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At least 199 records · Page 11

Hydrogen-terminated silicon substrates for low-temperature molecular beam epitaxy

The preparation of hydrogen-terminated silicon surfaces for use as starting substrates for low-temperature MBE growth is examined in detail. The procedure involves the ex situ removal under nitrogen of residual oxide from a silicon substrate using a spin-clean with HF in ethanol, followed by the in situ low-temperature desorption (150 C) of physisorbed etch residues. The critical steps and the chemical basis for these steps are examined using X-ray photoelectron spectroscopy. Impurity residues at the epilayer-substrate interface following subsequent homoepitaxial growth are studied using AES, SIMS and TEM. Finally, scanning tunneling microscopy is used to examine the effect of cleaning methods on substrate morphology.

Grunthaner, P. J.↗

A determination of Mg(+)-ligand binding energies

Theoretical calculations employing large basis sets and including correlation are carried out for Mg(+) with methanol, water, and formaldehyde. For Mg(+) with ethanol and acetaldehyde, the trends in the binding energies are studied at the self-consistent-field level. The predictions for the binding energy of Mg(+) to methanol and water of 41 + or - 5 and 36 + or - 5 kcal/mol, respectively, are much less than the experimental upper bounds, of 61 + or - 5 and 60 + or - 5 kcal mol, determined by using photodissociation techniques. The theoretical results are inconsistent with the onset of Mg(+) production observed in the photodissociation experiments, as the smallest absorptions are calculated at about 80 kcal/mol for both Mg(+)-CH3OH and Mg(+)-H2O, and these transitions are to bound excited states. The binding energy for Mg(+) with formaldehyde is predicted to be similar to Mg(+)-H2O. The relative binding energies are in reasonable agreement with experiment. The binding energy of a second water molecule to Mg(+) is predicted to be similar to the first. This suggests that the reduced reaction rate observed for the second ligand is not a consequence of a significantly smaller binding energy, at least for the smaller ligards such as those considered in this work.

Bauschlicher, Charles W., Jr.↗

Studies of proton irradiated H2O + CO2 and H2O + CO ices and analysis of synthesized molecules

Infrared spectra of H2O + CO2 and H2O + CO ices before and after proton irradiation showed that a major reaction in both mixtures was the interconversion of CO2 yields CO. Radiation synthesized organic compounds such as carbonic acid were identified in the H2O + CO2 ice. Different chemical pathways dominate in the H2O + CO ice in which formaldehyde, methanol, ethanol, and methane were identified. Sublimed material was also analyzed using a mass spectrometer. Implications of these results are discussed in reference to comets.

Moore, M. H.↗

Toughened uni-piece fibrous insulation

A porous body of fibrous, low density silica-based insulation material is at least in part impregnated with a reactive boron oxide containing borosilicate glass frit, a silicon tetraboride fluxing agent and a molybdenum silicide emittance agent. The glass frit, fluxing agent and emittance agent are separately milled to reduce their particle size, then mixed together to produce a slurry in ethanol. The slurry is then applied to the insulation material and sintered to produce the porous body.

Leiser, Daniel B↗

Stability and reactivity of dimethylethoxysilane

The chemistry of the compound dimethylethoxysilane (DMES) is discussed especially as it relates to waterproofing silica surfaces. Some of the desirable properties of this compound are that it readily reacts with silica in the vapor phase, it is a low boiling point liquid (54 C), and the by-product of its reaction with silica is the rather inert substances ethanol. It is currently used by NASA to re-waterproof the HRSI shuttle tiles before relaunching the vehicle. Very little information is available on this particular compound in the literature or even on related silane compounds that have both a hydride group and an alkoxy group. Since the close proximity of two groups often drastically affects the chemical behavior of each group, chemical reactions were carried out in the laboratory with DMES to verify the expected behavior of these two functional groups located on DMES. Some of the reactions tested would be potentially useful for quantitative or qualitative measurements on DMES. To study the reactions of DMES with silica surfaces, cabosil was used as a silica substrate because of its high surface area and the ease of detection by infrared spectroscopy as well as other techniques.

