Growth mechanism of β-SiC nanowires in SiC reticulated porous ceramics

Polycarbosilane (PCS) was used as a precursor to prepare SiC reticulated porous ceramics (RPCs) with in situ growth of β-SiC nanowires at 1000–1300 °C. The nanowires in diameters of ∼50 nm exist on the surface of the strut and in the fracture surface of strut in SiC RPCs. High resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) indicate that the nanowire consists of a twinned β-SiC, which grows along the 〈1 1 1〉 direction. Field emission scanning electron microscopy (FESEM) and energy dispersive spectroscopy (EDS) reveal that β-SiC nanowire grows by the vapor–liquid–solid (VLS) process at low temperature. The morphologies of the nanowire formed at different temperatures testify the process. As the heat-treated temperature increased, the growth mechanism of the nanowire changes from VLS to vapor–solid (VS).     

Low-Temperature Fabrication of Porous β-SiC Ceramics in Sodium Vapor

β-silicon carbide (SiC) porous ceramics were synthesized from pelletized powder mixtures of silicon (Si) and fullerene or Si and amorphous carbon (carbon black) at 1000 K for 24 h in sodium (Na) vapor. The relative density of the ceramics was 29%–34% of the theoretical density of SiC. Scanning electron microscopic observation of the fracture surface showed that the ceramics prepared with fullerene were agglomerates of submicrometer-sized SiC particles and open spaces. The samples prepared with carbon black had a smooth fracture surface with cavities and voids. Using transmission electron microscopy, grains of over 250 nm and a diffuse electron diffraction ring pattern of β-SiC were observed for the sample prepared with fullerene, and grains of 10–20 nm with a β-SiC spot ring pattern for the sample prepared with carbon black. A surface area of 11–17 m²/g and a mesopore size distribution in the range of 2–10 nm were shown by a nitrogen adsorption technique. Energy-dispersive X-ray analysis detected 1–5 at.% of Na against Si on the fracture surface of the ceramics.     

Porous SiCnw/SiC ceramics with unidirectionally aligned channels produced by freeze-drying and chemical vapor infiltration

The current study introduces a methodology for the fabrication of porous silicon carbide nanowire/silicon carbide (SiC_nw/SiC) ceramics with macroscopic unidirectionally aligned channels and reports on their microstructural and mechanical properties. The material was produced by freezing of a water-based slurry of β-SiC nanowires (SiC_nw) with control of the ice growth direction. Pores were subsequently generated by sublimation of the columnar ice during freeze-drying. Chemical vapor infiltration (CVI) of SiC into the open pore network of the SiC_nw aerogel with unidirectionally aligned channels, resulted in the formation of highly porous SiC_nw/SiC ceramics which exhibited a unique microstructure as identified by scanning electron microscopy. The pore size distribution and the mechanical properties of the as-fabricated porous ceramics were examined by mercury intrusion porosimetry and three-point bending and compression tests, respectively, while phase composition was investigated through X-ray diffraction.     

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.     

Electron Microscopy of Defects in Epitaxical β-SiC Thin Films Grown on Silicon and Carbon {0001} Faces of α-SiC Substrates

Defects present in β-SiC thin films epitaxically grown on hexagonal 6 H α-SiC substrates via chemical vapor deposition have been characterized by transmission electron microscopy. These defects are different from those previously observed in β-SiC films grown on (100) silicon, which were predominantly stacking faults and microtwins. The most common defects in the films grown on α-SiC were large domains rotated 60° with respect to each other and were identified as double positioning boundaries. These boundaries are a special type of incoherent twin boundary. Differences observed in films grown on either the silicon or carbon face of the {0001}α-SiC are characterized as a function of the mechanism of formation of the defects and type of substrate used for growth.     

