基体改性C／C—HfC—HfB2-SiC复合材料抗烧蚀性能研究

以碳化铪有机前驱体、硼化铪有机前驱体和聚碳硅烷混合溶液为浸渍剂,采用化学气相渗透（CVI）和液相浸渍-裂解（PIP）T艺制得了准3DC／C-HfC-HfB2-SiC碳陶复合材料。采用电弧风洞结合扫捕电子显微镜（SEM）和X射线衍射分析（XRD）对复合材料的结构及氧化失效行为进行了初步探讨。结果表明,高密度的基体改性C／C．HfC—HfB2-SiC复合材料具有良好的抗烧蚀性能,复合材料在2300K／600S电弧风洞（含水5％）试验条件下的质量烧蚀率和线烧蚀率分别仅为1．22×10^-6g／（cm^2·s）和1．33X10^-5mm／s。密度和温度对复合材料抗烧蚀性能影响较大,密度从2．63g／cm^3增加到3．75g／cm^3时,复合材料在2300K条件下的线烧蚀率降低了3个数量级,当温度从2300K升高的2400K时,高密度复合材料的线烧蚀率增加了约1000倍,烧蚀过程中较高密度的复合材料表面容易形成更为致密的氧化膜是其具有良好的抗氧性能的重要因素。     

Oxidation behavior of CVI,MSI and CVI+MSI C/SiC composites

The oxidation behavior of chemical vapor infiltration(CVI),molten silicon infiltration(MSI)and CVI+MSI C/SiC composites at 500-1 400℃was studied.The oxidation below 900℃increased successively for CVI,CVI+MSI and MSI composites.However,the oxidation of CVI composite above 1 000 ℃was much faster thanthat of MSI and CVI+MSI composites. As active carbon atoms produced by siliconization of fibers during MSI process were oxidized first and decreased initial oxidation temperature.The initial oxidation temperature of MSI,MSI+CVI and CVI composites was 526,552 and 710℃,respectively.New active carbon atoms were generated due to the breaking of 2D molecular chains during oxidation,so the activation energy of three C/SiC composites was decreased gradually at 500-800℃with oxidation process,exhibiting a self-catalytic characteristic.     

Microstructure and mechanical properties of C/C composite joint brazed with Ni-based filler

The novel Ni-based brazing filler was used to join C/C composites. When brazing temperature increased from 1080 to 1100 °C, the wetting angle decreased from 23° to 14°, and the brazing filler had good wettability on the surface of C/C composites. The brazing seam of the brazed joint consisted of Ni(s,s) and Cr₃C₂ phases. As brazing temperature increased, lots of Cr₃C₂ phases were generated at the bonding interface, and the thick reaction layer was formed. When brazing temperature was 1120 °C, the shear strength of C/C joint reached the maximum value of 31.5 MPa. The fracture path extended in the C/C matrix close to the bonding interface.     

Ablative Property of C/C-SiC-HfC Composites Prepared via Precursor Infiltration and Pyrolysis under 3,000°C Oxyacetylene Torch

C/C-SiC-HfC composites were fabricated via precursor infiltration and pyrolysis using a mixture solution of organic hafnium-containing polymer and polycarbosilane as precursor. The microstructures and the phases of the composites were analyzed by scanning electron microscopy and X-ray diffraction. The ablation resistance of the composites was evaluated under 3,000^°C oxyacetylene torch. After ablation for 120s, the composites exhibit good ablation properties with the linear and mass ablation rates of 9.1×10^-4mm/s and 1.30×10^-3g/s, which are far lower than those of the C/C-SiC composites. The excellent ablative property of the C/C-SiC-HfC composites is resulted from the formation of HfO₂ molten layer on the surface of the composites, which could play a positive role in reducing heat transfer and preventing oxygen transport to the underlying carbon substrate.     

