基体炭对无粘结剂C/C复合材料性能的影响

研究了在相同的工作制度下，基体炭（生石油焦）的热物理性质，机械 化学处理后的主要特征（粒径、比表面、含氧官能团），结果表明，在所选用的基体炭源中，荆门生焦更适合作为无粘结剂C／C复合材料的基体炭。     

C/C复合材料中基体炭的微观结构表征

采用扫描电子显微镜、金相偏光显微镜对不同结构基体炭,包括热解炭、沥青炭、树脂炭进行形貌表征和分析。通过试验观察到热解炭的微观结构主要分为粗糙层结构、光滑层结构、过渡层结构和各向同性结构,热解炭表面为球冠形结构;沥青炭的主要形貌结构主要有镶嵌型结构,区域与镶嵌并存结构,区域与流线型并存结构,流线型结构;树脂碳的结构主要为表面光滑的块状结构。     

炭基体结构状态对C/C复合材料抗烧蚀性能的影响

碳基体在C／C复合材料的组成中占有很大的比重，因此炭基体不同的结构状态往往对C／C复合材料的各项性能有显著的影响。本文利用不同的原料和加工工艺制备出了三种具有不同炭基体的C／C复合材料，这三种碳基体分别是热解炭，沥青炭以及解热炭－树脂炭混合炭基体。对这三种材料多项性能的测试结果表明，炭基体的结构状态如石墨化度，炭片层结构的取向度的不同对C／C复合材料的各项性能均有显著的影响；基本趋势是C／C材料的石墨化度越高，材料的导电性能，导热性能以及抗烧蚀性能越好，压缩强度越低。三种炭基体中沥青炭基体沿纤维轴向的取向度最低，其抗烧蚀性能最差。     

热解炭结构对C/C复合材料热物理性能影响

炭布叠层为预制体，采用等温CVI工艺制备出炭/炭（C/C）复合材料。通过调节丙烯与氢气的比例得到热解炭结构分别为粗糙层（RL），光滑层（SL），各向同性（ISO）的三种C/C复合材料，研究了热解炭组织结构对C/C复合材料热导率的影响，讨论了C/C复合材料的导热机理。结果表明：RL织构C/C复合材料的热导率无论是在平行方向还是在垂直方向上都明显高于SL和ISO织构C/C复合材料，在两个方向上，RL织构C/C复合材料的最大热导率比SL织构C/C复合材料分别大41.0%和31.7%，是ISO织构C/C复合材料的2倍多，且3种C/C复合材料的热导率随温度的升高呈现不同的变化趋势。     

不同炭基体对炭/炭复合材料力学性能的影响

结合化学气相沉积（CVD）和前驱体浸渍裂解工艺,分别以丙烯、糠酮树脂和煤沥青为前驱体制备了密度在1.85g/cm3以上的三维炭/炭（C/C）复合材料,对比研究了沥青炭、热解炭+沥青炭以及热解炭+树脂炭结构（分别为A、B、C组）的等三种不同炭基体C/C复合材料的增密效率与力学性能,采用排水法表征C/C复合材料的孔隙率及密度,利用扫描电镜进行炭基体的微观结构表征,采用万用电子力学试验机进行拉伸强度、压缩强度、剪切强度等力学性能表征。结果表明,在热解炭质量含量相同的前提下,树脂浸渍裂解增密速率低于沥青浸渍裂解工艺,树脂炭基体孔隙率低于沥青炭基体。不同炭基体结构的C/C复合材料力学性能次序为：热解炭+树脂炭双元炭基体最高,纯沥青炭基体次之,热解炭+沥青炭双元炭基体最低,分析原因为热解炭与树脂炭双元炭基体的界面结合强度高,而沥青炭为混乱无序碳结构,热解炭和沥青炭双元炭基体界面结合强度弱,因此力学强度最低。     

基体炭种类对C/C复合材料断裂韧性的影响

以针刺网胎/无纬布为预制体,采用CVD法和液相浸渍法制备了热解炭基、树脂炭基、沥青炭基C/C复合材料,并研究了这些材料的断裂韧性及其断裂机理。研究表明:沥青炭基C/C复合材料的XY向断裂韧性明显高于热解炭基和树脂炭基,其XY向和Z向分别达到4.54MPa·m~(1/2)和3.15 MPa·m~(1/2),表现为假塑性断裂;三种基体炭C/C复合材料的XY向断裂韧性均大于Z向。     

