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At least 469 records · Page 26

Dependence of interstellar depletion on hydrogen column density - Possibilities and implications

A reexamination of the observed column densities of various elements in diffuse clouds suggests that almost all elements including oxygen, nitrogen, sulfur, and argon may be depleted with respect to hydrogen in interstellar clouds with large hydrogen column density. The amount of depletion varies from element to element and increases with increasing column density of hydrogen nuclei. This result is in qualitative agreement with the depletion of oxygen and sulfur independently inferred from the gas phase chemistry of sulfur in dense clouds. The rate of increase of depletion with hydrogen column density implied by the present study is large. It is possible that observational selection effects may have amplified the real dependence on N(H). A broad spectrum of C/O ratios ranging from values greater than unity to values less than unity appears possible for interstellar clouds, which would have the effect of a large variation in chemical composition from cloud to cloud.

Tarafdar, S. P.↗

Measuring EUV Line Emission from the Hot Interstellar Medium

In the local interstellar medium, the presence of hot gas was inferred from measurements of oxygen VI absorption in the ultraviolet, and from diffuse emission in the extreme ultraviolet (EUV) and soft X-ray regions. A spectrometer that is very sensitive to gas in this temperature range is described. The spectrometer uses an array of plane ruled gratings at grazing incidence in the extreme off plane mount. A set of Kirkpatrick-Baez mirrors focuses the conically diffracted light on to one of two microchannel plate detectors. The field of view of the instrument is 0.2 deg by 12 deg. The predicted sensitivity ranges from 50 to 200 ph/(sq cm sec str) with a resolving power of 15 to 50 over the 50 to 700 angstrom wavelength band.

Labov, S.↗

Structural defects in crystalline silicon

The basic photovoltaic properties of a given crystalline silicon specimen seem to be governed by density and nature of two to three dimensional lattice defects. These are mainly generated by primary growth conditions as grain boundaries of more or less intrinsic character or second phase precipitates from supersaturated solutions of carbon or oxygen. Considerably high values of both solubility and diffusivity in connection with their abundance in common refractory material systems account for the predominance of the two particular elements. Unsaturated dislocations of different types very often can be seen as a consequence of the existence of more dimensional defects as described initially. The final performance of a solar cell is dependent of the concentration and distribution of recombination active centers in the different regions of this device. Typical representatives are fast diffusing transition metals in form of either single atoms or simple complexes. Their avoidance, annihilation, or removal is of great concern in different fields of electronic materials development.

Sirtl, E.↗

Ventilation-perfusion matching during exercise

In normal subjects, exercise widens the alveolar-arterial PO2 difference (P[A-a]O2) despite a more uniform topographic distribution of ventilation-perfusion (VA/Q) ratios. While part of the increase in P(A-a)O2 (especially during heavy exercise) is due to diffusion limitation, a considerable amount is caused by an increase in VA/Q mismatch as detected by the multiple inert gas elimination technique. Why this occurs is unknown, but circumstantial evidence suggests it may be related to interstitial pulmonary edema rather than to factors dependent on ventilation, airway gas mixing, airway muscle tone, or pulmonary vascular tone. In patients with lung disease, the gas exchange consequences of exercise are variable. Thus, arterial PO2 may increase, remain the same, or fall. In general, patients with advanced chronic obstructive pulmonary disease (COPD) or interstitial fibrosis who exercise show a fall in PO2. This is usually not due to worsening VA/Q relationships but mostly to the well-known fall in mixed venous PO2, which itself results from a relatively smaller increase in cardiac output than VO2. However, in interstitial fibrosis (but not COPD), there is good evidence that a part of the fall in PO2 on exercise is caused by alveolar-capillary diffusion limitation of O2 transport; in COPD (but not interstitial fibrosis), a frequent additional contributing factor to the hypoxemia of exercise is an inadequate ventilatory response, such that minute ventilation does not rise as much as does CO2 production or O2 uptake, causing arterial PCO2 to increase and PO2 to fall.