LaB6改性C/C-ZrC-SiC复合材料的制备及其抗烧蚀性能

采用料浆浸渍结合树脂浸渍裂解法制备了含9.73 wt.% LaB6的LaB6-C/C预制体,再利用反应熔体浸渍法（RMI）制备了LaB6改性C/C-ZrC-SiC复合材料,考察了材料的微观结构和烧蚀行为,探究LaB6对材料抗烧蚀性能的作用机理。结果表明：在热流密度为2380 kw/m2的氧乙炔焰烧蚀120 s后,LaB6改性C/C-ZrC-SiC复合材料的质量烧蚀率和线烧蚀率分别为1.05×10-3 g/s和2.17×10-3 mm/s,较未改性C/C-ZrC-SiC复合材料分别降低了74.8 %和61.9 %。烧蚀过程中,LaB6发生氧化反应生成La2O3和B2O3,La2O3与ZrO2之间的固溶作用以及化学反应,再加之液态B2O3具有促进固相反应传质的作用,使得材料表面形成大面积连续稳定的ZrO2-La2Zr2O7-La0.1Zr0.9O1.95熔融态保护层,这是材料优异抗烧蚀性能的主要原因。     

高密度预制体制备炭/炭复合材料的弯曲力学性能与断裂机制

以丙烯作为碳源,氮气作为载气,采用初始密度为0.94g/cm3三维正交PAN基12K炭纤维预制体,利用自制的快速CVI炉制备基体热解炭结构为带状结构的C/C复合材料。力学性能测试结果表明,材料的弯曲断裂特征与制备过程中受到的高温热处理次数有关。从载荷-位移曲线来看,当C/C复合材料经过两次热处理时,C/C复合材料呈明显假塑性断裂特征。当C/C复合材料经过三次热处理时,载荷-位移曲线趋于稳定平滑,抗弯强度降低。从C/C复合材料断面的SEM图可以观察到材料断裂可以分为层间断裂和层内断裂,而层内断裂又因热解炭填充密度变化呈明显的分区断裂。由于热解炭和纤维含量在C/C复合材料中分布的差异,材料在不同的区域表现出不同的断裂特征,从而使得材料具备良好的弯曲强度同时具有一定的韧性特征。     

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。     

Numerical simulation on thermal expansion coefficient of 3D braided C/C composites简

To effectively get the thermal expansion coefficient(CTE) of three-dimensional(3D) braided C/C composites and study the variations, a VC?? program with graphical user interfaces was obtained, based on the yarn unit model and numerical analysis. With the limited basic properties of carbon fibers and carbon matrix, CTE of 3D braided C/C composites is obtained at 85 °C. The deviation between the simulated and experimental axial CTE of 3D braided C/C composites is no more than 11 %. The effects of different parameters(including the braiding angle of 3D braided preform, the fiber volume fraction and the porosity of 3D braided C/C composites, and the elastic modulus, Poisson's ratio and CTEs of carbon fibers and carbon matrix) were analyzed with the program. The results show that the axial CTE of C/C composites decreases with the increase of the braiding angle, the fiber volume fraction, and the porosity of 3D braided C/C composites. The transverse elastic modulus of carbon fibers has the greatest effect on the axial CTE among the studied mechanical parameters, followed by the elastic modulus and Poisson's ratio of carbon matrix.     

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。     

准三维C/C复合材料的层间剪切性能及其断裂机理

以炭纤维针刺毡为预制体, 采用化学气相浸渗(CVI)法或结合液相法制备了热解炭、树脂炭和沥青炭基质的准三维C/C复合材料, 研究了这些材料的层间剪切性能及其断裂机理. 结果表明: CVI基质炭比沥青基质炭更有利于C/C复合材料的层间剪切性能的提高; 剪切强度随密度增高而增大, 致密度越高, 基体支撑越强, 同时微裂纹和孔隙度就越低, 断裂裂纹不易形成或扩展, 强度性能就越好; 纯沥青基质炭试样为"突发"的脆性断裂方式, 其他基质炭试样表现为韧性断裂方式.     

