CN112409003B - 一种杂化基体碳化硅基复合材料及其制备方法 - Google Patents
一种杂化基体碳化硅基复合材料及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种杂化基体碳化硅基复合材料及其制备方法,属于复合材料技术领域。本发明基于液相前驱体转化工艺,首先通过织物骨架定型和前期致密化,获得一定密度的无机态碳化硅基复合材料多孔毛坯,之后通过在多孔毛坯中直接浸渍有机前驱体,并进行原位固化及后固化,获得轻质、高强的有机/无机杂化基体碳化硅基复合材料,该设计思路实现了轻质、高致密度的树脂基复合材料与高温、抗烧蚀陶瓷基复合材料的有机结合,与临近空间飞行器主被动段服役环境差异性需求更加匹配。通过调控前驱体组成、致密化轮次及处理温度,可以获得不同耐温及力学性能的杂化基体复合材料,满足不同应用环境需求,该方法具有适用性广、制造周期短、成本低等显著特点。
Description
技术领域
本发明属于复合材料技术领域,特别涉及一种杂化基体碳化硅基复合材料及其制备方法。
背景技术
临近空间高超声速飞行器具有速度快、机动性高、精确度高、破坏性强等突出特点,可实现快速响应、高精度打击及远程投送任务,由于其极强的威慑力和突出的军事价值,成为近年来世界各国竞先发展的重要战略武器。临近空间飞行器超高速、大机动、长航时等特性对轻质、高强的高温防热/热结构材料在超常服役环境下的防热性能及高温承载性能提出了迫切需求。
先进耐高温树脂基防热材料是一类应用广泛的轻质防热复合材料,具有低密度、短周期、低成本、高强度、高刚度等显著特点,且随着新型结构树脂开发及改性技术的应用,树脂基复合材料的耐温性有了很大的提升。但受树脂高温热解温度的限制,相比高温金属及陶瓷基复合材料,树脂基复合材料的长时耐温性和高温力学性能仍然较低,一般都需要依赖金属冷结构,导致整体重量偏重,难以满足临近空间飞行器轻质化的需求。而以碳化硅为代表的陶瓷基复合材料具有耐高温、抗氧化、抗烧蚀及优良的高温力学性能等重要特性,是新型临近空间高超声速飞行器防热与热结构材料的重要候选材料,但陶瓷基复合材料制备周期长、成本高、复合应力大及难加工等特点也限制了其工程应用。
因而,亟需研发提供一种轻质、高强、耐高温防热复合材料的快速、低成本的制备方法,并满足多型号应用差别化需求。
发明内容
为了克服现有技术中的不足,本发明人进行了锐意研究,提供了一种杂化基体碳化硅基复合材料及其制备方法,开发的新型有机无机杂化基体陶瓷基复合材料有望吸收树脂基和陶瓷基复合材料的双重优点,实现轻质、高强、耐高温防热复合材料的快速、低成本制备及多型号应用差别化需求,从而完成本发明。
本发明提供的技术方案如下:
第一方面,一种杂化基体碳化硅基复合材料的制备方法,包括如下步骤:
步骤1,采用耐高温无机纤维制备纤维预制体;
步骤2,采用含硅前驱体或碳基前驱体浸渍纤维预制体,结合仿形精密成型工装,经高温裂解处理,实施纤维预制体的骨架定型;
步骤3,采用液相含硅浸渍剂通过多轮次循环浸渍/裂解工艺,并结合复合防变形工装的实时维型,实施前期致密化,获得密度为1.4~1.9g/cm3中间状态碳化硅陶瓷基复合材料多孔毛坯;
步骤4,将完成前期致密化的中间状态碳化硅陶瓷基复合材料多孔毛坯在1200~1800℃条件下进行高温处理;
步骤5,采用含无机填料的液相含硅浸渍剂,通过真空吸入/压力组合浸渍方式,浸渍碳化硅陶瓷基复合材料多孔毛坯;
步骤6,将完成浸渍的碳化硅陶瓷基复合材料多孔毛坯装入烘箱或固化罐中,在100~300℃、0.1~2MPa下处理4~20h,实施复合材料有机基体的原位固化;
步骤7,对完成原位固化的碳化硅陶瓷基复合材料,在300~600℃、0.1~2MPa下处理2~15h,实施复合材料有机基体的后固化。
