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.     

原位生长SiC纳米纤维及其对C/C-ZrC复合材料耐烧蚀性能的影响

采用化学气相反应法在C/C复合材料上原位生长SiC纳米纤维,然后通过高温熔渗反应制备C/C-SiC-ZrC复合材料。通过XRD、SEM、等离子体烧蚀设备分别对其结构、形貌和耐烧蚀性能等进行分析研究。结果表明:C/C复合材料表面生长的SiC纳米纤维直径介于100 nm与1μm之间,最佳反应温度在1 500℃左右。等离子体枪烧蚀30 s后,C/C-ZrC复合材料的质量烧蚀率和线烧蚀率分别为-0.32 mg/s和2.57μm/s;而C/C-SiC-ZrC复合材料的质量烧蚀率和线烧蚀率分别为-0.24 mg/s和1.66μm/s,生长了SiC纳米纤维的C/C-ZrC复合材料展示了更优异的耐烧蚀性能。     

碳/碳复合材料SiC–HfSi_2–TaSi_2抗烧蚀复合涂层

采用包埋技术在碳纤维增强碳(carbon fiber reinforced carbon,C/C)复合材料表面制备了碳化硅-硅化铪-硅化钽(SiC-HfSi2-TaSi2)抗烧蚀复合涂层.采用氧已炔火焰烧蚀试验评价了. C/C复合材料样品的抗烧蚀性能.通过X射线衍射分析、扫描电镜观察及能谱分析研究了SiC-HfSi-TaSi2作为 C/C复合材料抗烧蚀涂层的表面和断面相组成、元素分布及形貌.结果表明:由于烧蚀过程中生成的Hf02,Ta205具有高温稳定性,使得该涂层表现 出良好的抗烧蚀性能,在3 000℃下烧蚀20s后,线烧蚀率为0.009 mm/s,质量烧蚀率为0.003 85 g/s.     

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。     

氧化钇掺杂ZrB_2-SiC陶瓷基复合材料的抗烧蚀性能研究

采用热压烧结工艺制备了氧化钇掺杂Zr B2-Si C陶瓷基复合材料,利用高频等离子体电弧风洞对氧化钇掺杂Zr B2-Si C进行了2300℃和2400℃的抗氧化烧蚀性能测试,分析了氧化钇对陶瓷材料抗烧蚀性能的影响,探讨了稀土氧化物掺杂Si C-Zr B2陶瓷材料的抗烧蚀机理。结果表明,在升温及降温过程中均未开裂,材料具有较好的抗热冲击性能,质量烧蚀率分别为0.0344 g/s和0.0365 g/s,氧化层厚度分别为1 mm和2 mm,表面烧蚀中心和边缘的氧化产物分别为低温稳定相Zr O2和Si O2,氧化层结构仍旧是连续的,体现了材料较好的抗氧化烧蚀性能。     

先驱体转化法制备2D C/C-ZrB2复合材料及其性能研究

本文针对C/C复合材料存在高温抗氧化和抗冲刷性能较差等缺点,提出对C/C复合材料进行改性以改善其性能.通过碳布叠层工艺均匀刷涂浆料,采用先驱体转化法制备了三种不同ZrB2含量的2D C/C-ZrB2复合材料,探索ZrB2含量对其力学、抗氧化、抗烧蚀等性能和微观形貌的影响.结果表明:刷涂料浆(ZrB2体积分数10%)制备的复合材料综合性能优异,其弯曲强度为250.37 MPa,断裂韧性为13.84 MPa·m1/2;样品经1200 ℃氧化30 min后质量保留率达到90.65%,强度保留率达到85.14%;经氧乙炔焰烧蚀60 s后,其质量烧蚀率为0.01802 g/s,线烧蚀率为0.01217 mm/s.     

C/C复合材料ZrB2-SiC涂层的微观结构及烧蚀性能研究

采用包埋法在密度为1.63g/cm~3的C/C复合材料上制备了不同ZrB_2含量的ZrB_2-SiC复相陶瓷涂层,考察了不同配比包埋粉料对涂层微观结构和抗烧蚀性能的影响。结果表明,当包埋粉料中ZrB_2质量分数为50%时,涂层ZrB_2含量最多,氧乙炔烧蚀60s时,其线烧蚀率、质量烧蚀率最低,分别为5.3×10~(-4) mm/s和2.1×10~(-3)g/s;在烧蚀过程中,SiC氧化产物SiO_2发生了相变,形成玻璃态,吸收大量热量。玻璃态的SiO_2相包裹着ZrO_2相,使得在烧蚀过程中,有效降低了烧蚀火焰冲击对ZrO_2造成的损失,ZrO_2导热系数低,是一种优异的热障材料,从而降低了复合材料烧蚀率。     

