Microstructure Evolution and Reaction Mechanism of Biomorphous SiSiC Ceramics

Liquid Si infiltration (LSI) of beech wood-derived biocarbon (C_B) templates at 1550°C yields biomorphous SiSiC ceramics with the morphology of the initial biological preform. The biomorphous SiSiC ceramic consists of solidified Si in the cell lumina, polycrystalline β-SiC and residual carbon islands located at the position of former wood cell walls. The evolution of the microstructure during reactive Si melt infiltration was assessed by infiltration experiments at various times and investigated by X-ray diffraction as well as light scanning electron and transmission electron microscopy in combination with elemental analysis by energy-dispersive X-ray spectrometry. Four different stages of the reactive infiltration process could be distinguished, starting with a heterogeneous nucleation of nano-grained SiC on the pore surfaces of the C_B template by a Si vapor phase reaction below the Si melting temperature. After spontaneous Si melt infiltration, a stepwise reaction results in the simultaneous formation of a nano-grained SiC layer and a coarse-grained SiC phase on the inner pore surfaces. Further reaction proceeds slowly by diffusion of the reactants through the formed SiC layer and the microstructure evolution is dominated by dissolution and re-crystallization processes.     

The effects of high-temperature annealing on microstructure and performance of Cf/C-SiC composites modified by FeSi2

FeSi₂ modified C/C-SiC composites (C/C-SiC-FeSi₂) are fabricated by chemical vapor infiltration (CVI) combined with reactive melt infiltration (RMI) with FeSi75 alloy. The effects of high-temperature annealing (1600?°C, 1650?°C, 1700?°C) on the microstructure and performance of C/C-SiC-FeSi₂ are investigated. With the elevation of annealing temperature, the porosity of the composites and the content of SiC increase due to the evaporation of liquid Si and the further reaction of Si and C. The mechanical performance gradually decreases due to the catalytic graphitization of the carbon fiber, the high porosity and the thermal residual stress (TRS) caused by thermal mismatch of different phases. The coefficient of thermal expansion and thermal diffusivity slightly decrease with increasing annealing temperature for the increase of porosity. However, the friction performance of the heat treated materials at high braking speed are greatly improved attributing to the increase of SiC content and the capturing and storage function of pores on hard particles.     

Effects of zirconium addition on microstructure and ablation resistance of carbon fibre reinforced carbon and SiC ceramic matrix composite prepared by reactive melt infiltration

Abstract

Carbon fibre reinforced C and SiC binary ceramic matrix composites (C/C–SiC) were fabricated by a quick and low cost reactive melt infiltration (RMI) method with Si–Zr25 and Si melts. Effects of zirconium addition in infiltrated Si melt on microstructure and ablation resistance of the composite were investigated. The composite by Si–Zr25 melt infiltration was composed of SiC, ZrC, C and a little amount of ZrSi₂ without residual silicon, overcoming the problem of residual silicon in C/C–SiC composite by Si RMI. Compared with the composite by Si melt infiltration, the ablation resistance of the composite by Si–Zr25 was greatly improved by zirconium addition due to ZrO₂ and SiO₂ protecting layer formed during ablation.     

Reactive alloy melt infiltration for SiC composite matrices: Mechanistic insights

A comparative study of reactive melt infiltration using Si and Si‐Y alloys is presented to provide insight into the governing processes that control the effectiveness of the melt interaction with a carbonaceous preform and the temperature capability of the SiC matrix for ceramic matrix composites. Through experiments on two substantially different scales of capillaries in porous graphite tubes using Si and Si‐Y alloys, the current study has characterized the phenomena that play a role in the infiltration of the melt and its reaction with the preform. It is shown that (i) the interface reaction controls wetting in both large and small capillaries and the climb rate is enhanced by the presence of Y; (ii) reaction choking occurs at critical throats within the pore network, usually behind the infiltration front; and (iii) different residual silicides can form during reaction and upon cooling. A potential mechanism for SiC growth is described, and the implications for the interplay between SiC growth and infiltration are discussed.     

