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At least 145 records · Page 8

Shock-tube studies of silicon-compound vapors

Test gas mixtures containing SiO, SiO2, Si2, and SiH were produced in a shock tube by processing shock waves through a mixture of SiCl4 + N2O + Ar, SiH4 + Ar, or SiH4 + O2 + Ar. Absorption spectra of the test gases were studied photographically in the reflected shock region using a xenon flash lamp as the light source in the range of wavelengths between 250 and 600 nm. SiO was found to be a dominant species in the vapors produced by the SiCl4 + N2O and SiH4 + O2 mixtures. Spontaneous combustion was observed in the SiH4 + O2 + Ar mixture prior to the shock arrival, and the resulting solid SiO2 particles evaporated behind the shock wave. Spectral absorption characteristics of SiO, SiO2, Si2, and SiH were determined by studying the test gases.

Park, C.↗

Infrared spectroscopy of simulated Martian surface materials

Mineralogy inferred from the Viking X-ray fluorescence spectrometry (XRFS) is compared with mineralogy indicated by spectral data. The comparison is done by taking laboratory spectra of Viking analog minerals. Both XRFS and infrared data are consistent with clays as the dominant SiO2 containing minerals on Mars. The X-ray fluorescence data might also be consistent with the dominance of certain mafic SiO2 igneous minerals, but the spectral data are probably inconsistent with such materials. Sulfates, inferred by XRFS, are consistent with the spectral data. Inferences following Mariner 9 that high-SiO2 minerals were important on Mars may have been biased by the presence of sulfates. Calcium carbonate, in the quantities indirectly suggested by XRFS are inconsistent with the spectral data, but smaller quantities of CaCO3 are consistent, as are large quantities of other carbonates.

Toon, O. B.↗

Reactions of calcium orthosilicate and barium zirconate with oxides and sulfates of various elements

Calcium orthosilicate and barium zirconate were evaluated as the insulation layer of thermal barrier coatings for air cooled gas turbine components. Their reactions with various oxides and sulfates were studied at 1100 C and 1300 C for times ranging up to 400 and 200 hours, respectively. These oxides and sulfates represent potential impurities or additives in gas turbine fuels and in turbine combustion air, as well as elements of potential bond coat alloys. The phase compositions of the reaction products were determined by X-ray diffraction analysis. BaZrO3 and 2CaO-SiO2 both reacted with P2O5, V2O5, Cr2O3, Al2O3, and SiO2. In addition, 2CaO-SiO2 reacted with Na2O, BaO, MgO, and CoO and BaZrO3 reacted with Fe2O3.

Zaplatynsky, I.↗

The role of P2O5 in silicate melts

Phase equilibria data in the systems SiO2-P2O5, P2O5-M(x)O(y), and P2O5-M(x)O(y)-SiO2 are employed in conjunction with chromatographic and spectral data to investigate the role of P2O5 in silicate melts. P2O5 depolymerizes pure SiO2 melts by entering the network as a four-fold coordinated cation, but polymerizes melts in which an additional metal cation other than silicon is present. In this complex system P2O5 acts to increase phase separation by further enrichment of the high charge density cations Ti, Fe, Mg, Mn, Ca, in the ferrobasaltic liquid. The dual behavior of P2O5 is explained in a model which requires complexing of phosphate anions and metal cations in the melt. This interaction destroys Si-O-M-O-Si bonds polymerizing the melt. The higher concentration of Si-O-M-O-Si bond complexes in immiscible ferrobasaltic liquids relative to their conjugate immiscible granite liquids explains the partitioning of P2O5 into the ferrobasaltic liquid.

Ryerson, F. J.↗

Advanced indium antimonide monolithic charge coupled infrared imaging arrays

The continued process development of SiO2 insulators for use in advanced InSb monolithic charge coupled infrared imaging arrays is described. Specific investigations into the use of plasma enhanced chemical vapor deposited (PECVD) SiO2 as a gate insulator for InSb charge coupled devices is discussed, as are investigations of other chemical vapor deposited SiO2 materials.