炭前驱体形态对C/C复合材料导热系数的影响

利用热塑性中间相沥青为黏结剂,短炭纤维.增强体,一步热压成型制备C/C导热复合材料.采用SEM和偏光显微镜观察等分析手段,研究了2∶1,2.5∶1和3∶1三种不同管径比对C/C复合材料的影响.结果表明:通过热压模具空腔结构的改变可以引起炭前驱体挤出形态的变化,使得轴向基体炭有序生长与短炭纤维增强体呈现有序排列,其中间相液晶分子垂直和平行于模压压力方向均排列成纤维状长程有序结构,短切纤维呈现出与压力平行方向排布.当空腔管径比为3:1,轴向导热系数由86.2 W/(m·K)增大至115.5 W/(m· K),各向异性比由1.6减小为1.2.由此所得块体C/C复合材料具有显著的二维取向结构,轴径向导热系数趋于平衡.     

先驱体转化法制备C/C-SiC复合材料研究

以多孔C/C复合材料为预制型,聚碳硅烷(PCS)为先驱体,制备了C/C-SiC复合材料。研究了浸渍液浓度和不同C/C复合材料预制体密度等级对C/C-SiC复合材料的密度和力学性能的影响。结果表明:当浸渍液浓度为50%时,复合材料的密度均达到最佳值;不同的预制体密度对制得的复合材料性能有很大的影响,其中初始密度为1.2g/cm3试样制得的复合材料性能达到最优,其密度达到1.786g/cm3,弯曲强度达204.1MPa,剪切强度为16.1MPa,断裂韧性为6.83MPa·m1/2。     

基体改性剂含量对C/C复合材料抗氧化性能的影响

采用氧化烧蚀试验研究了改性剂硼玻璃含量对Ｃ／Ｃ复合材料抗氧化性能的影响,通过扫描电镜（ＳＥＭ）观察分析了其抗氧化机理。结果表明：随着改性剂硼玻璃含量的增加,基体改性Ｃ／Ｃ复合材料的显气孔率逐渐降低,抗氧化能力逐渐增强,当硼玻璃的含量超高９．０ｗｔ％后,Ｃ／Ｃ复合材料抗氧化能力的提高趋于平缓;在基体改性Ｃ／Ｃ复合材料的氧化过程中,改性剂硼玻璃起到了内外涂层的作用,使其抗氧化能力大大提高。     

炭/炭复合材料的抗氧化研究现状

介绍了目前提高C／C复合材料抗氧化能力的方法，简述了抗氧化涂层的制备方法，综述了抗氧化涂层的几种典型结构。提出了对于C／C复合材料高温氧化保护研究方向的一些看法，阐明了其发展趋势及前景。     

Effect of carbon nanotubes on the strength of adhesive lap joints of C/C and C/C-SiC ceramic fibre composites

Similar substrates of carbon/carbon (C/C) and carbon/carbon-silicon carbide (C/CSiC) composites were bonded with pure epoxy resin and the one containing 3% multiwall carbon nanotubes (MWCNTs). The results show that MWCNT/filled epoxy resin bonded C/CC/C and C/CSiCC/CSiC substrates have a higher adhesive joint strength than those bonded with epoxy resin alone. MWCNTs increase the toughness and strength of the epoxy resin, which increases the interface bond strength between two similar matching surfaces.     

Gradient HfB2-SiC multilayer oxidation resistant coating for C/C composites

The gradient HfB₂ modified SiC coating was prepared on the surface of SiC-coated C/C composites by in-situ synthesis. Anti-oxidation behaviors of the coated C/C samples at 1773, 1873 and 1973?K were investigated. The results show that the gradient HfB₂ modified SiC coatings possess excellent oxidation resistance, which can protect C/C substrates from oxidation for 800, 305 and 100?h at 1773, 1873 and 1973?K, respectively. In addition, with the oxidation temperature increasing, the evaporation of the Hf-Si-O glass layer and the active oxidation of SiC were accelerated, which is the reason for the worst oxidation resistance of the sample at 1973?K among the three temperatures.     

