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At least 325 records · Page 18

Low-Power RIE of SiO2 in CHF3 To Obtain Steep Sidewalls

A reactive-ion etching (RIE) process has been developed to enable the formation of holes with steep sidewalls in a layer of silicon dioxide that covers a silicon substrate. The holes in question are through the thickness of the SiO2 and are used to define silicon substrate areas to be etched or to be built upon through epitaxial deposition of silicon. The sidewalls of these holes are required to be vertical in order to ensure that the sidewalls of the holes to be etched in the substrate or the sidewalls of the epitaxial deposits, respectively, also turn out to be vertical.

Turner, Tasha↗

Electron Beam Induced Luminescence of SiO2 Optical Coatings

Optical coatings of disordered thin film SiO,/SiO, samples undergoing electron beam bombardment exhibited a cathodoluminescence effect. Measurements were made of the absolute illuminance and emission spectra as functions of incident electron energy (0.2 keV to 30 keV). flux (approx. 0.1 nA/sq cm to > 100 nA/sq cm) and power (<50 nW/sq cm to > 3mW/sq cm) for coatings (approx.60 nm to approx.200 nm thick) on reflective metal substrates over a range of sample temperatures (approx.40 K to approx.400 K) and emission wavelengths (approx.260 nm to approx.5000 nm). Illuminance reached a plateau saturation intensity I(sub sat) approx. 10(exp -4)W/sq cm. scaling as [I(sub mc)/(I + I(sub mc)/I(sub sat)] as incident power I(sub mc) approached I(sub sat). Well below I(sub sat), illuminance scaled linearly with incident power for lower-energy non-penetrating radiation that deposited all of its energy in the dielectric film. At higher incident energies (> 1-5 keV) electrons penetrate the dielectric, depositing only a fraction of their energy in the dielectric film, where deposited energy scales as the ratio of film thickness to penetration range. Since electron range exhibits a peak below approx. 1 keV, the illuminance decreased with increasing energy for penetrating radiation. The temperature dependence of the illuminance. in general, increased with decreasing temperature. Changes in apparent color with temperature were also observed. Four bands in the UV/VIS/NIR range from 300 nm to 1000 nm were observed in spectral measurements; no significant luminescence was detected in a range from approx. 1000 nm to approx. 5000 nm. These different bands either increased or decreased in intensity and shifted slightly in energy with decreasing temperature. Our measurements are explained in terms of simple disordered band theory models based on atomic-scale stochastic transport of electrons in highly disordered insulating materials. The theoretical models provide a fundamental basis for understanding the dependence of cathodoluminescence on irradiation time, incident flux and energy. and sample thickness and temperature. The observed luminescence occurs when an incident high energy electron excites a valence band electron into the conduction band. Following the excitation. a complex series of transitions take place between the extended conduction states and the long-lived localized trapped states (or chromophores) associated with structural or compositional defects in the dielectric materials. Thc transport equations and models of thc spatial and energy distribution of the trapped states below the mobility edge, their occupancy, and transitions provide microscopic scale insights into this macroscopic phenomenon. Our observations and theoretical models are also compared with similar previous room temperature studies of similar SiO2 films.

Dennison, J. R.↗

Acid-Sulfate Alteration at Gusev Crater and Across Mars: High-SiO2 Residues and Ferric Sulfate Precipitates

The Mars Exploration Rover Spirit ended its mission in Gusev crater on sol 2210 after it had become stuck in a deposit of fined-grained and sulfate rich soil with dust covered solar panels unfavorably pointed toward the sun. Final analysis of remaining data from Spirit's Moessbauer spectrometer (Fe redox and mineralogy) for sols 1529 through 2071 is now complete. We focus here on chemical (APXS) and MB data for targets having high-SiO2 or high-SO3 and process link the targets through mixing and geochemical modelling to an acid-sulfate system centered at Home Plate, which is considered to be a hydrovolcanic complex.

