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At least 109 records · Page 6

The origin and evolution of oxygenic photosynthesis

The evolutionary developments that led to the ability of photosynthetic organisms to oxidize water to molecular oxygen are discussed. Two major changes from a more primitive non-oxygen-evolving reaction center are required: a charge-accumulating system and a reaction center pigment with a greater oxidizing potential. Intermediate stages are proposed in which hydrogen peroxide was oxidized by the reaction center, and an intermediate pigment, similar to chlorophyll d, was present.

Review, Tutorial↗

CO2 Reduction Assembly Prototype Using Microlith-Based Sabatier Reactor for Ground Demonstration

The utilization of CO2 to produce life support consumables, such as O2 and H2O, via the Sabatier reaction is an important aspect of NASA's cabin Atmosphere Revitalization System (ARS) and In-Situ Resource Utilization (ISRU) architectures for both low-earth orbit and long-term manned space missions. Carbon dioxide can be reacted with H2, obtained from the electrolysis of water, via Sabatier reaction to produce methane and H2O. Methane can be stored and utilized as propellant while H2O can be either stored or electrolyzed to produce oxygen and regain the hydrogen atoms. Depending on the application, O2 can be used to replenish the atmosphere in human-crewed missions or as an oxidant for robotic and return missions. Precision Combustion, Inc. (PCI), with support from NASA, has previously developed an efficient and compact Sabatier reactor based on its Microlith® catalytic technology and demonstrated the capability to achieve high CO2 conversion and CH4 selectivity (i.e., ≥90% of the thermodynamic equilibrium values) at high space velocities and low operating temperatures. This was made possible through the use of high-heat-transfer and high-surface-area Microlith catalytic substrates. Using this Sabatier reactor, PCI designed, developed, and demonstrated a stand-alone CO2 Reduction Assembly (CRA) test system for ground demonstration and performance validation. The Sabatier reactor was integrated with the necessary balance-of-plant components and controls system, allowing an automated, single "push-button" start-up and shutdown. Additionally, the versatility of the test system prototype was demonstrated by operating it under H2-rich (H2/CO2 of >4), stoichiometric (ratio of 4), and CO2-rich conditions (ratio of <4) without affecting its performance and meeting the equilibrium-predicted water recovery rates. In this paper, the development of the CRA test system for ground demonstration will be discussed. Additionally, the performance results from testing the system at various operating conditions and the results from durability testing will be presented.

Junaedi, Christian↗

The response of the ionosphere to the injection of chemically reactive vapors

As a gas released in the ionosphere expands, it is rapidly cooled. When the vapor becomes sufficiently tenuous, it is reheated by collisions with the ambient atmosphere and its flow is then governed by diffusive expansion. As the injected gas becomes well mixed with the plasma, a hole is created by chemical processes. In the case of diatomic hydrogen release, depression of the electron concentrations is governed by the charge exchange reaction between oxygen ions and hydrogen, producing positive hydroxyl ions. Hydroxyl ions rapidly react with the electron gas to produce excited oxygen and hydrogen atoms. Enhanced airglow emissions result from the transition of the excited atoms to lower energy states. The electron temperature in the depleted region rises sharply causing a thermal expansion of the plasma and a further reduction in the local plasma concentration.

Bernhardt, P. A.↗

Redox regulation of energy transfer efficiency in antennas of green photosynthetic bacteria

The efficiency of energy transfer from the peripheral chlorosome antenna structure to the membrane-bound antenna in green sulfur bacteria depends strongly on the redox potential of the medium. The fluorescence spectra and lifetimes indicate that efficient quenching pathways are induced in the chlorosome at high redox potential. The midpoint redox potential for the induction of this effect in isolated chlorosomes from Chlorobium vibrioforme is -146 mV at pH 7 (vs the normal hydrogen electrode), and the observed midpoint potential (n = 1) decreases by 60 mV per pH unit over the pH range 7-10. Extraction of isolated chlorosomes with hexane has little effect on the redox-induced quenching, indicating that the component(s) responsible for this effect are bound and not readily extractable. We have purified and partially characterized the trimeric water-soluble bacteriochlorophyll a-containing protein from the thermophilic green sulfur bacterium Chlorobium tepidum. This protein is located between the chlorosome and the membrane. Fluorescence spectra of the purified protein indicate that it also contains groups that quench excitations at high redox potential. The results indicate that the energy transfer pathway in green sulfur bacteria is regulated by redox potential. This regulation appears to operate in at least two distinct places in the energy transfer pathway, the oligomeric pigments in the interior of the chlorosome and in the bacteriochlorophyll a protein. The regulatory effect may serve to protect the cell against superoxide-induced damage when oxygen is present. By quenching excitations before they reach the reaction center, reduction and subsequent autooxidation of the low potential electron acceptors found in these organisms is avoided.