Microstructural Control for Strengthening of Silicon Carbide Ceramics

Fine-grained (<1 μm) silicon carbide ceramics with high strength were obtained by using ultrafine (∼90 nm) β-SiC starting powders and a seeding technique for microstructural control. The microstructures of the as-hot-pressed and annealed ceramics without α-SiC seeds consisted of fine, uniform, and equiaxed grains. In contrast, the annealed material with seeds had a uniform, anisotropic microstructure consisting of elongated grains, owing to the overgrowth of β-phase on α-seeds. The strength, the Weibull modulus, and the fracture toughness of fine-grained SiC ceramics increased with increasing grain size up to ∼1 μm. Such results suggested that a small amount of grain growth in the fine grained region (<1 μm) was beneficial for mechanical properties. The flexural strength and the fracture toughness of the annealed seeded materials were 835 MPa and 4.3 MPa·m^1/2, respectively.     

Effect of Annealing Conditions on Microstructural Development and Phase Transformation in Silicon Carbide

The effect of annealing with and without applied pressure on the microstructural development and phase transformation was investigated in fine-grained β-SiC ceramics containing α-SiC seeds. Materials annealed without pressure had a microstructure consisting of elongated grains, while materials annealed with pressure showed a duplex microstructure consisting of small matrix grains and some of elongated grains. However, annealing with pressure (25 MPa) was found to greatly retard phase transformation from β→α polytypes and inhibit grain growth. This change in lattice parameter suggests that the retardation of phase transformation and grain growth might be attributed to a reduced mass transport rate, which is the result of Al being introduced into the SiC by the annealing pressure.     

Intrinsic microstructures of silica-bonded porous nano-SiC ceramics

Silica-bonded porous SiC ceramics were fabricated using nano-β-SiC powder-carbon black template compacts by sintering in air at 600°C-1200°C. The intrinsic microstructures of the porous ceramics were characterized by high-resolution transmission electron microscopy, which led to the following observations: (a) a core (SiC)-shell (SiO₂) structure was formed, owing to the partial oxidation of nano-SiC particles during sintering; (b) a low-temperature (800°C) β-to-α polytypic phase transformation was observed, owing to the oxidation-induced residual thermal stresses; and (c) non-graphitic carbons were precipitated inside the SiC core, owing to the segregation of C atoms emitted at the strained SiC-SiO₂ interface.     

Microstructural Development of Silicon Carbide Containing Large Seed Grains

Fine (}0.1μm) β-SiC powders, with 3.3 wt% large (}0.44μm) α-SiC or β-SiC particles (seeds) added, were hot-pressed at 1750°C and then annealed at 1850°C to enhance grain growth. Microstructural development during annealing was investigated using image analysis. The introduction of larger seeds into β-SiC accelerated the grain growth of elongated large grains during annealing, in which no appreciable β→α phase transformation occurred. The growth of matrix grains in materials with β-SiC seeds was slower than that in materials with α-SiC seeds. The material with β-SiC seeds, which was annealed at 1850°C for 4 h, had a bimodal microstructure of small matrix grains and large elongated grains. In contrast, the material with α-SiC seeds, also annealed at 1850°C for 4 h, had a uniform microstructure consisting of elongated grains. The fracture toughnesses of the annealed materials with α-SiC and β-SiC seeds were 5.5 and 5.4 MPa·^1/2, respectively. Such results suggested that further optimization of microstructure should be possible with β-SiC seeds, because of the remnant driving force for grain growth caused by the bimodal microstructure.     

Comparison of Microwave Hybrid and Conventional Heating of Preceramic Polymers to Form Silicon Carbide and Silicon Oxycarbide Ceramics

Six different preceramic polymers were pyrolyzed via conventional and microwave hybrid heating; these polymers provide a range of carbon content and local atomic coordination. The products were compared with each other using X-ray diffractometry and transmission electron microscopy. Nanocrystalline β-SiC was the principal crystal phase detected, and the amount and size of the nanocrystals increased as the processing temperature increased. Differences were observed in the amount and size of the β-SiC nanocrystals and the graphitization of residual carbon between the microwave hybrid heating and the conventional oven heating of polycarbosilanes. Conventional heating of a high-carbon polysiloxane in an oven (in flowing argon) produced a greater amount of β-SiC from carbothermal reduction at high temperature. Microwave hybrid heating led to better β-SiC nanocrystal development for polyureasilazane.     

