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At least 181 records · Page 10

Methane Post-Processing for Oxygen Loop Closure

State-of-the-art United States Atmospheric Revitalization carbon dioxide (CO2) reduction is based on the Sabatier reaction process, which recovers approximately 50% of the oxygen (O2) from crew metabolic CO2. Oxygen recovery from carbon dioxide is constrained by the limited availability of reactant hydrogen. Post-processing of methane to recover hydrogen with the Umpqua Research Company Plasma Pyrolysis Assembly (PPA) has the potential to further close the Atmospheric Revitalization oxygen loop. The PPA decomposes methane into hydrogen and hydrocarbons, predominantly acetylene, and a small amount of solid carbon. The hydrogen must then be purified before it can be recycled for additional oxygen recovery. Long duration testing and evaluation of a four crew-member sized PPA and a discussion of hydrogen recycling system architectures are presented.

Greenwood, Zachary W.↗

High Energy Density Matter for Rocket Propulsion

The objective of the High Energy Density Matter (HEDM) program is to identify, develop, and exploit high energy atomic and molecular systems as energetic sources for rocket propulsion applications. It is a high risk, high payoff program that incorporates both basic and applied research, experimental and theoretical efforts, and science and engineering efforts. The HEDM program is co-sponsored by the Air Force Office of Scientific Research (AFOSR) and the Phillips Laboratory (PURKS). It includes both in-house and contracted University/Industry efforts. Technology developed by the HEDM program offers the opportunity for significant breakthroughs in propulsion system capabilities over the current state-of-the-art. One area of great interest is the use of cryogenic solids to increase the density of the propellant and to act as a stable matrix for storage of energetic materials. No cryogenic solid propellant has ever been used in a rocket, and there remain engineering challenges to such a propellant. However, these solids would enable a wide class of highly energetic materials by providing an environment that is at very low temperatures and is a physical barrier to recombination or energy loss reactions. Previous to our experiments only hydrogen atoms had been isolated in solid hydrogen. To date we have succeeded in trapping B, Al, Li, N, and Mg atoms in solid H2. Small molecules, such as B2 and LiB, are also of interest. Current efforts involve the search for new energetic small molecules, increasing free radical concentrations up to 5 mole percent, and scale-up for propulsion testing.

Carrick, Patrick G.↗

Interfacial impurities and the reaction between Si and evaporated Al

As commonly formed, the interface between substrate Si and evaporated Al is laden with impurities. Subsequent heating causes modest dissolution of Si into solid Al, the dissolution morphology being influenced by the interface impurities. In the present experiments, the amount of Si dissolving was considerably enhanced, causing sufficient interface movement to carry most interfaces clear of the original impurities. Under these conditions, the Si/Al interface assumes, during brief heat treatment, a simple shape composed of a few 111 plane-type facets. Such Si/Al interfaces produced in situ should be useful for low-temperature solid-state growth of Si.

Best, J. S.↗

Material growth and characterization for solid state devices

During the reporting period, InGaAs was grown on Fe-doped (semi-insulating) (100) InP substrates by current controlled liquid phase epitaxy (CCLPE) at 640 C and current densities of 2.5A sq/cm to 5 A/sq cm for periods from 5 to 30 minutes. Special efforts were made to reduce the background carrier concentration in the grown layers as much as possible. The best layers exhibited carrier concentrations in the mid-10 to the 15th power/cu cm range and up to 10,900 sq cm/V-sec room temperature mobility. InGaAsP quaternary layers of energy gap corresponding to wavelengths of approximately 1.5 microns and 1.3 microns were grown on (100) InP substrates by CCLPE. In the device fabrication area, work was directed toward processing MISFET's using InGaAs. SiO2, Si3N4 and Al2O3 were deposited by ion beam sputtering, electron beam evaporation and chemical vapor reaction on Si, GaAs, and InGaAs substrates. SiO2 and Si3N4 sputtered layers were found to possess a high density of pinhole defects that precluded capacitance-voltage analysis. Chemical vapor deposited Al2O3 layers on Si, GaAs and InGaAs substrates also exhibited a large number of pinhole defects. This prevented achieving good MIS devices over most of the substrate surface area.

