Preparation of silicon carbide powders by chemical vapour deposition of the SiH4-CH4-H2 system

Chemical vapour deposition (CVD) of the SiH₄ + CH₄ + H₂ system was applied to synthesize-silicon carbide powders in the temperature range 1523 to 1673 K. The powders obtained at 1673 K were single-phase-SiC containing neither free silicon nor free carbon. The powders obtained below 1623 K were composite powders containing free silicon. The carburization ratio (SiC/(SiC + Si)) increased with increasing reaction temperature and total gas flow rate, and with decreasing reactant concentration. The average particle sizes measured by TEM ranged from 46 to 114nm, The particle size increased with the reaction temperature and gas concentration but decreased with gas flow rate. The-SiC particles obtained below 1623 K consisted of a silicon core and a-SiC shell, as opposed to the-SiC particles obtained at 1673 K which were hollow. Infrared absorption peaks were observed at 940 and 810 cm^–1 for particles containing a silicon core; whereas a single peak at about 830 cm^–1 with a shoulder at about 930 cm^–1 was observed for the-SiC hollow particles. The lattice parameter of-SiC having a carburization ratio lower than 70 wt%, was larger than that of bulk-SiC and decreased with the increasing carburization ratio. However, when the carburization ratio exceeded 70 wt%, the lattice parameter became approximately equal to that of bulk-SiC.     

Preparation of nanocrystal SiC powder by chemical vapour deposition

Nanosized silicon carbide powders of high purity and low oxygen content have been prepared by thermal chemical vapour deposition (CVD) of dimethyldichlorosilane at pyrolytic temperatures, 1100–1400 °C. The nanosized silicon carbide particles prepared at 1400 °C consist of small crystallites of -SiC arranged randomly in the particles. At pyrolytic temperature below 1300 °C, the particles consist of amorphous phase and -type SiC crystallites. The average particle size changed from 70 nm to 40 nm and the average size of the -SiC crystallite changed from 7.3 nm to 1.8 nm depending on the pyrolysis conditions. The C/Si molar ratios of the product powders changed from 0.5 to 1.07 with the CVD conditions. The near theoretical values of C/Si molar ratio of the product powders within 0.95–1.05 can be controlled by CVD conditions such as pyrolytic temperature and reactant concentration. Finally, the product powders were characterized by chemical analysis, X-ray diffraction, electron microscopy, and infrared spectroscopy.     

Strength and fracture toughness of in situ-toughened silicon carbide

Fine β-SiC powders either pure or with the addition of 1 wt % of α-SiC particles acting as a seeding medium, were hot-pressed at 1800 °C for 1 h using Y₂O₃ and Al₂O₃ as sintering aids and were subsequently annealed at 1900 °C for 2, 4 and 8 h. During the subsequent heat treatment, the β → α phase transformation of SiC produced a microstructure of “in situ composites” as a result of the growth of elongated large α-SiC grains. The introduction of α-SiC seeds into the β-SiC accelerated the grain growth of elongated large grains during annealing which led to a coarser microstructure. The sample strength values decreased as the grain size and fracture toughness continued to increase beyond the level where clusters of grains act as fracture origins. The average strength of the in situ-toughened SiC materials was in the range of 468–667 MPa at room temperature and 476–592 MPa at 900 °C. Typical fracture toughness values of 8 h annealed materials were 6.0 MPa m^1/2 for materials containing α-SiC seeds and 5.8 MPa m^1/2 for pure β-SiC samples. This revised version was published online in November 2006 with corrections to the Cover Date.     

Properties of reaction bonded silicon nitride obtained from slip cast preforms

Fabrication of silicon preforms of high green density (>1·2 g/cm³) by slip casting of silicon (in aqueous medium) has been studied. The nitridation product consists of 59–85% α-Si₃N₄, 7–22%β-Si₃N₄ and 7–23% Si₂N₂O phase. The amounts of un-nitrided silicon were negligible. The microstructure is either granular or consists of needle-like grains (α-Si₃N₄) and whiskers deposited in the large pores. MOR values of the specimens are almost constant up to 1000°C or 1400°C or show slight increase up to 1000°C or 1200°C. In some cases a little dip around 1200°C, then a sharp increase in MOR up to 1400°C was observed.K _ic values are almost constant up to 1000°C, and thereafter increase sharply. Pore size distribution, existence of Si₂N₂O phase and oxidation of RBSN at high temperatures have been considered for the explanation of the observed behaviour.     