Characterization of Precursor-Derived Silicon-Carbon-Nitrogen Ceramics after Creep Testing

Precursor-derived Si-C-N ceramics after creep testing in air were characterized using X-ray diffractometry (XRD) and transmission electron microscopy (TEM). XRD analysis showed that the crept Si-C-N ceramics were covered by an α-cristobalite layer. TEM observations revealed that the precipitated nanocrystallites in the crept Si-C-N ceramics were β-SiC. Between α-cristobalite and crept Si-C-N ceramic, there was an intermediate zone in which Si₂N₂O nanocrystallites were distributed homogeneously. Moreover, Si₂N₂O nanocrystallites were often found covering the surface of nanosized gas channels in the crept Si-C-N ceramics, where no α-cristobalite phase was detected. Based on these observations, a two-step oxidation mechanism of Si-C-N ceramics during creep testing in air was proposed.     

Conversion of Oak to Cellular Silicon Carbide Ceramic by Gas-Phase Reaction with Silicon Monoxide

Oak has been converted to a porous biocarbon template by annealing in an inert atmosphere above 800°C. Subsequent infiltration with gaseous SiO at 1550–1600°C under flowing argon of atmospheric pressure finally resulted in the formation of a porous, cellular β-SiC ceramic. The conversion retains the biomorphic cellular morphology of oak tissue. While pores in the cell walls with a diameter less than ∼1 μm vanished, two distinct pore channel maxima representing tracheidal cells and large vessels remained in the SiC ceramic. Depending on the cellular morphology of different kinds of wood, e.g., strut thickness and pore size distribution, gas-phase conversion to single-phase β-SiC can be used to manufacture cellular ceramics with a wide range of pore channel diameters.     

β→α Transformation in Polycrystalline SiC: I, Microstructural Aspects

The effects of annealing conventionally sintered, hot-pressed, and reaction-sintered Sic have been investigated by optical and transmission electron microscopy. In conventionally sintered and hot-pressed bodies, "composite" grains consisting of α-SiC plates sandwiched between recrystallized β-SiC envelopes grow rapidly into the fie-grained β matrix; thickening of these α plates within the p envelopes is relatively sluggish. The existence of the composite plates can be explained by the extreme anisot-ropy of the interfacial energy between β- and α-Sic: {111)β(000l)_α interfaces have energies several orders of magnitude lower than random β/α interfaces. In reaction-sintered Sic, this anisotropy is manifested by rapid growth of α seeds along their basal planes into the epitaxial β reaction product; slow growth occurs perpendicular to the basal planes.     

High-Resolution Electron Microscopy Observations of Stacking Faults in β-SiC

Structural images of the stacking faults in β-SiC were obtained with a high-resolution electron microscope. Stacking faults initially present in β-SiC powder particles were eliminated as grain growth proceeded at elevated temperatures.     

Characterization of β-Silicon Carbide by Silicon-29 Solid-State NMR, Transmission Electron Microscopy, and Powder X-ray Diffraction

Increased interest in ceramic materials, particularly for high-temperature, high-stress applications, has created the need for rapid and reliable analytical techniques to monitor microcrystalline structure of commercial ceramic powders. A comparative evaluation of commercially available β-SiC powders is undertaken to analyze the potential of nuclear magnetic resonance (NMR) in the characterization of β-SiC powder. NMR provides an acceptable, rapid method for characterization of powders both during powder manufacturing as well as for powder analyses priror to sintering studies. The results of transmission electron microscopy and X-ray diffraction are correlated with the NMR spectra to explain some newly observed features in the NMR spectra of β-SiC powders and to illustrate the sensitivity of NMR to microcrystalline disorder.     

