多元耦合场 CVI法炭/炭复合材料制备及结构分析

为了降低成本,以液化石油气作碳源气体,炭毡作增强体,利用多元耦合场CVI方法快速制备了炭/炭复合材料．研究表明,炭纤维预制体在650℃较低温度条件下沉积15h,密度达到了1．71g·cm~(-3)；采用偏光显微镜研究了热解炭的显微结构．结果表明,在同一试样中存在粗糙层、光滑层和带状结构的热解炭,并且材料密度均匀性较好．同时分析了致密化的工艺过程并讨论了热解炭沉积机理．     

乙醇热解制备炭/炭复合材料工艺探索及组织特征

以密度0.47g/cm³的碳毡为预制体,乙醇为前驱体,氮气为载气,在1125℃,压力为20kPa的条件下,用等温压力梯度化学气相渗透法,经114h致密化,制备出密度为1.67g/cm³的炭/炭复合材料.经测试,材料的弯曲强度为137MPa.偏光显微分析显示：该材料各区域沉积的基体热解碳组织结构均为高织构,其消光角为19.5°～20.5°,石墨化处理后测得热解碳的d₀₀₂为0.3362nm.断口扫描电子显微分析结果也进一步证实获得的热解碳组织为高织构.表明乙醇是一种极具潜力的制备炭/炭复合材料的前驱体.     

压力梯度CVI工艺制备2D炭/炭复合材料的弯曲断裂行为

采用三点弯曲方法测试了压力梯度化学气相浸渗法(CVI)工艺制备的2D炭／炭复合材料的性能，借助于扫描电镜研究了断口和界面形貌，分析了密度和纤维基体界面对材料力学性能的影响。结果表明，随试样密度增加，2D炭／炭复合材料的断裂模式从剪切断裂、层问分离向拉伸断裂转变。材料密度对弯曲强度和模量影响很大，但对弯曲挠度基本没有影响。揭示了影响2D炭／炭复合材料弯曲挠度的关键因素是纤维与热解炭基体界面的结合情况。     

热处理温度对热解炭及炭/炭复合材料力学性能的影响

以丙烷为气源,采用等温等压化学气相渗透技术制备了炭/炭复合材料,利用X射线衍射、偏光显微镜、扫描电镜、纳米压痕仪、三点弯曲法研究了热处理温度对热解炭以及炭/炭复合材料微观结构和力学性能的影响.微观结构观察显示随着热处理温度的升高,热解炭层间距减小,同时石墨化度提高;由于发生了局部应力石墨化,热解炭出现同心微裂纹,并且随热处理温度的升高裂纹的数量和宽度增加.纳米压痕测试表明,热解炭的纳米压痕行为是完全的弹性形变,完全卸载后热解炭表面没有残余压痕,但加载和卸载曲线没有重合而是存在一定的能量耗散,随着热处理温度的升高,热解炭的弹性模量增大.热处理后纤维强度降低,并且纤维与基体炭界面脱离,导致炭/炭复合材料的弯曲强度和模量下降.     

空气氧化处理的中间相沥青基炭/炭复合材料的组织和弯曲性能

通过引入225℃空气氧化处理,在较短周期内采用常压浸渍炭化工艺制备了中间相沥青基炭/炭复合材料.采用偏光显微镜、万能力学试验机及扫描电镜等检测手段研究了炭/炭复合材料微观组织和弯曲力学性能.研究结果表明,225℃空气氧化处理后,炭化收率显著提高,经过四次常压浸渍-炭化循环后炭/炭复合材料密度达到了1.73g/cm3,弯曲强度为152.39MPa,比未经过空气氧化处理的试样提高了62.87%.空气氧化处理制备的试样呈现典型的假塑性断裂特征,而未经空气氧化处理制备的试样主要从层间断裂,其弯曲强度较低.通过偏光显微分析,未经空气氧化处理的炭/炭复合材料组织大部分为小域组织,只有少量的镶嵌型组织和广域组织,而经过225℃空气氧化处理后的试样,以广域型组织为主,并在其间夹着流线型组织和小域组织.     

