Preparation and mechanical properties of carbon/carbon composites with high textured pyrolytic carbon matrix

Short carbon fiber felts with an initial porosity of 89.5% were deposited by isobaric, isothermal chemical vapor infiltration using natural gas as carbon source. The bulk density of the deposited carbon/carbon (C/C) composites was 1.89 g/cm³ after depositing for 150 h. The microstructure and mechanical properties of the C/C composites were studied by polarized light microscopy, X-ray diffraction, scanning electron microscopy and three-point bending test. The results reveal that high textured pyrolytic carbon is deposited as the matrix of the composites, whose crystalline thickness and graphitization degree highly increase after heat treatment. A distinct decrease of the flexural strength and modulus accompanied by the increase of the toughness of the C/C composites is found to be correlated with the structural changes in the composites during the heat treatment process.     

CVI炭/炭复合材料微观结构和生长模型

采用自行设计的多元耦合物理场CVI炉增密炭/炭（C/C）复合材料,用炭毡作为纤维增强体,在坯体内部设计特殊的导电发热层,使坯体内部的温度场、气体反应的中间产物浓度场、电磁场等多元物理场实现耦合,实现坯体的快速增密。采用偏光显微镜研究沉积热解炭的组织结构;用X射线衍射仪研究C/C复合材料的石墨化度和微晶尺寸;用扫描电镜观察材料断口和热解炭沉积表面的形貌;并对CVI热解炭的生长方式进行研究。研究表明：获得SL、RL和带状等多种热解炭结构;不同的结构具有不同的形貌特征,其中SL的断口平整,RL的断口呈沟槽构造;并提出前者为小分子平滑生长模型、后者为大分子锥状生长模型。     

C／C复合材料的导热系数

用热物性综合测试仪测定了不同热处理温度下Ｃ／Ｃ复合材料的导热系数，通过Ｘ射线衍射石墨化度的测定及晶粒尺寸计算，分析了材料的材质。进一步讨论了热处理温度、石墨化度与导热系数之间的关系。表明试样中存在性质不同的３个组元，随热处理温度的升高，平行于碳纤维长向的导热系数值从２２００℃的１４７Ｗ／ｍ·Ｋ升高到２８００℃的１８０Ｗ／ｍ·Ｋ左右，而垂直方向从相应的４９Ｗ／ｍ·Ｋ升高到７０Ｗ／ｍ·Ｋ。     

预制体对C／C复合材料热膨胀系数的影响

以天然气为前驱气体,整体碳毡和2D针刺碳毡为预制体,采用热悌度化学气相渗积技术制备了两种C／C复合材料,其表观密度均为1．74g／cm^3。借助光学显微镜和扫描电子显微镜观察了热解碳基体的生长特征和微观形貌,采用热膨胀仪测量了两种材料的热膨胀系数（CTE）,研究了由不同预制体增强C／C复合材料的CTE,解释了造成材料不同方向CTE差异的主要原因。结果表明,随着温度升高,材料A和B的CTE是逐渐升高的,且Z向CTE值均大于XY向。当两种材料在Z向的纤维体积分数接近时,随着XY方向纤维体积分数增大,材料在Z向的CTE增大,在XY向的CTE降低,两种材料存XY和Z向的CTE旱如下分布：αB—z〉dAz〉αA—xy〉αBxY-C／C复合材料的CTE主要取决于纤维体积分数和排市、碳基体及材料中的孔隙分布情况,前者起决定作用。     

Oxidation behavior of C/C composites with the fibre/matrix interface modified by carbon nanotubes grown in situ at low temperature

Carbon nanotubes (CNTs) were grown in situ on the fibre surface of unidirectional carbon fibre preform. The carbon fibre preform with nanotube modified fibres was then densified by chemical vapor infiltration to obtain CNT-reinforced C/C (CNT-C/C) composite. The effects of CNTs on the oxidation kinetics and mechanism of C/C composites were investigated. The results show that due to the growth of CNTs, a more perfect structure of pyrolytic carbon (PyC) and better fibre/PyC interface had been obtained, which in turn result in slower mass loss. Furthermore, higher graphitization degree leads to larger activation energy of CNT-C/C composite, compared with C/C composite.     