Effects of α-Sic versus β-Sic Starting Powders on Microstructure and Fracture Toughness of Sic Sintered with Al2O3-Y2O3 Additives

Dense Sic ceramics were obtained by pressureless sintering of β-Sic and α-Sic powders as starting materials using Al₂O₃-Y₂O₃ additives. The resulting microstructure depended highly on the polytypes of the starting SiC powders. The microstructure of SiC obtained from α-SiC powder was composed of equiaxed grains, whereas SiC obtained from α-SiC powder was composed of a platelike grain structure resulting from the grain growth associated with the β→α phase transformation of SiC during sintering. The fracture toughness for the sintered SiC using α-SiC powder increased slightly from 4.4 to 5.7 MPa.m^1/2 with holding time, that is, increased grain size. In the case of the sintered SiC using β-SiC powder, fracture toughness increased significantly from 4.5 to 8.3 MPa.m^1/2 with holding time. This improved fracture toughness was attributed to crack bridging and crack deflection by the platelike grains.     

Effect of β-to-α Phase Transformation on the Microstructural Development and Mechanical Properties of Fine-Grained Silicon Carbide Ceramics

Ultrafine β-SiC powders mixed with 7 wt% Al₂O_3, 2 wt% Y₂O₃, and 1.785 wt% CaCO₃ were hot-pressed and subsequently annealed in either the absence or the presence of applied pressure. Because the β-SiC to α-SiC phase transformation is dependent on annealing conditions, the novel processing technique of annealing under pressure can control this phase transformation, and, hence, the microstructures and mechanical properties of fine-grained liquid-phase-sintered SiC ceramics. In comparison to annealing without pressure, the application of pressure during annealing greatly suppressed the phase transformation from β-SiC to α-SiC. Materials annealed with pressure exhibited a fine microstructure with equiaxed grains when the phase transformation from β-SiC to α-SiC was <30 vol%, whereas materials annealed without pressure developed microstructures with elongated grains when phase transformation was >30 vol%. These results suggested that the precise control of phase transformation in SiC ceramics and their mechanical properties could be achieved through annealing with or without pressure.     

Chemistry and Structure of Beta Silicon Carbide Implanted with High-Dose Aluminum

Single-crystal β-SiC was implanted with aluminum to 3.90 × 10¹⁷ ions/cm² at 168 keV at 773 K. The resultant compositional and structural characteristics were studied by Rutherford backscattering spectrometry, Auger electron spectroscopy, X-ray photoelectron spectroscopy, and cross-sectional transmission electron microscopy. No aluminum redistribution was observed during implantation. The Si-to-C ratio exhibited a negative deviation from unity in the implanted region. The shift in the photoelectron binding energies indicated the formation of aluminum carbide. The studies by electron microscopy showed that the implanted region consists of slightly misoriented β-SiC crystals and textured crystalline aluminum carbide precipitates     

Atomic-Level Characterization of Cubic Silicon Carbide Surfaces—A Review

Scanning tunneling microscopy (STM) images of the cubic β-SiC (100) and β-SiC (111) surfaces are taken after annealing to 1200°C to eliminate the surface oxide. Low-energy electron diffraction (LEED) patterns of the β-SiC (111) surface show a 6 √ 3 × 6 √ 3 geometry, while STM images show a 6 × 6 geometry. Contrast reversal is observed as tunneling voltage bias is reversed. Spectroscopic I/V measurements indicate the presence of a graphite layer on the top surface. A model of the surface is proposed where an incommensurate graphite monolayer is grown over a (1 × 1) Si-terminated β-SiC (111) surface. This model helps to explain the discrepancy between the 6 √ 3 × 6 √ 3 LEED pattern and the 6 × 6 geometry observed in STM images. Charge transfer between certain carbon atoms and silicon atoms gives rise to the 6 × 6 geometry and the contrast reversal.     

Growing SiC Nanowires on Tyranno-SA SiC Fibers

A new in situ process for growing SiC nanowires on Tyranno-SA SiC fibers (2-D, plain-woven) was developed using the thermal decomposition of methyltrichlorosilane in hydrogen. The process was performed using a chemical vapor infiltration system. β-SiC nanowires ∼100-nm thick and several tens of micrometers long were successfully synthesized on the fibers. The growing of the SiC nanowires suggests a conditions-dependent process.