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Feasibility of using very thin CVD coatings to provide both protection against oxidation and surfaces of low catalytic activity for thin metallic heat-shield materials demonstrated. Use of aluminum in compositions increases emittances of coatings and reduces transport of oxygen through coatings to substrates. Coatings light in weight and applied to foil-gauge materials with minimum weight penalties.
Many residential and commercial buildings with centralized, recirculating, heating ventilation and air conditioning systems suffer from 'Sick Building Syndrome.' Ventilation rates are reduced to save energy costs, synthetic building materials off-gas contaminants, and unsafe levels of volatile organic compounds (VOC's) accumulate. These unsafe levels of contaminants can cause irritation of eyes and throat, fatigue and dizziness to building occupants. Increased ventilation, the primary method of treating Sick Building Syndrome is expensive (due to increased energy costs) and recently, the effectiveness of increased ventilation has been questioned. On spacecraft venting is not allowed, so the primary methods of air quality control are; source control, active filtering, and destruction of VOC's. Four non-venting contaminant removal technologies; strict material selection to provide source control, ambient temperature catalytic oxidation, photocatalytic oxidation, and uptake by higher plants, may have potential application for indoor air quality control.
Trace chemical contaminant generation inside crewed spacecraft cabins is a technical and medical problem that must be continuously evaluated. Although passive control through materials selection and active control by adsorption and catalytic oxidation devices is employed during normal operations of a spacecraft, contaminant buildup can still become a problem. Buildup is particularly troublesome during the stages between the final closure of a spacecraft during ground processing and the time that a crewmember enters for the first time during the mission. Typically, the elapsed time between preflight closure and first entry on orbit for spacecraft such as Spacelab modules was 30 days. During that time, the active contamination control systems are not activated and contaminants can potentially build up to levels which exceed the spacecraft maximum allowable concentrations (SMACs) specified by NASA toxicology experts. To prevent excessively high contamination levels at crew entry, the Spacelab active contamination control system was operated for 53 hours just before launch.
The recombination of CO and O2 formed by the dissociation of CO2 in a sealed CO2 laser discharge zone is examined. Conventional base-metal-oxide catalysts and conventional noble-metal catalysts are not effective in recombining the low O2/CO ratio at the low temperatures used by the lasers. The use of Pt/SnO2 as the noble-metal reducible-oxide (NMRO), or other related materials from Group VIIIA and IB and SnO2 interact synergistically to produce a catalytic activity that is substantially higher than either componet separately. The Pt/SnO2 and Pd/SnO2 were reported to have significant reaction rates at temperatures as low as -27 C, conditions under which conventional catalysts are inactive. The gas temperature range of lasers is 0 + or - 40 C. There are three general ways in which the NMRO composite materials can interact synergistically: one component altering the properties of another component; the two components each providing independent catalytic functions in a complex reaction mechanism; and the formation of catalytic sites through the combination of two components at the atomic level. All three of these interactions may be important in low temperature CO oxidation over NMRO catalysts. The effect of the noble metal on the oxide is discussed first, followed by the effect of the oxide on the noble metal, the interaction of the noble metal and oxide to form catalytic sites, and the possible ways in which the CO oxidation reaction is catalyzed by the NMRO materials.
Atom recombination catalytic rates for surface coatings of various candidate thermal protection system materials for the space shuttle vehicle were obtained from measurements in arc jet, air flow. The coatings, chrome oxides, siliconized carbon/carbon, hafnium/tantalum carbide on carbon/carbon, and niobium silicide, were bonded to the sensitive surface of transient slug calorimeters that measured the heat transfer rates to the coatings. The catalytic rates were inferred from these heat transfer rates Surface temperatures of the calorimeters varied from approximately 300 to 410 K.
Reusable surface insulation materials, which were developed as heat shields for the space shuttle, were tested over a range of conditions including heat-transfer rates between 160 and 620 kW/sq m. The lowest of these heating rates was in a range predicted for the space shuttle during reentry, and the highest was more than twice the predicted entry heating on shuttle areas where reusable surface insulation would be used. Individual specimens were tested repeatedly at increasingly severe conditions to determine the maximum heating rate and temperature capability. A silica-base material experienced only minimal degradation during repeated tests which included conditions twice as severe as predicted shuttle entry and withstood cumulative exposures three times longer than the best mullite material. Mullite-base materials cracked and experienced incipient melting at conditions within the range predicted for shuttle entry. Neither silica nor mullite materials consistently survived the test series with unbroken waterproof surfaces. Surface temperatures for a silica and a mullite material followed a trend expected for noncatalytic surfaces, whereas surface temperatures for a second mullite material appeared to follow a trend expected for a catalytic surface.
