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At least 865 records · Page 48

Oxidation of high-temperature intermetallics; Proceedings of the Workshop, Cleveland, OH, Sept. 22, 23, 1988

The present conference on the high-temperature oxidation behavior of aerospace structures-applicable intermetallic compounds discusses the influence of reactive-element additions on the oxidation of Ni3Al base alloys, the effect of Ni3Al oxidation below 850 C on fracture behavior, the oxidation of FeAl + Hf, Zr, and B, the synergistic effect of Al and Si on the oxidation resistance of Fe alloys, and pack cementation coatings of Cr-Al on Fe, Ni, and Co alloys. Also discussed are the formation of alumina on Nb- and Ti-base alloys, the oxidation behavior of titanium aluminide alloys, silicide coatings for refractory metals, the oxidation of chromium disilicide, and the oxidation behavior of nickel beryllides.

Grobstein, Toni↗

Oxidation of Al2O3 continuous fiber-reinforced/NiAl composites

The 1200 C and 1300 C isothermal and cyclic oxidation behavior of Al2O3 continuous fiber-reinforced/NiAl composites were studied. Oxidation resulted in formation of Al2O3 external scales in a similar manner as scales formed on monolithic NiAl. The isothermal oxidation of an Al2O3/NiAl composite resulted in oxidation of the matrix along the fiber/matrix interface near the fiber ends. This oxide acted as a wedge between the fiber and the matrix, and, under cyclic oxidation conditions, led to further oxidation along the fiber lengths and eventual cracking of the composite. The oxidation behavior of composites in which the Al2O3 fibers were sputter coated with nickel prior to processing was much more severe. This was attributed to open channels around the fibers which formed during processing, most likely as a result of the diffusion of the nickel coating into the matrix.

Doychak, J.↗

Oxidation performance of platinum-clad Mo-47Re alloy

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.

Clark, Ronald K.↗

Design, analysis, and fabrication of oxide-coated iridium/rhenium combustion chambers

Iridium-coated rhenium (Ir/Re) combustion chambers provide high temperature, oxidation-resistant operation for radiation-cooled liquid-fueled rocket engines. A 22-N (5-lb(sub f)) chamber has been operated for 15 hours at 2200 C (4000 F) using nitrogen tetroxide/monomethyl hydrazine (NTO/MMH) propellant, with negligible internal erosion. The oxidation resistance of these chambers could be further increased by the addition of refractory oxide coatings, providing longer life and/or operation in more oxidizing and higher temperature environments. The oxide coatings would serve as a thermal and diffusion barrier for the iridium coating, lowering the temperature of the iridium layer while also preventing the ingress of oxygen and egress of iridium oxides. This would serve to slow the failure mechanisms of Ir/Re chambers, namely the diffusion of rhenium to the inner surface and the oxidation of iridium. Such protection could extend chamber lifetimes by tens or perhaps hundreds of hours, and allow chamber operation on stoichiometric or higher mixture ratio oxygen/hydrogen (O2/H2) propellant. Extensive thermomechanical, thermochemical, and mass transport modeling was performed as a key material/structure design tool. Based on the results of these analyses, several 22-N oxide-coated Ir/Re chambers were fabricated and delivered to NASA Lewis Research Center for hot-fire testing.

Jang, Q.↗

X-Ray Absorption Spectroscopy in High Temperature Oxidation of Metals and Alloys

An experimental technique is described that allows for the joint study of the kinetics and of the oxide structure during the high temperature oxidation of metal surfaces. Oxygen is supplied at the metal through an electrochemical oxygen pump and the oxygen pressure, at the metal surface, is measured during oxidation by a YSZ (yttria stabilized zirconia) oxygen sensor. XAS (x-ray absorption spectroscopy) is performed in fluorescence mode at the cation K edge and after each oxidation step. An appropriate analysis of the XAS spectra could provide information on both the oxidation kinetics and oxide structure. Experimental data on the high temperature oxidation of nickel, cobalt, and Fe(64%)Ni(36%) alloy, at low oxygen pressure, are reported and analyzed according to the proposed data reduction. These results indicate the presented technique to be particularly suitable for studying the hot corrosion of oxide film too thick for common surface spectroscopy (AUGER, ESCA) and too thin for conventional thermogravimetric technique.

