SRM喉衬用炭/炭复合材料烧蚀性能研究
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摘要
喷管是固体火箭发动机(SRM)的一个关键部件,而喉衬是发动机喷管中工作环境最恶劣的部位。随着更大载荷、更大推力和更高燃气温度、更远射程SRM的发展,SRM对喉衬材料烧蚀性能提出了更高要求。炭/炭(C/C)复合材料具有轻质、高强、良好的烧蚀性能、优异的抗热震性能,以及性能的可设计性等特点,是理想的喉衬材料,已广泛应用于SRM喷管喉衬。本研究以SRM喷管喉衬用C/C复合材料为背景,采用电弧驻点烧蚀试验方法,系统研究了烧蚀条件、炭纤维预制体和基体炭类型及结构等对C/C复合材料烧蚀性能的影响,揭示了其烧蚀机理;结合武器型号用SRM喷管喉衬的研制,解剖分析了地面点火试验后C/C复合材料喉衬的烧蚀形貌,探讨了其烧蚀机理;在此基础上,开展了添加难熔金属碳化物和SiC表面涂层制备工艺及其烧蚀性能的研究,并对2种常用的考核C/C复合材料烧蚀性能的方法进行了评价。
系统考察了电弧驻点烧蚀条件(驻点压强、总焓、烧蚀时间等)对C/C复合材料烧蚀性能的影响规律。3000℃左右的温度范围内,焓值(温度)越高,烧蚀越严重;烧蚀时间延长,烧蚀量增加明显;C/C复合材料的烧蚀性能对驻点压强十分敏感,压强提高一倍,烧蚀率成倍地增长。
系统研究了C/C复合材料的本征烧蚀性能,揭示了各因素的影响规律。C/C复合材料平行方向的烧蚀性能优于垂直方向烧蚀性能。热解炭和树脂炭混合增密的C/C复合材料烧蚀性能优于纯树脂炭增密的C/C复合材料烧蚀性能;典型粗糙层结构的C/C材料烧蚀性能优于典型光滑层结构的材料烧蚀性能;热解炭沉积密度越高,烧蚀性能越好。随着穿刺密度的增加,细编穿刺结构C/C复合材料烧蚀性能提高。
揭示了C/C复合材料的烧蚀机理,建立了烧蚀模型。C/C复合材料烧蚀分为热化学烧蚀和机械剥蚀两部分,机械剥蚀决定材料宏观烧蚀形貌,热化学烧蚀决定材料微观烧蚀形貌。C/C复合材料的烧蚀优先从界面、缺陷、孔隙处开始并向纵深发展,导致炭纤维与热解炭、热解炭内部、热解炭与树脂炭之间的界面分离,以及孔洞、缺陷的进一步增大。此外,因热应力等新生成的裂纹及固有的裂纹变宽,不断延伸、扩展,甚至彼此贯穿。在外界剪切力、涡旋分离力或内部热应力的作用下引起材料的机械剥蚀。
结合武器型号用SRM喷管喉衬的研制,解剖分析了SRM地面点火试验后C/C复合材料喉衬的烧蚀形貌,阐明了其烧蚀机理;针刺整体毡结构的C/C复合材料喉衬整体性完好、烧蚀均匀、烧蚀率低,但由于z向纤维含量较少,z向强度较低,在喉部、接近喉部位置易产生层间裂纹;细编穿刺毡结构C/C复合材料具有良好的热性能和力学性能,且材料性能各向异性小,烧蚀性能较好。随着压强的升高,C/C复合材料喉衬的烧蚀率增加。C/C喉衬的烧蚀主要由热化学烧蚀和机械剥蚀两部分组成。颗粒的冲刷将加强对烧蚀材料的传热、改变材料的性质和强度甚至破坏材料的结构,加速热化学烧蚀。
查明了烧蚀过程中WC改性C/C复合材料中WC发生的系列物理化学变化及其作用。WC改性C/C复合材料宏观和微观烧蚀形貌较C/C复合材料的烧蚀形貌的有较大变化。WC改性C/C复合材料的高温烧蚀包括:C/C复合材料中炭与烧蚀气流中氧化气氛的反应;WC的氧化及熔融;WC的熔化;WO_3和WC液膜的形成和剥蚀以及C/C复合材料的剥蚀。
查明了SiC涂层对C/C复合材料烧蚀性能的作用机理。指出烧蚀过程中SiC氧化及SiO_2熔融,从而降低了C/C复合材料烧蚀率,改善了其烧蚀均匀性。
比较研究了C/C复合材料烧蚀性能测试方法等离子体烧蚀试验方法,简单、价格低,但与实际环境偏差大,烧蚀率数值小,重复性差;可作为参考,定性地断定材料的烧蚀性能。电弧驻点烧蚀试验方法比较接近实际环境,可根据要求调节驻点温度、驻点压强和烧蚀时间;烧蚀率数值适中;系统可靠,数据可重复性好;能较好地模拟固体火箭发动机喷管喉衬的真实烧蚀情况,但相对SRM地面点火试验,其试验费用低,试验准备周期短、简单。
研究所得结果为下一步低烧蚀率C/C喉衬材料的开发和应用奠定了基础。
Nozzle is one of the key components in Solid Rocket Motor (SRM) and throat is the most important part in nozzles for it works in the most serious conditions. With the development of SRM for more loads, huger propulsion, elevated temperature and farther shot, its working conditions becomes more and more severe. The requirements for nozzle materials are accordingly increased. Carbon/carbon (C/C) composites have superior characteristics of low density, high strength, excellent ablation property, good thermal shock resistance, designable characteristic and so on. These outstanding properties make them the essential candidate materials for high temperature applications, which is especially true for SRM throats.With the application background of C/C composites for SRM throat, influences of ablation conditions, reinforcements as well as types and structure of carbon matrix on ablation properties of C/C composites were investigated after arc stagnation ablation test and the ablation mechanism were discussed;Combine with preparation of SRM throats, ablation morphilogies of C/C throats were observed and their ablation mechanisms were discussed; Furthermore, C/C composites added with refractory carbide or with SiC coating were prepared, and their ablation behaviors and properties were analysized; In addition, the common used methods for testing ablation rates of C/C composites were evaluated.