NASA Discipline Exobiology↗

Cold plasma processing of local planetary ores for oxygen and metallurgically important metals

The utilization of a cold plasma in chlorination processing is described. Essential equipment and instruments were received, the experimental apparatus assembled and tested, and preliminary experiments conducted. The results of the latter lend support to the original hypothesis: a cold plasma can both significantly enhance and bias chemical reactions. In two separate experiments, a cold plasma was used to reduce TiCl4 vapor and chlorinate ilmenite. The latter, reacted in an argon-chlorine plasma, yielded oxygen. The former experiment reveals that chlorine can be recovered as HCl vapor from metal chlorides in a hydrogen plasma. Furthermore, the success of the hydrogen experiments has lead to an analysis of the feasibility of direct hydrogen reduction of metal oxides in a cold plasma. That process would produce water vapor and numerous metal by-products.

Lynch, D. C.↗

Numerical Simulation of One- and Two-Phase Flows in Propulsion Systems

In this report, we present some results of problems investigated during joint research between the Hampton University Fluid Mechanics and Acoustics Laboratory (HU/FM&AL), NASA GRC, and the LaRC Hyper-X Program. This work is supported by joint research between the NASA GRC and the Institute of Mechanics at Moscow State University (IM/MSU) in Russia under a CRDF grant. The main areas of current scientific interest of the HU/FM&AL include an investigation of the proposed and patented advanced methods for aircraft engine thrust and noise benefits. These methods are based on nontraditional 3D corrugated and composite nozzle, inlet, propeller and screw designs such as a Bluebell and Telescope nozzle, Mobius-shaped screw, etc. This is the main subject of our other projects, of which one is presented at the current conference. Here we analyze additional methods for exhaust jet noise reduction without essential thrust loss and even with thrust augmentation. Such additional approaches are: (1) to add some solid, fluid, or gas mass at discrete locations to the main supersonic gas stream to minimize the negative influence of strong shock waves formed in propulsion systems. This mass addition may be accompanied by heat addition to the main stream as a result of the fuel combustion or by cooling of this stream as a result of the liquid mass evaporation and boiling; (2) Use of porous or permeable nozzles and additional shells at the nozzle exit for preliminary cooling of the hot jet exhaust and pressure compensation for off-design conditions (so-called continuous ejector with small mass flow rate); and (3) to propose and analyze new effective methods of fuel injection into the flow stream in air-breathing engines. The research is focused on a wide regime of problems in the propulsion field as well as in experimental testing and theoretical and numerical simulation analyses for advanced aircraft and rocket engines. The FM&AL Team uses analytical methods, numerical simulations, and experimental tests at the Hampton University campus, NASA, and IM/MSU. The main outcomes during this reporting period are: (1) Publications: The AIAA Paper #01-1893 has been accepted for the AIAA/NAL-NASDA-ISAS 10th International Space Planes and Hypersonic Systems and Technologies Conference, 24-27 April 2001, Kyoto, Japan. The AIAA Paper #01-3204 has been accepted for presentation at the 37th AIAA/ASME/SAE/ASEE Joint Propulsion Conference being held on 08-11 July, in Salt Lake City, UT; (2) Grants and proposals: The HU/FM&AL was awarded the NASA grant NAG3-2495 in October 2000 and the CRDF award was granted to the NASA GRC-HU FM&AL and IM/MSU (Russia) in July 2000. A solicited proposal was submitted for the NASA NRA-01GRC-02 competition and two unsolicited proposals to NASA are in preparation; (3) Theory and numerical simulations: Analytical theory, numerical simulation, comparison of theoretical with experimental results, and modification of theoretical approaches, models, grids, etc. Such investigations have been conducted for three main problems: (a) Combustion efficiency optimization in the half-duct combustor system; (b) Drag reduction effects for blunt bodies with solid needles; and (c) Solid particle injection from the butt-end against a supersonic flow. The NASA CFL3D, HU/FM&AL, and IM/MSU GODUNOV codes were used and modified for solution of these problems. The codes are based on full Euler and Navier-Stokes solvers with and without nonequilibrium oxygen-nitrogen and air-hydrogen chemical reactions in laminar and turbulent gas flow regimes; (4) Experimental tests: In the IM/MSU supersonic wind tunnel, experimental tests were conducted with different number, location, and geometric parameters of solid needles mounted at the front of the butt-end in supersonic flow. Optimal parameters were determined that provide minimal butt-end drag in the stationary flow regime. Experimental and numerical simulation results are in good agreement; (5) Student Research Activity: Involvement of one graduate and two undergraduate students as research assistants in the current project.

