The oxidation and sublimation of graphite in simulated re-entry environments
Graphite oxidation and sublimation in simulated reentry environments
TEMPERATURE EFFECT↗
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Characterization of Iridium Coated Rhenium Used in High-Temperature, Radiation-Cooled Rocket Thrusters
Materials used for radiation-cooled rocket thrusters must be capable of surviving under extreme conditions of high-temperatures and oxidizing environments. While combustion efficiency is optimized at high temperatures, many refractory metals are unsuitable for thruster applications due to rapid material loss from the formation of volatile oxides. This process occurs during thruster operation by reaction of the combustion products with the material surface. Aerojet Technical Systems has developed a thruster cone chamber constructed of Re coated with Ir on the inside surface where exposure to the rocket exhaust occurs. Re maintains its structural integrity at high temperature and the Ir coating is applied as an oxidation barrier. Ir also forms volatile oxide species (IrO2 and IrO3) but at a considerably slower rate than Re. In order to understand the performance limits of Ir-coated Re thrusters, we are investigating the interdiffusion and oxidation kinetics of Ir/Re. The formation of iridium and rhenium oxides has been monitored in situ by Raman spectroscopy during high temperature exposure to oxygen. For pure Ir, the growth of oxide films as thin as approximately 200 A could be easily detected and the formation of IrO2 was observed at temperatures as low as 600 C. Ir/Re diffusion test specimens were prepared by magnetron sputtering of Ir on Re substrates. Concentration profiles were determined by sputter Auger depth profiles of the heat treated specimens. Significant interdiffusion was observed at temperatures as low as 1000 C. Measurements of the activation energy suggest that below 1350 C, the dominant diffusion path is along defects, most likely grain boundaries, rather than bulk diffusion through the grains. The phases that form during interdiffusion have been examined by x ray diffraction. Analysis of heated test specimens indicates that the Ir-Re reaction produces a solid solution phase of Ir dissolved in the HCP structure of Re.
Stulen, R. H.↗
Diffusion mechanisms in Ir-coated Re for high-temperature, radiation-cooled rocket thrusters
Materials used for radiation-cooled rocket thrusters must be capable of surviving under extreme conditions of high temperatures and oxidizing environments. Thruster chambers were developed using chemical-vapor-deposited (CVD) Re coated with CVD Ir on the inside surface which is exposed to hot combustion gases. Ir serves as an oxidation barrier protecting the Re which maintains structural integrity at high temperatures. In order to predict and extend the performance limits of these Ir-coated Re thrusters, the diffusion kinetics of CVD materials at temperature are studied. Thruster end ring sections were examined using electron microprobe analysis both before and after exposure to high temperature vacuum environments. The resulting elemental maps for Re, Ir, and Mo in the near-surface region allow identification of diffusion mechanisms operating at these temperatures. Line scans for Ir and Re were fit using a diffusion model to extract relevant diffusion constants. The fastest diffusion process is seen to be grain boundary diffusion with Re diffusing down grain boundaries in the Ir overlayer. The measured dependence of the diffusion rate on temperature will allow prediction of operating lifetimes for these thrusters.
Hamilton, J. C.↗
Atmospheric Hydroperoxides in West Antarctica: Links to Stratospheric Ozone and Atmospheric Oxidation Capacity
The troposphere above the West Antarctic Ice Sheet (WAIS) was sampled for hydroperoxides at 21 locations during 2-month-long summer traverses from 2000 to 2002, as part of US ITASE (International Transantarctic Scientific Expedition). First time quantitative measurements using an HPLC method showed that methylhydroperoxide (MHP) is the only important organic hydroperoxide occurring in the Antarctic troposphere, and that it is found at levels ten times those previously predicted by photochemical models. During three field seasons, means and standard deviations for hydrogen peroxide (H2O2) were 321+/-158 pptv, 650+/-176 pptv and 330+/-147 pptv. While MHP was detected, but not quantified in December 2000, levels in summer 2001 and 2002 were 317+128 pptv and 304+/-172.2 pptv. Results from firn air experiments and diurnal variability of the two species showed that atmospheric H2O2 is significantly impacted by a physical snow pack source between 76 and 90degS, whereas MHP is not. We show strong evidence of a positive feedback between stratospheric ozone and H2O2 at the surface. Between November-27 and December-12 in 2001, when ozone column densities dropped below 220 DU (means in 2000 and 2001 were 318 DU and 334 DU, respectively), H2O2 was 1.7 times that observed in the same period in 2000 and 2002, while MHP was only 80% of the levels encountered in 2002. Photochemical box