Characterization of the Microstructure of Three-Dimensional-Needled Carbon/Silicon Carbide Composites

Three-dimensional-needled, carbon-fiber-reinforced silicon carbide matrix composites (C/SiC) were prepared by a chemical vapor infiltration and reactive melt infiltration method. It was found that two kinds of SiC existed in the C/SiC composites, that is, micro-β-SiC grains within the range of 5–15 μm and nano-β-SiC grains with a size of about 100 nm. The interface of C/SiC and the distribution of SiC showed evidence for the reaction mechanism of the reactive melt infiltration process.     

Microstructure and ablation behaviors of a novel gradient C/C-ZrC-SiC composite fabricated by an improved reactive melt infiltration

An improved reactive melt infiltration (RMI) route using Zr, Si tablet as infiltrant was developed in order to obtain high-performance and low-cost C/C-ZrC-SiC composite with well defined structure. Two other RMI routes using Zr, Si mixed powders and alloy were also performed for comparison. Effects of different infiltration routes on the microstructure and ablation behavior were investigated. Results showed that C/C-ZrC-SiC composite prepared by Zr, Si tablets developed a dense gradient microstructure that content of ZrC ceramic increased gradually along the infiltration direction, while that of SiC ceramic decreased. Composites prepared by Zr, Si mixed powders and alloy showed a homogeneous microstructure containing more SiC ceramic. In addition, two interface patterns were observed at the carbon/ceramic interfaces: continuous SiC layer and ZrC, SiC mixed layers. It should be due to the arising of stable Si molten pool in the tablet. Among all as-prepared samples, after exposing to the oxyacetylene flame for 60 s at 2500 °C, C/C-ZrC-SiC composite infiltrated by Zr, Si tablet exhibited the best ablation property owing to its unique gradient structure.     

Comparative study of carbide-derived carbons obtained from biomorphic TiC and SiC structures

Biomorphic carbide ceramics, TiC and SiC, derived from paper performs by chemical vapor infiltration were converted into high porous carbon by carbide-derived carbon (CDC) approach using selective etching in chlorine or hydrogen/chlorine gas mixture in a temperature range of 400-1200 °C. A comparative study of both carbide precursors was performed regarding reaction kinetics, influence of hydrogen as well as microstructure of the resulting carbon. SiC showed lower reactivity than TiC. Temperatures below 650 °C are not sufficient to remove Si from SiC. Addition of hydrogen to the reactive gas inhibits the chlorination reaction. A linear decrease of etching rate with increasing hydrogen/chlorine ratio was observed for both carbide precursors. A critical ratio, where no etching takes place, was estimated to be 0.72 for TiC-CDC and 0.66 for SiC-CDC. The etching rate of TiC is independent from the temperature. In the case of SiC activation energy of the chlorination reaction of about 50 kJ/mol was estimated in the temperature range 650-800 °C. The structural ordering of CDC with increasing synthesis temperature affects also its oxidation resistance as shown by thermo gravimetric analysis.     

Microstructure,Thermophysical, and Ablative Performances of a 3D Needled C/C–SiC Composite

The microstructure, thermophysical, and ablative properties of a 3D needled C/C–SiC composite fabricated by chemical vapor infiltration combined with the liquid silicon infiltration process were investigated. The composite was composed of 64 wt% C, 20 wt% SiC, and 16 wt% Si. The thermal diffusivity in the plane direction was much higher than that in the through-the-thickness direction, while it was reversed for the coefficients of thermal expansion, and the differences reduced with increasing temperature. The linear and mass ablation rates in the oxyacetylene flame were 0.0039 mm/s and 0.0016 g/s on average, respectively. Various ablation processes including sublimation, thermochemical denudation, and oxidations occurred in different sections.     

