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At least 505 records · Page 28

Thermochemical analysis of chemical processes relevant to the stability and processing of SiC-reinforced Si3N4 composite

Chemical processes relevant to the stability and processing of SiC-reinforced Si3N4 composites have been examined from thermochemical considerations. The thermodynamic stabilities of various interfaces, such as SiC-Si3N4, SiC-Si3N4-Si2ON2, and SiC-Si3N4-SiO2, have been examined as a function of temperature, and the temperatures above which these interfaces become unstable have been calculated. The degradation of SiC during the processing of the composite has been examined. The processing routes considered in this study include the reaction bonded silicon nitride (RBSN) process and the pressure-assisted sintering processes with suitable sintering additives.

Misra, Ajay K.↗

Oxidation instability of SiC and Si3N4 following thermal excursions

The effect of thermal excursion and thermal cycling on the oxidation stability of chemical vapor-deposited (CVD) SiC and Si3N4 was studied at 1350 C. Thermal cycling alone produced no noticeable change in oxidation kinetics. However, TEM showed that oxide scales grown in cycles consist of alternating layers of SiO2 and Si2N2O. When the oxidation of CVD SiC or Si3N4 at 1350 C was interrupted with a 1.5-h annealing in Ar at 1500 C, the kinetics of reoxidation at 1350 C were found to be drastically increased. The SiC and Si3N4 then oxidized essentially at the same rate, which is over 50 times the preannealing rate, and comparable to the expected oxidation rate of these materials at 1500 C.

Ogbuji, Linus U. J. T.↗

Effect of particle size of Martian dust on the degradation of photovoltaic cell performance

Glass coverglass and SiO2 covered and uncovered silicon photovoltaic (PV) cells were subjected to conditions simulating a Mars dust storm, using the Martian Surface Wind Tunnel, to assess the effect of particle size on the performance of PV cells in the Martian environment. The dust used was an artificial mineral of the approximate elemental composition of Martian soil, which was sorted into four different size ranges. Samples were tested both initially clean and initially dusted. The samples were exposed to clear and dust laden winds, wind velocities varying from 23 to 116 m/s, and attack angles from 0 to 90 deg. It was found that transmittance through the coverglass approximates the power produced by a dusty PV cell. Occultation by the dust was found to dominate the performance degradation for wind velocities below 50 m/s, whereas abrasion dominates the degradation at wind velocities above 85 m/s. Occultation is most severe at 0 deg (parallel to the wind), is less pronounced from 22.5 to 67.5 deg, and is somewhat larger at 90 deg (perpendicular to the wind). Abrasion is negligible at 0 deg, and increases to a maximum at 90 deg. Occultation is more of a problem with small particles, whereas large particles (unless they are agglomerates) cause more abrasion.

Gaier, James R.↗

The chemistry of Saudi Arabian sand: A deposition problem on helicopter turbine airfoils

Recent operations in the Persian Gulf have exposed military helicopter turbines to excessive amounts of ingested sand. Fine particles, less than 10 microns, are able to bypass the particle separators and enter the cooling and combustion systems. The initial sand chemistry varies by location, but is made up of a calcium aluminum silicate glass, SiO2 low quartz (Ca,Mg) CO3 dolomite, CaCO3 calcite, and occasionally CaCl rocksalt. The sand reacts in the hot combustion gases and deposits onto the turbine vanes as CaSO4, glass, and various crystalline silicates. Deposits up to 0.25 in. thick have been collected. Although cooling hole plugging is a considerable problem, excessive corrosion is not commonly observed due to the high melting point of GaSO4.

