C/C复合材料正压CVI工艺的实验探索

研究了沉积温度、反应气浓度等因素对沉积过程的影响,并对所得试样的微观组织结构及其内部孔隙的分布规律进行了分析。研究表明,当沉积温度低于900℃时,可以避免或减少沉积过程中炭黑的生成,在该前提下,正压CVI工艺可在较短时间内制备出具有合理微观组织结构的C／C复合材料制作,因此提高了反应气体的利用率,正压CVI工艺是一种低成本的C／C复合材料制备工艺。     

纤维含量对C／C复合材料力学性能的影响

研究了炭纤维含量对C/C复合材料力学性能的影响,用扫描电镜（SEM）对材料的断口进行分析,结果表明：当炭纤维的体积分数小于8.3%时,随着炭纤维体积分数的增加,复合材料的抗折强度逐渐升高;之后,随着炭纤维的体积分数的增加,复合材料的抗折强度逐渐下降,短纤维增强C/C复合材料的断口特征为大量纤维拔出,其断裂过程为界面破坏所控制。     

纤维种类对C/C-SiC复合材料力学性能的影响

分别以PAN基预氧丝和炭纤维为原材料,采用准三维针刺工艺制备2种纤维预制体,然后采用化学气相渗积(CVI)工艺制备出密度相近的C/C复合材料坯体,最后对坯体进行熔融渗硅处理得到C/C-SiC复合材料,研究了纤维种类对C/C-SiC复合材料力学性能和断裂机理的影响。结果表明:纤维种类对C/C-SiC复合材料的力学性能和断裂机理有显著影响,炭纤维增强C/C-SiC复合材料的弯曲强度较高,达到140.3 MPa,断裂失效模式为"假塑性"断裂;预氧丝C/C-SiC复合材料的弯曲强度较低,为112.6 MPa,呈脆性断裂。产生以上结果的主要原因是增强纤维的力学性能不同,纤维表面形貌不同,进而导致所制备的C/C-SiC复合材料增强纤维与基体的结合强度不同。     

C/C预制体孔隙率与气相硅浸渗制备C/SiC复合材料性能关系的模型研究

建立了C/C预制体孔隙率与C/SiC复合材料组成的关系模型,并通过表征不同孔隙率的C/C预制体气相硅浸渗制备的C/SiC复合材料的组成和力学性能对模型进行了验证。研究发现,实验结果与模型预测结果基本一致。随着C/C预制体孔隙率的增大,C/SiC复合材料的密度出现先上升后下降的规律,力学性能也遵从同样的规律。XRD分析和相含量测试结果均表明复合材料的相含量与模型预测结果基本一致。实验结果与模型预测结果产生偏差的主要原因是裂解碳反应不完全。     

加压焙烧法制备短纤维增强C/C复合材料

采用加压焙烧工艺制备了短纤维增强C／C复合材料，研究了基体材料配比及纤维含量对其力学性能的影响，结果发现，基体材料中粘接剂沥青的最佳含量为30w%，当炭纤维含量小于8．3vol%时，随着炭纤维含量的增加，复合材料的抗折强度逐渐升高，之后，随着炭纤维的体积含量的增加，复合材料的抗折强度有所下降。     

碳/碳复合材料力学性能的研究进展

本文综述了碳/碳复合材料力学性能的研究进展,包括碳纤维、基体炭、界面性能、制备工艺及工艺参数等对碳/碳复合材料力学性能的影响。同时简单介绍了当今单向碳/碳复合材料力学性能的表征手段。希望对碳/碳复合材料力学性能的研究及应用提供帮助。     

先驱体转化法制备C/C-SiC复合材料研究

以多孔C/C复合材料为预制型,聚碳硅烷(PCS)为先驱体,制备了C/C-SiC复合材料。研究了浸渍液浓度和不同C/C复合材料预制体密度等级对C/C-SiC复合材料的密度和力学性能的影响。结果表明:当浸渍液浓度为50%时,复合材料的密度均达到最佳值;不同的预制体密度对制得的复合材料性能有很大的影响,其中初始密度为1.2g/cm3试样制得的复合材料性能达到最优,其密度达到1.786g/cm3,弯曲强度达204.1MPa,剪切强度为16.1MPa,断裂韧性为6.83MPa·m1/2。     

化学气相沉积致密针刺C/C复合材料的结构及力学性能研究

以T300炭纤维无纬布、网胎为原材料,层叠针刺成型炭纤维预制体,并采用化学气相沉积工艺对预制体进行致密,制成密度为1.55 g/cm3的针刺C/C复合材料。对针刺C/C复合材料的微观结构进行了观察分析,并对材料力学性能进行了测试。结果表明:化学气相沉积致密的针刺C/C复合材料呈现出以层间大量垂直纤维束为节点的类钉板状网状结构,这种特殊结构使材料层间结合更好,材料整个结构更加紧密;针刺C/C复合材料内部纤维被沉积形成的热解炭所包裹,热解炭的织构类型为光滑层(SL)和粗糙层(RL)并存;针刺C/C复合材料的各项力学性能均达到了较高水平,并且高温力学性能比常温力学性能有了很大幅度的提高。     