The Sample Analysis at Mars (SAM) instrument onboard the Curiosity rover detect-ed O2 and HCl gas releases from the Rocknest (RN) eolian bedform and the John Klein (JK) and Cumberland (CB) drill hole materials in Gale Crater. Chlorinated hydrocarbons have also been detected by the SAM quadrupole mass spectrometer (QMS) and gas chromatography/mass spectrometer (GCMS). These detections along with the detection of perchlorate (ClO4-) by the Mars Phoenix Lander’s Wet Chemistry Laboratory (WCL) suggesting perchlorate is a possible candidate for evolved O2 and chlorine species. Laboratory thermal analysis of perchlorates has yet to provide an unequivocal temperature match to the SAM O2 and HCl release data. Iron mineralogy found in the Rocknest materials when mixed with Ca-perchlorate does cause O2 release temperatures to be closer match to the SAM O2 release data but more work is required in evaluating the catalytic effects of Fe mineralogy on perchlorate decomposition. Chlorates (ClO3-) are relevant Mars materials and potential O2 and Cl sources. The objective of this work is to evaluate the thermal decomposition of select chlorate (ClO3-) salts as possible sources of the O2 and HCl releases in the Gale Crater materials.
A sol-gel process has been developed as a superior alternative to a prior process for making platinum-ruthenium alloy catalysts for electro-oxidation of methanol in fuel cells. The starting materials in the prior process are chloride salts of platinum and ruthenium. The process involves multiple steps, is time-consuming, and yields a Pt-Ru product that has relatively low specific surface area and contains some chloride residue. Low specific surface area translates to incomplete utilization of the catalytic activity that might otherwise be available, while chloride residue further reduces catalytic activity ("poisons" the catalyst). In contrast, the sol-gel process involves fewer steps and less time, does not leave chloride residue, and yields a product of greater specific area and, hence, greater catalytic activity. In this sol-gel process (see figure), the starting materials are platinum(II) acetylacetonate [Pt(C5H7O2)2, also denoted Pt-acac] and ruthenium(III) acetylacetonate [Ru(C5H7O2)3, also denoted Ru-acac]. First, Pt-acac and Ru-acac are dissolved in acetone at the desired concentrations (typically, 0.00338 moles of each salt per 100 mL of acetone) at a temperature of 50 C. A solution of 25 percent tetramethylammonium hydroxide [(CH3)4NOH, also denoted TMAH] in methanol is added to the Pt-acac/Ruacac/ acetone solution to act as a high-molecular-weight hydrolyzing agent. The addition of the TMAH counteracts the undesired tendency of Pt-acac and Ru-acac to precipitate as separate phases during the subsequent evaporation of the solvent, thereby helping to yield a desired homogeneous amorphous gel. The solution is stirred for 10 minutes, then the solvent is evaporated until the solution becomes viscous, eventually transforming into a gel. The viscous gel is dried in air at a temperature of 170 C for about 10 hours. The dried gel is crushed to make a powder that is the immediate precursor of the final catalytic product. The precursor powder is converted to the final product in a controlled-atmosphere heat treatment. Desirably, the final product is a phase-pure (Pt phase only) Pt-Ru powder with a high specific surface area. The conditions of the controlled- atmosphere heat are critical for obtaining the aforementioned desired properties. A typical heat treatment that yields best results for a catalytic alloy of equimolar amounts of Pt and Ru consists of at least two cycles of heating to a temperature of 300 C and holding at 300 C for several hours, all carried out in an atmosphere of 1 percent O2 and 99 percent N2. The resulting powder consists of crystallites with typical linear dimensions of <10 nm. Tests have shown that the powder is highly effective in catalyzing the electro-oxidation of methanol.
