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At least 127 records · Page 7

Fundamental studies of gas phase ionic reactions by ion mobility spectrometry

Ion mobility spectrometry (IMS) provides a promising approach to the study of gas phase ionic reactions in buffer gases at unusually high pressures. This point is illustrated here by studies of the Sn2 nucleophilic displacement reaction, Cl(-) + CH3Br yields Br + CH3Br, using IMS at atmospheric pressure. The equilibrium clustering reaction, Cl(-)(CHCI3)(n - 1) + CHCI3 yields Cl(-)(CHCI3)(n), where n = 1 and 2, and the effect of clustering on the Sn2 reaction with CH3Br have also been characterized by this IMS-based kinetic method. Present problems and anticipated improvements in the application of ion mobility spectrometry to studies of other gas phase ionic processes are discussed.

Giles, K.↗

Analysis and design of a gas-lubricated, sectored, floating ring seal

Helium buffered floating-ring seals used in cryogenic turbopumps are subject to large temperature variations, shaft centrifugal growth, and dynamic shaft excursions. To prevent dangerous contact friction over a wide range of operating conditions generally requires liberal clearances with consequent high leakage. Reduction of helium consumption translates into lower space vehicle helium storage requirements and thus increased payload. A hydrostatic sectored floating-ring seal is described with self-adjusting clearance capabilities that enables the seal to operate with small clearances over the operating range to minimize leakage.

Shapiro, W.↗

Optical Plasma Control During ARC Carbon Nanotube Growth

To improve nanotube production, we developed a novel optical control technique, based on the shape of the visible plasma zone created between the anode and the cathode in the direct current (DC) arc process. For a given inert gas, we adjust the anode to cathode distance (ACD) in order to obtain strong visible vortices around the cathode. This enhance anode vaporization, which improve nanotubes formation. In light of our experimental results, we focus our discussion on the relationship between plasma parameters and nanotube growth. Plasma temperature control during arc process is achieved using argon, helium, and their mixtures as a buffer gases. The variation of the gas mixture from pure argon to pure helium changes plasma temperature. As a consequence, the microscopic characteristics of nanotubes as diameter distribution is changed moving from smaller values for argon to higher diameters for helium. We also observe a dependence of the macroscopic characteristics of the final products as Brunauer-Emmett-Teller (BET) surface area.

Hinkov, I.↗

Areas of Seal R/D at GE

About four years ago, work was completed on a 36 inch diameter gas to gas carbon ring seal used to buffer low pressure turbine air at the rim of the forward outer flowpath on the GE36 unducted fan (UDF) engine. At about the same time, we were developing a long life counter-rotating intershaft air-oil seal of approximately 7.6 inch diameter for operation at 800 fps, 800 F, and 50 psid. Although we were successful in meeting most program goals with a split ring seal of the axial bushing type, the seal with the greatest payoff in life and air leakage rates, bearing many features in common with the GE36 seal, could not be successfully tested because of the structural weakness of the primary seal ring carbon material. This was a split ring seal using a hybrid combination of orifice compensated hydrostatic and shrouded hydrodynamic gas bearings. We are presently working to develop this design in conjunction with high strength materials being developed by Pure Carbon Co. In the area of engine secondary gas flow path-sealing for performance improvement, we are currently working with carbon and all metal face seals. A 15 inch diameter all metal 'aspirating' face seal, using self-acting hydrostatic bearings, was successfully tested to 700 fps, 100 psid, and 1000 F, demonstrating long life at flow reduction of 86 percent compared to a 'best' labyrinth. This seal will be developed through 1400 F, 900 fps, and 350 psid. The seal 'aspirates' closed at about idle speed pressure during engine start and reopens at engine shutdown. A hydraulic thrust balance seal, currently using orifice compensated hydrostatics, is under development. Other aspects of these projects are briefly covered.

