C/C复合材料结构显微激光喇曼光谱研究

采用显微激光喇曼光谱,以增强体为薄毡叠层、基体分别为粗糙层及光滑层结构热解炭的两种C/C复合材料为研究对象,分析、表征了两种材料炭结构的微观分布特征及其在石墨化过程中的变化状况。结果表明,不仅复合材料中不同组元,而且同一组元不同部位石墨微晶的完整度不同。在石墨化过程中,各自的石墨化进程及可石墨化能力存在差异:炭纤维体积含量较高的炭布层中的热解炭,与网胎层中的热解炭相比,石墨微晶的完整度较好,石墨化进程较快;在炭纤维体积含量较低的网胎层中,炭纤维及热解炭在其界面部位的石墨化进程较快;粗糙层结构热解炭比光滑层结构热解炭容易石墨化。借助激光喇曼光谱微区分析手段,有可能实现对复合材料中石墨化程度微观分布状态的调整和控制。     

C/C-ZrC复合材料的微观结构和力学性能研究

采用ZrOCl₂溶液浸渍法把锆化合物引入碳纤维预制体, 经热处理、热梯度化学气相渗透致密化和高温石墨化工艺制备了C/C-ZrC复合材料。性能测试结果表明, C/C复合材料的弯曲强度和模量随ZrC含量的增加而增大, ZrC含量为12.08wt%时, 其强度和模量分别为42.5 MPa 和9.6 GPa, 比未改性试样分别提高了70.0%和43.3%。基体中结合较弱的微米级ZrC颗粒的存在不利于碳基体强度的提高, 但其对材料最终性能的影响是次要的, 碳基体中亚微米/纳米级ZrC颗粒的存在和良好的ZrC-C界面结合, 提高了碳基体的强度和模量, 进而提高了复合材料的最终性能。     

Mechanical properties improvement of carbon/carbon composites by two different matrixes

Carbon/carbon (C/C) composites with two different matrixes of pitch carbon and pyrolytic carbon were fabricated using 2-dimensional (2D) carbon felts preform. In order to study the effects of matrixes on mechanical properties, C/C composites with single matrix of pitch carbon were prepared. The mechanical properties were tested on CMT5304-30KN universal testing machine. Polarization microscope and scanning electron microscope were used to investigate the microstructures and fracture surface of C/C composites. It was resulted that the flexural strength of C/C composites with two matrixes was improved by 96% compared with that of C/C composites with single matrix. Meanwhile, better toughness was also obtained with two matrixes. For the composites, multilayer microstructures were generated after filling up of voids caused during carbonization of mesophase pitch by pyrolytic carbon. The multilayer microstructures were beneficial to the improvement of mechanical properties of C/C composites, especially the toughness. More energy could be dissipated during mechanical tests while cracks might extend along multiple paths, such as the interface between fiber and matrix or the interface between different matrixes.     

耦合物理场CVI制备炭/炭复合材料及其机理

用液化石油气作碳源、炭毡作增强体,在坯体中埋置导电层诱导产生温度场和电磁场梯度,在自行设计的多元耦合物理场CVI炉中制备C/C复合材料,用偏光显微镜观察热解炭的显微结构,用XRD表征了材料的石墨化度和微晶尺寸等结构参数,所有样品均为一次性沉积所得,其增密曲线是采用把坯体密度与在线电阻进行拟合所得.研究了沉积温度、碳源气体分压对增密速度和材料结构的影响;并对物理场的耦合机理和热解炭的沉积机理作了探讨.研究表明,多元耦合物理场CVI工艺增密速度快,沉积20h,试样的密度达到1.71g/cm³;除了能获得中等织构的光滑层(SL)和带状结构的热解炭,还可获得高织构的粗糙层结构(RL)热解炭,在2300℃、2h热处理后,其石墨化度达到77%以上.     