Johnson, Richard E.↗

Gravimetric capillary method for kinematic viscosity measurements

A novel version of the capillary method for viscosity measurements of liquids is presented. Viscosity data can be deduced in a straightforward way from mass transfer data obtained by differential weighing during the gravity-induced flow of the liquid between two cylindrical chambers. Tests of this technique with water, carbon tetrachloride, and ethanol suggest that this arrangement provides an accuracy of about +/- 1 percent. The technique facilitates operation under sealed, isothermal conditions and, thus can readily be applied to reactive and/or high vapor pressure liquids.

Rosenberger, Franz↗

Test results of the SHARE II Mid-deck Flight Experiment

The SHARE II (Space Station Advanced Radiator Experiment II) Mid-deck Experiment was flown on board the Space Shuttle (STS-37) from April 5 to 12, 1991. The purpose of the experiment was to demonstrate the operation of several design changes proposed for the NASA/Grumman SHARE II heat pipe as a result of the lessons learned during the first SHARE flight (STS-29) in March 1989. Two test articles flew during the mission. The first, the Bubble Management Test Article, was a Plexiglas model of the monogroove heat pipe. This test article was primarily used to evaluate the performance of two 0-g bubble management devices; the redesigned evaporator screen artery and the condenser bubble trap. The second, the Blended Manifold Priming Test Article, also constructed of Plexiglas, was used to demonstrate passive self-priming of a heat pipe blended manifold connecting three evaporator legs to a single condenser leg. Both test articles used a 50/50 mixture of ethanol and water as the working fluid. Overall, the experiment was highly successful, with all the major test objectives fulfilled, including blended manifold priming, condenser bubble trap operation, screen artery bubble ingestion, and elimination of hydraulic diameter mismatch.

Brown, Richard F.↗

Small rocket research and technology

Small chemical rockets are used on nearly all space missions. The small rocket program provides propulsion technology for civil and government space systems. Small rocket concepts are developed for systems which encompass reaction control for launch and orbit transfer systems, as well as on-board propulsion for large space systems and earth orbit and planetary spacecraft. Major roles for on-board propulsion include apogee kick, delta-V, de-orbit, drag makeup, final insertions, north-south stationkeeping, orbit change/trim, perigee kick, and reboost. The program encompasses efforts on earth-storable, space storable, and cryogenic propellants. The earth-storable propellants include nitrogen tetroxide (NTO) as an oxidizer with monomethylhydrazine (MMH) or anhydrous hydrazine (AH) as fuels. The space storable propellants include liquid oxygen (LOX) as an oxidizer with hydrazine or hydrocarbons such as liquid methane, ethane, and ethanol as fuels. Cryogenic propellants are LOX or gaseous oxygen (GOX) as oxidizers and liquid or gaseous hydrogen as fuels. Improved performance and lifetime for small chemical rockets are sought through the development of new predictive tools to understand the combustion and flow physics, the introduction of high temperature materials to eliminate fuel film cooling and its associated combustion inefficiency, and improved component designs to optimize performance. Improved predictive technology is sought through the comparison of both local and global predictions with experimental data. Results indicate that modeling of the injector and combustion process in small rockets needs improvement. High temperature materials require the development of fabrication processes, a durability data base in both laboratory and rocket environments, and basic engineering property data such as strength, creep, fatigue, and work hardening properties at both room and elevated temperature. Promising materials under development include iridium-coated rhenium and a ceramic composite of mixed hafnium carbide and tantalum carbide reinforced with graphite fibers.

Schneider, Steven↗

Stabilized Alumina/Ethanol Colloidal Dispersion for Seeding High Temperature Air Flows

Seeding air flows with particles to enable measurements of gas velocities via laser anemometry and/or particle image velocimetry techniques can be quite exasperating. The seeding requirements are compounded when high temperature environments are encountered and special care must be used in selecting a refractory seed material. The pH stabilization techniques commonly employed in ceramic processing are used to obtain stable dispersions for generating aerosols of refractory seed material. By adding submicron alumina particles to a preadjusted pH solution of ethanol, a stable dispersion is obtained which when atomized produces a high quality aerosol. Commercial grade alumina powder is used with a moderate size distribution. The technique is not limited to alumina/ethanol and is also demonstrated with an alumina/H2O system. Other ceramic powders in various polar solvents could also be used once the point of zero charge (pH(sub pzc)) of the powder in the solvent has been determined.

