Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “PLATINUM OXIDES”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
NASA NTRS2002

Techniques Optimized for Reducing Instabilities in Advanced Nickel-Base Superalloys for Turbine Blades

The High-Speed Research (HSR) Airfoil Alloy program developed fourth-generation single-crystal superalloys with up to an 85 F increase in creep rupture capability over current production airfoil alloys. Recent results have been generated at the NASA Glenn Research Center on these fourth-generation alloys, but in coated form, for subsonic turbine blade applications under NASA's Ultra-Efficient Engine Technology (UEET) Program. One goal for UEET is to optimize the airfoil alloy/thermal barrier coating system for 3100 F turbine inlet temperatures. The state-of-the art turbine blade airfoil system consists of a superalloy single crystal that provides the basic mechanical performance of the airfoil. A thermal barrier coating is used to reduce the temperature of the base superalloy, and a bondcoat is deposited between the base material and the thermal barrier coating. The bondcoat improves the oxidation and corrosion resistance of the base superalloy and improves the spallation resistance of the thermal barrier coating. A commercial platinum aluminide bondcoat was applied to the HSR-developed alloys, and a diffusion zone developed as a result of interaction between the bondcoat and the superalloy. Optimized strength is obtained for superalloys when the refractory element content is high and the limits of microstructural stability are approached or exceeded slightly. For fourthgeneration alloys, instability leads to the formation of topologically close packed (TCP) phases, which form internally in the superalloy, and a secondary reaction zone (SRZ), which forms under the diffusion zone. There was a concern that excessive quantities of either TCP or SRZ might decrease the mechanical properties of the superalloy, with SRZ thought to be particularly detrimental and its formation unpredictable. Thus, an SRZreduction effort was initiated in the NASA UEET Program so that methods developed during the HSR project could be optimized further to reduce or eliminate the SRZ. An SRZ is a three-phase constituent composed of TCP and stringers of gamma phase in a matrix of gamma prime. An incoherent grain boundary separates the SRZ from the gammagamma prime microstructure of the superalloy. The SRZ is believed to form as a result of local chemistry changes in the superalloy due to the application of the diffusion aluminide bondcoat. Locally high surface stresses also appear to promote the formation of the SRZ. Thus, techniques that change the local alloy chemistry or reduce surface stresses have been examined for their effectiveness in reducing SRZ. These SRZ-reduction steps are performed on the test specimen or the turbine blade before the bondcoat is applied. Stressrelief heat treatments developed at NASA Glenn have been demonstrated to reduce significantly the amount of SRZ that develops during subsequent high-temperature exposures. Stress-relief heat treatments reduce surface stresses by recrystallizing a thin surface layer of the superalloy. However, in alloys with very high propensities to form SRZ, stress relief heat treatments alone do not eliminate SRZ entirely. Thus, techniques that modify the local chemistry under the bondcoat have been emphasized and optimized successfully at Glenn. One such technique is carburization, which changes the local chemistry by forming submicron carbides near the surface of the superalloy. Detailed characterizations have demonstrated that the depth and uniform distribution of these carbides are enhanced when a stress relief treatment and an appropriate surface preparation are employed in advance of the carburization treatment. Even in alloys that have the propensity to develop a continuous SRZ layer beneath the diffusion zone, the SRZ has been completely eliminated or reduced to low, manageable levels when this combination of techniques is utilized. Now that the techniques to mitigate SRZ have been established at Glenn, TCP phase formation is being emphasized in ongoing work under the UEET Program. The limitsf stability of the fourth-generation alloys with respect to TCP phase formation are currently being defined along with high-temperature creep rupture properties. In addition, a regression model is being developed at Glenn for the prediction of the presence of TCP phase in the microstructure and SRZ under the diffusion zone. The model is based on a design-of-experiments methodology with emphasis on the potential synergistic effects of alloying elements.

