Synthesis of Titanium Silicon Carbide

Synthesis of bulk titanium silicon carbide (Ti₃SiC₂) from the elemental Ti, Si, and C powders has been accomplished for the first time, using the arc-melting and annealing route. The effects of various parameters on the phase purity of the Ti₃SiC₂ have been examined, including the starting composition of the powders, compaction technique, arc-melting of the samples, and temperature and time of anneal. The best bulk samples, containing about 2 vol% TiC as the second phase, were made from Si-deficient and C-rich starting compositions. Based on electron probe microanalysis data from a number of bulk samples, it appears that Ti₃SiC₂ exists over a range of compositions; the Ti-Si-C ternary section has been modified to reflect this. The purest samples of the ternary phase were obtained by leaching powders of silicide-containing samples in diluted HF, and contained over99vol%Ti₃SiC₂.     

Low-Temperature Synthesis of Aluminum Silicon Carbide Using Ultrafine Aluminum Carbide and Silicon Carbide Powders

The conditions for preparing α-aluminum silicon carbide (α-Al₄SiC₄) were examined by heating stoichiometric mixtures of ultrafine A1₄C₃ and SiC powders with sizes of <0.1 μm at and below 1600°C. The starting A1₄C₃ powder was obtained by the pyrolysis of trimiethylaluminum; the starting SiC powders were obtained by the pyrolyses of triethylsilane (3ES), tetraethylsilane (4ES), and hexamethyldisilane (6MDS). The reactivity of SiC with Al₄C₃ to form α-Al₄SiC₄ varies according to the kind of starting alkylsilane: 3ES > 4ES > 6MDS. The reaction of 3ES-derived SiC with A1₄C₃ produced α-Al₄SiC₄ at temperatures as low as 1400°C for 240 min, regardless of the presence of A1₄C₃ (trace). Only α-Al₄SiC₄ was formed at and above 1500°C for 60 min; the crystal growth was appreciable.     

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.     

Silicon Carbide Powder Synthesis from Silicon Monoxide and Methane

SiC was synthesized via the gas-phase reaction between SiO and CH₄ at 1500° and 1560°C in a tubular flow reactor. SiO vapor was generated from equimolar powder mixtures of Si and SiO₂ in the reactor while CH₄ was externally supplied. Products of different morphologies were collected at different longitudinal locations: whiskers, crystal aggregates, scale, and powder. The total yield of SiC, based on the amount of SiO generated, reached as high as 99%, of which 25–46% by mass was fine powder with sizes ranging from 60 to 300 nm.     

Combustion Synthesis of Silicon Nitride-Silicon Carbide Composites

The feasibility of synthesizing silicon nitride-silicon carbide composites by self-propagating high-temperature reactions is demonstrated. Various mixtures of silicon, silicon nitride, and carbon powders were ignited under a nitrogen pressure of 30 atm (∼ 3 MPa), to produce a wide composition range of Si₃N₄-SiC powder products. Products containing up to 17 vol% of SiC, after being attrition milled, could be hot-pressed to full density under 1700°C, 3000 psi (∼ 21 MPa) with 4 wt% of Y₂O₃. The microhardness and fracture toughness of these composites were superior to those of the pure β-Si₃N₄ matrix material and compared very well with the properties of "traditionally" prepared composites.     

Microwave Synthesis of Ultrafine Silicon Carbide Whiskers

Silicon carbide (SiC) whiskers were formed by microwave and conventional heating in the present study. SiC whiskers with diameters in the nanometer range were synthesized by reducing silica (SiO₂) with various forms of carbon in a microwave furnace. Ultrafine SiO₂ powder, char, phenolformaldehyde resin, and carbon black were used as starting materials. The effects of temperature and type of heating on the production of SiC whiskers, as well as the role of carbon, are discussed here.     

Silicon Carbide Platelet/Silicon Carbide Composites

α-silicon carbide platelet/β-silicon carbide composites have been produced in which the individual platelets were coated with an aluminum oxide layer. Hot-pressed composites showed a fracture toughness as high as 7.2 MPa·m^1/2. The experiments indicated that the significant increase in fracture toughness is mainly the result of crack deflection and accompanying platelet pullout. The coating on the platelets also served to prevent the platelets from acting as nucleation sites for the α- to β-phase transformation, so that the advantageous microstructure remains preserved during high-temperature processing.     

