CN111285699B - 一种轻质可重复使用的防隔热材料及其制备方法 - Google Patents
一种轻质可重复使用的防隔热材料及其制备方法 Download PDFInfo
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- CN111285699B CN111285699B CN201811496800.1A CN201811496800A CN111285699B CN 111285699 B CN111285699 B CN 111285699B CN 201811496800 A CN201811496800 A CN 201811496800A CN 111285699 B CN111285699 B CN 111285699B
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Abstract
本发明涉及一种轻质可重复使用的防隔热材料及其制备方法。所述防隔热材料包含抗冲刷基体材料和与抗冲刷基体材料复合在一起的包含烧蚀树脂、凝胶固化剂和烧蚀填料的烧蚀复合材料;抗冲刷基体材料包含抗冲刷预制体和与抗冲刷预制体复合在一起的陶瓷基体,抗冲刷预制体包含上下纤维预制体层和中间纤维基体层。所述方法包括:将上下纤维预制体层和中间纤维基体层结合,制得抗冲刷预制体,然后与陶瓷基体复合,制得抗冲刷基体材料;用烧蚀复合材料混合溶液浸渍抗冲刷基体材料,然后将抗冲刷基体材料依次经过胶凝和固化的步骤,制得所述防隔热材料。本发明中所述防隔热材料具备烧蚀隔热性能优异、维形能力强和可重复使用的优点。
Description
技术领域
本发明属于防隔热材料制备技术领域,尤其涉及一种轻质可重复使用的防隔热材料及其制备方法。
背景技术
再入式航天飞行器在大气层内飞行时,飞行器外表面承受高气流冲刷,温度高达2000-10000℃,必须采用高效烧蚀吸热/隔热一体化系统对飞行器进行热防护。
传统烧蚀材料(包括低密度和高密度)以酚醛树脂、环氧树脂、有机硅树脂、聚四氟乙烯等为烧蚀基体,以纤维、酚醛微球、玻璃微球和玻璃钢蜂窝等作为填充剂或增强材料复合而成。在高气动热流下,通过表面烧蚀吸收热量,从而维持下表面材料在一定的温度以下,保证下表面材料的结构稳定性。然而该类型材料在工作环境下烧蚀量过大,烧蚀后热导率较大,无法进一步阻止热流传递,从而无法发挥材料的长期烧蚀/隔热性能;并且由于玻璃纤维、碳纤维、玄武岩棉、玻璃微球等增强材料或填料烧蚀后容易出现脱落、剥离等现象,该类材料难以维持烧蚀/隔热材料的气动外形。此外,目前传统烧蚀材料均为一次性的烧蚀材料,显然已经不能适用于可重复使用的航天飞行器。
中国专利申请201310360892.1公开了一种微烧蚀隔热材料,该材料由烧蚀树脂材料复合刚性隔热材料制备而成,该材料具有良好的烧蚀隔热性能,烧蚀过程中材料表面发生陶瓷化反应,具备维形能力;但是该材料密度较大,且该材料烧蚀掉包含的烧蚀树脂材料后,承载能力较低,难以保证飞行器在长期飞行过程中内部结构的安全性,也无法供飞行器重复使用。
发明内容
为了解决现有技术存在的技术问题,本发明提供了一种轻质可重复使用的防隔热材料及其制备方法。本发明中的轻质可重复使用的防隔热材料具备烧蚀隔热性能优异、维形能力强和可重复使用的优点。
为了实现上述目的,本发明在第一方面提供了一种轻质可重复使用的防隔热材料,所述轻质可重复使用的防隔热材料包含抗冲刷基体材料和与所述抗冲刷基体材料复合在一起的烧蚀复合材料;所述抗冲刷基体材料包含抗冲刷预制体和与所述抗冲刷预制体复合在一起的陶瓷基体,所述抗冲刷预制体包含结合在一起的上纤维预制体层、中间纤维基体层和下纤维预制体层;所述烧蚀复合材料包含烧蚀树脂、凝胶固化剂和烧蚀填料。
优选地,所述烧蚀复合材料与所述抗冲刷基体材料的质量比为(0.1~100):100;和/或所述抗冲刷基体材料的密度为0.3~1.2g/cm3。
优选地,所述抗冲刷预制体还包含缝合线材料,所述抗冲刷预制体由所述缝合线材料将所述上纤维预制体层、所述中间纤维基体层和所述下纤维预制体层缝合而成;所述中间纤维基体层的容重为80~400kg/m3,所述中间纤维基体层的厚度5~50mm;和/或所述上纤维预制体层和/或所述下纤维预制体层的厚度为0.5~10mm。