Friction and wear properties of pitch／resin densified carbon—carbon composites used for airbrakes

By use of X-ray diffractometry and scanning electron microscope(SEM),the friction and wear results obtained from MM-1000 dynamometer tests of CVI pitch/resin C/C composites were analyzed.By investigating the factors that affected the friction and wear properties,such as matrix carbon,applcation environment,graphitization degree and brake pressure,etc,friction and wear mechanism of carbon materials were probed.The results indicate that pitch densified CVI initially treated composite is more graphitizable with its graphitization degree up 59 62%,and which results in uniform small debris easier to generate,more smooth friction curves with the coefficient of 0.3-0.4 and relatively higher wear and mass loss,compared with CVI/resin C/C composites.It was further proved by SEM observation that tribological behavior of C/C composite was system dependent.Factors determining the friction and wear properties such as the size of debris and its influence on friction and wear,brake pressure,graphization degree and debris bilm formation interacted and affected each other.The friction and wear mechanism of C/C composites under different high temperature treatments needs further research.     

高密度预制体制备炭/炭复合材料的弯曲力学性能与断裂机制

以丙烯作为碳源,氮气作为载气,采用初始密度为0.94g/cm3三维正交PAN基12K炭纤维预制体,利用自制的快速CVI炉制备基体热解炭结构为带状结构的C/C复合材料。力学性能测试结果表明,材料的弯曲断裂特征与制备过程中受到的高温热处理次数有关。从载荷-位移曲线来看,当C/C复合材料经过两次热处理时,C/C复合材料呈明显假塑性断裂特征。当C/C复合材料经过三次热处理时,载荷-位移曲线趋于稳定平滑,抗弯强度降低。从C/C复合材料断面的SEM图可以观察到材料断裂可以分为层间断裂和层内断裂,而层内断裂又因热解炭填充密度变化呈明显的分区断裂。由于热解炭和纤维含量在C/C复合材料中分布的差异,材料在不同的区域表现出不同的断裂特征,从而使得材料具备良好的弯曲强度同时具有一定的韧性特征。     

炭/炭复合材料石墨化度的XRD均峰位法测定

采用XRD平均峰位法测定了4种C／C复合材料的石墨化度。研究结果表明：用平均峰位法测定C／C复合材料的石墨化度具有简便可靠、区分度高的优点。当C／C复合材料中炭纤维的含量低于基体炭含量时，难石墨化的炭纤维对C／C复合材料XRD谱线低角度一侧的线形有一定影响，但对最终的测量结果影响不大。     

C／C坯体对RMI C／C—SiC复合材料组织的影响

以PAN基炭纤维（Cf）针刺整体毡为预制体，用化学气相渗透（CVI）、浸渍炭化（IC）方法制备了不同炭纤维增强炭基体的多孔C／C坯体，采用反应熔渗（RMI）法制备C／C—SiC复合材料，研究了渗Si前后坯体的密度和组织结构。结果表明：不同C／C坯体反应溶渗硅后复合材料的物相组成为SiC相、C相及单质Si相；密度低的坯体熔融渗硅后密度增加较多；密度的增加与开口孔隙度并不是单调增加的关系，IC处理的坯体开口孔隙度低，但渗硅后复合材料的密度增加较多；IC坯体中分布分散的树脂C易与熔渗Si反应，CVI坯体中的热解C仅表层与熔渗Si反应，在Cf和SiC之间有热解C存在；坯体密度相同时，IC处理的坯体中SiC量较多，单质Si相含量少且分散较好，而CVI坯体中SiC量较少，单质Si相的量较多；制备方法相同时，高密度的C／C坯体，渗硅后C相较多。     

Influence of load on sliding tribology of C/C composite with 40Cr steel couple coated by Cr

With the 40Cr steel couple coated by Cr, the sliding tribology behavior of two kinds of C/C composites with different matrix was tested using a M2000 wear tester. The results show that with the increasing of load, the friction coefficients of the composite with resin carbon matrix（RC） decrease quickly from 0.156 under 60 N to 0.123 under 150 N, while those of the composite with rough lamination/smooth lamination/resin carbon （RL/SL/RC） change only between 0.122 and 0.101. The wear volume loss of the two composites increases except for under 100 N. The SEM morphology shows that with the increasing of load, the worn surface of the composite with RC becomes more and more integrated while the size of the debris becomes less and less. The Raman spectrum shows that the graphitization on the worn surface of the fibers draws down after 100 N, the graphitization of the boundary between the fiber and the matrix carbon rises up to 150 N, but the graphitization of the matrix carbon draws down all the while. With the increasing of load, the graphitization on the worn surface of all the worn areas becomes closer and closer, which indicates the worn surface of the different component has the similar friction ability. The composites with RL/SL/RC have better tribological characteristic than the composite with RC.     