Effects of ablation conditions (stagnation pressure, enthalpy, and ablating time) on ablation properties of C/C composites were investigated. The results show that around 3000℃, the higher of the enthalpy (temperature), the more serious ablation of the composites; The longer the ablating time, the much loss of the ablation quantity; But among them, stagnation pressure has greater influence on the ablation property of C/C composites.
The ablation properties of C/C composites were investigated with arc stagnation ablation test.The results show that ablation property of C/C composites of parallel ablation or with rough laminar carbon is respectively better than that of vertical ablation or with smooth laminar carbon. vertical ablation; In addition, the more of pyrolytic carbon or the increasing numbers of pierced carbon fibers, the better of ablation property.
Ablation mechanism of C/C composites was discussed and ablation models were built. The ablation process of C/C composites is controlled by chemical erosion and mechanical denudation; and macro morphology is mainly caused by mechanical denudation, while micro morphology is mainly caused by chemical erosion. Ablation always tends to occur at interfaces, defects and pores and furtherly spread. Thus make the gaps at the interfaces, defects and pores enlarged. In addition, newly born cracks formed by thermal stress and inherent cracks will extend and transfix. Under the shearing force and swirl force of the ablation gas or thermal stress, the surfaces of C/C composites would be blown away and form orderly new ablation section cause mechanical denudation.
Combining the development for SRM throat, C/C composite throats were discussed tothgether with their ablation mechianism. C/C throats with needled integrated carbon fiber performs have lower ablation rates and uniformed ablation surfaces. Because there are only a few fibers in Z direction, strength in Z direction is low, which is eay to cause a few cracks along carbon fiber layers at throat or the places close to throat; C/C throats with carbon fiber pierced performs have good thermal properties, mechanical properties, ablation properties, and small anisotropy; Besides, with the increasing of pressure in combustion chamber, ablation rate of C/C throat will increase. The ablation process of C/C throats includes chemical erosion and mechanical denudation. Erosion of particles will reinforce the transmition of heat, change or even destroy the structure of C/C composites and accelerate the chmical erosion process.
Changes and function of WC in C/C composites during the ablation process were analysized. Not only macro morphology but also micro morphology of C/C composites with WC were quite different from those without; the ablation process of C/C composites with WC includes: oxidation of carbon fibers, carbon matrices and WC, melting of WC and WO_3, together with denudation of WC, WO_3 and C/C composites.
Effect of SiC coating on ablation property of C/C composites was found. During the ablation process, SiC will be oxided and SiO_2 will be melt, therefore, SiC coating can low down the ablation rates of C/C composites and ameliorate their ablation surfaces.