Pressure‐less joining of C/SiC and SiC/SiC by a MoSi2/Si composite

A MoSi₂/Si composite obtained in situ by reaction of silicon and molybdenum at 1450°C in Ar flow is proposed as pressure‐less joining material for C/SiC and SiC/SiC composites. A new “Mo‐wrap” technique was developed to form the joining material and to control silicon infiltration in porous composites. MoSi₂/Si composite joining material infiltration inside coated and uncoated C/SiC and SiC/SiC composites, as well as its microstructure and interfacial reactions were studied. Preliminary mechanical strength of joints was tested at room temperature and after aging at service temperatures, resulting in interlaminar failure of the composites in most cases.     

自蔓延高温合成层状Ti3SiC2陶瓷的显微组织演变

本文采用燃烧波前沿淬熄法研究了层状Ti3SiC2陶瓷在自蔓延高温合成(SHS)过程中的显微组织转变过程。用扫描电子显微镜观察了SHS反应中其显微组织的转变过程,用能谱仪分析了各微区的成分变化,测量了燃烧温度TC,并通过XRD分析了燃烧产物的相组成。研究结果表明,层状Ti3SiC2陶瓷自蔓延高温合成(SHS)的反应机理为溶解—析出机制,Ti粉与Si粉的固态扩散导致低熔点Ti-Si溶液形成,Ti、Si、C粉粒逐渐向Ti-Si溶液中溶解,当溶液中的Ti、Si、C浓度饱和时,从中析出TiC、SiC颗粒。最后TiC和SiC与剩余的熔融Ti通过固—液反应转化生成最终产物Ti3SiC2。     

C/C–SiC composite prepared by Si–10Zr alloyed melt infiltration

A high performance and low cost C/C–SiC composite was prepared by Si–10Zr alloyed melt infiltration. Carbon fiber felt was firstly densified by pyrolytic carbon using chemical vapor infiltration to obtain a porous C/C preform. The eutectic Si–Zr alloyed melt (Zr: 10 at.%, Si: 90 at.%) was then infiltrated into the porous preform at 1450 °C to prepare the C/C–SiC composite. Due to the in situ reaction between the pyrolytic carbon and the Si–Zr alloy, SiC, ZrSi₂ and ZrC phases were formed, the formation and distribution of which were investigated by thermodynamics. The as-received C/C–SiC composite, with the flexural strength of 353.6 MPa, displayed a pseudo-ductile fracture behavior. Compared with the C/C preform and C/C composite of high density, the C/C–SiC composite presented improved oxidation resistance, which lost 36.5% of its weight whereas the C/C preform lost all its weight and the high density C/C composite lost 84% of its weight after 20 min oxidation in air at 1400 °C. ZrO₂, ZrSiO₄ and SiO₂ were formed on the surface of the C/C–SiC composite, which effectively protected the composite from oxidation.     

Microstructure and thermal expansion behavior of diamond/SiC/(Si) composites fabricated by reactive vapor infiltration

Diamond/SiC/(Si) composites were fabricated by Si vapor vacuum reactive infiltration. The coefficient of thermal expansion (CTE) of composites have been measured from 50 to 400 °C. With the diamond content increasing, CTE of composite decreased, simultaneously, the microstructure of the composites changed from core–shell particles embedded in the Si matrix to an interpenetrating network with the matrix. The CTEs of composites versus temperature matched well with those of Si. The Kerner model was modified according to the structural features of the composites, which exhibited more accurate predictions due to considering the core–shell structure of the composites. The thermal expansion behavior of the matrix was constrained by diamond/SiC network during heating.     

