石墨化处理对不同高织构含量C/C复合材料微结构的影响

采用化学气相沉积工艺制备出炭毡增强炭/炭(C/C)复合材料和3K炭布叠层增强C/C复合材料,并对材料进行2500℃高温石墨化处理。利用X射线衍射仪;偏光显微镜及拉曼光谱仪对所制材料进行表征。结果表明,炭毡C/C复合材料基体是单一的高织构(HT)热解炭,3K炭布叠层C/C复合材料的基体是带状组织,从纤维表面向外依次为各向同性热解炭、HT和中织构(MT)热解炭,其中HT含量低于50%;沉积态和热处理后,两种C/C复合材料都具有相似的石墨化度,且热处理后的石墨化度超过80%,但Lc值差异明显,炭纤维、MT和HT热解炭的La值均升高,其中HT热解炭升幅明显大于炭纤维和MT热解炭。HT热解炭的含量是导致这两种C/C复合材料具有相似石墨化度而Lc值却显著差异的原因。     

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。      

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。     

炭纤维热处理对C/C复合材料力学性能的影响

采用化学气相沉积工艺对未处理和2 500℃热处理的炭纤维预制体进行致密化,对致密化后的C/C复合材料进行弯曲力学性能测试,借助偏光显微镜和扫描电子显微镜观察热解炭的组织、纤维的表面和弯曲试样断口的形貌.结果显示:高温热处理后,纤维表面变的更加光滑,表面出现很多沿纤维轴向的沟槽;致密化后的两种C/C复合材料的基体消光角约为21°,均为高织构热解炭;与未处理纤维增强C/C复合材料相比,经高温热处理后纤维增强的C/C复合材料的弯曲强度和模量均大幅下降,断裂特征由脆性转变为典型的假塑性,断口处有大量纤维拔出,纤维表面未粘附热解炭,表明对纤维进行高温热处理显著降低了纤维和热解炭基体的界面结合强度,导致材料强度降低,断裂呈假塑性.     

2D-C/C复合材料及其石墨化制品烧蚀特性分析

以液化石油气为碳源,2D炭纤维织物为基体,通过1000℃~1100℃沉积热解炭,制备了沉积态2D-C/C复合材料。通过对沉积态2D-C/C复合材料在2800℃热处理10h制备了石墨态2D-C/C复合材料。采用小型发动机烧蚀实验对两种复合材料的烧蚀性能进行了测试和评价;通过比较两种复合材料的孔隙分布、基体和纤维的结合强度以及热导率,解释了它们不同的烧蚀特性和烧蚀机理。结果表明:沉积态2D-C/C复合材料由于孔隙分布少、基体和纤维结合强度大、面间热导小,烧蚀主要由热化学反应(氧化)控制,烧蚀表面平整,烧蚀率为0.033mm/s。石墨态2D-C/C复合材料由于孔隙分布多、基体和纤维结合强度小,烧蚀主要由氧化和机械剥蚀控制,烧蚀表面出现烧蚀坑,烧蚀率为0.046mm/s。     

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,采用热梯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1.74 g/cm3。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,两种材料在XY和Z向的CTE呈如下分布:αB-Z>αA-Z>αA-XY>αB-XY。C/C复合材料的CTE主要取决于纤维体积分数和排布、碳基体及材料中的孔隙分布情况,前者起决定作用。     

碳/碳复合材料密封性能分析

为使高性能碳/碳(C/C)复合材料在航天密封材料领域中得到进一步的应用,本文研究了碳布叠层以及碳毡结构的C/C复合材料在一定压力下气体的渗漏情况,对比试样为俄罗斯高强石墨密封环材料,采用扫描电镜观察分析气体通过C/C复合材料的途径.结果表明:C/C复合材料比高强石墨更适合用作航天动密封材料.碳毡C/C复合材料比碳布叠层C/C复合材料气密性更好.C/C复合材料中的穿刺纤维以及贯穿基体的孔隙和裂纹以及纤维与碳基体的结合情况对密封材料的密封性能会产生很大的影响.     

循环加载周期对二维C/C复合材料弯曲疲劳强度的影响

采用频率为10 Hz、 应力比为0.1的正弦波研究了室温下循环次数对二维炭毡C/C复合材料(2D炭毡C/C复合材料)的弯曲疲劳强度的影响, 并利用偏光显微镜和扫描电子显微镜对该材料的热解碳组织形貌以及疲劳前后的断口形貌和微观结构进行了观察。结果表明, 2D炭毡C/C复合材料的热解碳结构由光滑层和各向同性层组成, 其疲劳极限为76.5 MPa, 是静态弯曲强度的90%。在不同循环周次的疲劳载荷作用后, 材料的剩余弯曲强度和韧性都得到了提高。在疲劳加载过程中, 纤维/基体的界面结合强度发生弱化, 纤维的协同承载能力得到提高, 使C/C复合材料出现了疲劳强化现象。      