Daniele Gozzi↗

Hematite, pyroxene, and phyllosilicates on Mars: Implications from oxidized impact melt rocks from Manicouagan Crater, Quebec, Canada

Visible and near-IR refectivity, Moessbauer, and X ray diffraction data were obtained on powders of impact melt rock from the Manicouagan Impact Crater located in Quebec, Canada. The iron mineralogy is dominated by pyroxene for the least oxidized samples and by hematite for the most oxidized samples. Phyllosilicate (smectite) contents up to approximately 15 wt % were found in some heavily oxidized samples. Nanophase hematite and/or paramagnetic ferric iron is observed in all samples. No hydrous ferric oxides (e.g., goethite, lepidocrocite, and ferrihydrite) were detected, which implies the alteration occurred above 250 C. Oxidative alteration is thought to have occurred predominantly during late-stage crystallization and subsolidus cooling of the impact melt by invasion of oxidizing vapors and/or solutions while the impact melt rocks were still hot. The near-IR band minimum correlated with the extent of aleration Fe(3+)/Fe(sub tot) and ranged from approximately 1000 nm (high-Ca pyroxene) to approximately 850 nm (bulk, well-crystalline hematite) for least and most oxidized samples, respectively. Intermediate band positions (900-920 nm) are attributed to low-Ca pyroxene and/or a composite band from hematite-pyroxene assemblages. Manicouagan data are consistent with previous assignments of hematite and pyroxene to the approximately 850 and approximately 1000nm bands observed in Martian reflectivity spectra. Manicouagan data also show that possible assignments for intermediate band positions (900-920 nm) in Martian spectra are pyroxene and/or hematite-pyroxene assemblages. By analogy with impact melt sheets and in agreement with observables for Mars, oxidative alteration of Martian impact melt sheets above 250 C and subsequent erosion could produce rocks and soils with variable proportions of hematite (both bulk and nanophase), pyroxene, and phyllosilicates as iron-bearing mineralogies. If this process is dominant, these phases on Mars were formed rapidly at relativly high temperatures on a sporadic basis throughout the history of the planet. The Manicouagan samples also show that this mineralogical diversity can be accomplished at constant chemical composition, which is also indicated for Mars from the analyses of soil at the two Viking landing sites.

Morris, Richard V.↗

Design of a three-layer antireflection coating for high efficiency indium phosphide solar cells using a chemical oxide as first layer

It is well known that the behavior of III-V compound based solar cells is largely controlled by their surface, since the majority of light generated carriers (63% for GaAs and 79% for InP) are created within 0.2 mu m of the surface of the illuminated cell. Consequently, the always observed high surface recombination velocity (SRV) on these cells is a serious limiting factor for their high efficiency performance, especially for those with p-n junction made by either thermal diffusion or ion implantation. A good surface passivation layer, ideally a grown oxide as opposed to a deposited one, will cause a significant reduction in the SRV without adding interface problems, thus improving the performance of III-V compound based solar cells. Another significant benefit to the overall performance of the solar cells can be achieved by a substantial reduction of their large surface optical reflection by the use of a well designed antireflection (AR) coating. In this paper, we demonstrate the effectiveness of using a chemically grown thermally and chemically stable oxide, not only for surface passivation but also as an integral part of a 3-layer AR coating for thermally diffused p+n InP solar cells. A phosphorus-rich interfacial oxide, In(PO3)3, is grown at the surface of the p+ emitter using an etchant based on HNO3, o-H3PO4 and H2O2. This oxide has the unique properties of passivating the surface as well as serving as an efficient antireflective layer yielding a measured record high AMO open-circuit voltage of 890.3 mV on a thermally diffused InP(Cd,S) solar cell. Unlike conventional single layer AR coatings such as ZnS, Sb2O3, SiO or double layer AR coatings such as ZnS/MgF2 deposited by e-beam or resistive evaporation, this oxide preserves the stoichiometry of the InP surface. We show that it is possible to design a three-layer AR coating for a thermally diffused InP solar cell using the In(PO3)3 grown oxide as the first layer and Al2O3 and MgF2 as the second and third layers respectively, so as to yield an overall theoretical reflectance of less than 2%. Since chemical oxides are readily grown on III-V semiconductors materials, the technique of using the grown oxide layer to both passivate the surface as well as serve as the first of a multilayer AR coating should work well for all III-V compound-based solar cells.

