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Report describes experimental study of chemical reactions and chemical products of chemical-vapor deposition of silicon carbide from dimethyldichlorosilane. Topic important because it relates to current interest in lightweight refractory materials for use in advanced aircraft and spacecraft. Analyses showed that at temperature of 700 to 1,100 degrees C and contact time of about 1 minute, SiC forms by two chemical-reaction paths.
The bulk and microstructure of comet nuclei are derived from the morphological structure and chemical composition of submicron sized interstellar dust grains which have undergone cold aggregation in the pre-solar nebula. The evolutionary picture of dust which is emerging is a cyclic one in which the particles, before being destroyed or going into solar system bodies, find themselves during their 5 billion year lifetime alternately in diffuse clouds and in molecular clouds. A small silicate core captured within a molecular cloud accretes various ices and gradually builds up an inner mantle of organic refractory material which has been produced by photoprocessing of the volatile ices. Clumps of grains form, and then clumps of clumps, and so on, until finally we reach the size of the comet nucleus.
The effects of catastrophic collisional fragmentation and diffuse medium accretion on a the interstellar dust system are computed using a Monte Carlo computer model. The Monte Carlo code has as its basis an analytic solution of the bulk chemical evolution of a two-phase interstellar medium, described by Liffman and Clayton (1989). The model is subjected to numerous different interstellar processes as it transfers from one interstellar phase to another. Collisional fragmentation was found to be the dominant physical process that shapes the size spectrum of interstellar dust. It was found that, in the diffuse cloud phase, 90 percent of the refractory material is locked up in the dust grains, primarily due to accretion in the molecular medium. This result is consistent with the observed depletions of silicon. Depletions were found to be affected only slightly by diffuse cloud accretion.
Report describes experimental study of phase transformations occurring in monophasic and diphasic xerogels of overall stoichiometric mullite composition during thermal treatment. Mullite valued as refractory material because of relatively high mechanical strength, excellent resistance to thermal shock, high resistance to creep, low density, low thermal conductivity, and stability at high temperature. Part of continuing effort to develop precursor materials transformed into mullite and sintered at temperatures low enough to avoid degradation of non-mullite reinforcing fibers in manufacture of mullite/fiber composites.
Since the identification of the OH radical as an interstellar species, over 50 molecular species were identified as interstellar denizens. While identification of new species appears straightforward, an explanation for their mechanisms of formation is not. Most astronomers concede that large bodies like interstellar dust grains are necessary for adsorption of molecules and their energies of reactions, but many of the mechanistic steps are unknown and speculative. It is proposed that data from matrix isolation experiments involving the reactions of refractory materials (especially C, Si, and Fe atoms and clusters) with small molecules (mainly H2, H2O, CO, CO2) are particularly applicable to explaining mechanistic details of likely interstellar chemical reactions. In many cases, matrix isolation techniques are the sole method of studying such reactions; also in many cases, complexations and bond rearrangements yield molecules never before observed. The study of these reactions thus provides a logical basis for the mechanisms of interstellar reactions. A list of reactions is presented that would simulate interstellar chemical reactions. These reactions were studied using FTIR-matrix isolation techniques.
An understanding was sought for the mechanisms of nucleation of refractory materials, and the relative importance of factors controlling the rate of cluster formation and growth for astrophysically important species. The structure and composition of the condensates is being studied, with the goal of characterizing the grains present in the primitive solar nebula.
The present invention relates to a process for the production of an organoborosilicon preceramic polymer of the structure: wherein R 1 is selected from alkyl having from 1 to 10 carbon atoms or phenyl, and x is selected from 0, 1, 2 or 3; which is pyrolyzable to produce a refractory material comprising inorganic compounds of Si, C and B, which process comprises: contacting a silicon containing compound of the structure: (R 1 ) x --Si--(CH=CH 2 ) 4- x or (R 1 ) x Si--(C=CH) 4- x with a boron containing compound selected from H 3 B:BH 3 , H 3 B:NH 3 , BH 3 :N(R 2 ) 3 wherein R 2 is selected from methyl, ethyl, propyl, butyl or phenyl in an inert atmosphere at a temperature of between about 90° and 170° C. for between about 0.1 and 20 hr and recovering the prepolymer. The prepolymer is pyrolyzed to produce a ceramic article useful in high temperature (e.g., aerospace) or extreme environmental applications.
This paper reports the results of the scale model (1/22) testing of candidate refractory materials to be used as surface coatings for a solid rocket motor plume deflector structure. Five ROM tests were conducted to acquire data to support the selection, thickness determination, and placement of the materials. All data acquisition was achieved through nonintrusive methods. The tests demonstrated that little or no reductions in performance of the full-scale deflector would be experienced if the most economical materials were selected for construction.
