Silicon Carbide Oxidation in Steam up to 2 MPa

Growth and microstructure of a protective or nonprotective SiO₂ scale and the subsequent volatilization of scale formed on high‐purity chemical vapor deposited (CVD) SiC and nuclear‐grade SiC/SiC composites have been studied during high‐temperature 100% steam exposure. The environmental parameters of interest were temperature from 1200°C to 1700°C, pressure of 0.1 to 2 MPa and flow velocities of 0.23 to 145 cm/s. Scale microstructure was characterized via electron microscopy and X‐ray diffractometry. The Arrhenius dependence of the parabolic oxidation and linear volatilization rate constants were determined. The linear volatilization rate exhibited a strong dependence on steam partial pressure with a weaker dependence on flow velocity. At high steam pressures, the oxide scale developed substantial porosity, which significantly accelerated material recession. The dominant oxide phase for the conditions studied was cristobalite. The oxidation behavior of SiC/SiC composite was strongly dependent on the state of the surface, specifically whether steam could find easy entry into the material via surface‐exposed interface layers. For the case where these as‐machined interfaces were surface coated with matrix CVD SiC, composite recession was found to be essentially that of high‐purity CVD SiC.     

Steam Oxidation Resistance of Silicon Carbide Castables at Elevated Temperatures

Silicon carbide castables of different SiC contents (86％ and 71％,by mass) were prepared using white fused corundum,silicon carbide particles and fines,activated...     

Silicon Carbide Whisker‐Reinforced Ceramic Tape for High‐Power Components

An attempt to enhance both mechanical strength and thermal conductivity of glass‐based tapes is described. Flexural strength of ~420 MPa and thermal conductivity of ~10.3 W/m/K have been achieved in fully densified tape comprising calcium aluminoborosilicate glass, aluminum nitride, and silicon carbide whiskers. Silicon carbide whiskers aligned parallel to the casting direction contributed significantly to the reinforcement of the microstructure with accompanying extensive densification over a broad temperature range. These results are compared with the more typical alumina filler substituted for the aluminum nitride.     

Oxidation of Silicon Carbide

The rate of oxidation of silicon carbide was measured in an atmosphere of dry oxygen between 900° and 1600°C. The rate was studied by using a thermogravimetric apparatus and was found to be diffusion controlled. The products of oxidation were amorphous silica and cristobalite, depending on the temperature. The effect of surface area was determined, and a correlation between the various sizes was made with the aid of an equation derived on the assumptions that (1) the reaction was diffusion controlled, (2) the particles were essentially spherical, and (3) the interfacial area was constantly changing. The presence of water vapor in the gaseous atmosphere was found to be extremely critical.     

Variation of the Oxidation Rate of Silicon Carbide with Water-Vapor Pressure

Chemically vapor deposited silicon carbide (CVD SiC) was oxidized at temperatures of 1000°-1400°C in H₂O/O₂ gas mixtures with compositions of 10-90 vol% water vapor at a total pressure of 1 atm. Additional experiments were conducted in H₂O/argon mixtures at a temperature of 1100°C. Experiments were designed to minimize impurity and volatility effects, so that only intrinsic water-vapor effects were observed. The oxidation kinetics increased as the water-vapor content increased. The parabolic oxidation rates in the range of 10-90 vol% water vapor (the balance being oxygen) were approximately one order of magnitude higher than the rates that were observed in dry oxygen for temperatures of 1200°-1400°C. The power-law dependence of the parabolic oxidation rate on the partial pressure of water vapor at all temperatures of the study indicated that the molecular species was not the sole rate-limiting oxidant. The determination of an activation energy for diffusion was complicated by variations in the oxidation mechanism and oxide-scale morphology with the partial pressure of water vapor and the temperature.     

Oxidation Behavior of Silicon Carbide

The oxidation of purified green silicon carbide in controlled atmospheres was studied by weight-gain measurement and by observation of the surface reaction products, including optical measurement of the thickness of the oxide surface film. The rate of oxidation was much greater for silicon carbide in contact with fluid silicate glasses than for silicon carbide alone. In a vacuum of 0.1 mm., oxidation proceeded with loss of weight, because of the formation of volatile SiO₂, and at a greater rate than at atmospheric pressure. It is postulated that the rate-controlling process in the normal oxidation of silicon carbide is the formation of solid SiO₂ on the surface.     

Effects of Oxygen Partial Pressure on the Oxidation of Silicon Carbide

The rate of oxidation of silicon carbide was studied at different partial pressures of oxygen. The diffusion rate constant was found to vary with the logarithm of the partial pressure of oxygen according to the theory of oxidation of thin films as proposed by Engell and Hauffe. An alternative explanation based on the change of free energy with surface coverage was also found to fit the data.     