第二方面,一种杂化基体碳化硅基复合材料,通过上述第一方面所述的制备方法制得。
根据本发明提供的一种杂化基体碳化硅基复合材料及其制备方法,具有以下有益效果:
本发明提供的一种杂化基体碳化硅基复合材料的制备方法,基于液相前驱体转化工艺,首先通过织物骨架定型和前期致密化,获得一定密度的无机态碳化硅基复合材料多孔毛坯,之后通过在多孔毛坯中直接浸渍有机前驱体,并进行原位固化及后固化,获得有机/无机杂化基体碳化硅基复合材料的制备,且有机/无机杂化基体结构设计思路实现了轻质、高致密度的树脂基复合材料和高温、抗烧蚀陶瓷基复合材料的有机结合,与临近空间飞行器主被动段服役环境差异性需求更加匹配。同时,通过调控前驱体胶液组成、致密化轮次及处理温度,可以获得不同耐温及力学性能的碳化硅杂化基体复合材料,满足不同应用环境需求,且该方法具有适用性广、制造周期短、成本低等显著特点。
具体实施方式
下面通过对本发明进行详细说明,本发明的特点和优点将随着这些说明而变得更为清楚、明确。
根据本发明的第一方面,提供了一种杂化基体碳化硅基复合材料的制备方法,包括如下步骤:
步骤1,纤维预制体制备。按照轻质、高强、耐高温需求设计制备纤维预制体。纤维可选用炭纤维、碳化硅纤维等多种耐1200~1800℃高温的无机纤维,预制体结构可为二维铺层缝合结构、针刺结构、2.5D结构、三维四向结构等多种结构形式,具体结构参数及纤维铺叠方式依据力学性能指标及使用环境温度等要求确定。
步骤2,骨架定型。在获得纤维预制体后,采用固态聚碳硅烷溶液、液态聚碳硅烷等含硅前驱体或酚醛树脂、沥青等碳基前驱体浸渍纤维预制体,结合仿形精密成型工装精确成型,并通过在高温炉中600~1500℃下裂解处理2~5h,实现复合材料纤维预制体的骨架定型。
步骤3,前期致密化。在复合材料骨架定型基础上,采用固态聚碳硅烷溶液、液态聚碳硅烷或其他复配前驱体等液相含硅浸渍剂,通过2~10轮次循环浸渍/裂解工艺,并借助复合防变形工装的实时维型,实现碳化硅陶瓷基复合材料的前期致密化,获得密度为1.4~1.9g/cm3、具有孔隙的中间状态碳化硅陶瓷基复合材料多孔毛坯。
本发明中杂化基体碳化硅基复合材料中的无机基体是在纤维预制体骨架定型及前期致密化阶段完成,通过调配液相含硅浸渍剂及致密化轮次可以有效控制复合材料中无机基体的成分及含量。
本发明人经过研究发现,不同液相含硅浸渍剂的陶瓷产率不同,在无机基体含量相同的情况下,陶瓷产率低的浸渍剂需要循环致密化轮次多,陶瓷产率高的浸渍剂需要循环致密化轮次少。同时,不同液相含硅浸渍剂的真密度也有所差异,真密度高的浸渍剂所得复合材料毛坯的密度较高,真密度低的浸渍剂所得复合材料毛坯的密度较低。因此,基于相关研究结果,确定前期致密化阶段所需的循环浸渍/裂解轮次为2~10轮次,对应复合材料多孔毛坯的密度为1.4~1.9g/cm3。
步骤4,高温处理。将完成前期致密化的中间状态碳化硅陶瓷基复合材料多孔毛坯装入热处理炉中,在1200~1800℃条件下进行高温处理2~4h,实现碳化硅基复合材料基体组元的微结构优化及稳定化,并为复合材料的后续致密化提供开孔及浸渍通道。
步骤5,浸渍。采用含1~30wt%无机填料的液相含硅浸渍剂,通过真空吸入的方式浸没复合材料多孔毛坯,之后在1~3MPa压力下,对碳化硅陶瓷基复合材料多孔毛坯进行压力浸渍1~5h。
碳化硅基复合材料复合后期制备有机基体所用的液相前驱体为高陶瓷产率前驱体,且添加的高温无机填料可依据服役温度及功能进行选配,满足不同应用环境对高温复合材料的差别化需求。
本发明将液相含硅浸渍剂中引入高温无机填料,可进一步提高前驱体的转换率和复合材料的致密化效率,且无机填料的用量及粒径要适中。粒径过大则难以分散均匀,且难以浸入复合材料内部,用量过大或粒径过小则会对浸渍剂的粘度及致密化效率造成不利影响。基于上述考虑及相关经验,确定无机填料比较适宜的粒径范围为0.5~5μm,用量范围为1~30wt%。
