烧蚀材料高成碳树脂的研究进展

耐烧蚀材料在国防工业上有十分重要的应用价值,碳化型烧蚀材料是利用高分子材料在高温碳化吸热量的材料.树脂基烧蚀材料一般要求具有高相对分子质量、高芳基化、高交联密度、高C/O比,以使材料烧蚀后成碳率高.材料的烧蚀率与成碳率成反比关系,树脂的成碳率越高,其耐烧蚀性能越好.材料的成碳率高低由树脂的化学结构决定.目前烧蚀材料的研...     

三维针刺C/(SiC-TaC)复合材料的烧蚀性能及烧蚀机理

为了提高连续碳纤维增强碳化硅(SiC)复合材料的抗烧蚀性能,采用浆料浸渗结合化学气相浸渗SiC工艺制备出三维针刺碳纤维增强SiC-碳化钽(TaC)复合材料.采用氧-乙炔烧蚀试验测试复合材料烧蚀性能,用扫描电子显微镜分析烧蚀后材料表面的微观形貌,用X射线衍射、表面能谱分析对材料烧蚀后成分进行分析表征.结果表明:C/SiC-TaC)复合材料线烧蚀率为0.07mm/s,相对C/SiC复合材料而言表现出较好的抗烧蚀能力,添加TaC有助于提高C/SiC复合材料抗烧蚀性能.在中心区域,出现明显烧蚀坑,纤维与基体被致密的Ta2O5层覆盖,起到保护C纤维和基体的作用,复合材料的烧蚀以升华、氧化和机械剥蚀为主.在边缘和过渡区域,烧蚀以热化学氧化烧蚀为主.     

先驱体浸渗裂解法制备C/C-SiC复合材料的烧蚀性能

用先驱体浸渗裂解法制备了碳纤维增强碳(carbon fiber reinforced carbon,C/C)-SiC复合材料,用H2-D2火焰法检测其烧蚀性能.结果表明:C/C-SiC复合材料的烧蚀率随复合材料中的Si含量的增加而呈下降趋势;经过5次浸渍,C/C-SiC复合材料的密度从1.46 g/cm3增加到1.75 g/cm3,Si含量从5.06%增加到13.8%,线烧蚀率和质量烧蚀率分别下降474%和34.5%.密度为1.75g/cm3的C/C-SiC复合材料,其线烧蚀率和质量烧蚀率分别为2.22 μm/s和1.289 mg/s,其线烧蚀率和质量烧蚀率分别为密度1.78 g/cm3的C/C复合材料的21.7%和78.6%.基体中SiC的引入明显提高了C/C复合材料的抗氧化烧蚀性能.     

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。     

C/SiC复合材料在超高温燃烧室环境下的烧蚀行为

针对化学气相渗透法制备的C/SiC复合材料燃烧室,采用发动机燃烧风洞,研究了其在超高温燃气环境下的氧化烧蚀行为,分析了C/SiC复合材料燃烧室内各个区域的烧蚀形貌特征。结果表明:SiC在不同区域表现出不同的烧蚀行为,包括主被动氧化、层流冲刷、湍流冲刷等,这些烧蚀及其耦合作用使得SiC基体被侵蚀以及碳纤维被氧化,最终导致C/SiC复合材料在燃烧时失效。C/SiC复合材料是一种重要的超高温热防护材料,了解在服役环境下这种材料的失效机理是其应用和优化的基础。     

C/SiC复合材料在超高温燃烧室环境下的烧蚀行为EI北大核心CSCD

针对化学气相渗透法制备的C/SiC复合材料燃烧室,采用发动机燃烧风洞,研究了其在超高温燃气环境下的氧化烧蚀行为,分析了C/SiC复合材料燃烧室内各个区域的烧蚀形貌特征。结果表明:SiC在不同区域表现出不同的烧蚀行为,包括主被动氧化、层流冲刷、湍流冲刷等,这些烧蚀及其耦合作用使得SiC基体被侵蚀以及碳纤维被氧化,最终导致C/SiC复合材料在燃烧时失效。C/SiC复合材料是一种重要的超高温热防护材料,了解在服役环境下这种材料的失效机理是其应用和优化的基础。     

