Nonequiaxial Grain Growth and Polytype Transformation of Sintered α-Silicon Carbide and β-Silicon Carbide

α(6 H )- and β(3 C )-SiC powders were sintered with the addition of AlB₂ and carbon. α-SiC powder could be densified to ∼98% of the theoretical density over a wide range of temperatures from 1900° to 2150°C and with the additives of 0.67–2.7 mass% of AlB₂ and 2.0 mass% of carbon. Sintering of the β-SiC powder required a temperature of >2000°C for densification with these additives. Grains in the α-SiC specimens grew gradually from spherical-shaped to plate-shaped grains at 2000°C; the 6 H polytype transformed mainly to 4 H . On the other hand, grains in the β-SiC largely grew at >2000°C; the 3 C polytype transformed to 4 H , 6 H , and 15 R . The stacking faults introduced in grains were denser in β-SiC than in α-SiC. The rapid grain growth in the β-SiC specimen was attributed to polytype transformation from the unstable 3 C polytype at the sintering temperature.     

Densification and Properties of α-Silicon Carbide

Densification of a-Sic powders with no premixed sintering aids (type 1) and with premixed B and C (type 2) was investigated by sintering them at 2150° to 2200°C for 30 min. Flexure strengths, Weibull moduli, and fracture flaws were characterized for type 2 α-SiC only. The results were compared with those for a state-of-the-art sintered a-Sic material.     

Microstructural Analysis of Liquid-Phase-Sintered β-Silicon Carbide

The microstructures of fine-grained β-SiC materials with α-SiC seeds annealed either with or without uniaxial pressure at 1900°C for 4 h in an argon atmosphere were investigated using analytical electron microscopy and high-resolution electron microscopy (HREM). An applied annealing pressure can greatly retard phase transformation and grain growth. The material annealed with pressure consisted of fine grains with β-SiC as a major phase. In contrast, the microstructure in the material annealed without pressure consisted of elongated grains with half α-SiC. Energy-dispersive X-ray analysis showed no differences in the amount of segregation of aluminum and oxygen atoms at grain boundaries, but did show a significant difference in the segregation of yttrium atoms at grain boundaries along SiC grains for the two materials. The increased segregation of yttrium ions at grain boundaries caused by the applied pressure might be the reason for the retarded phase transformation and grain growth. HREM showed a thin secondary phase of 1 nm at the grain boundary interface for both materials. The development of a composite grain consisting of a mixture of β/α polytypes during annealing was a feature common to both materials. The possible mechanisms for grain growth and phase transformation are discussed.     

Thermoelastic Micromechanical Stresses Associated with a Large α-Silicon Carbide Grain in a Polycrystalline β-Silicon Carbide Matrix

The thermoelastic micromechanical stresses associated with a single large hexagonal α-SiC grain within a fine-grain-size cubic (3C) β-SiC matrix were calculated. The naturally occurring residual stresses which are created during cooling from the processing temperatures and the effects of superimposed applied external stresses are both considered. A significant effect of the shape or geometry of the α-SiC grain is revealed, with the largest residual stresses associated with the naturally occurring tabular or platelet structure. The stresses are compared with the published strength results for these materials, which suggests that the residual stresses assume a significant role in the strength reduction that is observed.     

Plasma-Induced Morphological Changes in α-Silicon Carbide

Significant alterations in the surface morphology of α-silicon carbide powders have been observed after exposure to a low-temperature Ar plasma. Surface alterations were observed in 3 min at 1900°C and 30 min at 1600°C. Powders heated with plasma exposure were characterized by contact development and particle rounding whereas without the plasma substantial faceting was observed at higher temperatures.     

Sintering and Microstructure Formation of β-Silicon Carbide

The effect of additions of B, Al, and B + Al on the pressureless sintering of β-Sic was examined. The influence of the sintering atmosphere and heating schedule on densification behavior, polytype transformation, and microstructure development was also studied. High densities were obtained at 1940°C by the simultaneous addition of B and Al. The decrease in the sintering temperature is attributed to the presence of a liquid phase which results in the formation of platelets (up to 200 # in size) of an α-polytype, predominantly 4H and 6H. Polytype transformation and exaggerated grain growth could be prevented by annealing the compact at 1650° to 18500°C for 0.5 to 1 h. This procedure results in a better redistribution of the sintering aids, giving a fine-grained microstructure, constituted primarily of the cubic 3C polytype.     