优选地,所述上纤维预制体层、所述中间纤维基体层、所述下纤维预制体层和/或所述缝合线材料由耐高温纤维制得,所述耐高温纤维的直径为1~20μm,和/或所述耐高温纤维的线密度为190~1200tex;所述上纤维预制体层和所述下纤维预制体层各自独立地选自石英纤维、氧化铝纤维、莫来石纤维、硅酸铝纤维、高硅氧纤维和碳化硅纤维中的一种或者多种耐高温纤维制得;所述中间纤维基体层选自氧化锆纤维、氧化铝纤维、石英纤维、高硅氧纤维和莫来石纤维中的一种或者多种耐高温纤维制得;和/或所述缝合线材料选自氧化铝纤维、莫来石纤维、氧化锆纤维和碳化硅纤维中的一种或者多种耐高温纤维制得。
优选地,所述烧蚀复合材料由以质量百分比计为19.9~99.8%的烧蚀树脂、0.1~10%的凝胶固化剂和0.1~80%的烧蚀填料组成;所述烧蚀树脂选自由硼酚醛树脂、钡酚醛树脂和高残炭酚醛树脂组成的组;所述凝胶固化剂选自由六次甲基四胺、苯胺、三聚氰胺、对甲苯磺酸、对甲苯磺酰氯和石油磺酸组成的组;和/或所述烧蚀填料为有机硅树脂,所述有机硅树脂选自由甲基硅树脂、乙基硅树脂、甲基乙基硅树脂、甲基苯基硅树脂和低聚倍半硅氧烷组成的组。
优选地,所述陶瓷基体复合在所述上纤维预制体层和所述下纤维预制体层中;所述陶瓷基体选自由氧化硅、氧化铝、氧化锆、莫来石、碳化硅、B4C、B4N和B2O3组成的组;所述陶瓷基体与所述抗冲刷预制体的质量比为(30~80):100,优选为(30~60):100;和/或所述防隔热材料还包含复合在所述抗冲刷基体材料中的高温粘结剂;所述高温粘结剂选自由氧化硅、B4C、B4N和B2O3组成的组;所述高温粘结剂与所述抗冲刷预制体的质量比为(1~20):100,优选为(1~10):100。
本发明在第二方面提供了本发明在第一方面所述的防隔热材料的制备方法,所述方法包括如下步骤:
(1)将上纤维预制体层、中间纤维基体层和下纤维预制体层结合,制得抗冲刷预制体;
(2)将步骤(1)制得的抗冲刷预制体与陶瓷基体复合,制得抗冲刷基体材料;和
(3)用包含烧蚀树脂、凝胶固化剂、烧蚀填料和溶剂的烧蚀复合材料混合溶液浸渍步骤(2)制得的抗冲刷基体材料,然后将浸渍后的所述抗冲刷基体材料依次经过胶凝步骤和固化步骤,由此制得所述防隔热材料。
优选地,所述方法还包括在进行步骤(1)之前,先通过疏水化试剂将中间纤维基体层进行疏水化处理的步骤,所述疏水化试剂选自由甲基三甲氧基硅烷、三甲基甲氧基硅烷和三乙基乙氧基硅烷组成的组。
优选地,所述方法还包括在进行步骤(3)之前,先将所述抗冲刷基体材料于500~800℃下进行高温处理0.5~2h,然后将高温处理后的所述抗冲刷基体材料与高温粘结剂复合的步骤。
优选地,所述胶凝在密闭体系中进行,所述固化在敞开体系中进行;和/或所述胶凝和/或所述固化的温度为60~150℃,所述胶凝和/或所述固化的时间为2~48h。
本发明与现有技术相比至少具有如下有益效果:
(1)本发明中的轻质可重复使用的防隔热材料包含抗冲刷基体材料和复合在所述抗冲刷基体材料中的烧蚀复合材料,烧蚀复合材料具备优异的烧蚀和隔热功能,抗冲刷基体材料具备强的维形和隔热功能,烧蚀复合材料和抗冲刷基体材料能在所述防隔热材料中充分发挥各自的优势;本发明人发现所述抗冲刷预制体采用结合在一起的上纤维预制体层、中间纤维基体层和下纤维预制体层形成的夹层结构,能有效维持所述防隔热材料的多孔结构,从而有效地降低所述轻质可重复使用的防隔热材料的密度并且能够有效地保证其在高温下的力学强度、维形能力和承载能力。
(2)本发明中的轻质可重复使用的防隔热材料为超级微纳米多孔结构,能有效地发挥自身优异的烧蚀隔热性能,具备强的承载和维形能力;本发明中的所述防隔热材料包含的烧蚀复合材料烧蚀完全后,仍然可以保持较高的承载能力,从而使得所述防隔热材料在完成烧蚀之后的孔位可以再次复合烧蚀复合材料,实现可重复使用。
(3)本发明中的所述防隔热材料最大的优点是:轻质(密度小)、安全可靠、可重复使用、适应外部加热变化的能力强、工作时间长、并可承受高气动热流,维形和隔热能力强;本发明中的所述防隔热材料在再入式航天飞行器的大面积热防护领域中具有重要的应用价值,特别是适用于高马赫数飞机大面积热防护系统,并且其特殊的可重复使用功能也可在高马赫数飞机上得到应用。
(4)本发明方法具有工艺简单、制备工艺可控,易于工业化实施等优点;本发明方法中的凝胶固化工序有利于形成有机无机杂化的多孔隔热材料,更有利于发挥所述防隔热材料的长时烧蚀隔热特性;本发明中的所述防隔热材料可设计性强、具有好的加工性能,本发明方法根据使用场合和部位可制得各种异型面和尺寸的所述防隔热材料。
附图说明