Pope, A. Nelson↗

Io's surface - Its phase composition and influence on Io's atmosphere and Jupiter's magnetosphere

The evidence and interpretations pertaining to the surface phase composition of Io and the mechanisms by which Io's surface influences its atmosphere are discussed. The mechanism by which Io's surface and/or atmosphere supplies neutral and ionic species to the region around the satellite and ultimately to the Jovian magnetosphere is also discussed. A model is suggested in which the global SO2 gas abundance is primarily controlled by buffering in the brightest, coldest regions. The net SO2 flux across the disk is limited by regional cold trapping on high albedo regions and possibly by the resistance of a tenuous non-SO2 residual atmosphere. The continuing migration of SO2 toward cooler regions and those lacking SO2 sources is opposed by SO2 destruction and planetary ejection processes, including sputtering, thus preventing buildup of thick, ubiquitous SO2 coverage.

Fanale, F. P.↗

Experimental Investigation of Organic Synthesis in Hydrothermal Environments

Seafloor hydrothermal systems may be the most likely locations on the early Earth for the emergence of life. Because of the disequilibrium inherent in such dynamic, mixing environments, abundant chemical energy would have been available for formation of the building blocks of life. In addition, theoretical studies suggest that organic compounds in these conditions would reach metastable states, due to kinetic barriers to the formation of stable equilibrium products (CO2 and methane). The speciation of organic carbon in metastable states is highly dependent on the oxidation state, pH, temperature, pressure and bulk composition of the system. The goal of our research is to investigate the effects of a number external variables on the formation, transformation, and stability of organic compounds at hydrothermal conditions. We have begun experimental work to attempt to control the oxidation state of simulated hydrothermal systems by using buffers composed of mineral powders and gas mixtures. We are also beginning to test the stability of organic compounds under these conditions. The experiments are being performed using the hydrothermal bomb apparatus at the U.S. Geological Survey in Menlo Park, CA and the supercritical water oxidizer (SCWO) at NASA Ames Research Center in Moffet Field, CA. The amino acids decomposed rapidly. Even after the approximately 15 minutes between addition of the amino acids and the first sampling, no amino acids were detected in the PPM system by GC- MS, while in the FeFeO system the amino acids were present at a level of less than 50% of original. Carboxylic acids, ammonia, and CO2 were the main products, along with some unidentified compounds. The ratios of carboxylic acids and concentrations of other products seem to have remained stable during the experiments, consistent with observations of other metastable systems and theoretical predictions.

Shock, Everett L.↗

Experimental Investigation of Organic Synthesis in Hydrothermal Environments

The results of the investigation were presented at a Astrobiology Institute General Meeting. Seafloor hydrothermal systems may be the most likely locations on the early Earth for the emergence of life. Because of the disequilibrium inherent in such dynamic, mixing environments, abundant chemical energy would have been available for formation of the building blocks of life. In addition, theoretical studies suggest that organic compounds in these conditions would reach metastable states, due to kinetic barriers to the formation of stable equilibrium products (CO2 and methane). The speciation of organic carbon in metastable states is highly dependent on the oxidation state, pH, temperature, pressure and bulk composition of the system. The goal of our research is to investigate the effects of a number external variables on the formation, transformation, and stability of organic compounds at hydrothermal conditions. We have begun experimental work to attempt to control the oxidation state of simulated hydrothermal systems by using buffers composed of mineral powders and gas mixtures. We are also beginning to test the stability of organic compounds under these conditions.

Shock, Everett L.↗

An Optical Oxygen Sensor for Long-Term Continuous Monitoring of Dissolved Oxygen in Perfused Bioreactors

