Effect of Carbon and Boron on the High-Temperature Oxidation of Silicon Carbide

Silicon carbide has good oxidation resistance, due to the formation of a protective silica layer. Although amorphous silica is an excellent oxygen barrier, it is very sensitive to impurity elements, which affect its viscosity, oxygen diffusivity, and crystallization kinetics. This paper compares the oxidation rates of CVD SiC, sintered α-SiC, and CVD SiC- coated graphite in 1 atm oxygen at 1500^deg;C to determine the effects of small additions of boron and carbon. The formation of bubbles in the silica scale formed on sintered α-SiC in oxygen between 1230° and 1550^deg;C is also discussed.     

Contribution to the Study of Moisture Expansion in Ceramic Materials

Measurements were made of the expansions produced by autoclaving coprecipitated and mixed gels of silica and alumina fired over the temperature range 850° to 1200°C. The effect of adding soda to gels of kaolinite composition was investigated and the compositions of the phases were determined. The results show that amorphous silica has a limited influence and must be modified by alumina or by soda and alumina to produce expansions comparable with those of ceramic bodies. The active material is an amorphous alkali aluminosilicate, to be distinguished from permutites and glass. Formation of glass and crystalline compounds reduces moisture expansion. At low firing temperatures (below 950° C.) the hydration of γyAl₂O₃ to boehmite produces high moisture expansions, but γ-Al₂O₃ modified by silica (silicon spinel) has only a limited influence. Some observations are made on the nature of cristobalite developed during the firing of pure amorphous silica and amorphous silica into which additives were introduced.     

Oxidation Behavior of Boron-Modified Mo5Si3 at 800°–1300°C

Mo₅Si₃ shows promise as a high-temperature creep-resistant material. The high-temperature oxidation resistance of Mo₅Si₃ has been found to be poor, however, limiting its use in oxidizing atmospheres. Undoped Mo₅Si₃ exhibits pest oxidation at 800°C. Mass loss occurs in the temperature range 900°–1200°C due to volatilization of molybdenum oxide, indicating that the silica scale that forms does not provide a passivating layer. The addition of boron results in protective scale formation and parabolic oxidation kinetics in the temperature range of 1050°–1300°C. The oxidation rate of Mo₅Si₃ was decreased by 5 orders of magnitude at 1200°C by doping with less than 2 wt% boron. Boron doping eliminates catastrophic pest oxidation at 800°C. The mechanism for improved oxidation resistance of borondoped Mo₅Si₃ is viscous sintering of the scale to close pores that form during the initial transient oxidation period, due to volatilization of molybdenum oxide.     

Kinetic Studies of Transitions from Amorphous Silica and Quartz to Coesite

The process of formation of coesite was investigated kinetically at 550° to 900°C under 23 to 55 kbars pressure using amorphous silica and quartz as starting materials. When amorphous silica transformed to coesite, strained quartz was observed as an intermediate phase. The rate process was concluded to be consecutive through quartz. When quartz transformed to coesite, a similar strained quartz was recognized as an intermediate stage from the broadness of the diffraction lines of the quartz phase. In the transition from amorphous silica, the formation rate of coesite increases with increasing pressure up to 40 kbars at 550°C but then decreases under pressures as high as 55 kbars. At 900°C, the formation of coesite from quartz was faster than that from amorphous silica under 23 and 31 kbars but slower under 40 kbars. These results are explained by assuming that the rate constant for each step depends on temperature and pressure.     

Calculation of Cooling Rate and Induced Stresses in Drawing of Optical Fibers

The rate of cooling of fused-silica fibers and the generation of stress in clad fibers of fused silica and 96%-silica glass (∼125 μm OD) pulled at 1750°C were studied. Experimental cooling rates reported by previous workers were fitted using low- and high-temperature heat-transfer coefficients derived from their data. The birefringence which developed in clad fibers consisting of silica and 96%-silica glass was measured and found to change in sign as a function of the magnitude of the pulling stress. A model involving differences in viscosity (mechanical stress) as well as differences in expansion coefficient (thermal stress) is proposed to account for this behavior.     