图1是本发明一个具体实施方式的制备流程图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚,下面将结合本发明实施例,对本发明的技术方案进行清楚、完整地描述。显然,所描述的实施例是本发明的一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例,都属于本发明保护的范围。
本发明在第一方面提供了一种轻质可重复使用的防隔热材料,所述轻质可重复使用的防隔热材料包含抗冲刷基体材料和与所述抗冲刷基体材料复合在一起的烧蚀复合材料;所述抗冲刷基体材料包含抗冲刷预制体和与所述抗冲刷预制体复合在一起的陶瓷基体,所述抗冲刷预制体包含结合在一起的上纤维预制体层、中间纤维基体层和下纤维预制体层;所述烧蚀复合材料包含烧蚀树脂、凝胶固化剂和烧蚀填料。在本发明中,所述中间纤维基体层例如可由纤维制成的纤维毡,此时,也将中间纤维基体层记作中间纤维毡层;在本发明中,所述上纤维预制体层和所述下纤维预制体层例如可以为编织布或者织物。
本发明中的所述抗冲刷预制体中复合有陶瓷基体,所述陶瓷基体使得所述抗冲刷基体材料致密化,能够有效提高所述防隔热材料的力学强度和承载能力。本发明中所述抗冲刷预制体为包含上纤维预制体层、中间纤维基体层和下纤维预制体层的夹层结构,本发明人意外发现采用这种抗冲刷预制体能有效维持所述抗冲刷基体材料以及所述防隔热材料的多孔结构,有效地降低所述轻质可重复使用的防隔热材料的密度并且能够有效地保证其在高温下优异的力学强度以及抗冲刷基体材料以及所述防隔热材料强的维形能力和承载能力;此外,这种所述抗冲刷基体材料利于复合所述烧蚀复合材料,提高所述防隔热材料的烧蚀性能并保证所述防隔热材料的隔热性能,可以克服一般耐高温夹层隔热材料无法同时兼顾防热性能(烧蚀性能)和隔热性能的缺点以及一般防隔热一体化材料由于受到其自身耐受温度的影响而限制了其在更高温度工作环境中应用的不足。
本发明中的轻质可重复使用的防隔热材料烧蚀复合材料为超级微纳米多孔结构,其包含的烧蚀复合材料具备优异的烧蚀和隔热功能,抗冲刷基体材料具备强的维形和隔热功能,所述烧蚀复合材料和所述抗冲刷基体材料在所述防隔热材料中能充分地发挥各自的优势;此外,本发明中的所述防隔热材料包含的烧蚀复合材料烧蚀完全后,仍然可以保持较高的承载能力,不会破坏所述抗冲刷基体材料以及所述防隔热材料的多孔结构,从而使得所述防隔热材料在完成烧蚀之后的孔位可以再次复合烧蚀复合材料,实现可重复使用。本发明所述的防隔热材料具有超高温烧蚀隔热性能优异、维形能力和承载能力强以及可重复使用的优点;由于所述轻质可重复使用的防隔热材料具有这些优点,在本发明中,也将轻质可重复使用的防隔热材料记作轻质维形可重复使用的发汗型防隔热材料。本发明所述的防隔热材料在再入式飞行器外防护领域,特别是高马赫数飞机大面积热防护领域具有非常好的应用前景。在本发明中,所述防隔热材料可重复使用,指的是所述防隔热材料在烧蚀掉烧蚀复合材料后,可以将烧蚀复合材料再次复合(例如依次通过浸渍或喷涂或涂刷渗入、胶凝、固化的步骤)进所述抗冲刷基体材料中,实现再生使用。
根据一些优选的实施方式,所述烧蚀复合材料与所述抗冲刷基体材料的质量比为(0.1~100):100(例如0.1:100、1:100、2:100、3:100、4:100、5:100、6:100、7:100、8:100、9:100、10:100、15:100、20:100、25:100、30:100、35:100、40:100、45:100、50:100、55:100、60:100、65:100、70:100、75:100、80:100、85:100、90:100、95:100或100:100);本发明中所述烧蚀复合材料与所述抗冲刷基体材料的质量比可调,使得所述防隔热材料的可设计性强,可以根据使用环境温度、热流等来设计不同烧蚀复合材料含量的所述防隔热材料;在本发明中,优选为所述烧蚀复合材料与所述抗冲刷基体材料的质量比为(0.1~100):100,所述烧蚀复合材料的含量不可过高时,否则会降低所述防隔热材料的机械性能,导致力学强度降低。
根据一些优选的实施方式,所述抗冲刷基体材料的密度为0.3~1.2g/cm3(例如0.3、0.35、0.4、0.45、0.5、0.55、0.6、0.65、0.7、0.75、0.8、0.85、0.9、0.95、1.0、1.05、1.1、1.15或1.2g/cm3);所述抗冲刷基体材料的密度不可太小,否则会导致所述防隔热材料的力学强度、维形能力以及承载能力降低;所述抗冲刷基体材料的密度也不可过大,否则会导致所述抗冲刷基体材料的气孔太小,不利于在所述防隔热材料在烧蚀掉烧蚀复合材料后再将烧蚀复合材料再次复合进所述抗冲刷基体材料中,影响所述防隔热材料的可重复使用性能。
