Pressure-pulsed chemical vapour infiltration of pyrolytic carbon into porous carbon or two-dimensional-carbon/SiC particulate preforms from C6H6–H2–N2

Pyrolytic carbon was infiltrated into porous carbon or two-dimensionally woven carbon fibre (2D-C)/SiC particulate preforms using pressure-pulsed chemical vapour infiltration from C6H6 (3–16%)–H2–N2 at 1273–1373 K. Residual porosity of porous carbon decreased from 29 to 10% after 1×104 pulses at 1323 K, and that of 2D-C/SiC particulate preform decreased from 30 to 7.5% after 4×104 pulses at 1273 K. Flexural strength of 2D-C/SiC preform reached about 150 MPa.     

Reinforcement and antioxidizing of porous carbon by pulse CVI of SiC

In order to reinforce and antioxidize porous carbon, chemical vapour infiltration (CVI) of SiC was investigated using a repetitive cycle of evacuation of vessel and instantaneous source-gas filling. From a source gas of 5% CH₃SiCl₃-H₂, a temperature range of 1273 to 1373 K was considered to be suitable to infiltrate SiC into a deep level, and surface deposition was enhanced at above 1373 K which led to pore blockage. With 3000 pulses, flexural strength was improved from 35 to about 90 MPa. Several specimens were exposed to air at 1573 K for 1070h during which the specimens were cooled to room temperature between four and seven times. SiC felt was also obtained by oxidation of a carbon skelton after pulse CVI.     

Pressure-pulsed chemical vapour infiltration of TiN to SiC particulate preforms

SiC particulate preforms were infiltrated by TiN matrix from a gas mixture of TiCl₄ (5%), nitrogen (30%) and hydrogen using a repeating pressure pulse between 760 and about 1 torr. SiC particle sizes of 5 and 20 m were used. For matrix packing into deep level, optimum temperature was determined between 800 and 850 °C, and the maximum packing ratio reached 67% after 4 × 10⁴ pulses at 850 °C. The increase of TiCl⁴ concentration to 10% resulted in higher deposition rate and packing ratio. The decrease of nitrogen concentration led to slower deposition, that is, a similar effect to temperature lowering. The maximum flexural strength measured was 140 MPa.     

Pressure-pulsed chemical vapour infiltration of SiC into two-dimensional-Tyranno/SiC particulate preforms from SiCl4–CH4–H2

SiC was infiltrated in two-dimensionally woven Tyranno/SiC particulate preforms from SiCl₄–CH₄–H₂ using pressure-pulsed chemical vapour infiltration (PCVI) in the temperature range 1348–1423 K. Above 1373 K, only β-SiC was deposited, whereas, at 1348 K, Si codeposition was found. At 1423 K, a macrosurface film was formed in the early stage of PCVI. At 1373 K, residual porosity decreased from 30% to 7.5% irrespective of the sample size. Three point flexural strength increased with decreasing residual porosity and increasing fibre volume fraction in the sample. Flexural strength of the sample having 48% fibre volume fraction reached about 325 MPa after 5 × 10⁴ pulses of CVI at 1373 K. Inter-laminar shear strength of the sample obtained at 1373 K reached 40 MPa at 7 × 10⁴ pulses. This revised version was published online in November 2006 with corrections to the Cover Date.     

Pressure pulsed chemical vapour infiltration of SiC to two-dimensional-Tyranno/SiC-C preforms

Preforms of two-dimensional Tyranno fibre (SiC base) of 7×20×1.3 mm³ were chemically vapour infiltrated with SiC at 850–1050 °C from a gas mixture of CH₃SiCl₃ (6%)-H₂ using pressure pulses between below 0.3 kPa and 0.1 MPa. Above 900 °C, films grew on the macrosurface dominantly. At 850 °C, residual porosity decreased to about 10% after 10⁵ pulses, and three point flexural strength reached about 200 MPa. X-ray diffractograms (XRDs) on the surface showed the deposits to be -SiC only.     

