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All sourcesNASA NTRSDOE OSTI
NASA NTRS1992

The Chemistry of Saudi Arabian Sand - A Deposition Problem on Helicopter Turbine Airfoils

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 NaCl 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 5 mm 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 CaSO4.

Smialek, James L.↗
NASA NTRS1990

Molten (Mg0.88Fe0.12)2SiO4 at lower mantle conditions - Melting products and structure of quenched glasses

Infrared spectra of quenched magnesium silicate glasses synthesized by fusing olivine at pressures in excess of 50 GPa and temperatures greater than 2500 K demonstrate that silicon is dominantly present in four-fold coordination with respect to oxygen within these quenched glasses. This low coordination is attributed, by analogy with the structural behavior of glasses compressed at 300 K, to the instability of higher coordinations in glasses of these compositions on decompression. Spectra of glasses formed in a hydrous environment document that water is extensively soluble in melts at these high pressures and temperatures. Also, these results are consistent with the melting of (Mg0.88Fe0.12)2SiO4 compositions to liquids near pyroxene in stoichiometry under these conditions, with iron-rich magnesiowuestite being the liquidus phase.

Williams, Quentin↗
NASA NTRS1979

Chemical reaction between water vapor and stressed glass

The crack velocity in soda-lime silicate glass was determined at room temperature at water-vapor pressures of 10 to 0.04 torr using the double torsion technique. A precracked glass specimen (70 x 16 x 1.6 mm) was placed in a vacuum chamber containing a four-point bending test apparatus. The plotted experimental results show that the crack propagation curve in water agrees fairly well with that of Wiederhorn (1967). Attention is given to the effect of water vapor pressure on crack velocity at K(I) = 550,000 N/m to the 3/2 power, with (Wiederhorn's data) or without N2 present. The plotted results reveal that the present crack velocity is about two orders of magnitude higher than that of Wiederhorn at high water-vapor conditions, but the difference decreases as the water-vapor concentration diminishes or the crack velocity slows down.

Soga, N.↗
NASA NTRS1985

Gamma radiation effects on the dynamic fatigue measurements of glass discs

Circular specimens of low iron soda lime silicate glass were blasted with grit after having a circular notch etched into their centers. After separation into two groups, one group was exposed to gamma radiation. The fracture strengths of all samples were then tested by the biaxial technique, i.e., specimens were balanced on three balls and loaded in the center by a piston. The irradiated samples had received a 140,000 Gy dose from a Co-60 source. An enhanced interaction between the ambient moisture and the grit-blasted central notch was observed in the irradiated samples, which displayed accelerated corrosion.

Ananaba, T. O. J.↗
NASA NTRS1991

Glass formation and crystallization in high-temperature glass-ceramics and Si3N4

The softening of glassy grain boundaries in ceramic matrix composites and Si3N4 at high temperatures reduces mechanical strength and the upper-use temperature. By crystallizing this glass to a more refractory crystalline phase, a material which performs at higher temperatures may result. Three systems were examined: a cordierite composition with ZrO2 as a nucleating agent; celsian compositions; and yttrium silicate glasses both in bulk and intergranular in Si3N4. For the cordierite compositions, a series of metastable phases was obtained. The crystallization of these compositions was summarized in terms of metastable ternary isothermal sections. Zircon formed at the expense of ZrO2 and spinel. In SiC composites, the transformations were slower. In celsian, two polymorphs were crystallized. One phase, hexacelsian, which always crystallized, even when metastable, had an undesirable volume change. The other phase, celsian, was very difficult to crystallize. In yttrium silicate bulk glasses, similar in composition to the intergranular glass in Si3N4, a number of polymorphs of Y2Si2O7 were crystallized. The conditions under which these polymorphs formed are compared with crystallization in Si3N4.