根据一些优选的实施方式,所述抗冲刷预制体还包含缝合线材料,所述抗冲刷预制体由所述缝合线材料将所述上纤维预制体层、所述中间纤维基体层和所述下纤维预制体层缝合而成,所述抗冲刷预制体优选为由所述缝合线材料一体化缝合而成,所述抗冲刷预制体的缝合针距和缝合方式可以根据实际情况自由选择,采用人工缝合即可完成,使得所述抗冲刷预制体具有易于制备的优点。
根据一些优选的实施方式,所述中间纤维基体层的容重为80~400kg/m3(例如80、100、120、150、180、200、220、250、280、300、320、350、380或400kg/m3),所述中间纤维基体层的厚度5~50mm(例如5、8、10、12、15、18、20、22、25、28、30、32、35、38、40、42、45、48或50mm);和/或所述上纤维预制体层和/或所述下纤维预制体层的厚度为0.5~10mm(例如0.5、1.5、2、2.5、3、3.5、4、4.5、5、5.5、6、6.5、7、7.5、8、8.5、9、9.5或10mm)。在本发明中,所述中间纤维基体层的容重指的是单位容积的所述中间纤维基体层含有的纤维基体的重量。在本发明中,优选为所述中间纤维基体层的容重为80~400kg/m3、所述中间纤维基体层的厚度5~50mm且所述上纤维预制体层和所述下纤维预制体层的厚度为0.5~10mm,本发明人发现,这一容重、这一厚度的中间纤维基体层以及这一厚度的上下纤维预制体层组成的所述抗冲刷预制体可以使得所述防隔热材料的超高温烧蚀隔热性能最优异、维形能力和承载能力最强以及可重复使用的效果最好。
根据一些优选的实施方式,所述中间纤维基体层的孔隙率为30~98%(例如30%、35%、40%、45%、50%、55%、60%、65%、70%、75%、80%、85%、90%、95%或98%);优选为所述中间纤维基体层的孔隙率为30%~80%(例如30%、35%、40%、45%、50%、55%、60%、65%、70%、75%或80%)。
根据一些优选的实施方式,所述上纤维预制体层、所述中间纤维基体层、所述下纤维预制体层和/或所述缝合线材料由耐高温纤维制得,所述耐高温纤维的直径为1~20μm(例如1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19或20μm),优选为3~15μm(例如3、4、5、6、7、8、9、10、11、12、13、14或15μm),和/或所述耐高温纤维的线密度为190~1200tex(例如190、200、250、300、350、400、450、500、550、600、650、700、750、800、850、900、950、1000、1050、1100、1150或1200tex),其中tex表示的是线密度的单位特克斯;所述上纤维预制体层和所述下纤维预制体层各自独立地选自石英纤维、氧化铝纤维、莫来石纤维、硅酸铝纤维、高硅氧纤维和碳化硅纤维中的一种或者多种耐高温纤维制得;所述中间纤维基体层选自氧化锆纤维、氧化铝纤维、石英纤维、高硅氧纤维和莫来石纤维中的一种或者多种耐高温纤维制得;和/或所述缝合线材料选自氧化铝纤维、莫来石纤维、氧化锆纤维和碳化硅纤维中的一种或者多种耐高温纤维制得。
根据一些优选的实施方式,所述耐高温纤维的耐温性不低于1000℃,优选为大于1200℃。
根据一些优选的实施方式,用于制得所述缝合线材料的耐高温纤维的直径为1~20μm,更优选为3~15μm,并且线密度为190~1200tex。
根据一些优选的实施方式,所述烧蚀复合材料由以质量百分比计为19.9~99.8%(例如19.9%、20%、25%、30%、35%、40%、45%、50%、55%、60%、65%、70%、75%、80%、85%、90%、95%、98%或99.8%)的烧蚀树脂、0.1~10%(例如0.1%、0.5%、1%、1.5%、2%、2.5%、3%、3.5%、4%、4.5%、5%、5.5%、6%、6.5%、7%、7.5%、8%、8.5%、9%、9.5%或10%)的凝胶固化剂和0.1~80%(例如0.1%、0.5%、1%、5%、10%、15%、20%、25%、30%、35%、40%、45%、50%、55%、60%、65%、70%、75%或80%)的烧蚀填料组成,在本发明中,优选为所述烧蚀复合材料的各组分含量在上述范围之内,如此可以使得所述烧蚀复合材料的烧蚀隔热性能最优化;所述烧蚀树脂选自由硼酚醛树脂、钡酚醛树脂和高残炭酚醛树脂组成的组;所述凝胶固化剂选自由六次甲基四胺、苯胺、三聚氰胺、对甲苯磺酸、对甲苯磺酰氯和石油磺酸组成的组;和/或所述烧蚀填料为有机硅树脂,所述有机硅树脂选自由甲基硅树脂、乙基硅树脂、甲基乙基硅树脂、甲基苯基硅树脂和低聚倍半硅氧烷组成的组。
