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At least 37 records · Page 2

Oxidation and Volatilization of Silica-Formers in Water Vapor

At high temperatures SiC and Si3N4 react with water vapor to form a silica scale. Silica scales also react with water vapor to form a volatile Si(OH)4 species. These simultaneous reactions, one forming silica and the other removing silica, are described by paralinear kinetics. A steady state, in which these reactions occur at the same rate, is eventually achieved, After steady state is achieved, the oxide found on the surface is a constant thickness and recession of the underlying material occurs at a linear rate. The steady state oxide thickness, the time to achieve steady state, and the steady state recession rate can all be described in terms of the rate constants for the oxidation and volatilization reactions. In addition, the oxide thickness, the time to achieve steady state, and the recession rate can also be determined from parameters that describe a water vapor-containing environment. Accordingly, maps have been developed to show these steady state conditions as a function of reaction rate constants, pressure, and gas velocity. These maps can be used to predict the behavior of silica formers in water-vapor containing environments such as combustion environments. Finally, these maps are used to explore the limits of the paralinear oxidation model for SiC and Si3N4

Opila, E. J.↗

Isocyanate Cross-Linked Silica: Structurally Strong Aerogels

Molecular-level synergism between the silica nanoparticles of pre-formed monoliths and molecular cross-linkers inverts the relative host-guest roles in glass-polymer composites, leading to new strong low-density materials. Attempts to load gels with variable amounts of polyurethane precursors such as di-ISO and diol end-capped polybutylene adipate followed by heat treatment, washing, and supercritical drying led to opaque materials, somewhat stronger than silica but still quite brittle and much inferior to the materials described above. Direct mixing of a diisocyanate and an alcohol-free sol has been attempted recently by Yim et al. Reportedly, that procedure leads to week-long gelation times and requires an at least equally long aging period. In our attempt to add various amounts of di-ISO in a base-catalyzed sol in PC, we also noticed a week-long gelation time. The resulting aerogels were translucent but no less brittle than native silica. According to more recent studies, if propylene carbonate is replaced with acetone, it leads not only to shorter processing times, but also to much stronger gels that can tolerate loads in excess of 40 kg in the arrangement presented. We attribute that behavior to the lower viscosity of acetone, that allows faster diffusion of the di-ISO solution within the pores before di-ISO has time to react with the surface of silica. Further studies are underway to vary the chemical identity of the diisocyanate, as well as the composition and density of silica.

Leventis, Nicholas↗

Quantification of Residual Stress from Photonic Signatures of Fused Silica

A commercially available grey-field polariscope (GFP) instrument for photoelastic examination is used to assess impact damage inflicted upon the outer-most pane of Space Shuttle windows made from fused silica. A method and apparatus for calibration of the stress-optic coefficient using four-point bending is discussed. The results are validated on known material (acrylic) and are found to agree with literature values to within 6%. The calibration procedure is then applied to fused-silica specimens and the stress-optic coefficient is determined to be 2.43 +/- 0.54 x 10(exp -12)/Pa. Fused silica specimens containing impacts artificially made at NASA's Hypervelocity Impact Technology Facility (HIT-F), to simulate damage typical during space flight, are examined. The damage sites are cored from fused silica window carcasses and examined with the GFP. The calibrated GFP measurements of residual stress patterns surrounding the damage sites are presented. Keywords: Glass, fused silica, photoelasticity, residual stress

Cramer, K. Elliott↗

Process for Preparing Epoxy-Reinforced Silica Aerogels

One-pot reaction process for preparing epoxy-reinforced monolithic silica aerogels comprising the reaction of at least one silicon compound selected from the group consisting of alkoxysilanes, orthosilicates and combination thereof in any ratio with effective amounts of an epoxy monomer and an aminoalkoxy silane to obtain an epoxy monomer-silica sol in solution, subsequently preparing an epoxy-monomer silica gel from said silica sol solution followed by initiating polymerization of the epoxy monomer to obtain the epoxy-reinforced monolithic silica aerogel.

Meador, Mary Ann B↗

Performance of Silica Gel in the Role of Residual Air Drying. Part II.

Removal of carbon dioxide (CO2) is a necessary step in air revitalization and is often accomplished with sorbent materials. Since moisture competes with CO2 in zeolite sorbent materials, it is necessary to remove the water first. This is typically accomplished in two stages: “bulk” removal and “residual” drying. Silica gel is used as the bulk drying material in the Carbon Dioxide Removal Assembly (CDRA) in operation on the ISS (International Space Station). There has been some speculation that silica gel may also be capable of serving as both bulk and residual drying material to reduce system mass and Foreign Object Debris (FOD). Previous research tested silica gel alone as drying material. However, the silica gel volume used was not comparable to the current amount used on the CDRA. Therefore, the tests were repeated with the new silica gel volume. This paper discusses the fabrication and assembly of the modified canister to accommodate the new volume, the testing, and the evaluation of the test results.