Non-NASA Center↗

Current Ground Test Options for Nuclear Thermal Propulsion (NTP)

About 20 different NTP engines/ reactors were tested from 1959 to 1972 as part of the Rover and Nuclear Engine for Rocket Vehicle Application (NERVA) program. Most were tested in open air at test cell A or test cell C, at the Nevada Test Site (NTS). Even after serious engine breakdowns of the reactor (e.g., Phoebus 1A), the test cells were cleaned up for other engine tests. The engine test stand (ETS) was made for high altitude (approximately 1 psia) testing of an NTP engine with a flight configuration, but still had the exhaust released to open air. The Rover/NERVA program became aware of new environmental regulations which would prohibit the release of any significant quantity of radioactive particulates and noble gases into the open air. The nuclear furnace (NF-1) was the last reactor tested before the program was cancelled in 1973, but successfully demonstrated a scrubber concept on how to filter the NTP exhaust. The NF-1 was demonstrated in the summer of 1972. The NF-1 used a 44MW reactor and operated each run for approximately 90 minutes. The system cooled the hot hydrogen exhaust from the engine with a water spray before entering a particle filter. The exhaust then passed through a series of heat exchangers and water separators to help remove water from the exhaust and further reduce the exhaust temperatures. The exhaust was next prepared for the charcoal trap by passing through a dryer and effluent cooler to bring exhaust temperatures close to liquid nitrogen. At those low temperatures, most of the noble gases (e.g., Xe and Kr made from fission products) get captured in the charcoal trap. The filtered hydrogen is finally passed through a flare stack and released to the air. The concept was overall successful but did show a La plating on some surfaces and had multiple recommendations for improvement. The most recent detailed study on the NTP scrubber concept was performed by the ARES Corporation in 2006. The concept is based on a 50,000 lbf thrust engine (approximately 1 GW) with a maximum burn time of 1 hour. The concept utilized lessons learned from NF-1. The strategy breaks down the exhaust into parallel paths to allow flexibility with engine size and mass flow of exhaust. Similar to NF-1, the exhaust is slowed down, cooled, filtered of particulates, filtered of noble gases, and then the clean hydrogen is flared to open air. Another concept proposed by Steve Howe (currently Director of the Center for Space Nuclear Research) to simplify the NTP exhaust filtering is to run the hydrogen exhaust into boreholes underground to filter the exhaust. The two borehole site locations proposed are at the NTS and at the Idaho National Laboratory (INL). At NTS, the boreholes are 8' diameter and 1200' deep. The permeability of hydrogen through the soil and its buoyancy will allow it to rise up through the soil and allow the filtering of noble gases and radioactive particulates. The exhaust needs to be cooled to 600C before entering the borehole to avoid soil glazing. Preliminary analysis shows a small buildup of back pressure with time which depends on permeability. Noble gases entering the borehole walls deep can take a long time before reaching the surface. Other factors affecting permeability include borehole pressure, water saturation, and turbulence. Also, a possible need to pump out contaminated water collected at the bottom of the borehole. At INL, the borehole concept is slightly different. The underground borehole has openings to the soil at special depths which have impermeable interbeds above the water table and below the surface to allow the exhaust to travel horizontal between the impermeable layers. Preliminary results indicate better permeability than at NTS. The last option is total containment of the exhaust during the test run. The concept involves slowing down the flow to subsonic in a water cooled diffuser. The hydrogen is burned off in an oxygen rich afterburner with the only products being steam, oxygen, and some noble gases. A heat exchanger and water spray pulls heat from the steam and lowers the temperature for condensation. The optimum ratio between the two is being investigated, with a goal to minimize the total volume of the water hold tanks. A water tank farm collects the contaminated water. The amount of water produced from burning the hydrogen is approximately 100,000 gallons (not including cooling water) for a 25k lbf engine operating for 50 minutes. Residual gases (e.g., oxygen and some noble gases) can be captured at cryogenic levels with a liquid nitrogen cooled dewar. After a few weeks post-test, the radiation levels can drop to more favorable levels before slowly draining each capture tank and using existing filters. With today's environmental regulations, the NTP exhaust is filtered to meet 10 mrem/year exposure to the general public (at a DOE site) or 100 mrem/year (via NRC when tested elsewhere), when natural background radiation exposure to the general public is 300- 600 mrem per year. The current society feels more comfortable with filtering even lower to as low as reasonably achievable (ALARA).

