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At least 217 records · Page 12

Acidic attack of perfluorinated alkyl ether lubricant molecules by metal oxide surfaces

The reactions of linear perfluoropolyalkylether (PFAE) lubricants with alpha-Fe203 and Fe203-based solid superacids were studied. The reaction with alpha-Fe203 proceeds in two stages. The first stage is an initial slow catalytic decomposition of the fluid. This reaction releases reactive gaseous products which attach the metal oxide and convert it to FeF3. The second stage is a more rapid decomposition of the fluid, effected by the surface FeF3. A study of the initial breakdown step was performed using alpha-Fe203, alpha-Fe203 preconverted to FeF3, and sulfate-promoted alpha-Fe203 superacids. The results indicate that the breakdown reaction involves acidic attack at fluorine atoms on acetal carbons in the linear PFAE. Possible approaches to combat the problem are outlined.

Zehe, Michael J.↗

Coating Carbon Fibers With Platinum

A process for coating carbon fibers with platinum has been developed. The process may also be adaptable to coating carbon fibers with other noble and refractory metals, including rhenium and iridium. The coated carbon fibers would be used as ingredients of matrix/fiber composite materials that would resist oxidation at high temperatures. The metal coats would contribute to oxidation resistance by keeping atmospheric oxygen away from fibers when cracks form in the matrices. Other processes that have been used to coat carbon fibers with metals have significant disadvantages: Metal-vapor deposition processes yield coats that are nonuniform along both the lengths and the circumferences of the fibers. The electrical resistivities of carbon fibers are too high to be compatible with electrolytic processes. Metal/organic vapor deposition entails the use of expensive starting materials, it may be necessary to use a furnace, and the starting materials and/or materials generated in the process may be hazardous. The present process does not have these disadvantages. It yields uniform, nonporous coats and is relatively inexpensive. The process can be summarized as one of pretreatment followed by electroless deposition. The process consists of the following steps: The surfaces of the fiber are activated by deposition of palladium crystallites from a solution. The surface-activated fibers are immersed in a solution that contains platinum. A reducing agent is used to supply electrons to effect a chemical reduction in situ. The chemical reduction displaces the platinum from the solution. The displaced platinum becomes deposited on the fibers. Each platinum atom that has been deposited acts as a catalytic site for the deposition of another platinum atom. Hence, the deposition process can also be characterized as autocatalytic. The thickness of the deposited metal can be tailored via the duration of immersion and the chemical activity of the solution.

Effinger, Michael R.↗

Viscous shock-layer solutions with nonequilibrium chemistry for hypersonic flows past slender bodies

Laminar nonequilibrium heat transfer to slender vehicles is discussed, with heating-rate results presented as a ratio of the noncatalytic to the corresponding fully catalytic value to illustrate the maximum potential for a heating reduction in dissociated nonequilibrium flow at a given flight condition. Larger blunted cone half-angles are shown to produce the most significant nonequilibrium effects at distances beyond 100 nose radii, except in the fore-cone region. Increasing nose bluntness is found to produce large reductions in the ratio for the smaller cone angles at relatively large downstream surface lengths. It is noted that the nose radius and freestream density are not independent scaling parameters in nonequilibrium flow.

Zoby, E. V.↗

Source Contaminant Control System Design, Operation, and Testing for the Trash Compaction and Processing System

The Trash Compaction and Processing System (TCPS) aims to reduce volume, biologically safen, physically stabilize, manage effluents, and recover resources from astronaut trash in the International Space Station (ISS). This process involves heating the trash to high temperatures, which in turn releases gaseous contaminants. Effluent management scenarios involve releasing these gases back to the ISS cabin after processing and/or directly venting these gases out to space via the Vacuum Exhaust System (VES). Concerns for recovering the gases back to cabin are crew health, safety, and spacecraft environmental impact. The Heat Melt Compactor (HMC) at NASA Ames Research Center (ARC) serves as a test system that supports TCPS development by conducting risk reduction activities associated with an ISS flight demonstration. Previous gas effluent studies were conducted on the HMC. The results consisted of contaminants from the trash exhaust to exceed Spacecraft Maximum Allowable Concentrations (SMAC), which are selected airborne contaminants that can elicit toxicity symptoms to crewmembers via exposure. The Source Contaminant Control System (SCCS) aims to reduce that risk by converting the contaminants into carbon dioxide (CO2) and water (H2O) vapor. The SCCS is composed of a carbon adsorbent bed, to avoid catalyst poisoning, and a catalytic oxidizer (CatOx), which promotes oxidation of the contaminants to CO2and H2O. In turn, the gases coming out of the SCCS should be compatible to the ISS cabin and systems such as the Trace Contaminant Control System (TCCS). Preparation for SCCS testing alongside the HMC Gen 3 are currently underway at ARC. The main objectives are to evaluate CatOx efficiency by CO2conversion and characterize effectiveness of removal by comparing contaminant results before and after CatOx. This paper will report on the SCCS design, operation, and testing with results.

