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.     

High-Temperature Oxidation of Chemically Vapor-Deposited Silicon Carbide in Wet Oxygen at 1823 to 1923 K

The oxidation of chemically vapor-deposited SiC in wet O₂ (water vapor partial pressure = 0.01 MPa, total pressure = 0.1 MPa) was examined using a thermogravimetric technique in the temperature range of 1823 to 1923 K. The oxidation kinetics follow a linear-parabolic relationship over the entire temperature range. The activation energies of linear and parabolic rate constants were 428 and 397 kJ · mol⁻¹, respectively. The results suggested that the rate-controlling step is a chemical reaction at an SiC/SiO₂ interface in the linear oxidation regime, and the rate-controlling step is an oxygen diffusion process through the oxide film (cristobalite) in the parabolic oxidation regime.     

High-Temperature Passive Oxidation of Chemically Vapor Deposited Silicon Carbide

The oxidation behavior of chemically vapor deposited (CVD) SiC at high temperature was investigated using a thermogravimetric technique in the temperatures range of 1823 to 1948 K. The specimens were prepared by chemical vapor deposition using SiCl₄, C₃H₈, and H₂ as source gases. The oxidation behavior of the CVD-SiC indicated "passive" oxidation and a two-step parabolic oxidation kinetics over the entire temperature range. The crystallization of the SiO₂ film formed may have caused this two-step parabolic behavior. The parabolic oxidation rate constant ( K _p) varied with the square root of the oxygen partial pressure ( P ^1/2_O2). The activation energy for the oxidation was determined to be 345 and 387 kJ · mol⁻¹. These values suggest that the diffusion process of the oxygen ion which passes through the SiO₂ film is rate-controlling.     

Oxidation Studies of Aluminum-Implanted NBD 200 Silicon Nitride

The effects of aluminum-ion-implantation on the oxidation behavior of NBD 200 Si₃N₄ were investigated over an implant concentration range of 0–30 at.%, at 800°–1100°C, in 1 atm dry O₂. Oxidation of both unimplanted and implanted samples follows a parabolic rate law. The parabolic rate constant decreases and the activation energy increases with aluminum concentration. Smooth and crack-free oxides are formed under the combination of high implant concentrations and low oxidation temperatures. Outward diffusion of Mg²⁺ from the bulk of NBD 200 to the oxide layer remains the rate-limiting step for aluminum-implanted samples. The enhancement of the oxidation resistance of NBD 200 by aluminum implantation is attributed to the retardation of the outward diffusion of Mg²⁺.     

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.     

Paralinear Oxidation of Silicon Nitride in a Water-Vapor/Oxygen Environment

Three Si₃N₄ materials were exposed to dry oxygen flowing at 0.44 cm/s at temperatures between 1200° and 1400°C. Weight change was measured using a continuously recording microbalance. Parabolic kinetics were observed. When the same materials were exposed to a 50% H₂O–50% O₂ gas mixture flowing at 4.4 cm/s, all three types exhibited paralinear kinetics. The material was oxidized by water vapor to form solid SiO₂. The protective SiO₂ was in turn volatilized by water vapor to form primarily gaseous Si(OH)₄. Nonlinear least-squares analysis and a paralinear kinetic model were used to determine parabolic and linear rate constants from the kinetic data. Volatilization of the protective SiO₂ scale could result in accelerated consumption of Si₃N₄. Recession rates under conditions more representative of actual combustors were compared with the furnace data.     

Effect of Physical Nature of Powders and Firing Atmosphere on ZnAI2O4 Formation

The rate of ZnA1₂O₄ formation for binary powder mixtures of ZnO and α-Al₂O₃ (dense coarse particles and weak agglomerates of fine powder) fired in air or O₂ atmospheres was measured and the microstructures of those systems were observed by scanning electron microscopy. With dispersed dense particles of α-Al₂O₃, the Al₂O₃ surfaces were covered with ZnO and the spinel grew into the particles maintaining essentially a constant reaction interface area. Calculations based on geometric measurements and use of Jander's equation gave a similar high activation energy, 354 kJ/mol, which corresponds to the activation energy of volume diffusion of Zn²⁺ in ZnAl₂O₄. An oxygen atmosphere had no effect. With a matrix of fine α-Al₂O₃ powder and dispersed granules of ZnO, a higher reaction rate occurred because of an increase in reaction interface area due to penetration of the powder compact matrix by ZnO vapor, which was enhanced by an O₂ atmosphere. The reaction layer grew into the alumina matrix adjoining the ZnO granules with a parabolic rate law. Apparent activation energies below ∼200 kJ/mol were calculated.     