Method for increasing <Emphasis Type="Italic">β</Emphasis>-SiC yield on solid state reaction of coal fly ash and activated carbon powder

A novel process for increasing β-SiC yield on solid state reaction of coal fly ash and micro powder activated carbon powder has been proposed. β-SiC powder was synthesized at temperature 1300°C for 2 h under vacuum condition with 1 l/min argon flow. Cycling synthesis process has been developed for increasing β-SiC yield on solid state reaction of coal fly ash and activated carbon powder. Synthesized products were analyzed by XRD with Cu-Kα radiation, FTIR spectrometer and SEM fitted with EDAX. The results show that the amount of relative β-SiC is increased with the number of cycling synthesis.     

KMg2AlSi4O12 phyllosiloxide as potential interphase material for ceramic matrix composites: Part 1 Chemical compatibility

KMg₂AlSi₄O₁₂ is a phyllosiloxide isostructural with phlogopite mica, but totally free of OH^- ions. It decomposes at ≈ 950 °C at atmospheric pressure but remains stable up to at least 1350 °C under high pressures. Its chemical compatibility with α-alumina, MgAl₂O₄ spinel, forsterite, β-SiC and borosilicate glass selected as representative of fibres and matrices in ceramic matrix composites (CMCs), has been assessed via annealing experiments on multilayers and particulate composites at 900–1200 °C. At T = 900 °C and P = 100 MPa, the phyllosiloxide is chemically stable with respect to all the ceramics. At higher temperatures, interdiffusion occurs with the formation of various reaction products. At T = 1050 °C and P = 2 GPa, the extent of the reaction zone is larger for both α-alumina and forsterite than for spinel and β-SiC, whereas at 1200 °C, the reactivity of the phyllosiloxide with all the ceramics becomes about the same. Borosilicate glass with a softening point lower than the decomposition onset of KMg₂AlSi₄O₁₂ at relatively low pressures seems to be an ideal model matrix material for assessing the potential of the phyllosiloxide as an interphase material in CMCs. This revised version was published online in November 2006 with corrections to the Cover Date.     

Infrared absorption ofβ-SiC particles prepared by chemical vapour deposition

Infrared absorption characteristics of-SiC particles prepared by chemical vapour deposition were studied. These particles were either solid or had a silicon core and/or were hollow. The solid particles exhibited a single absorption peak between the transverse optical frequency (_TO = 794 cm^–1) and the longitudinal optical frequency (_LO = 976 cm^–1) of-SiC. This absorption peak shifted to a lower frequency with increasing lattice parameter of-SiC and increasing free silicon content. The particles containing a silicon core and/or were hollow exhibited double absorption peaks close to _TO and _LO. The peak at the LO side shifted to a lower frequency and that at the TO side to a higher frequency with decreasing silicon core size and increasing hollow size. Using the calculations based on the effective medium theory assuming surface phonon mode, the relationship between the infrared absorption characteristics and microstructures of the-SiC particles are explained.     

Production of submicron SiC particles by d.c. thermal plasma: a systematic approach based on injection parameters

Aiming at producing high temperature structural ceramics, ultra-fine SiC powders were synthesized by the gas phase reaction of silicon tetrachloride with methane in a d.c. thermal plasma. The influence of parameters as the SiCl₄ feeding rate, C/Si and H₂/C molar ratios and internal pressure on the powder properties were investigated. The SiC powders were characterized by chemical analysis, Fourier transform infrared spectroscopy, X-ray diffraction and scanning electronic microscopy. The experimental set-up allows the production of β-SiC powders at a rate of 200 g h⁻¹ with particle size around 0.1 μm. The main impurities in the as-produced powder handled at ambient atmosphere are: oxygen (1.8–2.5%) and free carbon (3–4%). Interesting relationships were found between the SiCl₄ feeding rate and the H₂/C molar ratio and between the C/Si molar ratio and the internal pressure. The internal pressure plays a major role in controlling the particle size.     

Preparation of SiC-W2C nano-composite powders by chemical vapour deposition of the SiH4-CH4-WF6-H2 system

SiC-W₂C composite powders were prepared by chemical vapour deposition (CVD) using SiH₄ + CH₄ + WF₆ + H₂ as source gases at a temperature of 1673 K. X-ray diffraction, TEM observation and infrared absorption were used to characterize the structures of the powders. The prepared powders consisted of SiC-W₂C composite particles and hollow -SiC particles. The SiC-W₂C composite particles had a W₂C core and an SiC shell. The average particle diameters of the SiC-W₂C composite and hollow SiC particles increased from 18 to 30 nm and from 40 to 70 nm, respectively, with an increase of SiH₄ concentration. TEM and infrared spectrum analyses showed that the W₂C core diameter was unchanged (about 18 nm), while the SiC shell thickness varied from 1 to 6 nm with reaction conditions.     