For long-term growth of man1ITlalian cells in perfused bioreactors, it is essential to monitor the concentration of dissolved oxygen (DO) present in the culture medium to quantitate and control level of DO. Continuous measurement of the amount of DO in the cell culture medium in-line under sterile conditions in NASA's perfused bioreactor requires that the oxygen sensor provide increased sensitivity and be sterilizable and nontoxic. Additionally, long-term cell culture experiments require that the calibration be maintained several weeks or months. Although there are a number of sensors for dissolved oxygen on the market and under development elsewhere, very few meet these stringent conditions. An optical oxygen sensor (BOXY) based on dynamic fluorescent quenching and a pulsed blue LED light source was developed in our laboratory to address these requirements. Tris( 4,7 -diphenyl-l, 1 O-phenanthroline )ruthenium(II) chloride is employed as the fluorescent dye indicator. The sensing element consists of a glass capillary (OD 4.0 mm; ID 2.0 mm) coated internally with a thin layer of the fluorescent dye in silicone matrix and overlayed with a black shielding layer. Irradiation of the sensing element with blue light (blue LED with emission maximum at 475 nm) generates a red fluorescence centered at 626 nm. The fluorescence intensity is correlated to the concentration of DO present in the culture medium, following the modified non-linear Stern-Volmer equation. By using a pulsed irradiating light source, the problem of dye-bleaching, which is often encountered in long-term continuous measurements of tIns type, 'is minimized. To date we achieved sensor resolution of 0.3 mmHg at 50 mmHg p02, and 0.6 mmHg at 100 mmHg p02, with a response time of about one minute. Calibration was accomplished in sterile phosphate-buffered saline with a blood-gas analyzer (BGA) measurement as reference. Stand-alone software was also developed to control the sensor and bioreactor as well as to acquire data. Two HOXY sensors with a single calibration were employed to continuously monitor the DO in GTSF-2 medium during a Baby Hamster Kidney (BHK-21) cell culture in a Rotating Wall Perfused Vessel (RWPV) bioreactor for 90 days. HOXY sensors were located at the inlet to and outlet from the bioreactor. One of the sensors was placed between an oxygenator and the inlet to the bioreactor. The dissolved oxygen concentrations determined by both sensors were compared with those measured regularly with the BGA reference. The cell culture was maintained for 110 days. Sensor output was found to correlate well with the BGA data throughout the experiment, where the DO of the medium ranged between 25 and 50 mmHg at the bioreactor outlet and 90-130 mmHg at the bioreactor inlet. Measuring DO with the HOXY sensors versus the BGA reference indicated bias values of -2 mmHg and -15 mmHg, and precision values of +/-3mmHg and +/-16 mmHg at the bioreactor inlet and outlet, respectively.

Gao, F. G.↗

Growth and micro structural studies on Yittria Stabilized Zirconia (YSZ) and Strontium Titanate (STO) buffer layers

Microstructure of Yittria Stabilized Zirconia (YSZ) and Strontium Titanate (STO) of radio frequency magnetron sputtered buffer layers was studied at various sputtering conditions on Si (100), Sapphire and LaAlO3 (100) substrates. The effect of substrate temperatures up to 800 C and sputtering gas pressures in the range of 50 mTorr. of growth conditions was studied. The buffer layers of YSZ and STO showed a strong tendency for columnar growth was observed above 15 mTorr sputtering gas pressure and at high substrate temperatures. Post annealing of these films in oxygen atmosphere reduced the oxygen deficiency and strain generated during growth of the films. Strong c-axis oriented superconducting YBa2Cu3O7-x (YBCO) thin films were obtained on these buffer layers using pulsed laser ablation technique. YBCO films deposited on multilayers of YSZ and STO were shown to have better superconducting properties.

Srinivas, S.↗

Labyrinth seal testing for lift fan engines

An abradable buffered labyrinth seal for the control of turbine gas path leakage in a tip-turbine driven lift fan was designed, tested, and analyzed. The seal configuration was not designed to operate in any specific location but was sized to be evaluated in an existing test rig. The final sealing diameter selected was 28 inches. Results of testing indicate that the flow equations predicted seal air flows consistent with measured values. Excellent sealing characteristics of the abradable coating on the stator land were demonstrated when a substantial seal penetration of .030 inch into the land surface was encountered without appreciable wear on the labyrinth knife edges.