model runs suggest that NO and OH levels on WAIS are closer to coastal values, while Antarctic Plateau levels are higher, confirming that region to be a highly oxidizing environment. The modeled sensitivity of H2O2 and particularly MHP to NO offers the potential to use atmospheric hydroperoxides to constrain the NO background and thus estimate the past oxidation capacity of the remote atmosphere. Index Terms: 0365 Atmospheric Composition and Structure: Troposphere: composition and chemistry; 0322 Atmospheric Composition and Structure: Constituent sources and sinks; 1610 Global Change: Atmosphere (03 15,0325); 0736 Cryosphere: Snow (1827, 1863); 0724 Cryosphere: Ice Cores (4932) Keywords: hydrogen peroxide, methylhydroperoxide, Antarctica, air-snow exchange, stratospheric ozone, atmospheric oxidation capacity
Frey, Markus M.↗
Friction and wear behaviour of ion beam modified ceramics
In the present study, the sliding friction coefficients and wear rates of carbide, oxide, and nitride materials for potential use as sliding seals (ring/liner) were measured under temperature, environmental, velocity, and loading conditions representative of a diesel engine. In addition, silicon nitride and partially stabilized zirconia discs were modified by ion mixing with TiNi, nickel, cobalt and chromium, and subsequently run against carbide pins, with the objective of producing reduced friction via solid lubrication at elevated temperature. Unmodified ceramic sliding couples were characterized at all temperatures by friction coefficients of 0.24 and above. However, the coefficient at 800 C in an oxidizing environment was reduced to below 0.1, for certain material combinations, by the ion implantation of TiNi or cobalt. This beneficial effect was found to derive from lubricious titanium, nickel, and cobalt oxides.
Lankford, J.↗
Effects of Oxygen Concentration on Radiative Loss from Normal-Gravity and Microgravity Methane Diffusion Flames
Laminar diffusion flames of methane, burning in quiescent oxidizing environments at atmospheric pressure, have been studied under both normal-gravity and microgravity conditions. Radiation from these flames is measured using a wide-view-angle, thermopile detector radiometer. The oxidizer was 18, 21, and 30 percent oxygen in nitrogen.
Bahadori, M. Y.↗
The Effect of Microgravity on Flame Spread over a Thin Fuel
A flame spreading over a thermally thin cellulose fuel was studied in a quiescent microgravity environment. Flame spread over two different fuel thicknesses was studied in ambient oxygen-nitrogen environments from the limiting oxygen concentration to 100 percent oxygen at 1 atm pressure. Comparative normal-gravity tests were also conducted. Gravity was found to play an important role in the mechanism of flame spread. In lower oxygen environments, the buoyant flow induced in normal gravity was found to accelerate the flame spread rate as compared to the microgravity flame spread rates. It was also found to stabilize the flame in oxidizer environments, where microgravity flames in a quiescent environment extinguish. In oxygen-rich environments, however, it was determined that gravity does not play an important role in the flame spread mechanism. Fuel thickness influences the flame spread rate in both normal gravity and microgravity. The flame spread rate varies inversely with fuel thickness in both normal gravity and in an oxygen-rich microgravity environment. In lower oxygen microgravity environments, however, the inverse relationship breaks down because finite-rate kinetics and heat losses become important. Two different extinction limits were found in microgravity for the two thicknesses of fuel. This is in contrast to the normal-gravity extinction limit, which was found to be independent of fuel thickness. In microgravity the flame is quenched because of excessive thermal losses, whereas in normal gravity the flame is extinguished by blowoff.
Olson, Sandra L.↗
A unique high Mn/Fe microgabbro in the Parnallee (LL3) ordinary chondrite - Nebular mixture or planetary differentiate from a previously unrecognized planetary body?
We studied a unique microgabbro fragment from the Parnallee (LL3) unequilibrated ordinary chondrite. The fragment, which was originally identified by its ophitic to sub-ophitic texture, exhibits features characteristic of lunar and terrestrial tholeiitic basalts (i.e., extreme compositional zoning in clinopyroxene (Wo10En65Fs25 to Wo15En2FS83), a multiply saturated major element composition similar to mid-ocean ridge basalt with 3.1 wt pct Na2O and 0.15 wt pct K2O, and uniformly enriched rare earth elements (c. 10 x C1). A high bulk MnO/FeO ratio (0.064) distinguishes the microgabbro from other basaltic rocks and suggests the precursor material formed or reached equilibrium in a reducing environment. However, the absence of Fe metal and the extreme enrichment of FeO (up to 40 wt pct), in late crystallizing pyroxferroite, requires the last crystallization event to have occurred in a relatively oxidizing environment. We suggest the microgabbro formed by partial melting in a planetary body after removal of metallic Fe.
