist between olefin metathesis activity and acid strength of surface Lewis and Brønsted sites. Here, prior studies primarily focused on supported ReO x /Al 2 O 3 and the lack of examination of non-Al 2 O 3 supported rhenia catalysts precluded comparison between efficient and inefficient olefin metathesis catalysts, which prevented identifying the catalytic active site for olefin metathesis by supported ReO x catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanographene Coupled with Interfacial Pyrene Derivatives for Thermally Stable Perovskite Solar Cells

Although high-efficiency perovskite solar cells (PSCs) have been achieved using a hole-extracting material, spiro-MeOTAD, thermal stability has been unattainable due to the low glass transition temperature of spiro-MeOTAD and additives therein. In this paper we report on the use of nanographene-based hole-transporting materials coupled with a pyrene derivative as an interface modifier for thermally stable and high efficiency PSCs. Asymmetric methyl and methoxy groups are introduced in the diphenylamino group that is attached to the hexa-peri-hexabenzocoronene (HBC) nanographene core, coded HBC-DPAMeOMe. 1-Pyrenemethylammonium iodide is coupled to enhance the chemical interaction between perovskite and HBC-DPAMeOMe, which leads to a power conversion efficiency over 23%. A thermal stability test at 85 degrees C for 1000 h reveals that 83.6% of the initial efficiency (23.04% --> 19.25%) is maintained for the device with HBC-DPAMeOMe, while a significant degradation from 20.69% to 5.08% is observed for the device with spiro-MeOTAD. Nanographene-based hole conductors shed light on the thermal stability issue in PSCs.

14 SOLAR ENERGY↗

Early fluid activity on Ryugu inferred by isotopic analyses of carbonates and magnetite

Samples from asteroid Ryugu returned by the Hayabusa2 mission contain evidence of extensive alteration by aqueous fluids and appear related to the CI chondrites. To understand the sources of the fluid and the timing of chemical reactions occurring during the alteration processes, we investigated the oxygen, carbon and 53 Mn– 53 Cr systematics of carbonate and magnetite in two Ryugu particles. Here we find that the fluid was initially between 0 and 20 °C and enriched in 13 C, 17 O and 18 O, and subsequently evolved towards lighter carbon and oxygen isotopic compositions as alteration proceeded. Carbonate ages show that this fluid–rock interaction took place within approximately the first 1.8 million years of Solar System history, requiring early accretion either in a planetesimal less than ~20 km in diameter or within a larger body that was disrupted and reassembled.

58 GEOSCIENCES↗