Smialek, James L.↗

Atomic oxygen durability of solar concentrator materials for Space Station Freedom

The findings are reviewed of atomic oxygen exposure testing of candidate solar concentrator materials containing SiO2 and Al2O3 protective coatings for use on Space Station Freedom solar dynamic power modules. Both continuous and iterative atomic oxygen exposure tests were conducted. Iterative air plasma ashing resulted in larger specular reflectance decreases and solar absorptance increases than continuous ashing to the same fluence, and appears to provide a more severe environment than the continuous atomic oxygen exposure that would occur in the low Earth orbit environment. First generation concentrator fabrication techniques produced surface defects including scratches, macroscopic bumps, dendritic regions, porosity, haziness, and pin hole defects. Several of these defects appear to be preferential sites for atomic oxygen attack leading to erosive undercutting. Extensive undercutting and flaking of reflective and protective coatings were found to be promoted through an undercutting tearing propagation process. Atomic oxygen erosion processes and effects on optical performance is presented.

Degroh, Kim K.↗

Polyimides containing pendent siloxane groups

The incorporation of siloxane units into the backbone of aromatic polyimides has been shown to impart certain advantages over the unmodified polyimides. These include enhanced solubility, lower moisture adsorption, lower dielectric constant, improved toughness and surface modification. Also, when exposed to an atomic oxygen environment these materials form an in-situ silicate (SiO2) surface coating which protects the underlying material from further erosion. These unique advantages make polyimide-siloxanes useful in a variety of electronic and aerospace applications. As part of an effort on high performance polymeric materials for potential aerospace applications, polyimides containing pendent siloxane groups are under study. These materials were prepared by reacting a functionalized siloxane compound with polyimides containing benzhydrol groups. Thin films of the polymers exhibited glass transition temperatures ranging from 167 to 235 C. Tensile strengths and moduli measured at 23 C ranged from 11 to 14 ksi and 250 to 450 ksi, respectively. The dielectric constant was lowered substantially from that of the unmodified polyimide.

Connell, John W.↗

Superheat in magma oceans

The existence of 'totally molten' planets implies the existence of a superheat (excess of heat) in the magma reservoirs since the heat buffer (i.e., presence of crystals having high latent heat of fusion) does not exist in a large, completely molten reservoir. Any addition of impacting material results in increase of the temperature of the melt and under favorable circumstances heat is stored. The behavior of superheat melts is little understood; therefore, we experimentally examined properties and behavior of excess heat melts at atmospheric pressures and inert gas atmosphere. Highly siliceous melts (70 percent SiO2) were chosen for the experiments because of the possibility of quenching such melts into glasses, the slow rate of reaction in highly siliceous composition, and the fact that such melts are present in terrestrial impact craters and impact-generated glasses. Results from the investigation are presented.

Jakes, Petr↗

Mg-perovskite/silicate melt partition coefficients in the CMS system at 2430 C and 226 Kbars

The partitioning of elements among lower mantle phases and silicate melts is of interest in unraveling the early thermal history of the Earth. Because of the technical difficulty in carrying out such measurements, only one direct set of measurements has been reported, and these results as well as interpretations based on them have generated controversy. The first set of direct measurements on a synthetic system in the CaO-MgO-SiO2 (CMS) is reported. An experiment was conducted at Stony Brook, using the USSA-2000 split sphere anvil apparatus. An experiment in the CMS system doped with oxides of Al, Ti, Sc, and Sm and run at a nominal temperature of 2380 C and pressure of 226 kbars is reported. Nominal temperatures were measured with a W 3 percent Re/W 25 percent Re thermocouple. The hot spot temperature, where the liquidus is located, is estimated to be at 2430 C. A 10 mm MgO octahedron was used in concert with 4 mm truncation edge lengths on the WC cubes. The sample was contained in a Re capsule which was inserted into a LaCrO3 furnace. Pressure was calibrated at 2000 C. Run duration was approximately 3 minutes. The charge was mounted in epoxy and analyzed using a CAMECA SX-50 electron microprobe. Standard operating conditions were employed, although counting time for the less abundant elements was increased to improved counting statistics. The melt is unquenchable, and forms a dendritic intergrowth of quench crystals and residual melt. It was analyzed using a 30 micron raster. The structural identity of the Mg-perovskite phase was confirmed using x ray microdiffractometry. The results of the investigation are presented.