The testing methods for ablation properties of C/C composites were compared. The plasma ablation method is easy to operated, but its ablation conditions are quite different from real throat; Furthermore, the ablation rates are too small and the repetition testing results are bad, so it can only test ablation properties in a qualitative way; In arc stagnation ablation test, stagnation temperature, pressure and ablation time can be adjusted, its ablation rates are moderate and the ablation results can be repeated, thus it can model real throats better. In addition, compared with SRM fire test, it is much easier and cost much less.
Those results will have meaningful worthiness for further development and applications of C/C composites with lower ablation rates.
系统考察了电弧驻点烧蚀条件(驻点压强、总焓、烧蚀时间等)对C/C复合材料烧蚀性能的影响规律。3000℃左右的温度范围内,焓值(温度)越高,烧蚀越严重;烧蚀时间延长,烧蚀量增加明显;C/C复合材料的烧蚀性能对驻点压强十分敏感,压强提高一倍,烧蚀率成倍地增长。
系统研究了C/C复合材料的本征烧蚀性能,揭示了各因素的影响规律。C/C复合材料平行方向的烧蚀性能优于垂直方向烧蚀性能。热解炭和树脂炭混合增密的C/C复合材料烧蚀性能优于纯树脂炭增密的C/C复合材料烧蚀性能;典型粗糙层结构的C/C材料烧蚀性能优于典型光滑层结构的材料烧蚀性能;热解炭沉积密度越高,烧蚀性能越好。随着穿刺密度的增加,细编穿刺结构C/C复合材料烧蚀性能提高。
揭示了C/C复合材料的烧蚀机理,建立了烧蚀模型。C/C复合材料烧蚀分为热化学烧蚀和机械剥蚀两部分,机械剥蚀决定材料宏观烧蚀形貌,热化学烧蚀决定材料微观烧蚀形貌。C/C复合材料的烧蚀优先从界面、缺陷、孔隙处开始并向纵深发展,导致炭纤维与热解炭、热解炭内部、热解炭与树脂炭之间的界面分离,以及孔洞、缺陷的进一步增大。此外,因热应力等新生成的裂纹及固有的裂纹变宽,不断延伸、扩展,甚至彼此贯穿。在外界剪切力、涡旋分离力或内部热应力的作用下引起材料的机械剥蚀。
结合武器型号用SRM喷管喉衬的研制,解剖分析了SRM地面点火试验后C/C复合材料喉衬的烧蚀形貌,阐明了其烧蚀机理;针刺整体毡结构的C/C复合材料喉衬整体性完好、烧蚀均匀、烧蚀率低,但由于z向纤维含量较少,z向强度较低,在喉部、接近喉部位置易产生层间裂纹;细编穿刺毡结构C/C复合材料具有良好的热性能和力学性能,且材料性能各向异性小,烧蚀性能较好。随着压强的升高,C/C复合材料喉衬的烧蚀率增加。C/C喉衬的烧蚀主要由热化学烧蚀和机械剥蚀两部分组成。颗粒的冲刷将加强对烧蚀材料的传热、改变材料的性质和强度甚至破坏材料的结构,加速热化学烧蚀。
查明了烧蚀过程中WC改性C/C复合材料中WC发生的系列物理化学变化及其作用。WC改性C/C复合材料宏观和微观烧蚀形貌较C/C复合材料的烧蚀形貌的有较大变化。WC改性C/C复合材料的高温烧蚀包括:C/C复合材料中炭与烧蚀气流中氧化气氛的反应;WC的氧化及熔融;WC的熔化;WO_3和WC液膜的形成和剥蚀以及C/C复合材料的剥蚀。
查明了SiC涂层对C/C复合材料烧蚀性能的作用机理。指出烧蚀过程中SiC氧化及SiO_2熔融,从而降低了C/C复合材料烧蚀率,改善了其烧蚀均匀性。
比较研究了C/C复合材料烧蚀性能测试方法等离子体烧蚀试验方法,简单、价格低,但与实际环境偏差大,烧蚀率数值小,重复性差;可作为参考,定性地断定材料的烧蚀性能。电弧驻点烧蚀试验方法比较接近实际环境,可根据要求调节驻点温度、驻点压强和烧蚀时间;烧蚀率数值适中;系统可靠,数据可重复性好;能较好地模拟固体火箭发动机喷管喉衬的真实烧蚀情况,但相对SRM地面点火试验,其试验费用低,试验准备周期短、简单。
研究所得结果为下一步低烧蚀率C/C喉衬材料的开发和应用奠定了基础。
Nozzle is one of the key components in Solid Rocket Motor (SRM) and throat is the most important part in nozzles for it works in the most serious conditions. With the development of SRM for more loads, huger propulsion, elevated temperature and farther shot, its working conditions becomes more and more severe. The requirements for nozzle materials are accordingly increased. Carbon/carbon (C/C) composites have superior characteristics of low density, high strength, excellent ablation property, good thermal shock resistance, designable characteristic and so on. These outstanding properties make them the essential candidate materials for high temperature applications, which is especially true for SRM throats.With the application background of C/C composites for SRM throat, influences of ablation conditions, reinforcements as well as types and structure of carbon matrix on ablation properties of C/C composites were investigated after arc stagnation ablation test and the ablation mechanism were discussed;Combine with preparation of SRM throats, ablation morphilogies of C/C throats were observed and their ablation mechanisms were discussed; Furthermore, C/C composites added with refractory carbide or with SiC coating were prepared, and their ablation behaviors and properties were analysized; In addition, the common used methods for testing ablation rates of C/C composites were evaluated.
