Microstructure and ablation properties of zirconium carbide doped carbon/carbon composites

Carbon/carbon composites doped with zirconium carbide were prepared by a three-step process. Carbon fiber felts were first immersed in a zirconium oxychloride solution, followed by rapid densification using thermal gradient chemical vapor infiltration. The densified carbon/carbon composites were then graphitized at 2500 °C. The phase composition and morphology of the composites were investigated by X-ray diffraction and scanning electron microscopy. The ablation properties were tested in an oxyacetylene torch. The results show that the linear and mass ablation rates of the composites after doping with 4.14 wt.% zirconium carbide decreased by 83.0% and 77.0%, respectively. The ablated surface of the carbon matrix for pure carbon/carbon composites was very smooth and glossy, while that for doped carbon/carbon composites was honeycombed and dim. The bonding between carbon fibers and matrix decreased because of the formation of more zirconium dioxide, resulting in carbon fibers peeling off the matrix and the ablation resistance of carbon fibers could not be brought into play when the zirconium carbide contents achieved 4.14 wt.%. Although mechanical denudation does not seem to play a dominant role, the ablation was mainly controlled by heterogeneous mass transfer.     

Mechanical properties and ablation resistance of HfC nanowire modified carbon/carbon composites

Hafnium carbide nanowires (HfCnws) were in-situ grown in carbon/carbon (C/C) composites, and subsquently the preforms were densified by isothermal chemical vapor infiltration to obtain HfCnws modified carbon/carbon (HfCnws-C/C) composites. Morphology and microstructure of HfCnws were examined, and the effect of HfCnws on the mechanical property and ablation resistance of C/C composites were also investigated. Results show that introducing HfCnws refined the grain size of pyrolytic carbon (PyC). The out-of-plane compression, interlaminar shear and flexual strength of HfCnws-C/C composites increased by 120.80%, 45.60% and 94.65%, respectively compared with pure C/C, and the HfCnws-C/C shows good ablation resistance under oxy-acetylene flame ablation.     

Study of the ablation of a carbon/carbon composite at ∼25 MW/m2 with a nitrogen plasma torch

Ablation of carbon/carbon (C/C) composites was investigated in a nitrogen plasma torch with a heat flux of ∼25 MW/m². The reaction products of carbon in C/C composites and nitrogen plasma jet were calculated based on the principle of free energy minimum. The calculated results show that the thermal chemical ablation and sublimation of carbon occur and C_n(g) (n = 1–3), CN(g), C₂N(g) and C₂N₂(g) may be the major reaction products consuming carbon. Ablation is apt to begin at the interfaces, especially the fibre-matrix interface and interfaces inside the matrix. Ablation of C/C composites is mainly controlled by the thermal chemical ablation, sublimation of carbon, and mechanical breakage. The formation of needle-shaped fibres and shell-shaped matrices is attributed to both the thermal chemical ablation and sublimation of carbon, while carbon fragments and fractured fibres or matrices result from 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.     

Effect of fiber architecture and density on the ablation behavior of carbon/carbon composites modified by Zr–Ti–C

Three carbon/carbon (C/C) composites modified by Zr–Ti–C, with different fiber architecture in preforms and the same density, were prepared using chemical vapor infiltration and reactive melt infiltration methods. Two other samples with the same architecture in preforms and different density were also fabricated by the same methods. Their ablation behaviors were examined by oxy-acetylene flame. The results showed that the samples with chopped web needled perform had better ablation resistance than that of the samples with needle-integrated and fine-weave pierced perform. In the models of ablation behaviors, the sealing time of pores and gaps on the ablated surfaces has been defined to indirectly estimate the ablation property. The analysis of models also indicated that high density of the composites and appropriate small diameter of bundles of carbon fibers led to the short sealing time and good ablation resistance of the C/C–carbide composites.     

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.     