Preparation of gas-permeable SiC shape by pressure-pulsed chemical vapour infiltration into carbonized cotton-cloth preforms

Carbonized cotton-fibre preforms were partially infiltrated with SiC by pressure-pulsed chemical vapour infiltration (CVI) from SiCl4–CH4–H2. Fibrous carbon/SiC of 10 mm dia. and 20 mm long having the porosity of 83% was obtained after 15 000 pulses at 1150°C. Pores of the sample after 10 000 pulses distributed below 100 m (average pore size, 30 m). Pressure drop of the sample after 15 000 pulses under the axial air-flow was 11 kPa at a face velocity of 1.1 m s-1. On the samples after 15 000 pulses, 15% of preform-carbon were lost within 5 h by air oxidation at 1000°C, and tensile strength along the axis reached 10 MPa, which was close to that before oxidation. In the case of the sample after 5000 pulses, tensile strength lowered significantly after oxidation, however, the strength was recovered by application of 4000 pulses of second CVI. © 1998 Chapman & Hall     

A wax-mold route to fabricate polymer-derived SiC scaffold

A wax-mold route was developed to fabricate phenolic resin-derived SiC scaffold. Firstly, a wax-mold with the desired structure of the scaffold was obtained. Then resin mixtures were poured into the mold. After curing and pyrolyzing, porous carbon preform was obtained. The wax-mold was removed through being melted during curing, and the pattern material could be recycled. Finally, the SiC scaffold was fabricated by infiltrating liquid silicon into the preform. The dimension shrinkage of SiC scaffold was between 1.3 and 3 % before/after infiltration, which was affected by the infiltrating temperature and the starting components in resin mixtures, and there is no distortion. When the preform with apparent porosity of 45.5% was employed, the flexural strength and the density of SiC scaffold were 445 MPa and 3.07 g/cm³, respectively.     

Pulsed chemical vapour infiltration of SiC to three-dimensional carbon fibre preforms

Three-dimensional carbon fibre preforms were infiltrated with silicon carbide from a gas system of CH₃SiCl₃-H₂ using a process of pressure pulsed chemical vapour infiltration. To infiltrate to a deep level, the temperature had to be lowered to 870–900°C, and the hold time per pulse below 1.0 s. Three-dimensional carbon fibre preforms partly filled with SiC fine powder were compared with those without filler. The weight of the preforms increased linearly with increasing number of pulses up to 10⁵ when no filler was present. However, the weight increase slowed down above 8×10⁴ pulses when the filler was used. Preforms with and without SiC filler showed three-point flexural strengths of 160 and 80 MPa after CVI of 10⁵ pulses, respectively. In order to improve the strength, a denser filling of SiC powder is necessary.     

Mechanical and microstructural properties of cordierite-bonded porous SiC ceramics processed by infiltration technique using various pore formers

Cordierite-bonded porous SiC ceramics were prepared by air sintering of cordierite sol infiltrated porous powder compacts of SiC with graphite and polymer microbeads as pore-forming agents. The effect of sintering temperature, type of pore former and its morphology on microstructure, mechanical strength, phase composition, porosity and pore size distribution pattern of porous SiC ceramics were investigated. Depending on type and size of pore former, the average pore diameter, porosities and flexural strength of the final ceramics sintered at 1400 °C varied in the range of ~ 7.6 to 10.1 µm, 34–49 vol% and 34–15 MPa, respectively. The strength–porosity relationship was explained by the minimum solid area (MSA) model. After mechanical stress was applied to the porous SiC ceramics, microstructures of fracture surface appeared without affecting dense struts of thickness ~ 2 to 10 µm showing restriction in crack propagation through interfacial zone of SiC particles. The effect of corrosion on oxide bond phases was investigated in strong acid and basic salt medium at 90 °C. The residual mechanical strength, SEM micrographs and EDX analyses were conducted on the corroded samples and explained the corrosion mechanisms.     

Pressure-pulsed chemical vapour infiltration of SiC to porous carbon from a gas system SiCl4-CH4-H2

SiC matrix was deposited into porous carbon from a gas system SiCl₄-CH₄-H₂ in the temperature range 900–1200 °C using pressure-pulsed chemical vapour infiltration (PCVI) process. At 1000 °C, silicon single phase, a mixed phase of (Si + SiC), and SiC single phase, were detected by X-ray diffractions for specimens obtained with the reaction time per pulse of 1, 2–3, and 5 s, respectively. At 1100 °C, SiC single phase was obtained with a reaction time of only 0.3s. Between 1050 and 1075 °C, deposition rate accelerated suddenly. The increase of SiCl₄ concentration increased the deposition rate linearly up to 4%–6%. The residual porosity decreased from 29% to 6% after 2×10⁴ pulses of CVI at 1100 °C, and the flexural strength was 110 MPa.     