Koch, T. L.↗

Influence of CO2 on melting of model granulite facies assemblages - A model for the genesis of charnockites

It is shown that partial melting studies at crustal pressures in SiO2-rich portions of the system KAlSiO4-Mg2SiO2-H2O-CO2 can be used in modeling the anatectic origin of charnockites. The univariant reaction phlogopite + sanidine + quartz + vapor = enstatite + liquid yields an SiO2-rich melt (granite analog) at 3 kbar; the vapor composition at the solidus is buffered to high H2O contents by virtue of the coexistence of phlogopite with its breakdown products. With higher pressures (8 and 15 kbar), the fluid phase is buffered to higher CO2 contents and the melt composition becomes enriched in K2O and MgO (charnockite analog). Melting relations are controlled through the expansion of the quartz liquidus field relative to the enstatite and sanidine fields with increasing pressure. It is noted that partial melts generated at the base of the crust in the presence of CO2-rich fluid will be of an alkaline nature and will crystallize enstatite at lower pressures. CO2-saturated melting of similar SiO2-rich bulk compositions (phlogopite-absent) through the reaction enstatite + sanidine + quartz + CO2 - liquid occurs at temperatures above 1000 C to about 15 kbar.

Wendlandt, R. F.↗

Mechanisms of devitrification of grain boundary glassy phases in Si3N4 materials

Changes in the grain boundary (g.b.) phases of Si3N4 are analyzed, the effects of composition and thermal history on devitrification of the g.b. phases are determined, devitrification of the g.b. phases of Si3N are related to mechanical behavior and oxidation sensitivity of the material. The phase relationships that occur within the grain boundaries of Si3N4 containing various densification aids are reviewed. Comparisons of the effects of MgO, Y2O3, CeO2, and Y2O3 + AL2O3 are made in terms of the phase equilibria of the Si3N4 + SiO2 + additive compositional system. Two new equilibrium phase diagrams for the Si3N4-SiO2 and Y2O3 and Si3N4-SiO2-Ce2O3 systems are preented. The effects of Y2O3 vs CeO2 densification aids on the fracture surfaces of Si3N4 are compared. Auger electron spectroscopy shows that both oxides are concentrated within the fracture surface. Scanning electron microscopy shows evidence that Si3N4 with CeO2 formed an intergranular structure of fine grained oxynitride reaction products, as predicted by phase quilibria, whereas the Y2O3 containing sample shows evidence of an intergranular glassy phase.

Hench, L. L.↗

Sputtered coatings for protection of spacecraft polymers

Kapton polyimide oxidizes at significant rates (4.3x10(-24) gram/incident oxygen atom) when exposed in low Earth orbit to the ram atomic oxygen flux. Ion beam sputter deposited thin films of Al2O3 and SiO2 as well as a codeposited mixture of predominantly SiO2 with a small amount of polytetrafluoroethylene were evaluated and found to be effective in protecting Kapton from oxidation in both laboratory plasma ashing tests as well as in space on board shuttle flight STS-8. A protective film of or = 96 percent SiO2 and or = 4 percent polytetrafluoroethylene was found to be very flexible compared to the pure metal oxide coatings and resulted in mass loss rates that were 0.2 percent of that of the unprotected Kapton. The optical properties of Kapton for wavelengths investigated between 0.33 and 2.2 microns were not significantly altered by the presence of the coatings or changed by exposure of the coated Kapton to the low Earth orbital ram environment.

Banks, B. A.↗

The damage equivalence of electrons, protons, alphas and gamma rays in rad-hard MOS devices

This paper reports on a study of damage equivalence in rad-hard MOS devices with 100,000 rads (SiO2) capability. Damage sensitivities for electrons of 1, 2, 3, 5, and 7 MeV, protons of 1, 3, 7, 22, and 40 MeV, 3.4-MeV alphas, and Co-60 gammas were measured and compared. Results indicated that qualitatively the same charge recombination effects occurred in hard oxide devices for doses of 100,000 rads (SiO2) as in soft oxide parts for doses of 1 to 4 krads (SiO2). Consequently, damage equivalency or non-equivalency depended on radiation type and energy. However, recovery effects, both during and after irradiation, controlled relative damage sensitivity and its dependency on total dose, dose rate, supply bias, gate bias, radiation type, and energy. Correction factors can be derived from these data or from similar tests of other hard oxide type, so as to properly evaluate the combined effects of the total space environment.

