Mechanical and ablation properties of 2D-carbon/carbon composites pre-infiltrated with a SiC filler

In order to improve the mechanical and ablation properties of 2D-carbon/carbon composites, a SiC filler was added to a 2D-preform before isothermal chemical vapor infiltration densification by using a powder infiltration technique. Backscattered electron images showed that the SiC filler was mainly concentrated between the fiber bundles and between the layers. The tensile and flexural strengths of the composites were improved by the addition of the SiC filler because of the increase of interfacial surface areas between the bundles and between the layers, the less residual open porosity, and also the strong bonding between the SiC particles and the pyrocarbon matrix. The composites with filler experienced a 15.2% lower thickness erosion rate and a 51.7% lower mass erosion rate, compared to those C/C without filler. This was attributed to the low oxygen permeability of the SiO₂ shielding the exterior inter-bundle pores as well as to a thermal barrier effect.     

The catalytic effect of boric acid on polyacrylonitrile-based carbon fibers and the thermal conductivity of carbon/carbon composites produced from them

The catalytic effect of boric acid on the graphitization and surface structure of polyacrylonitrile-based carbon fibers was investigated by dipping fibers in boric acid before heating at 2500 °C. The thermal conductivity of carbon/carbon composites produced from the modified carbon performs by chemical vapor infiltration was also studied. The results show that the treatment by boric acid has a catalytic-graphitization effect on the fibers that increases the crystallinity and changes the surface state of carbon fibers during high temperature treatment. The modified carbon fibers induce the deposition of pyrocarbon with high crystallinity and an obvious transition interface between the carbon fiber and pyrocarbon during chemical vapor infiltration. By changing the microscopic structure of the carbon fibers, the interface bonding between fibers and pyrocarbon is improved and the microstructure of pyrocarbon is regulated. The thermal conductivity of the carbon/carbon composites is therefore improved, especially that in the direction perpendicular to fiber axis.     

An environmentally friendly route to prepare hierarchical carbon/carbon–SiC composites by carbothermal reduction

Hierarchical carbon/carbon–SiC composites have been prepared by a carbothermal reduction process using impregnated silica as a precursor and 3D needle-punched C/C composites as templates at 1450 °C. Dense SiC layers surrounding the pyrocarbon were synthesized by further heat-treatments at 1600 °C. The resulting composites are composed of turbostratic carbon, β-SiC and 4H type α-SiC, and show pseudo-plastic fracture behavior and excellent toughness. The flexural strength of parallel and perpendicular direction to carbon fiber clothes of the composites are about 155 and 100 MPa. The preparation of these composites releases very small amounts of corrosive gases and the materials obtained are easily machined.     

C/C多孔体对C/C-SiC复合材料微观结构和弯曲性能的影响

以4种纤维含量相同(32%,体积分数,下同),用化学气相渗透(chemical vapor infiltration,CVI)法制备了4种密度的碳纤维增强碳(carbon fiber reinforced carbon,C/C)多孔体,基体炭含量约20%～50%.利用液相渗硅法(liquid silicon infiltration,LSI)制备了C/C-SiC复合材料,研究了C/C多孔体对所制备的C/C-SiC复合材料微观结构和弯曲性能的影响.结果表明:不同密度的C/C多孔体反应渗硅后,复合材料的物相组成均为SiC,C及单质Si;随着C/C多孔体中基体炭含量的增加,C/C-SiC复合材料中SiC含量逐渐减少而热解炭含量逐渐增加.C/C-SiC复合材料弯曲强度随着材料中残留热解炭含量增加而逐渐增加,热解炭含量为约42%的C/C多孔体所制备的C/C-SiC复合材料的弯曲强度最大,达到320 MPa.     

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.     

涂层工艺对C/C复合材料结构和弯曲性能的影响

采用热处理和包埋工艺制备了Ｃ／Ｃ复合材料的ＭｏＳｉ２／ＳｉＣ抗氧化涂层,对组织结构、界面、弯曲断口进行了显微观察,分析了氧化保护涂层及其工艺对其机械性能的影响,结果表明,该工艺在Ｃ／Ｃ复合材料表面生成涂层的同时,使基材内部的界面也被硅化;并且发现,热解炭基体比炭纤维更易与Ｓｉ反应生成ＳｉＣ。Ｃ／Ｃ复合材料经涂层工艺处理后,弯曲强度降低;热处理过程中发生的材料氧化是弯曲强度下降的主要原因     

Environment-friendly deposition of SiCN interlayer for reinforcing carbon fibers in C/SiC composites