Air Revitalization↗

Residual Strength of Hypervelocity Impacted Silica

Windows in the International Space Station are subjected to on-going micrometeoroid and orbital debris damage (MMOD). The reliability of the windows is being ensured by monitoring of damage, life prediction, and measurement of the residual strength of man-made and natural hypervelocity impact damage. The residual strength of man-made craters and MMOD craters harvested from space shuttle windows were used to estimate strength as a function of damage dimensions and thereby derive design allowables for U.S. and Russian fused silicas used in the ISS. US and Russian silica exhibit similar mechanical properties. An effect of impact angle is apparent, with 0o impacts exhibiting the lowest strength for Russian quartz-derived silica. The crater morphology for fused silica consists of a central pit, crush zone, shallow rings and radial cracks dividing petaloids. Morphology of alkaline glass is different from than that of fused silica, with a more distinct pit and pulverized region, and bell and tail-like features below the pit.

Silicia↗

Residual Strength of Hypervelocity Impacted Silica

Windows in the International Space Station (ISS) are subject to ongoing micrometeoroid and orbital debris (MMOD) damage. The reliability of the windows is ensured by monitoring of damage, life prediction, and measurement of the residual strength of man-made and natural hypervelocity impacted window materials. Information on the residual strength of man-made craters and MMOD craters harvested from space shuttle windows was used to estimate strength as a function of damage dimensions and thereby derive design allowables for U.S. and Russian fused silicas used in the ISS. An effect of impact angle is apparent, with 0° impacts exhibiting the lowest strength for Russian quartz-derived silica. The crater morphology for fused silica consists of a central pit, crush zone, shallow rings, and radial cracks dividing shallow, petal-like lateral cracks (petaloids). The morphology of alkaline glass differs from that of fused silica, with a more distinct pit and pulverized region, and bell-shaped and tail-like features below the pit.

International space station,↗

High-purity silica reflecting heat shield development

A high-purity, fused-silica reflecting heat shield for the thermal protection of outer-planet probes was developed. Factors that strongly influence the performance of a silica heat shield were studied. Silica-bonded silica configurations, each prepared by a different technique, were investigated and rated according to its relative merits. Slip-casting was selected as the preferred fabrication method because it produced good reflectivity and good strength, and is relatively easy to scale up for a full-size outer-planet probe. The slips were cast using a variety of different particle sizes: continuous particle-size slips; monodisperse particle-size slips; and blends of monodisperse particle-size slips were studied. In general, smaller particles gave the highest reflectance. The monodisperse slips as well as the blend slips gave a higher reflectance than the continuous particle-size slips. An upgraded and fused natural quartz was used to study the effects of microstructure on reflectance and as the baseline to ascertain the increase in reflectance obtained from using a higher-purity synthetic material.

Congdon, W. M.↗

High-silica /greater than 60%/ lunar glasses in an Apollo 14 soil sample - Evidence for silicic lunar volcanism

The major-element compositions of 93 low-specific-gravity (less than 2.60) high-silica (greater than 60%) glass particles from a sample of lunar fines (14259,20) were determined by electron microprobe analyses. The size, shape, abundance, mineralogy, and major-element composition of more than 60% of the high-silica glasses is consistent with their being fragments of interstitial glass from mare basalts. However, one group of 30 glasses with between 72% and 78% SiO2 and an average of approximately 2.6% FeO can be distinguished from other high-silica glasses both chemically and petrographically. Glass particles with this composition do not contain crystalline inclusions and are fairly homogeneous not only within a single particle but also from particle to particle. The chemistry and petrology of these glasses suggest that they are not fragments of interstitial glass or shock-melted particles from a 'granitic' source rock. Rather, the homogeneity and lack of crystalline inclusions suggest that this group of high-silica glasses was the product of lunar acidic volcanism.

Glass, B. P.↗

Silica activity in lunar lavas

Calculated values of log alpha SiO2 in lunar magmas range from approximately -0.8 to unity in the temperature range of 1100-1300 C. High-titanium mare basalts begin crystallizing at silica activities insufficient for orthopyroxene saturation; in contrast to terrestrial lavas, silica activities rise substantially with crystallization and cause silica saturation in the residuum. Igneous rocks of the highland regions have relatively higher initial silica activities than mare basalts. Thermodynamic calculations indicate that high-titanium mare basalts could be derived from a 90 to 240-km deep source region containing olivine and orthopyroxene in addition to other phases.