Wernet, Judith H.↗

Demonstration of a stabilized alumina/ethanol colloidal dispersion technique for seeding high temperature air flows

Laser anemometry enables the measurement of complex flow fields via the light scattered from small particles entrained in the flow. In the study of turbomachinery, refractory seed materials are required for seeding the flow due to the high temperatures encountered. In this work we present a pH stabilization technique commonly employed in ceramic processing to obtain stable dispersions for generating aerosols of refractory seed material. By adding submicron alumina particles to a preadjusted pH solution of ethanol, a stable dispersion is obtained which when atomized, produces a high quality aerosol. Commercial grade alumina powder is used with a moderate size distribution. Other metal oxide powders in various polar solvents could also be used once the point of zero charge (pH(pzc)) of the powder in the solvent has been determined. Laser anemometry measurements obtained using the new seeding technique are compared to measurements obtained using Polystyrene Latex (PSL) spheres as the seed material.

Wernet, Mark P.↗

Ecosystem and physiological controls over methane production in northern wetlands

Peat chemistry appears to exert primary control over methane production rates in the Canadian Northern Wetlands Study (NOWES) area. We determined laboratory methane production rate potentials in anaerobic slurries of samples collected from a transect of sites through the NOWES study area. We related methane production rates to indicators of resistance to microbial decay (peat C: N and lignin: N ratios) and experimentally manipulated substrate availability for methanogenesis using ethanol (EtOH) and plant litter. We also determined responses of methane production to pH and temperature. Methane production potentials declined along the gradient of sites from high rates in the coastal fens to low rates in the interior bogs and were generally highest in surface layers. Strong relationships between CH4 production potentials and peat chemistry suggested that methanogenesis was limited by fermentation rates. Methane production at ambient pH responded strongly to substrate additions in the circumneutral fens with narrow lignin: N and C: N ratios (delta CH4/delta EtOH = 0.9-2.3 mg/g) and weakly in the acidic bogs with wide C: N and lignin: N ratios (delta CH4/delta EtOH = -0.04-0.02 mg/g). Observed Q(sub 10) values ranged from 1.7 to 4.7 and generally increased with increasing substrate availability, suggesting that fermentation rates were limiting. Titration experiments generally demonstrated inhibition of methanogenesis by low pH. Our results suggest that the low rates of methane emission observed in interior bogs during NOWES likely resulted from pH and substrate quality limitation of the fermentation step in methane production and thus reflect intrinsically low methane production potentials. Low methane emission rates observed during NOWES will likely be observed in other northern wetland regions with similar vegetation chemistry.

Valentine, David W.↗

VRA Modeling, phase 1

The destruction of organic contaminants in waste water for closed systems, such as that of Space Station, is crucial due to the need for recycling the waste water. A co-current upflow bubble column using oxygen as the gas phase oxidant and packed with catalyst particles consisting of a noble metal on an alumina substrate is being developed for this process. The objective of this study is to develop a plug-flow model that will predict the performance of this three phase reactor system in destroying a multicomponent mixture of organic contaminants in water. Mass balances on a series of contaminants and oxygen in both the liquid and gas phases are used to develop this model. These mass balances incorporate the gas-to-liquid and liquid-to-particle mass transfer coefficients, the catalyst effectiveness factor, and intrinsic reaction rate. To validate this model, a bench scale reactor has been tested at Michigan Technological University at elevated pressures (50-83 psig,) and a temperature range of 200 to 290 F. Feeds consisting of five dilute solutions of ethanol (approx. 10 ppm), chlorobenzene (approx. 20 ppb), formaldehyde (approx. 100 ppb), dimethyl sulfoxide (DMSO approx. 300 ppb), and urea (approx. 20 ppm) in water were tested individually with an oxygen mass flow rate of 0.009 lb/h. The results from these individual tests were used to develop the kinetic parameter inputs necessary for the computer model. The computer simulated results are compared to the experimental data obtained for all 5 components run in a mixture on the differential test column for a range of reactor contact times.