MacKay, Rebecca A.↗
NASA NTRS1991

Recovery of precious metals from space

The overall objective is to develop efficient and economical separation and recovery methods for the platinum group and other precious metals. The separation of Pd(II) from Pt(II), Ir(III), and Rh(III) with trioctylphosphine oxide (TOPO) in heptane using centrifugal partition chromatography (CPC) was investigated. Activities to achieve this objective focussed on selection and evaluation of extraction systems for the PGM and modification of selected systems for multistage operation with a view to scaling up to desired macro levels. On the basis of preliminary evaluation of a series of simple metal complexing agents and chelating agents, the TOPO in heptane was selected as a likely system for isolating of Pd(II) and Pt(II) from the other PGM. A multistage apparatus capable of configuration as a simple rugged device, a centrifugal partition chromatograph (CPC), was shown to be effective. The extraction of Pd(II) was studied by CPC and batch solvent extraction. The distribution ratios for Pd(II) determined by both methods agree well. In low HCl concentrations (less than 0.1 M), the extracted species was PdCl2.(TOPO)2, irrespective of the chloride concentration, while at acid concentrations above 0.1 M, the Pd was extracted as the ion pair, 2(TOPO.H+).(PdCl4)2-. Base line separation of Pd(II) and Pt(II) in CPC was obtained under a variety of chloride and HCl concentration. It was demonstrated that the efficiency of CPC for metal separation was limited by chemical kinetic factors rather than instrumental factors, strongly suggesting that dramatic improvements can be achieved by studying reaction kinetics of formation and dissociation of the extractable metal complex.

Freiser, Henry↗
NASA NTRS2013

Nanostructured Platinum Alloys for Use as Catalyst Materials

A series of binary and ternary Pt-alloys, that promote the important reactions for catalysis at an alloy surface; oxygen reduction, hydrogen oxidation, and hydrogen and oxygen evolution. The first two of these reactions are essential when applying the alloy for use in a PEMFC.

Hays, Charles C.↗
NASA NTRS2015

Nanostructured Platinum Alloys for Use as Catalyst Materials

A series of binary and ternary Pt-alloys, that promote the important reactions for catalysis at an alloy surface; oxygen reduction, hydrogen oxidation, and hydrogen and oxygen evolution. The first two of these reactions are essential when applying the alloy for use in a PEMFC.

Hays, Charles C.↗
NASA NTRS1986

Biosynthetic Porphyrins and the Origin of Photosynthesis

Since the prebiotic atmosphere was anaerobic, if not reducing, a useful function of primordial photosynthesis would have been to photooxidize reduced substrates such as Fe(+2), S(-2) or reduced organic molecules and to emit hydrogen. Experiments have shown that the early biogenic pigments uroporphyrin and coproporphyrin do photooxidize organic compounds and emit hydrogen in the presence of a platinum catalyst. These experiments were carried out in dilute aqueous solution near neutral pH under anaerobic atmosphere, and quantum yields near 10-2 were obtained. Thus relevant prebiotic conditions were maintained. Rather then to further optimize conditions, attempts were made to replace the platinum catalyst by a more prebiotically suitable catalyst. Trials with an Fe4S4(SR)4 cluster, in analogy to the present hydrogenase and nitrogenase, were not successful. However, experiments using cobalt complexes to catalyze the formation of hydrogen are promising. In analogy with biological photosynthetic systems which group pigments, electron transfer molecules and enzymes in clusters for efficiency, it was found that binding the biogenic porphyrins to the polyvinyl alcohol used to support the platinum catalyst did increase the quantum yield of the reaction. It was also found that ultraviolet light can serve to photo-oxidize porphyrinogens to porphyrins under anaerobic conditions. Thus the formation of the colorless porphyriogens by the extraordinarily simple biosynthetic pathway would not be a problem because of the prevalence of UV light in the prebiotic, anoxic atmosphere.

