气体滞留时间对微波热解CVI工艺制备C/C复合材料性能的影响

以炭毡为预制体, N₂为稀释气体, 甲烷为炭源前驱体, 其分压为10kPa, 沉积温度为1100℃的工艺条件下,研究了不同的气体滞留时间(0.05、0.1、0.15、0.2s)对微波热解CVI工艺制备炭/炭复合材料的致密化速率、样品的体积密度及其密度均匀性的影响, 并对其组织结构进行了观察. 分析了气体的滞留时间对微波热解CVI工艺制备炭/炭复合材料的影响规律及组织结构的变化. 结果表明: 采用微波热解CVI工艺在1100℃90h内制备出体积密度为1.70g·cm^-3的炭/炭复合材料, 在滞留时间为0.15s时预制体呈现从内到外逐步致密的规律. 同时, 随着滞留时间的延长, 热解炭的组织结构从低织构到中等织构变化.     

微波热解CVI法制备C/C复合材料

在传统CVI工艺的基础上,提出了一种新的炭/炭复合材料沉积致密化技术-微波热解CVI工艺.该工艺采用微波炉加热炭毡预制体,预制体自身发热,并通过控制微波场强分布和热传导过程产生温度梯度,加上微波对极性分子的极化作用和对热解反应和表面沉积反应的催化作用,使预制体从中心至表面逐层快速致密.通过考察炭毡预制体经微波加热后的温度场分布和沉积样品的体积密度变化和径向密度分布,观察材料的微观结构,分析了预制体的致密化过程.结果表明:微波热解CVI工艺在1075℃～1150℃的沉积温度下,以甲烷为碳源前驱体,经90 h的热解沉积,成功制备出体积密度为1.70 g/nc3的炭/炭复合材料,平均致密化速率达到0.0189g/(cm3·h);避免了表面结壳现象,热解炭沿着纤维表面层状生长;采用该工艺制备了结构均匀、主要为中等织构的热解炭.     

载气对C/C复合材料CVI热解炭显微结构的影响

在1000℃,0.5 kPa丙烯分压条件下,以N₂、H₂为载气和无载气情况下于热梯度CVI炉中制备了C/C复合材料,研究了载气特别是氢气对材料基体热解炭显微结构的影响。通过偏光显微镜测定材料不同区域CVI热解炭的消光角,分析热解炭显微结构在试样中的分布规律。结果表明: N₂在CVI过程中充当惰性角色,不影响热解炭的显微结构; H₂可以调节热解炭沉积时的微环境气氛,更有利于得到粗糙层结构热解炭。试样增密延长炭源气滞留时间,引起带状结构热解炭中显微结构的突变。借助氢气作为载气,可以实现对C/C复合材料中热解炭显微结构的更优控制。      

CVI热解炭微观结构的参数控制研究

化学气相渗透(CVI)制备炭/炭复合材料涉及气体扩散和气相沉积2个过程,其工艺控制决定炭纤维坯体的增密速度、热解炭的结构和炭/炭材料的性能.工艺过程的控制主要有4类参数:第一参数包括沉积温度、系统压力、碳源浓度、碳源分压等,第二参数包括均相反应、异相反应和滞留时间等,第三参数为A_s/V_R,也就是沉积基体的表面面积与炉内气体的自由体积之比,以及目前以计算机模拟为主要手段的"第四参数"的研究.在固体表面沉积热解炭的科学研究已经持续了几十年,但至今为止还没有形成一种完善的表面沉积机理,分析了CVI工艺参数发展的趋势,说明了对热解炭微观结构形成机理的认识是一个不断深入的过程.     

碳/碳复合材料热解碳基体的织构界面形成机制Monte Carlo模拟

基于热解碳沉积的Particle-Filler（P-F）概念模型和Langmuir-Hinshelwood理论,提出了包含吸附/解吸附/脱氢的多步非均相反应动力学机制,实现了碳/碳复合材料制备中热解碳基体在碳纤维表面连续沉积及其织构形成过程的理论建模,并采用Gibbs系综Monte Carlo （MC）方法对化学气相渗透（CVI）工艺中热解碳基体的织构界面形成过程进行了数值模拟。研究表明：由于气相中小的芳香烃组分C₆的吸附比线性小分子烃组分C₂的吸附更容易受到抑制,因而限制了沉积表面的P-F双分子反应;随C₆与C₂浓度比值R的变化,热解碳的织构形成过程呈现双稳态分布,导致了2种不同的亚稳相碳即中织构（MT）和高织构（HT）热解碳的生成,并在碳/碳复合材料热解碳基体内部形成了鲜明的织构界面。进一步的计算表明：热解碳织构双稳态转变存在一个迟滞域,其大小受气相成分的组成参数R、线性小分子烃C₂的初始浓度及沉积温度T的影响;为了得到均一织构的热解碳,应当在迟滞域外的区域合理选取CVI的工艺参数。     

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.     