Moulot, Jacques↗

Oxygenic Photosynthesis and the Oxidation State of Mars

The oxidation state of the Earth's surface is one of the most obvious indications of the effect of life on this planet. The surface of Mars is highly oxidized, as evidenced by its red color, but the connection to life is less apparent. Two possibilities can be considered. First, the oxidant may be photochemically produced in the atmosphere. In this case the fundamental source of O2 is the loss of H2 to space and the oxidant produced is H2O2. This oxidant would accumulate on the surface and thereby destroy any organic material and other reductants to some depth. Recent models suggest that diffusion limits this depth to a few meters. An alternative source of oxygen is biological oxygen production followed by sequestration of organic material in sediments - as on the Earth. In this case, the net oxidation of the surface was determined billions of years ago when Mars was a more habitable planet and oxidative conditions could persist to great depths, over 100 m. Below this must be a compensating layer of biogenic organic material. Insight into the nature of past sources of oxidation on Mars will require searching for organics in the martian subsurface and sediments.

Hartman, Hyman↗

Hematite, pyroxene, and phyllosilicates on Mars: Implications from oxidized impact melt rocks from Manicouagan Crater, Quebec, Canada

Visible and near-IR reflectivity, Mossbauer, and X ray diffraction data were obtained on powders of impact melt rock from the Manicouagan Impact Crater located in Quebec, Canada. The iron mineralogy is dominated by pyroxene for the least oxidized samples and by hematite for the most oxidized samples. Phyllosilicate (smectite) contents up to 15 wt % were found in some heavily oxidized samples. Nanophase hematite and/or paramagnetic ferric iron is observed in all samples. No hydrous ferric oxides (e.g., goethite, lepidocrocite, and ferrihydrite) were detected, which implies the alteration occurred above 250 C. Oxidative alteration is thought to have occurred predominantly during late-stage crystallization and subsolidus cooling of the impact melt by invasion of oxidizing vapors and/or solutions while the impact melt rocks were still hot. The near-IR band minimum correlated with the extent of aleration (Fe(3+)/Fe(sub tot)) and ranged from approx. 1000 nm (high-Ca pyroxene) to approx. 850 nm (bulk, well-crystalline hematite) for least and most oxidized samples, respectively. Intermediate band positions (900-920 nm) are attributed to low-Ca pyroxene and/or a composite band from hematite-pyroxene assemblages. Manicouagan data are consistent with previous assignments of hematite and pyroxene to the 850 and 1000 nm bands observed in Martian reflectivity spectra. Manicouagan data also show that possible assignments for intermediate band positions (900-920 nm) in Martian spectra are pyroxene and/or hematite-pyroxene assemblages. By analogy with impact melt sheets and in agreement with observables for Mars, oxidative alteration of Martian impact melt sheets above 250 C and subsequent erosion could produce rocks and soils with variable proportions of hematite (both bulk and nanophase), pyroxene, and phyllosilicates as iron-bearing mineralogies. If this process is dominant, these phases on Mars were formed rapidly at relatively high temperatures on a sporadic basis throughout the history of the planet. The Manicouagan samples also show that this mineralogical diversity can be accomplished at constant chemical composition, which is also indicated for Mars from analyses of soil at the two Viking landing sites.