Effects of ablation conditions (stagnation pressure, enthalpy, and ablating time) on ablation properties of C/C composites were investigated. The results show that around 3000℃, the higher of the enthalpy (temperature), the more serious ablation of the composites; The longer the ablating time, the much loss of the ablation quantity; But among them, stagnation pressure has greater influence on the ablation property of C/C composites.
The ablation properties of C/C composites were investigated with arc stagnation ablation test.The results show that ablation property of C/C composites of parallel ablation or with rough laminar carbon is respectively better than that of vertical ablation or with smooth laminar carbon. vertical ablation; In addition, the more of pyrolytic carbon or the increasing numbers of pierced carbon fibers, the better of ablation property.
Ablation mechanism of C/C composites was discussed and ablation models were built. The ablation process of C/C composites is controlled by chemical erosion and mechanical denudation; and macro morphology is mainly caused by mechanical denudation, while micro morphology is mainly caused by chemical erosion. Ablation always tends to occur at interfaces, defects and pores and furtherly spread. Thus make the gaps at the interfaces, defects and pores enlarged. In addition, newly born cracks formed by thermal stress and inherent cracks will extend and transfix. Under the shearing force and swirl force of the ablation gas or thermal stress, the surfaces of C/C composites would be blown away and form orderly new ablation section cause mechanical denudation.
Combining the development for SRM throat, C/C composite throats were discussed tothgether with their ablation mechianism. C/C throats with needled integrated carbon fiber performs have lower ablation rates and uniformed ablation surfaces. Because there are only a few fibers in Z direction, strength in Z direction is low, which is eay to cause a few cracks along carbon fiber layers at throat or the places close to throat; C/C throats with carbon fiber pierced performs have good thermal properties, mechanical properties, ablation properties, and small anisotropy; Besides, with the increasing of pressure in combustion chamber, ablation rate of C/C throat will increase. The ablation process of C/C throats includes chemical erosion and mechanical denudation. Erosion of particles will reinforce the transmition of heat, change or even destroy the structure of C/C composites and accelerate the chmical erosion process.
Changes and function of WC in C/C composites during the ablation process were analysized. Not only macro morphology but also micro morphology of C/C composites with WC were quite different from those without; the ablation process of C/C composites with WC includes: oxidation of carbon fibers, carbon matrices and WC, melting of WC and WO_3, together with denudation of WC, WO_3 and C/C composites.
Effect of SiC coating on ablation property of C/C composites was found. During the ablation process, SiC will be oxided and SiO_2 will be melt, therefore, SiC coating can low down the ablation rates of C/C composites and ameliorate their ablation surfaces.
The testing methods for ablation properties of C/C composites were compared. The plasma ablation method is easy to operated, but its ablation conditions are quite different from real throat; Furthermore, the ablation rates are too small and the repetition testing results are bad, so it can only test ablation properties in a qualitative way; In arc stagnation ablation test, stagnation temperature, pressure and ablation time can be adjusted, its ablation rates are moderate and the ablation results can be repeated, thus it can model real throats better. In addition, compared with SRM fire test, it is much easier and cost much less.
Those results will have meaningful worthiness for further development and applications of C/C composites with lower ablation rates.
引文
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