Microstructure and mechanical properties of 3D fine-woven punctured C/C composites with PyC/SiC/TaC interphases

The 3D fine-woven punctured C/C-(P_yC/SiC/TaC) composites, composed of P_yC/SiC/TaC interphases and pyrocarbon (PyC) matrix, were synthesized by isothermal chemical vapor infiltration (ICVI) methods. The alternating layers and the structure of these composites were examined by polarized light microscopy (PLM), X-ray diffractometry (XRD) and scanning electron microscopy (SEM). It is found that the P_yC matrix has rough laminar (RL) structure, the TaC layer has NaCl-type cubic structure, and the SiC layer has few wurtzite type 10H-SiC besides β-SiC structure. The effects of fiber coating and the bulk density on the tensile and flexural properties of composites along X or Y and Z direction were investigated. It is shown that fiber coated 3D woven punctured C/C composites have good tensile and flexural strength, and the maximum of flexural strength is 375 MPa in X or Y direction at density of 1.89 g/cm³, which is about three times higher than that of samples without TaC/SiC fiber coating. The flexural strength and bending strength increase with increasing the density of the composites. The analysis of fracture surfaces reveals that fibers and fiber bundles are pulled out in composites, indicating that the composite exhibits a non-linear failure behavior through propagation and deflection of the cracks.     

PIP工艺制备2D C/SiC复合材料Z-向穿刺工艺

针对2D C/SiC复合材料存在碳布层间缺乏纤维增强,层间结合较差的问题,提出通过Z-向穿刺工艺提高碳布层间结合,克服材料使用时可靠性不高的问题,并比较了穿刺工艺对复合材料微观结构和力学性能的影响.结果表明,通过Z-向穿刺工艺制得试样2D C/SiC-Z_(pin)的弯曲强度、弯曲模量和剪切强度分别为247.8 MPa、37.8 GPa和32.1 MPa,而未穿刺试样2D C/SiC的弯曲强度、弯曲模量和剪切强度分别只有219.3 MPa、34.4 GPa和23.3 MPa,由此可见,采用Z-向穿刺工艺能明显提高复合材料的力学性能.微观结构分析认为,试样力学性能提高的根本原因在于采用Z-向穿刺纤维加强了碳布层间结合,使材料具有较好的整体性,克服了复合材料层间结合较弱对力学性能带来的不利影响.     

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.     

Ni71CrSi中间层钎焊连接C／C复合材料与镍基高温合金GH3044

以Ni71CrSi为中间层存1180℃×30min的钎焊条件下,对C／C复合材料和镍基高温合金进行钎焊试验。,研究了Ni7lCrSi对C／C复合材料和表面SiC改性的C／C复合材料的润湿性。利用扫捕电子显微镜、能谱分析仪、万能试验机和做米压痕仪分别对接头的界面组织、显微硬度和剪圳断裂过程进行了研究。结果表明,表面未改性的C／C复合材料在连接过程中直接失效,而表而SiC改性的C／C复合材料与镍基合金的接头连接良好,且接头剪切强度达到35．08MPa,断裂方式呈假塑性断裂。机理分析表明,镍基钎料较好地润湿表面SiC改性的C／C复合材料,接头的显做硬度分布旱中问高两边低的变化趋势,且形成了表面改性C／C／Ni（s．s）＋Cr7C3＋Ni3Si／Ni（s．s）＋cr3c2＋Ni3Si／Ni（s．s）＋cr3c2＋MC＋Ni3Si／Ni3Si＋MC＋Ni（s．s）／GH3044界面结构。     