Stefanakos, E. K.↗

Heterogeneous processes: Laboratory, field, and modeling studies

The efficiencies of chemical families such as ClO(x) and NO(x) for altering the total abundance and distribution of stratospheric ozone are controlled by a partitioning between reactive (active) and nonreactive (reservoir) compounds within each family. Gas phase thermodynamics, photochemistry, and kinetics would dictate, for example, that only about 1 percent of the chlorine resident in the lower stratosphere would be in the form of active Cl or ClO, the remainder existing in the reservoir compounds HCl and ClONO2. The consistency of this picture was recently challenged by the recognition that important chemical transformations take place on polar regions: the Airborne Antarctic Ozone Experiment (AAOE) and the Airborne Arctic Stratospheric Expedition (AASA). Following the discovery of the Antarctic ozone hole, Solomon et al. suggested that the heterogeneous chemical reaction: ClONO2(g)+HCl(s) yields Cl2(g)+HNO3(s) could play a key role in converting chlorine from inactive forms into a species (Cl2) that would rapidly dissociate in sunlight to liberate atomic chlorine and initiate ozone depletion. The symbols (s) and (g) denote solid phase, or adsorbed onto a solid surface, and gas phase, respectively, and represent the approach by which such a reaction is modeled rather than the microscopic details of the reaction. The reaction was expected to be most important at altitudes where PSC's were most prevalent (10 to 25 km), thereby extending the altitude range over which chlorine compounds can efficiently destroy ozone from the 35 to 45 km region (where concentrations of active chlorine are usually highest) to lower altitudes where the ozone concentration is at its peak. This chapter will briefly review the current state of knowledge of heterogeneous processes in the stratosphere, emphasizing those results obtained since the World Meteorological Organization (WMO) conference. Sections are included on laboratory investigations of heterogeneous reactions, the characteristics and climatology of PSC's, stratospheric sulfate aerosols, and evidence of heterogeneous chemical processing.

Poole, Lamont R.↗

Arylethynyl Substituted 9,lO-Anthraquinones: Tunable Stokes Shifts by Substitution and Solvent Polarity

2-Arylethynyl- and 2,6- and 2,7-diarylethynyl-substituted 9,lO-anthraquinones were synthesized via Sonogashira coupling reactions of 2-bromo-, 2,6-dibromo-, and 2,7-dibromo-9,10- anthraquinone with para-substituted phenylacetylenes. While the redox properties of those compounds are almost insensitive to substitution, their absorption maxima are linearly related to the Hammett constants with different slopes for electron donors and electron acceptors. ABI compounds are photoluminescent both in solution (quantum yields of emission <= 6 %), and as solids. The emission spectra have the characteristics of charge-transfer bands with large Stokes shifts (100-250 nm). The charge-transfer character of the emitting state is supported by large dipole moment differences between the ground and the excited state as concluded on the basis of molecular modeling and Lippert-Mataga correlations of the Stokes shifts with solvent polarity. Maximum Stokes shifts are attained by both electron-donating and -withdrawing groups. This is explained by a destabilization of the HOMO by electron donors and a stabilization of the LUMO by electron acceptors. X-ray crystallographic analysis of, for example, 2,7-bisphenylethynfl- 9,lO-anthraquinone reveals a monoclinic P21In space group and no indication for pi-overlap that would promote quenching, thus explaining emission from the solid state. Representative reduced forms of the title compounds were isolated as stable acetates of the corresponding dihydrs-9,10- anthraquinones. The emission of these compounds is blue-shifted relative to the parent oxidized forms and is attributed to internal transitions in the dihydro-9,lO-anthraquinone core.

Yang, Jinhua↗

Charged particle activation studies on the surface of LDEF spacecraft

High energy proton induced nuclear reaction products are examined using seven elements, namely: Al, Si, Ni, Co, Zr, Ta, and W. Activities were detected due to Na-22 from Al, Co-56 from Ni, Co-58 from Cu, and Y-88 from Zr targets. No induced activity was observed in Si, Ta, and W, most probably due to the long cooling times. Only Zr sample contained a weak Be-7 peak, although Ta and W were also located at the leading edge of the spacecraft. Gamma rays of individual isotopes were measured using high resolution Ge(Li) solid state detector coupled to 4096 multichannel analyzer. Activities were calculated for Co-56 (846 keV) and Co-57 (122 and 136 keV's) at the time of the entry of the spacecraft and found to be 0.014 + or - c/sec g, 0.018 + or - 0.002 c/sec g, and 0.0024 + or - 0.0007 c/sec g, respectively.

