Oxidation of Low-Oxygen Silicon Carbide Fibers (Hi-Nicalon) in Carbon Dioxide

Polycarbosilane-derived low-oxygen SiC fibers, Hi-Nicalon, were heat-treated for 36 ks at temperatures from 1273 to 1773 K in CO₂ gas. The oxidation of the fibers was investigated through the examination of mass change, crystal phase, resistivity, morphology, and tensile strength. The mass gain, growth of β-SiC crystallites, reduction of resistivity of the fiber core, and formation of protective SiO₂ film were observed for the fibers after heat treatment in CO₂ gas. SiO₂ film crystallized into cristobalite above 1573 K. Despite the low oxygen potential of CO₂ gas ( p _O2= 1.22 Pa at 1273 K − 1.78 × 10² Pa at 1773 K), Hi-Nicalon fibers were passively oxidized at a high rate. There was a large loss of tensile strength in the as-oxidized state at higher temperatures because of imperfections in the SiO₂ film. On the other hand, the fiber cores showed better strength retention even after oxidation at 1773 K.     

Stacking Faults in Chemically-Vapor-Deposited Beta Silicon Carbide

A high density of planar defects, often forming closed figures on {111} planes, was observed in chemically-vapor-deposited β-SiC. The defects were identified as extrinsic stacking faults by electron diffraction contrast analysis.     

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.     

Oxidation of Chemically-Vapor-Deposited Silicon Nitride and Slnglem-Crystal Silicon

Oxidation of {111} single-crystal silicon and dense, chemically-vapor-deposited silicon nitride was done in clean silica tubes at temperatures of 1000° to woo°C. The oxidation rates of silicon nitride under various atmospheres (dry O₂, wet O₂, wet inert gas, and steam) were several orders of magnitude slower than those of silicon under the identical conditions. The activation energy for the oxidation of silicon nitride decreased from 330 to 259 kJ/mol in going from dry O₂ to steam while that for Si decreased from 120 to 94 kJ/mol. The parabolic rate constant for Si increased linearly as the water vapor pressure increased. However, the parabolic rate constant for silicon nitride showed nonlinear dependency on the water vapor pressure in the presence of oxygen. The oxidation kinetics of silicon nitride is explained by the formation of nitrogen compounds (NO and NH₃) at the reaction interface and the counterpermeation of these reaction products.     

Oxidation Behavior of Chemically-Vapor-Deposited Silicon Carbide and Silicon Nitride from 1200° to 1600°C

The isothermal oxidation of pure CVD SiC and Si₃N₄ has been studied for 100 h in dry, flowing oxygen from 1200° to 1600°C in an alumina tube furnace. Adherent oxide formed at temperatures to 1550°C. The major crystalline phase in the resulting silica scales was alpha-cristobalite. Parabolic rate constants for SiC were within an order of magnitude of literature values. The oxidation kinetics of Si₃N₄ in this study were not statistically different from that of SiC. Measured activation energies were 190 kJ/mol for SiC and 186 kJ/mol for Si₃N₄. Silicon oxynitride did not appear to play a role in the oxidation of Si₃N₄ under the conditions herein. This is thought to be derived from the presence of ppm levels of sodium impurities in the alumina furnace tube. It is proposed that sodium modifies the silicon oxynitride, rendering it ineffective as a diffusion barrier. Material recession as a function of oxide thickness was calculated and found to be low. Oxidation behavior at 1600°C differed from the lower temperatures in that silica spallation occurred after exposure.     

Oxidation of the Carbon Interface in Nicalon-Fiber-Reinforced Silicon Carbide Composite

The recession rates for 10^-6-m-thick C interfaces in chemical vapor infiltrated SiC reinforced with Nicalon fibers were calculated from thermogravimetric data, assuming all of the mass losses were due to C oxidation, and found to be consistent with the measured recession distances of the C interface, which were surprisingly uniform across the composite. Agreement between the two approaches for a microstructurally complex material indicates thermogravimetric analysis could be an important tool for understanding environmental effects in ceramic composites with reactive interfaces. Mass losses were linear within the first 1.08× 10⁴ s to 2.16× 10⁴ s between 1073 and 1373 K and between 3.1× 10² and 2.5× 10³ Pa O₂. Calculated reaction orders with respect to O₂ were between 0.5 and 1.0 at 1373 K, and activation energies were about 50 kJmol^-1. Analysis of the kinetic data and estimates of gas boundary layer thickness suggest the mechanism for the C-interface oxidation involved reaction control, but the possibility of diffusion control for some conditions cannot be ruled out.     

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.     

Oxidation Resistance of Multiwalled Carbon Nanotubes Coated with Silicon Carbide

Multiwalled carbon nanotubes (MWCNTs) were coated with a SiC layer using SiO vapor. The growth mechanism of SiC and the oxidation resistance of the SiC-coated MWCNTs were studied. The growth of the SiC layer was controlled by adjusting the partial pressure of CO₂ using carbon felt placed in a crucible. The nanometer-sized SiC particles were deposited onto the tubes by the reaction between SiO( g ) and CO( g ). On the other hand, the thin surface of the MWCNTs was converted to the SiC layer when the carbon felt was not used. The oxidation durability of MWCNTs was improved by the SiC coating. MWCNTs were oxidized completely in air at 650°C for 60 min. However, about 90 mass% of the SiC-coated MWCNTs remained after the same oxidation test.     