Preparation and properties of 2D C/ZrB2-SiC ultra high temperature ceramic composites

Two-dimensional C/ZrB₂-SiC composites were fabricated by chemical vapor infiltration (CVI) process combined with slurry paste (SP) method. ZrB₂ was introduced in the matrix by stacking the pasted carbon cloth with ZrB₂-polycarbosilane slurry. After heat-treated at 900 °C, the stacked carbon cloth preform was infiltrated SiC by CVI process to obtain 2D C/ZrB₂-SiC composites. Mechanical properties such as flexural strength and interlaminar shear strength were investigated. The ablation tests were carried out on an oxyacetylene torch flame. The small linear erosion rates indicate that the composites have good ablation resistance properties. These results demonstrate that CVI combined with SP method is a useful way to fabricate 2D C/ZrB₂-SiC composites.     

Oxidation behavior and mechanical properties of C/SiC composites with Si-MoSi2 oxidation protection coating

A new kind of oxidation protection coating of Si-MoSi₂ was developed for three dimensional carbon fiber reinforced silicon carbide composites which could be serviced upto 1550 °C. The overall oxidation behavior could be divided into three stages: (i) 500 °C < T < 800 °C, the oxidation mechanism was considered to be controlled by the chemical reaction between carbon and oxygen; (ii) 800 °C < T < 1100 °C, the oxidation of the composite was controlled by the diffusion of oxygen through the micro-cracks, and; (iii) T > 1100 °C, the oxidation of SiC became significant and was controlled by oxygen diffusion through the SiC layer. Microstructural analysis revealed that the oxidation protection coating had a three-layer structure: the out layer is oxidation layer of silica glass, the media layer is Si + MoSi₂ layer, and the inside layer is SiC layer. The coated C/SiC composites exhibited excellent oxidation resistance and thermal shock resistance. After the composites annealed at 1550 °C for 50 h in air and 1550 °C 100 °C thermal shock for 50 times, the flexural strength was maintained by 85% and 80% respectively. The relationship between oxidation weight change and flexural strength revealed the criteria for protection coating was that the maximum point of oxidation weight gain was the failure starting point for oxidation protection coating.     

Interfacial reaction and adhesion between SiC and thin sputtered cobalt films

Thin sputtered cobalt films on SiC were annealed in an Ar/4 vol% H₂ atmosphere at temperatures between 500 and 1450 °C for various times. The reaction process and the reaction-product morphology were characterized using optical microscopy, surface profilometry, X-ray diffraction, scanning electron microscopy and electron probe microanalysis. The relative adhesive strength between the film and substrate was determined by the scratch test method. Below 850 °C sputtered cobalt with a thickness of 2 m on SiC showed no detectable reaction products. Cobalt initially reacted with SiC at 850 °C producing Co₂Si and unreacted cobalt in the reaction zone. At 1050 °C the first-formed Co₂Si layer reacted to CoSi, and carbon precipitates were formed in the reaction zones. Sputtered thin cobalt layers reacted completely with SiC after annealing at 1050 °C for 2 h. Above 1250°C only CoSi was observed with carbon precipitates having an oriented structure in the reaction zone. Above 1450°C, a significant amount of graphitic carbon in the reaction zone was detected.     

Preparation of mullite bonded porous SiC ceramics by an infiltration method

A powder compact of α-SiC and α-Al₂O₃ was infiltrated with a liquid precursor of SiO₂, which on subsequent heat treatment at 1500 °C produced a mullite bonded porous SiC ceramics. Results showed that infiltration rate could be estimated by using weight gain measurements and theoretical analysis. The bond phase was composed of needle-shaped mullite which was observed to be grown from a siliceous melt formed during the process of oxide bonding. The porous SiC ceramics exhibited a density and porosity of 2 g cm⁻³ and 30 vol%, respectively, and also a pore size distribution in a range of 2–15 μm with an average pore size of 5 μm. No appreciable degradation of room temperature flexural strength (51 MPa) was observed at high temperatures (1100 °C).     

三维碳化硅/碳化硅陶瓷基编织体复合材料

采用化学气相浸渗法（CVI）,制备出三维Hi-Nicalon SiC/SiC陶瓷基纺织体复合材料,经30hCVI致密化处理后,复合材料的密度达到2．5g.cm^-3。所研制的三维SiC/SiC复合材料不仅具有较高的强度,而且表现出优异的韧性和类似金属材料非灾难性的断裂特征,复合材料的主要功能力学性能指标为：弯曲强度860MPa,断裂位移1．2mm,断裂韧性41．5MPa.m^1/2,断裂功28．1kJ.m^-2,冲击韧性360.0kJ.m^-2。     

Thermal effects on the mechanical properties of SiC fibre reinforced reaction-bonded silicon nitride matrix composites

The elevated temperature four-point flexural strength and the room-temperature tensile and flexural strength properties after thermal shock were measured for ceramic composites consisting of 30 vol% uniaxially aligned 142 m diameter SiC fibres in a reaction-bonded Si₃N₄ matrix. The elevated temperature strengths were measured after 15 min exposure in air at temperatures upto 1400 ° C. The thermal shock treatment was accomplished by heating the composite in air for 15 min at temperatures up to 1200 ° C and then quenching in water at 25 ° C. The results indicate no significant loss in strength properties either at temperature or after thermal shock when compared with the strength data for composites in the as-fabricated condition.     