Dobek, L. J.↗

Anisotropic transport in modulation-doped quantum-well structures

Anisotropic electron transport has been observed in GaAs modulation-doped quantum wells grown by molecular-beam epitaxy on a thick (001) Al(0.3)Ga(0.7)As buffer grown at 620 C. Thicker quantum wells (150, 200, and 300 A) show progressively less anisotropy, which vanishes for a 300-A quantum well. The degree of anisotropy is also reduced or eliminated by suspending growth of the Al(0.3)Ga(0.7)As for a period of 300 s prior to growing the GaAs quantum well. Growing the Al(0.3)Ga(0.7)As buffer at higher temperatures (680 C) also reduces the degree of anisotropy. Higher two-dimensional electron gas sheet densities result in less anisotropy.The anisotropy is eliminated by replacing the thick Al(0.3)Ga(0.7)As buffer with a periodic multilayer structure comprising 15 A of GaAs and 200 A of Al(0.3)Ga(0.7)As. The degree of anisotropy is related to the thickness and growth parameters of the Al(0.3)Ga(0.7)As layer grown just prior to the growth of the GaAs.

Radulescu, D. C.↗

The effect of Na vapor on the Na content of chondrules

Chondrules contain higher concentrations of volatiles (Na) than expected for melt droplets in the solar nebula. Recent studies have proposed that chondrules may have formed under non-canonical nebular conditions such as in particle/gas-rich clumps. Such chondrule formation areas may have contained significant Na vapor. To test the hypothesis of whether a Na-rich vapor would minimize Na volatilization reaction rates in a chondrule analog and maintain the Na value of the melt, experiments were designed where a Na-rich vapor could be maintained around the sample. A starting material with a melting point lower that typical chondrules was required to keep the logistics of working with Na volatilization from NaCl within the realm of feasibility. The Knippa basalt, a MgO-rich alkali olivine basalt with a melting temperature of 1325 +/- 5 C and a Na2O content of 3.05 wt%, was used as the chondrule analog. Experiments were conducted in a 1 atm, gas-mixing furnace with the fO2 controlled by a CO/CO2 gas mixture and fixed at the I-W buffer curve. To determine the extent of Na loss from the sample, initial experiments were conducted at high temperatures (1300 C - 1350 C) for duration of up to 72 h without a Na-rich vapor present. Almost all (up to 98%) Na was volatilized in runs of 72 h. Subsequent trials were conducted at 1330 C for 16 h in the presence of a Na-rich vapor, supplied by a NaCl-filled crucible placed in the bottom of the furnace. Succeeding Knudsen cell weight-loss mass-spectrometry analysis of NaCl determined the P(sub Na) for these experimental conditions to be in the 10(exp -6) atm range. This value is considered high for nebula conditions but is still plausible for non-canonical environments. In these trials the Na2O content of the glass was maintained or in some cases increased; Na2O values ranged from 2.62% wt to 4.37% wt. The Na content of chondrules may be controlled by the Na vapor pressure in the chondrule formation region. Most heating events capable of producing chondrules are sufficient to volatile Na. Sodium volatilization reaction rates will be reduced to varying degrees from melt droplets, depending on the magnitude of the P(sub Na) generated. A combination of Na vapor during, and Na diffusion back into chondrules after, formation could maintain and/or enrich Na concentrations in chondrules.

Lewis, R. Dean↗

The Relationship Between Clinopyroxene Fe3+ Content and Oxygen Fugacity

The intrinsic oxygen fugacity (fO2) imposed on a magma has the ability to influence the crystallization sequence of the melt, as well as the composition of the resulting minerals. fO2 is an easily controlled parameter in the lab, either through gas-mixing equilibria or with a solid-state buffer assemblage. In nature, the fO2 of a closed system is imposed on the system internally through multivalent equilibria involving the phenocryst-melt assemblage. This results in a characteristic oxidation state. The physical parameter used to quantify oxidation state is oxygen fugacity. Iron is the only major rock forming element in basaltic melts to exist in multiple valence states and, therefore, it is commonly used to assess fO2. Traditional methods to quantify fO2 utilize the ferric content of glasses or coexisting Fe-Ti oxides. However, many rocks, such as the Martian meteorites, do not contain the necessary phases or have oxides which have suffered reequilibration, thereby rendering them unmeasureable by current techniques. For these rocks, new methods, utilizing other phases are needed. Mafic minerals have Fe(3+)/SigmaFe ratios that are a function of two factors: 1) crystal chemistry and 2) their intrinsic fO2 during crystallization. Olivine and orthopyroxene, for example, have steric constraints on the extent to which Fe(3+) can be incorporated in their structures, and may not record changes in magmatic fO2 in a way that can easily be measured. The chemistry of clinopyroxene, however, allows for extensive incorporation of Fe(3+) in its crystal structure, making it a potentially useful oxybarometer. To date, there have been few, if any, systematic experimental studies of the variation of the Fe(3+)/SigmaFe ratio as a function of fO2 in clinopyroxene. This study seeks to address this lack of data.