步骤6,原位固化。将完成浸渍的碳化硅陶瓷基复合材料多孔毛坯装入烘箱或固化罐中,在100~300℃及0.1~2MPa下处理4~20h,实现复合材料有机基体的原位固化。
在本发明一种优选的实施方式中,原位固化后,可根据复合材料填充有机基体后的致密度及表面质量情况选择性进行二次浸渍及固化,具体为重复步骤5及步骤6,对碳化硅陶瓷基复合材料中有机基体填充不太致密时所形成的缝隙及孔洞进行填缝及表面整平处理,实现复合材料有机基体的二次增密。
步骤7,后固化。对完成原位固化的碳化硅陶瓷基复合材料,在300~600℃及0.1~2MPa下处理2~15h,实现复合材料有机基体的后固化,进一步提高复合材料的刚度及高温稳定性,最终获得有机无机杂化基体碳化硅基复合材料。
根据本发明的第二方面,提供了一种杂化基体碳化硅基复合材料,通过上述第一方面所述的制备方法制得。
实施例
实施例1
预先制备二维铺层缝合结构炭纤维增强体,装入仿形精密成型工装中,采用液态聚碳硅烷前驱体浸渍剂,在高温炉中800℃处理4h后,实现二维铺层缝合结构碳化硅基复合材料的骨架定型,接着采用液相含硅浸渍剂液态聚碳硅烷进行真空/压力循环浸渍及裂解处理8次,获得密度为1.90g/cm3的中间状态碳化硅基复合材料毛坯,之后通过1600℃处理2h后,继续采用含10Wt%ZrC、SiO2耐高温组元的液态聚碳硅烷浸渍剂进行2轮次的循环浸渍/原位固化处理(通过真空吸入的方式浸没复合材料多孔毛坯,之后在3MPa下,对复合材料多孔毛坯进行压力浸渍4h,将完成浸渍的复合材料毛坯装入烘箱或固化罐中,在220℃及1MPa下处理8h,实现复合材料有机基体的原位固化),最后在300℃下后固化2h,获得密度为1.98g/cm3、拉伸强度为360MPa、弯曲强度为450MPa、压缩强度为480MPa、模量为110GPa的有机无机杂化基体碳化硅基复合材料。
实施例2
预先制备针刺结构炭纤维增强体,装入仿形精密成型工装中,采用固态聚碳硅烷的二甲苯溶液浸渍剂,在高温炉中1200℃处理4h后,实现针刺结构碳化硅基复合材料的骨架定型,接着采用液相含硅浸渍剂液态聚碳硅烷进行真空/压力循环浸渍及裂解处理4次,获得密度为1.6g/cm3的中间状态碳化硅基复合材料毛坯,之后通过1500℃处理3h后,继续采用含15Wt%ZrO2、B4C耐高温组元的液态聚碳硅烷浸渍剂进行浸渍/原位固化处理(通过真空吸入的方式浸没复合材料多孔毛坯,之后在1MPa下,对复合材料多孔毛坯进行压力浸渍5h,将完成浸渍的复合材料毛坯装入烘箱或固化罐中,在180℃及2MPa下处理10h,实现复合材料有机基体的原位固化),最后在400℃下后固化2h,获得密度为1.82g/cm3、拉伸强度260MPa、弯曲强度为302MPa、压缩强度为358MPa、模量为85GPa的有机无机杂化基体碳化硅基复合材料。
实施例3
预先制备2.5D结构碳化硅纤维增强体,装入仿形精密成型工装中,采用固液聚碳硅烷复配浸渍剂,在高温炉中1000℃处理3h后,实现2.5D结构碳化硅基复合材料的骨架定型,接着采用液相含硅浸渍剂固液聚碳硅烷复配溶液进行真空/压力循环浸渍及裂解处理5次,获得密度为1.8g/cm3的中间状态碳化硅基复合材料毛坯,之后通过1400℃处理4h后,继续采用含5Wt%BN、SiO2耐高温组元的固液聚碳硅烷复配浸渍剂进行浸渍/原位固化处理(通过真空吸入的方式浸没复合材料多孔毛坯,之后在3MPa下,对复合材料多孔毛坯进行压力浸渍3h,将完成浸渍的复合材料毛坯装入烘箱或固化罐中,在260℃及1MPa下处理4h,实现复合材料有机基体的原位固化),最后在450℃下后固化3h,获得密度为1.9g/cm3、拉伸强度282MPa、弯曲强度325MPa、压缩强度341MPa、模量为105GPa的有机无机杂化基体碳化硅基复合材料。
