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.     

Strengthening and Prevention of Oxidation of Aluminum Nitride by Formation of a Silica Layer on the Surface

A silica (SiO₂) layer was deposited on the surface of an AlN ceramic in order to increase the strength and to prevent the high-temperature oxidation of the material. The layer was formed on the surface by exposing coupons to the atmosphere downstream of a bed of SiC powder in a flowing H₂–0.1% H₂O atmosphere at 1450°C. A reaction between the SiC powder and H₂O in the H₂ gas resulted in the generation of SiO₂"smoke" in the product gas stream. Part of the SiO₂ smoke was subsequently deposited on the surface of the AlN specimen to form a dense and uniform SiO₂ layer. The strength of AlN was improved by about 20% apparently because of blunting of surface defects by SiO₂. More importantly, the layer was very effective in protecting the AlN from the oxidation at elevated temperatures, through the inhibition of transport of oxidants to the sample surface.     

Etching of Silicon Carbide Materials at Elevated Temperatures in a Nitrogen-Based Gas

Two sintered SiC-based materials were heat-treated for 150 h at 1300°C in a nitrogen-based gas (1.2% H₂, 0.6% CO) at a total pressure of 130 Pa. Sintered SiC samples were also preoxidized and then exposed to this gas under the same conditions to evaluate the protective nature of an SiO₂ scale. In this atmosphere, SiO gas and cyanogens are predicted to form, rather than SiO₂. Experimental studies confirmed that etching of sintered SiC occurs. Preoxidation does not provide protection from etching, because of the rapid removal of SiO₂ by H₂ as H₂O and SiO.     

Grain-Boundary Viscosity of Polycrystalline Silicon Carbides

Internal friction experiments were conducted on three SiC polycrystalline materials with different microstructural characteristics. Characterizations of grain-boundary structures were performed by high-resolution electron microscopy (HREM). Observations revealed a common glass-film structure at grain boundaries of two SiC materials, which contained different amounts of SiO₂ glass. Additional segregation of residual graphite and SiO₂ glass was found at triple pockets, whose size was strongly dependent on the amount of SiO₂ in the material. The grain boundaries of a third material, processed with B and C addition, were typically directly bonded without any residual glass phase. Internal friction data of the three SiC materials were collected up to similar/congruent2200°C. The damping curves as a function of temperature of the SiO₂-bonded materials revealed the presence of a relaxation peak, arising from grain-boundary sliding, superimposed on an exponential-like background. In the directly bonded SiC material, only the exponential background could be detected. The absence of a relaxation peak was related to the glass-free grain-boundary structure of this polycrystal, which inhibited sliding. Frequency-shift analysis of the internal friction peak in the SiO₂-containing materials enabled the determination of the intergranular film viscosity as a function of temperature.     

Grain Growth Phenomena in the Interface Region of α-Alumina Bilayer Composites

Microstructural development in the interface region of α-Al₂O₃ bilayer composites has been systematically investigated in terms of the sintering additive CaO–SiO₂, residual impurity level in the starting powders (particularly MgO), and sintering conditions. The interfacial microstructure is strongly related to relative CaO–SiO₂ doping levels in the two constituting layers and to residual impurities in the starting powders. The presence of high levels of impurities in the starting powder can substantially modify the features of CaO–SiO₂-Al₂O₃ liquid at the interface region, thereby strongly influencing α-Al₂O₃ grain growth across the interface. Three grain growth modes in the interface region thus have been identified for different combinations of impurity level and CaO–SiO₂ dopant in the α-Al₂O₃ bilayer. This provides an important mechanism for controlling two-dimensional structures in coatings, films, and layered ceramic materials for various engineering applications.     