Elevated-Temperature Fracture Resistance of a Sintered α-Silicon Carbide

The fracture toughness of a dense, sintered commercial α-silicon carbide was determined for temperatures from 20° to 1400°C using both straight- and chevron-notched test specimens and also controlled-surface-microflaw specimens, all in three-point bending. The flexural strengths were also measured for the same range of temperatures and the trend is compared with that of the toughness. Measurements from this study are discussed and also compared with other results in the literature. Analysis reveals the importance of contrasting sharp crack and blunt crack techniques and also the need for addressing the microhardness indentation method separately. It is concluded that the fracture toughness of this silicon carbide is about 3 MPa · m½ and that the crack growth resistance is characterized by a flat R -curve behavior, both of which are independent of temperature from 20° to 1400°C.     

Formation of Carbide-Derived Carbon on β-Silicon Carbide Whiskers

Carbon was synthesized on β-SiC whiskers by extraction of Si atoms from SiC. In this study, three different elevated temperature extraction methods were used to remove Si atoms from SiC: treatments in either Cl₂ or HCl and vacuum decomposition. In all chlorination experiments and vacuum treatment at 1700°C, carbon preserved the original shape of SiC whiskers. At higher temperatures (2000°C), vacuum decomposition led to a distortion in the shape of the whiskers. High-resolution transmission electron microscopy and Raman spectroscopy showed that the structure of carbide-derived carbon depends on the Si extraction method and the process parameters. Chlorination of SiC resulted in the formation of mostly amorphous nanoporous carbon. High-temperature treatment of SiC in HCl environment produced fullerene-like structures, while high-temperature vacuum decomposition resulted in the formation of graphite. Transmission electron microscopy studies of the carbon coating thickness produced in Cl₂ at various chlorination times revealed linear reaction kinetics at 700°C. Raman studies showed that the carbon structure became more ordered with increasing chlorination temperature. The results obtained demonstrate that by using the silicon extraction technique, one can precisely control the thickness and morphology of the carbon coating.     

Side-Surface Structure of a Commercial β-Silicon Carbide Whisker

The side surfaces of a commercial β-SiC whisker were analyzed by calculating the surface energy and observing the microstructure of the whiskers. The results indicated that the side surfaces displayed a type of zigzag structure and were composed of {111}, {110}, and {100} crystal planes.     

Creep of 6H α-Silicon Carbide Single Crystals

The compressive creep behavior of single-crystal 6H α-SiC was measured for orientations parallel to and at 45° to [0001]. Deformation of the 45° orientation was dominated by basal slip. Steady-state creep rates above 10^-7/s were measured at temperatures as low as 800°C. An activation energy of 277 kJ/mol and a stress exponent of 3.32 were determined. Creep testing with applied stresses parallel to [0001] was performed at 1650°C to 1850°C, yielding a stress exponent and activation energy of 4.93 and 180 kJ/mol, respectively. The occurrence of basal slip in the [0001] specimens suggested that significant off-axis stresses were present during testing.     

Structural Analysis of Inclusions in β-Silicon Carbide Whiskers Grown from Rice Hulls

Microcrystalline inclusions in the core of β-SiC whiskers derived from the pyrolysis of rice hulls have been studied by transmission electron microscopy using conventional brightfield and dark-field imaging. The electron diffraction patterns from the whiskers show extra reflections arising from these inclusions. Dark-field images from these reflections are consistent with the presence of three different variants of inclusions, all of which are oriented with their [001] axes parallel to the heavily faulted [111] growth axis of the whiskers. A structural model for these inclusions is proposed which accounts satisfactorily for the extra reflections in the electron diffraction patterns.     

Sea-Salt Corrosion and Strength of a Sintered α-Silicon Carbide

A commercially available, sintered silicon carbide was exposed to a temperature of 982°C for up to 50 h in a burner rig pressurized to 500 kPa. Synthetic sea salt added to the flame (5 ppm) resulted in the deposition of sodium sulfate and formation of a sodium magnesium silicate corrosion product. A 16% reduction in room-temperature strength occurred after 5 h of exposure; this reduction was due to the formation of surface pits. Exposure for longer times resulted in continued strength reduction, up to 56% at 25 h. Samples exposed for 50 h were so degraded that mechanical tests could not be conducted. The strength after 25 h of exposure to a salt concentration of 2 ppm was similar to the as-received strength, whereas exposures to 10 ppm of salt resulted in strengths similar to that observed with 5 ppm of salt.     