C／C复合材料中纤维和基体的结合程度与碳纤维表面状态的关系

采用液相氧化法对PAN系碳纤维进行了表面处理,研究了不同条件下,碳纤维表面状态对C/C复合材料中纤维和基体结合程度的影响规律,并通过扫描电镜的观察,分析了影响因素与结合状态的关系。     

C/C–ZrB_2–SiC复合材料的制备及其性能

结合化学气相渗透工艺(chemical vapor infiltration)与前驱体浸渍裂解(precursor infiltration and pyrolysis,PIP)工艺,制备了C/C–Zr B_2–Si C复合材料,并对材料的力学性能和烧蚀性能进行了分析。结果表明:PIP工艺制备的C/C–Zr B_2–Si C复合材料的拉伸、弯曲及剪切强度分别为91.2、214和35.8 MPa,优于通过浆料浸渍工艺制备的复合材料。同时,热流3 200 k W/m~2,时间600 s的氧乙炔火焰试验表明,PIP工艺制备的C/C–Zr B_2–Si C复合材料具有良好的抗氧化烧蚀性能,其线烧蚀率和质量烧蚀率分别为0.002 mm/s和0.7 mg/s。     

Deposition mechanism of pyrolytic carbons at temperature between 800–1200 °C

The textures, growth features, microstructures and binding of carbon atoms of pyrolytic carbons prepared by chemical vapor deposition (CVD) at a temperature between 800–1200 °C on graphite substrate and carbon fibers were studied. The intermediate product phase of pyrolytic carbons was also investigated. Based on the present study a deposition model of viscous droplet was proposed in this paper. The viscous droplet here refers to all kinds of fine spheroids that are more or less viscous. The mechanism of the formation of three typical textures namely, smooth laminar, rough laminar and isotropic carbons can be satisfactorily explained by this model.     

Microstructure and elastic properties of individual components of C/C composites

Carbon fiber reinforced carbon matrix (C/C) composites are often used for structural and frictional applications at a wide range of temperatures due to their excellent mechanical and thermal properties. Tailoring of mechanical properties through optimization of microstructure is critical for achieving maximum composite performance. This article addresses the evolution of the fiber and matrix microstructure and related nano-mechanical properties in two different C/C composites after being subjected to heat treatment at temperatures between 1800 and 2400 °C. Microstructure and corresponding nano-mechanical properties of C/C composites were studied using Polarized Light Microscopy (PLM), High-Resolution Transmission Electron Microscopy (HRTEM) and nanoindentation techniques. Increased heat treatment temperature (HTT) led to formation of a better-organized microstructure of fiber and matrix and also to formation of thermal cracks. The elastic modulus of rough laminar CVI pyrocarbon decreased from 18 to 12 GPa with increased HTT. In contrast, the isotropic CVI pyrocarbon and charred resin matrix displayed only a slight change of elastic modulus. The elastic modulus of PAN fiber increased from 18 to 34 GPa, indicating the development of a better-organized microstructure in the fiber-axial direction.     

Densification behavior and microstructure of carbon/carbon composites prepared by chemical vapor infiltration from xylene at temperatures between 900 and 1250 °C

Carbon/carbon composites were prepared by film boiling chemical vapor infiltration from xylene pyrolysis. Their densification behaviors such as the mass gain, the deposition rate and the density profile were investigated. The microstructure was studied by polarized light microscopy and characterized quantitatively with average extinction angle (Ae). Results showed that, under the particular experimental equipment and process, the initial deposition rate and the average Ae of pyrocarbon (PyC) increased with the increasing deposition temperature (T_d). The structural transition of PyC from rough laminar (RL) to smooth laminar along both the axial and radial directions of the composites was retarded as T_d increased from 900 to 1100 °C; PyC was deposited by the heterogeneous nucleation and growth. The homogeneous nucleation was generated producing isotropic PyC at the bottom of the composites for 1200–1250 °C deposition. The matrix produced at 1100–1250 °C was dominated by RL PyC, and the composites with high average density and uniform RL matrix were rapidly produced for T_d around 1100 °C.     

Effect of gas phase conditions on resultant matrix pyrocarbons in carbon/carbon composites

The various microstructures obtained by the low temperature (< 1500°C) chemical vapor deposition (CVD) of carbon in carbon fiber substrates fall into three major types identified as rough laminar, smooth laminar, and isotropic. It is shown that the type of microstructure is a function of the temperature of deposition, the total gas pressure, and the carbon to hydrogen ratio of the source gas. These experimental results are found to be in good agreement with a previously reported carbon CVD model which relates the microstructure to a single parameter, the equilibrium gas phase $\text{C}{}_2\text{H}{}_2\text{C}{}_6\text{H}{}_6$ molar ratio.The densities and crystallographic parameters of the heat-treated composites are significantly affected by the type of microstructure. The rough laminar material has by far the most graphitic characteristics and is followed by the smooth laminar and isotropic materials, in that order.     