Olmez, Ilhan↗

Comet Shoemaker-Levy 9, Jupiter, and Impact Shock Chemistry

Four years ago this month, a hitherto unknown comet in loose orbit around Jupiter passed so near the giant planet that it was torn apart into 20 fragments by tides. One orbit later, two years ago this month, the fragments of doomed comet P/Shoemaker Levy (SL9) fell into Jupiter. The enormous energies of these impacts (the largest fragments were nearly 1 km across and, hitting at 60 km/s, released some 2-4 x 10(exp 27) ergs) produced enormous explosions. Several of the ejecta plumes were imaged towering 3000 km above Jupiter's limb. The heat released when the plumes fell was considerable and easily observed on Earth. The impacts produced strong shocks, both promptly at the impact site and again, later, and over thousands of kilometers, when the ejecta plume reentered the atmosphere. The focus of this talk will be to discuss what the SL9 impacts taught us about impact shock chemistry - the processes, the ingredients, the results - and what inferences we may draw for impacts on early Earth. Shock chemistry generates a suite of molecules not usually seen on Jupiter. The most surprising report was of a huge amount of diatomic sulfur S2 at the site of the G impact. Other unusual products include CS, CS2, OCS, H2S, SO2, HCN, CO, and H2O; although H2S and H2O are doubtless abundant below the visible clouds. Hot or enhanced CH4 and NH3 were also detected. A general rule of shock chemistry is that CO forms until either C or O is exhausted. If O greater than C, the other products are oxidized, and excess O goes to H2O. If C greater than O, the other products are reduced, and excess C goes to HCN, C2H2, and a wide variety of more complicated organics. Ultimately, given time, the carbon would react all the way to graphite, but in practice the reactions are incomplete. The dark ejecta debris were probably composed in part of carbonaceous particles generated by the shocks. In a sense, the SL9 impacts performed the famous Miller-Urey experiment on a grand scale, with one result being the production of a lot of complex brown organic solids (called "tholins"). We use, a straightforward chemical kinetics model for the H, N, C, O, S system to follow the nonequilibrium chemistry behind the shocks. The model traces the evolving chemical composition of a parcel of gas by directly integrating the web of chemical reactions. Pressure and temperature histories of the parcels are patterned after those calculated by numerical hydrodynamic simulations of the ejecta plume. A given plume parcel is generally shocked twice; t.e a parcel shocked near the impact site is ejected at high velocity and is shocked again when it reenters the atmosphere. The final state of the gas depends mostly on the second shock, provided that the latter is hot enough. The chemical evidence is ambiguous, but most indications are that C greater than O in the shocked, reacting gas. Telltale signatures of abundant oxygen - SO2, SO, CO2, O2 - were not seen, while signatures of abundant carbon - CS, CS2, and HCN - were. On the other hand, abundant H2O would appear to require O greater than C, and two other observed sulfur species, S2 and OCS, appear to form more easily in a somewhat oxidized gas, presumable vaporized from the comet itself. Since on general principles one expects the -comet to have had a more-or-less cosmic composition, i.e. O greater than C, the production of CS, CS2, and HCN probably requires C greater than O in the shocked jovian air. This in turn implies that even the largest fragments released the bulk of their energy above the jovian water table, in all likelihood above 5 bars . There is no evidence in favor of the proposition that a significant amount of wet jovian air was shocked strongly enough to coax water to react; i.e. wet jovian air saw only temperatures significantly below 2000 K.

Zahnle, Kevin↗

The effect of solid phase reactions on the ballistic properties of propellants

The combustion of NHClO4 composite propellants was studied between 15 and 3000 psi. The emphasis was on determining the mechanisms by which the fuel components influence the burning rate of the composites. All combustion experiments were performed with pressed powder strands. The fuels affected the combustion mechanism of the composite through their effect on the oxidizer decomposition mechanism, the composite surface temperature, and by reacting heterogeneously with the oxidizer on the surface of the composite. The results indicate that the fuel component has a significant effect on the surface temperature in both catalyzed and uncatalyzed composites. The data suggest that the contribution, to the overall combustion reaction, of heterogeneous reactions increases with increasing pressure. There is also evidence that even in steady state combustion the ignition of individual oxidizer particles is an important parameter in determining the combustion characteristics of the composite.

Schmidt, W. G.↗

Hydrazine reduction of transition metal oxides - In situ characterization using X-ray photoelectron spectroscopy

The transition metal oxides (TMOs) V2O5, FeO3, Co3O4, NiO, CuO, and ZnO were exposed to hydrazine at various pressures. The metallic surfaces were surveyed by in situ X-ray photoelectron spectroscopy to determine the irrelative rate of reduction by hydrazine. The most easily reducible oxide, CuO, could be reduced to the metallic state at room temperature and 10 to the -6th torr. The reaction is first order with respect to CuO, with an activation energy of about 35 kJ/mol. Two types of adsorption were seen to occur at 295 K: (1) a reversible component in which the measured N:Cu ratio increased to 0.60 at hydrazine pressures up to 0.5 torr, and (2) an irreversible component, with a N:Cu ratio of 0.28, which could not be removed by extended vacuum pumping. The results of this study are useful for the identification of TMO's that can be used as solid neatallizers of hydrazine spills, and for the preparation of metal surfaces for electroplating and evaporative thin-film coating.