TCPS↗

Structural Model for the Flip-Flop Action in Thiamin Pyrophosphate-Dependent Human Pyruvate Dehydrogenase

The derivative of vitamin B1 thiamin pyrophosphate (TPP) is a cofactor of enzymes performing catalysis in pathways of energy production, including (i) decarboxylation of alpha-keto acids followed by (ii) transketolation. These enzymes have shown a common mechanism of TPP activation by imposing an active V-conformation of this coenzyme that brings the N4 atom of the aminopyrimidine ring to the distance required for the intramolecular C-H N hydrogen-bonding with the C2- atom of the thiazolium ring. The reactive C2 atom of TPP is the nucleophile that attacks the carbonyl carbon of different substrates used by the TPP-dependent enzymes. The structure of the heterotetrameric human pyruvate dehydrogenase (Elp) recently determined in our laboratory (1) revealed the association pattern of the subunits and the specifics of two chemically equivalent cofactor binding sites. Dynamic nonequivalence of these two cofactor sites directs the flip-flop action of this enzyme, depending upon which two active sites effect each other (2). The crystal structure derived from the holo-form of Elp provided the basis for the model of the flip-flop action of Elp in which different steps of the catalytic reaction are performed in each of the two cofactor sites at any given moment, where these steps are governed by the concerted shuttle-like motion of the subunits. It is further proposed that balancing a hydrogen-bond network and related cofactor geometry determine the continuity of catalytic events.

Ciszak, Ewa↗

The chemical and radiative effects of the Mount Pinatubo eruption

To clarify the mechanisms leading to effects on stratospheric ozone, time-dependent stratospheric aerosol and gas experiment II (SAGE II) and cryogenic limb array elaton spectrometer (CLAES) aerosol optical extinction data and SAGE II surface area density are used as parameters in a two-dimensional (2-D) zonally averaged chemical radiative transport model. The model was integrated with time from before the eruption through December 1993. The modeled impact on global ozone results from increased rates of heterogeneous reactions on sulfate aerosols and from the increased radiative heating and scattering caused by these aerosols. When the aerosol heating is allowed to modify the temperature distribution, the maximum change calculated in equatorial column ozone is -1.6%. The calculated equatorial temperature change and peak local ozone change in October 1991 are +6K and -4%, respectively. When aerosol heating perturbs the circulation in the model, the maximum change in equatorial column ozone is -6%. Increased heterogeneous processing on sulfate aerosols is calculated to have changed equatorial column ozone in late 1991 by -1.5%. Global column ozone in the model in 1992 and 1993 changed by -2.8% and -2.4%, respectively. The relationship of ozone-controlling processes in the lower stratosphere is altered as well; HO(x) becomes the most important catalytic cycle, followed by ClO(x) and NO(x). This is driven by significant changes in trace gas concentrations. In October 1991, lower stratospheric, equatorial NO(x) decreased by 40%, ClO(x) increased by 60%, and HO(x) increased by 25%. When the effect of heterogeneous chemical processing on sulfate aerosols is combined with aerosol heating, modifying either circulation or temperature, dramatically different ozone fingerprints with time and latitude are predicted. Model-derived changes in the equatorial region in column ozone best represented the observed data when perturbed circulation was combined with heterogeneous chemical effects. However, at high latitudes, the increased ozone production from the strengthening of the mean circulation tends to cancel the heterogeneous reduction of ozone. This is not in good agreement with observed data, especially in 1992 and 1993. When the circulation is held fixed and the temperature allowed to change, and heterogeneous chemical effects are included, the equatorial ozone decrease predicted was too small for 1991. However, the mid- to high-latitude decrease in 1992 and 1993 is in better agreement with observed data.

Kinneson, Douglas E.↗

Stratospheric ozone and temperature perturbations - An examination of synergistic effects

Experiments have been carried out to investigate the time-dependent effects of combined releases of CO2 and chlorofluoromethanes (CFM) on stratospheric ozone and temperature. The analysis also examines the effects of steady-state variations in CFM, CO2, and solar UV flux levels on surface temperature and latitudinal temperature distribution. Results indicate that ozone depletion, due to combined effects of CO2 and CFM increases, may show a local maximum of about 6% at about the time CO2 doubles (approximately 60 yr from now). After that, the downward trend in ozone due to Cl(x) catalytic destruction is reestablished and continues, reaching approximately 15% depletion. At steady state, compensation due to CO2 increases is approximately 1% for two to four times the ambient CO2 levels.