Mcfarlane, Elisabeth A.↗

Gibbs free energy of reactions involving SiC, Si3N4, H2, and H2O as a function of temperature and pressure

Silicon carbide and silicon nitride are considered for application as structural materials and coating in advanced propulsion systems including nuclear thermal. Three-dimensional Gibbs free energy were constructed for reactions involving these materials in H2 and H2/H2O. Free energy plots are functions of temperature and pressure. Calculations used the definition of Gibbs free energy where the spontaneity of reactions is calculated as a function of temperature and pressure. Silicon carbide decomposes to Si and CH4 in pure H2 and forms a SiO2 scale in a wet atmosphere. Silicon nitride remains stable under all conditions. There was no apparent difference in reaction thermodynamics between ideal and Van der Waals treatment of gaseous species.

Isham, M. A.↗

Thermal degradation study of silicon carbide threads developed for advanced flexible thermal protection systems

Silicon carbide (SiC) fiber is a material that may be used in advanced thermal protection systems (TPS) for future aerospace vehicles. SiC fiber's mechanical properties depend greatly on the presence or absence of sizing and its microstructure. In this research, silicon dioxide is found to be present on the surface of the fiber. Electron Spectroscopy for Chemical Analysis (ESCA) and Scanning Electron Microscopy (SEM) show that a thin oxide layer (SiO2) exists on the as-received fibers, and the oxide thickness increases when the fibers are exposed to high temperature. ESCA also reveals no evidence of Si-C bonding on the fiber surface on both as-received and heat treated fibers. The silicon oxide layer is thought to signal the decomposition of SiC bonds and may be partially responsible for the degradation in the breaking strength observed at temperatures above 400 C. The variation in electrical resistivity of the fibers with increasing temperature indicates a transition to a higher band gap material at 350 to 600 C. This is consistent with a decomposition of SiC involving silicon oxide formation.

Tran, Huy Kim↗

Pressure drop of He II flow through a porous media

The paper reports on measurements of He II pressure drop across two porous SiO2 ceramic filter materials. These materials vary only in porosity, having values of 0.94 and 0.96. The average fiber diameter in both cases is approximately 5 microns. The experiment consists of a glass tube containing a piece of this sponge in one end. The tube is rapidly displaced downward in a bath of helium and the liquid levels are allowed to equilibrate over time producing variable velocities up to 10 cm/sec. The results are compared with those previously obtained using fine mesh screens. Good qualitative agreement is observed for turbulent flow; however, the behavior in the laminar flow regime is not fully understood.

Maddocks, J. R.↗

Screening programme to select a resin for Gravity Probe-B composites

The Gravity Probe-B (GP-B) program undertook a screening program to select a possible replacement resin for the E-787 resin currently used in composite neck tubes and support struts. The goal was to find a resin with good cryogenic and structural properties, low-helium permeation and an easily repeatable fabrication process. Cycom 92, SCI REZ 081 and RS-3 were selected for comparison with E-787. Identical composite tubes made from each resin and gamma-alumina fiber (85 percent Al2O3, 15 percent SiO2) were evaluated for cryogenic and structural performance and for processability. Cryogenic performance was evaluated by measuring low-temperature permeation and leaks to determine cryogenic strain behavior. Structural performance was evaluated by comparing the resin-dominated shear strength of the composites. Processability was evaluated from fabrication comments and GP-B's own experience. SCI REZ 081 was selected as the best overall resin with superior strength and cryogenic performance and consistent processability.

Will, E. T.↗

Solubility and partitioning of Ne, Ar, Kr, and Xe in minerals and synthetic basaltic melts

The solubilities of Ne, Ar, Kr, and Xe gases were measured in natural samples of anorthite, diopside, forsterite, spinel, and synthetic basaltic melts, the samples which represent equilibrium pairs in the Fo-An-Di-SiO2 system. Results show that, in natural minerals, the solubilities of these gases increase with increasing atomic number. In contrast, the solubilities of noble gases in the synthetic basaltic melts decreased with increasing atomic number. The partition coefficients increased with increasing atomic number for all mineral/melt pairs.