Oxidation of Silicon Carbide-Reinforced Oxide-Matrix Composites at 1375° to 1575°C

Oxidation studies were conducted on Al₂O₃-SiC and mullite-SiC composites at 1375° to 1575°C in O₂ and in Ar-1% O₂. The composites were prepared by hot-pressing mixtures of Al₂O₃ or mullite and SiC powders. The reaction products contained alumina, mullite, an aluminosilicate liquid, and gas bubbles. The parabolic rate constants were about 3 orders of magnitude higher than those expected for the oxidation of SiC. Higher rates are caused by higher oxygen permeabilities through the reaction products than through pure silica. Our results suggest that oxygen permeabilities are comparable in the three condensed phases observed in the reaction products.     

Improved Oxidation Resistance of Silicon Nitride by Aluminum Implantation: I, Kinetics and Oxide Characteristics

Hot-isostatically-pressed, additive-free Si₃N₄ ceramics were implanted with aluminum at multi-energies and multidoses to achieve uniform implant concentrations at 1, 5, and 10 at.% to a depth of about 200 nm. The oxidation behavior of unimplanted and aluminum-implanted Si₃N₄ samples was investigated in 1 atm flowing oxygen entrained with 100 and 220 ppm NaNO₃ vapor at 900–1100°C. Unimplanted Si₃N₄ exhibits a rapid, linear oxidation rate with an apparent activation energy of about 70 kJ/mol, independent of the sodium content in the gas phase. Oxides formed on the unimplanted samples are rough and are populated with cracks and pores. In contrast, aluminum-implanted Si₃N₄ shows a significantly reduced, parabolic oxidation rate with apparent activation energies in the range of 90–140 kJ/mol, depending on the sodium content as well as the implant concentration. The oxides formed on the implanted samples are glassy and mostly free from surface flaws. The alteration of the oxidation kinetics and mechanism of Si₃N₄ in a sodium-containing environment by aluminum implantation is a consequence of the effective modification of the properties of the sodium silicates through aluminum incorporation.     

Preparation of Mesoporous Silicon Nitride via a Nonaqueous Sol–Gel Route

A silicon diimide gel Si(NH) _x (NH₂) _y (NMe₂) _z was prepared by an acid-catalyzed ammonolysis of tris(dimethylamino)silylamine. Pyrolysis of the gel at 1000°C under NH₃ flow led to the formation of an amorphous silicon nitride material without carbon contamination. All of the gel and pyrolyzed products exhibited a mesoporous structure with a high surface area and narrow pore-size distribution. The effective surface area of the pyrolyzed silicon nitride residues decreases with increasing temperature, but the heating rate during pyrolysis has little influence on the surface area and pore-size distribution of the final mesoporous ceramic Si₃N₄ products because of the highly cross-linked structures of the precursor silicon diimide gel.     

Oxidation of Silicon Nitride in Wet Air and Effect of Lutetium Disilicate Coating

Oxidation behavior of silicon nitride (Si₃N₄) was investigated in flowing air (2.45 cm/s) containing 10%–50% H₂O at a total pressure of 1.8–10 atm at 1300°–1500°C for 100 h. The oxidation of Si₃N₄ progressed with volatilization of the SiO₂ scale; it was more enhanced at a high partial pressure of H₂O rather than at high temperature. The total pressure had little effect on the oxidation. In order to avoid the oxidation, Si₃N₄ substrate was coated with lutetium disilicate (Lu₂Si₂O₇) layer through the intermediate SiO₂-rich phase. While the coating layer well suppressed the oxidation in case of small amount of water vapor, it was not sufficiently effective to suppress the oxidation when the water vapor was rich. SiO₂ volatilization was observed between the layer and substrate. The flexural strength of the coated Si₃N₄ at room temperature was somewhat increased after the oxidation in wet air, while that of the uncoated one was almost unchanged. This increase was attributable to crack healing of the substrate during the oxidation.     

