METHOD FOR THE DETERMINATION OF OXYGEN IN MICROGRAM QUANTITIES OF OXIDES OF PLATINUM AND OTHER REDUCIBLE OXIDES
Determination of oxygen in oxides of platinum and other reducible oxides
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Determination of oxygen in oxides of platinum and other reducible oxides
Results of studies utilizing normal and rare oxygen isotopes in the catalytic oxidation of carbon monoxide over a platinum-tin oxide catalyst substrate are presented. Chemisorption of labeled carbon monoxide on the catalyst followed by thermal desorption yielded a carbon dioxide product with an oxygen-18 composition consistent with the formation of a carbonate-like intermediate in the chemisorption process. The efficacy of a method developed for the oxygen-18 labeling of the platinum-tin oxide catalyst surface for use in closed cycle pulsed care isotope carbon dioxide lasers is demonstrated for the equivalent of 10 to the 6th power pulses at 10 pulses per second.
Composition determination of microgram quantities of oxides of platinum
Kinetics and mechanism of enhanced oxidation of platinum in activated oxygen as function of partial pressure of oxygen atoms
Platinum-thorium oxide alloy for resistojet thruster showing increase in stress rupture life
Pressure dependency in oxidation of platinum above 800 degrees C explained by boundary layer diffusion mechanism
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Platinum on tin oxide (Pt/SnO2) good catalyst for oxidation of carbon monoxide at or near room temperature. Catalytic activity peaks at about 17 weight percent Pt. Catalysts with platinum loadings as high as 46 percent fabricated by technique developed at Langley Research Center. Work conducted to determine optimum platinum loading for this type of catalyst. Major application is removal of unwanted CO and O2 in CO2 lasers.
A commercial platinized tin oxide catalyst used for low-temperature CO oxidation has been characterized using ion scattering spectroscopy (ISS), Auger electron spectroscopy (AES) and Electron Spectroscopy for Chemical Analysis (ESCA) before and after reduction in 40 Torr of CO for 1 hour at various temperatures from 75 to 175 C. The reduction results in loss of surface oxygen, formation of metallic tin, conversion of platinum oxides to Pt-O-Sn and Pt(OH)2 and a small amount of metallic Pt which alloys with the tin. These results should be useful in understanding how the pretreatment temperature affects the catalytic activity of platinized tin oxide toward CO oxidation.
The alloy Mo-47Re has favorable mechanical properties at temperatures above 1400 C, but it undergoes severe oxidation when used in air with no protective coating. To shield the alloy from oxidation, platinum cladding has been evaluated. The unprotected alloy undergoes catastrophic oxidation under static and dynamic oxidation conditions. The platinum cladding provides good protection from static and dynamic oxidation for moderate times at 1260 C. Samples tested for longer times under static oxidation conditions experienced severe oxidation. The data suggest that oxidation results from the transport of oxygen through the grain boundaries and through the pinhole defects of the platinum cladding.
A number of samples of optical thin film materials were flown on Shuttle flight STS-8 as part of an experiment to evaluate their interaction with residual atomic oxygen in low earth orbit. Osmium was selected because of its usefulness as a reflective optical coating for far-UV instruments and for confirmation of results from previous Shuttle flights in which such coatings disappeared. Reflectance data and photographic evidence are presented to support the hypothesis that the osmium disappearance is due to reaction with oxygen to form a volatile oxide. Platinum and iridium, which were included for comparison, fared much better.
Diamines have shown their utility in the formation of many polymers. Examples of these polymers include polyimides, polyamides, and epoxies. The properties of these polymers are often dependent on the diamine which is used to make the polymer. By the present invention, a process was developed to make a diamine containing pentafluorosulfanylbenzene moiety. This process involves two steps: the preparation of a dinitro precursor and the reduction of the dinitro compound to form the diamine. This diamine was then reacted with various dianhydrides, diacidchlorides, and epoxy resins to yield the corresponding polyimide, polyamide, and epoxy polymers. These polymers were then used to make films, a wire coating enamel, and a semi-permeable membrane. The novelty of this invention resides in the process to make the diamine. Traditionally, dinitro compounds are reduced with hydrazine or a catalyst such as palladium on charcoal. The catalyst which is used in this invention is platinum oxide. When this catalyst is used, it makes it possible to form a polymer-grade diamine.
Solar selective coatings are envisioned for use on minisatellites, for applications where solar energy is to be used to power heat engines or to provide thermal energy for remote regions in the interior of the spacecraft. These coatings are designed to have the combined properties of high solar absorptance and low infrared emittance. The coatings must be durable at elevated temperatures. For thermal bus applications, the temperature during operation is likely to be near 100 C. For heat engine applications. the temperature is expected to be much greater. The objective of this work was to screen candidate solar selective coatings for their high temperature durability. Candidate solar selective coatings were composed of molecular mixtures of metal and dielectric, including: nickel and aluminum oxide, titanium and aluminum oxide, and platinum and aluminum oxide. To identify high temperature durability, the solar absorptance and infrared emittance of the candidate coatings were evaluated initially, and after heating to temperatures in the range of 400 C to 700 C. The titanium and aluminum oxide molecular mixture was found to be the most durable.