Broadhurst, C. L.↗

Precautions toward XTEM of Si3N4/SiO2

Severe difficulties are encountered in the preparation of oxidized Si3N4 specimens for XTEM transmission electromicroscopic inspection, in virtue of the extreme difference between Si3N4 and SiO2 mechanical properties. Attention is presently given to a preparation method in which an overlayer of the nitride is always occluded; this protects the oxide through most of the thinning that specimen preparation entails. An XTEM image of the oxide/nitride interface is presented.

Ogbuji, Linus U. J. T.↗

Geochemistry of impact glasses from the K/T boundary in Haiti - Relation to smectites and a new type of glass

Detailed element analyses were carried out on 12 black and seven yellow glasses from the K/T boundary section at Beloc (Haiti), and of three samples from smectite mantles around black glasses. The results obtained for bulk black and yellow glasses show differences between these, confirming the results of Sigurdsson et al. (1991) and Izett (1991), and the results obtained on individual spherules and shards are in agreement with bulk data. The present data also demonstrate, for the first time, the existence of yellow glass samples with high CaO but low S contents, which might have formed by fusion of various proportions of carbonates and evaporites or carbonates alone. One of the black glasses was found to have higher than average SiO2 and K2O abundances but lower concentrations of all other major elements. This suggests the existence of a third glass type, named the high Si-K variety (HSi,K) glass.

Koeberl, Christian↗

Impactites from Popigai Crater

Impactites (tagamites and suevites) from Popigai impact crater, whose diameter is about 100 km, are distributed over an area of 5000 sq km. The continuous sheet of suevite overlies the allogenic polymict breccia and partly authogenic breccia, and may also be observed in lenses or irregular bodies. The thickness of suevites in the central part of the crater is more than 100 m. Suevites may be distinguished by content of vitroclasts, lithoclasts, and crystalloclasts, by their dimensions, and by type of cementation, which reflects the facial settings of ejection of crushed and molten material, its sedimentation and lithification. Tagamites (impact melt rocks) are distributed on the surface predominantly in the western sector of the crater. The most characteristic are thick sheetlike bodies overlying the allogenic breccia and occurring in suevites where minor irregular bodies are widespread. The maximal thickness of separate tagamite sheets is up to 600 m. Tagamites, whose matrix is crystallized to a different degree, include fragments of minerals and gneiss blocks, among them shocked and thermally metamorphosed ones. Tagamite sheets have a complex inner structure; separate horizontal zones distinguish in crystallinity and fragment saturation. Differentiation in the impact melt in situ was not observed. The average chemical compositions of tagamites and suevites are similar, and correspond to the composition of biotite-garnet gneisses of the basement. According to the content of supplied Ir, Ni, and other siderophiles, impact melt was contaminated by 5 percent cosmic matter of collided body, probably ordinary chondrite. The total volume of remaining products of chilled impact melt is about 1750 cu km. Half this amount is represented by tagamite bodies. Though impact melt was in general well homogenized, the trend analysis showed that the concentric zonation is distribution of SiO2, MgO, and Na2O and the bandlike distribution of FeO and Al2O3 content testifies to a certain inheritance and heterogeneity in country rock composition laterally and vertically in the melting zone.