Effects of High Water-Vapor Pressure on Oxidation of Silicon Carbide at 1200°C

The oxidation of SiC at 1200°C in a slowly flowing gas mixture of either air or air + 15 vol% H₂O at 10 atm (1 MPa) was studied for extended times to examine the effects of elevated water-vapor pressure on oxidation rates and microstructural development. At a water-vapor pressure of 1.5 atm (150 kPa), distinct SiO₂ scale structures were observed on the SiC; thick, porous, nonprotective cristobalite scales formed above a thin, nearly dense vitreous SiO₂ layer, which remained constant in thickness with time as the crystalline SiO₂ continued to grow. The pore morphology of the cristobalite layer differed depending on the type of SiC on which it was grown. The crystallization and growth rates of the cristobalite layer were significantly accelerated in the presence of the high water-vapor pressure and resulted in rapid rates of SiC surface recession that were on the order of what is observed when SiO₂ volatility is rate controlling at high gas-flow velocities (30 m/s). The recession process can be described by a paralinear kinetic model controlled by the conversion of dense vitreous SiO₂ to porous, nonprotective SiO₂.     

Sintering of High‐Performance Silicon Nitride Ceramics Under Vibratory Pressure

To improve mechanical behaviors of silicon nitride ceramics, here we introduced a novel external field—vibratory pressure into the sintering of Si₃N₄ ceramics with advantages of higher density, more uniform distribution of interfacial phase, higher sintering motivation in the width direction, and therefore more favorable mechanical properties than traditional sintering methods. Grain size and aspect ratio of the two ceramics were investigated with linear intercept method. Flexural strength of the vibratory‐assisted hot‐pressing (VAHP) specimen increased from 936 ± 27.2 MPa to 1247 ± 28.9 MPa, and an increase of 10% was achieved in fracture toughness. It is believed that such VAHP method can provide a universal approach and new opportunities for the fabrication of covalent‐bonded ceramics or composites with enhanced performances.     

Oxidation of 6H-α Silicon Carbide Platelets

Oxidation on the 2 crystal faces of SiC platelets was studied. The oxidation of the C face followed a simple parabolic law and was oxide-diffusion controlled, whereas that of the opposite crystal face exhibited a linear growth rate which was surface-reaction controlled. Previous investigators, who studied the oxidation of Sic by measuring weight change, found that the oxidation rate follows a simple parabolic law. At high temperatures and long reaction times, there is an increase in the oxidation rate which has previously been attributed to a change in the state of the oxide. The present investigation, however, indicates that this change occurs as the linear oxidation rate becomes dominant.     

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.     

Oxidation of Chemically-Vapor-Deposited Silicon Carbide in Carbon Dioxide

Chemically-vapor-deposited silicon carbide (CVD SiC) was oxidized in carbon dioxide (CO₂) at temperatures of 1200–1400°C for times between 96 and 500 h at several gas flow rates. Oxidation weight gains were monitored by thermogravimetric analysis (TGA) and were found to be very small and independent of temperature. Possible rate-limiting kinetic mechanisms are discussed. Passive oxidation of SiC by CO₂ is negligible compared to the rates measured for other oxidants that are also found in combustion environments, oxygen and water vapor.     

Oxidation of Zirconium Diboride–Silicon Carbide at 1500°C at a Low Partial Pressure of Oxygen

The oxidation behavior of zirconium diboride containing 30 vol% silicon carbide particulates was investigated under reducing conditions. A gas mixture of CO and ∼350 ppm CO₂ was used to produce an oxygen partial pressure of ∼10⁻¹⁰ Pa at 1500°C. The kinetics of the growth of the reaction layer were examined for reaction times of up to 8 h. Microstructures and chemistries of reaction layers were characterized using scanning electron microscopy and X-ray diffraction analysis. The kinetic measurements, the microstructure analysis, and a thermodynamic model indicate that oxidation in CO–CO₂ produced a non-protective oxide surface scale.     

Heat Integration in Straight‐Through Sulfur Recovery Units to Increase Net High‐Pressure Steam Production

Energy conservation is of paramount importance in oil and gas industries. Sulfur recovery units (SRUs) in oil and gas industries are required to meet the stringent environmental emission regulations, and are often viewed as production costs. They are normally net energy exporters and a considerable portion of heat is recovered as high‐pressure steam. However, SRUs processing lean acid gas streams require significant amounts of acid gas and air preheating before they enter the reaction furnace. Some portion of the generated high‐pressure steam is used in preheating these streams. This reduces the overall net high‐pressure steam generated from the SRU. Here, heat integration is used and an existing SRU facility is retrofitted such that there is an increase in net high‐pressure steam production. Seven new heat‐integrated SRU configurations are proposed, and key aspects such as net high‐pressure steam production, investment costs, and payback period for each of the new retrofitted configurations are compared.     