Wettability of Silica Substrates by Silver–Copper Based Brazing Alloys inVacuo

The sessile drop method has been used to determine the time dependence of the contact angle at 850°C in vacuo for Ag–28 wt% Cu, Ag–35 wt% Cu–1.5 wt% Ti, and Ag–27 wt% Cu–12 wt% In–2 wt% Ti on vitreous and devitrified fused quartz substrates. Nonwetting behavior (θ > 90°) was observed for Ag–28 wt% Cu on both substrates with no evident effect of time at temperature. The silica substrate structure, whether crystalline or amorphous, as well as its surface condition, whether smooth or rough, made no significant difference. In contrast, with Ag–35 wt% Cu–1.5 wt% Ti and Ag–27 wt% Cu–12 wt% In–2 wt% Ti the contact angle continuously decreased with time for both silica substrates, and the structure and surface condition of the substrates had a negligible effect in the case of Ag–27 wt% Cu–12 wt% In–2 wt% Ti, which produced essentially the same contact angles on both silica substrates at a given time of hold at 850°C. The contact angles produced by Ag–35 wt% Cu–1.5 wt% Ti on devitrified fused quartz were consistently higher than those produced on the vitreous substrates, with increasing holding time at 850°C. This is attributable to the presence of extensive cracks in the α-cristobalite layer at the surface of the devitrified substrates, which obstruct wetting and spreading. These results, when correlated with the wettability of preoxidized silicon carbide by the same alloys reported in previous work, could account for the adverse effect on wetting of the high-temperature silica films formed on the surface of the SiC in that work.     

Nitridation of Amorphous Silica with Ammonia

The reaction between amorphous silica and ammonia in the temperature range 200° to 1230°C has been investigated. The reaction process was monitored with respect to the nitrogen content of the reaction product, the specific surface area of the amorphous nitrided silica, and the decomposition of ammonia. A surface reaction was observed at temperatures between 300° and 500°C, but in agreement with other studies bulk reaction only occurred above 800°C, reaching its maximum rate at about 1000°C. It is suggested that the decomposition of ammonia, which also becomes important above 800°C, is essential for the bulk nitridation reaction. At temperatures above 1050°C the nitridation yield decreases, until gas-phase reaction between SiO( g ) and N₂ or NH₃ becomes dominant at 1230°C, leading to the formation of α-Si₃N₄.     

Fabrication of Mullite and Mullite-Matrix Composites by Transient Viscous Sintering of Composite Powders

Mullite was fabricated by a process referred to as transient viscous sintering (TVS). Composite particles which consisted of inner cores of α-alumina and outer coatings of amorphous silica were used. Powder compacts prepared with these particles were viscously sintered to almost full density at relatively low temperatures (∼1300°C). Compacts were subsequently converted to dense, fine-grained mullite at higher temperatures (∼1500°C) by reaction between the alumina and silica. The TVS process was also used to fabricate mullite/zirconia/alumina, mullite/silicon carbide particle, and mullite/silicon carbide whisker composites. Densification was enhanced compared with other recent studies of sintering of mullite-based composites. This was attributed to three factors: viscous flow of the amorphous silica coating on the particles, avoidance of mullite formation until higher temperatures, and increased threshold concentration for the development of percolation networks.     

Differential Thermal Calorimetric Determination of the Thermodynamic Properties of Kaolinite

Four samples of kaolinite were investigated to determine the exothermic reaction enthalpy by differential thermal calorimetry. The measured 9 kcal/mol for the 980°C exothermic reaction enthalpy corresponds to the calculated heat of crystallization of silica at this temperature. Literature evidence discounts the crystallization of the other participating phases, mullite and silicon spinel. An NaOH extraction technique was used to remove the amorphous silica from a kaolinite fired at 850°C; this extraction removed the 980°C exotherm. It is tentatively suggested, therefore, that most of the heat release at 980°C on firing kaolinite accompanies the reaction SiO₂(amorphous) → SiO₂(β-quartz).     

Influence of Alumina Reaction Tube Impurities on the Oxidation of Chemically-Vapor-Deposited Silicon Carbide

Pure coupons of chemically vapor deposited (CVD) SiC were oxidized for 100 h in dry flowing oxygen at 1300°C. The oxidation kinetics were monitored using thermogra-vimetry (TGA). The experiments were first performed using high-purity alumina reaction tubes. The experiments were then repeated using fused quartz reaction tubes. Differences in oxidation kinetics, scale composition, and scale morphology were observed. These differences were attributed to impurities in the alumina tubes. Investigators interested in high-temperature oxidation of silica formers should be aware that high-purity alumina can have significant effects on experimental results.     