High-Temperature Active Oxidation and Active-to-Passive Transition of Chemically Vapor-Deposited Silicon Nitride in N2–O2 and Ar–O2 Atmospheres

The oxidation behavior of chemically vapor-deposited silicon nitride in N₂–O₂ and Ar–O₂ atmospheres was studied using a thermogravimetric technique at temperatures 1823 to 1923 K. Active oxidation was observed at low oxygen partial pressures. The active oxidation rates increased with increasing oxygen partial pressure ( P _O2) up to a certain P _O2, and then passive oxidation occurred. The transition oxygen partial pressures from active to passive oxidation were determined. The rate-controlling step for the active oxidation could be oxygen diffusion through a gaseous boundary layer near the Si₃N₄ surface. Decomposition of Si₃N₄ does not seem to be associated with the mass loss behavior. The Wagner model was employed to explain the oxidation behavior.     

Oxidation of a Silicon Nitride-Titanium Nitride Composite: Microstructural Investigations and Phenomenological Modeling

The high-temperature oxidation of a silicon nitride-titanium nitride (Si₃N₄–TiN) composite has been investigated via scanning electron microscopy and energy-dispersive and wavelength-dispersive spectrometry. At 1150°C, the oxidation of both the silicon nitride and titanium nitride phases takes place. Several oxidation processes act simultaneously and/or successively. First, the oxidation of the titanium nitride occurs and leads to the formation of a continuous titanium oxide (TiO₂) crystal layer at the surface. Next, the TiO₂ formation takes place in the sublayer at the same time as the Si₃N₄ oxidation. The oxidation of this last phase leads to the formation of vitreous silica (SiO₂). For long a duration of oxidation (>50 h), a continuous layer of SiO₂ is formed under the outer TiO₂ scale. Large pores grow in this layer and deform the outer oxide layers, whereas the oxidation occurs in the material. Based on these results and bibliographical data, a phenomenological model is proposed to describe the stages of the high-temperature oxidation of Si₃N₄–TiN materials.     

Kinetics of Silicon Monoxide Ammonolysis for Nanophase Silicon Nitride Synthesis

Silicon monoxide vapor generated from Si/SiO₂ mixed-powder compacts was used with NH₃ to synthesize silicon nitride in a tubular flow reactor operated at temperatures in the range of 1300°-1400°C. The ammonolysis of SiO with excess NH₃ was very rapid, yielding three different types of silicon nitride at different longitudinal locations in the reactor: amorphous nanophase powder of an average size of about 20 nm, amorphous whiskers of a few micrometers in diameter, and α-polycrystals. The amorphous products were heat-treated for crystallization at temperatures between 1300° and 1560°C in a stream of dissociated NH₃, N₂, or N₂/H₂ mixture gas. When dissociated NH₃ was used, nanophase powder was crystallized at 1300°C. The yield of nanophase silicon nitride from SiO varied from 13% to 43%, depending on operating conditions.     

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.     

Ractions of SiC with H2/H2O/Ar Mixtures at 1300°C

The reactions of a sintered α-SiC with 5% H₂/H₂O/Ar at 1300°C were studied. Thermomchemical modeling indicates that three reaction regions are expected, depending on the initial water vapor or equivalently oxygen content of the gas stream. A high oxygen content ( P (O₂) > 10⁻²² atm) leads to a SiO₂ formation. This generally forms as a protective film and limits consumption of the SiC (passive oxidation). An intermediate oxygen content (10⁻²² atm > P (O₂) > 10⁻²⁶ atm) leads to SiO and CO formation. These gaseous products can lead to rapid consumption of the SiC (active oxidation). Thermogravimetric studies in this intermediate region gave reaction rates which appear to be controlled by H₂O gas-phase transport to the sample and reacted microstructures showed extensive grain-boundary attack in this region. Finally, a very low oxygen content ( P (O₂) < 10⁻²⁶ atm) is thermochemically predicted to lead to selective removal of carbon and formation of free silicon. Experimentally low weight losses and iron silicides are observed in this region. The iron silicides are attributed to reaction of free silicon and iron impurities in the system.     

