一维高导热C/C复合材料的制备研究

以三种沥青作为基体前驱体, 实验室自制的AR中间相沥青基纤维为增强体, 通过500℃热压成型, 随后经炭化和石墨化处理制备出一维炭/炭(C/C)复合材料。研究了前驱体沥青种类和热处理温度对复合材料导热性能的影响, 并采用扫描电子显微镜和偏光显微镜对其石墨化样品的形貌和微观结构进行表征。结果表明; C/C复合材料在沿纤维轴向的室温热扩散系数和导热率均随热处理温度的升高而逐渐增大; 由AR沥青作为基体前驱体所制备的C/C复合材料具有更加明显的沿纤维轴向取向的石墨层状结构以及最好的导热性能, 其3000℃石墨化样品沿纤维轴向的室温热扩散系数和导热率分别达到594.5 mm²/s和734.4 W/(m·K)。     

三维针刺C/SiC刹车材料的热物理性能

通过化学气相渗透(CVI)法结合反应熔体浸渗(RMI)法制备了三维针刺C/SiC刹车材料, 系统研究了三维针刺C/SiC刹车材料的热物理性能。结果表明: C/SiC刹车材料的热膨胀系数随温度升高总体呈增大趋势, 但呈规律性波动; 在相同温度下, 垂直于摩擦面方向的热膨胀系数远大于平行方向的。从室温至1300 ℃, 平行和垂直于摩擦面方向的平均热膨胀系数分别为1.75×10-6K-1和4.41×10-6K-1; C/SiC刹车材料的比定压热容随温度的升高而增大, 但增大速率逐渐减小。温度从100 ℃升到1400 ℃, 其比定压热容从1.41 J/(g·K) 增大到1.92 J/(g·K); C/SiC刹车材料的热扩散率随温度的升高而降低, 并趋于常量。平行于摩擦面方向的热扩散率明显大于垂直于摩擦面方向的热扩散率。      

鳞片石墨掺杂对单向C/C复合材料结构和性能的影响

以大直径(40~50μm)中间相沥青基炭纤维为导热相,以掺杂一定量不同粒径天然鳞片石墨的中间相沥青为黏结剂,经500℃热压成型、高温炭化及石墨化处理制备出单向高导热炭/炭(C/C)复合材料。采用偏光显微镜和扫描电子显微镜对复合材料石墨化样品的形貌和微观结构进行表征,并探讨鳞片石墨掺杂对复合材料不同方向导热性能的影响。结果表明,掺杂鳞片石墨对复合材料的体积密度影响较小,但对复合材料不同方向的导热性能有显著影响,复合材料沿纤维长度方向的室温热扩散系数随鳞片石墨体积分数和粒径的增加而减小,而垂直纤维长度方向的室温热扩散系数呈现上升趋势;添加16 vol.%粒径约为60μm的鳞片石墨所制复合材料沿纤维长度方向热扩散系数由掺杂前的650.5 mm~2/s降至510.9 mm~2/s,下降了21%,而垂直纤维长度方向的室温热扩散系数由22.4 mm~2/s提高到48.9 mm~2/s,增加了118%。掺杂鳞片石墨明显提高了复合材料垂直纤维长度方向的导电性能和抗弯性能。     

具有莫来石界面的C/Si-C-N复合材料热物理性能

以PIP方法制备界面层、CVI工艺制备基体,制备以Si-C-N陶瓷为基体、以莫来石为界面的碳纤维增强陶瓷基复合材料(C/mullite/Si-C-N).采用热膨胀仪和激光导热仪分别测试C/mullite/Si-C-N的热膨胀性能和热扩散性能,采用SEM和XRD分析材料的组织和形貌,采用DSC/TG同步分析仪分析基体材料的结构变化.结果表明:在25～1200℃范围内,C/mullite/Si-C-N复合材料的平均热膨胀率为1.58×10-6℃-1,线膨胀率为0.18％.复合材料的热扩散率与温度呈指数下降关系,这种指数关系是由基体的非晶结构造成的.热处理后的C/mullite/Si-C-N相对于未热处理的试样室温下的热扩散率显著下降,300℃以上的高温区段则略有升高,其在1000℃以下结构稳定,能满足工程应用需求.     

