Laminated biomorphous SiC/Si porous ceramics made from wood veneer

Biomorphous SiC/Si porous ceramics with laminated structure are prepared from beech veneer and phenolic resin. The preparation involves carbonization under vacuum and reaction with melted silicon to obtain the biomorphous carbide template. X-ray diffraction confirms that the biomorphous SiC/Si porous ceramics are mainly composed of β-SiC, free silicon and residual carbon. Scanning election microscopy observations indicate a laminated structure and 1–10 μm microporous structures, which suggest retention of the native characteristics of the wood. This paper examines mechanical properties of the final composite in relation to the lamination, porous structure, and free silicon content. The bending strength of the ceramics decreases as the apparent porosity increases. The fracture toughness increases initially with apparent density and then decreases. The fracture toughness load–displacement curve presents a step-like pattern, which suggests that the laminated SiC/Si porous ceramics have high fracture toughness.     

微孔碳陶瓷化反应机理的研究

研究了微孔碳制备SiC陶瓷的反应过程及反应机理.SiC陶瓷的最终组织受C/Si质量比及渗硅时间的影响.较低C/Si质量比时试样中心未被硅化,较高C/Si质量比时制得由SiC、Si及极少量未反应C组成的复相陶瓷.随渗硅时间延长,复相陶瓷中SiC颗粒的形状由长条状向无规则状转变,颗粒分布则由局部有序向无序转变.反应过程为：液硅因毛细作用自发的渗入微孔碳孔道,同时与溶解的碳壁发生反应生成SiC.因孔道及碳壁尺寸的不同造成液硅渗入深度和碳壁被溶解厚度的差异,结果出现被SiC包裹的小颗粒碳.随后被包裹的碳通过SiC层扩散到液硅中,沉积在先形成的SiC上促使大量先形成SiC的合并以及部分硅被SiC包裹,进而改变SiC陶瓷的显微组织.     

Wear-mechanical properties of filler-added liquid silicon infiltration C/C–SiC composites

A carbon fiber reinforced silicon carbide matrix (C/C–SiC) composites material was manufactured by introducing a filler into the liquid silicon infiltration (LSI) process. The filler consisted of Si:Carbon black = 1:1 mixed with a phenol resin. Use of the filler resulted in a negligible reduction in the residual free Si of approximately 0.7% but increased 15% of reacted SiC amount. Dilatometer and X-ray diffraction (XRD) evaluations also confirmed improved formation of reaction-bonded silicon carbide (SiC) in the matrix. The wear rate was decreased more than 2.5-fold, indicating significantly improved wear-resistance properties. However, flexural strength gradually decreased and fiber damage was observed in fracture surface with increases in filler content.     

木材陶瓷化反应机理的研究

研究了木材制备ＳｉＣ陶瓷的反应过程及熔融硅与多孔木炭反应的机理．结果表明,木材制得的ＳｉＣ陶瓷的最终组织取决于渗硅处理温度．较低温度下形成碳化硅多孔材料,较高温度下形成 Ｓｉ／ＳｉＣ复相致密材料．分析指出,木材制备 ＳｉＣ陶瓷中 Ｓｉ／Ｃ反应的大致过程为：熔融硅沿木炭毛细管壁上升,同时与接触的碳反应形成碳化硅,碳化硅层不断向碳层推进直至多孔碳骨架完全转化为碳化硅．生成的碳化硅在反应后期会发生再结晶,最终组织形态表现为多边形大颗粒碳化硅分布在自由硅基体上．     

碳模板转化法制备管状SiC/Si复合陶瓷

利用纸作为原材料,通过卷曲、树脂浸渍、碳化预制备出具有层状结构的管状碳模板,之后在1550℃通过原位反应液相渗Si0.5-1h,在常压烧结条件下制备出具有层状结构特征的SiC/Si管状陶瓷复合材料.采用XRD、SEM对碳模板反应前后的物相变化和显微结构进行了研究.结果表明了该材料的最终产物为β-SiC和Si,且两者分布表现出明显的交替成层现象,呈现出层状陶瓷的结构特征.     