模压高碳酚醛树脂基烧蚀复合材料制备与成型

采用常规性能分析、傅里叶变换红外光谱分析、差示扫描量热分析、热重分析、凝胶渗透色谱分析等对模压高碳酚醛树脂进行表征,通过模压成型分别制备了碳纤维和高硅氧纤维增强模压高碳酚醛树脂复合材料,测试了不同成型压力下两种复合材料的力学性能和耐烧蚀性能,最后通过超声无损检测方法对复合材料密实度进行表征。结果表明,模压高碳酚醛树脂苯环上以邻位取代为主,其游离酚和游离醛含量较低,180℃的凝胶时间低于50 s,适用于较高温度下的快速模压成型工艺;该树脂分子量小,对纤维的浸润性好,适宜的固化温度为(190±5)℃,900℃的残炭率可达67.13%。随成型压力增加,碳纤维和高硅氧纤维增强复合材料的拉伸和弯曲性能均逐渐提高,但当成型压力大于45 MPa后,增加趋势变缓;当成型压力为45 MPa时,两种复合材料具有最好的耐烧蚀性能,其中碳纤维增强复合材料的线烧蚀率和质量烧蚀率分别为0.006 8 mm/s和0.055 9 g/s,高硅氧纤维增强复合材料的线烧蚀率和质量烧蚀率分别为0.116 4 mm/s和0.070 8 g/s。通过超声无损检测方法可以初步判断碳纤维增强复合材料的密实度。     

PyC/SiC界面改性C/C-SiC-ZrC复合材料的等离子烧蚀性能研究

以丙烯(C_3H_6),三氯甲基硅烷(MTS)为原料,利用化学气相渗透(CVI)技术在炭纤维预制体的纤维表面依次制备了热解炭(PyC)与碳化硅(SiC)界面层,随后结合CVI及前驱体浸渍裂解(PIP)工艺对材料进行增密,制得了密度为1.92 g/cm~3的界面改性C/C-SiC-ZrC复合材料。利用X射线衍射仪(XRD)与扫描电子显微镜(SEM)对复合材料的物相组成与微观形貌结构进行分析表征。采用等离子火焰对复合材料进行烧蚀性能测试,经过30 s的烧蚀后,材料的线烧蚀率与质量烧蚀率分别为3.33μm·s~(-1),0.91 mg·s~(-1);烧蚀后材料表面无明显烧蚀坑,烧蚀中心形成了明显的白色氧化物,生成了连续致密的氧化膜,阻碍了氧气对材料的进一步侵蚀。     

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.     

Ablation of the carbon/carbon composite nozzle-throats in a small solid rocket motor

Ablation of needled carbon/carbon (C/C) composite nozzle-throats was studied by hot-fire testing in a small solid rocket motor. The composition of the combustion gases was estimated by principle of free energy minimum. The ablation morphology was investigated by scanning electron microscopy. The ablation mechanism of C/C composites was also studied. The results showed that the ablation performance of C/C composites was determined by mechanical breakage of fibers/matrix together with thermal chemical ablation from the heterogeneous reactions on the throat surface. The mechanical breakage of fibers/matrix dominated the ablation of the composites at high pressure based on the calculated ablation rate. Cone-shaped fibers were formed after ablation in high fiber density area; but in low fiber density area, the fibers were peeled off because of the weakened strength after ablation. Meanwhile, the matrix around the fiber bundles was ablated into a shell shape, while the matrix between the cone-shaped fibers might be blown away by the combustion gases. Oxidation of C/C composites led to the formation of the cone-shaped fibers and shell-shaped matrix, as well as the loss of matrix between the cone-shaped fibers. The fiber/matrix fragments on the ablation surface were caused by the mechanical breakage.     

Erosion of carbon/carbon composites using a low-velocity,high-particle-concentration two-phase jet in a solid rocket motor

The erosion of a four-direction carbon/carbon composite test piece using a low-velocity, high-particle-concentration two-phase jet was studied by the hot firing test of a small solid rocket motor with an elaborately designed flow path. The linear ablation rates were measured. The ablation surface and microstructure of the carbon/carbon composites were studied by scanning electron microscopy, and the ablation mechanism was investigated. Within the parameter range studied in this paper, mechanical erosion is found to play a dominant role in the ablation of carbon/carbon composites in the impact region. Moreover, the effect of chemical ablation is weak. The erosion of carbon/carbon composites results in blunt fracture tip fibers and a lamellar matrix. The particle impact mass flux is more dominant than the particle impact velocity in the erosion of carbon/carbon composites. At mesoscale, the carbon rods are more resistant to mechanical erosion than fiber bundles. At microscale, the carbon fibers are more susceptible to mechanical erosion than the carbon matrix, whereas the carbon fibers are more resistant to chemical ablation than the matrix and interface.     

Morphology and microstructure of SiC/SiC composites ablated by oxyacetylene torch at 1800°C

An oxyacetylene torch tested the ablation of SiC/SiC composites at 1800℃. According to the distribution of ablation product silica, the morphology could be divided into three regions. The fibers in the oval central region were ablated and broken, and the fracture surface is the conical tip. The silica liquid film in the transition region plays a role in resisting the ablation of the material. However, the generation of airflow channels destroys the liquid film's continuity and reduces the material's ablation resistance. Bean sprouts-like nano-sized silica was grown on the surface of the dome-top SiC matrix in the marginal region.     