Fracture mechanism of 2D-C/C composites with pure smooth laminar pyrocarbon matrix under flexural loading

Using natural gas as carbon source, 2D needle felt as preform, 2D-C/C composites were prepared by thermal gradient chemical vapor infiltration. Their microstructures were observed under polarized light microscope (PLM) and scanning electron microscope (SEM), and the flexural behaviors before and after heat-treatment were studied with a universal mechanical testing machine. The fracture mechanism of the composites was discussed in detail. The results show that, carbon matrix exhibits pure smooth laminar (SL) characteristic including numerous wrinkled layered structures and some inter-laminar micro-cracks. With the decreasing density, the strength of the composites decreases and the toughness increases slightly; after 2500 °C heat-treatment, the inter-laminar micro-cracks in matrix increase, the strength decreases, and the toughness obviously increases. The fracture mode of the composites changes from brittle to pseudo-plastic characteristic due to more crack deflections in SL matrix.     

准三维C/C复合材料的层间剪切性能及其断裂机理

以炭纤维针刺毡为预制体, 采用化学气相浸渗(CVI)法或结合液相法制备了热解炭、树脂炭和沥青炭基质的准三维C/C复合材料, 研究了这些材料的层间剪切性能及其断裂机理. 结果表明: CVI基质炭比沥青基质炭更有利于C/C复合材料的层间剪切性能的提高; 剪切强度随密度增高而增大, 致密度越高, 基体支撑越强, 同时微裂纹和孔隙度就越低, 断裂裂纹不易形成或扩展, 强度性能就越好; 纯沥青基质炭试样为"突发"的脆性断裂方式, 其他基质炭试样表现为韧性断裂方式.     

多孔C泡沫预制体液相渗硅制备C/SiC复合材料研究

以多孔C泡沫为预制体,利用液相渗Si工艺制备了C/SiC复合材料。采用酚醛树脂浸渍-裂解工艺对C泡沫预制体的孔隙率进行调整,考察浸渍-裂解周期对C泡沫预制体孔隙率的影响,研究了C泡沫预制体孔隙率对C/SiC复合材料密度、力学性能、组成和结构的影响。结果表明:预制体孔隙率为72%时制备的C/SiC复合材料性能较好,其密度为2.58g/cm3、弹性模量为81.39GPa,抗弯曲强度为83.88MPa;随着预制体孔隙率的降低,复合材料的密度、弹性模量和抗弯曲强度不断降低,预制体孔隙率的降低影响液相Si充分扩散与C反应,造成复合材料内部存在大量闭孔,这是导致C/SiC复合材料性能下降的主要原因。     

溶胶浸渍抗氧化涂层对C/C复合材料摩擦特性的影响

采用溶胶浸渍技术对4种C／C复合材料进行抗氧化处理。在M2000型摩擦实验机上测试了4种C／C材料的摩擦特性。结果表明：在相同载荷下，光滑层CVI（SL）的C／C材料浸渍后试样与未浸渍试样的摩擦因数值最接近：树脂炭（RC）的C／C材料中，浸渍后试样的摩擦因数均低于未浸渍的试样且相差最大；粗糙层CVI（RL）的C／C材料中，中高载荷下浸渍溶胶试样的摩擦因数低于未浸渍溶胶的试样：而具有粗糙层／光滑层／树脂炭（RL／SL／RC）的C／C材料中，中高载荷下浸渍溶胶后试样的摩擦因数变化比未浸渍试样的高。随载荷增加，SL炭材料未浸渍和己浸渍试样摩擦因数的变化幅度均最低，RC炭材料未浸渍试样和己浸渍试样的摩擦因数变化幅度最大，RL／SL／RC、RL结构的试样是否浸渍溶胶对其摩擦因数的影响无明显规律。石墨化度高的材料的摩擦行为受浸渍溶胶的影响高于石墨化度低的材料。     

Infiltration mechanism and factors influencing carbon/carbon–Zr–Ti–C composites prepared by liquid metal infiltration

The effects of fibre architecture, reaction temperature and holding time on the infiltration performance of carbon/carbon (C/C)–Zr–Ti–C composites prepared by liquid metal infiltration were investigated. The results indicated that samples with a chopped-web needled preform and low initial density had a high final density. Increasing the reaction temperatures resulted in a decrease of the final density of samples. Additionally, increasing the initial holding time appeared to obviously result in a high final density, but its effectiveness was not obvious in later observations. An analysis of the infiltration kinetics and mechanisms indicated that the diffusivity of carbon in the carbide, the open-pore sizes and their distribution in C/C composites were the essential characteristics that controlled the height of infiltrating melts.     