等离子喷涂 NiCr / Cr3 C2 -hBN 复合涂层的制备及摩擦性能研究

目的加入h BN作为固体润滑剂,提高Ni Cr/Cr3C2复合涂层的摩擦性能。方法采用化工冶金包覆、喷雾造粒和固相合金化技术制备Ni Cr/Cr3C2-10%h BN复合粉体,再采用等离子喷涂技术制备复合涂层。通过扫描电子显微镜(SEM)、X射线衍射(XRD)和高温摩擦磨损试验等手段研究粉体和涂层的显微结构、物相组成以及室温至800℃的摩擦磨损性能,探讨Ni Cr/Cr3C2-10%h BN复合涂层在室温和400,800℃下的磨损机理。结果等离子喷涂Ni Cr/Cr3C2-10%h BN复合涂层呈典型的层状结构,涂层结合强度可达24 MPa,孔隙率为(8.47±0.5)%。涂层的摩擦系数和磨损率均随着温度的升高而先升高,后逐渐降低,400℃时最高,分别约为0.59和9.2×10-4mm3/(N·m),800℃时分别降至0.45和4.1×10-4mm3/(N·m)。高温下,h BN润滑膜和金属氧化物的形成是摩擦系数和磨损率降低的主要原因。室温下涂层的主要磨损机制是脆性断裂;400℃时,涂层的主要磨损机制是脆性断裂、塑形变形和轻微粘着磨损;800℃时,涂层的主要磨损机制是塑性变形、氧化、粘着磨损和涂层转移至对偶件。结论等离子喷涂Ni Cr/Cr3C2-10%h BN复合涂层在室温和高温下的润滑性能较好。     

Influence of additives on oxidation resistance of binderless C/C composite

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碳/碳复合材料高温抗氧化涂层的研究进展

阐述了国内外近几年来碳/碳复合材料抗氧化涂层的研究新进展,并从碳/碳复合材料的氧化机理、抗氧化涂层的基本条件以及抗氧化涂层类型等方面重点介绍了抗氧化涂层技术。并指出了目前关于抗氧化涂层技术研究中存在的问题。     

连接温度对C/C复合材料及Cu连接接头残余应力的影响

采用热弹塑性有限元数值模拟方法,研究了连接温度对C/C复合材料与Cu平面对接接头残余应力的影响。结果表明:最大拉应力的分布具有方向性,在连接界面法线方向上,最大拉应力出现在靠近接头界面的C/C复合材料侧,位于连接件的棱边上;在平行连接界面方向上,最大拉应力出现在靠近接头界面的Cu侧表面。最大剪切应力位于接头界面处。随着连接温度的升高,接头残余应力峰值逐渐增大,但接头残余应力的分布形态相似。对于连接界面尺寸为4 mm×4 mm的接头,在连接温度为1 000℃时,离接头界面1.2 mm的C/C复合材料侧最容易发生断裂。     

Joining of C/C Composites and GH3128 Ni-based Superalloy with Ni-Ti Mixed Powder as an Interlayer

通过包埋工艺在C/C复合材料表面制备了改性SiC涂层.采用Ni-Ti粉末作中间层连结材料,利用真空热压扩散工艺成功制备了SiC涂层改性C/C复合材料与GH3128镍基高温合金的连接样件.借助X射线衍射仪、扫描电子显微镜、能谱分析仪和材料万能试验机,研究了SiC涂层改性C/C复合材料与GH3128镍基高温合金连接接头及其界面的元素分布、微观结构及力学性能.结果表明,在C/C复合材料表面制备SiC涂层,不仅充分改善了C/C复合材料对Ni-Ti中间层连结材料的润湿性,而且还有效缓解C/C复合材料与GH3128连接界面因热膨胀不匹配而造成的热应力.经过SiC涂层改性处理的连接接头,其室温剪切强度可达22.49 MPa;而没有经过SiC涂层改性处理的连接接头,其室温剪切强度几乎为零.     

碳/碳复合材料超高温抗氧化铱涂层研究现状

综述了碳/碳复合材料抗氧化铱涂层的制备技术,阐述了该涂层应用存在的问题及解决方法,并对碳/碳复合材料超高温抗氧化铱涂层的发展趋势进行了展望。