Thin films composed of molecular mixtures of metal and dielectric are being considered for use as solar selective coatings for a variety of space power applications. By controlling molecular mixing during ion-beam sputter deposition, researchers can tailor the solar selective coatings to have the combined properties of high solar absorptance and low infrared emittance. On orbit, these combined properties simultaneously maximize the amount of solar energy captured by the coating and minimize the amount of thermal energy radiated. The solar selective coatings are envisioned for use on minisatellites, for applications where solar energy is used to power heat engines or to heat remote regions in the interior of the spacecraft. Such systems may be useful for various missions, particularly those to middle Earth orbit. Sunlight must be concentrated by a factor of 100 or more to achieve the desired heat inlet operating temperature. At lower concentration factors, the temperature of the heat inlet surface of the heat engine is too low for efficient operation, and at high concentration factors, cavity type heat receivers become attractive. The an artist's concept of a heat engine, with the annular heat absorbing surface near the focus of the concentrator coated with a solar selective coating is shown. In this artist's concept, the heat absorbing surface powers a small Stirling convertor. The astronaut's gloved hand is provided for scale. Several thin-film molecular mixtures have been prepared and evaluated to date, including mixtures of aluminum and aluminum oxide, nickel and aluminum oxide, titanium and aluminum oxide, and platinum and aluminum oxide. For example, a 2400- Angstrom thick mixture of titanium and aluminum oxide was found to have a solar absorptance of 0.93 and an infrared emittance of 0.06. On the basis of tests performed under flowing nitrogen at temperatures as high as 680 C, the coating appeared to be durable at elevated temperatures. Additional durability testing is planned, including exposure to atomic oxygen, vacuum ultraviolet radiation, and high-energy electrons.
Heterogeneous catalyst of platinum, tin oxide, and silica gel combines small concentrations of laser dissociation products, CO and O2, to form CO22 during long times at ambient temperature. Developed as means to prevent accumulation of these products in sealed CO2 lasers. Effective at ambient operating temperatures and installs directly in laser envelope. Formulated to have very high surface area and to chemisorb controlled quantities of moisture: chemisorbed water contained within and upon its structure, makes it highly active and very longlived so only small quantity needed for long times.
The effects were studied of anions and cations on hydrogen chemisorption and anodic oxide film formation on Pt by linear sweep voltammetry, and on oxygen generation on Pt by potentiostatic overpotential measurement. The hydrogen chemisorption and anodic oxide film formation regions are greatly influenced by anion adsorption. In acids, the strongly bound hydrogen occurs at more cathodic potential when chloride and sulfate are present. Sulfate affects the initial phase of oxide film formation by produced fine structure while chloride retards the oxide-film formation. In alkaline solutions, both strongly and weakly bound hydrogen are influenced by iodide, cyanide, and barium and calcium cations. These ions also influence the oxide film formation. Factors considered to explain these effects are discussed. The Tafel slope for oxygen generation was found to be independent on the oxide thickness and the presence of cations or anions. The catalytic activity indicated by the exchange current density was observed decreasing with increasing oxide layer thickness, only a minor dependence on the addition of certain cations and anions was found.
Spectroscopic methods are proposed for detection of thermal barrier coating (TBC) spallation from engine hot zone components. These methods include absorption and emission of airborne marker species originally embedded in the TBC bond coat. In this study, candidate marker materials for this application were evaluated. Thermochemical analysis of candidate marker materials combined with additional constraints such as toxicity and uniqueness to engine environment, provided a short list of four potential species: platinum, copper oxide, zinc oxide. and indium. The melting point of indium was considered to be too low for serious consideration. The other three candidate marker materials, platinum, copper oxide, and zinc oxide were placed in a high temperature furnace and emission and absorption properties were measured over a temperature range from 800-1400 C and a spectral range from 250 to 18000 nm. Platinum did not provide the desired response, likely due to the low vapor Pressure of the metallic species and the low absorption of the oxide species. It was also found, however. that platinum caused a broadening of the carbon dioxide absorption at 4300 nm. The nature of this effect is not known. Absorption and emission caused by sodium and potassium impurities in the platinum were found in the platinum tests. Zinc oxide did not provide the desired response, again, most likely due to the low vapor pressure of the metallic species and the low absorption of the oxide species. Copper oxide generated two strongly temperature dependent absorption peaks at 324.8 and 327.4 nm. The melting point of copper oxide was determined to be too low for serious consideration as marker material.