C/C-SiC-ZrC复合材料抗氧化烧蚀性能研究

采用化学气相渗透(CVI-C)和液相浸渍裂解(PIP-SiC、PIP-ZrC)工艺制备了2.5D C/C-SiC-ZrC陶瓷基复合材料。通过液氧煤油超音速火焰对蘑菇头驻点试验件进行烧蚀试验,并采用扫描电子显微镜(SEM)和能谱分析仪(EDS)对材料的微观形貌及抗氧化烧蚀机理进行了初步探讨。结果表明,C/C-ZrC-SiC复合材料基体中SiC:ZrC质量比约为4:6,在2200K~2400K液氧煤油超音速火焰烧蚀试验环境下具有良好的抗烧蚀性能,100s蘑菇头驻点线烧蚀率仅为0.0054mm/s。研究发现,C/C-ZrC-SiC复合材料中合适的SiC和ZrC基体配比,高温氧化烧蚀过程中,材料表面形成了以ZrO_(2)颗粒为骨架的连续致密粘稠熔融层,有效封填材料表面的裂纹、孔洞,降低氧化性气氛向材料内部扩散的速率,对材料形成了较好的保护。     

C/C-SiC复合材料的低成本制备及其耐烧蚀性能

以正硅酸乙酯(TEOS)为硅源,酚醛树脂为碳源配制SiC先驱体,以编入了SiC粉末的炭纤维毡为预制体,采用先驱体浸渍裂解(PIP)与反应熔渗(RMI)相结合的方法制备出密度为1.93 g/cm3的C/C-SiC复合材料。借助X射线衍射仪和扫描电子显微镜(SEM)对先驱体及复合材料的相组成和微观结构进行分析。采用等离子体烧蚀枪进行烧蚀试验,测试C/C-SiC复合材料的耐烧蚀性能。烧蚀30 s后,材料表面保持完整,无明显裂纹及烧蚀坑,烧蚀中心出现了明显的氧化层及白色粉末状烧蚀产物,材料的质量烧蚀率和线烧蚀率分别为0.137 mg·s-1,5.50μm·s-1。     

C／SiC复合材料热性能及抗氧化性能的研究

本文研究了聚碳硅烷化学转化法制备C/SiC复合材料过程中碳纤维(CF)、碳化硅(SiC)基体的热物理性能对C/SiC复合材料性能的影响,并提出了一种可以提高复合材料抗氧化能力的简单有效的方法。     

碳／碳化硅复合材料的结构与性能

一、前言 碳/碳(C/C)复合材料仍属于碳素材料,它克服了石墨材料的某些缺点。具有强度高、抗热震性能好等优点,因而在一些工业部门得到广泛应用。随着对C/C材料性能的改进和人们对它不断深入的了解,其使用范围在不断扩大。抗氧化性能差和容易磨损是它的重要弱点。 碳化硅(SiC)是一种力学性能较好(强度、硬度)、在1000～1500℃范围内抗氧化性能好的材料,其密度较低,与碳有良好的物理化学匹配性,因此,用SiC来改进     

Morphology and anti-ablation properties of PIP Cf/C–SiC composites with different CVI carbon content under 4.2 MW/m2 heat flux oxy-acetylene test

In this work, the needled carbon fiber preforms were used to make seven groups of carbon/carbon composite billets with different matrix carbon contents by controlling the processing time of chemical vapor infiltration (CVI). C_f/C–SiC composites were prepared by infiltration of SiC into these C/C composites billets using polycarbosilane (PCS) through precursor infiltration and pyrolysis (PIP). After oxy-acetylene torch testing (heat flux of 4.2 MW/m²) for 200s, 300s and 400s, respectively, it revealed that the anti-ablation properties of the C_f/C–SiC composite samples were enhanced by a higher content of SiC matrix. Additionally, specimens bearing longer duration tests showed a trend of lower average ablation rates. The lowest linear ablation rate is 0.008 mm/s and the mass ablation rate is 0.0019 g/s for those high SiC content samples tested for 400s. The SEM images of the tested samples showed the mechanism and the non-linear process of ablation resistance progression.     