2D C/SiC复合材料氧化损伤的红外热波成像检测

采用红外热波成像技术分别对二维叠层C/SiC(2D C/SiC)复合材料的无SiC涂层盲孔试样和有SiC涂层的三点弯曲强度试样的氧化损伤进行无损检测。分析了材料氧化损伤与热辐射强度信号之间的关系, 以及热扩散系数与材料密度、抗弯强度之间的关系, 探索了采用红外热波成像检测和评价2D C/SiC氧化损伤的可行性。检测结果表明: 红外热波成像可以直观地反映2D C/SiC复合材料的氧化损伤。2D C/SiC氧化后的密度随热扩散系数的减小呈对数降低, 其抗弯强度随热扩散系数的减小呈抛物线降低。由此得出, 热扩散系数可以作为衡量陶瓷基复合材料的氧化损伤程度的依据, 红外热波成像是一种无损检测陶瓷基复合材料氧化损伤的有效方法。      

热处理温度对高导热3D C/C复合材料性能的影响

通过化学气相渗透和前驱体浸渍裂解复合工艺对三向碳纤维织物进行致密化,获得密度为1.95 g/cm3的高导热3D C/C复合材料.利用SEM,XRD,导热系数测试,线膨胀系数测试和三点弯曲实验,研究2350,2550,2850℃不同热处理温度对3D C/C复合材料微观形貌、结构、导热系数、线膨胀系数和弯曲性能的影响.结果表明:随着热处理温度的升高,中间相沥青基碳纤维石墨片层结构更加明显,均匀包裹在碳纤维周围的热解碳片层排列的有序度提高,且片层之间排列更加致密;3D C/C复合材料的石墨化度和导热系数提高;在测试温度250～1400℃区间,线膨胀系数随着测试温度的升高略微增大,不同热处理温度后的3D C/C复合材料线膨胀系数均在-1×10-6～2×10-6℃-1,表现出良好的"零膨胀性".此外,当热处理温度升高,3D C/C复合材料的碳纤维与基体的结合减弱,导致材料的弯曲强度和弯曲模量降低,2850℃高温热处理后的材料弯曲断裂面出现大量长纤维拔出,总体来说,3种不同热处理温度后的断裂均表现出"假塑性"断裂特征.     

C/ C坯体对 C/ C2Cu复合材料摩擦磨损行为的影响

采用无压熔渗方法制备炭纤维整体织物/炭2铜 (C/ C2Cu) 复合材料 , 在 MM22000型环2块摩擦磨损试验机上考察复合材料的摩擦磨损性能 , 利用扫描电子显微镜观察分析磨损表面形貌 , 研究 C/ C坯体对材料的摩擦磨损行为的影响及机制。结果表明 : 随着 C/ C坯体密度的增加 , 摩擦系数及 C/ C2Cu材料自身和对偶的磨损量均降低 ; 采用浸渍/炭化 ( I/ C) 坯体的 C/ C2Cu材料摩擦系数及自身和对偶件的磨损量均高于采用化学气相渗透(CVI) 坯体的试样; 摩擦面平行于纤维取向的试样摩擦系数低于垂直于纤维取向的试样 , 但磨损率较高。     

C/C复合材料在原子氧辐照下的结构性能演变

通过分析失重率、显微形貌变化讨论了原子氧辐照对C/C复合材料以及SiC基体改性C/C复合材料(C/C-SiC)的损伤机制; 并通过热膨胀系数(CTE)、热扩散率(TD)以及弯曲强度等性能的变化, 进一步讨论了原子氧辐照损伤对材料热物理及力学性能影响。结果表明, C/C复合材料受原子氧辐照损伤是物理化学综合作用, 属于冲击诱发-增强表面化学刻蚀; SiC组元表现出良好的抗原子氧侵蚀性能, 阻碍了原子氧向材料内部侵蚀, 但是SiC组元在更长时间辐照后出现机械破损; C/C复合材料在原子氧辐照下失重率呈线性增加, 而C/C-SiC复合材料失重率小于C/C复合材料且增长幅度越来越小; C/C复合材料和C/C-SiC复合材料的整体结构性能在辐照损伤后发生了一定变化。     

不同C/C复合材料飞机刹车盘基本性能的对比分析

通过对比分析Dunlop、 B.F.Goodrich、Missier、Bendix和中南大学粉末冶金研究所制备的几种炭/炭复合材料的显微组织、石墨化度、导热系数、洛氏硬度、抗压、抗弯、层间剪切强度、摩擦磨损性能后,得出如下结论:C/C复合材料作为一种性能优良的制动材料,必须具有合理的炭纤维骨架结构,一定比例的粗糙层气相沉积炭结构,较高的石墨化度和垂直摩擦面方向上的导热系数;我国具有自己知识产权的C/C复合材料飞机刹车盘的研制工作已取得了较大的进展和突破,其各项性能指标与国外同类产品性能相当。     