Stassinopoulos, E. G.↗

Achondrite ALHA77005 - Alteration of chromite and olivine

The olivine crystals of the 77005 achondrite are brown except for colorless shock lamellae, mottled patches, and grains adjacent to pools of impact melt. Sporadic dark alteration patches in brown olivine and Cr-rich spinel gave the following average electron-microprobe analyses: (olivine) P2O5 0.9, SiO2 57.9, TiO2 0, Al2O3 0.7, Cr2O3 0.4, V2O3 0, Fe2O3 (assumed oxidation state) 17.0, MgO 1.6, CaO 0.2, Na2O 0, K2O 1.8, SO3 (assumed oxidation state) 9.2, Cl 0.1, sum 89.8 wt pct; (spinel) P2O5 3.5, SiO2 2.1, TiO2 2.2, Al2O3 2.1, Cr2O3 13.4, V2O3 0.8, Fe2O3 40.7, MgO 0.9, CaO 0.1, Na2O 0, K2O 2.0, SO3 11.1, Cl 0.1, sum 79.0 wt pct. Ion-microprobe analyses revealed H in both. Rare orange patches in brown olivine from another area gave SiO2 33-35, FeO 30-28, MgO 28-32, sum 93 wt pct. Thermal metamorphism under dry oxidizing conditions is discussed as a possible alternative to shock-induced oxidation for generation of the brown olivine (McSween and Stoeffler, 1980). Because alteration patches transgress shock lamellae, and because sulfatic alteration occurs in fusion crusts of Antarctic meteorites (Gibson et al., 1983), alteration of the 77005 achondrite at the Antarctic surface is preferred to a complex series of processes needed for preterrestrial alteration.

Smith, J. V.↗

A kinetic model for the thermal nitridation of SiO2/Si

To explain the observed nitrogen distributions in thermally nitridated SiO2 films, a kinetic model is proposed in which the nitridation process is simulated, using the first-order chemical kinetics and Arrhenius dependence of the diffusion and reaction rates on temperature. The calculations show that initially, as the substrate reacts with diffusing nitrogen, a nitrogen-rich oxynitride forms at the SiO2-Si interface, while at nitridation temperatures above 1000 C, an oxygen-rich oxynitride subsequently forms at the interface, due to reaction of the substrate with an increasingly concentrated oxygen displaced by the slower nitridation of the SiO2. This sequence of events results in a nitrogen distribution in which the peak of the interfacial nitrogen concentration occurs away from the interface. The results are compared with the observed nitrogen distribution. The calculated results have correctly predicted the positions of the interfacial nitrogen peaks at the temperatures of 800, 1000, and 1150 C. To account for the observed width of the interfacial nitrogen distribution, it was found necessary to include in the simulations the effect of interfacial strain.

Vasquez, R. P.↗

Thermodynamics of Si-C-O system

The Si-C-O predominance diagram, in conjunction with a free-energy minimum of the gas phase, has been used to explain several observations in the reactions of SiC and/or carbon with SiO2. In the predominance diagram, the axes are chosen as the primary activity units for carbon and oxygen. The predominance diagram shows only the stable condensed phases SiO2, SiC, carbon, and silicon. It also shows the isobars for SiO(g) and CO(g), which are the primary gas-phase species. Only the thermodynamics of the system is considered. The observations explained include the general adjustment of carbon-rich SiC to a free-energy minimum on the SiC/SiO2 coexistence line and the inability to form free silicon from SiO2 and carbon, except at very high temperatures.