High-Temperature Mixed Oxidation of Nitride-Bonded Silicon Carbide in Oxidizing Gas Mixtures Containing 2% Cl2

Nitride-bonded silicon carbide ceramics have lower processing costs than many other SiC-based ceramics and adequate properties for use as high-temperature heat exchangers in oxidizing environments. Silicon nitride has much better resistance to attack by chlorine at temperatures above 900°C than silicon carbide. When nitride-bonded silicon carbide ceramics are exposed to gas mixtures containing 2% Cl₂ and small amounts of oxygen in this temperature range, the SiC is selectively chlorinated, leaving behind a porous matrix of silicon nitride. The rate of corrosion is controlled by a combination of interfacial kinetics at the surfaces of the SiC grains and transport of volatile species through the silicon nitride skeleton. In more oxidizing environments, the rate of chlorination is suppressed by the formation of a protective SiO₂ film. In highly oxidizing environments at temperatures in excess of 1200°C, the formation of volatile chloride reaction products at the interface between the SiC and the passivating SiO₂ layer causes bubbles to form in the SiO₂, which accelerates the oxidation.     

A Model of Gas-Phase Transport During the Initial Stages of Sintering of Silicon Carbide

Carbon, which is often used as an additive to silicon carbide powder, is thought to facilitate densification during sintering by aiding the removal of the native SiO₂ layer, which is present on the starting SiC powder. The mechanism is the reduction of SiO₂ to SiC with the formation of primarily CO gas, which diffuses out from the porous compact at a temperature below the normal sintering temperature. It has been found beneficial to hold the compact at an intermediate temperature to allow time for the CO and other gases to diffuse out before the pores close. We investigate this process using a computational model based on codiffusion of multiple gas species, which enables prediction of the gas and condensed phase compositions as a function of time and position in the specimen. The results are used to determine the optimum holding time for complete SiO₂ removal as a function of key parameters, such as specimen thickness, particle size, temperature, etc., as well as the necessary amount of C additive. The results of the modeling are consistent with the experimentally observed spatial variation of density and composition in SiC compacts.     

Oxygen Transport in Silica at High Temperatures: Implications of Oxidation Kinetics

The apparent change in activation energy describing the parabolic rate constant for the passive oxidation of SiC is examined. New data are combined with reevaluated previous results to determine the influences of crystallinity, impurity contamination, and multiple flux mechanisms. The results suggest that the high-temperature transition from interstitial-dominant to network-dominant oxygen transport is a property of amorphous SiO₂ scales and does not exist for cristobalite. Highly crystalline scales do not show this transition. Agreement among various studies also suggests that, for high-purity SiO₂ scales, there is no difference between the rates of interstitial oxygen transport in amorphous SiO₂ and in β-cristobalite.     

Influence of Silica and Aluminum Contents on Sintering of and Grain Growth in 6H-SiC Powders

To clarify the influence of impurities on the sintering of SiC powder, three 6H-SiC powder samples—with different levels of SiO₂ and aluminum impurities—were sintered with additions of boron and carbon. The densification, grain growth, and transformation of 6H-SiC during sintering were studied qualitatively. The powder that contained the most SiO₂ required the greatest amount of boron additive for complete densification. SiO₂ apparently reacted with the boron additive and was consumed during sintering. The powder with the greater aluminum impurity level exhibited partial transformation of 6H-SiC to 4H-SiC, and the sintered SiC from this powder had elongated grains. The partial transformation in the SiC crystal accelerated non-equiaxial grain growth.     

Oxidation and Volatilization of Silica Formers in Water Vapor

At high temperatures, SiC and Si₃N₄ react with water vapor to form a SiO₂ scale. SiO₂ scales also react with water vapor to form a volatile Si(OH)₄ species. These simultaneous reactions, one forming SiO₂ and the other removing SiO₂, are described by paralinear kinetics. A steady state, in which these reactions occur at the same rate, is eventually achieved. After steady state is achieved, the oxide found on the surface is a constant thickness, and recession of the underlying material occurs at a linear rate. The steady-state oxide thickness, the time to achieve steady state, and the steady-state recession rate can be described in terms of the rate constants for the oxidation and volatilization reactions. In addition, the oxide thickness, the time to achieve steady state, and the recession rate also can be determined from parameters that describe a water-vapor-containing environment. Accordingly, maps have been developed to show these steady-state conditions as a function of reaction rate constants, pressure, and gas velocity. These maps can be used to predict the behavior of SiO₂ formers in water-vapor-containing environments, such as combustion environments. Finally, these maps are used to explore the limits of the paralinear oxidation model for SiC and Si₃N₄.     