根据一些优选的实施方式,所述陶瓷基体复合在所述上纤维预制体层和所述下纤维预制体层中,在本发明中,优选为所述陶瓷基体仅复合在所述上纤维预制体层和所述下纤维预制体层中,使得所述陶瓷基体在增强所述防隔热材料的力学强度的同时,不至于使得所述抗冲刷基体材料内的中间纤维基体层也过于致密化,从而影响了所述抗冲刷基体材料复合所述烧蚀复合材料的能力以及待所述烧蚀复合材料烧蚀掉后再次复合的能力;在本发明中,所述陶瓷基体复合在所述上纤维预制体层中形成了上纤维面板层,所述陶瓷基体复合在所述下纤维预制体层中形成了下纤维面板层;所述陶瓷基体选自由氧化硅、氧化铝、氧化锆、莫来石、碳化硅、B4C(碳化硼)、B4N和B2O3(三氧化二硼)组成的组;所述陶瓷基体与所述抗冲刷预制体的质量比为(30~80):100(例如30:100、35:100、40:100、45:100、50:100、55:100、60:100、65:100、70:100、75:100或80:100),优选为(30~60):100(例如30:100、35:100、40:100、45:100、50:100、55:100或60:100),在此质量比范围内的陶瓷基体,能够进一步保证所述防隔热材料的力学强度和承载能力,而不会使得所述抗冲刷基体材料过于致密化。
根据一些优选的实施方式,所述防隔热材料还包含复合在所述抗冲刷基体材料中的高温粘结剂;所述高温粘结剂选自由氧化硅、B4C(碳化硼)、B4N和B2O3(三氧化二硼)组成的组;所述高温粘结剂与所述抗冲刷预制体的质量比为(1~20):100(例如1:100、2:100、3:100、4:100、5:100、6:100、7:100、8:100、9:100、10:100、11:100、12:100、13:100、14:100、15:100、16:100、17:100、18:100、19:100或20:100),优选为(1~10):100(例如1:100、2:100、3:100、4:100、5:100、6:100、7:100、8:100、9:100或10:100)。在本发明中,所述高温粘结剂与所述抗冲刷预制体的质量比优选为(1~20):100,如此可以有效地增强所述防隔热材料的力学强度而不会对所述防隔热材料的其它性能带来不利的影响。
本发明在第二方面提供了本发明在第一方面所述的防隔热材料的制备方法,所述方法包括如下步骤:
(1)将上纤维预制体层、中间纤维基体层和下纤维预制体层结合(例如通过粘接、缝合或缠绕等方式进行结合),制得抗冲刷预制体;
(2)将步骤(1)制得的抗冲刷预制体与陶瓷基体复合,制得抗冲刷基体材料;例如可以将所述陶瓷基体配制成水溶胶(陶瓷基体前驱体)后与所述抗冲刷预制体浸渍复合,从而实现所述上下纤维预制体层的致密化,制得所述抗冲刷基体材料;所述上下纤维预制体层的致密程度例如也可以根据浸渍次数有效调节;在所述抗冲刷基体材料中,所述陶瓷基体与所述抗冲刷预制体的质量比例如也可以根据浸渍次数有效调节;
(3)用包含烧蚀树脂、凝胶固化剂、烧蚀填料和溶剂的烧蚀复合材料混合溶液浸渍(例如通过真空/打压浸渍的方式)步骤(2)制得的抗冲刷基体材料,然后将浸渍后的所述抗冲刷基体材料依次经过胶凝步骤和固化步骤,由此制得所述防隔热材料。本发明对所述溶剂没有特别的限制,只有能溶解所述烧蚀树脂、凝胶固化剂和烧蚀填料即可,优选地,所述溶剂选自由乙醇、甲苯和丙酮组成的组。
在本发明中,先将所述上纤维预制体层、中间纤维基体层和下纤维预制体层结合制得所述抗冲刷预制体后,再与所述陶瓷基体复合,并且优选为所述陶瓷基体与所述抗冲刷预制体的质量比为(30~80):100,更优选为(30~60):100,如此可以使得所述陶瓷基体仅与所述上纤维预制体层、所述下纤维预制体层复合,且使得所述上下纤维预制体层的致密化程度不至于过高,在提高所述抗冲刷预制体的力学强度和承载能力的同时,保证所述中间纤维基体层的结构以及所述抗冲刷预制体的孔隙率不受影响,从而能够有效保证制得的所述防隔热材料的可重复使用性能。
根据一些优选的实施方式,通过缝合线材料将上纤维预制体层、中间纤维基体层和下纤维预制体层一体化缝合,制得所述抗冲刷预制体。