In Situ Synthesis of Silicon Carbide Whiskers from Silicon Nitride Powders

Silicon carbide whiskers were synthesized in situ by direct carbothermal reduction of silicon nitride with graphite in an argon atmosphere. Phase evolution study reveals that the formation of β-SiC was initiated at 1400° to 1450°C; above 1650°C silicon was formed when carbon was deficient. Nevertheless, Si₃N₄ could be completely converted to SiC with molar ratio Si₃N₄:C = 1:3 at 1650°C. The morphology of the SiC whiskers is needlelike, with lengths and diameters changing with temperature. SiC fibers were produced on the surface of the sample fired at 1550°C with an average diameter of 0.3 μm. No catalyst was used in the syntheses, which minimizes the amount of impurities in the final products. A reaction mechanism involving the decomposition of silicon nitride has been proposed.     

Combustion Synthesis of Silicon Carbide in Nitrogen Atmosphere

Fine SiC powders were synthesized by burning the mixed reactionts Si and C in a nitrogen atmosphere of 3 to 10 MPa. The exothermic synthesis reaction propagated spontaneously after igniting the reactants at room temperature. The SiC powders obtained had a uniform size distribution of about 0.2 μm. The combustion velocity was 0.8 to 1.5 mm / s. The maximum temperature measured at the reaction was 2500 K, which was higher than the adiabatic combustion temperature of SiC, but slightly lower than the decomposition temperature of Si₃N₄ under nitrogen pressure.     

Synthesis and Characterization of Crystalline Silicon Carbide Nanoribbons

In this paper, a simple method to synthesize silicon carbide (SiC) nanoribbons is presented. Silicon powder and carbon black powder placed in a horizontal tube furnace were exposed to temperatures ranging from 1,250 to 1,500°C for 5–12 h in an argon atmosphere at atmospheric pressure. The resulting SiC nanoribbons were tens to hundreds of microns in length, a few microns in width and tens of nanometers in thickness. The nanoribbons were characterized with electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, Raman spectroscopy and X-ray photoelectron spectroscopy, and were found to be hexagonal wurtzite–type SiC (2H-SiC) with a growth direction of [10[`1]0] [10bar{1}0] . The influence of the synthesis conditions such as the reaction temperature, reaction duration and chamber pressure on the growth of the SiC nanomaterial was investigated. A vapor–solid reaction dominated nanoribbon growth mechanism was discussed.     

Silicon Carbide/Silicon and Silicon Carbide/Silicon Carbide Composites Produced by Chemical Vapor Infiltration

Composites of SiC/Si and SiC/SiC were prepared from single yarns of SiC. The use of carbon coatings on SiC yarn prevented the degradation normally observed when chemically vapor deposited Si is applied to SiC yarn. The strength, however, was not retained when the composite was heated at elevated temperatures in air. In contrast, the strength of a SiC/C/SiC composite was not reduced after this composite was heated at elevated temperatures, even when the fiber ends were exposed.     

Silicon Carbide Monofilament-Reinforced Silicon Nitride or Silicon Carbide Matrix Composites

SiC-monofilament-reinforced SiC or Si₃N₄ matrix composites were fabricated by hot-pressing, and their mechanical properties and effects of filaments and filament coating layers were studied. Relationships between frictional stress of filament/matrix interface and fracture toughness of SiC monofilament/Si₃N₄ matrix composites were also investigated. As a result, it was confirmed experimentally that in the case of composites fractured with filament pullout, the fracture toughness increased as the frictional stress increased. On the other hand, when frictional stress was too large (>about 80 MPa) for the filament to be pulled out, fracture toughnesses of the composites were almost the same and not so much improved over that of Si₃N₄ monolithic ceramics. The filament coating layers were found to have a significant effect on the frictional stress of the SiC monofilament/Si₃N₄ matrix interface and consequently the fracture toughness of the composites. Also the crack propagation behavior in the SiC monofilament/Si₃N₄ matrix composites was observed during flexural loading and cyclic loading tests by an in situ observation apparatus consisting of an SEM and a bending machine. The filament effect which obstructed crack propagation was clearly observed. Fatigue crack growth was not detected after 300 cyclic load applications.     

Detonation Synthesis and Crystal Structure of Six-Layer Silicon Carbide

Results of an x-ray study of a single crystal of silicon carbide SiC 6H formed from silicon dioxide and graphite upon detonation are presented. The structure is determined by direct methods and is then refined using the full-matrix least-squares method in anisotropic approximation on the basis of 312 reflections to R₁ = 0.0194.     