Kennedy, A. K.↗
Composites: Processing and Fabrication Methodologies of Nonoxide Ceramic Composites. Processing HfB2 Composites for Use in Extreme Environments
HfB2 and ZrB2 composites containing SiC are known to have good thermal shock and configurational stability at elevated temperatures. These are promising ultra-high temperature ceramics (UHTCs) for use on the sharp leading edges of next generation space vehicles. Sharp leading edges on these vehicles will need to: withstand repeated exposures to temperatures > 2200 C in oxidizing environments; have good thermal shock and ablation resistance; and withstand the mechanical stress of launch and reentry. The HfB2/SiC composite is currently undergoing processing improvements in an effort to better the performance of a material that has been studied for approx. 35 years. The potential for HfB2/SiC composites to meet the requirements of hypersonic flight depends on controlling processing techniques. This presentation will focus on understanding processing steps now being undertaken to optimize the material properties of HfB2/SiC composites at NASA Ames Research Center. Correlation between processing techniques and microstructure will be shown. Preliminary oxidation studies will also be discussed.
Gusman, Michael I.↗
High frequency capacitance-voltage characteristics of thermally grown SiO2 films on beta-SiC
Silicon dioxide films grown under dry and wet oxidation environment on beta-SiC films have been studied. The beta-SiC films had been heteroepitaxially grown on both on-axis and 2-deg off-axis (001) Si substrates. Capacitance-voltage and conductance-voltage characteristics of metal-oxide-semiconductor structures were measured in a frequency range of 10 kHz to 1 MHz. From these measurements, the interface trap density and the effective fixed oxide charge density were observed to be generally lower for off-axis samples.
Tang, S. M.↗
Atomic oxygen interaction with solar array blankets at protective coating defect sites
Atomic oxygen in the low-Earth-orbital environment oxidizes SiOx protected polyimide Kapton solar array blankets at sites which are not protected such as pin windows or scratches in the protective coatings. The magnitude and shape of the atomic oxygen undercutting which occurs at these sites is dependent upon the exposure environment details such as arrival direction and reaction probability. The geometry of atomic oxygen undercutting at defect sites exposed to atomic oxygen in plasma asher was used to develop a Monte Carlo model to simulate atomic oxygen erosion processes at defect sites in protected Kapton. Comparisons of Monte Carlo predictions and experimental results are presented for plasma asher atomic oxygen exposures for large and small defects as well as for protective coatings on one or both sides of Kapton. The model is used to predict in-space exposure results at defect sites for both directed and sweeping atomic oxygen exposure. A comparison of surface textures predicted by the Monte Carlo model and those experimentally observed from both directed space ram and laboratory plasma asher atomic oxygen exposure indicate substantial agreement.
Banks, Bruce A.↗
The Upside-Down Biosphere: Evidence for the Partially Oxygenated Oceans During the Archean Eon
This is a commentary on the preceding chapter by Ohmoto et al., in which it is suggested that oxygen concentrations have been high throughout Earth history. This is a contentious suggestion at odds with the prevailing view in the field, which contends that atmospheric oxygen concentrations rose from trace levels to a few percent of modern-day levels around 2.5 b.y. ago. This comment notes that many of the data sets cited by Ohmoto et al. as evidence for a relatively oxidized environment come from deep-ocean settings. This presents a possibility to reconcile some of these data and suggestions with the overwhelming evidence for an atmosphere free of oxygen at that time. Specifically, it is possible that deep-ocean waters were relatively oxidized with respect to certain redox pairs. These deep-ocean waters would have been more oxidized than surface waters, thus representing an "upside-down biosphere," as originally proposed 25 years ago by Jim Walker.
oxygenated oceans↗
Wear of Selected Oxide Ceramics and Coatings
The use of oxide ceramics and coatings for moving mechanical components operating in high-temperature, oxidizing environments creates a need to define the tribological performance and durability of these materials. Results of research focusing on the wear behavior and properties of Al2O3/ZrO2 (Y2O3) eutectics and coatings under dry sliding conditions are discussed. The importance of microstructure and composition on wear properties of directionally solidified oxide eutectics is illustrated. Wear data of selected oxide-, nitride-, and carbide-based ceramics and coatings are given for temperatures up to 973K in air.
Miyoshi, K.↗
Thermochemical characterization of some thermoplastic materials
The thermochemical and flammability characteristics of some typical thermoplastic materials currently in use or being considered for use in aircraft interiors are described. The properties studied included thermomechanical properties such as glass-transition and melt temperature, changes in polymer enthalpy, thermogravimetric analysis in anerobic and oxidative environments, oxygen index, smoke evolution, relative toxicity of the volatile products of pyrolysis, and selected physical properties. The generic polymers evaluated included acrylonitrile butadiene styrene, bisphenol A polycarbonate, 9,9 bis (4-hydroxyphenyl) fluorene polycarbonate-poly (dimethylsiloxane) block polymer, phenolphthalein-bisphenol A polycarbonate, phenolphthalein polycarbonate, polyether sulfone, polyphenylene oxide, polyphenylene sulfide, polyaryl sulfone, chlorinated polyvinyl chloride homopolymer, polyvinyl fluoride, and polyvinylidene fluoride. Processing parameters, including molding characteristics of some of the advanced polymers, are described. Test results and relative rankings of some of the flammability, smoke, and toxicity properties are presented. Under these test conditions, some of the advanced polymers evaluated were significantly less flammable and toxic than or equivalent to polymers in current use.