Reaction kinetics and ablation properties of C/C-ZrC composites fabricated by reactive melt infiltration

Carbon/carbon-zirconium carbide (C/C-ZrC) composites were prepared by reactive melt infiltration. Carbon fiber felt was firstly densified by carbon using chemical vapor infiltration to obtain a porous carbon/carbon (C/C) skeleton. The zirconium melt was then infiltrated into the porous C/C at temperatures higher than the melting point of zirconium to obtain C/C-ZrC composites. The infiltration depth as a function of annealing temperature and dwelling time was studied. A model based on these results was built up to describe the kinetic process. The ablation properties of the C/C-ZrC were tested under an oxyacetylene torch and a laser beam. The results indicate that the linear and mass ablation rates of the C/C-ZrC composites are greatly reduced compared with C/SiC-ZrB₂, C/SiC, and C/C composites. The formation of a dense layer of ZrC and ZrO₂ mixture at high temperatures is the reason for high ablation resistance.     

化学气相渗透法制备三维针刺C/SiC复合材料的烧蚀性能

用化学气相渗透法制备了三维针刺碳纤维增强碳化硅陶瓷基复合材料,复合材料的平均密度为2.15 g/cm3,气孔率为16.0%.用氧乙炔焰研究了复合材料的烧蚀性能,用扫描电镜分析了烧蚀表面的形貌,用表面能谱分析了烧蚀产物的成分.复合材料的线烧蚀率和质量烧蚀率分别为0.03mm/s和0.004 7 g/s.在烧蚀中心区,烧蚀最严重,表层只有C纤维骨架,且C纤维呈针状,复合材料的烧蚀以升华和冲刷为主.在烧蚀过渡区,垂直于烧蚀面的C纤维表现出端部锐化、根部细化的特性,平行于烧蚀面的C纤维呈针状,复合材料的烧蚀以氧化和机械剥蚀为主.烧蚀边缘烧蚀不明显,烧蚀产物和SiC基体熔融后覆盖在烧蚀表面,阻碍了复合材料的进一步烧蚀,复合材料的烧蚀以氧化为主.     

Mechanical and ablation properties of 2D-carbon/carbon composites pre-infiltrated with a SiC filler

In order to improve the mechanical and ablation properties of 2D-carbon/carbon composites, a SiC filler was added to a 2D-preform before isothermal chemical vapor infiltration densification by using a powder infiltration technique. Backscattered electron images showed that the SiC filler was mainly concentrated between the fiber bundles and between the layers. The tensile and flexural strengths of the composites were improved by the addition of the SiC filler because of the increase of interfacial surface areas between the bundles and between the layers, the less residual open porosity, and also the strong bonding between the SiC particles and the pyrocarbon matrix. The composites with filler experienced a 15.2% lower thickness erosion rate and a 51.7% lower mass erosion rate, compared to those C/C without filler. This was attributed to the low oxygen permeability of the SiO₂ shielding the exterior inter-bundle pores as well as to a thermal barrier effect.     

Microstructure and ablation behavior of SiC coated C/C–SiC–ZrC composites prepared by a hybrid infiltration process

In this study, C/C–SiC–ZrC composites coated with SiC were prepared by precursor infiltration pyrolysis combined with reactive melt infiltration. The pyrolysis behavior of the hybrid precursor was investigated using thermal gravimetric analysis-differential scanning calorimetry, X-ray diffraction, and scanning electron microscopy techniques. The microstructure and ablation behavior of the composites were also investigated. The results indicate that the composites exhibit an interesting structure, wherein a ceramic coating composed of SiC and a small quantity of ZrC covers the exterior of the composites, and the SiC–ZrC hybrid ceramics are partially embedded in the matrix pores and distributed around the carbon fibers as well. The composites exhibit good ablation resistance with a surface temperature of over 2300 °C during ablation. After ablation for 120 s, the mass and linear ablation rates of the composites are 0.0026 g/s and 0.0037 mm/s, respectively. The great ablation resistance of the composites is attributed to the formation of a continuous phase of molten SiO₂ containing SiC and ZrO₂, which seals the pores of the composites during ablation.     