Drummond, Charles H., III↗
NASA NTRS1983

Spectral chemistry of green glass-bearing 15426 regolith

The detection of appreciable concentrations of ferric iron in a synthetic green glass equilibrated at an oxygen fugacity of 10 to the -11th atm prompted a Moessbauer spectral study of pristine emerald-green glass spherules carefully handpicked from regolith sample 15426. No Fe(3+) ions were detected in this lunar sample or in a synthetic green glass simulant equilibrated at fO2 = 10 to the -14th atm, suggesting that the green glass clods in rock 15426 formed under conditions of correspondingly low oxygen fugacities. The Moessbauer spectra indicated the presence of olivine crystallites in the lunar emerald green glass spherules. Measurements of homogeneous and partially devitrified synthetic silicate glasses revealed that significant changes of coordination environment about Fe(2+) ions in the glass structure occur during crystallization of olivine crystals from the melt.

Burns, R. G.↗
NASA NTRS1990

Low temperature synthesis of CaO-SiO2 glasses having stable liquid-liquid immiscibility by sol-gel process

Calcium silicate glass compositions lying within the liquid-liquid immiscibility dome of the phase diagram, which could not have been prepared by the conventional melting method, were synthesized by the sol-gel process. Hydrolysis and polycondensation of tetraethyl orthosilicate (TEOS) solutions containing up to 20 mol percent calcium nitrate resulted in the formation of clear and transparent gels. The gel formation time decreased with increase in water:TEOS mole ratio, calcium content, and the reaction temperature. Smaller values of gel times in the presence of calcium nitrate are probably caused by lowering of the ionic charge on the sol particles by the salt present. The gelation activation energy, E(sub gel), was evaluated from temperature dependence of the gel time. Presence of Ca(2+) ions or the water:TEOS mole ratio did not have an appreciable effect on the value of E(sub gel). Presence of glycerol in the solution helped in the formation of crack-free monolithic gel specimens. Chemical and structural changes occurring in the gels, as a function of the heat treatments, have been monitored using DTA, TGA, IR-spectroscopy, x ray diffraction, surface area and pore size distribution measurements.

Bansal, Narottam P.↗
NASA NTRS1992

Low temperature synthesis of CaO-SiO2 glasses having stable liquid-liquid immiscibility by the sol-gel process

Calcium silicate glass compositions lying within the liquid-liquid immiscibility dome of the phase diagram, which could not have been prepared by the conventional melting method, were synthesized by the sol-gel process. Hydrolysis and polycondensation of tetraethyl orthosilicate (TEOS) solutions containing up to 20 mol percent calcium nitrate resulted in the formation of clear and transparent gels. The gel formation time decreased with increase in water: TEOS mole ratio, calcium content, and the reaction temperature. Smaller values of gel times in the presence of calcium nitrate are probably caused by lowering of the ionic charge on the sol particles by the salt present. The gelation activation energy, E(sub gel), was evaluated from temperature dependence of the gel time. Presence of Ca(2+) ions or the water:TEOS mole ratio did not have an appreciable effect on the value of E(sub gel). Presence of glycerol in the solution helped in the formation of crack-free monolithic gel specimens. Chemical and structural changes occurring in the gels, as a function of the heat treatments, have been monitored using DTA, TGA, IR-spectroscopy, X-ray diffraction, surface area and pore size distribution measurements.