CLVI技术制备炭/炭复合材料

利用化学液气相沉积工艺以煤油为前驱体,采用密度为0.4g/cm3的针刺炭纤维毡为预制体,10h内制备了壁厚为40mm,密度沿径向均匀分布,密度达1.70g/cm3的炭/炭复合材料盘形件.同时还阐明了用于制备炭/炭复合材料的化学液气相沉积工艺原理及工艺过程,利用偏光显微镜观察所得材料的微观组织结构属光滑层结构的热解炭.     

不同甲烷氢气比例前驱体制备炭/炭复合材料的研究

以不同比例甲烷氢气(CH4、CH4/H2=3/1、CH4/H2=2/1)作为前驱体,采用等温等压化学气相渗积工艺,在1100℃,气压为5kPa下,经过500h制备相应的炭/炭复合材料样品。研究了密度随致密化时间的变化规律和样品的密度分布,采用偏光显微镜、高温热处理后X射线衍射、三点弯曲实验对材料进行了表征,结果表明:甲烷体系中氢气的加入在致密化初期会对沉积速率有明显的减小作用,最终得到的样品密度分布均匀。同时CH4/H2=2/1前驱体获得近乎单一的粗糙层结构,具有最高的石墨化度,氢气的加入提高了材料密度,提高了炭/炭复合材料的力学性能。     

准三维炭／炭复合材料力学性能分析

以针刺网胎无纬布交替叠层准三维结构为预制体,采用热梯度化学气相沉积（TCVI）和树脂压力浸渍-炭化（PIC）混合致密方法得到不同密度的炭／炭复合材料,研究了密度和热处理温度对炭／炭复合材料弯曲和压缩性能的影响,并对其机理进行了探讨。结果表明：增大材料的密度可以提高材料的弯曲和压缩性能,破坏机理发生改变,密度较低时,弯曲破坏方式为“假塑性”的分层破坏模式,压缩破坏为压溃式破坏;高密度的试样,弯曲破坏为拉应力或压应力破坏模式,压缩破坏为剪切和分层破坏模式,表现出一定的脆性;热处理温度升高,降低了材料的弯曲和压缩强度或模量,但明显改变了材料的破坏模式,增多了裂纹扩展或偏转的途径,表现出更好的“假塑性”;由分析得出,准三维炭／炭复合材料承压时,针刺处是力学薄弱点,易产生分层。     

影响炭／炭复合材料摩擦学性能的因素分析：材料的性质

影响炭／炭复合材料摩擦性能的因素很多，综述了国内外的研究现状，评价了材料的譬质对炭／炭复合材料摩擦磨损性能的影响，阐述了模量、石墨化度、密度、预制体的类型、基体类型、热解炭结构等因素。     

多元耦合场CVI法快速致密化炭/炭复合材料研究

以液化石油气为碳源气体,采用多元耦合场CVI工艺方法快速制备了炭/炭复合材料.在自制冷壁CVI炉中,使用普通炭毡作为炭纤维预制体,设置特殊的导电发热层,沉积温度为650～1050℃,系统的气氛压力为0.1～30kPa,流量为0.1～0.5m3/h,沉积时间12h的条件下可将预制体一次性快速增密至1.75g/cm3.XRD分析表明:该材料经过2300℃,2h高温石墨化处理,其石墨化度(g)可达到61.3%,晶粒尺寸达到16.1nm.PLM分析表明所得材料偏光形貌表现为光滑层(SL)结构,SEM形貌照片测算可知热解炭沉积速率在6.6μm/h以上.分析了炭/炭致密化的过程和热解炭的沉积机理,说明多元耦合场加速了热解炭的沉积,缩短了致密化时间,降低了成本.     

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。     

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。     

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.     

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.     

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.     

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.     

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.     

Horizontally oriented carbon nanotubes coated with nanocrystalline carbon

Single-walled carbon nanotubes (CNTs) and multi-walled CNTs of length 2-5 mm were grown from Fe/Mo nanoparticles and Fe thin film catalyst, respectively, by thermal chemical vapor deposition. Following CNT growth, the CNTs were in-situ coated with nanocrystalline carbon shells of thickness 100-1500 nm. Horizontally oriented CNTs with carbon shells in the direction of the feeding gas were visible under a regular optical microscope. They were easily manipulated by optical manipulators, and CNT probes can thus be fabricated.