PYROLYTIC GRAPHITE THRUST CHAMBER DEVELOPMENT.
Thermal stresses in a pyrolytic graphite thrust chamber
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Thermal stresses in a pyrolytic graphite thrust chamber
A new model of the production of the uniformly low plagioclase and Al contents of ureilites is proposed. It is argued that those contents are consequences of widespread explosive volcanism during the evolution of the parent asteroid(s). It is noted that the great abundance of graphite on the ureilite asteroid(s) made them ideal sites for explosive volcanism driven by oxidation of graphite in partial melts ascending within the asteroid(s).
The process of ablation for Earth atmospheric entry is simulated using a computational approach that allows thermo-chemical nonequilibrium of the flow field and ablation gases. The heat pulse into the heat shield is modeled. The flowfield and graphite heat shield are coupled through surface mass and energy balances. The surface thermochemistry involves the oxidation of graphite and allows for catalytic recombination of diatomic oxygen. Steady-state simulations are performed on a one meter nose radius sphere at an altitude of 65/km and at freestream velocities of 8 km/s and 10 km/s. A transient simulation is performed at 65 km altitude and a freestream velocity of 10 km/s.
A thorough understanding of oxidation is important when considering the health and integrity of graphite components in graphite reactors. For the next generation of graphite reactors, HTGRs specifically, an unlikely air ingress has been deemed significant enough to have made its way into the licensing applications of many international licensing bodies. While a substantial body of literature exists on nuclear graphite oxidation in the presence of molecular oxygen and significant efforts have been made to characterize oxidation kinetics of various grades, the value of existing information is somewhat limited. Often, multiple competing processes, including reaction kinetics, mass transfer, and microstructural evolution, are lumped together into a single rate expression that limits the ability to translate this information to different conditions. This article reviews the reaction of graphite with molecular oxygen in terms of the reaction kinetics, gas transport, and microstructural evolution of graphite. It also presents the foundations of a model for the graphite-molecular oxygen reaction system that is kinetically independent of graphite grade, and is capable of describing both the bulk and local oxidation rates under a wide range of conditions applicable to air-ingress.
Equilibrium carbon monoxide pressures measured by torsion effusion studies of reaction of graphite with hafnium and uranium dioxides at high temperatures
Intrinsic structural and oxidic defects activate graphitic carbon electrodes towards electrochemical reactions underpinning energy conversion and storage technologies. Yet, these defects can also disrupt the long-range and periodic arrangement of carbon atoms, thus, the characterization of graphitic carbon electrodes necessitates in-situ atomistic differentiation of graphitic regions from mesoscopic bulk disorder. Here, we leverage the combined techniques of in-situ attenuated total reflectance infrared spectroscopy and first-principles calculations to reveal that graphitic carbon electrodes exhibit electric-field dependent infrared activity that is sensitive to the bulk mesoscopic intrinsic disorder. With this platform, we identify graphitic regions from amorphous domains by discovering that they demonstrate opposing electric-field-dependent infrared activity under electrochemical conditions. Our work provides a roadmap for identifying mesoscopic disorder in bulk carbon materials under potential bias.
The thermooxidative stability in air at 316 C of unidirectional, uncoated and aluminum-coated Celion 6000 graphite fiber/PMR 15 polyimide composites has been determined for exposure times up to nominally 2000 h. Comparison of the weight loss data and microstructural integrity reveals that a thin aluminum-foil coating can provide significant protection from oxidation. A quantitative description of the average depth of the reaction zone and the maximum length of cracks produced during oxidation as a function of time in uncoated Celion 6000/PMR 15 are given.
Catalytic effect of impurities on oxidation rate for selected artificial graphites
Aluminum carbide may form at aluminum-graphite interfaces during the high-temperature processing of graphite fiber-reinforced aluminum metal matrix composites. The chemical interactions leading to the formation of the aluminum carbide in the solid state involve the breaking of the carbon-carbon bonds within the graphite, the transport of the carbon atoms across the interface, and the reaction with the aluminum to form Al4C3. The aluminum carbide formation process has been followed using X-ray photoelectron spectroscopy of model, thin-film, reaction couples. The overall reaction is shown to be catalyzed by the presence of water vapor. Water at the interface increases reaction kinetics by apparently weakening the bonds between the surface carbon atoms and their substrate. This result is in general agreement with what is known to occur during the oxidation of graphite in air.
The discovery of presolar grains in meteorites is one of the most exciting recent developments in meteoritics. Six types of presolar grain have been discovered: diamond, Sic, graphite, Si3N4, Al2O3 and MgAl2O4. These grains have been identified as presolar because their isotopic compositions are very different from those of Solar System materials. Comparison of their isotopic compositions with astronomical observations and theoretical models indicates most of the grains formed in the envelopes of highly evolved stars. They are, therefore, a new source of information with which to test astrophysical models of the evolution of these stars. In fact, because several elements can often be measured in the same grain, including elements that are not measurable spectroscopically in stars, the grain data provide some very stringent constraints for these models. Our primary goal is to create large, unbiased, multi-isotope databases of single presolar Sic, Si,N,, oxide and graphite grains in meteorites, as well as any new presolar grain types that are identified in the future. These will be used to: (i) test stellar and nucleosynthetic models, (ii) constrain the galactic chemical evolution (GCE) paths of the isotopes of Si, Ti, 0 and Mg, (iii) establish how many stellar sources contributed to the Solar System, (iv) constrain relative dust production rates of various stellar types and (v) assess how representative of galactic dust production the record in meteorites is. The primary tool for this project is a highly automated grain analysis system we have developed for the Carnegie 6f ion probe.