Morris, R. V.↗

Thermochemistry of CaO-MgO-Al2O3-SiO2 (CMAS) and Advanced Thermal and Environmental Barrier Coating Systems

CaO-MgO-Al2O3-SiO2 (CMAS) oxides are constituents in a broad number of materials and minerals which have recently inferred to discussions in materials science, planetary science, geochemistry and cosmochemistry communities. In materials science, there is increasing interest in the degradation studies of thermal (TBC) and environmental (EBC) barrier coatings of gas turbines by molten CMAS. CMAS minerals usually are carried by the intake air into gas turbines, e.g. in aircraft engines, and their deposits react at high temperatures (1000C) with the coating materials. This causes degradation and accelerated failure of the static and rotating components of the turbine engines. We discuss some preliminary results of the reactions between CMAS and Rare-Earth (RE Y, Yb, Dy, Gd, Nd and Sm) oxide stabilized ZrO2 or HfO2 systems, and the stability of the resulting oxides and silicates. Plasma sprayed hollow tube samples ( 2.2 mm and 26 mm height) were half filled with CMAS powder, wrapped and sealed with platinum foil, and heat treated at 1310 C for 5h. Samples were characterized by differential scanning calorimetry, X-ray diffraction and cross section electron microscopy analysis.

degradation↗

High Temperature Degradation of Advanced Thermal and Environmental Barrier Coatings (TEBCs) by CaO-MgO-Al2O3-SiO2 (CMAS)

There is increasing interest in the degradation studies of thermal and environmental barrier coatings (TEBCs) of gas turbines by molten CaO-MgO-Al2O3-SiO2 (CMAS). CMAS minerals are usually referred as silica-containing sand dust and volcano ash materials that are carried by the intake air into gas turbines, e.g. aircraft engines. The low-melting deposits react at high temperatures (1000C) with the coating materials. This causes degradation and accelerated coating failure of the static and rotating components of the turbine engines. We discuss some preliminary results of the reactions between CMAS and Rare-Earth (RE Y, Yb, Dy, Gd, Nd and Sm) oxide stabilized ZrO2 or HfO2 systems, and the stability of the resulting oxides and silicates. Plasma sprayed hollow tube samples (outer diameter 4.7 mm, wall thickness 0.76 mm and 26 mm height) were half filled with CMAS powder, wrapped and sealed with platinum foil, and heat- treated at 1310 C for 5h. Samples were characterized by differential scanning calorimetry, X-ray diffraction and cross section electron microscopy analysis.

Thermal and environmental barrier coatings↗

Materials Data on MgFe(SiO2)2 by Materials Project

MgSiO2FeOSiO crystallizes in the orthorhombic Pmc2_1 space group. The structure is two-dimensional and consists of one FeOSiO sheet oriented in the (0, 0, 1) direction and one MgSiO2 sheet oriented in the (0, 0, 1) direction. In the FeOSiO sheet, Fe is bonded in a 3-coordinate geometry to three O atoms. There are two shorter (2.03 Å) and one longer (2.08 Å) Fe–O bond lengths. Si is bonded in a distorted trigonal non-coplanar geometry to three O atoms. There is one shorter (1.65 Å) and two longer (1.79 Å) Si–O bond length. There are two inequivalent O sites. In the first O site, O is bonded in a distorted T-shaped geometry to two equivalent Fe and one Si atom. In the second O site, O is bonded in a trigonal planar geometry to one Fe and two equivalent Si atoms. In the MgSiO2 sheet, Mg is bonded in a 3-coordinate geometry to three O atoms. There are two shorter (1.94 Å) and one longer (2.07 Å) Mg–O bond lengths. Si is bonded in a distorted trigonal non-coplanar geometry to three O atoms. There is one shorter (1.65 Å) and two longer (1.78 Å) Si–O bond length. There are two inequivalent O sites. In the first O site, O is bonded in a distorted trigonal planar geometry to two equivalent Mg and one Si atom. In the second O site, O is bonded in a trigonal planar geometry to one Mg and two equivalent Si atoms.