The Relation of Viscosity, Nuclei Formation, and Crystal Growth in Titania-Opacified Enamel

This investigation shows that there is a relationship between viscosity, number of nuclei, and crystal growth during the firing of titania-opacified enamels. This agrees with a similar relationship which Tammann found in his experiments with organic glasses. The history of the development of the size, shape, and relative number of particles per unit area of titanium dioxide crystals was traced from 650° to 1300°C. As the temperature increased from 700° to 1100°C., the color of the specimens viewed under reflected light changed from light blue to white and then to cream-white. The methods used in this investigation were the measurement of viscosity, X-ray analysis, differential thermal analysis, and the study by light microscopy and electron microscopy of very thin heat-treated films which had been produced by blowing bubbles from high-temperature melts.     

Oxidation of Polymer-Derived SiAlCN Ceramics

The oxidation behavior of polymer-derived amorphous SiAlCNs was studied in the temperature range of 900°–1200°C. The results revealed that while at 900°C the oxidation of the SiAlCNs follows typical parabolic kinetics, at higher temperatures the oxidation rates of the materials decrease with annealing time. Long-term oxidation rate of the SiAlCNs is much lower than the lowest values reported for chemical vapor deposition of SiC and Si₃N₄. Structures of the oxide scales were studied using solid-state nuclear magnetic resonance. We proposed that oxide scales formed for the SiAlCNs possess a unique network structure of the oxide scale in which aluminum atoms block the path of oxygen diffusion, thus lowering the oxidation rates. Such a unique structure was likely formed gradually with annealing time, leading to a continuous decrease in oxidation rate.     

Oxidation Behavior of Hot-Pressed Si3N4

The high-temperature chemical stability of hot-pressed Si₃N₄ was studied between 600° and 1450°C. Reactions were followed by X-ray diffraction and scanning electron microscopy. In air, this material begins to oxidize at 700° to 750°C; a distinct amorphous siO₂ surface layer results after 24 h at 750°C-Concomitant formation of cristobalite occurs, depending on exposure time, and is enhanced as temperature is Increased. Magnesium and calcium magnesium silicates form above 1000°C. The data suggest that impurities, e.g. Mg, Ca, and Fe, greatly lower the oxidation resistance of Si₃N₄ in air.     

Effect of Thermal Exposures on the Strengths of Nextel™ 550 and 720 Filaments

The effects of thermal exposure on the strengths of Nextel™ 550 and 720 tows, bare and coated with carbon, were determined by room-temperature tensile testing of single filaments extracted from tows that had been exposed to different thermal environments (i.e., air or vacuum) at temperatures from 550° to 1400°C. The results help define the allowable composite processing conditions when using these tows. A 28% drop in the strength of Nextel 550 filaments occurred after a thermal exposure at 1100°C for 2 h in air. After an exposure of 1300°C/2 h/air, a strength degradation of ∼47% resulted. Filaments exposed above 1100°C under vacuum showed more severe strength degradation than filaments exposed in air. The observed strength degradation may stem from a combination of phase transformations of the alumina, the onset of mullite crystallization, and/or exaggerated mullite grain growth. Strength after heat treatment under vacuum at 1050° and 1150°C did not deteriorate as rapidly as after heat treatment under vacuum between 950° and 1050°C or between 1150° and 1250°C. This may be a result of the competition between healing of flaws by the amorphous silica and its evaporation (leading to an increase in its viscosity or loss) and/or densification of the filaments. Nextel 720 filaments exhibited about 9% strength loss after an exposure at 1100°C/2 h/air. The filaments maintained 75% of their strength after a 1300°C/2 h/air heat treatment. The observed strength degradation may stem from thermal grooving, grain growth, and/or annealing of the mullite subgrain boundaries. Thermal exposure of >10 h at 1300°C was required to produce measurable grain growth. Strength loss between 1200° and 1300°C (air heat treatment) was not as great as between 1100° and 1200°C or 1300° and 1400°C.     