Synthesis of β-SiC nanostructures via the carbothermal reduction of resorcinol–formaldehyde/SiO2 hybrid aerogels

The novel resorcinol–formaldehyde/SiO₂ (RF/SiO₂) hybrid aerogels were chosen to synthesize the cubic silicon carbide (β-SiC) nanostructures via a carbothermal reduction route. In this process, the in situ polymerized RF/SiO₂ aerogels were used as both the silicon and carbon sources. The morphologies and structures of SiC nanostructures were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and high-resolution transmission electron microscope (HRTEM) equipped with EDS. The effects of C/Si atomic ratios in RF/SiO₂ aerogels and heat treatment temperatures on the formation of SiC nanomaterials were investigated in detail. It was shown that β-SiC nanowhiskers with diameters of 50–150 nm and high crystallinity were obtained at the temperatures from 1400 to 1500 °C. The role of the interpenetrating network of RF/SiO₂ hybrid aerogels in the carbothermal reduction was discussed and a possible mechanism was proposed.     

Evolution of crystallization and its effects on properties during pyrolysis of Si–Al–C–(O) precursor fibers

The high-temperature resistant Si–Al–C–(O) fibers were prepared through polymer-derived method using continuous polyaluminocarbosilane (PACS) fibers. Evolutions of the crystallization during the pyrolysis of the Si–Al–C–(O) precursor fibers were investigated by a series analysis. The structure of the fibers transforms from organic state to inorganic state and the crystalline phases appear during the pyrolysis. The β-SiC crystallite size increases when the temperature is higher than 1,300 °C. At the same time, the α-SiC appears. At 1,600 and 1,800 °C, the grain size of β-SiC of the fibers is 15.4 and 22.1 nm, respectively. The growth of β-SiC and the appearing of α-SiC have a great influence on the properties of the fibers. The change of the tensile strength of the pyrolysis products is divided into three stages with the growth of the crystal. The tensile strength of the Si-Al-C fibers is higher than 1.9 GPa.     

Preparation of nanosized β-tricalcium phosphate particles with Zn substitution

Nanosized β-ZnTCP powders with different Zn contents were prepared through coprecipitation of ACP out of the CaCl₂-ZnCl₂-Na₃PO₄-PEG system, and calcination of the ACP precursor at 800 °C for 3 h. The characterizations of the products showed that the products belong to β-TCP phase, and the particles sizes of them are about 300 nm, smaller than that of β-TCP (500 nm). Both the Zn_2p binding energy and lattice parameter variations of β-TCP evidenced that Zn had substituted for Ca in the lattice. Such nanosized β-ZnTCP powders could be used as bone repair materials with desired and sustained release of Zn.     

Manufacturing of cellular β-SiAlON/β-SiC composite ceramics from cardboard

Light-weight, cellular β-SiAlON/SiC ceramics were produced via dip-coating of an Al/Si-powder containing preceramic polymer slurry into corrugated cardboard. The coated cardboard preforms were pyrolyzed in Ar-atmosphere at 1200°C, where the cellulose fibres decomposed into carbon. Simultaneously the Al/Si melt infiltrated into the porous carbon and formed β-SiC. Subsequent nitridation at temperatures between 1200–1530°C resulted in the formation of a β-SiC-containing composite. Different pre-oxidation treatment resulted in a variation of the oxygen content in the solid solution phase (z = 0.6–1.2).     

Preparation of nanosized silicon carbide powders by chemical vapor deposition at low temperatures

Liquid carbosilane was synthesized and analyzed by infrared (IR) and H-NMR (nuclear magnetic resonance) spectroscopy. Silicon carbide (SiC) powders were prepared by chemical vapor deposition (CVD) at 850°C and 900°C from liquid carbosilanes. The product powders were characterized by IR spectroscopy, X-ray diffractometry (XRD) and scanning electron microscopy (SEM). Results show that liquid carbosilane synthesized was the mixture of several oligomers that had a Si-C backbone. The powders prepared at 850°C contain some organic segments, and those prepared at 900°C are pure nanosized SiC powders, which are partly crystallized, the size of which is about 50–70 nm. Translated from Journal of Functional Materials and Devices, 2006, 12(5): 447–450 (in Chinese)     

Crystalline plate-like SiO2 precipitates in silicon and their relation with new donors

Czochralski grown silicon annealed at 750° C has been investigated with high-resolution electron microscopy, Hall effect and infrared measurement. Crystalline plate-like precipitates were observed and identified asβ-cristobalite. The structure of the coherent interface of the new phase and its connection with the origin of the new donor are discussed.     