Interest in thermal protection systems for high-speed vehicles is increasing because of the stringent requirements of such new projects as the Space Exploration Initiative, the National Aero-Space Plane, and the High-Speed Civil Transport, as well as the needs for improved capabilities in existing thermal protection systems in the Space Shuttle and in turbojet engines. This selection of 13 papers from NASA and industry summarizes the history and operational experience of thermal protection systems utilized in the national space program to date, and also covers recent development efforts in thermal insulation, refractory materials and coatings, actively cooled structures, and two-phase thermal control systems.
Reports covering the period from 1 Nov. 1991 to 31 Oct. 1992 and documenting progress at the NASA Space Engineering Research Center are included. Topics covered include: (1) processing of propellants, volatiles, and metals; (2) production of structural and refractory materials; (3) system optimization discovery and characterization; (4) system automation and optimization; and (5) database development.
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The author's current simulations of Giant Impacts on the protoearth show the development of large hot rock vapor atmospheres. The Balbus-Hawley mechanism will pump mass and angular momentum outwards in the equatorial plane; upon cooling and expansion the rock vapor will condense refractory material beyond the Roche distance, where it is available for lunar formation. During the last seven years, the author together with several colleagues has carried out a series of numerical investigations of the Giant Impact theory for the origin of the Moon. These involved three-dimensional simulations of the impact and its aftermath using Smooth Particle Hydrodynamics (SPH), in which the matter in the system is divided into discrete particles whose motions and internal energies are determined as a result of the imposed initial conditions. Densities and pressures are determined from the combined overlaps of the particles, which have a bell-shaped density distribution characterized by a smoothing length. In the original series of runs all particle masses and smoothing lengths had the same values; the matter in the colliding bodies consisted of initial iron cores and rock (dunite) mantles. Each of 41 runs used 3,008 particles, took several weeks of continuous computation, and gave fairly good representations of the ultimate state of the post-collision body or bodies but at best crude and qualitative information about individual particles in orbit. During the last two years an improved SPH program was used in which the masses and smoothing lengths of the particles are variable, and the intent of the current series of computations is to investigate the behavior of the matter exterior to the main parts of the body or bodies subsequent to the collisions. These runs are taking times comparable to a year of continuous computation in each case; they use 10,000 particles with 5,000 particles in the target and 5,000 in the impactor, and the particles thus have variable masses and smoothing lengths (the latter are dynamically adjusted so that a particle typically overlaps a few tens of its neighbors). Since the matter in the impactor provides the majority of the mass left in orbit after the collision, and since the masses of the particles that originated in the impactor are smaller than those in the target, the mass resolution in the exterior parts of the problem is greatly improved and the exterior particles properly simulate atmospheres in hydrostatic equilibrium.
There are a variety of isotopic data for meteorites which suggest that the protostellar nebula existed and was involved in making planetary materials for some 10(exp 7) yr or more. Many cosmochemists, however, advocate alternative interpretations of such data in order to comply with a perceived constraint, from theoretical considerations, that the nebula existed only for a much shorter time, usually stated as less than or = 10(exp 6) yr. In this paper, we review evidence relevant to solar nebula duration which is available through three different disciplines: theoretical modelling of star formation, isotopic data from meteorites, and astronomical observations of T Tauri stars. Theoretical models based on observations of present star-forming regions indicate that stars like the Sun form by dynamical gravitational collapse of dense cores of cold molecular clouds in the interstellar medium. The collapse to a star and disk occurs rapidly on a time scale of the order 10(exp 5) yr. Disks evolve by dissipating energy while redistributing angular momentum, but it is difficult to predict the rate of evolution, particularly for low mass (compared to the star) disks which nonetheless still contain enough material to account for the observed planetary system. There is no compelling evidence, from available theories of disk structure and evolution, that the solar nebula must have evolved rapidly and could not have persisted for more than 1 Ma. In considering chronologically relevant isotopic data for meteorites, we focus on three methodologies: absolute ages by U-Pb/Pb-Pb, and relative ages by short-lived radionuclides (especially Al-26) and by evolution of Sr-87/Sr-86. Two kinds of meteoritic materials-refractory inclusions such as CAIs and differentiated meteorites (eucrites and angrites) - appear to have experience potentially dateable nebular events. In both case, the most straightforward interpretations of the available data indicate nebular events spanning several Ma. We also consider alternative interpretations, particularly the hypothesis of radically heterogeneous distribution of Al-26, which would avoid these chronological interpretations. The principal impetus for such alternative interpretations seems to be precisely the obviation of the chronological interpretation (i.e., the presumption rather than the inference of a short (less than or = Ma) lifetime of the nebula). Astronomical observations of T Tauri stars indicate that the presence of dusty disks is a common if not universal feature, that the disks are massive enough to accomodate a planetary system such as ours, and that at least some persist for 10(exp 7) yr or more. The results are consistent with the time scales inferred from the meteorite isotopic data. They cannot be considered conclusive with regard to solar nebula time scales, however,in part because it is difficult to relate disk observations to processes that affect meteorites, and in part because the ages assigned for these stars could be wrong by a factor of several in either direction. We conclude that the balance of available evidence favors the view that the nebula existed and was active for at least several Ma. However, because the evidence is not definitive, it is important that the issue be perceived to be an open question, whose answer should be sought rather than presumed.