Nash, W. P.↗

Procedure to prepare transparent silica gels

This invention relates to the production of silica gels and in particular to a process for the preparation of silica gels which can be used as a crystal growth medium that simulates the convectionless environment of space to produce structurally perfect crystals. Modern utilizations of substances in electronics, such as radio transmitters and high frequency microphones, often require single crystals with controlled purity and structural perfection. The near convectionless environment of silica gel suppresses nucleation, thereby reducing the competitive nature of crystal growth. This competition limits the size and perfection of the crystal; and it is obviously desirable to suppress nucleation until, ideally, only one crystal grows in a predetermined location. A silica gel is not a completely convectionless environment like outer space, but is the closest known environment to that of outer space that can be created on Earth.

Barber, Patrick G.↗

Silazine to silica

Thin film silica and/or methyl silicone were detected on most external surfaces of the retrieved LDEF. Both solar ultraviolet radiation and atomic oxygen can convert silicones to silica. Known sources of silicone in or on the LDEF appear inadequate to explain the ubiquitous presence of the silica and silicone films. Hexamethyldisilazane (HMDS) was used as the Challenger tile waterproofing compound for the Challenger/LDEF deployment mission. HMDS is both volatile and chemically reactive at STP. In addition, HMDS releases NH3 which depolymerizes silicone RTV's. Polyurethanes are also depolymerized. Experiments are reported that indicate much of the silicone and silica contamination of LDEF resulted directly or indirectly from HMDS.

Harvey, Gale A.↗

Fayalite-silica association in unequilibrated ordinary chondrites: Evidence for aqueous alteration on a parent body

We report ten occurrences of high-fayalite (Fa56-99 mol%; four with Fa greater than 82 mol%) olivine in association with silica in type-3 ordinary chondrites. Pyroxene with high Fs contents is much less common; Fs contents do not exceed 66 mol%, and most maxima are less than 50 mol%. In those cases where the amount of fayalite is minor relative to that of silica, the fayalite forms a layer on the silica, and shows textural evidence of formation by reaction of silica with oxidized Fe; the latter seems to have resulted from reaction of metallic Fe-Ni with an oxidant, most likely H2O vapor. The fayalite is generally in contact with pyroxene (and, in one case, olivine) having a much lower Fe/(Fe + Mg) ratios, indicating that lattice diffusion has been minimal. Formation of fayalite from SiO2 explains the low Mg content of this olivine; the Mg was sequestered inside the lattices of mafic minerals and was thus inaccessible. In contrast, the moderately high Mn contents of the fayalite indicate that an appreciable fraction of the Mn in the precursor assemblage was accessible; it was probably sited in the matrix in the form of tiny, poorly crystallized oxide grains produced by nebular condensation at temperatures too low to permit diffusion into forsterite or enstatite. The reaction of SiO2 with FeO produced by oxidation (during metamorphism) of Fe-Ni can also account for fayalitic olivine associated with SiO2 microspherules in the fine-grained matrices of type-3 ordinary chondrites and, because matrix is SiO2 normative, for other occurrences of fayalite in matrix. The presence of Mn in the fayalitic rims on the olivine of carbonaceous chondrites does not require a nebular sign.

Wasson, John T.↗

Coated Fused Silica Fibers for Enhanced Sensitivity Torsion Pendulum

In order to investigate the fundamental thermal noise limit of a torsion pendulum using a fused silica fiber, we systematically measured and modeled the mechanical losses of thin fused silica fibers coated by electrically conductive thin metal films. Our results indicate that it is possible to achieve a thermal noise limit for coated silica lower by a factor between 3 and 9, depending on the silica diameter, compared to the best tungsten fibers available. This will allow a corresponding increase in sensitivity of torsion pendula used for weak force measurements, including the gravitational constant measurement and ground-based force noise testing for the Laser Interferometer Space Antenna (LISA) mission.

Numata, Kenji↗

Structure-Property Relationships in Porous 3-D Nanostructures as a Function of Preparation Conditions: Isocyanate Cross-Linked Silica Aerogels

Sol-gel derived silica aerogels are attractive candidates for many unique thermal, optical, catalytic, and chemical applications because of their low density and high mesoporosity. However, their inherent fragility has restricted use of aerogel monoliths to applications where they are not subject to any load. We have previously reported cross-linking the mesoporous silica structure of aerogels with di-isocyanates, styrenes or epoxies reacting with amine decorated silica surfaces. These approaches have been shown to significantly increase the strength of aerogels with only a small effect on density or porosity. Though density is a prime predictor of properties such as strength and thermal conductivity for aerogels, it is becoming clear from previous studies that varying the silica backbone and size of the polymer cross-link independently can give rise to combinations of properties which cannot be predicted from density alone. Herein, we examine the effects of four processing parameters for producing this type of polymer cross-linked aerogel on properties of the resulting monoliths. We focus on the results of C-13 CP-MAS NMR which gives insight to the size and structure of polymer cross-link present in the monoliths, and relates the size of the cross-links to microstructure, mechanical properties and other characteristics of the materials obtained.