David Mauzerall↗
NASA NTRS2001

Study of Electrical Contacts and Devices in Advanced Semiconductors

Research conducted at Tuskegee University concentrates on electrical contacts to GaN films and their characterization with the objective of understanding contact formation and realizing low-resistance metal contacts. Contact properties are known to be strongly related to surface preparation. It appears that the as-received material had a thin oxide film on the surface of the GaN film. Various cleaning treatments were employed in order to render the surface contamination free and removal of the oxide film. Metal films were then deposited by e-beam evaporation. Electrical characteristics of these contacts indicated that the optimal treatment was an organic solvent cleaning followed by etching in buffered oxide solution. Contacts established with Al were observed to be ohmic in nature, whereas Au, Cr, Ti, and Pt exhibit rectifying contacts. Platinum contacts were almost ideal as shown by an ideality factor of 1.02.

Hall, H. P.↗
NASA NTRS1961

Effect of Surface Preparation and Gas Flow on Nitrogen Atom Surface Recombination

The effects of surface preparation and gas flow on the recombination of nitrogen atoms at copper and platinum surfaces were determined. Atoms were generated by an electrodeless 2450-megacycle-per-second discharge, and their concentration was measured by gas-phase titration with nitric oxide. Test surfaces were either vacuum-evaporated films or spheres machined from bulk metal and cemented around small glass-bead thermistors. Heat released by recombination was measured as the difference in electrical energy required to maintain a given thermistor temperature with and without a catalytic surface exposed. Recombination coefficients measured at flow velocities of 1120, 1790, 2250, and 3460 centimeters per second and at pressures of 0.42 and 0.59 millimeter of mercury showed that flow conditions had no effect. The results were also independent of atom concentration. A rough indication of the temperature dependence was obtained; it was greater for copper than for platinum. Platinum films deposited on platinum or on glass had the same activity - about 3 percent of the atoms impinging recombined. With copper, however, the glass substrate greatly reduced the percent of atoms recombining over that of a bulk copper substrate where 4 percent of the impinging atoms recombined. This effect could be overcome by depositing a second film on top of the first. Bulk metal samples were subjected to various surface treatments including polishing, degreasing with a chlorinated hydrocarbon, washing with nitric acid, and rinsing with water. Polished, degreased platinum had low activity compared to an evaporated film, but nitric acid treatment made it equivalent. Polished, degreased copper was only slightly less active than a copper film; nitric acid etching decreased the activity still further, probably by preferentially exposing facets of low catalytic efficiency.

Prok, George M.↗
NASA NTRS1974

Catalytic oxidation of trace levels of methane in oxygen in a tubular reactor

An experimental investigation of catalytic oxidation of trace levels of methane in oxygen was conducted in a tubular reactor. Two noble metal solid catalysts were explored: a 1-percent platinum on gamma alumina and a 0.5-percent rhodium on gamma alumina. For each catalyst the activity was determined as a function of temperature, pressure, space velocity, and methane concentration. The rhodium catalyst was considerably more active than the platinum catalyst. For each catalyst mass transfer had a pronounced effect upon activity at low space velocity.

Warshay, M.↗
NASA NTRS2017

Thermochemistry of CaO-MgO-Al2O3-SiO2 (CMAS) and Advanced Thermal and Environmental Barrier Coating Systems

CaO-MgO-Al2O3-SiO2 (CMAS) oxides are constituents in a broad number of materials and minerals which have recently inferred to discussions in materials science, planetary science, geochemistry and cosmochemistry communities. In materials science, there is increasing interest in the degradation studies of thermal (TBC) and environmental (EBC) barrier coatings of gas turbines by molten CMAS. CMAS minerals usually are carried by the intake air into gas turbines, e.g. in aircraft engines, and their deposits react at high temperatures (1000C) with the coating materials. This causes degradation and accelerated failure of the static and rotating components of the turbine engines. We discuss some preliminary results of the reactions between CMAS and Rare-Earth (RE Y, Yb, Dy, Gd, Nd and Sm) oxide stabilized ZrO2 or HfO2 systems, and the stability of the resulting oxides and silicates. Plasma sprayed hollow tube samples ( 2.2 mm and 26 mm height) were half filled with CMAS powder, wrapped and sealed with platinum foil, and heat treated at 1310 C for 5h. Samples were characterized by differential scanning calorimetry, X-ray diffraction and cross section electron microscopy analysis.

