Microstructure of carbon fiber preform and distribution of pyrolytic carbon by chemical vapor infiltration

The carbon/carbon composites were made by chemical vapor infiltration(CVI) with needled felt preform. The distribution of the pyrolytic carbon in the carbon fiber preform was studied by polarized light microscope (PLM) and scanning electronic microscope(SEM). The experimental results indicate that the amount of pyrolytic carbon deposited on the surface of chopped carbon fiber is more than that on the surface of long carbon fiber. The reason is the different porosity between the layer of chopped carbon fiber and long carbon fiber. The carbon precursor gas which passes through the part of chopped carbon fibers decomposes and deposits on the surface of chopped carbon fiber. The pyrolytic carbon on the surface of long carbon fibers is produced by the carbon precursor gas diffusing from the chopped fiber and the Z-d fiber. Uniform pore distribution and porosity in preform are necessary for producing C/C composites with high properties.     

Preparation and mechanical properties of carbon/carbon composites with high textured pyrolytic carbon matrix

Short carbon fiber felts with an initial porosity of 89.5% were deposited by isobaric, isothermal chemical vapor infiltration using natural gas as carbon source. The bulk density of the deposited carbon/carbon (C/C) composites was 1.89 g/cm³ after depositing for 150 h. The microstructure and mechanical properties of the C/C composites were studied by polarized light microscopy, X-ray diffraction, scanning electron microscopy and three-point bending test. The results reveal that high textured pyrolytic carbon is deposited as the matrix of the composites, whose crystalline thickness and graphitization degree highly increase after heat treatment. A distinct decrease of the flexural strength and modulus accompanied by the increase of the toughness of the C/C composites is found to be correlated with the structural changes in the composites during the heat treatment process.     

添加BN对光滑层热解炭结构的C/C复合材料摩擦性能的影响

通过粉末层铺法向全网胎炭纤维预制体中添加六方氮化硼粉末和化学气相沉积热解炭增密制备C/C-BN复合材料。在MM 1000摩擦试验机上对其摩擦磨损性能进行测试,并对摩擦表面进行光学形貌观察以及对材料的组织结构和磨屑进行SEM形貌观察。结果表明:与C/C复合材料相比,C/C-BN复合材料的线性磨损率降低了40%,质量磨损率降低了70%;摩擦表面中的六方BN在摩擦过程中始终保持稳定,BN的存在使光滑层热解炭结构的C/C复合材料的摩擦因数曲线变得平稳、波动小并且对刹车压力响应迅速,摩擦表面上形成了一层薄的摩擦膜。     

Flexural destructive process of unidirectional carbon/carbon composites reinforced with in situ grown carbon nanofibers

Unidirectional carbon/carbon (C/C) composites modified with in situ grown carbon nanofibers (CNFs) were prepared by catalysis chemical vapor deposition. The effect of in situ grown CNFs on the flexural properties of the C/C composites was investigated by detailed analyses of destructive process. The results show that there is a sharp increase in the flexural load-displacement curve in the axial direction of the CNF-C/C composites, followed by a serrated yielding phenomenon similar to the plastic materials. The failure mode of the C/C composites modified with in situ grown CNFs is changed from the pull-out of single fiber to the breaking of fiber bundles. The existence of interfacial layer composed by middle-textured pyrocarbon, CNFs and high-textured pyrocarbon can block the crack propagation and change the propagation direction of the main crack, which leads to the higher flexural strength and modulus of C/C composites.     

不同预制体炭/炭复合材料在髋关节模拟试验机中的磨损颗粒表征(英文)

采用髋关节模拟试验机检测穿刺碳布预制体和碳毡预制体炭/炭复合材料的磨损行为。分离提取产生的磨损颗粒,检测颗粒形貌和尺寸分布并提出颗粒的演化过程。结果表明:炭/炭复合材料磨损颗粒的尺寸分布在亚微米至数十微米之间,颗粒形貌呈现破损纤维状、纤维碎片状、片状和球状。穿刺碳布预制体炭/炭复合材料比碳毡预制体炭/炭复合材料的磨损颗粒尺寸分布范围更广泛,磨损颗粒中的破损碳纤维状和片状形貌较多。热解碳颗粒的演变主要是其表面的规则化过程,而碳纤维颗粒的演变主要与髋关节模拟试验机提供的应力方向有关。     