Friction behaviors of carbon/carbon composites with different pyrolytic carbon textures

Friction and wear properties of carbon/carbon (C/C) composites with a smooth laminar (SL), a medium textured rough laminar (RL) and a high textured RL pyrolytic carbon texture were investigated with a home-made laboratory scale dynamometer to simulate airplane normal landing (NL), over landing (OL) and rejected take-off (RTO) conditions. The morphology of worn surfaces at different braking levels was observed with scanning electron microscopy. The results show that C/C composites with RL have nearly constant friction coefficients, stable friction curves and proper wear loss at different braking levels, while friction coefficients of C/C composites with SL pyrolytic carbon decrease intensely and their oxidation losses increase greatly under OL and RTO conditions. Therefore, C/C composites with a high and medium textured RL pyrolytic carbon may satisfy the requirements of aircraft brakes. The good friction and wear properties of C/C composites with RL are due to the properties of RL, which leads to a uniform friction film forming on the friction surface.     

Deposition mechanism and microstructure of pyrocarbon prepared by chemical vapor infiltration with kerosene as precursor

Large-size carbon/carbon composites (Φ 450 × Φ 230 × 15 mm³) have been produced by chemical vapor infiltration with kerosene as precursor. The microstructure of pyrocarbon was examined by polarized light microscopy and scanning electron microscopy. The infiltration kinetics was analyzed to investigate the infiltration rate limitation by parameters such as temperature. The results show that rough laminar carbon constitutes the majority of the matrix at a medium temperature (about 1100 °C), while smooth laminar and isotropic structures occur at temperatures lower than 1000 °C and higher than about 1200 °C, respectively. The apparent activation energy of kerosene decomposition in the temperature range 900-1200 °C is about 125.6 kJ/mol.     

以环己烷为前驱体制备炭/炭复合材料

以环己烷为前驱体利用化学液气相沉积工艺,采用针刺炭纤维毡为预制体,制备了具有光滑层和粗糙层结构的炭/炭复合材料。利用金相显微镜、高分辨扫描电子显微镜进行了材料的微观组织结构的分析,分析了在不同位置不同织构热解炭的形成机理。同时阐述了化学液气相沉积工艺原理。实验结果表明,通过调整工艺参数,利用化学液气相沉积工艺可以制备具有不同微观组织结构的炭/炭复合材料。     

Floating catalyst chemical vapor infiltration of nanofilamentous carbon reinforced carbon/carbon composites – Integrative improvement on the mechanical and thermal properties

Nanofilamentous carbon (NFC) reinforced carbon/carbon composites were produced by floating catalyst chemical vapor infiltration with ferrocene content ranging 0–2.0?wt%. The NFCs and increased graphitization degree led to an improvement on the mechanical and thermal properties. An excellent combination of high strength and thermal conductivity (TC), and low coefficient of thermal expansion (CTE) was reached by adding 0.5–0.8?wt% catalyst. When the content exceeded 0.8wt%, the strength and TC were decreased by the limited NFC growth and matrix transited from rough laminar to isotropic pyrocarbon. After the treatment of 2500?°C, the strength and CTE decreased whereas the TC was increased. With the catalyst contents at 0.5–0.8?wt%, the flexural and shear strength retention ratios achieved a high value of 73.1–74.5 and 79.1–79.4%, respectively, and the in-plane and out-of-plane TCs exhibited maxima of 339.1 and 72.5?W/(m?K). Relatively low CTE was obtained at 2.0?wt% catalyst owing to the increased amount of cracks and pores.     

炭/炭复合材料界面微观结构的研究

炭纤维增强炭基（炭／炭）复合材料中的界面结构直接影响着炭／炭材料的力学、热物理等各种性能。采用SEM、TIM等微观观察手段,就几种炭／炭复合材料界面的微观结构进行考察。对观察到的炭纤维与基体炭间的界面、同一纤维束中两根纤维间的界面,基体与其他外加物质间的界面、不同取向炭纤维间的界面、不同基体前驱体层间的界面等界面类型的细微结构进行了图示分析与讨论。     

Characterization of low temperature pyrocarbons obtained by densification of porous substrates

TEM and X-ray diffraction techniques were used to study the texture, the microtexture and the ability to graphitize of low temperature pyrocarbons obtained from carbon-carbon composites prepared by CVD. Pyrocarbons were found to be heterogeneous and composed of lamellae (main part of rough laminar pyrocarbons), micropores (which are the main part of isotropic pyrocarbons) and flattened pores characteristic of smooth laminar pyrocarbons.Lamellae are graphitizing carbon while micropores are not. Flattened pores are more or less partially graphitizing carbon depending on the diameter of the pores.