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Shock temperatures of SiO2 and their geophysical implications

High pressure shock state temperatures of SiO2 were measured in specimens of single crystal alpha-quartz and fused quartz. Projectile impact and pyrometry techniques were employed to impart pressures in the 60-140 GPa range. Shock-induced phase transformations were observed near 70 and 50 GPa along the alpha- and fused-quartz Hugoniots. It is suggested that the transformation consists of melting of the shock-synthesized stishovite, with melting delayed by the superheating of the crystalline phase. Details of the stishovite-liquid phase boundaries have been determined, including stishovite melting at 4500 K under 70 GPa, with the melting accompanied by a relative volume change of about 2.7% and a latent heat of fusion of about 2.4 MJ/kg. At 100 GPa, an approximate limit of 3500 K for the melting of SiO2 is indicated for solid mantle mineral assemblages, such as the earth's mantle

Lyzenga, G. A.↗

Behavior of Al2O3 and SiO2 with heating in a Cl2 + CO stream

Differential thermal analysis (DTA) and Thermogravimetric analysis (TGA) were used to study the chlorination of alpha-Al2O3, gamma-Al2O3 and amorphous SiO2 in a Cl + CO stream, for the preparation of AlCl3 and SiCl4. The chlorination starting temperatures were 235 deg for Al2O3 and 680 deg for SiO2. The chlorination of alpha- and gamma-Al2O3 takes place via the formation of AlOCl as an intermediate product, and its subsequent dissociation at 480 to 560 deg, according to 3AlOCl yields AlCl3 + Al2O3. The chlorination activation energies are given for the three oxides.

Shchetinin, L. K.↗

Characteristics of Si3N4-SiO2-Ce2O3 compositions sintered in high-pressure nitrogen

Full-density Si3N4-SiO2-Ce2O3 compositions were prepared by sintering with 2.5 MPa nitrogen pressure at temperatures of 1900 and 2090 C. Room-temperature flexural strengths near 700 MPa for sintered material compared favorably with the strength of hot-pressed material. At 1370 C, where flexural strengths as high as 363 MPa were obtained, it was observed that the coarsest structure was the strongest and the finest structure was the weakest. One of the compositions tested, Si3N4-8.7 wt pct SiO2-8.3 wt pct-Ce2O3, was found to have excellent 200-h oxidation resistance at 700, 1000, and 1370 C, without incidence of 700 to 1000 C phase instability and cracking.

Sanders, W. A.↗

Study of the kinetics and mechanism of the thermal nitridation of SiO2

X-ray photoelectron spectroscopy (XPS) has been used to study the nitridation time and temperature dependence of the nitrogen distribution in thermally nitrided SiO2 films. The XPS data show that the maximum nitrogen concentration near the (SiO(x)N(y)/Si interface is initially at the interface, but moves 20-25 A away from the interface with increasing nitridation time. Computer modeling of the kinetic processes involved is carried out and reveals a mechanism in which diffusing species, initially consisting primarily of nitrogen, react with the substrate, followed by formation of the oxygen-rich oxynitride due to reaction of the diffusing oxygen displaced by the slower nitridation of the SiO2. The data are consistent with this mechanism provided the influence of the interfacial strain on the nitridation and oxidation kinetics is explicitly accounted for.

Vasquez, R. P.↗

Chemical effects in ion mixing of a ternary system (metal-SiO2)

The mixing of Ti, Cr, and Ni thin films with SiO2 by low-temperature (- 196-25 C) irradiation with 290 keV Xe has been investigated. Comparison of the morphology of the intermixed region and the dose dependences of net metal transport into SiO2 reveals that long range motion and phase formation probably occur as separate and sequential processes. Kinetic limitations suppress chemical effects in these systems during the initial transport process. Chemical interactions influence the subsequent phase formation.

Banwell, T.↗

The growth and in situ characterization of chemical vapor deposited SiO2

This paper reports the results of studies of the kinetics of remote (indirect) plasma enhanced low pressure CVD growth of SiO2 on Si and InP and of the in situ characterization of the electrical surface properties of InP during CVD processing. In the latter case photoluminescence was employed as a convenient and sensitive noninvasive method for characterizing surface trap densities. It was determined that, provided certain precautions are taken, the growth of SiO2 occurs in a reproducible and systematic fashion that can be expressed in an analytic form useful for growth rate prediction. Moreover, the in situ photoluminescence studies have yielded information on sample degradation resulting from heating and chemical exposure during the CVD growth.

Iyer, R.↗

Devitrification and delayed crazing of SiO2 on single-crystal silicon and chemically vapor-deposited silicon nitride

The linear growth rate of cristobalite was measured in thin SiO2 films on silicon and chemically vapor-deposited silicon nitride. The presence of trace impurities from alumina furnace tubes greatly increased the crystal growth rate. Under clean conditions, the growth rate was still 1 order-of-magnitude greater than that for internally nucleated crystals in bulk silica. Crystallized films cracked and lifted from the surface after exposure to atmospheric water vapor. The crystallization and subsequent crazing and lifting of protective SiO2 films on silicon nitride should be considered in long-term applications.