degradation↗
NASA NTRS1976

Studies of noble-metal thermocouple stability at high temperatures

Two investigatory studies on performance characteristics of noble-metal thermocouples are described. (1) thermoelectric stability as affected by preferential oxidation of iridium in the system iridium-40% rhodium versus iridium, and (2) the effects of temperature gradients on the emf stability of the systems platinum-13% rhodium versus platinum and iridium-40% rhodium versus iridium, operating in air. The stability investigation was carried out at three temperatures - 1700, 1850, and 2000 C - by comparing the output of the test thermocouple in air with the output of an identically constructed reference thermocouple in nitrogen. The results show that no calibration shift was observed producing a change in output greater than that corresponding to a 2.0% change in the indicated temperature for all samples tested. The investigation of gradient effects was carried out by subjecting test thermocouples to both severe and mild gradients for periods up to 200 hours. For the platinum system, the operating temperature was 1500 C with gradients of 1475 and 700 C/cm; for the iridium system, 2000 C with gradients of 700, 1500, and 1975 C/cm. Exposure to temperature gradients was found to introduce significant changes in calibration for both systems. In both investigations, the thermoelements were examined by means of electron-probe analysis and by metallographic methods to detect chemical and structural changes. Data and micrographs are presented.

Freeze, P.↗
NASA NTRS1981

Thermal fatigue behavior of H-13 die steel for aluminum die casting with various ion sputtered coatings

Sputtered coatings of Mo, W, Pt, Ag, Au, Co, Cr, Ni, Ag + Cu, Mo + Pt, Si3N4, A1N, Cr3C2, Ta5Si3, and ZrO2 were applied to a 2-inch-square, 7-inch-long thermal fatigue test specimen which was then internally water cooled and alternately immersed in molten aluminum and cooled in air. After 15,000 cycles the thermal fatigue cracks at the specimen corners were measured. Results indicate that a significant improvement in thermal fatigue resistance was obtained with platinum, molybdenum, and tungsten coatings. Metallographic examination indicates that the improvement in thermal fatigue resistance resulted from protection of the surface of the die steel from oxidation. The high yield strength and ductility of molybdenum and tungsten contributed to the better thermal fatigue resistance.

Nieh, C. Y.↗
NASA NTRS1988

Oxidation-Resistant Surfaces For Solar Reflectors

Thin films on silver provide highly-reflective, corrosion-resistant mirrors. Study evaluated variety of oxidation-resistant reflective materials for use in solar dynamic power system, one that generates electricity by focusing Sunlight onto reciever of heat engine. Thin films of platinum and rhodium deposited by ion-beam sputtering on various substrate materials. Solar reflectances measured as function of time of exposure to radio-frequency-generated air plasma. Several protective coating materials deposited on silver-coated substrates and exposed to plasma. Analyzed before and after exposure by electon spectroscopy for chemical analysis and by Auger spectroscopy.

Gulino, Daniel A.↗
NASA NTRS1992

Experimental study of the electrolysis of silicate melts

Melting and electrolyzing lunar silicates yields oxygen gas and potentially can be practiced in situ to produce oxygen. With the present experiments conducted with simulant oxides at 1425-1480 C, it was ascertained that oxygen can be obtained anodically at feasible rates and current efficiencies. An electrolysis cell was operated with platinum anodes in a sealed vessel, and the production of gas was monitored. In these electrolysis experiments, stability of anodes remained a problem, and iron and silicon did not reduce readily into the liquid silver cathode.

Keller, Rudolf↗
NASA NTRS1986

Oxidation-resistant reflective surfaces for solar dynamic power generation in near Earth orbit

Reflective surfaces for space station power generation systems are required to withstand the atomic oxygen-dominated environment of near Earth orbit. Thin films of platinum and rhodium, which are corrosion resistant reflective metals, have been deposited by ion beam sputter deposition onto various substrate materials. Solar reflectances were then measured as a function of time of exposure to a RF-generated air plasma. Similarly, various protective coating materials, including MgF2, SiO2, Al2O3, and Si3N4, were deposited onto silver-coated substrates and then exposed to the plasma. Analysis of the films both before and after exposure by both ESCA and Auger spectroscopy was also performed. The results indicate that Pt and Rh do not suffer any loss in reflectance over the duration of the tests. Also, each of the coating materials survived the plasma environment. The ESCA and Auger analyses are discussed as well.