炭/炭复合材料热解炭基体微观结构转变动力学

对热解炭沉积和织构形成过程进行动力学建模,重点分析C/C复合材料CVI制备工艺中基体炭形成时中织构/高织构(MT/HT)热解炭之间轮廓分明的急剧转变现象。基于Langmuir-Hinshelwood(L-H)理论和Particle-filler(P-F)概念模型,将MT和HT热解炭作为炭的两种亚稳相,以气相中占优的两种中间组分作为基体炭前驱体(线性小分子烃和小分子芳香烃),考虑基体表面单分子沉积形成MT热解炭和P-F双分子反应形成HT热解炭的过程,建立包含吸附/解吸附/脱氢的多步非均相热解炭沉积和织构形成反应动力学模型,研究该动力学系统达到稳态时热解炭随气相组成变化的情况。结果表明,热解炭沉积和织构形成过程曲线呈现"S"型特征,该曲线的线性稳定性分析表明热解炭沉积中的织构转变是一个包含迟滞区间的双稳态过程,进一步的计算表明此迟滞区间的大小明显受初始直链烃浓度以及沉积温度的影响。     

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．     

化学气相沉积与渗透过程中热解炭织态结构生成机理研究

为研究热解炭织态结构的生成规律，采用不同压强的甲烷为碳源，在1100℃条件下进行了化学气相沉积和化学气相渗透实验。化学气相沉积以具有不同表面积／自由体积比（[A／V]值）的直通方形多孔陶瓷为基体；化学气相渗透实验在直径为1mm细直孔内表面沉积和对炭纤维体积分数为7％的炭毡进行致密化。借助正交偏光显微镜（消光角）和透射电子显微镜（定向角）对在不同实验条件下制备的热解炭进行分析和定量表征。研究发现：热解炭的织态结构可以在两种不同的沉积条件下形成。当甲烷压强较低时为化学生长阶段；当甲烷压强较高时为物理形核阶段。在化学生长控制阶段，热解炭的织态结构可以利用之前提出的“颗粒填充模型（P-F模型）”加以解释。该模型假设高织构热解炭的沉积一定对应于气相中存在具有合适比例的芳香化合物（例如苯）和线性小分子（主要是C2H2），当二者的浓度比偏离该最优比（或者偏大，或者偏小），均将导致中织构甚至低织构热解炭的生成。在化学生成控制阶段，化学气相沉积和化学气相渗透对热解炭织态结构影响的差别，除了[A／V]值而外，还有氢气的作用。在化学气相渗透过程中，基体内部生成的氢气快速扩散至基体表面，使内外沉积速率和织态结构均发生较大变化。     

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.     

Microstructure and Mechanical Properties of Multilayertextured 2D Carbon/Carbon Composites

Two-dimensional（2D） carbon/carbon（C/C） composites with multilayered texture, especially with different thickness of high-textured（HT） pyrocarbon layer, were prepared by isothermal, isobaric chemical vapor infiltration（CVI） technique. The influence of matrix microstructure on mechanical properties of C/C composites was investigated by polarized light microscopy, scanning electron microscopy and three-point bending test. The results show that the samples with multilayer-textured pyrocarbon matrix own a higher flexural strength than the one with pure medium-textured structure, which is attributed to multiple crack deflection and interfacial sliding between different textured pyrocarbon layers and between sub-layers within HT layer. The increase in thickness of HT pyrocarbon layer improves the plasticity of the samples and renders the fracture in pseudo-plastic behavior.     