Choi, Doo Jin↗

Vacuum ultraviolet thin films. I - Optical constants of BaF2, CaF2, LaF3, MgF2, Al2O3, HfO2, and SiO2 thin films. II - Vacuum ultraviolet all-dielectric narrowband filters

An iteration process matching calculated and measured reflectance and transmittance values in the 120-230 nm VUV region is presently used to ascertain the optical constants of bulk MgF2, as well as films of BaF2, CaF2, LaF3, MgF2, Al2O3, HfO2, and SiO2 deposited on MgF2 substrates. In the second part of this work, a design concept is demonstrated for two filters, employing rapidly changing extinction coefficients, centered at 135 nm for BaF2 and 141 nm for SiO2. These filters are shown to yield excellent narrowband spectral performance in combination with narrowband reflection filters.

Zukic, Muamer↗

Atomic oxygen undercutting of defects on SiO2 protected polyimide solar array blankets

Low Earth Orbital (LEO) atomic oxygen can oxidize SiO2-protected polyimide kapton solar array blanket material which is not totally protected as a result of pinholes or scratches in the SiO2 coatings. The probability of atomic oxygen reaction upon initial impact is low, thus inviting oxidation by secondary impacts. The secondary impacts can produce atomic oxygen undercutting which may lead to coating mechanical failure and ever increasing mass loss rates of kapton. Comparison of undercutting effects in isotropic plasma asher and directed beam tests are reported. These experimental results are compared with computational undercutting profiles based on Monte Carlo methods and their implication on LEO performance of protected polymers.

Banks, Bruce A.↗

Y1Ba2Cu3O(6+delta) growth on thin Y-enhanced SiO2 buffer layers on silicon

SiO2 buffer layers as thin as 2 nm have been developed for use in the growth of Y1Ba2Cu3O(6+delta) thin films on silicon substrates. The SiO2 layers are formed through Y enhancement of silicon oxidation, and are highly stoichiometric. Y1Ba2Cu3O(6+delta) film growth on silicon with thin buffer layers has shown c orientation and Tc0 = 78 K.

Robin, T.↗

SiC Recession Due to SiO2 Scale Volatility Under Combustor Conditions

One of today's most important and challenging technological problems is the development of advanced materials and processes required to design and build a fleet of supersonic High Speed Civil Transport (HSCT) airliners, a follow-up to the Concorde SST. The innovative combustor designs required for HSCT engines will need high-temperature materials with long-term environmental stability. Higher combustor liner temperatures than today's engines and the need for lightweight materials will require the use of advanced ceramic-matrix composites (CMC's) in hot-section components. The HSCT is just one example being used to demonstrate the need for such materials. This thesis evaluates silicon carbide (SiC) as a potential base material for HSCT and other similar applications. Key issues are the environmental durability for the materials of interest. One of the leading combustor design schemes leads to an environment which will contain both oxidizing and reducing gas mixtures. The concern is that these environments may affect the stability of the silica (SiO2) scale on which SiC depends for environmental protection. A unique High Pressure Burner Rig (HPBR) was developed to simulate the combustor conditions of future gas turbine engines, and a series of tests were conducted on commercially available SiC material. These tests are intended as a feasibility study for the use of these materials in applications such as the HSCT. Linear weight loss and surface recession of the SiC is observed as a result of SiO2 volatility for both fuel-lean and fuel-rich gas mixtures. These observations are compared and agree well with thermogravimetric analysis (TGA) experiments. A strong Arrhenius-type temperature dependence exists. In addition, the secondary dependencies of pressure and gas velocity are defined. As a result, a model is developed to enable extrapolation to points outside the experimental space of the burner rig, and in particular, to potential gas turbine engine conditions.

Robinson, Raymond Craig↗

SiC and Si3N4 Recession Due to SiO2 Scale Volatility Under Combustor Conditions

SiC and Si3N4 materials were tested under various turbine engine combustion environments, chosen to represent either conventional fuel-lean or fuel-rich mixtures proposed for high speed aircraft. Representative CVD, sintered, and composite materials were evaluated in both furnace and high pressure burner rig exposure. While protective SiO2 scales form in all cases, evidence is presented to support paralinear growth kinetics, i.e. parabolic growth moderated simultaneously by linear volatilization. The volatility rate is dependent on temperature, moisture content, system pressure, and gas velocity. The burner tests were used to map SiO2 volatility (and SiC recession) over a range of temperature, pressure, and velocity. The functional dependency of material recession (volatility) that emerged followed the form: exp(-QIRT) * P(exp x) * v(exp y). These empirical relations were compared to rates predicted from the thermodynamics of volatile SiO and SiO(sub x)H(sub Y) reaction products and a kinetic model of diffusion through a moving, boundary layer. For typical combustion conditions, recession of 0.2 to 2 micron/h is predicted at 1200- 1400C, far in excess of acceptable long term limits.