碳源组成对化学气相渗透C/C复合材料致密化及热解炭结构的影响

为分析碳源在化学气相渗透过程中的沉积机制,以碳纤维针刺整体毡为预制体,添加丙烯（C₃H₆）的天然气混合气体为碳源,研究了碳源组成对C/C复合材料致密化及热解炭结构的影响。结果表明:相比于以天然气为碳源,以添加了适当比例C₃H₆的天然气为碳源,可有效提高C/C复合材料的致密化速率及密度分布均匀性;同时,有利于生成高织构的热解炭。最优条件（9vol% C₃H₆）下沉积100 h后,C/C复合材料的密度和径向密度偏差分别为1.40 g/cm3和0.04 g/cm3,热解炭为均一的粗糙层结构,石墨化度高;而以天然气作碳源时,密度和径向密度偏差分别为1.17 g/cm3和0.07 g/cm3,热解炭为二元带状结构,石墨化度较低;当C₃H₆比例增加到17vol%时,其密度和径向密度偏差分别为1.28 g/cm3和0.10 g/cm3,密度及密度分布均匀性较最优条件下制备的复合材料明显降低。      

Graphitization behaviour of carbon fibre-glassy carbon composites

Carbon fibre-carbon composites were fabricated by aligning PAN-based carbon fibre unidirectionally in furfuryl alcohol resin char. The graphitization behaviour was investigated by an X-ray diffraction technique and by the measurement of magnetoresistance. The time-temperature superimposition study for interlayer spacing resulted in an activation energy of 242±35 kcal mol⁻¹. The kinetic study on magnetoresistance agreed with the result of X-ray measurement. The activation energy is that for the graphitization of the layer structure formed in the glassy carbon matrix of the composites. The graphitization mechanism of the layer structure is the same as that of soft carbons.     

不同纤维体积分数CVI 炭/ 炭复合材料的石墨化度

为确定不同纤维体积分数的化学气相浸渗(CVI) C/ C 复合材料的最佳热处理工艺, 以40 %、30 %、25 %三种不同纤维体积分数的针刺整体毡为坯体, 经三次CVI 后制得C/ C 复合材料, 采用X射线衍射和拉曼光谱微区分析测试了三种不同纤维体积分数的CVI C/ C 复合材料试样未经热处理及经2200 ℃、2400 ℃热处理下宏观和微区石墨化度。结果表明: 三次CVI 热解炭均为光滑层结构, 且纤维体积分数越高, C/ C 复合材料的石墨化度也越高;纤维与光滑层热解炭界面及两种不同热解炭界面在高温热处理时会发生应力石墨化, 应力石墨化程度前者大于后者, 这是纤维体积分数高的C/ C 复合材料石墨化度高的原因; 热处理温度越高, 应力石墨化程度越大。      

碳／碳复合材料的宽温域自愈合抗氧化

在前期碳材料自愈合抗氧化研究的基础上,提出了通过多元陶瓷基体改性赋予碳／碳复合材料在较宽温度范围内实现自愈合抗氧化的基本原理和技术方案,分析了B4C—SiC、ZrC—SiC和ZrB2-ZrC—SiC等多元陶瓷的抗氧化机理,并采用新近合成的ZrB2-ZrC—SiC三元复相陶瓷有机前驱体,通过PIP技术制备了一系列超高温复相陶瓷改性的碳／碳复合材料,研究了该类复合材料在2200℃以下高速气流冲蚀环境中的协同抗氧化和抗烧蚀性能,发现材料表面生成的复合氧化物层能够在一定条件下赋予复合材料自愈合抗氧化能力。     

石墨化度及纤维含量对C/C复合材料性能的影响

以短切高模炭纤维为增强体.制备C/C复合材料,并采用XRD、SEM等方法研究了纤维体积含量和石墨化度对复合材料性能的影响.结果表明:当短切高模炭纤维体积含量小于7%时,随着炭纤维体积含量增加,C/C复合材料的力学性能逐渐升高,高于7%时力学性能降低;随着石墨化度提高,C/C复合材料的力学性能显著降低,短切高模炭纤维增强作用下降;C/C复合材料的石墨化度对电阻率影响大,纤维体积含量对电阻率几乎没有影响;C/C复合材料的石墨化度对材料的抗氧化性影响显著.     

In situ fabrication of carbon nanotube/mesocarbon microbead composites from coal tar pitch

Carbon nanotube/mesocarbon microbead composites have been synthesized from coal tar pitch with carbon nanotubes. How the carbon nanotubes affect the growth and the structure of mesocarbon microbeads are studied. The result shows that the size of beads decreases when more carbon nanotubes are added, and when the ratio of carbon nanotubes is set at 5%, we get the smallest sample with quite uniform shape. Carbon nanotubes exist both on the surface and inside of the samples and they will inhibit the growth and coalescence of these spheres. The addition of carbon nanotubes decreases the graphitization degree of the samples and makes their microtexture tend to be disordered.     