纳米碳颗粒/碳化硅陶瓷基复合材料的氧化行为

以微米硅(Si)和纳米碳黑(Cp)粉体为主要原料,采用经机械化学法合成的碳化硅(SiC)和15%和25%的纳米碳颗粒与碳化硅(Cp-SiC)的复合粉体,并经无压烧结得到了Cp/SiC陶瓷基复合材料,分析了在不同温度条件下Cp/SiC烧结体的氧化行为。结果表明:当温度小于700℃时,Cp/SiC复合陶瓷在空气中的氧化受C—O2反应控制,致使其为均匀氧化;700℃时,氧化后的复合材料显气孔率最大,弯曲强度达极小值;大于700℃,氧化过程受O2的气相扩散控制,呈非均匀氧化;700~900℃之间,O2通过微裂纹的扩散控制着Cp/SiC的氧化过程;900~1 100℃之间,O2通过SiC缺陷的扩散控制着Cp/SiC的氧化过程,并在1 000℃时的最初的2 h内,复合材料弯曲强度增大,且达到了极大值。同时表明,纳米碳含量是影响复合材料强度及氧化行为的关键因素,添加纳米碳质量分数为15%的Cp/SiC复合陶瓷可以作为一种抗氧化性能优良的玻璃夹具材料。     

Carbon Dioxide laser Synthesis of Ultrafine Silicon Carbide Powders from Diethoxydimethylsilane

Ultrafine SiC powders have been synthesized from diethoxydimethylsilane by laser-induced vapor-phase reactions. The powders produced under different flow rates of the reactant vapor have been characterized by chemical analysis, transmission electron microscopy, infrared spectros-copy, and X-ray diffractometry. The results show that the powders are less than 30 nm in average particle diameter, uniformly distributed, spherical in shape, and amorphous. The oxygen and free carbon of the powders vary with the vapor flow rate of the reactant. Annealing of the powders at 1873 K in nitrogen for 1 h results in a complete transformation from amorphous SiC to β-SiC and a small amount of α-SiC.     

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.     

Mechanism of Material Removal from Silicon Carbide by Carbon Dioxide Laser Heating

The mechanism of material removal from SiC by CO₂ laser heating was studied using sintered and single-crystal α-SiC. Removal rate and width of the groove showed maxima when plotted as a function of translation speeds. Groove depth decreased as the translation speed of samples increased. Similar results were obtained if argon or air was used as gas assist, which indicated that the material removal mechanism is induced dissociation of SiC. Microstructure of the material deposited in and outside of the groove was studied by SEM. At low scanning speeds, columnar grains 10 to 50 μm long appeared. As the scanning speed increased, columnar grains became smaller and finally only irregular polycrystalline particles were observed. By using Raman spectroscopy, Auger analysis, and X-ray diffraction, phases inside and outside the groove were identified as Si, β-SiC, C, and SiO₂. Columnar grains were identified as β-SiC covered with thin layers of C, Si, and SiO₂. Slow scanning speeds enhanced the growth of β-SiC. At slow scanning speed, free silicon was always found in the grooves of lased single crystals but not in the grooves of lased sintered SiC. It can be concluded that the mechanism of material removal from silicon carbide by CO₂ laser heating is a vaporization process, and material found in the groove and on the surface near the groove is formed by condensation from the vapor.     

Strength-Degrading Mechanisms for Chemically-Vapor-Deposited SCS-6 Silicon Carbide Fibers in an Argon Environment

The room-temperature tensile strengths of chemically-vapor-deposited SCS-6 silicon carbide fibers were measured after 1 to 400 h heat treatments in 0.1 MPa of argon at temperatures up to 2100°C. The fibers heat-treated for 1 h above 1400°C and those heat-treated for 400 h above 1300°C showed strength degradation. Scanning and transmission electron microscopic examination of the degraded fibers showed formation of a recrystallization region within the outer zone of the SiC sheath and the growth of SiC particles in the carbon-rich surface coating. The activation energy for the growth of the recrystallization region was ∼370 kJ/mol. The tensile strength of the fibers was found to vary as an inverse function of the recrystallized zone thickness.     

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.     

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.     

Carbon Inclusions in Sintered Silicon Carbide

The carbon additions in the pressureless sintering of SiC are commonly used for the removal of SiO₂ layers on the starting powders. In practice, it is common to add more C than is necessary for stoichiometric removal to ensure a complete deoxidation. As a result, inclusions of excess free C are a general feature of the microstructure of sintered SiC. This phenomenon was studied by high-resolution Auger electron spectroscopy on ultra-high-vacuum-exposed fracture surfaces as well as by high-resolution transmission electron microscopy of B- and C-doped materials.     

High-Temperature Oxidation of Chemically Vapor-Deposited Silicon Nitride in a Carbon Monoxide-Carbon Dioxide Atmosphere

Oxidation behavior of chemically vapor-deposited silicon nitride (CVD-Si₃N₄) in CO─CO₂ atmospheres between 1823 and 1923 K was investigated using a thermogravimetric technique. Mass loss of Si₃N₄ (active oxidation) was observed in a region of P _CO2/P_CO < 1, while mass gain (passive oxidation) was observed at around P _CO2 P _CO= 10. In the active oxidation region below P _CO2P_CO= 10 ^–4, carbon particles were formed on the Si³N⁴ surface as an oxidation product, and the mass-loss rates were independent of P _CO2/ P _CO In the active oxidation region above P _CO2/ P _CO= 10^–4 the mass-loss rates decreased with increasing P _CO2/ P co. The critical P _CO2/ P _CO value from the active to passive oxidation was 2 orders of magnitude larger than the calculated value predicted from the Wagner model.     

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.