Gerrish, Harold P., Jr.↗

Green Propellant Test Capabilities of the Altitude Combustion Stand at the NASA Glenn Research Center

The NASA Glenn Research Center (GRC) is committed to providing simulated altitude rocket test capabilities to NASA programs, other government agencies, private industry partners, and academic partners. A primary facility to support those needs is the Altitude Combustion Stand (ACS). ACS provides the capability to test combustion components at a simulated altitude up to 100,000 ft. (approx.0.2 psia/10 Torr) through a nitrogen-driven ejector system. The facility is equipped with an axial thrust stand, gaseous and cryogenic liquid propellant feed systems, data acquisition system with up to 1000 Hz recording, and automated facility control system. Propellant capabilities include gaseous and liquid hydrogen, gaseous and liquid oxygen, and liquid methane. A water-cooled diffuser, exhaust spray cooling chamber, and multi-stage ejector systems can enable run times up to 180 seconds to 16 minutes. The system can accommodate engines up to 2000-lbf thrust, liquid propellant supply pressures up to 1800 psia, and test at the component level. Engines can also be fired at sea level if needed. The NASA GRC is in the process of modifying ACS capabilities to enable the testing of green propellant (GP) thrusters and components. Green propellants are actively being explored throughout government and industry as a non-toxic replacement to hydrazine monopropellants for applications such as reaction control systems or small spacecraft main propulsion systems. These propellants offer increased performance and cost savings over hydrazine. The modification of ACS is intended to enable testing of a wide range of green propellant engines for research and qualification-like testing applications. Once complete, ACS will have the capability to test green propellant engines up to 880 N in thrust, thermally condition the green propellants, provide test durations up to 60 minutes depending on thrust class, provide high speed control and data acquisition, as well as provide advanced imaging and diagnostics such as infrared (IR) imaging.

Testing↗

An Improved Theoretical Ni-Cd Battery Performance Model

Previous reports have shown how a battery model was developed using porous electrode theory. Since then the model has been upgraded and expanded. These upgrades include oxygen reation and positive electrode intercalation and proton diffusion. The effects of additional details of the solid state physics of the nickel electrode will be reported here.

battery↗

Effects of non-unity Lewis numbers in diffusion flames

The purpose of this work is to carry out direct numerical simulations of diffusion controlled combustion with non-unity Lewis numbers for the reactants and products, thus accounting for the differential diffusion effects of the temperature and concentration fields. We use a formulation based on combining the conservation equations in a way to eliminate the reaction terms similar to the method used by Burke and Schumann (1928) for unity Lewis numbers. We present calculations for an axisymmetric fuel jet and for a planar, time evolving mixing layer, leaving out the effects of thermal expansion and variations of the transport coefficients due to the heat release. Our results show that the front of the flame shifts toward the fuel or oxygen sides owing to the effect of the differential diffusion and that the location of maximum temperature may not coincide with the flame. The dependence of the distribution of the reaction products on their Lewis number has been investigated.

Linan, A.↗

Heteroatom anchoring to enhance electrochemical reversibility for high-voltage P2-type oxide cathodes of sodium-ion batteries

P2-type cathode has received extensive attention due to its faster Na+ diffusion and a high theoretical capacity in sodium-ion batteries (SIBs). However, undesirable phase transformations have induced dramatic capacity decay of SIBs during the cycling process. In this study, heteroatom anchoring through Cu/Mg dual doping is introduced into P2-type Na 0.67 Ni 0.33 Mn 0.67 O 2 cathode to enhance high-voltage electrochemical reversibility and modulate interfacial Na + kinetics. Further, the as-prepared Na 0.67 Ni 0.23 Mg 0.05 Cu 0.05 Mn 0.67 O 2 exhibits an outstanding capacity retention (83.4% after 2000 cycles at 10C) and rate performance (73 mAh g -1 at 10C, accounting for 58.7% of that at 0.1 C) over the voltage range of 2.5–4.4 V. Intensive explorations further manifest that the modified mechanism of dual-ion doping strategy is attributed to the synergistic coupling effect of a substantial change in Na occupancy distribution and an increase in oxygen vacancy buffer. Thus, the optimized cathode expedites Na + diffusion and reduces detrimental phase transformation, which favors high-rate performance and long-term cycling stability. This study develops a route to rationally design high-voltage cathode materials for SIBs.