Morris, Richard V.↗

Long-Term Cyclic Oxidation Behavior of Uncoated and Coated Re-108 and In-939 at 980 and 870 C

Very long-term cyclic oxidation behavior of Re-108 and ln-939 with and without a protective coating was evaluated at 980 and 870 C, respectively. Re-108 and ln-939 without a protective coating began to show rapid weight loss at 3000 h due to scale spallation, indicating the need for an oxidation protective coating for longer than thousands of hours of oxidative life. NiAl-base coatings of a vapor phase aluminide (VPA), a pack aluminide (CODEP), and a slurry paint aluminide (SERMALOY J) were applied on Re-108 and ln-939. VPA and CODEP on Re-108 and all three coatings on ln-939 showed excellent cyclic oxidation resistance out to 10000 hr. Coated alloys were annealed in an inert atmosphere to determine the loss of Al from the coating into the alloy substrate through diffusion. The Al loss from the coating through diffusion was twice as great as the Al loss through oxidation after 10000 h of cyclic exposure. Oxidation life of VPA-coated Re-108 was estimated by calculating the amount of Al initially available for protective oxidation and the amount of Al lost through oxidation and diffusion.

Lee, K. N.↗

Design of a Three-Layer Antireflection Coating for High Efficiency Indium Phosphide Solar Cells Using a Chemical Oxide as First Layer

It is well known that the behavior of III-V compound based solar cells is largely controlled by their surface, since the majority of light generated carriers (63% for GaAs and 79% for InP) are created within 0.2 microns of the illuminated surface of the cell. Consequently, the always observed high surface recombination velocity (SRV) on these cells is a serious limiting factor for their high efficiency performance, especially for those with the p-n junction made by either thermal diffusion or ion implantation. A good surface passivation layer, ideally, a grown oxide as opposed to a deposited one, will cause a significant reduction in the SRV without adding interface problems, thus improving the performance of III-V compound based solar cells. Another significant benefit to the overall performance of the solar cells can be achieved by a substantial reduction of their large surface optical reflection by the use of a well designed antireflection (AR) coating. In this paper, we demonstrate the effectiveness of using a chemically grown, thermally and chemically stable oxide, not only for surface passivation but also as an integral part of a 3- layer AR coating for thermally diffused p(+)n InP solar cells. A phosphorus-rich interfacial oxide, In(PO3)3, is grown at the surface of the p(+) emitter using an etchant based on HNO3, o-H3PO4 and H2O2. This oxide has the unique properties of passivating the surface as well as serving as a fairly efficient antireflective layer yielding a measured record high AM0, 25 C, open-circuit voltage of 890.3 mV on a thermally diffused InP(Cd,S) solar cell. Unlike conventional single layer AR coatings such as ZnS, Sb2O3, SiO or double layer AR coatings such as ZnS/MgF2 deposited by e-beam or resistive evaporation, this oxide preserves the stoichiometry of the InP surface. We show that it is possible to design a three-layer AR coating for a thermally diffused InP solar cell using the In(PO3)3 grown oxide as the first layer and Al2O3, MgF2 or ZnS, MgF2 as the second and third layers respectively, so as to yield an overall theoretical reflectance of less than 2%. Since chemical oxides are readily grown on III-V semiconductor materials, the technique of using the grown oxide layer to both passivate the surface as well as serve as the first of a multilayer AR coating, should work well for essentially all III-V compound-based solar cells.

Moulot, Jacques↗

Long-Term Cyclic Oxidation Behavior of Uncoated and Coated Re-108 and In-939 at 980 and 870 C

Very long-term cyclic oxidation behavior of Re108 and In939 with and without a protective coating was evaluated at 980 and 870 C, respectively. Re-108 and In-939 without a protective coating began to show a rapid weight loss at 3000 h due to scale spallation, indicating the need for an oxidation protective coating for longer than thousands of hours of oxidative life. NiAl-base coatings of a vapor phase aluminide (VPA), a pack aluminide (CODEP), and a slurry paint aluminide (SERMALOY J) were applied on Re-108 and In-939. The VPA and CODEP on Re-108 and all three coatings on In-939 showed excellent cyclic oxidation resistance out to 10,000 h. Coated alloys were annealed in an inert atmosphere to determine the loss of Al from the coating into the alloy substrate through diffusion. The Al loss from the coating through diffusion was twice as great as the Al loss through oxidation after 10,000 h of cyclic exposure. The oxidation life of VPA-coated Re-108 was estimated by calculating the amount of Al initially available for protective oxidation and the amount of Al lost through oxidation and diffusion.