The formation of abundant carbonaceous material in meteorites is a long standing problem and an important factor in the debate on the potential for the origin of life in other stellar systems. Many mechanisms may contribute to the total organic content in protostellar nebulae, ranging from organics formed via ion-molecule and atom-molecule reactions in the cold dark clouds from which such nebulae collapse, to similar ion-molecule and atom-molecule reactions in the dark regions of the nebula far from the proto star, to gas phase reactions in sub-nebulae around growing giant planets and in the nebulae themselves. The Fischer-Tropsch-type (FTT) catalytic reduction of CO by hydrogen was once the preferred model for production of organic materials in the primitive solar nebula. The Haber-Bosch catalytic reduction of N2 by hydrogen was thought to produce the reduced nitrogen found in meteorites. However, the clean iron metal surfaces that catalyze these reactions are easily poisoned via reaction with any number of molecules, including the very same complex organics that they produce and both reactions work more efficiently in the hot regions of the nebula. We have demonstrated that many grain surfaces can catalyze both FTT and HB-type reactions, including amorphous iron and magnesium silicates, pure silica smokes as well as several minerals. Although none work as well as pure iron grains, and all produce a wide range of organic products rather than just pure methane, these materials are not truly catalysts.
A synthesis is presented of the computer simulations of the flow over the Orbital Reentry Vehicle (ORV) at the 92.8 km and 63.6 km Earth altitude trajectory points that were discussed at the First Europe-U.S. High Speed Flow Field Database Workshop Part 2, Napoli, Italy, November 1997. For the materials used on the surface of ORV, the non-catalytic wall condition is appropriate at 92.8 km and the finite-rate catalytic wall condition at 63.6 km. Additional simulations are required for establishing the independency of the discussed results from numerics. The proper modeling of natural phenomena needs further sensitivity studies. The uncertainties of inferred flight data are lacking for a proper evaluation of the presented results.
The partial electrochemical reduction of CO2 using ceramic oxygen generators (COGs) is well known and has been studied. Conventional COGs use yttria-stabilized zirconia (YSZ) electrolytes and operate at temperatures greater than 700 C (1, 2). Operating at a lower temperature has the advantage of reducing the mass of the ancillary components such as insulation. Moreover, complete reduction of metabolically produced CO2 (into carbon and oxygen) has the potential of reducing oxygen storage weight if the oxygen can be recovered. Recently, the University of Florida developed ceramic oxygen generators employing a bilayer electrolyte of gadolinia-doped ceria and erbia-stabilized bismuth oxide (ESB) for NASA s future exploration of Mars (3). The results showed that oxygen could be reliably produced from CO2 at temperatures as low as 400 C. These results indicate that this technology could be adapted to CO2 removal from a spacesuit and other applications in which CO2 removal is an issue. This strategy for CO2 removal in advanced life support systems employs a catalytic layer combined with a COG so that the CO2 is reduced completely to solid carbon and oxygen. First, to reduce the COG operating temperature, a thin, bilayer electrolyte was employed. Second, to promote full CO2 reduction while avoiding the problem of carbon deposition on the COG cathode, a catalytic carbon deposition layer was designed and the cathode utilized materials shown to be coke resistant. Third, a composite anode was used consisting of bismuth ruthenate (BRO) and ESB that has been shown to have high performance (4). The inset of figure 1 shows the conceptual design of the tubular COG and the rest of the figure shows schematically the test apparatus. Figure 2 shows the microstructure of a COG tube prior to testing. During testing, current is applied across the cell and initially CuO is reduced to copper metal by electrochemical pumping. Then the oxygen source becomes the CO/CO2. This presentation details the results of testing the COG.
The formation of abundant carbonaceous material in meteorites is a long standing problem and an important factor in the debate on the potential for the origin of life in other stellar systems. The Fischer-Tropsch-type (FTT) catalytic reduction of CO by hydrogen was once the preferred model for production of organic materials in the primitive solar nebula. We have demonstrated that many grain surfaces can catalyze both FTT and HB-type reactions, including amorphous iron and magnesium silicates, pure silica smokes as well as several minerals. Graphite is not a particularly good FTT catalyst, especially compared to iron powder or to amorphous iron silicate. However, like other silicates that we have studied, it gets better with exposure to CO. N2 and H2 over time: e.g., after formation of a macromolecular carbonaceous layer on the surfaces of the underlying gains. While amorphous iron silicates required only 1 or 2 experimental runs to achieve steady state reaction rates, graphite only achieved steady state after 6 or more experiments. We will present results showing the catalytic action of graphite grains increasing with increasing number of experiments and will also discuss the nature of the final "graphite" grains aster completion of our experiments.