The effect of zirconium addition on the microstructure and properties of chopped carbon fiber/carbon composites

Carbon/carbon composites containing zirconium were prepared using chopped carbon fiber, mesophase pitch and Zr powder by the traditional process including molding, carbonization, densification and graphitization. The influence of Zr on the microstructure and properties of the composites were investigated. Results show that Zr can improve the interface bonding, promote more perfect and larger crystallites and enhance the conductive/mechanical properties of the composites. The high in-plane thermal conductivity of 464 W/(m K) and excellent bending strength of 83.6 MPa was obtained for a Zr content of 13.9 wt% at heat treatment temperature(HTT) of 2500 °C. However the conductive/mechanical properties of the composites decrease dramatically for an higher HTT of 3000 °C. SEM micrograph of the fracture surface for the composites shows that lower disorder crystallite arrangement of fiber and carbon matrix come into being in the composites during HTT of 3000 °C, which should be responsible for the low properties. Correlation between the content of Zr and the microstructure and properties are discussed.     

热处理对炭/炭-铜复合材料载流磨损行为的影响

为探明炭/炭(C/C)多孔体热处理对炭/炭-铜(C/C-Cu)复合材料载流磨损行为的影响,采用化学气相渗透法(CVI)增密的C/C多孔体,再通过压力熔渗法制备C/C-Cu复合材料.采用载流动态磨损试验机测试C/C-Cu复合材料载流磨损行为,利用数字式三维视频显微镜和扫描电子显微镜观察复合材料磨损前后的表面形貌,研究了C/C多孔体经过2 000℃热处理对C/C-Cu复合材料载流磨损行为的影响.结果表明:C/C-Cu复合材料的质量磨损率和线磨损率比C/C多孔体未经热处理的复合材料分别降低了34.42%和17.84%;C/C多孔体经过2 000℃热处理,石墨化度提高,片层劈裂阻力减小,在载荷的作用下石墨片层易于劈裂形成细小的石墨微晶碎片,迅速填充修复表面缺陷,形成具有一定润滑作用、平整的摩擦膜,有效抑制了局部非均匀磨损的扩大,减弱了磨粒磨损和电弧放电引起的烧蚀、粘着、氧化磨损之间的循环交替磨损,载流磨损性能提高.     

Effects of polymer derived SiC interphase on the properties of C/ZrC composites

Polymer derived silicon carbide (SiC) interphase was introduced by precursor infiltration and pyrolysis (PIP) to prevent carbon fiber erosion and to improve the fiber–matrix interface bonding of C/ZrC composites prepared by PIP. Introducing SiC interphase increased the density of the composites. The SiC interphase not only protected carbon fibers effectively from erosion by carbo-thermal reduction, but also enhanced the mechanical properties of C/ZrC composites by strengthening the interface bond. The flexural strength and fracture toughness of C/ZrC composites with SiC interphase prepared by two PIP cycles were 319 MPa and 18.8 MPa m^1/2 respectively. The ablation properties of C/ZrC composites were with rising content of SiC interphase but then decreased when excessive. The mass loss rate and the linear recession rate of the C/ZrC composites with SiC interphase prepared by one PIP cycle were 0.0079 g/s and 0.0084 mm/s, respectively.     

Effects of pressure on the pore formation of carbon/carbon composites during carbonization

In this study, porosity and graphitizability of coal tar pitch with the treatment pressure were investigated. 4-directional carbon/carbon composites (4D C/C) were made from the matrix precursor of coal tar pitch through the process of impregnation and carbonization. Then the effects of applied pressure during the densification on the composites were observed. The matrix pitch which had 600 bar applied during the carbonization process had one and a half times less pore area ratio than that treated at 1 bar. When the pitch was heat treated up to 2300°C after the high pressure carbonization, the degree of graphitization was improved on a small scale and the crystal size tended to reduce. As the applied pressures to 4D C/C composites increased from 1 to 600 bar, the densification ratio was greatly improved. In the pore size distribution of the 4D C/C composites, the macropore portion was decreased while the mesopore portion increased, when high pressures were applied.     