36 MATERIALS SCIENCE↗

Experimental and Computational Studies of the Production of 1,3-Butadiene from 2,3-Butanediol Using SiO2-Supported H3PO4 Derivatives

Silica-supported phosphoric acid and metal phosphate catalyzed 1,3-butadiene (BDE) production from 2,3-butanediol (2,3-BDO) was studied using experimental and computational techniques. The catalyst was initially tested in a continuous flow reactor using commercially available 2,3-BDO, leading to maximum BDE yields of 63C%. Quantum chemical mechanistic studies revealed 1,2-epoxybutane is a kinetically viable and thermodynamically stable intermediate, supported by experimental demonstration that this epoxide can be converted to BDE under standard reaction conditions. Newly proposed E2 and SN2' elementary steps were studied to rationalize the formation of BDE and all detected side-products. Additionally, using quantum mechanics/molecular mechanics (QM/MM) calculations, we modeled silica-supported phosphate catalysts to study the effect of the alkali metal center. Natural population analysis showed that phosphate oxygen atoms are more negatively charged in CsH2PO4/SiO2 than in H3PO4/SiO2. In combination with temperature-programmed desorption experiments using CO2, the results of this study suggest that the improved selectivity achieved when adding the metal center is related to an increase in the basicity of the catalyst.

butadiene↗

Producing cement clinker assemblages in the system: CaO-SiO2-Al2O3-SO3-CaCl2-MgO

Highlights: • Alinite formation conditions are optimised. • Ye'elimite and alinite cannot be simultaneously produced. • Ternesite and chlormayenite are compatible at 1150 °C. • Alite is formed at a reduced temperature of 1300 °C. • Wadalite and chlorellestadite can incorporate chloride in cement clinker assemblages. The cement industry is carbon-intensive, and the valorisation of industrial side-streams/residuals for use as alternative raw materials can enable the cement industry to reduce its carbon footprint as well as promote resource efficiency. Apart from key clinker ingredients such as CaO, Al{sub 2}O{sub 3}, and SiO{sub 2}, industrial residues can also contain MgO, CaCl{sub 2}, and SO{sub 3}. Therefore, this study investigates the formation of cement clinker assemblages in the system CaO-SiO{sub 2}-Al{sub 2}O{sub 3}-SO{sub 3}-CaCl{sub 2}-MgO at temperatures ranging between 1100 and 1300 °C. The production of a clinker composed mainly of alinite and ye'elimite is first attempted; it is found that these phases cannot be simultaneously produced. Ternesite is also not compatible with alinite under the conditions studied. Wadalite is compatible with both ye'elimite and ternesite, while ternesite is also compatible with chlormayenite at 1150 °C. Additionally, the low-temperature formation of alite was also observed with the presence of CaCl{sub 2} in the raw-material mix.

36 MATERIALS SCIENCE↗

Predicting CaO-(MgO)-Al2O3-SiO2 glass reactivity in alkaline environments from force field molecular dynamics simulations

In this investigation, force field-based molecular dynamics (MD) simulations have been employed to generate detailed structural representations for a range of amorphous quaternary CaO-MgO-Al{sub 2}O{sub 3}-SiO{sub 2} (CMAS) and ternary CaO-Al{sub 2}O{sub 3}-SiO{sub 2} (CAS) glasses. Comparison of the simulation results with select experimental X-ray and neutron total scattering and literature data reveals that the MD-generated structures have captured the key structural features of these CMAS and CAS glasses. Based on the MD-generated structural representations, we have developed two structural descriptors, specifically (i) average metal oxide dissociation energy (AMODE) and (ii) average self-diffusion coefficient (ASDC) of all the atoms at melting. Both structural descriptors are seen to more accurately predict the relative glass reactivity than the commonly used degree of depolymerization parameter, especially for the eight synthetic CAS glasses that span a wide compositional range. Hence these descriptors hold great promise for predicting CMAS and CAS glass reactivity in alkaline environments from compositional information.

36 MATERIALS SCIENCE↗