Littrell, D. M.↗

CFD Assessment of Forward Booster Separation Motor Ignition Overpressure on ET XT 718 Ice/Frost Ramp

Computational fluid dynamics assessment of the forward booster separation motor ignition over-pressure was performed on the space shuttle external tank X(sub T) 718 ice/frost ramp using the flow solver OVERFLOW. The main objective of this study was the investigation of the over-pressure during solid rocket booster separation and its affect on the local pressure and air-load environments. Delta pressure and plume impingement were investigated as a possible contributing factor to the cause of the debris loss on shuttle missions STS-125 and STS-127. A simplified computational model of the Space Shuttle Launch Vehicle was developed consisting of just the external tank and the solid rocket boosters with separation motor nozzles and plumes. The simplified model was validated by comparison to full fidelity computational model of the Space Shuttle without the separation motors. Quasi steady-state plume solutions were used to calibrate the thrust of the separation motors. Time-accurate simulations of the firing of the booster-separation motors were performed. Parametric studies of the time-step size and the number of sub-iterations were used to find the best converged solution. The computed solutions were compared to previous OVERFLOW steady-state runs of the separation motors with reaction control system jets and to ground test data. The results indicated that delta pressure from the overpressure was small and within design limits, and thus was unlikely to have contributed to the foam losses.

Tejnil, Edward↗

Charged particle activation studies on the surface of LDEF spacecraft

High energy proton induced nuclear reaction products are examined using seven elements, namely: aluminum, silicon, nickel, copper, zirconium, tantalum, and tungsten. We detected activities due to Na-22 from Al, Co-56 and Co-57 from Ni, Co-58 from Cu, and Y-88 from Zr targets. No induced activity was observed in Si, Ta, and W, most probably due to the long cooling times. Only the Zr sample contained a weak Be-7 peak, although Ta and W were also located at the leading edge of the spacecraft. Gamma-rays of individual isotopes were measured using a high-resolution Ge(Li) solid state detector coupled to a 4096-multichannel analyzer. Activities were calculated for Co-56 (846 keV) and Co-57 (122 and 136 keV's) at the time of the entry of the spacecraft and found to be 0.014 +/- 0.005 c/s-g, 0.018 +/- 0.002 c/s-g, and 0.0024 +/- 0.0007 c/s-g, respectively.

Olmez, Ilhan↗

Continuous coal processing method

A coal pump is provided in which solid coal is heated in the barrel of an extruder under pressure to a temperature at which the coal assumes plastic properties. The coal is continuously extruded, without static zones, using, for example, screw extrusion preferably without venting through a reduced diameter die to form a dispersed spray. As a result, the dispersed coal may be continuously injected into vessels or combustors at any pressure up to the maximum pressure developed in the extrusion device. The coal may be premixed with other materials such as desulfurization aids or reducible metal ores so that reactions occur, during or after conversion to its plastic state. Alternatively, the coal may be processed and caused to react after extrusion, through the die, with, for example, liquid oxidizers, whereby a coal reactor is provided.

Ryason, P. R.↗

Series Bosch System Development

State-of-the-art (SOA) carbon dioxide (CO2) reduction technology for the International Space Station produces methane as a byproduct. This methane is subsequently vented overboard. The associated loss of hydrogen ultimately reduces the mass of oxygen that can be recovered from CO2 in a closed-loop life support system. As an alternative to SOA CO2 reduction technology, NASA is exploring a Series-Bosch system capable of reducing CO2 with hydrogen to form water and solid carbon. This results in 100% theoretical recovery of oxygen from metabolic CO2. In the past, Bosch-based technology did not trade favorably against SOA technology due to a high power demand, low reaction efficiencies, concerns with carbon containment, and large resupply requirements necessary to replace expended catalyst cartridges. An alternative approach to Bosch technology, labeled "Series-Bosch," employs a new system design with optimized multi-stage reactors and a membrane-based separation and recycle capability. Multi-physics modeling of the first stage reactor, along with chemical process modeling of the integrated system, has resulted in a design with potential to trade significantly better than previous Bosch technology. The modeling process and resulting system architecture selection are discussed.