We have undertaken a project called STARDUST which is a collaboration with Italian and American investigators. The goals of this program are to study the condensation and coagulation of refractory materials from the vapor and to study the properties of the resulting grains as analogs to cosmic dust particles. To reduce thermal convective currents and to develop valuable experience in designing an experiment for the Gas-Grain Simulation Facility aboard Space Station, Freedom we have built and flown a new chamber to study these processes under periods of microgravity available on NASA's KC-135 Research Aircraft. Preliminary results from flights with magnesium and zinc are discussed.
There are a variety of isotopic data for meteorites which suggest that the protostellar nebula existed and was involved in making planetary materials for some 10(exp 7) yr or more. Many cosmochemists, however, advocate alternative interpretations of such data in order to comply with a perceived constraint, from theoretical considerations, that the nebula existed only for a much shorter time, usually stated as less than or equal to 10(exp 6) yr. In this paper, we review evidence relevant to solar nebula duration which is available through three different disciplines: theoretical modeling of star formation, isotopic data from meteorites, and astronomical observations of T Tauri stars. Theoretical models based on observations of present star-forming regions indicate that stars like the Sun form by dynamical gravitational collapse of dense cores of cold molcular clouds in the interstellar clouds in the interstellar medium. The collapse to a star and disk occurs rapidly, on a time scale of the order 10(exp 5) yr. Disks evolve by dissipating energy while redistributing angular momentum, but it is difficult to predict the rate of evolution, particularly for low mass (compared to the star) disks which nonetheless still contain enough material to account for the observed planetary system. There is no compelling evidence, from available theories of disk structure and evolution, that the solar nebula must have evolved rapidly and could not have persisted for more than 1 Ma. In considering chronoloically relevant isotopic data for meteorites, we focus on three methodologies: absolute ages by U-Pb/Pb-Pb, and relative ages by short-lived radionuclides (especially Al-26) and by evolution of Sr-87/Sr-86. Two kinds of meteoritic materials-refractory inclusions such as CAIs and differential meteorites (eucrites and augrites) -- appear to have experienced potentially dateable nebular events. In both cases, the most straightforward interpretations of the available data indicate nebular events spanning several Ma. We also consider alternative interpretations, particularly the hypothesis of radically heterogeneous distribution of Al-26, which would avoid these chronological interpretations. The principal impetus for such alternative interpretations seems to be precisely the obviation of the chronological interpretation (i.e., the presumption rather than the inference of a short (less than or equal to 1 Ma) lifetime of the nebula). Astronomical observations of T Tauri stars indicate that the presence of dusty disks is a common if not universal feature, that the disks are massive enough to accomodate a planetary system such as ours, and that at least some persist for 110(exp 7) yr or more. The results are consistent with the time scales inferred from the meteoritic isotopic data. They cannot be considered conclusive with regard to solar nebula time scales, however, in part because it is difficult to relate disk observations to processes that affect meteorites, and in part because the ages assigned for these stars could be wrong by a factor of several in either direction. We conclude that the balance of available evidence favors the view that the nebula existed and was active for at least several Ma. However, because the evidence is not definitive, it is important that the issue be perceived to be an open question, whose answer should be sought rather than presumed.
Computer-controlled machine-tool system uses laser beam assisted by directed flow of air to cut refractory materials into complex three-dimensional shapes. Velocity, position, and angle of cut varied. In original application, materials in question were thermally insulating thick blankets and tiles used on space shuttle. System shapes tile to concave or convex contours and cuts beveled edges on blanket, without cutting through outer layer of quartz fabric part of blanket. For safety, system entirely enclosed to prevent escape of laser energy. No dust generated during cutting operation - all material vaporized; larger solid chips dislodged from workpiece easily removed later.
Infrared spectroscopy of pre-main sequence stars with dusty protostellar disks provide information about the evolution of refractory materials in such systems. These systems exhibit varying degrees of strength and structure in the silicate emission band situated at 10 microns wavelength. Band strength is affected by the mean grain size, while band structure is determined by the chemical composition and degree of crystallinity. In some objects, the silicate band is strong and featureless, similar to that seen in the interstellar medium. In others, the band is often weaker, and exhibits structure consistent with the presence of crystalline olivine. In these latter objects, the band is similar to that of some solar system comets. The strength and structure of the silicate band may be related to the processing history of the system.