The discovery of presolar grains in meteorites is one of the most exciting recent developments in meteoritics. Six types of presolar grain have been discovered: diamond, Sic, graphite, Si3N4, Al2O3 and MgAl2O4. These grains have been identified as presolar because their isotopic compositions are very different from those of Solar System materials. Comparison of their isotopic compositions with astronomical observations and theoretical models indicates most of the grains formed in the envelopes of highly evolved stars. They are, therefore, a new source of information with which to test astrophysical models of the evolution of these stars. In fact, because several elements can often be measured in the same grain, including elements that are not measurable spectroscopically in stars, the grain data provide some very stringent constraints for these models. Our primary goal is to create large, unbiased, multi-isotope databases of single presolar Sic, Si,N,, oxide and graphite grains in meteorites, as well as any new presolar grain types that are identified in the future. These will be used to: (i) test stellar and nucleosynthetic models, (ii) constrain the galactic chemical evolution (GCE) paths of the isotopes of Si, Ti, O and Mg, (iii) establish how many stellar sources contributed to the Solar System, (iv) constrain relative dust production rates of various stellar types and (v) assess how representative of galactic dust production the record in meteorites is. The primary tool for this project is a highly automated grain analysis system on the Carnegie 6f ion probe.
The discovery of presolar grains in meteorites is one of the most exciting recent developments in meteoritics. Six types of presolar grain have been discovered: diamond, Sic, graphite, Si3N4, Al2O3 and MgAl2O4 (NIITLER, 2003). These grains have been identified as presolar because their isotopic compositions are very different from those of Solar System materials. Comparison of their isotopic compositions with astronomical observations and theoretical models indicates that most of the grains formed in the envelopes of highly evolved stars. They are, therefore, a new source of information with which to test astrophysical models of the evolution of these stars. In fact, because several elements can often be measured in the same grain, including elements that are not measurable spectroscopically in stars, the grain data provide some very stringent constraints for these models. Our primary goal is to create large, unbiased, multi-isotope databases of single presolar Sic, Si3N4, oxide and graphite grains in meteorites, as well as any new presolar grain types that are identified in the future. These will be used to: (i) test stellar and nucleosynthetic models, (ii) constrain the galactic chemical evolution (GCE) paths of the isotopes of Si, Ti, O and Mg, (iii) establish how many stellar sources contributed to the Solar System, (iv) constrain relative dust production rates of various stellar types and (v) assess how representative of galactic dust production the record in meteorites is. The primary tool for this project is a highly automated grain analysis system on the Carnegie 6f ion probe. This proposal was part of a long-standing research effort that is still ongoing.
Nanoparticles have been developed over the past 10 years and have found several applications. This work presents the use of carbon nano-onions as a potential oil additive for aerospace applications. Researchers at the NASA Glenn Research Center tested lubricant lifetimes in ambient air and ultrahigh vacuum and characterized the breakdown products of the friction and wear. These carbon nanoparticles can provide adequate lubrication very similar to that of graphitic material when run in air. Soot represents one of the very first nanostructured materials, although it has rarely been considered as such. Changes in the carbon nanostructure, resulting in increased graphitic layer plane length, correlate with reactivity loss. Upon heating spherically shaped nanometer-sized carbon black in the absence of oxidant, graphene sheets form, and the initial soot particle templates the growth of a graphitic particle into what is best described as a sphere with many flat sides having a hollow interior. Because there are no edge sites, these polygonal graphitic particles, or nano-onions, are relatively resistant to oxidation. Graphite is used as a solid lubricant because of its stability at moderately high temperatures. However, the temperature at which graphite oxidizes rapidly is strongly influenced by surface area. With the size of particles typically employed in lubrication, a great amount of thermal stability is lost because of size reduction either during preparation or during lubrication of contacting parts. Therefore, we have undertaken a study of the lubricating ability of graphitic nano-onions (ref. 1).
Mixture of uranium oxide, niobium oxide, and graphite of various carbon-to-oxygen ratios is heated to a temperature below the melting point of the noibium-uranium alloy. The alloy is produced by this method with voids predetermined as to size and total volume.
Mass spectrometric techniques and instrumentation for the dynamic sampling of laser-induced vapor clouds during their submillisecond expansion periods are discussed. Illustrations are drawn primarily from the results of pulsed-laser heating of some oxides and graphites; these include comparisons of incident laser beam pulses with the resultant pulses of positive ions and selected neutral species. Observed characteristics of vapor pulses from graphite are shown to correlate with calculated surface temperature response. Dynamic velocity measurements of individual vapor species are described and, from these velocities, vaporization temperatures are derived and compared using four gas dynamic models for vapor expansion into vacuum. Additional measurements indicate that the laser beam may interact directly with the neutral vapors to produce ions.