Several C/SiC composites with no interlayer, single pyrocarbon (PyC) interlayer and PyC/SiCN interlayer were fabricated by polymer infiltration and pyrolysis process. The microstructure and mechanical properties were investigated. The results verified that SiCN interlayer was formed on carbon fibers. Both bulk density and flexural stress of C/SiC composite with PyC/SiCN interlayer were slightly higher than composite fabricated with single PyC interlayer. When the weight fraction of SiCN interlayer in the composite was about 18 wt%, the flexural stress of the composite was enhanced to 416 MPa from 352 MPa for composite with single PyC interlayer. The observations of pulled-out fibers on fracture surfaces revealed non-catastrophic fracture features for PyC/SiCN deposited C/SiC composite.     

Effect of pyrocarbon interphase texture and thickness on tensile damage and fracture in T-700™ carbon fiber–reinforced silicon carbide minicomposites

In this paper, T-700™ carbon fiber–reinforced silicon carbide (C/SiC) minicomposites with pyrocarbon (PyC) interphase with different textural microstructure and thickness were fabricated using the chemical vapor infiltration method. The interface properties (i.e., textural microstructure, thickness, hardness, and modulus) were obtained through multiple testing methods (i.e., Raman spectroscopy, X-ray diffraction, scanning electron microscopy, and nanoindentation tests). Relationships between the deposition temperature and residence time with the texture type (i.e., low, medium, and high texture) were established. Uniaxial tensile experiments were conducted for C/SiC minicomposites with different PyC interphases to characterize the composite's internal damage evolution and fracture. Relationships between the composite's tensile nonlinear damage evolution, fracture strength and strain, PyC interphase texture, and thickness were established. The composite's tensile strength and fracture strain were the highest for the C/SiC minicomposite with medium-high texture PyC interphase. For the C/SiC minicomposite with the same texture interphase, the composite's tensile strength and fracture strain were affected by the coating thickness. The higher the thickness of the coating, the lower the composite's tensile strength and fracture strain.     

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.     

Ablative and mechanical properties of C/C-SiC-ZrC composites modified with PyC/SiC and PyC/BN interface layers

Two kinds of novel modified C/C-SiC-ZrC composites were prepared via precursor infiltration and pyrolysis, as pyrocarbon (PyC)/silicon carbide (SiC) and PyC/boron nitride (BN) dual-layer interphases were separately structured on the fibers by means of chemical vapor infiltration. Data analysis and conclusions are served for investigating the effects of these two interface layers on mechanical and anti-ablative properties. On the mechanical property hand, both PyC/BN and PyC/SiC interphase layers play positive roles, resting with the reduction of fiber damage during the fabrication process. Compared with BN, SiC shows better enhancement as the flexural strength of PyC/BN and PyC/SiC interphase-modified composites are 214.9 and 229.2 MPa, respectively. On the ablative property hand, after oxyacetylene flame ablation for 60 s, the mass and linear ablation rates of the composites modified by PyC/SiC interface were 2.2 mg/s and 9.7 μm/s, which is much lower than that modified by PyC/BN. The inferior ablation properties of PyC/BN-CSZ were attributed to the vaporization of the B₂O₃ gas that destroys the integrity of the oxide film and oxygen erosion on the substrate through the damaged BN interface.     

Effect of precoated carbon layer on microstructure and anti‐erosion properties of SiC coating for 2D‐C/C composites

To improve the erosion resistant of carbon‐carbon composites, an SiC coating was synthesized on carbon‐carbon composites by the in situ reaction method. They are firstly coated with carbon layer by slurry, and then SiC coatings are obtained by chemical vapor reaction. The effects of precoated carbon layer on the microstructure and anti‐erosion properties of SiC‐coated C‐C composites were studied and characterized. The thickness of the SiC coating increased with the increase in the precoated carbon layer thickness. The different thickness of carbon layer affects hardness of the SiC coatings, resulting in diverse erosion resistance of the coatings. The SiC coating prepared with moderate thickness of precoated carbon layer exhibits the best erosion resistance, and show better resistance at an impact angle of 30° than 90°. The eroded surface revealed that coating cracking and brittle fracture, fiber‐matrix debonding, fiber breakage, and material removal, and the additional microcutting and microploughing at oblique impact angle are the major erosion mechanism of SiC coating for C/C composites.     