Gilinsky, Mikhail↗

Development and Validation of High Performance Unshrouded Centrifugal Impeller

The feasibility of using a two-stage unshrouded impeller turbopump to replace the current three-stage reusable launch vehicle engine shrouded impeller hydrogen pump has been evaluated from the standpoint of turbopump weight reduction and overall payload improvement. These advantages are a by-product of the higher tip speeds that an unshrouded impeller can sustain. The issues associated with the effect of unshrouded impeller tip clearance on pump efficiency and head have been evaluated with one-dimensional tools and full three-dimensional rotordynamic fluid reaction forces and coefficients have been established through time dependent computational fluid dynamics (CFD) simulation of the whole 360 degree impeller with different rotor eccentricities and whirling ratios. Unlike the shrouded impeller, the unshrouded impeller forces are evaluated as the sum of the pressure forces on the blade and the pressure forces on the hub using the CFD results. The turbopump axial thrust control has been optimized by adjusting the first stage impeller backend wear ring seal diameter and diverting the second stage backend balance piston flow to the proper location. The structural integrity associated with the high tip speed has been checked by analyzing a 3D-Finite Element Model at maximum design conditions (6% higher than the design speed). This impeller was fabricated and tested in the NASA Marshall Space Flight Center water-test rig. The experimental data will be compared with the analytical predictions and presented in another paper. The experimental data provides validation data for the numerical design and analysis methodology. The validated numerical methodology can be used to help design different unshrouded impeller configurations.

Chen, Wei-Chung↗

Catalyst cartridge for carbon dioxide reduction unit

A catalyst cartridge, for use in a carbon dioxide reducing apparatus in a life support system for space vehicles, is described. The catalyst cartridge includes an inner perforated metal wall, an outer perforated wall space outwardly from the inner wall, a base plate closing one end of the cartridge, and a cover plate closing the other end of the cartridge. The cover plate has a central aperture through which a supply line with a heater feeds a gaseous reaction mixture comprising hydrogen and carbon dioxide at a temperature from about 1000 to about 1400 F. The outer surfaces of the internal wall and the inner surfaces of the outer wall are lined with a ceramic fiber batting material of sufficient thickness to prevent carbon formed in the reaction from passing through it. The portion of the surfaces of the base and cover plates defined within the inner and outer walls are also lined with ceramic batting. The heated reaction mixture passes outwardly through the inner perforated wall and ceramic batting and over the catalyst. The solid carbon product formes is retained within the enclosure containing the catalyst. The solid carbon product formed is retained within the enclosure containing the catalyst. The water vapor and unreacted carbon dioxide and any intermediate products pass through the perforations of the outer wall.

Holmes, R. F.↗

Propulsion and Cryogenics Advanced Development (PCAD) Project Propulsion Technologies for the Lunar Lander

The Propulsion and Cryogenics Advanced Development (PCAD) Project in the Exploration Technology Development Program is developing technologies as risk mitigation for Orion and the Lunar Lander. An integrated main and reaction control propulsion system has been identified as a candidate for the Lunar Lander Ascent Module. The propellants used in this integrated system are Liquid Oxygen (LOX)/Liquid Methane (LCH4) propellants. A deep throttle pump fed Liquid Oxygen (LOX)/Liquid Hydrogen (LH2) engine system has been identified for the Lunar Lander Descent Vehicle. The propellant combination and architecture of these propulsion systems are novel and would require risk reduction prior to detailed design and development. The PCAD Project addresses the technology requirements to obtain relevant and necessary test data to further the technology maturity of propulsion hardware utilizing these propellants. This plan and achievements to date will be presented.