Thermophysical properties of carbon/carbon composites and physical mechanism of thermal expansion and thermal conductivity

Five different carbon/carbon composites (C/C) have been prepared and their thermophysical properties studied. These were three needled carbon felts impregnated with pyrocarbons (PyC) of different microstructures, chopped fibers/resin carbon + PyC, and carbon cloth/PyC. The results show that the X-Y direction thermal expansion coefficient (CTE) is negative in the range 0-100 °C with values ranging from −0.29 to −0.85 × 10⁻⁶/K. In the range 0-900 °C, their CTE is also very low, and the CTE vs. T curves have almost the same slope. In the same temperature range composites prepared using chopped fibers show the smallest CTE values and those using the felts show the highest. The microstructure of the PyC has no obvious effect on the CTE for composites with the same preform architecture. Their expansion is mainly caused by atomic vibration, pore shrinkage and volatilization of water. However, the PyC structure has a large effect on thermal conductivity (TC) with rough laminar PyC giving the highest value and isotropic PyC giving the lowest. All five composites have a high TC, and values in the X-Y direction (25.6-174 W/m K) are much larger than in the Z direction (3.5-50 W/m K). Heat transmission in these composites is by phonon interaction and is related to the preform and PyC structures.     

High density carbon fiber/boron nitride matrix composites: Fabrication of composites with exceptional wear resistance

This paper describes the fabrication of high density (ρ ∼ 1.75 g/cc) composites containing a hybrid (carbon and boron nitride), or complete boron nitride matrix. The composites were reinforced with either chopped or 3D needled carbon fibers. The boron nitride was introduced via liquid infiltration of a borazine oligomer that can exhibit liquid crystallinity. The processing scheme was developed for the chopped carbon fiber/boron nitride matrix composites (C/BN) and later applied to the 3D carbon fiber reinforced/boron nitride matrix composites (3D C/BN). The hybrid matrix composites were produced by infiltrating the borazine oligomer into a low density 3D needled C/C composite to yield 3D C/C-BN. In addition to achieving high densities, the processing scheme yielded d₀₀₂ spacings of 3.35 Å, which afforded boron nitride with excellent hydrolytic stability. The friction and wear properties of the composites were explored over the entire energy spectrum for aircraft braking using an inertial brake dynamometer. The C/BN composites outperformed both the previously reported C/C-BN and chopped fiber reinforced C/C. The high density 3D C/BN performed as well as both the 3D C/C and the C/BN. The 3D C/C-BN provided outstanding wear resistance, incurring nearly zero wear across the entire testing spectrum. The coefficient of friction was relatively stable with respect to energy level, varying from 0.2 to 0.3.     

Effect of initial density on thermal conductivity of new micro-pipeline heat conduction C/SiC composites

C/SiC composites prepared by chemical vapor infiltration technique (CVI) have been regarded as thermal structural materials widely. However, these composites still suffer from poor functional properties like low thermal conductivity, especially in thickness direction of the composites, limiting their large-scale applications. Herein, mesophase pitch based carbon fiber (MPCF) and continuous wave laser machining were utilized to construct highly effective heat conductive micro-pipelines within CVI C/SiC composite. The effect of initial density on the final density and thermal conductivity of the as-obtained MPCF-C/SiC composites were investigated. The results revealed that higher initial density would directly enhance the thermal conductivity and reduce the negative impact of the bottle-neck effect. At temperatures between 100°C and 500°C, MPCF-C/SiC composites preserved more than threefold of the thermal conductivity (340%) when compared to reference C/SiC composites. This work provides a highly effective route for enhancing the thermal conductivity of C/SiC, which would broaden their future applications.     