射频辉光放电等离子体辅助化学气相沉积法制备类金刚石碳膜工艺与性能表征

使用射频辉光放电等离子体辅助化学气相沉积技术（简称RFGDPECVD）在玻璃载玻片表面沉积类金刚石薄膜。用原子力显微镜（AFM）、摩擦试验仪、划痕试验机测定了其表面形貌、耐磨性及附着性。采用X射线光电子能谱（XPS）、分光光度计对两种气源（C4H10、C2H2）制备的DLC薄膜微观组成和透光率进行了检测和对比。结果表明：DLC薄膜的表面光滑、平整,表面粗糙度随沉积时间的增加单调递增;耐磨性及附着性优良;与C4H10相比使用C2H2作为碳源气体可以得到较高Sp^3含量和较低Sp^1含量的DLC膜;C2H2制备DLC薄膜的透光率低于C4H10;同一种碳源气体,反应流量比例越小,则DLC薄膜的透光性越好。     

C／C坯体对RMI C／C—SiC复合材料组织的影响

以PAN基炭纤维（Cf）针刺整体毡为预制体，用化学气相渗透（CVI）、浸渍炭化（IC）方法制备了不同炭纤维增强炭基体的多孔C／C坯体，采用反应熔渗（RMI）法制备C／C—SiC复合材料，研究了渗Si前后坯体的密度和组织结构。结果表明：不同C／C坯体反应溶渗硅后复合材料的物相组成为SiC相、C相及单质Si相；密度低的坯体熔融渗硅后密度增加较多；密度的增加与开口孔隙度并不是单调增加的关系，IC处理的坯体开口孔隙度低，但渗硅后复合材料的密度增加较多；IC坯体中分布分散的树脂C易与熔渗Si反应，CVI坯体中的热解C仅表层与熔渗Si反应，在Cf和SiC之间有热解C存在；坯体密度相同时，IC处理的坯体中SiC量较多，单质Si相含量少且分散较好，而CVI坯体中SiC量较少，单质Si相的量较多；制备方法相同时，高密度的C／C坯体，渗硅后C相较多。     

碳纤维表面生长纳米碳管及其增强的炭/炭复合材料

采用化学气相沉积工艺在碳纤维表面生长了纳米碳管,将此种碳纤维作为增强材料,以中间相沥青为基体炭前驱体采用浸渍炭化工艺制备了炭/炭复合材料.观察了所得复合材料断口的微观形貌,测试了抗弯强度及热物理性能.结果表明,碳纤维表面的纳米碳管可以有效地提高纤维与基体的粘结力,复合材料的抗弯性能提高了50%,而对复合材料的导热性能影响较小.     

活性炭载体的超声波处理对Pt／C催化剂活性的影响分析

通过对活性炭载体进行不同条件的超声波处理获得了具有不同表面化学性质的载体，使用比表面积（BET）、酸碱滴定等技术手段对载体的物理化学性质进行了表征。将经过超声波处理的活性炭载体制备成Pt／C催化剂，并将催化剂直接用于催化反应，考察了活性炭载体的不同超声波处理条件对Pt／C催化剂性能的影响。实验发现，活性炭载体经过超声波处理后，表面灰分含量、pH值和中孔孔容有较大的变化；使用经过60min超声波处理后中孔孔容较大的活性炭作为载体制备的Pt／C催化剂，在催化加氢反应性能测试中显示了最高的催化活性。在此基础上，就活性炭载体的超声波处理对Pt／C催化剂活性的影响进行了讨论。     

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,采用热悌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1．74g／cm^3。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,两种材料存XY和Z向的CTE旱如下分布：αB—z〉dAz〉αA—xy〉αBxY-C／C复合材料的CTE主要取决于纤维体积分数和排市、碳基体及材料中的孔隙分布情况,前者起决定作用。     

CF／Al—4.5Cu复合材料界面产物的反应与生成机制

利用挤压铸造法制备了ＣＦ／Ａｌ－４．５Ｃｕ金属基复合材料，研究了该材料基体凝固过程中界面产物的反应与生成机制。实验结果表明：当界面反应温度高于５００℃时，生成Ａｌ４Ｃ３的办以应可自发进行，反应的活化能Ｑ＝２５４ｋＪ／ｍｏｌ．Ａｌ４Ｃ３的结晶与生长规律表现为：首先Ａｌ４Ｃ３依附在碳纤维表面形核；碳原子通过已形成的Ａｌ４Ｃ３和液态铝合金扩散，Ａｌ原子则通过Ａｌ４Ｃ３和液态铝合金扩散，Ａｌ原子则通过Ａｌ     

CVI炭/炭复合材料微观结构和生长模型

采用自行设计的多元耦合物理场CVI炉增密炭/炭（C/C）复合材料,用炭毡作为纤维增强体,在坯体内部设计特殊的导电发热层,使坯体内部的温度场、气体反应的中间产物浓度场、电磁场等多元物理场实现耦合,实现坯体的快速增密。采用偏光显微镜研究沉积热解炭的组织结构;用X射线衍射仪研究C/C复合材料的石墨化度和微晶尺寸;用扫描电镜观察材料断口和热解炭沉积表面的形貌;并对CVI热解炭的生长方式进行研究。研究表明：获得SL、RL和带状等多种热解炭结构;不同的结构具有不同的形貌特征,其中SL的断口平整,RL的断口呈沟槽构造;并提出前者为小分子平滑生长模型、后者为大分子锥状生长模型。     