Klem, Mark D.↗

Structural Basis for Flip-Flop Action of Thiamin Pyrophosphate-Dependent Enzymes Revealed by Human Pyruvate Dehydrogenase

Thiamin pyrophosphate (TPP), the biologically active form of vitamin BI, is a cofactor of enzymes catalyzing reactions involving the cleavage of a carbon-carbon bond adjacent to an oxo group. TPP-dependent enzymes show a common mechanism of TPP activation by: (1) forming the ionic N-H...O(sup -) hydrogen bonding between the N1' atom of the aminopirymidine ring of the coenzyme and intrinsic gamma-carboxylate group of glutamate and (2) imposing an "active" V-conformation that brings the N4' atom of the aminopirymidine to the distance required for the intramolecular C-H.. .N hydrogen bonding with the thiazolium C2 atom. Within these two hydrogen bonds that rapidly exchange protons, protonation of the N1' atom is strictly coordinated with the deprotonation of the 4' -amino group and eventually abstraction of the proton from C2. The human pyruvate dehydrogenase Elp, component of human pyruvate dehydrogenase complex, catalyzes the irreversible decarboxylation of the pyruvate followed by the reductive acetylation of the lipoyl group of dihydrolipoyl acyltransferase. Elp is alpha(sub 2)beta(sub2)-heterotetrameric with a molecular mass of I54 kDa, which has two catalytic sites, each providing TPP and magnesium ion as cofactors and each formed on the interface between the PP and PYR domains. The dynamic nonequivalence of two otherwise chemically equivalent catalytic sites has been observed and the flip-flop mechanism was suggested, according to which two active sites affect each other and in which different steps of the catalytic reaction are performed in each of the sites at any given moment. Based on specific futures of human pyruvate dehydrogenase including rigid and flexible connections between domains that bind the cofactor we propose a mechanistic model for the flip-flop action of this enzyme. We postulate that the dynamic protein environment drives the exchange of tautomers in the 4' -aminopyrimidine ring of the cofactor through a concerted shuttl-like motion of tightly connected domains. The dynamic exchange of those tautomers, in turns, is required during the reactions of pyruvate decarboxylation and reductive acetylation of lipoamide. Thus the shuttle-like motion of the domains is coordinated with the reactions of decarboxylation and acetylation, which are carried out in each of the cofactor sites resulting in a flip-flop action of the enzyme. The structure-derived mechanism of action of human pyruvate dehydrogenase may be likely common for other TPP-dependent enzymes.

Dominiak, Paulina↗

Development and study of chemical vapor deposited tantalum base alloys

A technique for the chemical vapor deposition of alloys was developed. The process, termed pulsing, involves the periodic injection of reactant gases into a previously-evacuated reaction chamber where they blanket the substrate almost instantaneously. Formation of alternating layers of the alloy components and subsequent homogenization allows the formation of an alloy of uniform composition with the composition being determined by the duration and relative numbers of the various cycles. The technique has been utilized to produce dense alloys of uniform thickness and composition (Ta- 10 wt % W) by depositing alternating layers of Ta and W by the hydrogen reduction of TaCl5 and WCl6. A similar attempt to deposit a Ta - 8 wt % W - 2 wt% Hf alloy was unsuccessful because of the difficulty in reducing HfCl4 at temperatures below those at which gas phase nucleation of Ta and W occurred.

Meier, G. H.↗

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.↗

High-temperature effect of hydrogen on sintered alpha-silicon carbide

Sintered alpha-silicon carbide was exposed to pure, dry hydrogen at high temperatures for times up to 500 hr. Weight loss and corrosion were seen after 50 hr at temperatures as low as 1000 C. Corrosion of SiC by hydrogen produced grain boundary deterioration at 1100 C and a mixture of grain and grain boundary deterioration at 1300 C. Statistically significant strength reductions were seen in samples exposed to hydrogen for times greater than 50 hr and temperatures above 1100 C. Critical fracture origins were identified by fractography as either general grain boundary corrision at 1100 C or as corrosion pits at 1300 C. A maximum strength decrease of approximately 33 percent was seen at 1100 and 1300 C after 500 hr exposure to hydrogen. A computer assisted thermodynamic program was also used to predict possible reaction species of SiC and hydrogen.