Ablation behavior of three-dimensional braided C/SiC composites by oxyacetylene torch under different environments

SiC ceramic matrix composites reinforced by three-dimensional braided carbon fibers were prepared via polycarbosilane infiltration pyrolysis (PIP). The ablation behavior of the composites was characterized by an oxyacetylene torch under different environments. The morphology and microstructure of the as-ablated composites were examined by scanning electron microscopy and the composition of the new phase was confirmed by energy dispersive spectroscopy. Two conditions showed different ablation mechanisms. The erosion mechanism of the high speed oxyacetylene torch was the main ablation behavior under oxygen free environment. Thermo-chemicals ablation was the main ablation behavior under abundant oxygen environment.     

Excellent ablation resistance and reusability of silicon carbide fiber reinforced silicon carbide composite in dissociated air plasmas

This work explores the potentials of SiC fiber reinforced SiC matrix composites (SiC_f/SiC) with SiC coating to resist aerodynamic ablations for thermal protection purpose. A plasma wind tunnel is employed to evaluate their anti-ablation property in dissociated air plasmas. The results suggest a critical ablation temperature of SiC coated SiC_f/SiC, ≈ 1910 °C, which is the highest ever reported in literatures. Benefited by ‘all-SiC’ microstructures and relative flat ablated surfaces, the SiC_f/SiC is still ablation-resistant up to ≈ 1820 °C after the occurrence of ablation. This implies an excellent ablation resistance and reusability property of SiC_f/SiC, which surpasses that of traditional carbon fiber reinforced composites. Finally, an ablation mechanism dominated by surface characteristic is proposed. For the SiC coated SiC_f/SiC, ablation is prone to take place at surface cracks formed by thermal mismatch; while for the ablated SiC_f/SiC, ablation is triggered at the exposed fiber bundles which is over-heated in the plasmas.     

Morphology and microstructure of 2.5 dimension C/SiC composites ablated by oxyacetylene torch

SiC ceramic matrix composites reinforced by 2.5 dimension carbon fibers were prepared by low-pressure chemical vapor infiltration. The ablation performance of the composites was characterized by an oxyacetylene torch. The morphology and microstructure of the as-ablated composite were examined by scanning electron microscopy. The composition of the new phase was confirmed by energy dispersive spectroscopy and X-ray diffraction. Three clear annular regions appeared on the surface of the as-ablated sample and each region had different ablation mechanism. Sublimation was the main ablation behavior in the centre region. Oxidation was the main ablation behavior in the middle region. Silica particles mainly resulted from the oxidation and deposition of Si and SiO gas from the centre to the outer region. The ablation mechanism of the C/SiC composites under oxyacetylene flame was a combined effect of thermo-physicals attack and thermo-chemicals ablation.     

Ablation behavior and mechanism of C/C–ZrC–SiC composites under an oxyacetylene torch at 3000 °C

C/C–ZrC–SiC composites with continuous ZrC–SiC ceramic matrix were prepared by a multistep technique of precursor infiltration and pyrolysis process. Ablation properties of the composites were tested under an oxyacetylene flame at 3000 °C for 120 s. The results show that the linear ablation rate of the composites was about an order lower than that of pure C/C and C/C–SiC composites as comparisons, and the mass of the C/C–ZrC–SiC composites increased after ablation. Three concentric ring regions with different coatings appeared on the surface of the ablated C/C–ZrC–SiC composites: (i) brim ablation region covered by a coating with layered structure including SiO₂ outer layer and ZrO₂–SiO₂ inner layer; (ii) transition ablation region, and (iii) center ablation region with molten ZrO₂ coating. Presence of these coatings which acted as an effective oxygen and heat barrier is the reason for the great ablation resistance of the composites.     

Laser ablation resistance and mechanism of Si-Zr alloyed melt infiltrated C/C-SiC composite

Ablation resistance of C/C-SiC composite prepared via Si-Zr alloyed reactive melt infiltration was evaluated using a facile and economical laser ablation method. Linear ablation rates of the composite increased with an increase in laser power densities and decreased with extended ablation time. The C/C-SiC composite prepared via Si-Zr alloyed melt infiltration presented much better ablation resistance compared with the C/SiC composite prepared by polymer infiltration and pyrolysis process. The good ablation resistance of the composite was attributed to the melted ZrC layer formed at the ablation center region. Microstructure and phase composition of different ablated region were investigated by SEM and EDS, and a laser ablation model was finally proposed based on the testing results and microstructure characterization. Laser ablation of the composite experienced three distinct periods. At the very beginning, the laser ablation was dominated by the oxidation process. Then for the second period, the laser ablation was dominated by the evaporation, decomposition and sublimation process. With the further ablation of the composite, chemical stable ZrC was formed on the ablated surface and the laser ablation was synergistically controlled by the scouring away of ZrC melts and evaporation, decomposition and sublimation process.     

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.