Origin of Density Gradients in Sintered β-Silicon Carbide Parts

Sintered densities of β-silicon carbide compacts were observed to decrease as the thickness of the compact increased. The chemistry and density gradients of these compacts were analyzed, as well as the weight loss and the CO evolution during sintering. The sintering cycle was altered to include a vacuum hold between the temperatures of 1400° and 1700°C, which resulted in increased density. Depending on the temperature of the vacuum soak, densities of 98% could be achieved on tiles with a thickness greater than 2.5 cm. The density gradients within the compact were significantly reduced, but not totally eliminated. It is suggested that these gradients are due to the effect of microstructural coarsening which occurs simultaneously with CO evolution.     

Characterization of β-Silicon Carbide Powders Synthesized by the Carbothermal Reduction of Silicon Carbide Precursors

Boron-doped and nondoped ultrafine β-silicon carbide (β-SiC) powders were synthesized via the carbothermal reduction of SiC precursors at temperatures of 1773–1973 K. Although the reaction rate of carbothermal reduction was generally higher when a boron-doped precursor was used, the reaction rate for the boron-doped precursor was reduced considerably at 1873 K. For boron-doped and nondoped precursors, the reaction rates were almost the same. Powder characterization via transmission electron microscopy indicated that the suppression of the reaction rate for boron-doped precursor at 1873 K was due to the formation of a special coexistent system with two types of particle agglomerates. As expected, boron doping inhibited the particle growth in the synthesis of SiC powder.     

Reactions between α-Silicon Carbide Ceramic and Nickel or Iron

The interactions of very pure and practically 100% dense α-SiC with nickel and iron at 850°C were investigated. Large reaction zones, consisting of carbon and silicides of Ni and Fe, were examined by microprobe analysis. By means of marker experiments, the diffusion mechanisms were investigated: only Ni and Fe migrate through the reaction layer. Isothermal sections of the ternary phase diagrams Ni-Si-C and Fe-Si-C at 850°C are presented.     

Occurrence and Distribution of Boron-Conitaining Phases in Sintered ş-Silicon Carbide

A variety of optical and analytical instruments have been employed to observe and characterize the mlcrostructure and composition of the B-containing phases which occur in sintered α-SiC as a result of either their use as a nensification aid or that which evolves as a result of annealing well below the sintering temperatures. The former have been identified as B₄C containing a small amount of Si. The latirr occur as ∼20-nm precipitates which have also been tentatively identified as B₄C and are believed to contain trace quantities of Si. No B phase was observed on the SiC grain boundaries; furthermore, the precipitate formation was not enhanced by the application of stress.     

Synthesis of Spherical β-Silicon Carbide Particles by Ultrasonic Spray Pyrolysis

Fine agglomerate-free spherical β-SiC powder was synthesized from a dispersion of colloidal silica, saccharose, and boric acid, by means of an ultrasonic spray pyrolysis method. Droplets of 2.2 μm were formed with an aerosol generator, operated at 2.5 MHz, and carried into a reaction furnace at 900°C with argon. Spherical X-ray amorphous gel particles of 1.1 μm were obtained. β-SiC particles with a mean diameter of 0.79 μm and spherical shape resulted when the SiC gel precursor particles were heated at 1500°C in argon.     

Growth of Twinned β -Silicon Carbide Whiskers by the Vapor-Liquid-Solid Process

Whiskers of twinned SiC in the cubic form were produced by the vapor-liquid-solid process as a byproduct of the corrosion of silicon nitride. These whiskers were characterized and their properties related to their use in reinforced materials.     

Kinetics and Mechanisms of High-Temperature Creep in Silicon Carbide: III, Sintered α-Silicon Carbide

The operative and controlling mechanisms of steady-state creep in sintered α-SiC have been determined both from kinetic data within the ranges of temperature and constant compressive stress of 1670 to 2073 K and 138 to 414 MPa, respectively, and from the results of extensive TEM and other analytical analyses. Dislocations in glide bands, B₄C precipitates, and the interaction of these two entities were the dominant microstructural features of the crept material. The stress exponent increased from 1.44 to 1.71 with temperature; it was not a function of stress at a given temperature. The curves of In ɛ vs 1/ T showed a change in slope at 1920 ± 20 K. The respective activation energies below and above this temperature interval were 338 to 434 and 802 to 914 kJ/mol. A synthesis of all this information leads to the conclusion that the controlling creep mechanism at low temperatures is grain-boundary sliding accommodated by grain-boundary self-diffusion; at high temperatures, the controlling mechanism becomes grain-boundary sliding accommodated by lattice diffusion. The parallel mechanism of dislocation glide contributes increasingly to the total strain as the number/volume of precipitates declines as a result of progressive coalescence with increasing temperature.