Preparation of SiC/SiC composites with high toughness by reaction of the SiCP+C double-cladding layer with liquid silicon

SiC/SiC composites prepared by liquid silicon infiltration (LSI) have the advantages of high densification, matrix cracking stress and ultimate tensile strength, but the toughness is usually insufficient. Relieving the residual microstress in fiber and interphase, dissipating crack propagation energy, and improving the crystallization degree of interphase can effectively increase the toughness of the composites. In this work, a special SiC particles and C (SiC_P +C) double-cladding layer is designed and prepared via the infiltration of SiC_P slurry and chemical vapor infiltration (CVI) of C in the porous SiC/SiC composites prepared by CVI. After LSI, the SiC generated by the reaction of C with molten Si combines with the SiC_P to form a layered structure matrix, which can effectually relieve residual microstress in fiber and interphase and dissipate crack propagation energy. The crystallization degree of BN interphase is increased under the effects of C-Si reaction exotherm. The as-received SiC/SiC composites possess a density of 2.64 g/cm³ and a porosity of 6.1%. The flexural strength of the SiC/SiC composites with layered structure matrix and highly crystalline BN interphase is 577 MPa, and the fracture toughness reaches up to 37 MPa·m^1/2. The microstructure and properties of four groups of SiC/SiC composites prepared by different processes are also investigated and compared to demonstrate the effectiveness of the SiC_P +C double-cladding layer design, which offers a strategy for developing the SiC/SiC composites with high performance.     

Effects of density and heat treatment of C/C preforms on microstructure and mechanical properties of C/C–SiC composites

Twill multidirectional carbon-fiber-reinforced carbon and silicon carbide composites (i.e., C/C–SiC) were prepared via chemical vapor infiltration combined with reactive melt infiltration process. The effect of heat treatment (HT) on the microstructure and mechanical properties of C/C–SiC composites obtained by C/C preforms with different densities was thoroughly investigated. The results show that as the bulk density of C/C preforms increases, the thickness of the pyrolytic carbon (PyC) layer increases and open pore size distribution narrows, making the bulk density and residual silicon content of C/C–SiC composites decrease. Moreover, the flexural strength and tensile strength of the C/C–SiC composites were improved, which can be attributed to the increased thickness of the PyC layer. The compressive strength reduces due to the decrease of the ceramic phase content. HT improves the graphitization degree of PyC, which reduces the silicon–carbon reaction rate and thereby the content of the SiC phase. HT induces microcracks and porosity but not obviously affects the mechanical properties of C/C–SiC composites. However, the negative impact of HT can be compensated by the increased density of the C/C preforms.     

Three-dimensional carbon fiber-reinforced silicon carbide matrix composites by vapor silicon infiltration

Three-dimensional carbon fiber-reinforced SiC matrix composites (C_f/SiC) were fabricated by vapor silicon infiltration (VSI) successfully. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and wavelength dispersive spectrometer (WDS) analysis revealed that the microstructure and composition of constituent phases are strongly dependent on temperature. At 1973 K, the obtained C_f/SiC composite mainly consists of SiC, carbon fiber and residual Si, and shows a densified microstructure. The flexural tests show non-catastrophic fracture behavior for composites fabricated by VSI process, and the ultimate flexural stress is comparable to those of composites fabricated by other processing techniques, demonstrating VSI is an effective way to fabricate the dense C_f/SiC composites with good mechanical properties.     

Microstructures and thermal conductivities of reaction sintered SiC ceramics

Abstract

Reaction sintered SiC ceramics were prepared by the silicon melt infiltration method over temperatures of 1450?1550°C. The effects of the carbon and silicon contents of the starting materials as well as the sintering temperature and time on the thermal conductivities and microstructures of the ceramic materials were studied. The thermal conductivities and microstructures of the samples were characterised using thermal conductivity measurements, X-ray diffraction analysis, scanning electron microscopy, energy-dispersive X-ray spectroscopy and mercury injection porosimetry. The results showed that sintering temperature and time as well as the carbon and silicon contents of the green specimens are the main factors affecting the microstructure and porosity of reaction bonded SiC ceramics. Increasing the reaction temperature and time decreased the porosity of the ceramics. This was due to the infiltration of the silicon melt into the ceramic specimens. The thermal conductivity and porosity of the sample sintered at 1550°C for 3 h in an argon atmosphere were 102·5 W m K^?1 and 0·3% respectively.     