Lee, K. N.↗

Characterization of Rhenium Oxides Using ESCA

High melting point and inherent ductility (toughness) over a wide range of temperature has made Rhenium an engineering material of choice for several thrust chambers in propulsion systems. Although the material remains tough at high temperatures, it still can readily transform to several oxides. As many as eight different oxides have been reported in literature. When characterized using ESCA (Electron Spectroscopy for Chemical Analyses) these oxides show large shifts in the Re 4f line positions. While this unique property could be used as a tool for oxide characterization, literature indicates that only a few of these oxides have been characterized. Current work focuses on characterizing oxides of Rhenium using ESCA. Spectral line Re 4f have been measured for various oxides and the results have been compared with the Re 4f line positions of real-time oxidation products from space hardware.

Panda, Binayak↗

Carbon Nanostructure: Its Evolution During its Impact Upon Soot Growth and Oxidation

The proposed work is a ground-based study to define and quantify soot nanostructural changes in response to growth conditions, thermal and oxidative treatments and to quantify their impact upon further oxidation and growth of highly ordered carbon materials. Experimental data relating soot oxidation rates to multiple oxidizing species concentrations will directly test for additive or synergistic soot oxidation rates. Such validation is central for assessing the applicability of individual soot oxidation rates and designing oxidative strategies for controlling soot loadings in and emissions from turbulent combustion processes. Through these experiments, new insights into soot nanostructure evolution during and its impact upon oxidation by O2 and OH will be realized. It is expected that the results of this effort will spawn new research directions in future microgravity and 1g environments. Issues raised by positive or even negative demonstration of the hypotheses of this proposal have direct bearing on modelling and controlling soot formation and its destruction in nearly every combustion process producing soot.

Source record↗

A Model for the Oxidation of C/SiC Composite Structures

A mathematical theory and an accompanying numerical scheme have been developed for predicting the oxidation behavior of C/SiC composite structures. The theory is derived from the mechanics of the flow of ideal gases through a porous solid. Within the mathematical formulation, two diffusion mechanisms are possible: (1) the relative diffusion of one species with respect to the mixture, which is concentration gradient driven and (2) the diffusion associated with the average velocity of the gas mixture, which is total gas pressure gradient driven. The result of the theoretical formulation is a set of two coupled nonlinear differential equations written in terms of the oxidant and oxide partial pressures. The differential equations must be solved simultaneously to obtain the partial vapor pressures of the oxidant and oxides as a function of space and time. The local rate of carbon oxidation is determined as a function of space and time using the map of the local oxidant partial vapor pressure along with the Arrhenius rate equation. The nonlinear differential equations are cast into matrix equations by applying the Bubnov-Galerkin weighted residual method, allowing for the solution of the differential equations numerically. The end result is a numerical scheme capable of determining the variation of the local carbon oxidation rates as a function of space and time for any arbitrary C/SiC composite structures.