Jacobson, N. S.↗

Evaporation in equilibrium, in vacuum, and in hydrogen gas

Evaporation experiments were conducted for SiO2 in three different conditions: in equilibrium, in vacuum, and in hydrogen gas. Evaporation rate in vacuum is about two orders of magnitude smaller than that in equilibrium, which is consistent with previous works. The rate in hydrogen gas changes depending on hydrogen pressure. The rate at 10 exp -7 bar of hydrogen pressure is as small as that of free evaporation, but at 10 exp -5 bar of hydrogen pressure it is larger than that in equilibrium. In equilibrium and in vacuum, the evaporation rate is limited by decomposition of SiO2 on the crystal surface, but it is limited by a diffusion process for evaporation in hydrogen gas. Therefore, evaporation rate of minerals in the solar nebula can be shown neither by that in equilibrium nor by that in vacuum. The maximum temperature of the solar nebula at the midplane at 2-3 AU where chondrites are believed to have originated is calculated to be as low as 150 K, 1500 K, or in between them. The temperature is, in any case, not high enough for total evaporation of the interstellar materials. Therefore, evaporation of interstellar materials is one of the most important processes for the origin and fractionation of solid materials. The fundamental process of evaporation of minerals has been intensively studied for these several years. Those experiments were carried out either in equilibrium or in vacuum; however, evaporation in the solar nebula is in hydrogen (and much smaller amount of helium) gas. In order to investigate evaporation rate and compositional (including isotopic) fractionation during evaporation, vaporization experiments for various minerals in various conditions are conducted. At first, SiO2 was adopted for a starting material, because thermochemical data and its nature of congruent vaporization are well known. Experiments were carried out in a vacuum furnace system.

Nagahara, Hiroko↗

Plasma-Sprayed Refractory Oxide Coatings on Silicon-Base Ceramics

Silicon-base ceramics are promising candidate materials for high temperature structural applications such as heat exchangers, gas turbines and advanced internal combustion engines. Composites based on these materials are leading candidates for combustor materials for HSCT gas turbine engines. These materials possess a combination of excellent physical and mechanical properties at high temperatures, for example, high strength, high toughness, high thermal shock resistance, high thermal conductivity, light weight and excellent oxidation resistance. However, environmental durability can be significantly reduced in certain conditions such as when molten salts, H2 or water vapor are present. The oxidation resistance of silicon-base materials is provided by SiO2 protective layer. Molten salt reacts with SiO2 and forms a mixture of SiO2 and liquid silicate at temperatures above 800C. Oxygen diffuses more easily through the chemically altered layer, resulting in a catastrophic degradation of the substrate. SiC and Si3N4 are not stable in pure H2 and decompose to silicon and gaseous species such as CH4, SiH, SiH4, N2, and NH3. Water vapor is known to slightly increase the oxidation rate of SiC and Si3N4. Refractory oxides such as alumina, yttria-stabilized zirconia, yttria and mullite (3Al2O3.2SiO2) possess excellent environmental durability in harsh conditions mentioned above. Therefore, refractory oxide coatings on silicon-base ceramics can substantially improve the environmental durability of these materials by acting as a chemical reaction barrier. These oxide coatings can also serve as a thermal barrier. The purpose of this research program has been to develop refractory oxide chemical/thermal barrier coatings on silicon-base ceramics to provide extended temperature range and lifetime to these materials in harsh environments.

Tewari, Surendra↗

Paralinear Oxidation of CVD SiC in Simulated Fuel-Rich Combustion

The oxidation kinetics of CVD SiC were measured by thermogravimetric analysis (TGA) in a 4H2 (central dot) 12H2O (central dot) 10CO (central dot) 7CO2 (central dot) 67N2 gas mixture flowing at 0.44 cm/s at temperatures between 1300 and 1450 C in fused quartz furnace tubes at I atm total pressure. The SiC was oxidized to form solid SiO2. At less than or = 1350 C, the SiO2 was in turn volatilized. Volatilization kinetics were consistent with the thermodynamic predictions based on SiO formation. These two simultaneous reactions resulted in overall paralinear kinetics. A curve fitting technique was used to determine the linear and parabolic rate constants from the paralinear kinetic data. Volatilization of the protective SiO2 scale resulted in accelerated consumption of SiC. Recession rates under conditions more representative of actual combustors were estimated from the furnace data.