根据一些优选的实施方式,所述方法还包括在进行步骤(1)之前,先通过疏水化试剂将中间纤维基体层进行疏水化处理(例如通过气相疏水方式)的步骤,所述疏水化试剂选自由甲基三甲氧基硅烷、三甲基甲氧基硅烷和三乙基乙氧基硅烷组成的组。在本发明中,优选为将所述中间纤维基体层进行疏水化处理后再与所述上纤维预制体层和所述下纤维预制体层结合,如此,可以使得在抗冲刷预制体与陶瓷基体复合的过程中,由于中间纤维基体层表面的疏水性可以有效避免陶瓷前驱体(水溶胶)进入所述中间纤维基体层中,使陶瓷基体仅复合在所述上纤维预制体层和所述下纤维预制体层中,从而能够有效避免本发明中所述防隔热材料密度的增大以及热导率的增大。
根据一些优选的实施方式,所述方法还包括在进行步骤(3)之前,先将所述抗冲刷基体材料于500~800℃(例如500℃、550℃、600℃、650℃、700℃、750℃或800℃)下进行高温处理0.5~2h,然后将高温处理后的所述抗冲刷基体材料与高温粘结剂复合的步骤;例如可以将所述高温粘结剂配制成水溶胶后与所述抗冲刷基体材料浸渍复合。在本发明中,将所述抗冲刷基体材料进行高温处理,可以有效地去除疏水化试剂,避免所述疏水化试剂对所述抗冲刷基体材料与所述高温粘结剂复合效果的影响,以及避免所述疏水化试剂对所述防隔热材料的综合性能的影响。
根据一些优选的实施方式,所述胶凝在密闭体系中进行,所述固化在敞开体系中进行,如此有利于生成多孔结构的轻质可重复使用的防隔热材料;和/或所述胶凝和/或所述固化的温度为60~150℃(例如60℃、65℃、70℃、75℃、80℃、85℃、90℃、95℃、100℃、105℃、110℃、115℃、120℃、125℃、130℃、135℃、140℃、145℃或150℃),所述胶凝和/或所述固化的时间为2~48h(例如2、4、6、8、10、12、15、20、24、30、36、40、45或48h)。
本发明方法具有工艺简单、制备工艺可控,易于工业化实施等优点;本发明方法中的凝胶固化工序有利于形成有机无机杂化的多孔隔热材料,更有利于发挥所述防隔热材料的长时烧蚀隔热特性。
下面结合实施例对本发明作进一步说明。这些实施例只是就本发明的优选实施方式进行举例说明,本发明的保护范围不应解释为仅限于这些实施例。
实施例1
①抗冲刷预制体的制备:选择莫来石纤维为中间纤维基体层,容重100kg/m3,厚度25mm,尺寸150×150mm,采用甲基三甲氧基硅烷为疏水化试剂,采用气相疏水方式对中间纤维基体层进行疏水化处理;选择氧化铝纤维编织2.5D的上纤维预制体层,氧化铝纤维直径10μm,编织厚度2mm,体积分数40%,石英纤维编织2.5D的下纤维预制体层,石英纤维直径8mm,编织厚度0.5mm,体积分数40%;将厚度为2mm的上纤维预制体层/中间纤维基体层/0.5mm的下纤维预制体层铺层叠加,进行一体化缝合,选择氧化铝纤维为缝合线材料,单根氧化铝纤维直径为8mm,线密度为800tex,缝合针距为10*10mm,制得抗冲刷预制体。
②抗冲刷基体材料的制备:选择质量百分含量为20%的氧化硅水溶胶为陶瓷基体前驱体,将缝合完成的抗冲刷预制体与陶瓷基体前驱体浸渍复合,从而实现了所述上下纤维预制体层的陶瓷化,获得抗冲刷基体材料;其中,陶瓷基体与所述抗冲刷预制体的质量比为50:100;最后,将制得的抗冲刷基体材料于600℃下高温处理30min,然后将高温处理后的所述抗冲刷基体材料与高温粘结剂复合,其中,高温粘结剂与抗冲刷预制体的质量比为10:100。
③烧蚀复合材料混合溶液的配制:取200g硼酚醛树脂加入到800g乙醇中,加入10g六次甲基四胺,用机械搅拌器搅拌溶解,配成20%的硼酚醛树脂乙醇溶液;待混合均匀后,加入80g有机硅树脂(甲基乙基硅树脂),搅拌均匀,得到烧蚀复合材料混合溶液待用。
④轻质可重复使用的防隔热材料的制备:用烧蚀复合材料混合溶液和复合有高温粘结剂的抗冲刷基体材料进行真空打压浸渍,然后置于80℃密闭烘箱进行胶凝24小时,然后于敞开体系中60℃下放置2h,100℃下放置2h,150℃下放置2h进行程序升温固化,制得轻质可重复使用的防隔热材料。