实施例4
预先制备三维四向结构炭纤维增强体,装入仿形精密成型工装中,采用沥青浸渍剂,在高温炉中800℃处理2h后,实现三维四向结构复合材料的骨架定型,接着采用液态聚碳硅烷浸渍剂,进行真空/压力循环浸渍及裂解处理5次,获得密度为1.7g/cm3的中间状态炭/炭-碳化硅基复合材料毛坯,之后通过1600℃处理4h后,继续采用含20Wt%SiC、ZrO2耐高温组元的液态聚碳硅烷浸渍剂进行2轮次的循环浸渍/原位固化处理(通过真空吸入的方式浸没复合材料多孔毛坯,之后在2MPa下,对复合材料多孔毛坯进行压力浸渍4h,将完成浸渍的复合材料毛坯装入烘箱或固化罐中,在200℃及2MPa下处理6h,实现复合材料有机基体的原位固化),最后在400℃下后固化3h,获得密度为1.85g/cm3、拉伸强度为405MPa、弯曲强度为418MPa、压缩强度为365MPa、模量为98GPa的有机无机杂化基体碳化硅基复合材料。
以上结合具体实施方式和范例性实例对本发明进行了详细说明,不过这些说明并不能理解为对本发明的限制。本领域技术人员理解,在不偏离本发明精神和范围的情况下,可以对本发明技术方案及其实施方式进行多种等价替换、修饰或改进,这些均落入本发明的范围内。本发明的保护范围以所附权利要求为准。
本发明说明书中未作详细描述的内容属本领域技术人员的公知技术。
Claims (8)
1.一种杂化基体碳化硅基复合材料的制备方法,其特征在于,包括如下步骤:
步骤1,采用耐高温无机纤维制备纤维预制体;
步骤2,采用含硅前驱体或碳基前驱体浸渍纤维预制体,结合仿形精密成型工装,经高温裂解处理,实施纤维预制体的骨架定型;
步骤3,采用液相含硅浸渍剂通过多轮次循环浸渍/裂解工艺,并结合复合防变形工装的实时维型,实施前期致密化,获得密度为1.4~1.9g/cm3中间状态碳化硅陶瓷基复合材料多孔毛坯;
步骤4,将完成前期致密化的中间状态碳化硅陶瓷基复合材料多孔毛坯在1200~1800℃条件下进行高温处理;
步骤5,采用含无机填料的液相含硅浸渍剂,通过真空吸入/压力组合浸渍方式,浸渍碳化硅陶瓷基复合材料多孔毛坯;液相含硅浸渍剂中含1~30wt%占比的无机填料,所述无机填料的粒径为0.5~5μm;
步骤6,将完成浸渍的碳化硅陶瓷基复合材料多孔毛坯装入烘箱或固化罐中,在100~300℃、0.1~2MPa下处理4~20h,实施复合材料有机基体的原位固化;
步骤7,对完成原位固化的碳化硅陶瓷基复合材料,在300~600℃、0.1~2MPa下处理2~15h,实施复合材料有机基体的后固化。
2.根据权利要求1所述的制备方法,其特征在于,步骤1中,所述纤维预制体包括二维铺层缝合结构、针刺结构、2.5D结构、以及三维四向结构。
3.根据权利要求1所述的制备方法,其特征在于,步骤2中,高温裂解处理的温度为600~1500℃,裂解处理时间为2~5h。
4.根据权利要求1所述的制备方法,其特征在于,步骤3中,循环浸渍/裂解工艺2~10轮次。
5.根据权利要求1所述的制备方法,其特征在于,步骤5中,压力浸渍在1~3MPa下浸渍1~5h。
6.根据权利要求1所述的制备方法,其特征在于,步骤7中,后固化的温度高于原位固化时的温度。
7.根据权利要求1所述的制备方法,其特征在于,原位固化后,根据复合材料填充有机基体后的致密度及表面质量情况,选择性进行二次浸渍及固化,二次浸渍及固化方式为重复步骤5及步骤6。
8.一种杂化基体碳化硅基复合材料,通过上述权利要求1至7之一所述的制备方法制得。
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