Fox, Dennis S.↗

Analysis of Aluminum-Nitride SOI for High-Temperature Electronics

We use numerical simulation to investigate the high-temperature (up to 500K) operation of SOI MOSFETs with Aluminum-Nitride (AIN) buried insulators, rather than the conventional silicon-dioxide (SiO2). Because the thermal conductivity of AIN is about 100 times that of SiO2, AIN SOI should greatly reduce the often severe self-heating problem of conventional SOI, making SOI potentially suitable for high-temperature applications. A detailed electrothermal transport model is used in the simulations, and solved with a PDE solver called PROPHET In this work, we compare the performance of AIN-based SOI with that of SiO2-based SOI and conventional MOSFETs. We find that AIN SOI does indeed remove the self-heating penalty of SOL However, several device design trade-offs remain, which our simulations highlight.

Biegel, Bryan A.↗

Thermodynamics of Silicon-Hydroxide Formation in H2O Containing Atmospheres

The formation of volatile silicon-hydroxide species from SiO2 in water containing atmospheres has been identified as a potentially important mode of degradation of Si-based ceramics. Availability of thermodynamic data for these species is a major problem. This study is part of an ongoing effort to obtain reliable, experimentally determined thermodynamic data for these species. The transpiration method was used to measure the pressure of Si-containing vapor in equilibrium with SiO2 (cristobalite) and Ar + H2O(g) with various mole fractions of water vapor, X(sub H2O), at temperatures ranging from 1000 to 1780 K. Enthalpies and entropies for the reaction, SiO2(s) + 2H2O(g) = Si(OH)4(g), were obtained, at X(sub H2O) = 0.15 and 0.37, from the variation of lnK with 1/T according to the 'second law method'. The following data were obtained: delta(H)deg = 52.9 +/- 3.7 kJ/mole and delta(S)deg = -68.6 +/- 2.5 J/mole K at an average temperature of 1550 K, and delta(H)deg = 52.5+/-2.0 kJ/mole and delta(S)deg= -69.7 +/- 1.5 J/moleK at an average temperature of 1384 K, for X(sub H2O)= 0.15 and 0.37, respectively. These data agree with results from the literature obtained at an average temperature of 1600 K, and strongly suggest Si(OH)4(g) is the dominant vapor species. Contradictory results were obtained with the determination of the dependence of Si-containing vapor pressure on the partial pressure of water vapor at 1187 and 1722 K. These results suggested the Si-containing vapor could be a mixture of Si(OH)4 + SiO(OH)2. Further pressure dependent studies are in progress to resolve these issues.

Copland, Evan↗

Sol-Gel Precursors for Ceramics from Minerals Simulating Soils from the Moon and Mars

Recent NASA mission plans for the human exploration of our Solar System has set new priorities for research and development of technologies necessary to enable a long-term human presence on the Moon and Mars. The recovery and processing of metals and oxides from mineral sources on other planets is under study to enable use of ceramics, glasses and metals by explorer outposts. We report some preliminary results on the production of sol-gel precursors for ceramic products using mineral resources available in Martian or Lunar soil. The presence of SiO2, TiO2, and A12O3 in both Martian (44 wt.% SiO2, 1 wt.% TiO2, 7 wt.% Al2O3) and Lunar (48 wt.% SiO2, 1.5 wt.% TiO2, 16 wt.% Al2O3) soils and the recent developments in chemical processes to solubilize silicates using organic reagents and relatively little energy indicate that such an endeavor is possible. In order to eliminate the risks involved in the use of hydrofluoric acid to dissolve silicates, two distinct chemical routes are investigated to obtain soluble silicon oxide precursors from Lunar and Martian simulant soils. Clear sol-gel precursors have been obtained by dissolution of silica from Lunar simulant soil in basic ethylene glycol (C2H4(OH)2) solutions to form silicon glycolates. Thermogravimetric Analysis and X-ray Photoelectron Spectroscopy were used to characterize the elemental composition and structure of the precursor molecules. Further concentration and hydrolysis of the products was performed to obtain gel materials for evaluation as ceramic precursors. In the second set of experiments, we used the same starting materials to synthesize silicate esters in acidified alcohol mixtures. Preliminary results indicate the presence of silicon alkoxides in the product of distillation.

Sibille, Laurent↗