Masaitis, V. L.↗

Bronzite Granophyre: New insight on Vredefort

The Vredefort Dome is located near the center of the Witwatersrand Basin, about 120 km southeast of Johannesburg, South Africa. Its origin is enigmatic, ranging from a major impact event to endogenous processes, either igneous or tectonic. A unique melt rock, the 'Bronzite' Granophyr, occurs in the Vredefort structure as vertical ring dikes along the contact between sedimentary collar and core of Archaean granites, and as vertical dikes extending northwest-southeast and northeast-southwest in the granitic core. The granophyre rocks have an unusual composition and high content of recrystallized sedimentary inclusions compared to common intrusive igneous rocks with similar SiO2 content (61 to 70 percent by weight). The unique nature of the granophyre has been underlined in previous studies and origin hypotheses as an impact melt or as a highly contaminated intrusive mafic magma have also been discussed. We present new results obtained from a recent detailed petrographic and geochemical study of a very large and texturally diverse suite of 'Bronzite' Granophyre, representing all dikes occurring at Vredefort.

Therriault, A. M.↗

Surface contamination on LDEF exposed materials

X-ray photoelectron spectroscopy (XPS) has been used to study the surface composition and chemistry of Long Duration Exposure Facility (LDEF) exposed materials including silvered Teflon (Ag/FEP), Kapton, S13GLO paint, quartz crystal monitors (QCM's), carbon fiber/organic matrix composites, and carbon fiber/Al Alloy composites. In each set of samples, silicones were the major contributors to the molecular film accumulated on the LDEF exposed surfaces. All surfaces analyzed have been contaminated with Si, O, and C; most have low levels (less than 1 atom percent) of N, S, and F. Occasionally observed contaminants included Cl, Na, K, P, and various metals. Orange/brown discoloration observed near vent slots in some Ag/FEP blankets were higher in carbon, sulfur, and nitrogen relative to other contamination types. The source of contamination has not been identified, but amine/amide functionalities were detected. It is probable that this same source of contamination account for the low levels of sulfur and nitrogen observed on most LDEF exposed surfaces. XPS, which probes 50 to 100 A in depth, detected the major sample components underneath the contaminant film in every analysis. This probably indicates that the contaminant overlayer is patchy, with significant areas covered by less that 100 A of molecular film. Energy dispersive x-ray spectroscopy (EDS) of LDEF exposed surfaces during secondary electron microscopy (SEM) of the samples confirmed contamination of the surfaces with Si and O. In general, particulates were not observed to develop from the contaminant overlayer on the exposed LDEF material surfaces. However, many SiO2 submicron particles were seen on a masked edge of an Ag/FEP blanket. In some cases such as the carbon fiber/organic matrix composites, interpretation of the contamination data was hindered by the lack of good laboratory controls. Examination of laboratory controls for the carbon fiber/Al alloy composites showed that preflight contamination was the most significant factor for all the contaminants generally detected at less than 1 atom percent, or detected only occasionally (i.e., all but Si, O, and C). Flight control surfaces, including sample backsides not exposed to space radiation or atomic oxygen flux, have accumulated some contamination on flight (compared to laboratory controls), but experimentally, the LDEF exposed surface contamination levels are generally higher for the contaminants Si and O. For most materials analyzed, Si contamination levels were higher on the leading edge surfaces than on the trailing edge surfaces. This was true even for the composite samples where considerable atomic oxygen erosion of the leading edge surfaces was observed by SEM. It is probable that the return flux associated with atmospheric backscatter resulted in enhanced deposition of silicones and other contaminants on the leading edge flight surfaces relative to the trailing edge. Although the Si concentration data suggested greater on-flight deposition of contaminants on the leading edge surfaces, the XPS analyses did not conclusively show different relative total thicknesses of flight deposited contamination for leading and trailing edge surfaces. It is possible that atomic oxygen reactions on the leading edge resulted in greater volatilization of the carbon component of the deposited silicones, effectively 'thinning' the leading edge deposited overlayer. Unlike other materials, exposed polymers such as Kapton and FEP-type Teflon had very low contamination on the leading edge surfaces. SEM evidence showed that undercutting of the contaminant overlayer and damaged polymer layers occurred during atomic oxygen erosion, which would enhance loss of material from the exposed surface.

Hemminger, Carol S.↗