Callis, L. B.↗

Advanced Catalysts for the Ambient Temperature Oxidation of Carbon Monoxide and Formaldehyde

The primary applications for ambient temperature carbon monoxide (CO) oxidation catalysts include emergency breathing masks and confined volume life support systems, such as those employed on the Shuttle. While Hopcalite is typically used in emergency breathing masks for terrestrial applications, in the 1970s, NASA selected a 2% platinum (Pt) on carbon for use on the Shuttle since it is more active and also more tolerant to water vapor. In the last 10-15 years there have been significant advances in ambient temperature CO oxidation catalysts. Langley Research Center developed a monolithic catalyst for ambient temperature CO oxidation operating under stoichiometric conditions for closed loop carbon dioxide (CO2) laser applications which is also advertised as having the potential to oxidize formaldehyde (HCHO) at ambient temperatures. In the last decade it has been discovered that appropriate sized nano-particles of gold are highly active for CO oxidation, even at sub-ambient temperatures, and as a result there has been a wealth of data reported in the literature relating to ambient/low temperature CO oxidation. In the shorter term missions where CO concentrations are typically controlled via ambient temperature oxidation catalysts, formaldehyde is also a contaminant of concern, and requires specially treated carbons such as Calgon Formasorb as untreated activated carbon has effectively no HCHO capacity. This paper examines the activity of some of the newer ambient temperature CO and formaldehyde (HCHO) oxidation catalysts, and measures the performance of the catalysts relative to the NASA baseline Ambient Temperature Catalytic Oxidizer (ATCO) catalyst at conditions of interest for closed loop trace contaminant control systems.

Nalette, Tim↗

HEART Aerothermodynamic Analysis

This paper presents an assessment of the aerothermodynamic environment around an 8.3 meter High Energy Atmospheric Reentry Test (HEART) vehicle. This study generated twelve nose shape configurations and compared their responses at the peak heating trajectory point against the baseline nose shape. The heat flux sensitivity to the angle of attack variations are also discussed. The possibility of a two-piece Thermal Protection System (TPS) design at the nose is also considered, as are the surface catalytic affects of the aeroheating environment of such configuration. Based on these analyses, an optimum nose shape is proposed to minimize the surface heating. A recommendation is also made for a two-piece TPS design, for which the surface catalytic uncertainty associated with the jump in heating at the nose-IAD juncture is reduced by a minimum of 93%. In this paper, the aeroshell is assumed to be rigid and the inflatable fluid interaction effect is left for future investigations.

Mazaheri, Alireza↗

High-Energy Atmospheric Reentry Test Aerothermodynamic Analysis

This paper presents an assessment of the aerothermodynamic environment around an 8.3 meter High Energy Atmospheric Reentry Test (HEART) vehicle. This study generated twelve nose shape configurations and compared their responses at the peak heating trajectory point against the baseline nose shape. The heat flux sensitivity to the angle of attack variations are also discussed. The possibility of a two-piece Thermal Protection System (TPS) design at the nose is also considered, as are the surface catalytic affects of the aeroheating environment of such configuration. Based on these analyses, an optimum nose shape is proposed to minimize the surface heating. A recommendation is also made for a two-piece TPS design, for which the surface catalytic uncertainty associated with the jump in heating at the nose-IAD juncture is reduced by a minimum of 93%. In this paper, the aeroshell is assumed to be rigid and the inflatable fluid interaction effect is left for future investigations