Meador, Mary Ann B.↗

Tailoring Elastic Properties of Silica Aerogels Cross-Linked with Polystyrene

The effect of incorporating an organic linking group, 1,6-bis(trimethoxysilyl)hexane (BTMSH), into the underlying silica structure of a styrene cross-linked silica aerogel is examined. Vinyltrimethoxysilane (VTMS) is used to provide a reactive site on the silica backbone for styrene polymerization. Replacement of up to 88 mol 1 of the silicon from tetramethoxyorthosilicate with silicon derived from BTMSH and VTMS during the making of silica gels improves the elastic behavior in some formulations of the crosslinked aerogels, as evidenced by measurement of the recovered length after compression of samples to 251 strain. This is especially true for some higher density formulations, which recover nearly 100% of their length after compression to 251 strain twice. The compressive modulus of the more elastic monoliths ranged from 0.2 to 3 MPa. Although some of these monoliths had greatly reduced surface areas, changing the solvent used to produce the gels from methanol to ethanol increased the surface area in one instance from 6 to 220 sq m2/g with little affect on the modulus, elastic recovery, porosity, or density.

Nguyen, Baochau N.↗

Structure-Property Relationships in Porous 3-D Nanostructures as a Function of Preparation Conditions: Isocyanate Cross-Linked Silica Aerogels

Sol-gel derived silica aerogels are attractive candidates for many unique thermal, optical, catalytic, and chemical applications because of their low density and high mesoporosity. However, their inherent fragility has restricted use of aerogel monoliths to applications where they are not subject to any load. We have previously reported cross-linking the mesoporous silica structure of aerogels with di-isocyanates, styrenes or epoxies reacting with amine decorated silica surfaces. These approaches have been shown to significantly increase the strength of aerogels with only a small effect on density or porosity. Though density is a prime predictor of properties such as strength and thermal conductivity for aerogels, it is becoming clear from previous studies that varying the silica backbone and size of the polymer cross-link independently can give rise to combinations of properties which cannot be predicted from density alone. Herein, we examine the effects of four processing parameters for producing this type of polymer cross-linked aerogel on properties of the resulting monoliths. We focus on the results of 13C CP-MAS NMR which gives insight to the size and structure of polymer cross-link present in the monoliths, and relates the size of the cross-links to microstructure, mechanical properties and other characteristics of the materials obtained.

Meador, Mary Ann B.↗

Multiscale Computer Simulation of Tensile and Compressive Strain in Polymer- Coated Silica Aerogels

While the low thermal conductivities of silica aerogels have made them of interest to the aerospace community as lightweight thermal insulation, the application of conformal polymer coatings to these gels increases their strength significantly, making them potentially useful as structural materials as well. In this work we perform multiscale computer simulations to investigate the tensile and compressive strain behavior of silica and polymer-coated silica aerogels. Aerogels are made up of clusters of interconnected particles of amorphous silica of less than bulk density. We simulate gel nanostructure using a Diffusion Limited Cluster Aggregation (DLCA) procedure, which produces aggregates that exhibit fractal dimensions similar to those observed in real aerogels. We have previously found that model gels obtained via DLCA exhibited stress-strain curves characteristic of the experimentally observed brittle failure. However, the strain energetics near the expected point of failure were not consistent with such failure. This shortcoming may be due to the fact that the DLCA process produces model gels that are lacking in closed-loop substructures, compared with real gels. Our model gels therefore contain an excess of dangling strands, which tend to unravel under tensile strain, producing non-brittle failure. To address this problem, we have incorporated a modification to the DLCA algorithm that specifically produces closed loops in the model gels. We obtain the strain energetics of interparticle connections via atomistic molecular statics, and abstract the collective energy of the atomic bonds into a Morse potential scaled to describe gel particle interactions. Polymer coatings are similarly described. We apply repeated small uniaxial strains to DLCA clusters, and allow relaxation of the center eighty percent of the cluster between strains. The simulations produce energetics and stress-strain curves for looped and nonlooped clusters, for a variety of densities and interaction parameters.

Good, Brian↗