Bansal, N. P.↗
NASA NTRS1989

Steps toward interstellar silicate dust mineralogy

One of the most certain facts on interstellar dust is that it contains grains with silicon oxygen tetrahedra (SOT), the internal vibrations of which cause the well known silicate bands at 10 and 18 microns. The broad and almost structureless appearance of them demonstrates lack of translation symmetry in these solids that must be considered amorphous or glassy silicates. There is no direct information on the cations in these interstellar silicates and on the number of bridging oxygens per tetrahedron (NBO). Comparing experimental results gained on amorphous silicates, e.g., silicate glasses, of cosmically most abundant metals (Mg, Fe, Ca, Al) with the observations is the only way to investigate interstellar silicate dust mineralogy (cf, Dorschner and Henning, 1986). At Jena University Observatory IR spectra of submicrometer-sized grains of pyroxene glasses (SSG) were studied. Pyroxenes are common minerals in asteroids, meteorites, interplanetary, and supposedly also cometary dust particles. Pyroxenes consist of linearly connected SOT (NBO=2). In the vitreous state reached by quenching melted minerals, the SOT remain nearly undistorted (Si-O bond length unchanged); the Si-O-Si angles at the bridging oxygens of pyroxenes, however, scatter statistically. Therefore, the original cation oxygen symmetry of the crystal (octahedral and hexahedral coordination by O) is completely lost. The blended bands at 10 and 18 microns lose their diagnostic differences and become broad and structureless. This illustrates best the basic problem of interstellar silicate mineral diagnostics. Optical data of glasses of enstatite, bronzite, hypersthene, diopside, salite, and hedenbergite have been derived. Results of enstatite (E), bronzite (B), and hypersthene (H) show very good agreement with the observed silicate features in the IR spectra of evolutionarily young objects that show P-type silicate signature according to the classification by Gurtler and Henning (1986). Compositional parameters and main characteristics of experimental SSG spectra in IR for the glasses E, B, and H are shown in tabular form. Results fit excellently the relations derived by Koike and Hasegawa (1987) and suggest that the band ratio of the astronomical silicate by Draine and Lee (1984) is too low.

Dorschner, J.↗
NASA NTRS1986

Channel waveguides in glass via silver-sodium field-assisted ion exchange

Multimode channel waveguides have been formed in sodium aluminosilicate glass by field-assisted diffusion of Ag(+) ions from vacuum-evaporated Ag films. The two-dimensional refractive index profiles of the waveguides were controlled by varying the diffusion time, the diffusion temperature, and the electric field strength. Estimates of the diffusion rate through a strip aperture were obtained, assuming the electric field was strong 120-240 V/mm. The maximum change in refractive index in the sodium aluminosilicate glasses was estimated near 65 percent of the change in soda-lime silicate glass. The physical properties of the glasses are given in a table.

Forrest, K.↗
NASA NTRS1989

Analysis of Nd3+:glass, solar-pumped, high-powr laser systems

The operating characteristics of Nd(3+):glass lasers energized by a solar concentrator were analyzed for the hosts YAG, silicate glass, and phosphate glass. The modeling is based on the slab zigzag laser geometry and assumes that chemical hardening methods for glass are successful in increasing glass hardness by a factor of 4. On this basis, it was found that a realistic 1-MW solar-pumped laser might be constructed from phosphate glass 4 sq m in area and 2 mm thick. If YAG were the host medium, a 1-MW solar-pumped laser need only be 0.5 sq m in area and 0.5 cm thick, which is already possible. In addition, Nd(3+) doped glass fibers were found to be excellent solar-pumped laser candidates. The small diameter of fibers eliminates thermal stress problems, and if their diameter is kept small (10 microns), they propagate a Gaussian single mode which can be expanded and transmitted long distances in space. Fiber lasers could then be used for communications in space or could be bundled and the individual beams summed or phase-matched for high-power operation.

Zapata, L. E.↗
NASA NTRS2016

Cooling Rates of Lunar Volcanic Glass Beads

It is widely accepted that the Apollo 15 green and Apollo 17 orange glass beads are of volcanic origin. The diffusion profiles of volatiles in these glass beads are believed to be due to degassing during eruption (Saal et al., 2008). The degree of degassing depends on the initial temperature and cooling rate. Therefore, the estimations of volatiles in parental magmas of lunar pyroclastic deposits depend on melt cooling rates. Furthermore, lunar glass beads may have cooled in volcanic environments on the moon. Therefore, the cooling rates may be used to assess the atmospheric condition in an early moon, when volcanic activities were common. The cooling rates of glasses can be inferred from direct heat capacity measurements on the glasses themselves (Wilding et al., 1995, 1996a,b). This method does not require knowledge of glass cooling environments and has been applied to calculate the cooling rates of natural silicate glasses formed in different terrestrial environments. We have carried out heat capacity measurements on hand-picked lunar glass beads using a Netzsch DSC 404C Pegasus differential scanning calorimeter at University of Munich. Our preliminary results suggest that the cooling rate of Apollo 17 orange glass beads may be ~12 K/min, based on the correlation between temperature of the heat capacity curve peak in the glass transition range and glass cooling rate. The results imply that the parental magmas of lunar pyroclastic deposits may have contained more water initially than the early estimations (Saal et al., 2008), which used higher cooling rates, 60-180 K/min in the modeling. Furthermore, lunar volcanic glass beads could have been cooled in a hot gaseous medium released from volcanic eruptions, not during free flight. Therefore, our results may shed light on atmospheric condition in an early moon.