反应熔渗法制备C/C-SiC复合材料及其反应机理和动力学的研究进展

对反应熔渗法制备C/C-SiC复合材料过程中Si的渗入行为以及Si/C的反应机理和动力学进行了综合评述.分析了高温下Si的密度、粘度、表面张力及Si/C润湿角对渗入能力的影响.概括了Washburn公式及其改进模型在液Si渗入行为方面的研究进展,给出了渗入时间、SiC生成速率与渗入高度之间的关系.对控制Si/C反应的溶解-沉淀机理和扩散机理进行了阐述,总结分析得出：不同阶段Si/C反应发生的区域不同,因而控制反应的机理也不同.最终的SiC相是由不同反应机理共同作用形成的.     

Application of the chemical vapor infiltration and reaction (CVI-R) technique for the preparation of highly porous biomorphic SiC ceramics derived from paper

Chemical vapor infiltration and reaction (CVI-R) is used to produce biomorphic high porous SiC ceramics based on biological structures such as paper. The paper fibers are first converted into a biocarbon (C_b) template by a carbonization step. In a second step methyltrichlorosilane (MTS) in excess of hydrogen is infiltrated into the C_b-template by CVI technique, depositing a Si/SiC layer around each fiber. The reaction (R) between biocarbon and excess silicon to form additional silicon carbide occurs during a subsequent thermal treatment as a third step of the ceramization process. Due to the mild infiltration conditions (850–900 °C) the initial micro- and macrostructure of the carbon preform is retained in the final ceramics. The applied characterization methods after every step of the ceramization process are X-ray Photoelectron Spectroscopy (XPS), Raman spectroscopy, Thermal Gravimetric Analysis (TGA), and Scanning Electron Microscopy (SEM). The bending strength of the resulting porous ceramics is measured by the double ring bending test. It is found that a slight excess of free Si in relation to the amount of carbon from the C_b-template must be deposited in the Si/SiC layer to achieve a nearly complete conversion of the C_b-templates into SiC ceramic. The weight gain after infiltration has to be at least 400 wt.%. Varying the infiltration conditions such as temperature, MTS concentration and infiltration time, ceramics in a wide range of porosity (55–80%) and mechanical properties (5–40 MPa) can be produced. A thermal treatment temperature of 1400 °C is found to be optimal for the reaction between the deposited Si and the biocarbon.     

三维针刺C/SiC复合材料无纬布纤维方向对材料力学性能的影响

通过化学气相渗透法结合反应熔体浸渗法制备了三维针刺C/SiC复合材料,采用扫描电子显微镜观察材料的显微结构,并研究了无纬布纤维方向对材料力学性能的影响.结果表明,三维针刺C/SiC复合材料由O°无纬布层、短纤维胎网层、90°无纬布层以及针刺纤维束组成,无纬布层纤维方向对材料性能有显著影响.试样的拉伸强度和弯曲强度随着无纬布纤维方向与试样长度方向的夹角θ(0 ～45°)值的增大而减小,面内剪切强度和冲击韧性随θ角的增大而增大.     

The Role of Infiltration Temperature in the Reaction Bonding of Boron Carbide by Silicon Infiltration

The present paper is concerned on the effect of infiltration temperature on the components, microstructure, and mechanical properties of reaction‐bonded boron carbide (RBBC) ceramics. RBBC ceramics were fabricated by reactive infiltration of molten silicon (Si) into porous preforms containing boron carbide (B₄C) and free carbon. It has been found that infiltration temperatures have significant influence on the infiltration reactions involved and therefore the evolution of different phases formed in the RBBC ceramics. An increase in grain size of boron carbide particles through the coalescence of neighboring grains was observed at certain infiltration temperatures. The morphology of silicon carbide (SiC) phases developed from discontinuous and cloud‐like SiC to continuous and integrated SiC zones with the increase of infiltration temperatures. With increasing temperatures up to 1600°C, the hardness, flexural strength, and fracture toughness all increased. When the temperatures exceeded 1600°C, while the hardness and flexural strength decreased, the fracture toughness continued to increase.