25 ENERGY STORAGE↗

Theoretical Analysis of Experimental Data of Sodium Diffusion in Oxidized Molybdenum Thin Films

In this work, the diffusion process of sodium (Na) in molybdenum (Mo) thin films while it was deposited on soda lime glass (SLG) was studied. A small amount of oxygen was present in the chamber while the direct-current (DC) magnetron sputtering was used for the deposition. The substrate temperatures were varied to observe its effect. Such molybdenum films, with or without oxidations, are often used in thin film solar cells, either as back contact or as hole transport layers. Secondary ion mass spectrometry (SIMS) was used to quantify the concentration of the species. A grain diffusion mechanistic model incorporating the effect of grain and grain boundary geometrical shape and size was developed. The model was used to provide an in-depth theoretical analysis of the sodium diffusion in molybdenum thin films that lead to the measured SIMS data. It was observed that not only diffusion coefficients should be considered when analyzing diffusion processes in thin films but also the ratio of grain boundary size to grain size. Both depend on substrate temperature and directly affect the amount of diffused species in the film. The data were analyzed under the light of the film growth speed versus diffusion front speed, the effect of oxygen content, and the effect of substrate temperature on the overall diffusion process. The temperature inversely affects the ratio of grain boundary size and grain size and directly affects the diffusion coefficient, which leads to a preferable temperature at which the highest amount of alkali can be found in the film.

36 MATERIALS SCIENCE↗

Sulfur transformations at the hydrogen sulfide/oxygen interface in stratified waters and in cyanobacterial mats

Stratified water bodies allow the development of several microbial plates along the water column. The microbial plates develop in relation to nutrient availability, light penetration, and the distribution of oxygen and sulfide. Sulfide is initially produced in the sediment by sulfate-reducing bacteria. It diffuses along the water column creating a zone of hydrogen sulfide/oxygen interface. In the chemocline of Solar Lake oxygen and sulfide coexist in a 0 to 10 cm layer that moves up and down during a diurnal cycle. The microbial plate at the chemocline is exposed to oxygen and hydrogen sulfide, alternating on a diurnal basis. The cyanobacteria occupying the interface switch from anoxygenic photosynthesis in the morning to oxygenic photosynthesis during the rest of the day which results in a temporal build up of elemental sulfur during the day and disappears at night due to both oxidation to thiosulfate and sulfate by thiobacilli, and reduction to hydrogen sulfide by Desulfuromonas sp. and anaerobically respiring cyanobacteria. Sulfate reduction was enhanced in the light at the surface of the cyanobacterial mats. Microsulfate reduction measurements showed enhanced activity of sulfate reduction even under high oxygen concentrations of 300 to 800 micrometer. Apparent aerobic SO sub 4 reduction activity is explained by the co-occurrence of H sub 2. The physiology of this apparent sulfate reduction activity is studied.

Cohen, Y.↗

The electron-transfer intermediates of the oxygen evolution reaction (OER) as polarons by in situ spectroscopy

The conversion of diffusive forms of energy (electrical and light) into short, compact chemical bonds by catalytic reactions regularly involves moving a carrier from an environment that favors delocalization to one that favors localization. While delocalization lowers the energy of the carrier through its kinetic energy, localization creates a polarization around the carrier that traps it in a potential energy minimum. The trapped carrier and its local distortion—termed a polaron in solids—can play a role as a highly reactive intermediate within energy-storing catalytic reactions but is rarely discussed as such. Here, we present this perspective of the polaron as a catalytic intermediate through recent in situ and time-resolved spectroscopic investigations of photo-triggered electrochemical reactions at material surfaces. The focus is on hole-trapping at metal–oxygen bonds, denoted M–OH*, in the context of the oxygen evolution reaction (OER) from water. The potential energy surface for the hole-polaron defines the structural distortions from the periodic lattice and the resulting “active” site of catalysis. This perspective will highlight how current and future time-resolved, multi-modal probes can use spectroscopic signatures of M–OH* polarons to obtain kinetic and structural information on the individual reaction steps of OER. A particular motivation is to provide the background needed for eventually relating this information to relevant catalytic descriptors by free energies. Lastly, the formation of the O–O chemical bond from the consumption of M–OH*, required to release O 2 and store energy in H 2 , will be discussed as the next target for experimental investigations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Recent work in advanced hydrogen production concepts