在本实施例中,测得抗冲刷基体材料形变10%时的压缩强度为2.2MPa,1000℃单面高温加热处理1000s之后,形变10%时的压缩强度为2.3MPa,其结果如表2所示,在表2中用基体材料表示本实施例中的抗冲刷基体材料;在本实施例中,测得制得的轻质可重复使用的防隔热材料的密度为0.58g/cm3,形变10%时的压缩强度为25.2MPa,1000℃单面高温加热处理1000s之后,形变10%时的压缩强度为12.2MPa,室温热导率为0.051W/m·K;在4.2MW/m2热流密度下,时间20s,测得线烧蚀为0.30mm,本实施例制得的轻质可重复使用的防隔热材料的性能指标如表2所示,其中,密度按照GB/T6343-2009方法测量;室温热导率根据GB/T10295-2008测量;压缩强度根据GB/T8489-2006进行测量,其中形变10%指的是材料的厚度发生了10%的形变。
如表2所示,本实施例制得的所述轻质可重复使用的防隔热材料在1000℃下高温处理1000s后,其压缩强度和拉伸强度仍较高,可重复使用;将本实施例中的烧蚀掉烧蚀复合材料的所述防隔热材料分别依次重复进行浸渍所述烧蚀复合材料然后再烧蚀(1000℃单面高温加热处理1000s)所述烧蚀复合材料的步骤1次、5次和10次(重复使用的次数)后,测得所述轻质可重复使用的防隔热材料的性能如表3所示。
实施例2~11与实施例1基本相同,其原料组成的不同之处如表1所示,实施例2~11制得的防隔热材料的性能指标如表2所示。
实施例12
实施例12与实施例1基本相同,不同之处在于:
在②中获得陶瓷基体与抗冲刷预制体的质量比为40:100的抗冲刷基体材料。
采用与实施例1相同的测试方法对本实施例制得的防隔热材料进行性能测试,性能测试结果如表2所示。
实施例13
实施例13与实施例1基本相同,不同之处在于:
在②中获得陶瓷基体与抗冲刷预制体的质量比为30:100的抗冲刷基体材料。
采用与实施例1相同的测试方法对本实施例制得的防隔热材料进行性能测试,性能测试结果如表2所示。
实施例14
实施例14与实施例1基本相同,不同之处在于:
在②中获得陶瓷基体与抗冲刷预制体的质量比为10:100的抗冲刷基体材料。
采用与实施例1相同的测试方法对本实施例制得的防隔热材料进行性能测试,性能测试结果如表2所示。
实施例15
实施例15与实施例1基本相同,不同之处在于:
在①中,未对所述中间纤维基体层进行疏水化处理。
采用与实施例1相同的测试方法对本实施例制得的防隔热材料进行性能测试,性能测试结果如表2。
实施例16
实施例16与实施例1基本相同,不同之处在于:
在②中,未对制得的抗冲刷基体材料进行高温处理,也未将抗冲刷基体材料与高温粘结剂复合。
采用与实施例1相同的测试方法对本实施例制得的防隔热材料进行性能测试,性能测试结果如表2所示。
对比例1
①采用3~5μm石英纤维、硼硅粘结剂和二氧化钛抗辐射剂,按100:3:10的质量比共混,制得刚性纤维基体,密度为0.2g/cm3。
②将尺寸为100mm×100mm×20mm的由步骤①制得的刚性纤维基体置于容器中,抽真空,排除材料孔隙里的气体,然后真空浸渍复合20%二氧化硅气凝胶前驱体水溶液,获得密度为0.40g/cm3的刚性隔热材料。
③取200g钡酚醛树脂加入到800g乙醇中,加入10g六次甲基四胺,用机械搅拌器搅拌溶解,配成20%的钡酚醛树脂乙醇溶液(烧蚀树脂材料乙醇溶液)。
④打开容器真空阀门,将配制好的酚醛树脂溶液在内外压强差作用下,自动注入到工装中,完全浸渍刚性隔热材料。
⑤将充分浸渍酚醛树脂的刚性隔热材料快速取出,置于烘箱内,固化,得到微烧蚀隔热复合材料。
采用与实施例1相同的测试方法对本对比例制得的微烧蚀隔热复合材料进行性能测试,性能测试结果如表表2所示,在表2中用基体材料表示本对比例中的刚性隔热材料。
将本对比例中的微烧蚀隔热复合材料进行烧蚀掉烧蚀树脂材料后,再用钡酚醛树脂乙醇溶液浸渍所述微烧蚀隔热复合材料,并测试其形变10%时的压缩强度以及拉伸强度,然后将该材料于1000℃单面高温加热处理1000s后测试压缩强度和拉伸强度,其结果如表3所示;从表3的结果可知,重复浸渍所述钡酚醛树脂乙醇溶液后的所述微烧蚀隔热复合材料的拉伸强度和压缩强度比较低,相比之前烧蚀掉烧蚀树脂材料的微烧蚀隔热复合材料力学强度增加很小,再次烧蚀后,未测得相应的数据,本对比例制得的微烧蚀隔热复合材料无法重复使用。
对比例2
①将厚度比为1:15的耐高温陶瓷面板与隔热气凝胶芯层通过缝合的方式结合在一起,得到预制体;用浓度为16wt%的二氧化硅溶胶前驱体浸渍复合所得到的预制体,得到耐高温夹层结构材料;其中,所述隔热气凝胶芯层由莫来石纤维与浓度为20wt%二氧化硅溶胶通过浸渍的方式复合制得,所述隔热气凝胶芯层中的耐高温纤维的含量为80wt%。
②烧蚀复合材料混合溶液的配制:取200g钡酚醛树脂加入到800g乙醇中,加入10g六次甲基四胺,用机械搅拌器搅拌溶解,配成20%的钡酚醛树脂乙醇溶液;待混合均匀后,加入80g有机硅树脂,搅拌均匀,得到烧蚀复合材料混合溶液待用。