Effect of stress level on fatigue behavior of 2D C/C composites

Laminated carbon fiber clothes were infiltrated to prepare carbon fiber reinforced pyrolytic carbon (C/C) using isothermal chemical vapor infiltration (CVI). The bending fatigue behavior of the infiltrated C/C composites was tested under two different stress levels. The residual strength and modulus of all fatigued samples were tested to investigate the effect of maximum stress level on fatigue behavior of C/C composites. The microstructure and damage mechanism were also investigated. The results showed that the residual strength and modulus of fatigued samples were improved. High stress level is more effective to increase the modulus. And for the increase of flexural strength, high stress level is more effective only in low cycles. The fatigue loading weakens the bonding between the matrix and fiber, and then affects the damage propagation pathway, and increases the energy consumption. So the properties of C/C composites are improved.     

Kinetic and morphological development of coke formation on heat-resistant alloys

The deposition of coke from a propylene-hydrogen mixture on to a range of austenitic Fe-Cr-Ni base alloys has been compared with deposition on pure nickel and pure copper. Nickel was catalytic to coking at temperatures below 900 °C, but at higher temperatures became encapsulated by pyrolytic coke. Copper showed no catalytic activity at any temperature in the range 600–1000 °C, and was instead covered with carbon deposited by homogeneous gas phase pyrolysis. Heat-resistant alloys formed pyrolytic coke at the same rates as copper and nickel at high temperatures, but displayed coking rates between those of the pure metals at lower temperatures. The alloys formed a chromium-rich carbide layer on their surface. This layer was initially protective, but eventually developed defects from which coke filaments grew. The formation of these filaments was catalysed by the chromium-depleted metal which became accessible to the gas following failure of the carbide layer. Once catalytic coke formation commenced, it was maintained by the presence within the coke of small metal particles rich in iron and nickel. The addition of steam to the gas slowed pyrolytic coking slightly through gas phase dilution. In the case of heat-resistant alloys, catalytic coking was largely suppressed by the formation of a surface scale containing chromium carbide and oxide. This scale was noncatalytic and was more successful than a simple carbide scale in preventing gas access to the underlying metal.     

热解碳涂层对Al_2O_3纤维编织体介电及吸波性能的影响(英文)

采用化学气相沉积法在Al2O3纤维编织体上沉积热解碳涂层,利用SEM及激光拉曼光谱表征沉积与未沉积热解碳界面层的纤维编织体,并研究热解碳沉积时间对纤维电导率及编织体X波段介电吸波性能的影响。结果表明:纤维电导率及编织体复介电常数随着热解碳沉积时间的延长而增大。电子松弛极化引起复介电常数实部的增大,电导损耗引起虚部的增大。热解碳涂层可以改善Al2O3纤维编织体的吸波性能,对于沉积60min热解碳涂层的编织体,反射率在9.5GHz附近达到-40.4dB,吸波频带接近4GHz.     

In-situ processing of carbon coatings on the surface of SiC-based fibers

Carbon coatings have been formed on the surface of free carbon containing Tyranno ZMI and Nicalon SiC-based fibers by reaction with chlorine gas (chlorination) in the temperature range 550-675 °C. The kinetics and growth mechanisms have been investigated for both fibers. Results have shown that, for similar experimental conditions, the reactivity of both fibers displayed noticeable discrepancies. It has thus been observed that the Nicalon fiber was more prone to chlorine-based treatment and displayed a thicker carbon coating than the ZMI fiber. These results have also revealed that, in both cases, these thicknesses can be closely monitored by physical parameters such as temperature and aging duration. The nature of the obtained coating has also been investigated by various experimental devices. AES, SEM and TEM analyses have thus evidenced that these carbon coatings were uniform and well adherent whereas AFM showed that the chlorine-based treatments resulted in a nanometer-range roughness at the fiber surface. Adsorption gas analyses also revealed a microporosity coupled with a high specific surface area. The chemical composition of the final products was determined by XPS and Mass Spectroscopy. Finally, the oxidation behavior which was investigated by thermogravimetric analysis revealed that oxidation occurs at a quite low temperature (225 °C).     