The Instrumentation Working Group compiled a summary of measurement techniques applicable to gas turbine engine aerosol precursors and particulates. An assessment was made of the limits, accuracy, applicability, and technology readiness of the various techniques. Despite advances made in emissions characterization of aircraft engines, uncertainties still exist in the mechanisms by which aerosols and particulates are produced in the near-field engine exhaust. To adequately assess current understanding of the formation of sulfuric acid aerosols in the exhaust plumes of gas turbine engines, measurements are required to determine the degree and importance of sulfur oxidation in the turbine and at the engine exit. Ideally, concentrations of all sulfur species would be acquired, with emphasis on SO2 and SO3. Numerous options exist for extractive and non-extractive measurement of SO2 at the engine exit, most of which are well developed. SO2 measurements should be performed first to place an upper bound on the percentage of SO2 oxidation. If extractive and non-extractive techniques indicate that a large amount of the fuel sulfur is not detected as SO2, then efforts are needed to improve techniques for SO3 measurements. Additional work will be required to account for the fuel sulfur in the engine exhaust. Chemical Ionization Mass Spectrometry (CI-MS) measurements need to be pursued, although a careful assessment needs to be made of the sampling line impact on the extracted sample composition. Efforts should also be placed on implementing non-intrusive techniques and extending their capabilities by maximizing exhaust coverage for line-of-sight measurements, as well as development of 2-D techniques, where feasible. Recommendations were made to continue engine exit and combustor measurements of particulates. Particulate measurements should include particle size distribution, mass fraction, hydration properties, and volatile fraction. However, methods to ensure that unaltered samples are obtained need to be developed. Particulate speciation was also assigned a high priority for quantifying the fractions of carbon soot, PAH, refractory materials, metals, sulfates, and nitrates. High priority was also placed on performing a comparison of particle sizing instruments. Concern was expressed by the workshop attendees who routinely make particulate measurements about the variation in number density measured during in-flight tests by different instruments. In some cases, measurements performed by different groups of researchers during the same flight tests showed an order of magnitude variation. Second priority was assigned to measuring concentrations of odd hydrogen and oxidizing species. Since OH, HO2, H2O2, and O are extremely reactive, non-extractive measurements are recommended. A combination of absorption and fluorescence is anticipated to be effective for OH measurements in the combustor and at the engine exit. Extractive measurements of HO2 have been made in the stratosphere, where the ambient level of OH is relatively low. Use of techniques that convert HO2 to OH for combustor and engine exit measurements needs to be evaluated, since the ratio of HO2/OH may be 1% or less at both the combustor and engine exit. CI-MS might be a viable option for H2O2, subject to sampling line conversion issues. However, H2O2 is a low priority oxidizing species in the combustor and at the engine exit. Two candidates for atomic oxygen measurements are Resonance Enhanced Multi-Photon Ionization (REMPI) and Laser-Induced Fluorescence (LIF). Particulate measurement by simultaneous extractive and non-extractive techniques was given equal priority to the oxidizer measurements. Concern was expressed over the ability of typical ground test sampling lines to deliver an unaltered sample to a remotely located instrument. It was suggested that the sampling probe and line losses be checked out by attempting measurements using an optical or non-extractive technique immediately upstream of the sampling probe. This is a possible application for Laser Induced Incandescence (LII) as a check on the volume fraction of soot. Optical measurements of size distribution are not well developed for ultrafine particles less than about 20 nm in diameter, so a non-extractive technique for particulate size distribution cannot be recommended without further development. Carbon dioxide measurements need to be made to complement other extractive measurement techniques. CO2 measurements enable conversion of other species concentrations to emission indices. Carbon monoxide, which acts as a sink for oxidizing species, should be measured using non-extractive techniques. CO can be rapidly converted to CO2 in extractive probes, and a comparison between extractive and non-extractive measurements should be performed. Development of non-extractive techniques would help to assess the degree of CO conversion, and might be needed to improve the concentration measurement accuracy. Measurements of NO(x) will continue to be critical due to the role of NO and NO2 in atmospheric chemistry, and their influence on atmospheric ozone. Time-resolved measurements of temperature, velocity, and species concentrations were included on the list of desired measurement. Thermocouples are typically adequate for engine exit measurements. PIV and LDV are well established for obtaining velocity profiles. The techniques are listed in the accompanying table; are divided into extractive and non-extractive techniques. Efforts were made to include a measurement uncertainty for each technique. An assessment of the technology readiness was included.