Grain-Boundary Viscosity of BaO-Doped SiC

Internal friction characterization of the viscosity of a residual SiO₂/BaO glass, segregated to grain boundaries of polycrystalline SiC, is presented. The anelastic relaxation peak of internal friction, arising from viscous slip along grain boundaries wetted by a glass phase, is analyzed. Two SiC polycrystals, containing SiO₂/BaO glasses with different compositions, are studied and compared with a SiC polycrystal containing only pure SiO₂. The internal friction peak is first analyzed with respect to its shift upon frequency change. This analysis allows quantitative assessment of both the intrinsic viscosity and the activation energy for viscous flow of the grain-boundary phase. Both parameters markedly decrease with increasing amounts of BaO dopant, which is consistent with data reported in the literature on SiO₂ and SiO₂/BaO bulk glasses with the same nominal composition. Analysis of the peak morphology is also attempted, considering the evolution of peak width while varying the grain-boundary glass composition. Moreover, the role of microstructural parameters, such as the distributions of grain size and grain-boundary angles, on the broadening of the internal friction peak is addressed, and a procedure is proposed that allows quantitative evaluation of the activation energy for viscous flow of intergranular glass merely from the width of the internal friction peak.     

Fabrication of Silicon Carbide-Mullite Composite by Melt Infiltration

The melt infiltration method was used to fabricate a SiC-mullite composite at high temperature. Mullite was successfully obtained from a SiO₂ and Al₂O₃ powder mixture by melting above 1830°C in a BN crucible with a lid. When infiltrated into a porous SiC preform, the mullite significantly reacted with SiC to form gaseous SiO and CO, even at the lowest investigated temperature of 1830°C, consuming SiO₂ and leaving Al₂O₃ and silicon phases in the sample. The relevant reactions were studied in detail. A closed system was adopted to suppress the reaction, and a dense composite was successfully obtained.     

Porous 2H-Silicon Carbide Ceramics Fabricated by Carbothermal Reaction between Silicon Nitride and Carbon

Porous SiC ceramics were synthesized by sintering pressed and pressed/CIPed powder compacts of α-Si₃N₄, carbon (Si₃N₄:C = 1:3 mol as ratio), and sintering aids, at 1600°C for few hours to achieve a reaction, and subsequently sintering at a temperature range of 1750°–1900°C, in an argon atmosphere. High porosities from 45%–65% were achieved by low shrinkage with large weight loss. Formation of pure 2H-SiC phase via a reaction between Si₃N₄ and carbon can be demonstrated by X-ray diffractometry. The resultant porous SiC samples were characterized by SiC grain microstructures, pore-size distribution, and flexural strength. This method has the advantage of fabricating high-porous SiC ceramics with fine microstructure and good properties at a relatively low temperature.     

Experimental Design Applied to Silicon Carbide Sintering

Silicon carbide is a promising structural ceramic used as abrasives and applied in metallurgical components, due to its low density, high hardness, and excellent mechanical properties. The composition and content of the additive can control liquid-phase sintering of SiC. Compositions based on the SiO₂–Al₂O₃–RE₂O₃ system (RE = rare earth) have been largely used to promote silicon carbide densification, but most studies are not systematically presented. The aim of this work is to study the effect of several oxide additives in the SiO₂–Al₂O₃–Y₂O₃ system on the densification of silicon carbide using experimental design. This technique seems to be effective in optimizing the values of maximum density with minimum weight loss.     

Role of Carbon in the Sintering of Boron-Doped Silicon Carbide

The effect of carbon on the sintering of boron-doped SiC was studied. The free carbon present in the green compact was found to react with the SiO₂ covering the surfaces of the SiC particles; however, even if no carbon was added, the surface SiO₂ reacted with the SiC itself at a slightly higher temperature. This latter reaction was associated with the onset of substantial pore growth in the shrinking green body, which, as the pores continued to grow at higher temperatures, prevented complete densification. Therefore, the reaction of the SiC with the SiO₂ may have led to the fracture of interparticle contacts, resulting in the onset of coarsening. Thus, the role of the carbon was to prevent reaction between the SiC and the surface SiO₂, by removing the SiO₂ at a temperature below that at which this reaction could occur.     