Hui, Hejiu↗
NASA NTRS1994

Origin of tektites

The origin of tektites has been obscure because of the following dilemma. The application of physical principles to the data available on tektites points strongly to origin from one or more lunar volcanoes; but few glasses of tektite composition have hitherto been reported from the lunar samples. Instead, the lunar silicic glasses consist chiefly of a material very rich in K2O and poor in MgO. The ratio of K2O/MgO is higher in these glasses than in any tektites reported. The solution of the dilemma seems to come from the study of some recently discovered terrestrial deposits of tektite glass with high values of K2O/MgO at the Cretaceous Tertiary boundary. These glasses are found to be very vulnerable to crystallization into sandine or to alteration to smectite. These end products are known and are more abundant than any terrestrial deposits of tektite glass. It seems possible that, in fact, the moon produces tektite glass, mostly of the high K2O-low MgO type; but on Earth these deposits are destroyed. The much less abundant deposits with lower K and higher Mg are observed because they survive. Other objections to the lunar origin hypothesis appear to be answerable.

O'Keefe, John A.↗
NASA NTRS1984

Glass on the surfaces of Io and Amalthea

The results of laboratory tests of the spectral reflectances of sulfur and sulfur-silicate glasses are compared with Voyager UV and IR spectral data of Io and Amalthea. Sulfur glasses, without the S8 allotrope, are formed when molten sulfur is quickly quenched to temperatures below 150 K. The trials involved heating sulfur to temperatures from 430-700 K, then quenching and recording the color that resulted. It was observed that the insulating properties of sulfur are so high that the glasses would probably only form in volcanic plumes, yielding particles in the 10-100 micron diameter range. Fumarole droplets could impact cold ground and leave 1 mm glass particles. Basalt-sulfur specimens heated to 1400 K to melt the basalt, then cooled, produced glasses of a color which matches the color of darker areas detected on Io. The surface colors of Amalthea, although definitely contaminated with particles from Io mass loss, exhibited only a few color matches with the basalt-sulfur glasses. More refined spectra of Amalthea are required if the surface constituents are to be identified.

Gradie, J.↗
NASA NTRS2015

Compositional and Microstructural Evolution of Olivine During Pulsed Laser Irradiation: Insights Based on a FIB/Field-Emission TEM Study