Hallum, G. W.↗

Effect of high-temperature hydrogen exposure on sintered alpha-SiC

Sintered alpha-silicon carbide was exposed to pure, dry hydrogen at high temperatures for times up to 500 hr. Weight loss and corrosion were seen after 50 hr at temperatures as low as 1000 C. Corrosion of SiC by hydrogen produced grain boundary deterioration at 1100 C and a mixture of grain and grain boundary deterioration at 1300 C. Statistically significant strength reductions were seen in samples exposed to hydrogen for times greater than 50 hr and temperatures above 1100 C. Critical fracture origins were identified by fractography as either general grain boundary corrosion at 1100 C or as corrosion pits at 1300 C. A maximum strength decrease of approximately 33 percent was seen at 1100 and 1300 C after 500 hr exposure to hydrogen. A computer assisted thermodynamic program was also used to predict possible reaction species of SiC and hydrogen.

Hallum, Gary W.↗

The effect of photochemical models on calculated equilibria and cooling rates in the stratosphere

Simplified models were developed for radiative heating and cooling and for ozone photochemistry in the region 22-60 km. The latter permit the inclusion of nitrogen and hydrogen reactions in addition to simple oxygen reactions. The simplicity of the scheme facilitates the use of a wide variety of cooling and reaction rates. It is shown that joint radiative-photochemical equilibrium is appropriate to the mean state of the atmosphere between 35 and 60 km. The relaxation of perturbations from joint radiative-photochemical equilibrium was also investigated. In all cases the coupling between temperature dependent ozone photochemistry and radiation lead to a reduction of the thermal relaxation time from its purely radiative value. The latter, which amounts to about 10 days, is reduced to 2-4 days at heights of 31-35 km. This greatly enhances the dissipation of waves traveling through the stratosphere.

Blake, D.↗

Effect of high temperature hydrogen exposure on the strength and microstructure of mullite

The corrosion of near stoichiometric mullite (3Al2O3-2SiO2) by pure dry hydrogen gas was studied at 1050 and 1250 C for times up to 500 hr. The hydrogen preferentially attacked the grain boundaries of the mullite where an aluminosilicate glass was present. Corrosion of the mullite grains was observed after 125 hr at 1250 C. The hydrogen reaction removed SiO2 from the glassy grain boundaries and the mullite grains resulting in a porous alumina rich surface. At 1250 C the strength increased after short exposure times (at least up to 125 hr) and decreased by 53 percent after 500 hr. At 1050 C, all exposure times (25 to 500 hr) decreased the strength. At 500 hr room temperature strength of mullite exposed to 1050 C was reduced by 22 percent. The strength reduction after short exposure times at 1050 C is attributed to crystallization of the grain boundary glass phase.

Herbell, Thomas P.↗

Electrode kinetics of oxygen reduction - A theoretical and experimental analysis of the rotating ring-disc electrode method

In order to calculate most of the rate constants for the intermediate formation of H2O2 in the electroreduction of O2 to H2O, the theoretical treatments of the rotating ring-disc electrode method by Damjanovic et al. (1966, 1967), Bagotskii et al. (1968, 1969), and Wroblowa et al. (1976) are modified. Rotating ring-disc electrode experimental data obtained for O2 reduction in Pt in 0.55 M H2SO4 are used to illustrate the calculations of rate constants according to the above theoretical treatments. A simple reaction model as proposed by the first author is consistent with the experimental data. The results indicate that O2 (97 percent) reduces to H2O in a direct four-electron transfer reaction. The adsorption of O2 is probably the rate-determining step in the potential region more negative than 0.5 V vs. reversible hydrogen electrode.

Hsueh, K.-L.↗

In-situ carbon dioxide fixation on Mars

The authors examine several novel proposals for CO2 fixation through chemical, photochemical, and photoelectrochemical means. For example, the reduction of CO2 to hydrocarbons such as acetylene (C2H2) can be accomplished with hydrogen. Acetylene has a theoretical vacuum specific impulse of about 375 s. The authors also examine potential uses of CO, as obtained or further reduced to carbon, as a reducing agent in metal oxide processing to form metals or metal carbides for use as structural or power materials. The CO2 can be recycled to generate O2 and CO. In this study, the authors examine reaction schemes for processing in situ resources. The authors highlight chemistry with hydrogen and carbon monoxide to produce propellants and other necessities of manned exploration.

Hepp, Aloysius F.↗