Kindt, Louis M.↗

Chemistry of Star-Forming Cores

Chemical effects arising from the exchange of molecules between dust and gas in dense clumps are described. Selective desorption of CO and N2 from grains in cool cores can account for the presence of ammonia in several cores in the NGC 2024 cloud. Evaporation of ices containing methanol and ethanol can lead to detectable abundances of (C2H5)(sub 2)O and CH3OC2H5. Results are presented for the hot core chemistries of sulphur and phosphorus which are initiated by evaporated hydrogen sulphide and phosphine. The implications of these studies for understanding the nature of molecular mantles, the evolution of molecular complexity in the gas phase, and the presence of small-scale abundance gradients in star-forming regions, are briefly discussed.

Charnley, S. B.↗

Development of CFC-Free Cleaning Processes at the NASA White Sands Test Facility

The NASA White Sands Test Facility (WSTF) is developing cleaning and verification processes to replace currently used chlorofluorocarbon-113- (CFC-113-) based processes. The processes being evaluated include both aqueous- and solvent-based techniques. The presentation will include the findings of investigations of aqueous cleaning and verification processes that are based on a draft of a proposed NASA Kennedy Space Center (KSC) cleaning procedure. Verification testing with known contaminants, such as hydraulic fluid and commonly used oils, established correlations between nonvolatile residue and CFC-113. Recoveries ranged from 35 to 60 percent of theoretical. WSTF is also investigating enhancements to aqueous sampling for organics and particulates. Although aqueous alternatives have been identified for several processes, a need still exists for nonaqueous solvent cleaning, such as the cleaning and cleanliness verification of gauges used for oxygen service. The cleaning effectiveness of tetrachloroethylene (PCE), trichloroethylene (TCE), ethanol, hydrochlorofluorocarbon-225 (HCFC-225), tert-butylmethylether, and n-Hexane was evaluated using aerospace gauges and precision instruments and then compared to the cleaning effectiveness of CFC-113. Solvents considered for use in oxygen systems were also tested for oxygen compatibility using high-pressure oxygen autoignition and liquid oxygen mechanical impact testing.

Beeson, Harold↗

Science Support for Space-Based Droplet Combustion: Drop Tower Experiments and Detailed Numerical Modeling

This program supports the engineering design, data analysis, and data interpretation requirements for the study of initially single component, spherically symmetric, isolated droplet combustion studies. Experimental emphasis is on the study of simple alcohols (methanol, ethanol) and alkanes (n-heptane, n-decane) as fuels with time dependent measurements of drop size, flame-stand-off, liquid-phase composition, and finally, extinction. Experiments have included bench-scale studies at Princeton, studies in the 2.2 and 5.18 drop towers at NASA-LeRC, and both the Fiber Supported Droplet Combustion (FSDC-1, FSDC-2) and the free Droplet Combustion Experiment (DCE) studies aboard the shuttle. Test matrix and data interpretation are performed through spherically-symmetric, time-dependent numerical computations which embody detailed sub-models for physical and chemical processes. The computed burning rate, flame stand-off, and extinction diameter are compared with the respective measurements for each individual experiment. In particular, the data from FSDC-1 and subsequent space-based experiments provide the opportunity to compare all three types of data simultaneously with the computed parameters. Recent numerical efforts are extending the computational tools to consider time dependent, axisymmetric 2-dimensional reactive flow situations.

Marchese, Anthony J.↗

New Approaches to Waterproofing of Space Shuttle Insulating Materials

Future reusable space vehicles will be in service much more frequently than current space shuttles. Therefore, rapid reconditioning of spacecraft will be required. Currently, the waterproofing of space shuttles after each re-entry takes 72 hours and requires substantial labor. In addition, the currently used waterproofing reagent, DiMethylEthoxySilane (DMES), is considered toxic, and ethanol fumes are released during its hydrolytic activation. Consequently, a long time period, which is not acceptable for future operations, is needed to ensure that 0 the excess volatile compounds are removed before further maintenance of the space vehicle can be performed. The objective of this project was to assist NASA Ames in finding improved waterproofing systems by identifying suitable waterproofing agents that can be applied by vapor phase deposition and will be less toxic, bond more rapidly to the insulation material surface, and potentially have higher thermal stability than the DMES system. Several approaches to achieve faster waterproofing with less toxicity were assessed using the following alternatives: Reactive volatile compounds that are rapidly deposited by chemical bonding at the surface and leave no toxic volatiles. Reactive reagents that are the least toxic. Nonvolatile reagents that are very reactive and bond strongly to the insulating material surface. Three specific types of potential reagents were chosen for evaluation in this project: 1. Volatile reagents with Si-Cl functional groups for vapor deposition 2. Volatile reagents with Si-H functional groups for vapor deposition 3. Nonvolatile oligomeric or polymeric reactive siloxanes that are assumed to have higher thermal stability and/or strong bonding to the insulating material. The chemistry involved in the project was targeted at the generation of intermediates having reactive Si-OH bonds for the formation of either volatile species or polymeric species that bond rapidly to the surface and also cure rapidly. We focused on two chemical reactions@-hydrolysis of Si-Cl bonds and catalytic dehydrocoupling of Si-H bonds.