低压化学气相渗透法制备2.5维SiCf/SiC复合材料

采用低压化学气相渗透法制备了具有和不具有热解炭界面层的2.5维连续SiC纤维增强的SiC复合材料(SiCf/SiC).SiC纤维的体积分数为30%和41%.所制备复合材料的气孔率为20%左右.当纤维为30%时,沉积有0.1 μm热解炭界面层的复合材料的弯曲强度由未加热解炭界面层的232MPa增加到328MPa,而且材料由灾难性断裂转变为非灾难性断裂.在同一制备条件下,纤维体积分数为41%的SiCf/SiC比30%的SiCf/SiC具有更高的气孔率.纤维为41%时,热解炭界面层厚度为0.1 μm的SiCf/SiC的弯曲强度只有244MPa,但是它具有更高的韧性和更长的纤维拔出长度.     

Densification rate and mechanical properties of carbon/carbon composites with layer-designed preform

In this work, carbon fiber needle-punching preforms were designed into two structure according to the density change along the thickness direction. One structure is designed to two layers with low-density layer and high-density layer, and the other is to three layers with low-density exterior layer and high-density interior layer. Then the effect of the preform with different structure on the densification rate and compressive properties of C/C composites was investigated. The results show that both two designed preforms can effectively avoid surface blocking, and lead to the faster densification rate of C/C composites during the chemical vapor infiltration processes. These results are attributable to the change of pore size distribution and pyrocarbon thickness, which was caused by fiber architecture designs. Meanwhile, these structural changes can improve the compressive strength of C/C composites, especially for the three-layer preforms. When the density of preforms is 0.45?g/cm³, C/C composites with three-layer preform has the highest compressive strength. The damage of most C/C composites with two and three-layer preforms is caused by shear or delamination failure, while that of C/C composites with common preforms usually caused by matrix collapse. Cracks in C/C composites with two and three-layer preforms always happened on the low-density layer, and consequently ceased or changed propagation direction in the interface between two layers.     

Effects of the single layer CVD SiC interphases on the mechanical properties of the SiCf/SiC composites fabricated by PIP process

Owing to the degradation of the mechanical properties of the SiC fiber reinforced SiC matrix (SiCf/SiC) composites with the pyrocarbon (PyC) and BN interphases under oxidation environment and neutron irradiation, single layer SiC interphases prepared by chemical vapor deposition (CVD) process were employed to substitute for them. Effects of the CVD SiC interphases on the mechanical properties and interfacial characteristics of the SiCf/SiC composites fabricated by precursor infiltration and pyrolysis (PIP) process were investigated. Compared with the as-received SiCf/SiC composites, the SiCf/SiC composites with the single layer CVD SiC interphases exhibit an obvious toughened fracture behavior, the flexural strength of which is about 4 times that of the as-received SiCf/SiC composites. From the microstructural analysis, it can be confirmed that the SiC interphases play a key part in protecting the fibers from damage during composite preparation and weakening interfacial bonding, which can provide high in situ fiber strength and appropriate interfacial bonding strength for the SiCf/SiC composites.     

Floating catalyst chemical vapor infiltration of nanofilamentous carbon reinforced carbon/carbon composites – Densification behavior and matrix microstructure

Nanofilamentous carbon (NFC) reinforced carbon/carbon composites were prepared by floating catalyst film boiling chemical vapor infiltration from xylene pyrolysis at 1000–1100 °C using ferrocene as a catalyst. The influence of the catalyst content on the densification behavior and matrix microstructure of the composites was studied. Results showed that the deposition rate of pyrocarbon (PyC) was enhanced remarkably by the catalyst. The density of the composites deposited at a catalyst content of 0–2.0 wt% decreased along both the axial and the negative radial directions. Rough laminar (RL) PyC matrix was formed at 0–0.8 wt% catalyst content by heterogeneous nucleation and growth. A hybrid matrix consisting of RL and isotropic (ISO) PyCs appeared at a catalyst content of 1.2–2.0 wt%. The reasons for this ISO PyC formation were attributed to the deposition of carbon encapsulated iron particles and homogeneous nucleation. A reinforcing network composed of NFCs and vapor grown carbon fibers was formed on the fiber/matrix interface and within the matrix in this floating catalyst process. The structure of NFC transformed from nanotube to nanofiber when the catalyst content was over 0.5 wt%, around which composites of a high density of 1.75 g/cm³ and uniform RL PyC matrix were produced rapidly.     