Sullivan, Roy M.↗

New Oxide Ceramic Developed for Superior High-Temperature Wear Resistance

Ceramics, for the most part, do not have inherently good tribological properties. For example friction coefficients in excess of 0.7 have been reported for silicon nitride sliding on silicon nitride or on bearing steel (ref. 1). High friction is always accompanied by considerable wear. Despite their inherently poor tribological properties, the high strength and high toughness of silicon nitride (Si3N4) ceramics has led to their successful use in tribological applications (refs. 1 to 4). The upper temperature limit for the application of Si3N4 as wear-resistant material is limited by reaction with the tribological environment (ref. 3). Silicon nitride is known to produce a thin silicon dioxide film with easy shear capability that results in low friction and low wear in a moist environment (ref. 5). At elevated temperatures, the removal of the reaction product that acts as lubricant causes the friction coefficient to increase and, consequently, the wear performance to become poor. New materials are sought that will have wear resistance superior to that of Si3N4 at elevated temperatures and in harsh environments. A new class of oxide ceramic materials has been developed with potential for excellent high-temperature wear resistance. The new material consists of a multicomponent oxide with a two-phase microstructure, in which the wear resistance of the mixed oxide is significantly higher than that of the individual constituents. This is attributed to the strong constraining effects provided by the interlocking microstructures at different length scales, to the large aspect ratio of the phases, to the strong interphase bonding, and to the residual stresses. Fretting wear tests were conducted by rubbing the new ceramic material against boron carbide (B4C). The new ceramic material produced a wear track groove on B4C, suggesting significantly higher wear resistance for the oxide ceramic. The new material did not suffer from any microstructural degradation after the wear test. The wear rate of the new ceramic material at 600 C was determined to be on the order of 10-10 mm3/N-m, which is 3 to 5 orders of magnitude lower than that for the current state-of-theart wear-resistant materials (Si3N4and B4C). The friction coefficient of the new ceramic materials is on the order of 0.4, which is significantly lower than that of silicon nitride. This new class of oxide materials has shown considerable potential for applications requiring high wear resistance at high temperatures and in harsh environments. New understanding of the wear behavior of ceramic materials is emerging as a result of the surprisingly high wear resistance of two-phase oxide ceramics. There is excellent potential for further improvements in the wear resistance of oxide ceramics through optimizing the microstructure and altering the crystallographic properties of specific oxide materials as a second phase to reduce the coefficient of friction at elevated temperatures.

Sayir, Ali↗

Stabilized tin-oxide-based oxidation/reduction catalysts

The invention described herein involves a novel approach to the production of oxidation/reduction catalytic systems. The present invention serves to stabilize the tin oxide reducible metal-oxide coating by co-incorporating at least another metal-oxide species, such as zirconium. In one embodiment, a third metal-oxide species is incorporated, selected from the group consisting of cerium, lanthanum, hafnium, and ruthenium. The incorporation of the additional metal oxide components serves to stabilize the active tin-oxide layer in the catalytic process during high-temperature operation in a reducing environment (e.g., automobile exhaust). Moreover, the additional metal oxides are active components due to their oxygen-retention capabilities. Together, these features provide a mechanism to extend the range of operation of the tin-oxide-based catalyst system for automotive applications, while maintaining the existing advantages.

Jordan, Jeffrey D.↗

Oxidation of SiC/BN/SiC Composites in Reduced Oxygen Partial Pressures

SiC fiber-reinforced SiC composites with a BN interphase are proposed for use as leading edge structures of hypersonic vehicles. The durability of these materials under hypersonic flight conditions is therefore of interest. Thermogravimetric analysis was used to characterize the oxidation kinetics of both the constituent fibers and composite coupons at four temperatures: 816, 1149, 1343, and 1538 C (1500, 2100, 2450, and 2800 F) and in oxygen partial pressures between 5% and 0.1% (balance argon) at 1 atm total pressure. One edge of the coupons was ground off so the effects of oxygen ingress into the composite could be monitored by post-test SEM and EDS. Additional characterization of the oxidation products was conducted by XPS and TOF-SIMS. Under most conditions, the BN oxidized rapidly, leading to the formation of borosilicate glass. Rapid initial oxidation followed by volatilization of boria lead to protective oxide formation and further oxidation was slow. At 1538C in 5% oxygen, both the fibers and coupons exhibited borosilicate glass formation and bubbling. At 1538C in 0.1% oxygen, active oxidation of both the fibers and the composites was observed leading to rapid SiC degradation. BN oxidation at 1538C in 0.1% oxygen was not significant.

Opila, Elizabeth J.↗