Blum, Yigal D.↗

Replacement Technologies for Precision Cleaning of Aerospace Hardware for Propellant Service

The NASA White Sands Test Facility (WSTF) is developing cleaning and verification processes to replace currently used chlorofluorocarbon-l13- (CFC-113-) based processes. The processes being evaluated include both aqueous- and solvent-based techniques. Replacement technologies are being investigated for aerospace hardware and for gauges and instrumentation. This paper includes the findings of investigations of aqueous cleaning and verification of aerospace hardware using known contaminants, such as hydraulic fluid and commonly used oils. The results correlate nonvolatile residue with CFC 113. The studies also include enhancements to aqueous sampling for organic and particulate contamination. Although aqueous alternatives have been identified for several processes, a need still exists for nonaqueous solvent cleaning, such as the cleaning and cleanliness verification of gauges used for oxygen service. The cleaning effectiveness of tetrachloroethylene (PCE), trichloroethylene (TCE), ethanol, hydrochlorofluorocarbon 225 (HCFC 225), HCFC 141b, HFE 7100(R), and Vertrel MCA(R) was evaluated using aerospace gauges and precision instruments and then compared to the cleaning effectiveness of CFC 113. Solvents considered for use in oxygen systems were also tested for oxygen compatibility using high-pressure oxygen autogenous ignition and liquid oxygen mechanical impact testing.

Harold Beeson↗

Organic Compounds Produced by Photolysis of Realistic Interstellar and Cometary Ice Analogs Containing Methanol

The InfraRed (IR) spectra of UltraViolet (UV) and thermally processed, methanol-containing interstellar / cometary ice analogs at temperatures from 12 to 300 K are presented. Infrared spectroscopy, H-1 and C-13 Nuclear Magnetic Resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry indicate that CO (carbon monoxide), CO2 (carbon dioxide), CH4 (methane), HCO (the formyl radical), H2CO (formaldehyde), CH3CH2OH (ethanol), HC([double bond]O)NH2 (formamide), CH3C([double bond]O)NH2 (acetamide), and R[single bond]C[triple bond]N (nitriles) are formed. In addition, the organic materials remaining after photolyzed ice analogs have been warmed to room temperature contain (in rough order of decreasing abundance), (1) hexamethylenetetramine (HMT, C6H12N4), (2) ethers, alcohols, and compounds related to PolyOxyMethylene (POM, ([single bond]CH2O[single bond](sub n)), and (3) ketones (R[single bond]C([double bond]O)[single bond]R') and amides (H2NC([double bond]O)[single bond]R). Most of the carbon in these residues is thought to come from the methanol in the original ice. Deuterium and C-13 isotopic labeling demonstrates that methanol is definitely the source of carbon in HMT. High concentrations of HMT in interstellar and cometary ices could have important astrophysical consequences. The ultraviolet photolysis of HMT frozen in H2O ice readily produces the 'XCN' band observed in the spectra of protostellar objects and laboratory ices, as well as other nitriles. Thus, HMT may be a precursor of XCN and a source of CN in comets and the interstellar medium. Also, HMT is known to hydrolyze under acidic conditions to yield ammonia, formaldehyde, and amino acids. Thus, HMT may be a significant source of prebiogenic compounds on asteroidal parent bodies. A potential mechanism for the radiative formation of HMT in cosmic ices is outlined.

Bernstein, Max P.↗