Carbon is a crucial atom in cosmochemistry. It is well-established that carbon is synthesized in stellar interiors after the main sequence, is ejected by red giants as small carbonaceous grains during their 'carbon star' phase, resides in the interstellar medium, and was later incorporated into the solar system. The mechanisms of carbon grain formation and later chemical processing are complex because, with only small thermodynamic differences, carbon can take on a bewildering variety of forms: diamond; oxides; carbides; graphite; aliphatic hydrocarbons; polycyclic aromatic hydrocarbons (PAH's); fullerenes; amorphous carbon; and other compounds. These are evidence for many of the forms of carbon found in astronomical observations. We seek to understand the possible astrophysical sites and conditions of the origins of different forms of carbon by combining state-of-the-art capabilities of carbon chemistry with astrophysical modeling. The work is a collaboration between Prof. Frenklach, a leading carbon materials scientist with both laboratory and computer modeling expertise and Prof. Feigelson, an astrophysicist with interests in star formation. The largest effort under this grant was devoted to developing this concept into a comprehensive quantitative model. In addition to explaining the astronomical properties of red giants producing carbonaceous grains, our model also can incorporate recent meteoritic findings. Finally, our induced nucleation grain formation model provides a natural explanation for the widespread presence of PAH emission bands in the Galactic interstellar medium. A brief synopsis of other activities sponsored under this grant and a list of publications from this grant is included.
Interstellar dust is characterized by strong absorption in the ultraviolet and the mid-IR. Current models of interstellar dust are based on three chemically distinct components: a form of carbon (usually graphite), a silicate, and a blend of polycyclic aromatic hydrocarbons or other carbonaceous material. Previous work using effective medium theories to understand the optical properties of cometary dust suggested that an amalgam of materials could reproduce the observed interstellar and cometary dust features. Recently, Lawler and Brownlee (1992) re-analyzed the PIA and PUMA-1 data sets from the Giotto flyby of P/Halley and discovered that the so-called "CHON" particles were actually composed of a blend of carbon-bearing and silicon-bearing materials. Based on effective medium theories, the absorption spectrum of such a material would display the spectral features of each of the components - strong UV absorption from the carbonaceous component and strong absorption in the IR from the silicate component. To test this idea, vapor-deposited samples were created using two different deposition techniques: sputtering with an argon RF magnetron and deposition from an argon plasma torch. Two different compositions were tested: a blend of graphite and silica in a 7:1 ratio and an amalgam of materials whose approximate composition matches the "CHON"-silicate abundances for the uncompressed PIA data set of Lawler and Brownlee: graphite, iron oxide, magnesium oxide, ammonium sulfate, calcium carbonate, and silica in mass ratios of 6:4.3:4:2.2:1:9. The samples were finely ground and pressed into 2" diameter disks using a 40 ton press. In all, four different experiments were performed: one with each of the compositions (C:SiO and "CHON") in both the RF magnetron and the plasma torch chambers. The RF magnetron created a uniform dark thin film on the substrate surface, and the plasma torch created a coating of small (<100 micron) diameter grey particles. The spectra of all four samples show a strong, broad absorption feature at around 220 nm as well as a strong but narrower absorption peak near 10 microns. The RF magnetron sputtered samples showed some sub-structure in the UV, and the peak of the absorption was shifted toward longer wavelengths. The UV absorption in the plasma torch deposited samples have no sub-structure, and the peak absorption is very near 220 nm. Strong absorption near 9 microns is seen in the spectra from both sample preparation techniques, and is consistent with the IR spectra of some terrestrial silicates. Other features, particularly at 6.2 and 8.6 microns, are seen in the interstellar medium. A strong feature near 2 microns is due to absorbed water in the sample. Based on the results of these experiments, there is evidence that a material with a composition similar to that detected in "CHON" particles in the coma of P/Halley have a spectral signature which reproduces the main absorption features of interstellar dust. This suggests that the "CHON" particles could be the interstellar component of cometary dust.
In 1971, Apollo 17 astronauts collected a 10 cm soil sample (74220) comprised almost entirely of orange glass spherules. Below this, a double drive-tube core sampled a 68 cm thick horizon comprised of orange glass and black beads (crystallized equivalents of orange glass). Primitive lunar glass spherules (e.g.-A17 orange glasses) are thought to represent ejecta from lunar mare fire fountains [1, 2]. The fire-fountains were apparently driven by a combination of C-O gas ex-solution from orange glass melt and the oxidation of graphite [3, 4]. Upon eruption, magmas lost their volatiles (e.g., S, CO, CO2) to space. Evidence for volatile escape remains as volatile-rich coatings on the exteriors of many spherules [e.g., 5,6]. Moreover, [7] showed that Type I and II Fe-Ni-rich metal particles found within orange glass olivine phenocrysts, or free-floating in the glass itself, are powerful evidence for the volatile driving force for lunar fire fountains.