Composite bone substitute materials based on β-tricalcium phosphate and magnesium-containing sol–gel derived bioactive glass

In the present study, bioceramic composites with improved mechanical and biological properties were synthesized by sintering mixtures of β-tricalcium phosphate and SiO₂–CaO–MgO–P₂O₅ sol–gel derived bioactive glass at 1000–1200°C. The physical, mechanical, structural and biological properties of the composites were evaluated by appropriate experiments such as microhardness, bending strength, XRD, SEM and MTT. The results showed that 1000 and 1100°C were not appropriate temperatures for sintering the composites and in contrast, the microhardness, bending strength and bulk density significantly increased by increasing in quantity of bioglass phase when the samples were sintered at 1200°C. No significant difference was found between the fracture toughness of the composites and pure β-tricalcium phosphate. β-tricalcium phosphate was structurally stable up to 1200°C and did not transform to its alpha form even in the presence of the bioglass phase but migration of magnesium cations from the glass composition into its lattice structure was found by right-shift in XRD patterns, especially when the composite contained higher amount of bioglass component. Calcium silicate was also crystallized in the composition of the composites, which was more detectable in higher sintering temperatures. The results of the MTT test showed that proliferation of human osteosarcoma cells on the composites was considerably better than that of pure β-TCP.     

Conversion of polycarbosilane (PCS) to SiC-based ceramic Part II Pyrolysis and characterisation

The conversion to ceramic of a commercial polycarbosilane (PCS) under various pyrolysis conditions has been investigated. The products of pyrolysis have been characterised by solid state ²⁹Si and ¹³C NMR spectroscopy and X-ray diffraction (XRD). Some of the phases identified in the present study were found to differ from those reported previously, particularly in the earlier literature. Oxidation-cured PCS, when pyrolyzed up to 1400 °C in argon, generally produced silicon oxycarbide (SiO _x C _y ) as the second major phase with -SiC as the major phase, and smaller amounts of free carbon. With increasing temperature above 1200 °C, the silicon oxycarbide phase decomposed to give -SiC. Silica (SiO₂) was also found to evolve from this silicon oxycarbide phase. Loss of some of the silica, probably by reaction with carbon, was found at 1400 °C, possibly yielding SiO, CO and SiC. At 1500 °C, crystalline -cristobalite was found as a minor phase with -SiC as the major phase and a lower amount of free carbon. Pyrolysis in vacuum leads to production and crystallization of -SiC at a lower temperature than required if pyrolyzed in argon flow. After pyrolysis at 1600 ° in vacuum, the cured PCS converted to almost stoichiometric -SiC.     

Microstructures and high temperature oxidation resistance of alloys from Nb–Cr–Si system

Oxidation behavior of Nb–30Si–(10,20)Cr alloys have been evaluated in air from 700 to 1400 °C by heating for 24 h and furnace cooling them. The lower weight gain per unit area has been observed for 20Cr alloy at 1200, 1300, and 1400 °C. Pesting has been observed at lower temperatures (700, 800, 900 °C). Analysis indicates that the powder formation at 900, 100, 1100 °C may be associated with β form of Nb₂O₅ (base centered monoclinic form). However the m-monoclinic form of Nb₂O₅ evolves at temperatures above 900 °C while o-orthorhombic Nb₂O₅ forms at below this temperature. The phases in the alloys have been calculated using the Pandat^TM software program at different temperatures using calculated Nb–Cr–Si phase diagrams.     

Crystallization and microstructural evolution process from the mechanically alloyed amorphous SiBCN powder to the hot-pressed nano SiC/BN(C) ceramic

The mechanically alloyed amorphous SiBCN powders were hot pressed at 1500, 1600, 1700, 1800, and 1900 °C under a pressure of 80 MPa in the nitrogen atmosphere for 30 min. The crystallization, the microstructural evolution, and the properties of the prepared ceramics were carefully studied by XRD, TEM, HRTEM, and property testing. Results show that the crystallization of β-SiC, turbostratic BN(C), and α-SiC in the amorphous matrix starts at about 1500, 1600, and 1700 °C, respectively. When the powder is hot pressed at the temperatures higher than 1700 °C, the prepared ceramics always consist of nano β-SiC, α-SiC, turbostratic BN(C), and amorphous body. With the increase of the sintering temperature, the ceramic crystallinity becomes higher, the grains get larger, and the amorphous content becomes lower. At the temperatures lower than 1800 °C, the bulk density, the relative density, the flexural strength, the Young’s modulus, and the fracture toughness of the prepared ceramics show persistent but insignificant increase. However, when the ceramic is sintered at 1,900 °C, these properties are rapidly improving to 2.6 g/cm³, 91.8 %, 331.0 MPa, 139.4 GPa, and 2.8 MPa m^1/2.     

CVD silicon carbide electric heaters

This paper describes the growth of tubular polycrystalline 3C-SiC samples by chemical vapor deposition (CVD). The use of propionitrile as a precursor for nitrogen doping ensures the growth of polycrystalline 3C-SiC layers with a 1000°C resistivity of 0.1–0.2 Ω cm and zero temperature coefficient of resistance. Such 3C-SiC tubes can be used as silicon carbide electric heaters.