The hydrogen photoelectrolytic conversion activity investigated the practicability of semiconductor electrolytic devises that use solar energy to decompose water into hydrogen and oxygen in an apparent single step process. The photocatalytic decomposition of inorganic hydrogen compounds; i.e., hydrobromic and hydriodic acids using rhodium organic bridge complexes were also studied. The feasibility of direct high temperature thermal decompositions of water with diffusion processes for separation of the equilibrium mixture of hydrogen and oxygen into usable energy sources was examined.

Lawson, D. D.↗

Permeation of oxygen through high purity, large grain silver

The permeation of high purity, large grain Ag membranes by oxygen has been studied over the temperature range 400 to 800 C. The permeability was found to be quite linear and repeatable, but the magnitude was 3.2 times smaller than that determined by past research. Since previous investigators studied substantially less pure Ag and conducted experiments within much poorer vacuum environments (which indicates that their grain boundary density was much greater), the data presented here suggest oxygen transport through the membrane is primarily by grain boundary diffusion. The diffusivity measurements were found to exhibit two distinct linear regions, one above and one below a critical temperature of 630 C. The high-temperature data have an activation energy (11.1 kcal/mole) similar to that reported by others, but the low-temperature data have a higher activation energy (15.3 kcal/mole), which can be explained by impurity trapping in the grain boundaries. Vacuum desorption of the oxygen-saturated Ag was found to occur at a threshold of 630 C, which is consistent with the onset of increased mobility within the grain boundaries.

Outlaw, R. A.↗

Understanding the impact of the gas diffusion layer structure on catalyst utilization in the PEM water electrolyzer

A multiphysics half-cell model of a polymer electrolyte membrane water electrolyzer (PEMWE) was developed to probe impacts of the detailed 3-dimensional pore structure of the gas diffusion layer (GDL) on performance characteristics. We show that pores in the titanium GDL mesh led to significant underutilization of the catalyst layer (CL), with only 45% of the catalyst effectively utilized. This contradicts the assumption of uniform electron flow across the CL, as shown in graphical abstract (a), as near-zero current was observed near GDL pore regions and the current distribution in CL was influenced by GDL structure, as shown in graphical abstract (b). Instead, oxygen generation was primarily concentrated under the solid titanium regions, diffusing out around the pore walls. High current density peaks were also noted at the GDL-catalyst contact, correlating with degradation hotspots that were directly observed in companion experiments, as shown in graphical abstract (c). Collectively, these findings point to the critical importance of the heterogeneous GDL porous architecture not only for PEMWE efficiency but also for uneven degradation of the CL.

COMSOL↗

Substitutional and Interstitial Diffusion in alpha2-Ti3Al(O)

The reaction between Al2O3 and alpha2-Ti3Al was studied with a series of Al2O3/alpha2-Ti3Al multiphase diffusion couples annealed at 900, 1000 and 1100 C. The diffusion-paths were found to strongly depend on alpha2- Ti3Al(O) composition. For alloys with low oxygen concentrations the reaction involved the reduction of Al2O3, the formation of a gamma-TiAl reaction-layer and diffusion of Al and O into the alpha2-Ti3Al substrate. Measured concentration profiles across the interaction-zone showed "up-hill" diffusion of O in alpha2-Ti3Al(O) indicating a significant thermodynamic interaction between O and Al, Ti or both. Diffusion coefficients for the interstitial O in alpha2-Ti3Al(O) were determined independently from the interdiffusion of Ti and Al on the substitutional lattice. Diffusion coefficients are reported for alpha2-Ti3Al(O) as well as gamma-TiAl. Interpretation of the results were aided with the subsequent measurement of the activities of Al, Ti and O in alpha 2-Ti3Al(O) by Knudsen effusion-cell mass spectrometry.