McCanta, M. C.↗

Nuclear light bulb propellant heating simulation using a tungsten/argon aerosol and radiation from a dc arc surrounded by a segmented mirror cavity

Experiments were conducted to simulate radiant heating of the propellant stream of a nuclear light bulb engine to obtain high bulk exit temperatures in the flowing simulated propellant stream by absorption of large fractions of the incident thermal radiation. A high-power, vortex-stabilized dc arc within an uncooled fused silica tube was used as the radiant energy source. It was surrounded by a mirror system to increase the radiation incident on the simulated propellant. The 12.7-cm-long by 2.3-cm-wide, diverging-duct test section had a transparent front wall and a reflecting rear wall. The central stream of seeded gas, a tungsten-particle/argon aerosol, had unseeded argon buffer layers on both sides to prevent coating of the duct walls. Arc operating times were approximately 0.5 sec with power levels up to 780 kW. Bulk exit temperatures were measured using a calorimeter downstream of the duct. The maximum simulated propellant bulk exit temperature obtained was 4515 K, compared with 3860 K in previous tests, 3300 to 3700 K expected in in-reactor tests in the Nuclear Furnace, and 6660 K in the reference nuclear light bulb engine. The maximum temperature in these tests was limited primarily by the amount of radiation incident on the test section (determined by the arc operating characteristics and the effectiveness of the mirror cavity).

Klein, J. F.↗

Using In-Situ Deposition of Metallic Thin Films on Mars to Monitor Atmospheric H20

We describe the use of a novel sensor, designed to characterize the reactive nature of the Martian atmosphere, to also characterize the instantaneous abundance of atmospheric H,O. The sensor deposits, in situ, a thin silver film onto a sapphire substrate and monitors oxidation by measuring resistance of the Ag film during both deposition and subsequent oxidation [1,2]. . The evaporation source is placed in the center of a hollow, open-ended tube. On flash heating the source, evaporated metallic silver rapidly reacts with oxidizing gases in the tube, depositing on the tube walls as a resisitive Ag oxide film. Unoxidized silver deposits over the Ag oxides, once the oxidizing gases in the vicinity of the source have been consumed. Since the ends of the tube are open, atmospheric gases in the tube cause a time delay as the evaporated silver initially reacts with the available O2, and H2O; once oxidizing gases in the tube are significantly depleted, a silver film closes the chemiresistor circuit. In principle this operation mode provides a repeatable measure of the variable H2O abundance, since O2, levels are constant in the atmosphere. To explore the utility of the instrument as an H2O sensor, predict its behavior, and identify possible failure modes, we developed a numerical model of the instrument, and exercised it for Mars conditions. The model predicts the behavior of the electrical circuit, the temperature dependence of resistivity for each component, and the resultant Joule heating. The model balances Joule heating against radiation, sensible heat loss to ambient CO2, and, latent heat loss from sublimating Ag. The flux of Ag atoms from the source is tracked continuously. In the gas phase, the number density of Ag, O2, and H2O is calculated, along with their reaction rates on collision. The model suggests that Ag substantially depletes H2O only near the center of the tube. The model supports the hypothesis that the onset of high conductivity between the A u electrodes is a function of the H2O abundance in the ambient gas, but only to a limit; when H2O abundances are buffered at or above 240K (an H2O abundance that would not have occurred on Mars), metallic Ag never deposits in excess of Ago, and the circuit does not close. A significant difference in the Mars simulation is that the Ag source sublimates more quickly, primarily because of differences in sensible heat fluxes from the source. This allows subsequent heating of the W filament used to support the Ag source. Had the originally-designed experimental sequence been carried out on Mars, the filament might have melted, making subsequent investigations impossible.