不同预制体结构C/C复合材料轴向热力学性能分析

主要对比了编织C/C复合材料和针刺C/C复合材料的轴向热力学性能.编织C/C复合材料主要有径棒法、轴棒法、轴向穿刺三种,针刺C/C复合材料主要有炭布叠层针刺、整体毡两种.编织预制体密度较高,平均可达到0.70g/cm3以上,针刺类整体毡密度在0.20g/cm3左右,炭布叠层预制体密度在0.45g/cm3左右,均低于编织预制体.径棒法、轴棒法、轴向穿刺预制体轴向纤维含量≥19%,针刺类预制体轴向纤维含量约为5%.C/C复合材料的轴向拉伸强度、热膨胀系数与预制体编织结构、轴向纤维含量有关,编织类C/C复合材料轴向拉伸强度平均值≥40MPa,针刺类C/C复合材料轴向拉伸强度在10MPa左右.轴棒法、轴向穿刺、炭布叠层针刺、整体毡等四种C/C复合材料(RT～800℃)轴向热膨胀系数基本相当.     

高温热处理对C/C-SiC复合材料制备与力学性能的影响

以针刺整体炭毡为坯体,采用树脂浸渍和化学气相沉积混合法制备C/C多孔体,然后熔硅浸渗制得C/C-S iC复合材料;研究了C/C多孔体的高温热处理对C/C-S iC复合材料密度、孔隙度、力学性能及断裂方式的影响。结果表明:炭涂层进行高温热处理可改变复合材料的弯曲断裂方式,使其具有一定的“假塑性”,弯曲强度下降约16%,压缩强度提高约20%,硬度增加;C/C多孔体的最终高温热处理可打开孔隙,有利于液S i的渗入,制备出密度较高(>2.0 g.cm-3)、开孔率较小(<4%)的复合材料,但导致其力学性能下降,基本上不影响其断裂方式。     

Study of the infiltration and mechanical behavior of C/C composites prepared by ECVI

Three kinds of preforms, chopped fibers/resin carbon, spreading layers of carbon cloth, and needle-pricked long fiber felt, were used in this study. The preforms were densified by using the electrified preform heating CVI method (ECVI), and infiltrated using natural gas. Initial thermal gradients were determined. Resistivity and density evolutions with infiltration time have been recorded. A tensile test was applied to investigate the influence of preform architecture on the tensile properties of the C/C composites. Results show that the architecture of preform strongly influences the uniformity of infiltration and fibers/matrix bonding. The samples prepared from using 1K plain carbon cloth have the smallest density variations with position (about 0.011 g/cm³), and possess the highest tensile strength and modulus, while the samples produced from chopped fibers/resin carbon possess the lowest tensile strength due to their strong interfacial bonding between resin carbon and carbon fibers and poor microstructure.     

Effect of Temperature on the Synthesis of SiC Coating on Carbon Fibers by the Reaction of SiO with the Deposited Pyrolytic Carbon Layer

The influence of reaction temperature on the preparation of SiC coating on carbon fibers by the reaction of silicon monoxide with the deposited pyrolytic carbon (PyC) layer has been discussed. With rising reaction temperature, the thickness of SiC layer increases and the SiC grain is coarsening. The apparent activation energy for the synthesis of SiC layer is about 103.3 kJ/mol. The oxidation resistance of carbon fiber can be improved by the SiC/PyC layers significantly. The initial oxidation temperature of the SiC/PyC coated carbon fiber is about 300°C higher than that of the uncoated carbon fiber. The oxidation of the SiC/PyC coated carbon fiber is owing to the diffusion of oxygen through the cracks generated by the mismatch of thermal expansion.     

针刺C/C复合材料面内拉伸强度预测

为研究针刺碳纤维增强碳基体复合材料(针刺C/C复合材料)面内拉伸强度与渐进损伤,建立了针刺C/C复合材料代表性体积单元有限元模型。模型包含无纬布层、网胎层、针刺纤维束、界面4类子区域,并考虑了孔隙的影响。采用基于应变的破坏准则及指数型损伤演化规律研究无纬布层及针刺纤维束损伤,采用弹塑性本构研究网胎层损伤,采用内聚力牵引分离定律和二次应力破坏准则分析界面损伤。通过两步法计算了孔隙对材料性能的折减效果,并得到上述4个子区域的力学性能,通过ABAQUS UMAT预测了材料的面内拉伸应力-应变曲线及各子区域损伤起始、演化与失效过程,非线性趋势及拉伸强度数值与试验数值吻合较好,验证了该模型有效性。      

Microstructure characterization of CVI-densified carbon/carbon composites with various fiber distributions

Mechanical behavior of multi-phase composites is crucially influenced by volume fractions, orientation distributions and geometries of microconstituents. In the case of carbon–carbon composites manufactured by chemical vapor infiltration, the microconstituents are carbon fibers, pyrolytic carbon matrix, and pores. The local variable thickness of the pyrolytic carbon coating, distribution of the fibers and porosity are the main factors influencing the properties of these materials. Two types of fiber arrangements are considered in this paper: 2D laminated preform and random felt. The materials are characterized by determining their densities and their fiber distribution functions, by establishing types of pyrolytic carbon matrix present in the composites, and by studying the porosity. A technique utilizing X-ray computed tomography for estimation of the orientation distribution of the fibers and pores with arbitrary shapes is developed. A methodology based on the processing of microstructure images with subsequent numerical simulation of the coating growth around the fibers is proposed for estimation of the local thickness of the coating. The obtained information is appropriate for micromechanical modeling and prediction of the overall thermo-mechanical properties of the studied composites.     