高导热碳/碳复合材料微观结构及导热性能EI北大核心CSCD

采用国产沥青基碳纤维与中间相沥青制备多孔碳/碳(C/C)复合材料,通过化学气相渗透法(CVI)与前驱体浸渍裂解法(PIP)复合工艺增密,经不同温度高温热处理(HTT)后制备单向C/C复合材料和两向正交C/C复合材料。利用SEM,XRD对不同温度热处理的材料进行微观结构分析,并结合导热机理,分析材料导热性能。结果表明:2300℃热处理后,高导热C/C复合材料结构致密,单向C/C复合材料X向(平行于碳纤维轴向)、两向正交C/C复合材料X向、Y向表现出优异的导热性能;3000℃热处理后,C/C复合材料石墨片层结构明显,石墨化度提高了18.84%,微晶尺寸增大,导热性能进一步提高。两向正交C/C复合材料X向、Y向导热系数可由单向C/C复合材料X向、Z向导热系数计算推导。     

短切炭纤维增强沥青基C/C复合材料的组织特征

利用新型、高效的模压半炭化成型工艺，在大气环境下制备出了短切炭纤维增强沥青基C／C复合材料制品，并借助光学显做镜和扫描电镜对其微观组织和断口形貌进行了观察。通过分析，解释了短切炭纤维增强沥青基C／C复合材料中炭纤维损伤的形成机制，提出了作为增强体相的短切炭纤维和焦炭颗粒与基体炭之间独特的界而结构模型。研究还表明：复合材料中明显存在着基体相和颗粒相一基体相的显微结构不仅呈层片状，而且层片状的结构好像数层桔子皮，将颗粒相包裹起来，这种“桔皮包裹”式的结构与炭纤维表面的POG结构基本相似。     

Kinetics of chemical vapor infiltration of carbon nanofiber-reinforced carbon/carbon composites

Preforms containing 0, 5, 10, 15 and 20 wt.% carbon nanofibers (CNFs) were fabricated by spreading layers of carbon cloth, and infiltrated by using the technique of isothermal chemical vapor infiltration (ICVI) at the temperature of 1100 °C under the total pressure of 1 kPa and with the flow of the mixture of propane/nitrogen in a ratio of 13:1. The infiltration rates increased with the rising of CNF content, and after 580 h of infiltration, the achievable degree of pore filling was the highest when the CNF content was 5 wt.%, but the composite could not be densified efficiently as the CNF content ranged from 10 to 20 wt.%. An analysis of the results, based on the effective diffusion coefficient and on the in-pore deposition rates, shows that the CNFs, due to their higher aspect ratio, accelerate overgrowth at pore entrances and thus lead to incomplete pore filling.     

短切炭纤维增强沥青基C/C复合材料的力学性能

利用模压半炭化成型工艺在大气环境下制备出了短切炭纤维增强沥青基C／C复合材料（简称SCFRC）。研究了短切炭纤维的体积分数对SCFRC材料的体积密度和力学性能的影响规律。借助光学显微镜和扫描电镜对其微观组织和断口形貌进行了观察，分析了短切炭纤维对SCFRC材料的增强机制。结果表明，当短切炭纤维的体积分数由0％增大到11．8％时，SCFRC材料的力学性能随之呈线性增加；短切炭纤维增强SCFRC材料的机制主要有裂纹偏转效应、桥联效应以及脱粘和拔出效应。     

软硬混编预制体增强沥青基4D-C/C材料的拉伸破坏行为

以X-Y平面依次铺设炭纤维束、Z向穿插炭棒的4D软硬混编为预制体,采用沥青液相常压、高压浸渍/炭化-石墨化循环致密工艺制备4D-C/C复合材料。通过该材料Z向(炭棒方向)的拉伸实验,测定其拉伸性能和力学行为,并采用SEM分析试样表面及断口形貌。结果表明:宏观上拉伸试样以炭棒整体拔出的形式破坏;细观尺度上,试样表面形成了与载荷方向垂直的贯穿性裂纹,裂纹以2 mm左右的距离呈等间距分布;材料进一步的破坏过程中,基体裂纹在X-Y向纤维束中呈线性扩展,快速分割了基体材料,使4D-C/C复合材料的拉伸破坏演变为1D-C/C复合材料的破坏模式,由于炭棒与基体炭界面结合弱,炭棒以拔出方式失效和破坏。     