Abney, Morgan B.↗

Charged particle activation studies on the surface of LDEF spacecraft

High energy proton induced nuclear reaction products are examined using seven elements, namely, Aluminum, Silicon, Nickel, Copper, Zirconium, Tantalum, and Tungsten. The samples were in the form of plates, 2 x 2 x 1/8 inches. Activities due to Na-22 from Al, Co-56 and Co-57 from Ni, Co-58 from Cu, and Y-88 from Zr targets were detected. No induced activity was observed in Si, Ta, and W, most probably due to the long cooling times. Only the Zr sample contained a weak Be-7 peak, although Ta and W were also located at the leading edge of the spacecraft. Gamma-rays of individual isotopes were measured using high-resolution Ge(Li) solid state detector coupled to 4096-multichannel analyzer. Activities were calculated for Co-56 (846 keV) and Co-57 (122 and 136 keV's) at the time of the entry of the spacecraft and found to be 0.014 plus or minus 0.005 c/sec. g, 0.018 plus or minus 0.002 c/sec. g, and 0.0024 plus or minus 0.0007 c/sec. g, respectively.

Olmez, Ilhan↗

Shielded Heavy-Ion Environment Linear Detector (SHIELD): an experiment for the Radiation and Technology Demonstration (RTD) Mission

Radiological assessment of the many cosmic ion species of widely distributed energies requires the use of theoretical transport models to accurately describe diverse physical processes related to nuclear reactions in spacecraft structures, planetary atmospheres and surfaces, and tissues. Heavy-ion transport models that were designed to characterize shielded radiation fields have been validated through comparison with data from thick-target irradiation experiments at particle accelerators. With the RTD Mission comes a unique opportunity to validate existing radiation transport models and guide the development of tools for shield design. For the first time, transport properties will be measured in free-space to characterize the shielding effectiveness of materials that are likely to be aboard interplanetary space missions. Target materials composed of aluminum, advanced composite spacecraft structure and other shielding materials, helium (a propellant) and tissue equivalent matrices will be evaluated. Large solid state detectors will provide kinetic energy and charge identification for incident heavy-ions and for secondary ions created in the target material. Transport calculations using the HZETRN model suggest that 8 g cm -2 thick targets would be adequate to evaluate the shielding effectiveness during solar minimum activity conditions for a period of 30 days or more.

NASA Center LaRC↗

Characterization of the relationship of the cure cycle chemistry to cure cycle processing properties

Dynamic Dielectric measurements made over a wide range of frequency provide a sensitive and convenient means for monitoring the cure process in thermosets and thermoplastics. The measurement of dielectric relaxation is one of only a few instrumental techniques available for studying molecular properties in both the liquid and solid states. Furthermore, it is probably the only convenient experimental technique for studying the polymerization process of going from a monomeric liquid of varying viscosity to a crosslinked, insoluble, high temperature solid. The objective of the research is to develop on-line dielectric instrumentation for quantitative nondestructive material evaluation and closed loop smart cure cycle control. The key is to relate the chemistry of the cure cycle process to the dielectric properties of the polymer system by correlating the time, temperature, and frequency dependent dielectric measurements with chemical characterization measurements. Measurement of the wide variation in magnitude of the complex permittivity with both frequency and state of cure, coupled with chemical characterization work, have been shown in the laboratory to have the potential to determine: resin quality, composition and age; cure cycle window boundaries; onset of flow and point of maximum flow; extent of and completion of reaction; evolution of volatiles; T sub g; and, crosslinking and molecular weight buildup.

Kranbuehl, D. E.↗

Some studies on a solid-state sulfur probe for coal gasification systems

As a part of a program for the development of a sulfur probe for monitoring the sulfur potential in coal gasification reactors, an investigation was conducted regarding the efficiency of the solid electrolyte cell Ar+H2+H2S/CaS+CaF2+(Pt)//CaF2//Pt)+CaF2+CaS/H2S+H2+Ar. A demonstration is provided of the theory, design, and operation of a solid-state sulfur probe based on CaF2 electrolyte. It was found that the cell responds to changes in sulfur potential in a manner predicted by the Nernst equation. The response time of the cell at 1225 K, after a small change in temperature or gas composition, was 2.5 Hr, while at a lower temperature of 990 K the response time was approximately 9 hr. The cell emf was insensitive to a moderate increase in the flow rate of the test gas and/or the reference gas. The exact factors affecting the slow response time of galvanic cells based on a CaF2 electrolyte have not yet been determined. The rate-limiting steps may be either the kinetics of electrode reactions or the rate of transport through the electrolyte.

Jacob, K. T.↗