Corrosion of Mullite by Molten Salts

The interaction of molten salts of different Na₂O activities and mullite is examined with furnace and burner tests. The more-acidic molten salts form small amounts of Al₂O₃; the more-basic molten salts form various Na₂O–Al₂O₃–SiO₂ compounds. The results are interpreted using the Na₂O–Al₂O₃–SiO₂ ternary phase diagram, and some possible diffusion paths are discussed. The generally higher melting points of Na₂O–Al₂O₃–SiO₂ compounds lead to better behavior of mullite in molten salts, as compared to SiO₂-protected ceramics such as SiC. Mullite-coated SiC is discussed, and the corrosion behavior is evaluated.     

Reactions of Silicon Carbide and Silicon(IV) Oxide at Elevated Temperatures

The reaction between SiC and SiO₂ has been studied in the temperature range 1400–1600 K. A Knudsen cell in conjunction with a vacuum microbalance and a high-temperature mass spectrometer was used for this study. Two systems were studied—1:1 SiC (2 wt% excess carbon) and SiO₂; and 1:1:1 SiC, carbon, and SiO₂. In both cases the excess carbon forms additional SiC within the Knudsen cell and adjusts to the direct reaction of stoichiometric SiC and SiO₂ to form SiO( g ) and CO( g ) in approximately a 3:1 ratio. These results are interpreted in terms of the SiC-O stability diagram.     

Strength of Nicalon Silicon Carbide Fibers Exposed to High-Temperature Gaseous Environments

The effects of exposures to high-temperature gaseous atmospheres on the strength of Nicalon SiC fibers were investigated. The exposure conditions were as follows: (1) H₂ with various P _H2O for 10 h at 1000° and 1200°C, and (2) air for 2 to 100 h at 800° to 1400°C. Individual fibers were tested in tension following each exposure. The strengths of the fibers were strongly influenced by the exposure atmosphere and temperature, but less affected by time at temperature. When exposed in air, a SiO₂ layer was formed on the surface, minimizing the degradation of strength. However, this beneficial effect was negated under conditions in which the SiO₂ layer became too thick. The most severe degradation resulted from exposure to a reducing atmosphere, presumably due to the reduction of SiO₂ inherent in the fibers.     

Characterization and Sintering of a Porous Glass-Ceramic in the System Na2O-B2O3-Sc2O3

Clear glasses which included droplet-like microphases were produced when SiO₂ in sodium borosilicate glasses was replaced by Sc₂O₃. Phase separation and/or crystallization occurred after heat treatment. The porous skeleton of leached glasses consisted of hexagonal ScBO₃. The specific surface areas and pore radii are comparable to those of porous SiO₂ glass. The sintering temperature of porous Sc-based material is higher than that of porous SiO₂. Alumina contamination influenced the structure of the porous material.     

Paralinear Oxidation of CVD SiC in Simulated Fuel-Rich Combustion

The oxidation kinetics of CVD SiC were measured by thermogravimetric analysis (TGA) in a 4H₂·12H₂O·10CO·7CO₂·67N₂ gas mixture flowing at 0.44 cm/s at temperatures between 1300° and 1450°C in fused quartz furnace tubes at 1 atm total pressure. The SiC was oxidized to form solid SiO₂. At ≥1350°C, the SiO₂ was in turn volatilized. Volatilization kinetics were consistent with the thermodynamic predictions based on SiO formation. These two simultaneous reactions resulted in overall paralinear kinetics. A curve fitting technique was used to determine the linear and parabolic rate constants from the paralinear kinetic data. Volatilization of the protective SiO₂ scale resulted in accelerated consumption of SiC. Recession rates under conditions more representative of actual combustors were estimated from the furnace data.