C／C复合材料等温CVI工艺模糊神经网络建模

C／C复合材料等温CVI工艺影响因素繁多，而效率极低，造成C／C复合材料的生产周期极长、制造成本极高。基于模糊神经网络技术及遗传算法，以有限元数值模拟结果作为网络训练的虚拟样本，建立了C／C复合材料等温CVI工艺预测系统，利用该系统挖掘得到了等温CVI工艺主要影响因素，如沉积温度，前驱气体组份比与流速等，对制件密度的作用规律，为CVI工艺的综合设计与优化提供了理论依据，提高了CVI工艺的设计水平，以期达到降低C／C复合材料制造成本的目的。     

Densification mechanism of chemical vapor infiltration technology for carbon/carbon composites

Carbon/carbon composites were fabricated using pressure-gradient chemical vapor infiltration（CVI） technology with propane （C3H6） as the carbon precursor gas and nitrogen （N2） as the carrier gas. The chemical process of deposition of pyrolytic carbon was deduced by analyzing the component of molecules in gas phase and observing the microstructure of deposition carbon. The results show that the process of deposition starts from the breakdown of C-C single bond of propene （C3H6）, and forms two kinds of active groups in the heterogeneous gas phase reaction. Afterwards, these active groups form many stable bigger molecules and deposit on carbon fiber surface. At the same time, hydrogen atoms of the bigger molecules absorbed on carbon fiber surface are eliminated and the solid pyrolytic carbon matrix is formed in the heterogeneous reaction process.     

热梯度CVI C/C材料的结构与性能

以炭纤维整体毡为预制体，采用热梯度CVI工艺制备了两种不同结构基体炭的C／C材料，即RL结构和SL结构材料。采用光学金相仪，X射线衍射仪，硬度计，激光导热仪等设备研究了沉积态和热处理态C／C材料的显微结构及热物理性能。对比研究了两种结构材料的力学性能及摩擦摩损性能。结果表明：当密度超过一定值后，密度对C／C材料的力学性能和摩擦性能的影响远不如CVD炭结构的影响大；不管是沉积态还是热处理态，RL结构材料的刹车性能曲线明显优于SL结构材料的刹车性能曲线，这意味着CVD炭的微观结构不同是造成C／C材料摩擦性能差异的根本原因。     

B、Si改性炭/炭复合材料及其摩擦磨损特性

以低密度的C/C复合坯体为预制体,分别采用反应熔渗(RMI)、化学气相沉积(CVD)、浸渍-原位反应技术对其进行陶瓷改性.结果表明:改性陶瓷分别以SiC和c-BN的形式渗入C/C复合坯体内.摩擦试验结果表明:采用RMI技术制备的C/C-SiC复合材料摩擦因数较高,高达0.3到0.9;采用CVD技术制备的C/C-SiC复合材料的摩擦因数在0.20～0.36之间;而采用浸渍-原位反应技术制备的c-BN改性C/C复合材料的摩擦因数较低,为0.10～0.20.SEM观察表明:采用RMI技术制备的C/C复合材料的摩擦表面粗糙、未形成完整的摩擦膜,而采用另两种技术制备的C/C复合材料均形成了较完整、致密的摩擦膜.     

超高碳钢热加工时的瞬时石墨化

喷射成形超高碳钢在热加工过程中有可能在极短的时间内发生石墨化.这种石墨化是在添加过多的非碳化物形成元素而使碳的活度超过1的热力学条件下,在Acm以下一段温度内、在足够大的变形量下发生的.这种与热变形直接相关的瞬时石墨化之所以能够发生,是因为预存孔洞提供了有利形核点;大变形促使渗碳体迅速溶解;大变形引入的大量位错提供了碳原子聚集的快速通道.