Mazaheri, Alireza↗

Exploring Connectivity in Sequence Space of Functional RNA

Emergence of replicable genetic molecules was one of the marking points in the origin of life, evolution of which can be conceptualized as a walk through the space of all possible sequences. A theoretical concept of fitness landscape helps to understand evolutionary processes through assigning a value of fitness to each genotype. Then, evolution of a phenotype is viewed as a series of consecutive, single-point mutations. Natural selection biases evolution toward peaks of high fitness and away from valleys of low fitness. whereas neutral drift occurs in the sequence space without direction as mutations are introduced at random. Large networks of neutral or near-neutral mutations on a fitness landscape, especially for sufficiently long genomes, are possible or even inevitable. Their detection in experiments, however, has been elusive. Although a few near-neutral evolutionary pathways have been found, recent experimental evidence indicates landscapes consist of largely isolated islands. The generality of these results, however, is not clear, as the genome length or the fraction of functional molecules in the genotypic space might have been insufficient for the emergence of large, neutral networks. Thorough investigation on the structure of the fitness landscape is essential to understand the mechanisms of evolution of early genomes. RNA molecules are commonly assumed to play the pivotal role in the origin of genetic systems. They are widely believed to be early, if not the earliest, genetic and catalytic molecules, with abundant biochemical activities as aptamers and ribozymes, i.e. RNA molecules capable, respectively, to bind small molecules or catalyze chemical reactions. Here, we present results of our recent studies on the structure of the sequence space of RNA ligase ribozymes selected through in vitro evolution. Several hundred thousands of sequences active to a different degree were obtained by way of deep sequencing. Analysis of these sequences revealed several large clusters defined such that every sequence in a cluster can be reached from any other sequence in the same cluster through a series of single point mutations. Sequences in a single cluster appear to adopt more than one secondary structure. The mechanism of refolding within a single cluster was examined. To shed light on possible evolutionary paths in the space of ribozymes, the connectivity between clusters was investigated. The effect of length of RNA molecules on the structure of the fitness landscape and possible evolutionary paths was examined by way of comparing functional sequences of 20 and 80 nucleobases in length. It was found that sequences of different lengths shared secondary structure motifs that were presumed responsible for catalytic activity, with increasing complexity and global structural rearrangements emerging in longer molecules.

Wei, Chenyu↗

Catalysts for long-life closed-cycle CO2 lasers

Long-life, closed-cycle operation of pulsed CO2 lasers requires catalytic CO-O2 recombination both to remove O2, which is formed by discharge-induced CO2 decomposition, and to regenerate CO2. Platinum metal on a tin (IV) oxide substrate (Pt/SnO2) has been found to be an effective catalyst for such recombination in the desired temperature range of 25 to 100 C. This paper presents a description of ongoing research at NASA-LaRC on Pt/SnO2 catalyzed CO-O2 recombination. Included are studies with rare-isotope gases since rare-isotope CO2 is desirable as a laser gas for enhanced atmospheric transmission. Results presented include: (1) achievement of 98% to 100% conversion of a stoichiometric mixture of CO and O2 to CO2 for 318 hours (greater than 1 x 10 to the 6th power seconds), continuous, at a catalyst temperature of 60 C, and (2) development of a technique verified in a 30-hour test, to prevent isotopic scrambling when CO-18 and O-18(2) are reacted in the presence of a common-isotope Pt/Sn O-16(2) catalyst.

Schryer, David R.↗

Research on catalysts for long-life closed-cycle CO2 laser oaperation

Long-life, closed-cycle operation of pulsed CO2 lasers requires catalytic CO-O2 recombination both to remove O2, which is formed by discharge-induced CO2 decomposition, and to regenerate CO2. Platinum metal on a tin-oxide substrate (Pt/SnO2) has been found to be an effective catalyst for such recombination in the desired temperature range of 25 to 100 C. This paper presents a description of ongoing research at NASA-Langley on Pt/SnO2 catalyzed CO-O2 recombination. Included are studies with rare-isotope gases since rare-isotope CO2 is desirable as a laser gas for enhanced atmospheric transmission. Results presented include: (1) the effects of various catalyst pretreatment techniques on catalyst efficiency; (2) development of a technique, verified in a 30-hour test, to prevent isotopic scrambling when C(O-18) and (O-18)2 are reacted in the presence of a common-isotope Pt/Sn(O-16)2 catalyst; and (3) development of a mathematical model of a laser discharge prior to catalyst introduction.

Sidney, Barry D.↗

The response of ozone to solar activity variations - A review

The effects of solar UV variations on the ozone concentration in the atmosphere are studied with respect to determinations of the global mean ozone concentrations as measured by satellite instrumentation. The Nimbus 4 satellite revealed an NO presence, which catalytically destroys ozone, during a solar proton event. An 11-year UV variability has been detected at increasing wavelengths above 1500 A, an energy band which causes photolysis of O2 into O3, N2O into NO, and NO production in the stratosphere. The latter two reactions decrease ozone destruction. IR interferometer spectrometer (IRIS) data is cited to show an ozone variation of about 3%, which is possible with a 20% solar UV variability at 1800 A; the variability has been confirmed to exist by measurements taken from the Atmospheric Explorer E satellite.