Fabrication of C/SiC composites by siliconizing carbon fiber reinforced nanoporous carbon matrix preforms and their properties

Reactive melt infiltration (RMI) has been proved to be one of the most promising technologies for fabrication of C/SiC composites because of its low cost and short processing cycle. However, the poor mechanical and anti-ablation properties of the RMI-C/SiC composites severely limit their practical use due to an imperfect siliconization of carbon matrixes with thick walls and micron-sized pores. Here, we report a high-performance RMI-C/SiC composite fabricated using a carbon fiber reinforced nanoporous carbon (NC) matrix preform composed of overlapping nanoparticles and abundant nanopores. For comparison, the C/C performs with conventional pyrocarbon (PyC) or resin carbon (ReC) matrixes were also used to explore the effect of carbon matrix on the composition and property of the obtained C/SiC composites. The C/SiC derived from C/NC with a high density of 2.50 g cm^?3 has dense and pure SiC matrix and intact carbon fibers due to the complete ceramization of original carbon matrix and the almost full consumption of inspersed silicon. In contrast, the counterparts based on C/PyC or C/ReC with a low density have a little SiC, much residual silicon and carbon, and many corroded fibers. As a result, the C/SiC from C/NC shows the highest flexural strength of 218.1 MPa and the lowest ablation rate of 0.168 µm s^?1 in an oxyacetylene flame of ～ 2200 °C with a duration time of 500 s. This work opens up a new way for the development of high-performance ceramic matrix composites by siliconizing the C/C preforms with nanoporous carbon matrix.     

Preparation and properties of 2D C/SiC-ZrB2-TaC composites

Two-dimensional (2D) C/SiC-ZrB₂-TaC composites were fabricated by chemical vapor infiltration (CVI) combined with slurry paste (SP) method. 2D laminate was prepared by stacking carbon cloth that was pasted with a mixture of polycarbosilane-ZrB₂-TaC slurry. A small amount of carbon fiber tows were introduced into the preform in the vertical direction. After heat-treated at 1800 °C, the 2D laminate was densified with SiC by CVI to obtain 2D C/SiC-ZrB₂-TaC composites. Properties including flexural strength, interlaminar shear strength, and thermal expansion of the composites were investigated. The ablation test was carried out under an oxyacetylene torch flame. The morphologies of the ablated specimens were analyzed. The results indicate that the adding vertical fiber tows and heat-treatment at 1800 °C can greatly improve the mechanical properties of the composites. The co-addition of TaC and ZrB₂ powders into C/SiC composite effectively enhance its ablation resistance.     

Comparative ablation behaviors of C/SiC-HfC composites prepared by reactive melt infiltration and precursor infiltration and pyrolysis routes

Carbon fiber reinforced silicon carbide-hafnium carbide (C/SiC-HfC) composites were prepared by reactive melt infiltration (RMI) and precursor infiltration and pyrolysis (PIP) routes. The ablation behaviors of the two composites were investigated and compared under an oxyacetylene torch flame. The C/SiC-HfC composites prepared by PIP showed a better ablation resistance than those synthetized by RMI. Microstructural observations revealed an island distribution of HfC for the sample prepared by RMI, which resulted in SiC being directly oxidized during the ablation process. In contrast, the PIP-prepared sample showed a uniform distribution of HfC, which resulted in SiC being oxidized via the Knudsen diffusion mechanism under ablation. The Knudsen diffusion of oxidants retarded the oxidation process, thereby increasing the ablation resistance of the C/SiC-HfC composites prepared by PIP.     

Morphology and Microstructure of Three-Dimensional Orthogonal C/SiC Composites Ablated by an Oxyacetylene Flame at 2900°C

C/SiC composites were prepared by polycarbosilane infiltration pyrolysis and ablated by oxy-acetylene flame at 2900°C for 180 s. The morphology and microstructure of C/SiC were observed by scanning electron microscopy. The phase transition and the composition were confirmed by energy-dispersive spectroscopy and X-ray diffraction. The ablation rates of the center region and the outer region were 2.5 and 1.1 μm/s, respectively. The ablated C/SiC was covered by a turbostratic carbon coating resulting from the pyrolysis of acetylene. White dross attached on the surface was composed of SiO₂ resulting from the sublimation and decomposition of SiC during ablation and oxidization of Si and SiC during cooling. The results indicated that the ablation was due to a combination of carbon coating deposition, decomposition of SiC, oxidation, and mechanical erosion.