Ablation mechanism of carbon/carbon composites in internal flow field comprising supersonic multiphase flow coupled with ground simulation supersonic ablation

A supersonic multiphase flow was coupled with a ground simulation supersonic ablation test system to evaluate internal flow-field ablation/erosion performances of three-dimensional four-way braided carbon/carbon (C/C) composites. The results showed that the C/C composite mass and linear ablation rates were 0.0123 g/s and 0.0106 mm/s, respectively, in the supersonic inner flow-field ablation environment wherein kerosene and oxygen were completely burned. The overall material ablation was dominated by mechanical ablation accompanied by some C/CO₂ and C/H₂O thermal oxidation ablations. With increasing oxygen enrichment, the composite mass and line ablation rates considerably increased to 0.0158 g/s and 0.0161 mm/s, respectively, in the 10%-oxygen-enriched internal flow-field ablation environment. And the composite thermal oxidation ablation was dominated by C/O₂ and supplemented by C/CO₂ and C/H₂O reactions accompanied by rapid-airflow-induced mechanical erosion. In addition, the condensed-phase particle-induced erosion considerably reduced the C/C composite ablation resistance in the supersonic internal flow-field ablation environment.     

Thermal and ablative properties of low temperature carbon fiber-phenol formaldehyde resin composites

The thermal and ablative properties of phenol formaldehyde resin (PF) composites reinforced with carbon fibers heat-treated at low temperature have been investigated. Low temperature carbon fibers (LTCF) were obtained by a continuous carbonization process from stabilized PAN fibers at 1100 °C. The properties of LTCF reinforced PF (LTCF-PF) composites are compared with those of high temperature carbon fiber (HTCF) reinforced PF (HTCF-PF) composites. The thermal conductivity of the LTCF-PF composite is lower than that of HTCF-PF composite by about 35 and 10% along the directions parallel and perpendicular to the laminar plane, respectively. It was found from the ablation test using an arc plasma touch flame that the erosion rate is higher by about 30% in comparison with HTCF-PF composite. The result suggests that use of LTCFs as reinforcement in a composite may improve the thermal insulation of the composite but decrease the ablative resistance.     

Advances in oxidation and ablation resistance of high and ultra-high temperature ceramics modified or coated carbon/carbon composites

Carbon/carbon (C/C) composites are considered as one of the most promising materials in structural applications owing to their excellent mechanical properties at high temperature. However, C/C composites are susceptible to high-temperature oxidation. Matrix modification and coating technology with ultra-high temperature ceramics (UHTCs) have proved to be highly effective to improve the oxidation and ablation resistance of C/C composites. In this paper, recent advances in oxidation and ablation resistance of C/C composites were firstly reviewed, with attention to oxidation and ablation properties of C/C composites coated or modified with UHTCs. Then, several new methods in improving oxidation and ablation resistance were discussed, such as by using nanostructures to toughen UHTCs coatings or carbon matrix and the combination of matrix modification and coating technology. In addition, relevant ablation tests with scaled models were also briefly introduced. Finally, some open problems and future challenges were highlighted in the development and application of these materials.     

酚醛气凝胶/碳纤维复合材料的结构调控及性能研究

以酚醛树脂为前体、碳纤维针刺预制体为增强体,采用溶胶-凝胶、常压干燥方法制备得到纳米孔酚醛气凝胶/碳纤维复合材料。在不改变材料密度的条件下,通过调节固化剂的用量来调控酚醛气凝胶的纳米颗粒尺寸及孔隙结构,改变气凝胶颗粒在碳纤维针刺预制体中的填充状态,制备出不同微观结构的复合材料。研究表明：随着固化剂用量的减少,气凝胶的颗粒粒径逐渐变小,平均孔径在230 nm~5μm范围内可调;与碳纤维复合后,随着气凝胶颗粒的减小,复合材料的力学性能逐渐提升、热导率逐渐降低、烧蚀性能明显提高。优化后的PAC复合材料具有极低的密度（0.27 g·cm^-3）、高弯曲强度（8.9 MPa）、较低的热导率（0.065 W·m^-1·K^-1）;在2000℃、30 s的中等热流烧蚀条件下,质量烧蚀率为0.0081 g·s^-1、线烧蚀率为0.0204 mm·s^-1。通过调控材料的纳米结构,能够有效地提升材料的力学、隔热以及烧蚀性能,满足高性能热防护应用需求。     

ZrC ablation protective coating for carbon/carbon composites

A zirconium carbide (ZrC) protective coating was deposited on carbon/carbon (C/C) composites by atmospheric pressure chemical vapor deposition. The phase compositions, surface and cross-section microstructures, and anti-ablative properties of the coatings were investigated. Results show that the method is an effective route to prepare a dense and thick ZrC coating on C/C composites. The coating can effectively protect C/C composites from ablation for 240 s in an oxy-acetylene torch system with a mass ablation rate of 1.1 × 10⁻⁴ g/cm² s and a linear ablation rate of 0.3 × 10⁻³ mm/s.     