Keating, G. M.↗

On the effect of the Fe(2+)/Fe(3+) redox couple on oxidation of carbon in hot H3PO4

Oxidation studies of graphite:glassy carbon composites have been carried out at 1 and 4.7 atm. pressures in conc. H3PO4 in the presence and absence of iron ions. The concentration of the acid was varied over 85-100 wt pct, and of the iron ions over 30-300 ppm; the temperature varied over 190-210 C. Unlike the effect of Fe, which has been observed to increase the corrosion of carbon in sulphuric acid, the corrosion in phosphoric acid was observed to be slightly decreased or not at all affected. This result arises because of the catalytic reduction of the oxidized surface groups of carbon by Fe(2+) ions. The catalytic reduction is possible because under the experimental conditions the redox potential of the Fe(2+)/Fe(3+) couple is lower than the open-circuit voltage of carbon.

Dhar, H. P.↗

Effects of Nonequilibrium at Edge of Boundary Layer on Convective Heat Transfer to a Blunt Body

This investigation is a continuation of a previous study on nonequilibrium convective heat transfer to a blunt body. In the previous study, for relatively high Reynolds number flows, it was found that: nonequilibrium convective heat transfer to a blunt body is not strongly dependent on freestream parameters, provided that the thermochemical equilibrium is reached at the edge of boundary layer; and successful testing of convective heat transfer in an arc-jet environment is possible by duplicating the surface pressure and total enthalpy. The nonequilibrium convective heat transfer computations are validated against the results of Fay and Riddell/Goulard theory. Present work investigates low Reynolds number conditions which are typical in an actual arc-jet flow environment. One expects that there will be departures from the Fay and Riddell/Goulard result since certain assumptions of the classical theory are not satisfied. These departures are of interest because the Fay and Riddell/Goulard formulas are extensively used in arc-jet testing (e.g., to determine the enthalpy of the flow and the catalytic efficiency of heat shield materials). For practical sizes of test materials, density of the test flow (and Reynolds number) in an arc-jet is such that thermochemical equilibrium may not be reached at the edge of boundary layer. For blunt body flows of nitrogen and air, computations will be presented to show the effects of thermochemical nonequilibrium at the boundary layer edge on nonequilibrium heat transfer.

Goekcen, Tahir↗

Ozone Measurements in the Mesosphere During a Solar Proton Event

Charged particle precipitation in the Earth's atmosphere produces odd nitrogen and odd hydrogen. These species take part in catalytic reactions which destroy atmospheric ozone in the stratosphere and mesosphere. Modeling efforts regarding the impact of these ionization events on the neutral atmosphere describe ozone depletions in good agreement with observations in the stratosphere and mesosphere. The photochemical effects of the solar proton event (SPE) of August 1972 are discussed, and calculations for higher altitudes (70 to 90 km) are presented that indicate after a brief reduction during and immediately following intense particle precipitation, ozone will later reach higher concentrations than those present before the event.

Lippert, W.↗

Non-noble electrocatalysts for alkaline fuel cells

Carbons activated with macrocyclics have attracted increasing attention as alternative electrocatalysts for oxygen reduction. Initial activity of these catalysts is good, but performance declines rapidly. Pyrolyzing the macrocyclic on the carbon support leads to enhanced stability and the catalysts retain good activity. The approach described is designed to develop bulk doped catalysts with similar structures to pyrolyzed macrocyclic catalysts. The transition metal and coordinated ligands are dispersed throughout the bulk of the conductive carbon skeleton. Two approaches to realizing this concept are being pursued, both involving the doping of carbon precursors. In one approach, the precursor is a solid phase carbon-containing ion-exchange resin. The precursor is doped with a transition metal and/or nitrogen, and the resulting mixture is pyrolyzed. In the other approach, the precursor is a gas-phase hydrocarbon. This is introduced with a transition metal species and nitrogen species into a reactor and pyrolyzed. Several studies have been conducted to determine if there is a synergistic effect between the transition metal and nitrogen and the effect of different methods of introducing the metal-nitrogen (M-N) coordination on performance. One approach was to introduce the metal and nitrogen separately, for example, by sequentially doping FeCl3 and NH4OH into the resin. Catalysts were prepared from an undoped ion-exchange resin, a resin doped only with N, a resin doped only with Fe, and a resin doped with both Fe and N. Introduction of nitrogen alone has no beneficial effect on the performance of the catalysts. The introduction of the Fe alone significantly improves the performance in both the high and low current density regions. When both Fe and N are introduced, the performance at lower current densities (catalytic activity) is increased beyond that of the Fe-doped carbon, but the performance at higher current densities is similar to the carbon containing only Fe. Catalysts prepared from resins-Fe(bipy)3SO4 precursors have performance that is only slightly less then CoTMPP adsorbed and pyroloyzed on Vulcan XC-72. Their performance is much better than carbons which have had the N and Fe introduced separately.

Sarangapani, S.↗