Microstructure and mechanical properties of SiC<Subscript>P</Subscript>/SiC and SiC<Subscript>W</Subscript>/SiC composites by CVI

37.2 vol.% SiC_P/SiC and 25.0 vol.% SiC_W/SiC composites were prepared by chemical vapor infiltration (CVI) process through depositing SiC matrix in the porous particulate and whisker preforms, respectively. The particulate (or whisker) preforms has two types of pores; one is small pores of several micrometers at inter-particulates (or whiskers) and the other one is large pores of hundreds micrometers at inter-agglomerates. The microstructure and mechanical properties of 37.2 vol.% SiC_P/SiC and 25.0 vol.% SiC_W/SiC composites were studied. 37.2 vol.% SiC_P/SiC (or 25.0 vol.% SiC_W/SiC) consisted of the particulate (or whisker) reinforced SiC agglomerates, SiC matrix phase located inter-agglomerates and two types of pores located inter-particulates (or whiskers) and inter-agglomerates. The density, fracture toughness evaluated by SENB method, and flexural strength of 37.2 vol.% SiC_P/SiC and 25.0 vol.% SiC_W/SiC composites were 2.94 and 2.88 g/cm³, 6.18 and 8.34 MPa m^1/2, and 373 and 425 MPa, respectively. The main toughening mechanism was crack deflection and bridging.     

Combustion synthesis and mechanical properties of molybdenum disilicide composites reinforced with SiC particulate

Intermetallic composites of molybdenum disilicide reinforced with silicon carbide were produced by combustion synthesis of the elemental powders. The combustion reaction was initiated near 700°C and completed within a few seconds. The end product was a porous composite which was subsequently hot pressed to >97% theoretical density. The grains of the matrix were 8–14 m in size surrounded by SiC particulate reinforcement of 1–5 m. The mechanical properties of the composites improved with increasing SiC reinforcement. The hardness of the materials increased from 10.1 GPa to 12.7 GPa with the addition of 20 vol% SiC reinforcement, while the strength increased from 195 MPa to 299 MPa. The fracture toughness also increased from 2.79 MPa m1/2 to 4.08 MPa m1/2 with 20 vol% SiC. © 1998 Chapman & Hall     

Preparation of silicon carbide powders by chemical vapour deposition of the (CH3)2SiCl2-H2 system

Silicon carbide (SiC) powders were prepared by chemical vapour deposition (CVD) using (CH₃)₂SiCl₂ and H₂ as source gases at temperatures of 1273 to 1673 K. Various kinds of SiC powders such as amorphous powder, -type single-phase powder and composite powder were obtained. The composite powders contained free silicon and/or free carbon phases of about a few nanometres in diameter. All the particles observed were spherical in shape and uniform in size. The particle size increased from 45 to 130 nm with decreasing reaction temperature and gas flow rate, as well as with increasing reactant concentration. The lattice parameter of the -SiC particles decreased with increasing reaction temperature. All the lattice parameters were larger than those of bulk -SiC.     

Preparation of high-temperature filter by pressure-pulsed chemical vapour infiltration of SiC into carbonized paper-fibre preforms

SiC was partially infiltrated into three types of carbonized paper-fibre preforms using pressure-pulsed chemical vapour infiltration from SiCl4(4%)–CH4(4%)–H2 at 1100 °C (A-type preforms, source fibres of filter paper; BH- and BL-type preforms, source fibres of recycled paper). The porosity of the preforms decreased linearly with the number of pulses. After 10 000 pulses, the porosity of A-, BH- and BL-type samples was 77,78 and 85%, respectively. Average pore sizes of A-, BH- and BL-type samples after 10 000 pulses were about 5.0, 2.7 and 7.0 m, respectively. On an A-type sample of 10 mm and 5 mm long after 10 000 pulses, pressure drop along the direction of axial air flow was 10 kPa at a face velocity of 0.8 m s–1. The order of pressure drop was BH,>, A >, BL. Flexural strength of A-type sample reached 10 MPa after 15,000 pulses.