Integrative improvement on thermophysical properties and ablation resistance of laminated carbon/carbon composites modified by in situ grown HfC nanowires onto carbon fiber cloths

HfC nanowires modified carbon fiber cloth laminated carbon/carbon (HfC_nw-C/C) composites were fabricated by in situ growth of HfC nanowires on carbon cloths via catalytic CVD, followed with lamination of the cloths and densification by pyrolytic carbon (PyC). Morphologies, thermal conductivity, coefficient of thermal expansion (CTE), and ablation resistance of the composites were investigated. Due to the loading of HfC nanowires, the matrix PyC with low texture was obtained; the thermal conductivity of the composites in the Z direction was enhanced from 100℃ to 2500℃; CTE along the X–Y direction also decreased in the range of 2060 ℃ – 2500 ℃, which reaches the maximum of 24 % at 2500℃. Moreover, the 20s-ablation-resistance of HfC_nw-C/C composites exhibits mass and linear ablation rates of 5.3 mg/s and 21.0 μm/s, which are 40 % and 37 % lower than those of pure C/C composites, respectively. Our work shows laminated HfC_nw-C/C composites are a promising candidate for high-temperature applications.     

Study of thermal stability and ablation behavior of carbon/epoxy‐novolac composites

The use of carbon/epoxy‐novolac composites as advanced ablative materials for insulation of exit cone of solid‐propellant rocket nozzles are studied. In this article, three types of carbon fabrics are used and their composites are prepared by use of impregnation and hand lay‐up methods. To study the thermal stability and ablation behavior, these composites are tested by thermal tests such as thermogravimetric analysis (TGA) and oxyacetylene standard flame tests; the latter test is one of the most important standard tests of ablative materials. The test apparatus is made according to American standard, ASTM‐E‐285‐80, and over 33 polymeric composites and 3 steel specimens were carried out according to its standards. It is found that the composites that are made up of C‐9750 fabric (high‐strength carbon fabric) in comparison with steel and the other types of carbon fabric specimens have the highest thermal stability and the best ablation behavior. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2455–2461, 2003     

Anti-oxidation and ablation properties of carbon/carbon composites infiltrated by hafnium boride

To improve the anti-oxidation and ablation properties of carbon/carbon (C/C) composites, they are modified by hafnium boride (HfB₂) using a two-step process of in situ reaction and thermal gradient chemical vapor infiltration. X-ray diffraction is used to monitor the composition of the samples. Scanning electron microscope images show that the carbon fibers are uniformly coated by HfB₂ particles. The oxidation onset temperature of carbon fibers is greatly increased from 300 to 700 °C after HfB₂ coating. After modification with HfB₂, the linear and mass ablation rates of the C/C composites are decreased by 51.80% and 24.32%. During oxidation and ablation, the interface between carbon matrix and fiber is effectively protected by HfB₂ due to the reaction of HfB₂ with the oxygen, and the resultant hafnium oxide may form the liquid film to resist the oxygen at high temperature.     

Rapid and low-cost carbon/carbon composites by using graphite slurry impregnated prepregs

A rapid and low-cost carbon/carbon (C/C) composites preparation method is proposed: graphite prepreg-coated carbon fiber fabric (CFF) is formed by hot pressing, followed by hot isostatic pressing and high temperature graphitization, to prepare C/C composite with low porosity and high crystallinity. In this method, the carbon fiber (CF) mass fraction can be precisely regulated in the range of 40–95% by the impregnation process conditions of CFF in graphite prepreg. The graphite particles in the preform were graphitized and bonded with CFF by high temperature graphitization. Finally, a ZrO₂ anti-ablative layer was applied using sol-gel method. The results show that when the CF mass fraction is 50%, the C/C composite with a crystallinity of 92.21 and a porosity of 3.47% can be obtained, with mass ablation rate of 0.23 mg/s and density of 1.62 g/m³. The method can prepare C/C composites with uniform density and high ablation resistance.     