C/C 复合材料增强体结构对性能影响的研究

研究了四种C/C 复合材料增强体(1K 碳布、3K 碳布、1K 碳布+ 碳纸、1K 碳布+ 特殊碳毡) 结构对弯曲性能的影响。结果表明: 用这四种增强体制备的C/C 复合材料表现出明显的假塑性, 弯曲断口的宏观形貌呈“之”字形, 其总体力学性能良好, 但也具有较大差异。本文作者结合材料的微观形貌对这些特点的成因进行了分析。      

原位生长的气相生长碳纤维增强C/C复合材料的制备及其弯曲性能

以丙烯为碳源, FeCl₃·6H₂O为催化剂, 采用化学气相沉积法(CVD)在碳毡和不同密度的C/C复合材料上原位气相生长碳纤维(VGCFs) , 并以含原位生长VGCFs的碳毡和不同密度的C/C复合材料为基体制备VGCFs-C/C复合材料。研究了反应压力、基体密度对VGCFs生长情况的影响, 借助扫描电镜(SEM)、光学显微镜观察原位生长VGCFs的形貌及基体原位生长VGCFs后热解炭形貌的变化, 并对比研究了C/C复合材料和VGCFs-C/C复合材料的弯曲性能。研究结果表明, 反应压力为3700 Pa, 基体密度低的情况更有利于VGCFs的生长; 原位生长的VGCFs改变了纤维表面热解炭的沉积形貌, 使得热解炭和碳纤维的结合面之间形成具有铆钉作用的球状结构, 增强了界面结合力, 从而提高了原位生长的高VGCFs含量样品的弯曲强度。     

自发梯度炭／炭复合材料弯曲性能研究

对包埋－粉末涂刷高温烧结工艺制备的自发梯度二维炭/炭（2D C／C）生物活性玻璃涂层复合材料进行了弯曲力学性能测试和断口形貌观察,结果表明：生物玻璃涂层的2D C／C试样的断口形貌显示,涂层与C／C结合紧密;部分纤维插入生物玻璃内;同时,生物玻璃涂层内的裂纹能沿纤维与其界面扩展,表明位于涂层内的纤维与涂层的结合为弱结合;统计分析表明,涂层处理后的试样弯曲模量、抗弯强度都有所提高,而挠度无显著差异。     

炭布叠层针刺预制体性能分析

通过X-Y向拉伸强度、Z向剥离强力、NOL环整体拉伸强度表征预制体性能,研究了炭布叠层针刺预制体的结构特点.结果表明:X-Y向拉伸强度反映了针刺对连续纤维的损伤程度,其随针刺密度升高而降低.网胎面密度对Z向预制体剥离强力的影响规律性不明显,3 K炭布针刺预制体剥离强力高于6K和12K炭布针刺预制体,斜纹炭布针刺预制体剥离强力高于缎纹炭布预制体.NOL整体拉伸环破坏有完全断裂、褶皱式不完全断裂、层间剥离三种模式;3 K缎纹炭布针刺预制体NOL环拉伸强度最低,只有3 MPa,呈现整体拉伸完全断裂破坏模式;12 K缎纹炭布针刺预制体呈现层间破坏模式;6 K缎纹炭布针刺预制体的破坏方式为褶皱式不完全断裂模式,整体力学性能较好.相同工艺预制体环向拉伸强度远大于X-Y向拉伸强度.     

Two opposite growth modes of carbon nanofibers prepared by catalytic decomposition of acetylene at low temperature

Helical carbon fibers were synthesized by the catalytic decomposition of acetylene as carbon source at low temperature of 240–260 °C with two nanocopper catalysts prepared by the hydrogen-arc plasma method and thermal decomposition of copper tartrate. Two growth modes for helical carbon fibers were obtained. One is mirror-symmetric growth mode, and the other is asymmetric growth mode. In the two growth modes, there were always only two helical fibers in regular shapes that were grown over a single copper nanoparticle. The two helical fibers had identical coil diameter, coil length, fiber diameter, cycle number, tight coil pitch, and cross section. In mirror-symmetric growth mode, the two helical fibers had absolutely opposite helical senses. The catalyst particle size was less than 50 nm and the coil diameter was <100 nm. Whereas in asymmetric growth mode, the two helical fibers had absolutely identical helical senses. The catalyst particle size was larger than 200 nm and their coil diameters reached 1 μm. The catalyst particle size had considerable effect on the growth mode for helical carbon fibers.