The Infiltration Process and Texture Transition of 2D C/C Composites

2D needle-punched fiber felt was infiltrated by a kind of rapid isothermal chemical vapor infiltration technique. The infiltration process and texture transition of the infiltrated C/C composites were investigated. The porosity and the variations of the cumulative pore volume were determined by mercury porosimetry. The texture of matrix carbon was studied under a polarized light microscope. The results show that the relative mass gain of the sample increases directly as the infiltration time at the initial stage until 20 h, and subsequently the increasing rate of the relative mass gain decreases gradually with the prolonging of infiltration time. Three layers of pyrocarbon were formed around fibers. Low-textured pyrocarbon was obtained at the initial stage. With the densification going on, high-textured pyrocarbon was formed on the surface of low-textured pyrocarbon. Then, low-textured pyrocarbon was produced again during the final stage of densification. The texture transition is ascribed to the variation of the ratio of cumulative inner surface area to volume of pores and the gas partial pressure in pores.     

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.     

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。      

Effect of interface structures on the fracture behavior of two-dimensional carbon/carbon composites by isothermal chemical vapor infiltration

The interface structures and fracture behavior of the two-dimensional carbon/carbon composites by isothermal vapor infiltration have been investigated. The results show that the graphene layers exhibit long-range order in high/textured pyrocarbon matrix and are curved in about 5-nm interface region of the fiber/high-textured. Some globular nanoparticles are formed on the fiber surface and the high-textured layer about 10 nm exists in the interface of the fiber/low-textured. The graphene layers stacks are scrolled and folded in the medium-textured and they are waved together in the interface of the fiber/medium-textured. The pseudo-plastic fracture behavior of the two-dimensional carbon/carbon composites is resulted from the dominant high-textured matrix and a moderate interfacial bonding force. A strong adhesion of the fiber/low-textured and the thicker fiber increased by surrounding low-textured layer result in the increasing flexural strength. The single medium-textured and a very strong bonding force of the fiber/medium-textured lead to the brittle fracture behavior.     

Microstructure and mechanical properties of carbon–carbon composites with multilayered pyrocarbon matrix

The effect of matrix microstructure on the mechanical properties of carbon fiber felts infiltrated by isothermal chemical vapor infiltration (CVI) has been studied by optical microscopy, scanning electron microscopy and three-point bending tests. The nonbrittle fracture behavior of the investigated composites is related to multiple crack deflections caused by the interfacial sliding between pyrocarbon layers with a varying texture degree and the delamination microcracking within the highly textured pyrocarbon layer. An increase of the flexural strength is observed by the composite having a multilayered pyrocarbon matrix.     

Improvement in electrochemical capacitance of activated carbon from scrap tires by nitric acid treatment

Activated carbon （AC） obtained from the industrial pyrolytic tire char is treated by concentrated nitric acid （AC-HNO3） and then used as the electrode material for supercapacitors. Surface properties and electrochemical capacitances of AC and AC- HNO3 are studied. It is found that the morphology and the porous texture for AC and AC- HNO3 have little difference, while the oxygen content increases and functional groups change after the acid treatment. Electrochemical results demonstrate that the AC-HNO3 electrode displays higher specific capacitance, better stability and cycling performance, and lower equivalent series resistance, indicating that AC obtained from the industrial pyrolytic tire char treated by concentrated nitric acid is applicable for supercapacitors.     

定向碳纳米管/炭纳米复合材料形貌和显微结构

以CVD法定向碳纳米管(ACNTs)阵列为骨架,利用化学气相渗透(CVI)工艺制备了新型定向碳纳米管/炭(ACNT/C)纳米复合材料。通过偏光金相显微镜(PLM)、扫描电子显微镜(SEM)、高分辨透射电子显微镜(HRTEM)、X射线衍射(XRD)和Raman光谱等分析方法对其显微结构和热解炭沉积机理进行了研究。结果表明:所制ACNT/C纳米复合材料的热解炭结构主要为类粗糙层结构,围绕碳纳米管生长的热解炭石墨层片结构清晰,并且碳纳米管和热解炭之间具有良好的界面结合;而在相同工艺条件下围绕炭纤维生长的热解炭为典型的光滑层结构。这可能是由于在热解炭沉积过程中存在碳纳米管"诱导"沉积过程,即沿着碳纳米管径向的离域化共轭π键和具有类似结构的芳香族大分子通过π-π非共价键作用相结合,并在CNTs纳米尺寸的影响下,芳香族大分子按照"软取向"(Softepitaxy)围绕碳纳米管生成环形层片状类石墨结构的热解炭。该研究结果有望为热解炭的可控沉积起到一定的借鉴作用。