Effect of preform and carbon matrix on bending strength of Cf/Cu/C composites

Aiming to obtain composites with appropriate mechanical properties for pantograph sliders, copper mesh modified carbon/carbon (C_f/Cu/C) composites were prepared by chemical vapor infiltration (CVI) in C₃H₆ +?N₂ atmosphere and impregnation-carbonization (I-C) with furan resin. In this paper, C_f/Cu/C composites with two kinds of preforms and carbon matrixes were obtained. The effect of preforms and carbon matrixes on bending strength was investigated. The results indicated that the bending strength of carbon fiber/copper mesh reinforced pyrolytic carbon matrix composites was about 181.39–195.43?MPa, while that reinforced resin carbon matrix composites had the worst bending strength around 54.45–57.04?MPa, in terms of the same preform. The bending strength of C_f/Cu/C composites in the parallel orientation and vertical orientation were also similar. As for C_f/Cu/C composites with the same carbon matrix, the bending strength of C_f/Cu/C composites with non-woven fiber/fiber web/copper mesh type preform was higher than that with fiber web/copper mesh type preform. However, the bending strength of carbon fiber/copper mesh reinforced resin carbon matrix composites showed the opposite trend, and its reasons were analyzed and discussed taking advantage of the fracture mechanisms.     

纳米改性碳/酚醛树脂基复合材料性能研究

针对碳/酚醛树脂基复合材料层间剪切强度低的缺点,采用纳米填料进行改性。测试了2种纳米填料(纳米碳纤维、碳纳米管)改性后酚醛树脂的热解性能,研究了纳米填料对复合材料力学性能、烧蚀性能以及高温炭化后力学性能的影响,并观察分析了复合材料测试后的微观形貌。研究结果表明,纳米填料改性后,复合材料的力学性能、烧蚀性能均有所改善。其中,纳米碳纤维改性后复合材料的常温层间剪切强度达到24.9 MPa,氧乙炔线烧蚀率为22.75μm/s,质量烧蚀率为23.58 mg/s。纳米碳纤维表面粗糙,与树脂基体的界面强度高,因此其改性后的力学性能和烧蚀性能优于碳纳米管。     

The influence of carbon fibre surface treatment on the mechanical properties of carbon/carbon composites

The influence of carbon fibre type and carbon fibre surface treatment on the mechanical properties of phenolic-based, unidirectionally reinforced carbon/carbon composites has been investigated.It was found that only the reinforcement of carbon/carbon composites with untreated type I fibres results in best mechanical properties. Surprisingly in that case also an optimised surface treatment of the fibres improve the yield of fibre strength. The experimental results have shown that the applicability of the rule of mixtures for the precalculation of the strength of carbon/carbon composites is limited and that the fracture behaviour is controlled by the amount of adhesion between carbon fibres and carbon matrix.     

Ablation behavior of HfC coating with different thickness for carbon/carbon composites at ultra-high temperature

The thickness of the different HfC coatings from 20 μm to 50 μm were prepared on the surface of carbon/carbon (C/C) composites by low pressure chemical vapor deposition (LPCVD). The microstructure and thermal stress of the coatings after ablation were investigated, as well as the effect of thickness and thermal stress on the ablation resistance of the HfC coating was analyzed. After being ablated at a heat flux of 2.4 MW/m² for 60 s, the thermal stress gradually increased at first and then rapidly increased with the increasing thickness of coating. The results indicated that the moderate coating thickness can effectively release the thermal stress generated during the ablation process. The 40 μm-thick HfC coating showed the best ablation resistance with the mass ablation rate and line ablation rate were only 0.13 mg/s and 0.09 μm/s, respectively.     

Effects of zirconium carbide content on thermal stability and ablation properties of carbon/phenolic composites

Ceramic particles were utilized to improve thermal stability and ablation properties of carbon/phenolic (C/Ph) composites. In this study, zirconium carbide (ZrC) modified C/Ph composites were fabricated by vacuum impregnation method, and effects of ZrC content on thermal stability and ablation properties were investigated by thermogravimetry analysis and plasma wind tunnel test. Moreover, morphological characterization was carried out using X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy. Experimental results showed that increasing ZrC content could lead to an evident increase in char yield, but an observable reduction in linear ablation rates and back-face temperatures because of the formation of ZrO₂ layer on the ablation surface. The work provided an effective way to improve thermal stability and ablation properties of C/Ph composites.