Fracture Behavior of Woven Silicon Carbide Fibers Exposed to High‐Temperature Nitrogen and Oxygen Plasmas

High‐temperature aero‐thermal heating in a 30 kW inductively coupled plasma torch was used to replicate the effects of harsh oxidizing environments during hypersonic atmospheric entry on fracture behavior and microstructure of two‐dimensional woven SiC fibers. Hi‐Nicalon SiC woven cloths were exposed to surface temperatures over 1400°C with different high‐enthalpy dissociated oxygen and nitrogen plasma flows, and were subsequently deformed in pure tension at room temperature. Changes in fiber microstructure and surface chemistry after thermal exposure were examined by scanning electron microscopy. Pure nitrogen plasmas resulted in a 50% decrease of strength in woven SiC fibers with minimal effects on the fiber structure, except for highly localized surface pitting caused by partial decomposition of silicon oxycarbonitride phase at high temperature. In contrast, exposure to dissociated oxygen and air plasmas led to severe strength reduction and embrittlement over significantly short time scales, corresponding to degradation rates up to 200 times higher than those reported with static heating at equivalent temperatures. The origin of accelerated embrittlement at microscopic scale was found related to complex gas‐surface interactions and high‐temperature oxidizing processes involving the formation of SiO₂ bubbles and microcracks on the surface. These findings are important for the development of outer fabric materials for new flexible thermal protection systems in space applications.     

Oxidation of Silicon and Silicon Carbide in Ozone-Containing Atmospheres at 973 K

The oxidation behavior of a silicon wafer, chemically vapor-deposited SiC, and single-crystal SiC was investigated in an oxygen—2%–7% ozone gas mixture at 973 K. The thickness of the oxide film that formed during oxidation was measured by ellipsometry. The oxidation rates in the ozone-containing atmosphere were much higher than those in a pure oxygen atmosphere. The parabolic oxidation kinetics were observed for both silicon and SiC. The parabolic rate constants varied linearly with the ozone-gas partial pressure. Inward diffusion of atomic oxygen formed by the dissociation of ozone gas through the SiO₂ film apparently was the rate-controlling process.     

渗硅碳化硅材料的高温氧化

研究了全碳粉反应渗硅碳化硅(PCRBSC)材料,在1300℃静态空气中的高温氧化行为.研究结果表明:PCRBSC材料的氧化过程遵循直线-抛物线规律,其结构对高温氧化有很大的影响,特别是游离硅fsi和游离碳fc的含量对氧化影响更大,fsi含量高的PCRBSC材料单位面积氧化增重(Δm/s)明显,fc含量高的PCRBSC材料氧化后表现为先减重后增重,氧化层断口经扫描电镜观察有明显的气孔存在.     

Some New Perspectives on Oxidation of Silicon Carbide and Silicon Nitride

This study provides new perspectives on why the oxidation rates of silicon carbide and silicon nitride are lower than those of silicon and on the conditions under which gas bubbles can form on them. The effects on oxidation of various rate-limiting steps are evaluated by considering the partial pressure gradients of various species, such as O₂, CO, and N₂. Also calculated are the parabolic rate constants for the situations when the rates are controlled by oxygen and/or carbon monoxide (or nitrogen) diffusion. These considerations indicate that the oxidation of silicon carbide and silicon nitride should be mixed controlled, influenced both by an interface reaction and diffusion.     

Active-to-Passive Transition in the Oxidation of Silicon Carbide and Silicon Nitride in Air

The active-to-passive transition in the oxidation of SiC and Si₃N₄ was determined in a flowing air environment as a function of temperature and total pressure. The experimentally observed transition temperatures ranged from a low of 1347°C to a high of 1543°C for partial pressures of oxygen of 2.5 and 123.2 Pa, respectively. The SiC and Si₃N₄ samples had approximately the same transition point for a given pressure. In general, the higher the flow rate, the higher the transition temperature for a given pressure. The transitions for SiC measured in this study agree with previous data for the transition of SiC measured in pure oxygen at reduced pressures and in oxygen inert gas mixtures.     

Yttrium Silicate Coatings for Oxidation Protection of Carbon–Silicon Carbide Composites

Yttrium silicate (Y₂SiO₅) coatings complement SiC coatings for protecting ceramic multilayer composite materials based on carbon-fiber-reinforced SiC composites (C-SiC). Thick (100 μm), dense Y₂SiO₅ coatings were prepared by dip coating, using concentrated aqueous slips. The resulting phases were studied by taking into account the simultaneous presence of oxide and non-oxide materials, which affected the chemical stability of the coatings. Thick, mechanically stable coatings were obtained by sintering in carbon crucibles and a SiC bed in an argon-flow furnace. Pure Y₂SiO₅ coatings completely separated from the SiC substrates. A high percentage of Y₂Si₂O₇ was necessary to fit the thermal expansion coefficients and ensure the stability of the coatings. Oxidation resistance of the coated substrates was investigated by isothermal and stepwise oxidation tests.