Manufacture of fibrous β-Si3N4-reinforced biomorphic SiC matrix composites for bioceramic scaffold applications

The manufacturing of the Si₃N₄ reinforced biomorphic microcellular SiC composites for potential medical implants for bone substitutions with good biocompatibility and physicochemical properties was performed in a two step process. First, wood-derived porous Si/SiC ceramics with various porosities were produced by liquid silicon infiltration (LSI) at 1550 °C with static nitrogen atmosphere protection (0.1 MPa), followed by subsequent partial removing of the Si in vacuo at 1700 °C for different periods of time. Secondly, the final porous Si₃N₄ fiber/SiC composite was obtained by further chemical reaction of nitrogen with the infiltrated residual silicon at 1400 °C for 4 h under high concentration flowing nitrogen atmospheres (0.5 MPa). The bending strengths of the porous Si₃N₄ fiber/SiC composite at axial and radial direction were measured as 180.03 MPa and 90 MPa respectively. The improvement in bending strength was primarily attributed to grain pull-out and bridging enhanced by the elongated β-Si₃N₄ grains cross-linked in the depth of the pore channels. The TG analysis showed an obvious improvement in oxidation resistance of the nitride specimens.     

Improvement of SiCf/SiC density by slurry infiltration and tape stacking

SiC fiber-reinforced SiC–matrix ceramic composites (SiC_f/SiC) were fabricated by vacuum infiltration of a SiC slurry into Tyranno™-SA grade-3 fabrics coated with a 200 nm-thick pyrolytic carbon (PyC) layer followed by hot pressing using a transient eutectic-phase. The density of the composite was improved using a special infiltration apparatus with a pressure gradient and alternating tape insertion between fabrics. Their overall properties were compared with those of monolithic SiC and composite containing chopped fibers. Although the density of the composites decreased with increasing fiber fraction, SiC_f/SiC containing 50 vol.% fibers had a density of 3.13 g/cm³, which is the highest reported thus far. The composites containing continuous fibers had a maximum flexural strength of 607 MPa and a step increase in the stress–displacement behavior during the three-point bending test due to fiber reinforcement, which was not observed in the monolith.     

A high-strength SiCw/SiC–Si composite derived from pyrolyzed rice husks by liquid silicon infiltration

A high-strength SiC composite with SiC whiskers (SiC_w) as reinforcement has been fabricated by liquid silicon infiltration (LSI) using pyrolyzed rice husks (RHs) as raw material. RHs were coked and pyrolyzed subsequently at high temperature to obtain a mixture containing SiC whiskers, particles, and amorphous carbon. The pyrolyzed RHs were then milled and modeled to preforms, which were then used to fabricate biomorphic SiC_w/SiC–Si composites by liquid silicon infiltration at 1,450, 1,550, and 1,600 °C, respectively. Dense composite with a density of 3.0 g cm⁻³ was obtained at the infiltration temperature of 1,550 °C, which possesses superior mechanical properties compared with commercial reaction-sintered SiC (RS-SiC). The Vickers hardness, flexure strength, elastic modulus, and fracture toughness of the biomorphic SiC_w/SiC–Si composite were 18.8 ± 0.6 GPa, 354 ± 2 GPa, 450 ± 40 MPa, and 3.5 ± 0.3 MPa m^1/2, respectively. Whereas the composites obtained at the other two infiltration temperatures contain unreacted carbon and show lower mechanical properties. The high flexure strength of the biomorphic composite infiltrated at 1,550 °C is attributed to the dense structure and the reinforcement of the SiC whiskers. In addition, the fracture mechanism of the composite is also discussed.     

液硅渗透法制备Ti3SiC2改性C/CSiC复合材料

采用浆料浸渗结合液硅渗透法原位生成高韧性Ti₃SiC₂基体, 制备Ti₃SiC₂改性C/C-SiC复合材料。研究了TiC颗粒的引入对熔融Si浸渗效果的影响, 分析了Ti₃SiC₂改性C/C-SiC复合材料的微结构和力学性能。实验结果表明: TiC与熔融Si反应生成Ti₃SiC₂是可行的, 而且C的存在更有利于生成Ti₃SiC₂; 在含TiC颗粒的C/C预制体孔隙(平均孔径22.3 μm)内, 熔融Si的渗透深度1 min内可达10.8 cm; Ti₃SiC₂取代残余Si后提高了 C/C-SiC复合材料的力学性能, C/C-SiC-Ti₃SiC₂复合材料的弯曲强度达203 MPa, 断裂韧性达到8.8 MPa·m1/2; 对于厚度为20 mm的试样, 不同渗透深度处材料均具有相近的相成分、 密度和力学性能, 无明显微结构梯度存在, 表明所采用的浆料浸渗结合液硅渗透工艺适用于制备厚壁Ti₃SiC₂改性C/C-SiC复合材料构件。      