Stability of Molybdenum Disilicide in Combustion Gak Environments

The stability of MoSi₂ in combustion gas at 1370° and 1600°C was evaluated using SOLGASMIX-PV thermodynamic modeling, periodic weight measurements, and characterization via XRD, SEM, EDS, and image analysis. Passive oxidation occurred at both temperatures. During an initial stage of exposure, specimen surfaces oxidized to form MoO_3(g) and amorphous SiO₂ via reduction of CO₂ and H₂O. After a short time (<6.5 min at 1370°C, <1 min at 1600°C), the oxidation mechanism switched; Mo₅Si₃ and amorphous SiO₂ formed as oxidation products. The first mechanism esulted in the formation of 46.1 vol% at 1370°C and 42.6 vol% at 1600°C of the amorphous silica surface coating. The attainment of a near-terminal weight gain implied silica formation was limited by H₂O and CO₂ diffusion through the silica coating.     

Low-Temperature Oxidation, Hydrothermal Corrosion, and Their Effects on Properties of SiC (Tyranno) Fibers

The effects of oxidation in air and corrosion in high-temperature, high-pressure water on the mechanical properties of three commercially available amorphous Si-Ti-C-O (Tyranno) fibers with different oxygen contents (12%–18%) and diameters (8–11 μm) were investigated. The fibers were exposed to isothermal treatments at elevated temperatures and subsequently tested at room temperature. Structural changes in the fibers after oxidation and corrosion were also studied in order to understand better the degradation mechanisms of the fibers. Oxidation resulted in the formation of vitreous silica films and decreases of strength and Young's modulus of the fibers. Hydrothermal corrosion under 100 MPa water pressure started above 300°C and resulted in the formation of a carbon layer on the surface of the fibers. Dissolution of silica in water during the treatment was observed. Corrosion at temperatures above 400°C led to the formation of relatively thick carbon films which delaminated easily. It caused a decrease of strength and Young's modulus of the fibers. The hydrothermal method can be used for producing carbon coatings with thickness up to 2 μm on the surface of silicon carbide fibers. The degrading of the mechanical properties after oxidation and corrosion was controlled by the thickness of the oxide or carbon layer. Based on this fact, it is possible to predict changes in the mechanical properties from the oxidation data.     

High-Temperature Mechanical Properties and Microstructures for Hot-Pressed Silicon Nitrides with Amorphous and Crystalline Intergranular Phases

Four-point flexure tests were performed at 1100° to 1350°C on two hot-pressed silicon nitrides, one in which the grain-boundary phase was amorphous and one in which it was largely crystalline. Fracture stress and relative K_1c were plotted vs temperature. Fracture regions were analyzed by scanning and transmission electron microscopy. Grain-boundary phases affected high-temperature fracture significantly.     

Oxidation Kinetics of Powdered Silicon Nitride

The oxidation kinetics of powdered silicon nitride were studied in dry oxygen and dry air at 1 atm pressure between 1065° and 1340°C. An automatic recording electrobalance was used to measure the weight gain as a function of time. Parabolic oxidation kinetics were observed with an activation energy of 61 kcal/mol in dry oxygen and 68 kcal/mol in dry air. The oxidation rate in dry oxygen was approximately twice that in air. The solid oxidation product was tridymite above 1125°C and amorphous silica at 1067°C.     

Preparation of Silica from Rice Husks

Preliminary leaching of rice husks with a solution of hydrochloric acid before their combustion at 600°C is shown to be required to obtain relatively pure silica (∼99.5%) with a high specific surface area (∼260 m²/g) that is maintained even after heating at 800°C. Transmission electron microscopy observations indicate that this material has a homogeneous size distribution of nanometric particles. However, if the leaching with HCl is performed on the white ashes obtained by combustion of the rice husks at 600°C, an amorphous silica with the same purity also is obtained, but its specific surface area decreases to 1 m²/g. This behavior is due to a strong interaction between the silica and the potassium contained in the rice husks, which leads to a dramatic decrease of the specific surface area if K⁺ cations are not removed prior to the heat treatment at 600°C. This finding leads to a better understanding of the effect of potassium on the morphology of silica.     

Oxidation of Submicroscopic Fibrous Silicon Carbide

The oxidation rate of silicon carbide fibers of submicroscopic dimensions in static air was investigated by a gravimetric technique at 800°, 900°, and 1000°C. The fibers can be held near 800°C for several hours without significant oxidation, but they rapidly oxidize at 1000°C. A theoretical model for diffusion-controlled oxidation of the fibers, taking into account a changing reaction interfacial area, was obeyed to more than 60% conversion of the silicon carbide to silica. For the diffusion-controlled oxidation an enthalpy of activation of 55.8 or 39.8 kcal/mole was calculated depending on whether an amorphous silica sheath was initially present.