Effects of channel modification on microstructure and mechanical properties of C/SiC composites prepared by LA-CVI process

Carbon fiber reinforced SiC matrix composites (C/SiC) with four different deposition channel sizes were fabricated via a novel laser-assisted chemical vapor infiltration (LA-CVI) method. Effects of infiltration channel sizes on microstructure and mechanical properties of C/SiC composites were investigated. The results showed that increasing the size of channels could expand infiltration passages and densification bands, which was consistent with theoretical calculations. Due to the presence of channels, the flexural strength of C/SiC composite increased by 14.47% when the channel diameter was 0.3?mm, compared to C/SiC composites prepared via conventional CVI process. Characteristics of matrix cracking and crack propagation on fracture surface were analyzed by using scanning electron microscopy. LA-CVI C/SiC composites displayed significantly improved damage-tolerant fracture behavior. Thus, findings of this work demonstrate that LA-CVI fabricated C/SiC composites are promising for a wide range of applications, particularly for enclosed-structure and thick-section C/SiC composites.     

基体改性对碳纤维增韧碳化硅复合材料结构与性能的影响

采用化学气相浸渗法对2D C/SiC复合材料进行基体改性,制备了二维碳纤维增韧碳-碳化硅二元基复合材料(two dimensional carbon fiber reinforced C-SiC binary matrix composites,2D C/C-SiC).2D C/C-SiC复合材料的基体为热解碳和碳化硅交替叠层的多层基体.研究了2D C/C-SiC复合材料的微观结构,比较了2DC/SiC复合材料和2DC/C-SiC复合材料的力学性能及断口形貌.结果表明:2DC/C-SiC复合材料可在基本保持2DC/SiC复合材料抗弯强度的基础上,其断裂韧性得到显著提高.基体改性的效果明显.纤维的逐级拔出是断裂韧性提高的原因.     

Microstructures and mechanical properties of carbon/carbon composites reinforced with carbon nanofibers/nanotubes produced in situ

Using ferrocene as catalyst and toluene as the liquid precursor, carbon/carbon (C/C) composites were prepared by chemical liquid-vapor infiltration at 850-1100 °C. The microstructures and properties of C/C composites obtained with different ferrocene contents were studied. The results show smooth laminar and isotropic pyrocarbon are obtained after adding ferrocene to the precursor. Carbon nanofibers can be formed as the catalyst content is 0.3-1 wt.%. When the ferrocene content is 2 wt.%, multi-walled carbon nanotubes with the diameter about 20-90 nm are obtained together with carbon-encapsulated iron nanoparticles. After adding ferrocene to the precursor, the fracture modes of the composites change from brittle facture to tough fracture. The flexural strength of the composites is a maximum for 0.3 wt.% ferrocene in the precursor, higher than for ferrocene contents of 0, 0.5, 1 and 2 wt.%. The flexural modulus of the composites decreases after adding ferrocene to the precursor.     

Transmission electron microscopy study of the microstructure of carbon/carbon composites reinforced with in situ grown carbon nanofibers

Introduction of carbon nanofibers (CNFs) into carbon/carbon (C/C) composites is an effective method to improve the mechanical properties of C/C composites. In situ grown CNFs reinforced C/C composites as well as conventional C/C composites without CNFs were fabricated by chemical vapor infiltration. Transmission electron microscopy investigations indicate that the entangled CNFs (30–120 nm) formed interlocking networks on the surface of carbon fibers (CFs). Moreover, a thin high-textured (HT) pyrocarbon (PyC) layer (～20 nm) was deposited on the surface of CFs during the growth of CNFs. We find the microstructure of C/C composites depends strongly on the local distribution density (LDD) of CNFs. In regions of low CNF LDD, a triple-layer structure was formed. The inner layer (attached to CF) is HT PyC (～20 nm), the middle layer (150–200 nm) is composed of HT PyC coated CNFs (HT/CNFs) and medium-textured PyC, and the outmost layer (several microns) is composed of HT/CNFs and micropores. In regions of high CNF LDD, a double-layer structure was formed. The inner layer is HT PyC (～20 nm), and the outer layer is composed of HT/CNFs, isotropic PyC and nanopores. However, only medium-textured PyC and micropores were found in the matrix of the conventional C/C composites.     

“三明治”C/C复合材料及其摩擦磨损性能

通过化学气相渗透法(CVI)制备出一种新型的"三明治"结构的C/C复合材料。其两侧是纯网胎结构的功能层,主要承担摩擦功能;中间为承担结构作用的结构层,与传统针刺毡结构一致。系统研究了材料的微观组织结构特征及其摩擦磨损性能。结果表明:"三明治"C/C复合材料各个区域的热解炭都为粗糙层结构;刹车性能较传统三维针刺结构C/C复合材料的摩擦性能稳定;在摩擦试验过程中,摩擦面能够形成一层连续均匀的薄膜,使材料在刹车过程中具有较稳定的摩擦系数并能够有效降低材料的磨损率。