氧化石墨烯的制备及其掺杂的炭/炭复合材料导热性能研究

设定两种不同配比强酸氧化剂,以鳞片石墨为原料,采用Hummers法,制备了氧化石墨烯,再经过高温炭化得到热处理氧化石墨烯。并分别以中间相沥青为基体炭前驱体,炭纤维为增强相,氧化石墨烯及其热处理物为热疏导功能体,制备出掺杂氧化石墨烯的炭/炭复合材料。TEM、SEM等表征表明,选用强酸氧化剂组合配比用量较少的制备出的氧化石墨烯,其形貌整体上要优于用量较多的,具有独特的褶皱结构;相比于氧化石墨烯,掺杂其热处理物的复合材料界面覆盖均匀平滑且结合更优良,且其导热系数可达到60 W.m-1.K-1,是无掺杂的纯复合材料两倍多,导热系数得到了较大幅度提高。     

Friction behaviors of carbon/carbon composites with different pyrolytic carbon textures

Friction and wear properties of carbon/carbon (C/C) composites with a smooth laminar (SL), a medium textured rough laminar (RL) and a high textured RL pyrolytic carbon texture were investigated with a home-made laboratory scale dynamometer to simulate airplane normal landing (NL), over landing (OL) and rejected take-off (RTO) conditions. The morphology of worn surfaces at different braking levels was observed with scanning electron microscopy. The results show that C/C composites with RL have nearly constant friction coefficients, stable friction curves and proper wear loss at different braking levels, while friction coefficients of C/C composites with SL pyrolytic carbon decrease intensely and their oxidation losses increase greatly under OL and RTO conditions. Therefore, C/C composites with a high and medium textured RL pyrolytic carbon may satisfy the requirements of aircraft brakes. The good friction and wear properties of C/C composites with RL are due to the properties of RL, which leads to a uniform friction film forming on the friction surface.     

Design of a C/SiC functionally graded coating for the oxidation protection of C/C composites

To reduce the residual thermal stress between the carbon fiber-reinforced carbon (C/C) composites and the SiC coating layer, functionally graded materials (FGM) consisting of a C/SiC compositionally graded layer (C/SiC interlayer) were adopted. After designing the compositional distribution of the C/SiC interlayer which can relieve the thermal stress effectively, the deposition conditions of the entire compositional range of the C/SiC composites were determined using a thermodynamic calculation. According to the design and calculation the C/SiC interlayer and the SiC outer layer were deposited on the C/C composites by a low pressure chemical vapor deposition (LPCVD) method at deposition temperatures of 1100 and 1300 °C. The stress calculation and the experimental results suggested that the SiC-rich compositional profile in the FGM layer is the most effective for relieving the thermal stress and increasing the oxidation resistance.     

Ablation resistance of HfB2-SiC coating prepared by in-situ reaction method for SiC coated C/C composites

To improve the ablation resistance of SiC coating, HfB₂-SiC coating was prepared on SiC-coated carbon/carbon (C/C) composites by in-situ reaction method. Owing to the penetration of coating powders, there is no clear boundary between SiC coating and HfB₂-SiC coating. After oxyacetylene ablation for 60 s at heat flux of 2400 kW/m², the mass ablation rate and linear ablation rate of the coated C/C composites were only 0.147 mg/s and 0.267 µm/s, reduced by 21.8% and 60.0%, respectively, compared with SiC coated C/C composites. The good ablation resistance was attributed to the formation of multiple Hf-Si-O glassy layer including SiO₂, HfO₂ and HfSiO₄.     

Effect of ZrC particle distribution on the ablation resistance of C/C-SiC-ZrC composites fabricated using precursor infiltration pyrolysis

C/C-SiC-ZrC composites with different ZrC distributions were fabricated using precursor infiltration pyrolysis combined with different drying processes. The microstructural and ablation resistance properties of the composites with different ZrC distributions were investigated. For the C/C-SiC-ZrC composites fabricated using conventional heating-drying, where ZrC particles were largely agglomerated into islands with a dimension range of 10–20 μm, the mass and linear ablation rates under a plasma flame for 60 s were 0.558 mg/s and 16.33 μm/s, respectively. By contrast, for the composites fabricated using freeze-drying, where isolated ZrC particles with a size range of 200–300 nm were uniformly dispersed in the matrix, the mass and linear ablation rates were only 0.078 mg/s and 14.20 μm/s, respectively. This difference in the distribution of ZrC particles led to the difference in ablation resistances, as the uniformly distributed fine ZrC particles were easily oxidized and well dispersed in SiO₂ molten glass, which increased the viscosity of the molten glass layer. The high-viscosity SiO₂-ZrO₂ molten layer covering the surface of the composites effectively prevented the penetration of oxygen and resisted the scour of airflow.