Microstructural evolution of carbon fiber reinforced SiC-based matrix composites during laser ablation process

In this work, four different carbon fiber reinforced SiC-based matrix composites (C/SiC) were prepared, and microstructure evolution during laser ablation process was characterized. Laser irradiation provided a special high-temperature environment up to 3500 °C. For all four composites, different morphologies can be obtained in the transition region due to the oxidation of different matrices. While only needle-shaped carbon fiber and nanolayered carbon without any matrix remained in the central region, indicating that graphitization process occurred in the center, resulting from the high-temperature and low-oxygen environment in the laser process. Therefore, the laser ablation of C/SiC composites is controlled by chemical and physical erosion, and mainly by the physical erosion in the center.     

Effect of matrix sub-layer interfacial fracture on residual strength improvement of the fatigued carbon/carbon composites

In the present study, flexural behavior of carbon fiber reinforced pyrolytic carbon matrix composites (C/C composites) before and after fatigue tests had been studied. The results showed that the residual flexural strengths of the samples had been improved after fatigue tests, and the fracture mechanisms of the original and post-fatigue specimens had some differences. Fracture mechanism of the original specimens could be described as fiber/matrix interfacial de-bonding, and the dominant damage of the post-fatigue specimens could be regarded as pyrolytic carbon sub-layers’ step-delamination. The degradation of matrix sub-layer interfacial bonding strength was beneficial to improve the mechanical properties of C/C composites.     

后热处理对C_f/ZrC复合材料微观结构及性能的影响

以C/C复合材料为基材、Zr_2Cu合金为渗剂,采用低温反应熔渗工艺制备得到碳纤维增强碳化锆陶瓷基复合材料(Cf/ZrC),重点研究后热处理对Cf/ZrC复合材料微观结构及性能的影响。结果表明:经1400~2200℃热处理后,材料密度下降,开孔率增大;材料在后热处理过程中会发生残余富铜熔体的流失、ZrC基体体积分数的增加以及ZrC基体结构的破坏;后热处理造成材料力学性能下降,热处理温度达到2200℃时,材料的弯曲强度保留率仅为52.3%。     

石墨化处理对双层热解炭基2DC/C复合材料微观结构的影响

综合采用偏光显微镜(PLM),X射线衍射仪(XRD),扫描电子显微镜(SEM),高分辨透射电子显微镜(HRTEM)等分析方法,逐层研究了2500℃高温石墨化(HTT)处理前后双层热解炭基2D C/C复合材料的不同织构以及纤维-基体界面的变化.结果表明:HTT处理后,d002值减小,石墨化度显著提高;内层低织构热解炭的断口微观形貌与晶格条纹几乎没有变化,而外层高织构热解炭晶格条纹更加平直,尤其是发现层间裂纹密度明显增大,使得处理后的高织构热解炭在受力时,裂纹易于在层间扩展和偏转,因此可有效提高材料的韧性;同时,纤维-基体界面发生弱化也是提高材料韧性的另一机制.HTT处理前后试样的三点弯曲力学性能试验结果证实了以上机制.     

C/Si-C-N复合材料的制备及其氧化行为研究

采用CVI方法制备出了以Si-C-N陶瓷为基体以热解炭为界面的炭纤维增强陶瓷基复合材料(C/Si-C-N)。采用热重法研究了C/Si-C-N复合材料在空气中的氧化行为,并探讨了基体制备温度对复合材料抗氧化性能的影响。研究表明:不同温度下制备的复合材料,其氧化行为完全不同。高温下制备的C/Si-C-N复合材料其氧化失重随氧化温度的升高而持续增加;低温下制备的C/Si-C-N复合材料则其氧化失重先随温度的升高而增加,随后在800~1000℃之间随温度的升高而减小,接着又随温度的升高而增加。较高的制备温度可使复合材料在900℃以下温度区间的抗氧化性能得到提高,但却使900℃以上温度区间的抗氧化性能降低。     

C/C复合材料石墨化度P1模型的表征及测定

C/C复合材料的石墨化度反映了材料中碳结构与理想石墨晶体结构的接近程度,并且是影响其性能的一个重要结构参数,石墨化度P1是一种能够比较准确地表示碳材料石墨程度结构的参数,本文利用P1的基本原理,编制了相应的计算程序,通过X光衍射（XRD）分析,计算了不同热处理温度C／C复合材料石墨化度P1,结果表明它可以较好的表征C／C复合材料的石墨化程度,并进一步讨论了热处理温度（HTT）与石墨化度的关系。