Hierarchical carbon nanostructure design: ultra-long carbon nanofibers decorated with carbon nanotubes

Hierarchical carbon nanostructures based on ultra-long carbon nanofibers (CNF) decorated with carbon nanotubes (CNT) have been prepared using plasma processes. The nickel/carbon composite nanofibers, used as a support for the growth of CNT, were deposited on nanopatterned silicon substrate by a hybrid plasma process, combining magnetron sputtering and plasma-enhanced chemical vapor deposition (PECVD). Transmission electron microscopy revealed the presence of spherical nanoparticles randomly dispersed within the carbon nanofibers. The nickel nanoparticles have been used as a catalyst to initiate the growth of CNT by PECVD at 600°C. After the growth of CNT onto the ultra-long CNF, SEM imaging revealed the formation of hierarchical carbon nanostructures which consist of CNF sheathed with CNTs. Furthermore, we demonstrate that reducing the growth temperature of CNT to less than 500°C leads to the formation of carbon nanowalls on the CNF instead of CNT. This simple fabrication method allows an easy preparation of hierarchical carbon nanostructures over a large surface area, as well as a simple manipulation of such material in order to integrate it into nanodevices.     

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.     

Diamond formation on carbon/carbon composite

A carbon/carbon composite was used as substrate for low-pressure diamond deposition. To enhanced diamond nucleation on carbon/carbon composites, a total of ten surface preparation methods have been investigated. These methods involved the use of atomic hydrogen etching, mechanical polishing, sonication, or coating. Diamond nucleation was found to occur on either the defects of the carbon/carbon composite substrates or diamond particulate left on the substrates. The defects were created primarily by atomic hydrogen etching during the coating process. Seeding with diamond powders was performed by dip coating, sonication, or spray-coating processes. It was found that these seeding processes resulted in excellent nucleation of diamond.     

Mesoscale evolution of non-graphitizing pyrolytic carbon in aligned carbon nanotube carbon matrix nanocomposites

Polymer-derived pyrolytic carbons (PyCs) are highly desirable building blocks for high-strength low-density ceramic meta-materials, and reinforcement with nanofibers is of interest to address brittleness and tailor multi-functional properties. The properties of carbon nanotubes (CNTs) make them leading candidates for nanocomposite reinforcement, but how CNT confinement influences the structural evolution of the PyC matrix is unknown. Here, the influence of aligned CNT proximity interactions on nano- and mesoscale structural evolution of phenol-formaldehyde-derived PyCs is established as a function of pyrolysis temperature (\(T_{\mathrm {p}}\)) using X-ray diffraction, Raman spectroscopy, and Fourier transform infrared spectroscopy. Aligned CNT PyC matrix nanocomposites are found to evolve faster at the mesoscale by plateauing in crystallite size at \(T_{\mathrm {p}}\) \(\sim\)800 \(^{\circ }\hbox {C}\), which is more than \(200\,\,^{\circ }\hbox {C}\) below that of unconfined PyCs. Since the aligned CNTs used here exhibit \(\sim\)80 nm average separations and \(\sim\)8 nm diameters, confinement effects are surprisingly not found to influence PyC structure on the atomic-scale at \(T_{\mathrm {p}}\) \(\le \)1400 \(^{\circ }\hbox {C}\). Since CNT confinement could lead to anisotropic crystallite growth in PyCs synthesized below \(\sim\)1000 \(^{\circ }\hbox {C}\), and recent modeling indicates that more slender crystallites increase PyC hardness, these results inform fabrication of PyC-based meta-materials with unrivaled specific mechanical properties.     

Vitreous joining of SiC-coated carbon/carbon composites

This paper investigated the feasibility of joining of carbon/carbon (C/C) composites by using a silicate as interlayer. A SiC coating was pre-prepared on C/C substrate by pack-cementation technique to improve the wettability of glass on C/C composites, then the joints were prepared by a one-shot and low cost way. Microstructure and morphologies of the as-received joints were characterized by XRD, SEM and EDS. The results indicated that the SiC coating not only had a strong bonding with C/C composites, but also had a good physical and chemical compatibility with silicate glass. The room-temperature shear strength of the joints gives encouraging results, which can be up to 26 MPa. The fracture mode and the fracture behavior were discussed also.