多孔氮化硅/碳化硅复合材料制备的反应机理分析

为了探索碳热还原法制备多孔氮化硅/碳化硅(Si₃N₄/SiC)复合陶瓷材料在高温阶段的反应机理,采用固化的酚醛树脂为碳源,通过热解产生具有反应性的碳,使之在1300-1780℃等不同温度下与表面包裹的氮化硅粉反应,氩气为保护气氛.通过对试样的XRD、TEM分析和显微结构观察,结合反应的热力学和动力学结果计算推测,树脂裂解碳与Si₃N₄反应生成SiC的机理主要为Si₃N₄分解生成Si(l)与C进一步发生的液-固反应,和Si(l)与反应过程中的中间产物CO(g)之间发生的液-气反应.其他还包括C与Si₃N₄间直接进行的固-固反应;C与Si₃N₄表面的SiO₂间的气-固反应以及由SiO(g)、Si(g)参与的气-固反应.树脂裂解碳与Si₃N₄从1400℃左右开始发生反应形成SiC,温度升高对SiC层的生长有促进,保温时间的延长对SiC层的生长厚度影响较大.     

Oxidation mechanism of Si3N4-bonded SiC ceramics by CO, CO2 and steam

This paper presents a theoretical and experimental investigation into the oxidation reactions of Si3N4-bonded SiC ceramics. Such ceramics which contain a small amount of silicon offer increased oxidation and wear resistance and are widely used as lining refractories in blast furnaces. The thermodynamics of oxidation reactions were studied using the JANAF tables. The weight gain was measured using a thermogravimetric analysis technique to study the kinetics. The temperature range of oxidation measurements is from 1073 to 1573 K and the oxidation atmosphere is water vapour, pure CO and CO–CO2 gas mixtures with various CO-to-CO2 ratios. Thermodynamic simulations showed that the oxidation mechanism of Si3N4-bonded SiC ceramics is passive oxidation and all components contribute to the formation of a silica film. The activated energies of the reactions follow the sequence Si3N4>SiC>Si. The kinetic study revealed that the oxidation of Si3N4-bonded SiC ceramics occurred in a mixed regime controlled by both interface reaction and diffusion through the silica film. Under the atmosphere conditions prevailing in the blast furnace, this ceramic is predicted to be passively oxidized with the chemical reaction rate becoming more dominant as the CO concentration increases. © 1998 Chapman & Hall     

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.     

Effects of microstructure on flexural strength of biomorphic C/SiC composites

Biomorphic C/SiC composites were fabricated from different kinds of wood by liquid silicon infiltration (LSI) following a two-step process. In the first-step, the wood is converted into carbon preforms by pyrolysis in a nitrogen atmosphere. The carbon preforms are then infiltrated by silicon melt at 1,560°C under vacuum to fabricate C/SiC composites. The mechanical properties of the C/SiC composites were characterized by flexural tests at ambient temperature, 1,000, and 1,300°C, and the relationship between mechanical properties and microstructure was analyzed. The flexural strength of the biomorphic composites was strongly dependent on the properties of the carbon preforms and the degree of silicon infiltration. The flexural strength increased with increasing SiC content and bulk density of composite, and with decreasing porosity in the C/SiC composite. An analysis of fractographs of fractured C/SiC composites showed a cleavage type fracture, indicating brittle fracture behavior.     

一种新型多孔SiC的制备与性能研究

以滤纸和酚醛树脂为原料, 通过模压成型、固化、碳化和渗硅制备出微观结构均匀的多孔碳化硅. 碳化的温度固定时, 多孔碳的气孔率随酚醛树脂用量的增大而减少, 弯曲强度随着酚醛树脂用量的增大而增大. 酚醛树脂/滤纸两种成分的质量比固定时, 气孔率随着碳化温度的升高而减小, 弯曲强度随着碳化温度的升高而增大, 从SEM照片可以看出, 由滤纸纤维的杂乱排列和碳化时不同的收缩率产生了相互连通不规则的孔, 在多孔碳化硅结构中也得以保留. 多孔碳化硅的气孔率随着排硅时间的增加而增大, 强度和韧性随着排硅时间的增加而减小. 在1650℃, 并经过30min排Si, 较大孔隙中的Si就可以排掉, 此时得到的多孔SiC具有较高的强度和韧性.     

Synthesis of Si3N4 whiskers in porous SiC bodies

Si₃N₄ whiskers were synthesized by the carbothermal reduction process in porous SiC bodies. The SiC bodies had a sponge microstructure with pore sizes of approximately 600 μm. The raw materials for the Si₃N₄ whiskers were powder mixtures of Si₃N₄, SiO₂ and Si for silicon and phenolic resin for carbon. Cobalt was used as a metal catalyst. The carbothermal reaction was performed at 1400 °C or 1500 °C for 1 or 2 h. The α-Si₃N₄ whiskers grew inside the SiC pores by the VLS process, and their diameters ranged from 0.1 to 1.0 μm. The length of the grown Si₃N₄ whiskers was over 100 μm and their growth direction was [100].     