Filamentous carbon formation caused by catalytic metal particles from iron oxide

The thermodynamic equilibrium between metallic iron, iron oxides, iron carbides and an hydrocarbon/hydrogen mixture was calculated at 600°C. On the basis of the metastable Fe‐C‐O phase diagram, both metallic iron and iron oxides can be directly converted into carbides in reducing and carburizing atmosphere. Thermogravimetric (ATG) measurements have been performed in iC₄H₁₀‐H₂‐Ar atmosphere at 600°C on reduced and pre‐oxidised iron samples. The kinetic of coke formation was studied on both surface states by sequential exposure experiments. The initial stages of the transformation were characterised by scanning electron microscopy (SEM) observations and X‐ray diffraction (XRD) analysis. On a reduced surface, the results are consistent with the mechanism currently proposed to explain catalytic coke formation. Cementite (Fe₃C) is formed on the iron surface after carbon supersaturation (a_c > 1). The graphite deposition on its surface (a_c = 1) induces its decomposition. Iron atoms from cementite diffuse through the graphite and agglomerate to small particles that act as catalysts for further carbon deposition. A new mechanism of catalytic particle formation is proposed when an oxide scale initially covers the iron surface. In the carburizing and reducing atmosphere, magnetite (Fe₃O₄) can be directly converted into cementite (Fe₃C). XPS analysis confirm that, in this process, metallic iron is not an intermediary specie of the oxide/carbide reaction. At the same time, graphite deposition occurs at the metal/oxide interface through the cracks present in the oxide scale. Iron carbide in contact with graphite is partially decomposed and acts as catalyst for graphitic filaments growth.     

原位生长碳纳米管及其在SiC_f/SiC复合材料中的应用

采用碳纳米管改善纤维与基体间的界面结合,同时利用碳纳米管自身的优异性能对碳化硅纤维增强碳化硅复合材料(SiCf/SiC)进行二次增强。通过化学气相沉积工艺(CVD)在SiC纤维编织件内原位生长碳纳米管,优化碳纳米管原位生长过程中的碳源流量、反应温度和反应时间等工艺参数,对碳纳米管的原位生长工艺及机理进行系统分析,并结合先驱体浸渍裂解工艺(PIP)制备CNTs-SiCf/SiC复合材料,探讨原位生长碳纳米管的引入对复合材料力学性能的影响。结果表明,优化后的工艺参数如下:反应温度750℃,C2H2、H2和N2流量比1/1/3,C2H2流量100~150 mL/min,反应时间60 min;碳纳米管的引入使SiCf/SiC复合材料的弯曲强度、弯曲模量和断裂韧性分别提高了16.3%、90.4%和106.3%。     

Improved properties of carbon fiber paper as electrode for fuel cell by coating pyrocarbon via CVD method

The fabrication of a pyrocarbon coated carbon paper and its application to the gas diffusion lay (GDL) of proton exchange membrane (PEM) fuel cell were described. This carbon paper was fabricated by using conventional carbon paper as the precursor, and coating it with pyrocarbon by pyrolyzing propylene via the chemical vapor deposition (CVD) method. For comparison, conventional carbon paper composites were also prepared by using PAN-based carbon fiber felt as the precursor followed by impregnation with resin, molding and heat-treatment. SEM characterization indicates that pyrocarbon is uniformly deposited on the surface of the fiber in the pyrocarbon coated carbon paper and made the fibers of carbon felt bind more tightly. In contrast, there are cracks in matrix and debonding of fibers due to carbonization shrinkage in the conventional carbon paper. Property measurements show that the former has much better conductivity and gas permeability than the latter. In addition, current density-voltage performance tests also reveal that the pyrocarbon coating can improve the properties of carbon paper used for electrode materials of fuel cell.     

RMI法制备穿刺C/C-SiC复合材料的微结构及烧蚀性能研究

以无纬布/网胎0°/90°叠层穿刺预制体为增强体,采用化学气相渗(Chemical vapor infiltration,CVI)、树脂浸渍碳化(Polymer infiltration carbonization,PIC)与反应熔渗(Reactive melt infiltration,RMI)复合工艺制备穿刺C/C-SiC复合材料,研究其微观组织及在C₂H₂-O₂焰中的烧蚀行为。结果表明：无纬布、穿刺纤维束由CVI+PIC制备的碳基体填充而形成致密C/C区域,RMI生成的SiC主要位于网胎层中,其含量37.3wt%。复合材料表面因过量硅化而形成了SiC富集层。烧蚀距离20mm、O₂:C₂H₂=2:1时,烧蚀600s后材料X-Y、Z向线烧蚀率分别为：0.8×10^_-4 mm/s、3.6×10^_-4 mm/s,比PIP工艺制备C/C-SiC材料烧蚀率小一个数量级。烧蚀面SiC富集层保护及被动氧化作用是材料具有优异抗氧化烧蚀性能的主要原因。随烧蚀距离由20mm向10mm减小,复合材料烧蚀率先缓慢变化后快速增大,烧蚀率快速增长阶段复合材料发生主动氧化烧蚀。