Copland, Evan↗

Synthesis, Processing, and Use of Isotopically Enriched Epitaxial Oxide Thin Films

Isotopic engineering has emerged as a key approach to study the nucleation, diffusion, phase transitions, and reactions of materials at an atomic level. It aims to uncover mass transport pathways, kinetics, and operational and failure mechanisms of functional materials and devices. Understanding these phenomena leads to deeper insights into important physical processes, such as the transport of ions in energy conversion and storage devices and the role of active sites and supports during heterogeneous catalytic reactions. Likewise, isotopic engineering is being pursued as a means of modifying functionality to enable future technological applications. In this Account, we summarize our recent work employing isotope labeling (e.g., 18 O 2 and 57 Fe) during thin film synthesis and postgrowth processing to reveal growth mechanisms, defect chemistry, and elemental diffusion under working and extreme conditions. Isotope-resolved analysis techniques with nanometer-scale spatial resolution, such as time-of-flight secondary ion mass spectrometry and atom probe tomography, facilitate the accurate quantification of isotopic placement and concentration in our well-defined heterostructures with precisely positioned, isotope-enriched layers. By measuring the nanometer-scale redistribution between natural abundance and isotopically enriched oxygen layers during the deposition of Fe 2 O 3 and Cr 2 O 3 by molecular beam epitaxy, we identified intermixing processes driven by surface adatoms occurring both at the film growth surface and within the first few layers below the surface. Further insights into synthesis mechanisms were gained by studying the tungsten oxide thin films grown by evaporating WO 3 powder in the presence of background 18 O 2 , revealing minimal incorporation of background oxygen during the film formation process. Thermal and radiation-enhanced diffusion in epitaxial Fe and Cr oxides were precisely tracked using 18 O and 57 Fe tracer layers incorporated into model epitaxial oxide thin films. This approach has allowed us to access thermal diffusion behavior at lower temperatures than previously measured, revealing a potential changeover in diffusion mechanism. Understanding radiation-enhanced diffusion in model oxides that represent the surface layers on the structural components of nuclear reactors informs our understanding of their corrosion behavior under irradiation. Isotopic labeling can also provide unique insights into the surface exchange reactions and defect chemistry of electrocatalysts. For instance, tracking the change in 18 O concentration at the surface of an epitaxial LaNiO 3 thin film after the electrocatalytic oxygen evolution reaction revealed the participation of lattice oxygen, confirming a hypothesis that had been proposed previously. Lastly, we highlight a new direction wherein we perform in situ processing studies utilizing isotopic tracers in conjunction with model epitaxial thin films within the atom probe tomography instrument. Additionally, this Account illustrates the great potential of isotopic engineering to enable fundamental mechanistic insights into physical processes and engineer functional properties in epitaxial films, heterostructures, and superlattices.

36 MATERIALS SCIENCE↗

An investigation of the solar zenith angle variation of D-region ionization

Model calculations are carried out with a view to interpreting the solar zenith angle variation of D-region ionization. A model is developed for the neutral chemistry including the transport terms relating to molecular and eddy diffusion. The diurnal behavior is described of the minor neutral constituents formed in an oxygen-hydrogen-nitrogen atmosphere, in the height interval between 30 and 120 km. Computations carried out for two cases of the eddy diffusion coefficients models indicate that the constituents which are important for the D-region positive-ion chemistry do not show a significant variation with zenith angle for values up to 75 deg over the D-region heights. In the ion chemistry model, ion-pair production rates are calculated for solar X-rays between 1 A and 100 A, EUV radiations from 100 A up to the Lyman-alpha line, precipitating electrons, and galactic cosmic rays. The solar zenith angle variation of the positive-ion composition, negative-ion composition, and the electron densities are described up to 75 deg zenith angle, in the height interval between 60 and 100 km.

Ratnasiri, P. A. J.↗