Gulino, D. A.↗
NASA NTRS1987

Oxidation-resistant reflective surfaces for solar dynamic power generation in near earth orbit

Reflective surfaces for Space Station power generation systems are required to withstand the atomic oxygen-dominated environment of near earth orbit. Thin films of platinum and rhodium, which are corrosion resistant reflective metals, have been deposited by ion beam sputter deposition onto various substrate materials. Solar reflectances were then measured as a function of time of exposure to a RF-generated air plasma.

Gulino, Daniel A.↗
NASA NTRS2010

Process for Making a Noble Metal on Tin Oxide Catalyst

To produce a noble metal-on-metal oxide catalyst on an inert, high-surface-area support material (that functions as a catalyst at approximately room temperature using chloride-free reagents), for use in a carbon dioxide laser, requires two steps: First, a commercially available, inert, high-surface-area support material (silica spheres) is coated with a thin layer of metal oxide, a monolayer equivalent. Very beneficial results have been obtained using nitric acid as an oxidizing agent because it leaves no residue. It is also helpful if the spheres are first deaerated by boiling in water to allow the entire surface to be coated. A metal, such as tin, is then dissolved in the oxidizing agent/support material mixture to yield, in the case of tin, metastannic acid. Although tin has proven especially beneficial for use in a closed-cycle CO2 laser, in general any metal with two valence states, such as most transition metals and antimony, may be used. The metastannic acid will be adsorbed onto the high-surface-area spheres, coating them. Any excess oxidizing agent is then evaporated, and the resulting metastannic acid-coated spheres are dried and calcined, whereby the metastannic acid becomes tin(IV) oxide. The second step is accomplished by preparing an aqueous mixture of the tin(IV) oxide-coated spheres, and a soluble, chloride-free salt of at least one catalyst metal. The catalyst metal may be selected from the group consisting of platinum, palladium, ruthenium, gold, and rhodium, or other platinum group metals. Extremely beneficial results have been obtained using chloride-free salts of platinum, palladium, or a combination thereof, such as tetraammineplatinum (II) hydroxide ([Pt(NH3)4] (OH)2), or tetraammine palladium nitrate ([Pd(NH3)4](NO3)2).

Davis, Patricia↗
NASA NTRS1990

Synthesis, characterization and evaluation of CO-oxidation catalysts for high repetition rate CO2 TEA lasers

An extremely active class of noble metal catalysts supported on titania was developed and fabricated at Hughes for the recombination of oxygen (O2) and carbon monoxide (CO) in closed-cycle CO2 TEA lasers. The incipient wetness technique was used to impregnate titania and alumina pellets with precious metals including platinum and palladium. In particular, the addition of cerium (used as an oxygen storage promoter) produced an extremely active Pt/Ce/TiO2 catalyst. By comparison, the complementary Pt/Ce/ gamma-Al2O3 catalyst was considerably less active. In general, chloride-free catalyst precursors proved critical in obtaining an active catalyst while also providing uniform metal distributions throughout the support structure. Detailed characterization of the Pt/Ce/TiO2 catalyst demonstrated uniform dendritic crystal growth of the metals throughout the support. Electron spectroscopy for Chemical Analysis (ESCA) analysis was used to characterize the oxidation states of Pt, Ce and Ti. The performance of the catalysts was evaluated with an integral flow reactor system incorporating real time analysis of O2 and CO. With this system, the transient and steady-state behavior of the catalysts were evaluated. The kinetic evaluation was complemented by tests in a compact, closed-cycle Hughes CO2 TEA laser operating at a pulse repetition rate of 100 Hz with a catalyst temperature of 75 to 95 C. The Pt/Ce/TiO2 catalyst was compatible with a C(13)O(16)2 gas fill.

Moser, Thomas P.↗