Kourtides, D. A.↗
Assessment of relative flammability and thermochemical properties of some thermoplastic materials
The thermochemical and flammability characteristics of some typical thermoplastic materials currently in use and others being considered for use in aircraft interiors are described. The properties studied included (1) thermal mechanical properties such as glass transition and melt temperature, (2) changes in polymer enthalpy by differential scanning calorimetry, (3) thermogravimetric analysis in an anaerobic and oxidative environment, (4) oxygen index, (5) smoke evolution, (6) relative toxicity of the volatile products of pyrolysis, and (7) selected physical properties. The generic polymers which were evaluated included: acrylonitrile-butadiene-styrene, bisphenol A polycarbonate, bisphenol fluorenone carbonatedimethylsiloxane block polymer, phenolphthalein-bisphenol A polycarbonate, phenolphthalein polycarbonate, polyether sulfone, polyphenylene oxide, polyphenylene sulfide, polyaryl sulfone, chlorinated polyvinyl chloride homopolymer, polyvinyl fluoride, and polyvinylidene fluoride. Processing parameters including molding characteristics of some of the advanced polymers are described. Test results and relative rankings of some of the flammability, smoke and toxicity properties are presented.
Kourtides, D. A.↗
Thermoplastic polymers for improved fire safety
The thermochemical and flammability characteristics of some typical thermoplastic materials currently in use and others being considered for use in aircraft interiors are described. The properties studied included (1) thermomechanical properties such as glass transition and melt temperature, (2) changes in polymer enthalpy by differential scanning calorimetry, (3) thermogravimetric analysis in anaerobic and oxidative environments, (4) oxygen index, (5) smoke evolution, (6) relative toxicity of the volatile products of pyrolysis, and (7) selected physical properties. The generic polymers that were evaluated included: acrylonitrile butadiene styrene, bisphenol A polycarbonate, 9,9 bis (4-hydroxyphenyl) fluorene polycarbonatepoly (dimethyl siloxane) block polymer, phenolphthalein bisphenol A polycarbonate, phenolphthalein polycarbonate, polyether sulfone, polyphenylene oxide, polyphenylene sulfide, polyaryl sulfone, chlorinated polyvinyl chloride homopolymer, polyvinyl fluoride, and polyvinylidene fluoride. Processing parameters, including molding characteristics of some of the advanced polymers, are described. Test results and relative ranking of some of the flammability, smoke, and toxicity properties are presented.
Kourtides, D. A.↗
Computational Chemistry and Lubrication
Members of NASA Lewis Research Center's Tribology and Surface Science Branch are applying high-level computational chemistry techniques to the development of new lubrication systems for space applications and for future advanced aircraft engines. The next generation of gas turbine engines will require a liquid lubricant to function at temperatures in excess of 350 C in oxidizing environments. Conventional hydrocarbon-based lubricants are incapable of operating in these extreme environments, but a class of compounds known as the perfluoropolyether (PFAE) liquids (see the preceding illustration) shows promise for such applications. These commercially available products are already being used as lubricants in conditions where low vapor pressure and chemical stability are crucial, such as in satellite bearings and composite disk platters. At higher temperatures, however, these compounds undergo a decomposition process that is assisted (catalyzed) by metal and metal oxide bearing surfaces. This decomposition process severely limits the applicability of PFAE's at higher temperatures. A great deal of laboratory experimentation has revealed that the extent of fluid degradation depends on the chemical properties of the bearing surface materials. Lubrication engineers would like to understand the chemical breakdown mechanism to design a less vulnerable PFAE or to develop a chemical additive to block this degradation.
Zehe, Michael J.↗
Filed emission cathodes for electrodynamic tethers: identifying compatible cathode materials
Several material combinations were considered as candidates for the electrodynamic tether application in the investigation discussed in this paper. Critical characteristics like work function, resistance, sputter yield and sensitivity to oxidizing environments were considered. The material investigation included, ZrC/Mo, Mo, MgPt, Pt, NbC/Nb, NbNi/Nb, Nb, RuTa/Ta, Ru/Ta and Ta. The results of the measurements suggest that NbC/Nb, NbNi/Nb, and MgPt are the most promising candidates.
electrodynamics tethers cathodes oxidation↗