Carbothermal Synthesis of Boron Nitride Coatings on Silicon Carbide

Pure BN coatings have been synthesized on the surface of SiC powders and fibers by a novel carbothermal nitridation method. Three stages are involved in the process: first, formation of a carbon layer on the SiC by the extraction of Si with chlorine; second, infiltration of the resulting nanoporous carbide-derived carbon (CDC) coating by a saturated boric acid solution; and finally, nitridation in ammonia at atmospheric pressure to produce the pure BN coating. X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and electron energy loss spectroscopy (EELS) were used to characterize the phase, elemental composition, and surface morphology of the coatings. The intermediate carbon layer acts as a template for BN growth, facilitates the formation of BN, and prevents the degradation of SiC fibers during nitridation. The whole process is simple, cost-effective, and less toxic due to the use of H₃BO₃ and NH₃ as precursors at atmospheric pressure compared with most commonly used chemical vapor deposition (CVD) methods. Uniform BN coatings obtained by this method prevent the bridging of fibers in the tow. The coating of powders is possible, which cannot be achieved by conventional CVD methods.     

碳热还原合成碳化硅过程的数值模拟

为揭示碳化硅合成过程中能量及物质扩散机理,从而为碳化硅的提质增产奠定理论基础,采用数值模拟的方法对碳化硅合成过程中的温度场、压力场、气体流动规律进行模拟研究。结果表明,随着合成时间的延长,炉内热量呈辐射状向外扩散,合成炉内气体呈现三维多向流动特性,反应进行到24 h时CO气体流量达到最大,而此时由于炉底透气性差的原因,致使炉底部压力高于其余位置,最大可达1.525×101 k Pa,此时可加入少量木屑以增加炉底透气性来改善因压力过高所造成的喷炉事故。模拟结果得到了生产实践验证。     

Stress-Corrosion Cracking of Silicon Carbide Fiber/Silicon Carbide Composites

Ceramic-matrix composites are being developed to operate at elevated temperatures and in oxidizing environments. Considerable improvements have been made in the creep resistance of SiC fibers and, hence, in the high-temperature properties of SiC fiber/SiC (SiC_f/SiC) composites; however, more must be known about the stability of these materials in oxidizing environments before they are widely accepted. Experimental weight change and crack growth data support the conclusion that the oxygen-enhanced crack growth of SiC_f/SiC occurs by more than one mechanism, depending on the experimental conditions. These data suggest an oxidation embrittlement mechanism (OEM) at temperatures <1373 K and high oxygen pressures and an interphase removal mechanism (IRM) at temperatures of ≳700 K and low oxygen pressures. The OEM results from the reaction of oxygen with SiC to form a glass layer on the fiber or within the fiber–matrix interphase region. The fracture stress of the fiber is decreased if this layer is thicker than a critical value ( d > d _c) and the temperature below a critical value ( T < T _g), such that a sharp crack can be sustained in the layer. The IRM results from the oxidation of the interfacial layer and the resulting decrease of stress that is carried by the bridging fibers. Interphase removal contributes to subcritical crack growth by decreasing the fiber-bridging stresses and, hence, increasing the crack-tip stress. The IRM occurs over a wide range of temperatures for d < d _c and may occur at T > T _g for d > d _c. This paper summarizes the evidence for the existence of these two mechanisms and attempts to define the conditions for their operation.     

Pressure-Sintered Silicon Carbide

Silicon carbide was hot-pressed to uniform densities of the order of 98% of the theoretical density, with slight additions of aluminum and iron aiding in this densification. Other elements having some effect were lithium, calcium, chromium, zirconium, and boron. This dense silicon carbide had very high strength at high temperatures; for example, it had a modulus of rupture of 70,000 1b. per sq. in. at 2500°F.     

Preparation and Characterization of Aluminum-Doped Silicon Carbide by Combustion Synthesis

Al-doped β-SiC powders were synthesized via combustion reaction of the Si/C system in a 0.1 MPa nitrogen atmosphere, using polytetrafluoroethylene as the chemical activator and Al as the dopant. The β-SiC powders produced have fine spherical particles and narrow particle size distribution. The impurity phase of Al₂O₃ is generated and the doped β-SiC contains N component when Al content is up to 10%. The electric permittivities of β-SiC samples were determined in the frequency range of 8.2–12.4 GHz. Results show that the β-SiC doped with 10% Al has the highest real part ɛ' and imaginary part ɛ" of permittivity. The mechanism of dielectric loss by doping has been discussed.     

Laser Ablation Synthesis and Optical Characterization of Silicon Carbide Nanowires

Silicon carbide (SiC) nanowires were synthesized at 900°C by the laser ablation technique. The growth morphology, microstructure, and defects in SiC nanowires were characterized by scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM). The Raman scattering study indicated that the Raman peaks corresponding to the TO and LO phonon modes of the SiC nanowires had larger red shifts compared to those of bulk SiC material. The red shift, broadening peak, and the asymmetry of the Raman peak could be explained by the size confinement effect in the radial and growth directions. The growth mechanism of SiC nano-wires was discussed based on the vapor–liquid–solid reaction.