Smialek, James L.↗

SiC and Si3N4 Recession Due to SiO2 Scale Volatility Under Combustor Conditions

Silicon carbide (SiC) and Si3N4 materials were tested in various turbine engine combustion environments chosen to represent either conventional fuel-lean or fuel-rich mixtures proposed for high-speed aircraft. Representative chemical vapor-deposited (CVD), sintered, and composite materials were evaluated by furnace and high-pressure burner rig exposures. Although protective SiO2 scales formed in all cases, the evidence presented supports a model based on paralinear growth kinetics (i.e., parabolic growth moderated simultaneously by linear volatilization). The volatility rate is dependent on temperature, moisture content, system pressure, and gas velocity. The burner tests were thus used to map SiO2 volatility (and SiC recession) over a range of temperatures, pressures, and velocities. The functional dependency of material recession (volatility) that emerged followed the form A[exp(-Q / RT)](P(sup x)v(sup y). These empirical relations were compared with rates predicted from the thermodynamics of volatile SiO and SiOxHy reaction products and a kinetic model of diffusion through a moving boundary layer. For typical combustion conditions, recession of 0.2 to 2 micrometers/hr is predicted at 1200 to 1400 C, far in excess of acceptable long-term limits.

Smialek, James L.↗

Fluorescence of Pentavalent Chromium in SiO2 Sol-Gel Glasses

Chromium ions are very attractive to optical spectroscopy and laser physics. It is well known that the first laser in the history is a ruby laser activated with Cr(3+). It was found in early nineties that Cr(4+) was also an interesting lasing ion in the near infrared, and various Cr(4+) lasers have been developed. Very recently, it was reported that Cr(2+) doped in CdSe crystals showed lasing action in the infrared. The above achievement have stimulated an interest in searching for Cr(5+) and investigating its optical properties. Cr(5+) is isoelectronic with Ti(3+) and V(4+), having electron configuration 3d1. Ti(3+) is the active center of commercial cw and femtosecond sapphire lasers, tunable in the range 680-1100 nm. V(4+) doped in YAlO3 and Al2O3 showed broad band emission near 635 nm. Although EPR results of Cr(5+) were reported, the optical properties were less studied. Herren et al. reported an observation of luminescence from Cr doped in SiO2 sol-gel glass. The luminescence spectrum was assigned to pentavalent ions in their first paper, and later it was identified to be the emission from the charge transfer transition of Cr(6+). The first observation of photoluminescence from octahedrally coordinated Cr(5+) in BaCaMg aluminate glasses was reported very recently. In this work, we report luminescence results of Cr doped SiO2 sol-gel glasses. The fluorescence spectra are very different from Herrens' results, and we believe it originates from pentavalent Cr.

Jia, Weiyi↗

Thermodynamics of the Lu2O3 – SiO2 system and comparison to other Rare Earth Silicates

Environmental barrier coatings are necessary to protect SiC based ceramics and composites from water vapor degradation in harsh engine environments. Currently, rare earth (RE) silicates are the most promising systems to protect SiC based ceramics and composites. This protection is largely based on reduced silica activity in these rare earth silicates which results in a lowered reactivity with water vapor. To that end, previous Knudsen effusion mass spectrometry (KEMS) studies have explored RE = Yb, Y silicates to measure the reduced silica activity and subsequent water vapor reactivity. Similarly, this work employs the KEMS technique to measure the SiO(g) vapor pressure in Lu containing RE silicates to calculate the activity of silica within the monosilicate [log(a(SiO2)) = -2351.1*1/T-1.6731] and the disilicate (log(a(SiO2)) = -4884.0*1/T + 2.2208) as a function of temperature. The enthalpies of formation for Lu monosilicate from the oxides and the elements were calculated to be -45±3 kJ/mol at 1550 K and -2831.1±12 kJ/mol at 298 K, respectively. The measured enthalpy of formation and those found in literature are compared to modeled values from density functional theory and those estimated using electronegativity.

Knudesen Effusion Mass Spectrometry↗

Materials Data on SiO2 by Materials Project

SiO2 is Rutile structured and crystallizes in the tetragonal P4_2/mnm space group. The structure is three-dimensional. Si4+ is bonded to six equivalent O2- atoms to form a mixture of corner and edge-sharing SiO6 octahedra. The corner-sharing octahedral tilt angles are 49°. There is four shorter (1.78 Å) and two longer (1.84 Å) Si–O bond length. O2- is bonded in a distorted trigonal planar geometry to three equivalent Si4+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on SiO2 by Materials Project

SiO2 is Fluorite structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Si4+ is bonded in a body-centered cubic geometry to eight equivalent O2- atoms. All Si–O bond lengths are 1.98 Å. O2- is bonded to four equivalent Si4+ atoms to form a mixture of corner and edge-sharing OSi4 tetrahedra.

36 MATERIALS SCIENCE↗

Materials Data on SiO2 by Materials Project

SiO2 is Hydrophilite-like structured and crystallizes in the orthorhombic Pbcn space group. The structure is three-dimensional. Si4+ is bonded to six equivalent O2- atoms to form a mixture of corner and edge-sharing SiO6 octahedra. The corner-sharing octahedral tilt angles are 51°. There is four shorter (1.78 Å) and two longer (1.84 Å) Si–O bond length. O2- is bonded in a distorted trigonal planar geometry to three equivalent Si4+ atoms.

36 MATERIALS SCIENCE↗