Zent, A. P.↗

Experimental Replication of Relict "Dusty" Olivine in Type 1B Chondrules

Introduction: Relict "dusty" olivine is considered to be a remnants of previous chondrule forming events based on petrographic and chemical evidence. Dynamic crystallization experiments confirm that dusty olivine can be produced by reduction of FeO-rich olivine in Unequilibrated Ordinary Chondrite (UOC) material. The results of these experiments compliment those of who also produced dusty olivine, but from synthetic starting materials. Techniques: Dynamic crystallization experiments were conducted in which UOC material was reduced in presence of graphite. Starting material was coarsely ground GR095554 or WSG95300 that contained olivine of Fo 65-98. Approximately 75 mg. of UOC material was placed in a graphite crucible and sealed in an evacuated silica tube. The tube was suspended in a gas-mixing furnace operated at 1 log unit below the IW buffer. The experiments were as brief as 1.5 hrs up to 121 hrs. Results: Dusty olivine was produced readily in experiments melted at 1400 C for I hr. and cooled between 5 and 100 C/hr or melted at 1300-1400 C for 24 hours. Fe-rich olivine (dusty olivine precursors) that have been partially reduced were common in the experiments melted at 1400 C and cooled at 1000 C/hr or melted at 1200 C for 24 hrs. Relict olivine is absent in experiments melted at 1400 for 24 hrs, melted above 1400 C, or cooled more slowly than 10 C/hr. Relict olivine in the experiments has minimum Fo value of 83 . Thus even in the shortest experiments the most Fe-rich olivine has been altered significantly. The precursor olivine disappears in a few to many hours depending on temperature. The experiments show Fe-rich olivine in all stages of transition to the new dusty form. The olivine is reduced to form dusty olivine in a matter of a few hours at temperatures less than 1400 C and in minutes at higher temperatures. The reduction appears to proceed from the rim of the crystal inward with time. The reduction appears initially rectilinear as if controlled by crystallography, but with time Fe-metal blebs are randomly distributed throughout the olivine. In a given experiment, dusty olivine can be found in varying stages of development, but in the longest experiments, the Fe-metal blebs are dominant and they appear to be migrating out of the olivine. The composition of the dusty olivine ranges from Fo 94-99. The Cr, Mn, and Ca content of the newly formed, dusty olivine is slightly less on average that the precursor olivine, but is till with the range of type 1 olivine. Chadacrysts in the low Ca pyroxene are most common in the higher temperature, more slowly cooled experiments and range in composition from Fo 90-99. Application to chondrule formation: These experiments place time-temperature limits on the preservation of Fe-rich olivine and the production of dusty olivine during chondrule forming events. The reduction process proceeds in a few hours at temperatures above 1400 C and in 10's of hours at temperature between 1200 and 1300 C. This result further confirms th at chondrules form in a few hours to days as suggested earlier. The experiments also confirm that dusty olivine can form from typical Fe-rich olivine in UOC material during the recycling of such olivine in the chondrule forming process.

Lofgren, Gary E.↗

Io's atmosphere from microwave detection SO2

The microwave detection of SO2 at 222 GHz in Io's atmosphere is reported. The observations imply an SO2 surface pressure of 4-35 nanobars, covering 3-15 percent of the surface on both leading and trailing sides of Io when illuminated by the sun. This supports atmospheric models in which the partial pressure of SO2 at the surface is determined by the Io surface temperature, favoring, in particular, the 'albedo cold-trap' models. The failure to detect H2S at 169 GHz suggests that the pressure of this gas is probably below 10 to the -10th bar. These results, taken together with Pioneer ionospheric data, suggest that an atmospheric gas other than SO2 is present. It is proposed that the locally buffered SO2 atmosphere coexists with a background atmosphere of oxygen with a partial surface pressure of about 20 nanobars.

Lellouch, Emmanuel↗