The measurement of surface temperatures on the thermal protection materials of the Space Shuttle Orbiter during reentry provides the basis for an important test of the prediction techniques developed over the past 10 years for reacting flows over reentry vehicles. The present investigation is concerned with comparisons of calculated temperatures with those measured during the second and third Space Shuttle missions. The general trends of the calculations compared favorably with the measurements. However, the calculations overpredicted the temperatures on the forward part of the windward centerline. Agreement was better farther aft, especially at the later times in the entry. The investigation has pointed out the significance of surface chemical reactions on the heat flux to the surface of the Orbiter and the need for further understanding.
The National Aeronautics and Space Administration has begun preparations for the flight of the Mars Observer Mission in the early 1990s. An advanced ground-based study is being conducted on a usefully limited suite of Mars Soil Analog Materials (MarSAM) intended to simulate the aeolian material covering the surface of Mars. A series of variably proportioned iron/calcium smectite clays were prepared from a typical montmorillonite clay using the Banin method. The effect of increasing iron on a diverse set of chemical and spectroscopic properties of the suite of clays is discussed. In order to chemically characterize the MarSAM and compare them with the Martian soil studied by Viking, the clays were analyzed for their major and minor elemental compositions by X-ray fluorescence and ion-coupled plasma techniques. It was concluded that the surface iron has a complex and hitherto uninvestigated impact on the catalytic and spectroscopic properties of clays and on the ability of these material to store energy.
A major oxygen release between 300 and 500 C was detected by the Mars Curiosity Rover Sample Analysis at Mars (SAM) instrument at the Rocknest eolian deposit. Thermal decomposition of perchlorate (ClO4-) salts in the Rocknest samples are a possible explanation for this evolved oxygen release. Releative to Na-, K-, Mg-, and Fe-perchlorate, the thermal decomposition of Ca-perchlorate in laboratory experiments released O2 in the temperature range (400-500degC) closest to the O2 release temperatures observed for the Rocknest material. Furthermore, calcium perchlorate could have been the source of Cl in the chlorinated-hydrocarbons species that were detected by SAM. Different components in the Martian soil could affect the decomposition temperature of calcium per-chlorate or another oxychlorine species. This interaction of the two components in the soil could result in O2 release temperatures consistent with those detected by SAM in the Rocknest materials. The decomposition temperatures of various alkali metal perchlorates are known to decrease in the presence of a catalyst. The objective of this work is to investigate catalytic interactions on calcium perchlorate from various iron-bearing minerals known to be present in the Rocknest material
Catalytic techniques for processing waste products onboard space vehicles were evaluated. The goal of the study was the conversion of waste to carbon, wash water, oxygen and nitrogen. However, the ultimate goal is conversion to plant nutrients and other materials useful in closure of an ecological life support system for extended planetary missions. The resulting process studied involves hydrolysis at 250 C and 600 psia to break down and compact cellulose material, distillation at 100 C to remove water, coking at 450 C and atmospheric pressure, and catalytic oxidation at 450 to 600 C and atmospheric pressure. Tests were conducted with a model waste to characterize the hydrolysis and coking processes. An oxidizer reactor was sized based on automotive catalytic conversion experience. Products obtained from the hydrolysis and coking steps included a solid residue, gases, water condensate streams, and a volatile coker oil. Based on the data obtained, sufficient component sizing was performed to make a preliminary comparison of the catalytic technique with oxidation for processing waste for a six-man spacecraft. Wet oxidation seems to be the preferred technique from the standpoint of both component simplicity and power consumption.
A simple method of predicting aerodynamic heating and corresponding radiation equilibrium surface temperature-time histories for critical locations on space shuttle orbiter-type vehicles is presented. The method is based on a generalization of correlation equations developed earlier by Rosner for predicting the energy transfer and radiation equilibrium temperatures of surfaces with arbitrary catalytic activity and total hemispheric emittance. Recently obtained experimental data for O and N atom recombination probabilities on candidate material surfaces above 1000 K are used to assess nonequilibrium effects for a range of nose radii and a specific space shuttle re-entry trajectory. It is concluded that low catalytic activity will be especially important in locations of large effective nose radii by both increasing oxidation-resistant coating lifetime and reducing energy transfer into the vehicle.
The water reclamation subsystems currently being evaluated for the Space Shuttle Freedom are briefly reviewed with emphasis on a waste water management system capable of processing wastes containing high concentrations of organic/inorganic materials. The process combines low temperature/pressure to vaporize water with high temperature catalytic oxidation to decompose volatile organics. The reclaimed water is of potable quality and has high potential for maintenance under sterile conditions. Results from preliminary experiments and modifications in process and equipment required to control reliability and repeatability of system operation are presented.