Fabrication of short carbon fiber preforms coated with pyrocarbon/SiC for liquid metal infiltration

A novel method of fabricating short carbon fiber preforms was proposed for liquid metal infiltration. The preforms were shaped by wet forming and strengthened by pyrocarbon (PyC). SiC layers were prepared on carbon fibers by the reaction of SiO and PyC at 1600 °C. X-ray Diffraction, Scanning Electron Microscopy, and Energy Dispersive X-ray Spectroscopy were applied in the characterization of the preforms. Gas pressure infiltration was done to demonstrate the feasibility of the preforms for the liquid metal infiltration. The microstructure analysis indicates that carbon fibers are uniformly distributed in the preforms, and fibers are coated with an inner layer of PyC and an outer layer of SiC. The infiltration experiment proves that the prepared preforms are feasible for liquid metal infiltration under low infiltration pressure and temperature.     

Microstructure and properties of 3D needle-punched carbon/silicon carbide brake materials

The carbon/silicon carbide brake materials were prepared by chemical vapor infiltration (CVI) combined with liquid melt infiltration (LMI). The carbon fiber preform was fabricated with the three dimension needling method. The microstructure, mechanical, thermophysical, and frictional properties of C/SiC composites were investigated. The results indicated that the composites were composed of 65 wt%C, 27 wt%SiC, and 8 wt%Si. The density and porosity were 2.1 g cm⁻³ and 4.4%, respectively. The C/SiC brake materials exhibited excellent toughness. The average dynamic friction coefficient and static friction coefficient of the materials were about 0.34 and 0.41, respectively. The friction coefficient was stable. The fade ratio of the friction coefficient under moist conditions was about 2.9%. The linear wear rate was less than 1.9 μm side⁻¹ cycle⁻¹. These results show that C/SiC composites have excellent properties for use as brake materials for aircraft.     

反应烧结微米级SiC陶瓷材料的结构与力学性能

选用粒径为7μm的SiC粉体,采用反应烧结工艺制备致密的SiC陶瓷材料,研究了反应烧结SiC陶瓷材料的物相组成、显微组织结构与力学性能及其断口形貌。结果表明:通过优化制备工艺,SiC陶瓷素坯中的SiC颗粒和纳米炭黑粉体分布均匀,且具有三维联通的孔隙结构,有良好的硅熔渗性能。反应烧结SiC陶瓷材料中的SiC含量高,游离硅含量少,密度可达3.01g.cm-3,抗弯强度达到410MPa,洛氏硬度达到95HRA,综合性能达到陶瓷机械密封件的技术要求。     

Preparation and microstructural evolution of carbon/carbon composites

Carbon/carbon (C/C) composites with characteristic matrix-crack pattern are key intermediate materials for preparation of carbon/silicon carbide (C/C–SiC) composites. The C/C composites were prepared by pyrolyzing carbon fiber/phenolic resin preform. The change of density, open porosity, mass loss and specially the microstructural evolution of the composites during pyrolysis at 200–900 °C was analyzed, which provided important information for preparation of C/SiC composites by infiltration of silicon. An increasing number of regular spacing cracks were formed above 400 °C. After pyrolysis at 900 °C, the pore volume was 0.17 cm³/g, and the pores in the radius range of 2.44–122.19 μm occupied 81% of the pore volume.     

三维针刺C/SiC复合材料显微结构演变分析

以三维针刺碳毡作为预制体,采用树脂浸渍-热解工艺制备C/C多孔体,然后采用反应熔体浸渍法(Reactive melt infiltration,RMI)对C/C多孔体分别浸渗Si和Si-Mo合金制备C/SiC复合材料。首先研究了C/C多孔体制备过程中的显微结构演变。结果表明,浸渍过程中树脂主要填充在纤维束内小孔隙中,热解后裂纹增多,生成网格状C/C亚结构单元;高温热处理使C/C复合材料裂纹进一步扩展,石墨化度提高,束内闭气孔打开,从而为RMI渗Si提供通道。然后对C/C多孔体分别渗Si和Si-Mo合金所得材料的物相组成和显微结构进行对比分析。发现纯Si浸渗得到的复合材料残余Si较多,束内纤维受损严重;而浸渗Si-Mo合金可以减少残余Si含量,束内纤维受损轻微,仍保持着完整的C/C亚结构单元。