Introduction: The use of pulsed laser irradiation to simulate the short duration, high-energy conditions characteristic of micrometeorite impacts is now an established approach in experimental space weathering studies. The laser generates both melt and vapor deposits that contain nanophase metallic Fe (npFe(sup 0)) grains with size distributions and optical properties similar to those in natural impact-generated melt and vapor deposits. There remains uncertainty, however, about how well lasers simulate the mechanical work and internal (thermal) energy partitioning that occurs in actual impacts. We are currently engaged in making a direct comparison between the products of laser irradiation and experimental/natural hypervelocity impacts. An initial step reported here is to use analytical TEM is to attain a better understanding of how the microstructure and composition of laser deposits evolve over multiple cycles of pulsed laser irradiation. Experimental Methods: We irradiated pressed-powder pellets of San Carlos olivine (Fo(sub 90)) with up to 99 rastered pulses of a GAM ArF excimer laser. The irradiated surface of the sample were characterized by SEM imaging and areas were selected for FIB cross sectioning for TEM study using an FEI Quanta dual-beam electron/focused ion beam instrument. FIB sections were characterized using a JEOL2500SE analytical field-emission scanning transmission electron microscope (FE-STEM) optimized for quantitative element mapping at less than 10 nm spatial resolutions. Results: In the SEM the 99 pulse pressed pellet sample shows a complex, inhomogeneous, distribution of laser-generated material, largely concentrated in narrow gaps and larger depressions between grains. Local concentrations of npFe0 spherules 0.1 to 1 micrometers in size are visible within these deposits in SEM back-scatter images. Fig. 1 shows bright-field STEM images of a FIB cross-section of a one of these deposits that continuously covers the top and sloping side of an olivine grain. The deposit has 3 microstructurally distinct sub-layers composed of silicate glass with varying modal fractions and size distributions of npFe( sup 0) spherules, along with nanocrystalline silicate material. A relatively thin (50-300 nm) topmost surface layer has a high-concentration of npFe0 spherules 5-20 nm in size. Element mapping shows the layer to be enriched in Fe by a factor of 2.5 relative to the olivine substrate, with Mg and Si depleted by 20% and 10% respectively. This is compositionally complementary to the underlying, middle layer of the deposit that is depleted in Fe, enriched in Mg and has a much lower npFe0 concentration. A third layer of nanocrystalline olivine occurs at the substrate interface. Discussion: The FE-STEM results suggest the topmost layer is a vapor deposit, underlain by a thicker microstructurally complex melt-generated layer. The compositional relations suggest the melt layer was partially vaporized, preferentially losing more volatile elements (e.g., Fe). The vaporized material re-condensed to form the thin, npFe(sup 0)-rich surface deposit during or immediately after the scan cycle. Nanocrystalline olivine that grew within the melt layer as it formed and cooled is similar in volume and microstructure to what we have observed in the impact melt lining of a micrometeorite impact crater in olivine. This suggest the time-temperature relations attained in the laser sample may not be too different from a micrometeorite impact. Our TEM observations, however, do not show evidence for the same level of mechanical dam-age (e.g., fracturing) seen around the natural micrometeorite crater.

Christoffersen, R.↗
NASA NTRS1973

Research Investigation on Dense Scintillation Glass for Use in Total Absorption Nuclear Cascade Detectors

Three approaches to the development of a high density scintillation glass were investigated: They include the increase of density of glass systems containing cerium - the only systems which were known to show scintillation, the testing of a novel silicate glass system containing significant concentrations of silver produced by ion exchange and never tested previously, and the hot pressing of a diphasic compact of low density scintillation glass with high density passive glass. In first two cases, while ultraviolet excited fluorescence was maintained in the glasses showing high density, scintillation response to high energy particles was not retained in the case of the cerium containing glasses or developed in the case of the silver containing glasses. In the case of the compacts, the extremely long path length caused by the multiple internal reflections which occur in such a body resulted in attenuation even with glasses of high specific transmission. It is not clear why the scintillation efficiency is not maintained in the higher density cerium containing glasses.

Hensler, J. R.↗
NASA NTRS1978

Alteration of glass as a possible source of clay minerals on Mars

Thermodynamic calculations show that, under present Martian surface conditions, favorable gas-solid weathering products of feldspar glasses should include beidellites (clays of the montmorillonite series) + carbonates + quartz. The gas-solid weathering of mafic silicate glass ( of volcanic or impact origin) may similarly favor the production of metastable Fe-rich montmorillonite clays. Simple mass-balance calculations suggest that gas-solid weathering of Martian proto-regolith containing 10% glass could conceivably produce a global blanket of clays at a rate of at least 0.4 cm/b.y. The production rate should be expected to increase significantly with the glass content and rate of reworking of the proto-regolith and with the availability of water. Complete extraction of altered glass from a lunar-like proto-regolith might yield a global Martian clay blanket about 10-100 cm in thickness.

Gooding, J. L.↗