Thermal Etching and Grain-Boundary Grooving Silicon Ceramics

Polished polycrystalline specimens of Si, Sic, and Si₃N₄ were heated to high temperatures and the rate of thermal etching was measured. Grain-boundary grooving occurred on silicon by surface diffusion, with a surface-diffusion coefficient given by Silicon carbide surfaces became extremely rough and very little grain-boundary grooving occurred. Silicon nitride decomposed in an N₂-H₂, atmosphere with an activation energy of 757 kJ/mol, which was very near the activation energy calculated from thermochemical data. The surfaces became fairly rough but grain-boundary grooves formed by an evaporation processsimilar to that for decomposition.     

Oxidation Kinetics of Chemically Vapor-Deposited Silicon Carbide in Wet Oxygen

The oxidation kinetics of chemically vapor-deposited SiC in dry oxygen and wet oxygen ( P _H2O= 0.1 atm) at temperatures between 1200° and 1400°C were monitored using thermogravimetric analysis. It was found that in a clean environment, 10% water vapor enhanced the oxidation kinetics of SiC only very slightly compared to rates found in dry oxygen. Oxidation kinetics were examined in terms of the Deal and Grove model for oxidation of silicon. It was found that in an environment containing even small amounts of impurities, such as high-purity Al₂O₃ reaction tubes containing 200 ppm Na, water vapor enhanced the transport of these impurities to the oxidation sample. Oxidation rates increased under these conditions presumably because of the formation of less protective sodium alumino-silicate scales.     

Development of a Self-Forming Ytterbium Silicate Skin on Silicon Nitride by Controlled Oxidation

A dense and uniform polycrystalline ytterbium silicate skin on silicon nitride ceramics was developed by a controlled oxidation process to improve the hot corrosion resistance of silicon nitride. The process consists of purposely oxidizing the silicon nitride by heating it at high temperatures. It was found that the ytterbium silicate phase was formed as an oxidation product on the surface of the silicon nitride when it was exposed to air at temperatures above 1250°C. The volume fraction of ytterbium silicate compared with that of SiO₂ on the silicon nitride surface increased with increasing oxidation time and temperature. The formation and growth of ytterbium silicate on the surface of silicon nitride is attributed to a nucleation and growth mechanism. Ultimately, a dense and uniform ytterbium silicate skin with 3–4 μm of skin thickness was obtained by oxidation at 1450°C for 24 h. The ytterbium silicate layer, formed by oxidation of the silicon nitride, is associated with the reaction of SiO₂ on the surface of silicon nitride with Yb₂O₃ introduced in the silicon nitride as a sintering additive. Preliminary tests showed that the ytterbium silicate skin appears to protect silicon nitride from hot corrosion. No observable evidence of a reaction between the skin and molten Na₂SO₄ was found when it was exposed to molten Na₂SO₄ at 1000°C for 30 min.     

High-Temperature Active Oxidation of Chemically Vapor-Deposited Silicon Carbide in an Ar─O2 Atmosphere

Active oxidation behavior of chemically vapor-deposited silicon carbide in an Ar─O₂ atmosphere at 0.1 MPa was examined in the temperature range between 1840 and 1923 K. The transition from active oxidation (mass loss) to passive oxidation (mass gain) was observed at certain distinct oxygen partial pressures ( P _O2^t). The values of P _O2^t increased with increasing temperature and with decreasing total gas flow rates. This behavior was well explained by Wagner's model and thermodynamic calculations. Active oxidation rates ( k _a) increased with increasing O₂ partial pressures and total gas flow rates. The rate-controlling step of the active oxidation was concluded to be O₂ diffusion through the gaseous boundary layer.