③防隔热材料的制备:用烧蚀复合材料混合溶液和耐高温夹层结构材料进行真空打压浸渍,然后置于80℃密闭烘箱进行胶凝24小时,然后于60℃下放置2h,100℃下放置2h,150℃下放置2h进行程序升温固化,制得防隔热材料。
采用与实施例1相同的测试方法对本对比例制得的防隔热材料进行性能测试,性能测试结果如表2所示,在表2中用基体材料表示本对比例中的耐高温夹层结构材料。
将本对比例中的防隔热材料进行烧蚀掉烧蚀树脂复合材料后,再用烧蚀复合材料混合溶液浸渍所述防隔热材料,并测试其形变10%时的压缩强度以及拉伸强度,然后将该材料于1000℃单面高温加热处理1000s后测试压缩强度和拉伸强度,其结果如表3所示;从表3的结果可知,重复浸渍所述烧蚀复合材料混合溶液后的所述防隔热材料的拉伸强度和压缩强度比较低,本对比例制得的所述防隔热材料重复使用次数明显减少。
表3:实施例1、实施例7以及对比例1~2中的材料重复使用后的性能指标。
表3中的符号“-”表示未测得相应的数据。
从表2和表3的结果可知,本发明中的轻质可重复使用的防隔热材料具备长时烧蚀隔热性能优异、维形能力强和可重复多次使用的优点。
最后说明的是:以上实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述实施例对本发明进行了详细说明,本领域普通技术人员应当理解:其依然可以对各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改或者替换,并不使技术方案的本质脱离本发明各实施例技术方案的精神和范围。
Claims (6)
1.一种轻质可重复使用的防隔热材料的制备方法,其特征在于,所述轻质可重复使用的防隔热材料包含抗冲刷基体材料和与所述抗冲刷基体材料复合在一起的烧蚀复合材料;所述抗冲刷基体材料包含抗冲刷预制体和与所述抗冲刷预制体复合在一起的陶瓷基体,所述抗冲刷预制体包含结合在一起的上纤维预制体层、中间纤维基体层和下纤维预制体层;所述烧蚀复合材料包含烧蚀树脂、凝胶固化剂和烧蚀填料;
所述方法包括如下步骤:
(1)将上纤维预制体层、中间纤维基体层和下纤维预制体层结合,制得抗冲刷预制体;所述方法还包括在进行步骤(1)之前,先通过疏水化试剂将中间纤维基体层进行疏水化处理的步骤,所述疏水化试剂选自由甲基三甲氧基硅烷、三甲基甲氧基硅烷和三乙基乙氧基硅烷组成的组;
(2)将步骤(1)制得的抗冲刷预制体与陶瓷基体复合,制得抗冲刷基体材料;所述陶瓷基体复合在所述上纤维预制体层和所述下纤维预制体层中;所述陶瓷基体选自由氧化硅、氧化铝、氧化锆、莫来石、碳化硅、B4C和B2O3组成的组;所述陶瓷基体与所述抗冲刷预制体的质量比为(30~60):100;
(3)用包含烧蚀树脂、凝胶固化剂、烧蚀填料和溶剂的烧蚀复合材料混合溶液浸渍步骤(2)制得的抗冲刷基体材料,然后将浸渍后的所述抗冲刷基体材料依次经过胶凝步骤和固化步骤,由此制得所述防隔热材料;所述胶凝在密闭体系中进行,所述胶凝的温度为60~150℃,所述胶凝的时间为2~48h;所述固化在敞开体系中进行,所述固化为:在敞开体系中60℃下放置2h,100℃下放置2h,150℃下放置2h;所述方法还包括在进行步骤(3)之前,先将所述抗冲刷基体材料于500~800℃下进行高温处理0.5~2h,然后将高温处理后的所述抗冲刷基体材料与高温粘结剂复合的步骤;所述高温粘结剂选自由氧化硅、B4C和B2O3组成的组;所述高温粘结剂与所述抗冲刷预制体的质量比为(1~20):100。
2.根据权利要求1所述的制备方法,其特征在于:
所述烧蚀复合材料与所述抗冲刷基体材料的质量比为(0.1~100):100;
所述抗冲刷基体材料的密度为0.3~1.2g/cm3。
3.根据权利要求1所述的制备方法,其特征在于:
所述抗冲刷预制体还包含缝合线材料,所述抗冲刷预制体由所述缝合线材料将所述上纤维预制体层、所述中间纤维基体层和所述下纤维预制体层缝合而成;
所述中间纤维基体层的容重为80~400kg/m3,所述中间纤维基体层的厚度5~50mm;
所述上纤维预制体层和所述下纤维预制体层的厚度为0.5~10mm。
4.根据权利要求3所述的制备方法,其特征在于:
所述上纤维预制体层、所述中间纤维基体层、所述下纤维预制体层和所述缝合线材料由耐高温纤维制得,所述耐高温纤维的直径为1~20μm,所述耐高温纤维的线密度为190~1200tex;
所述上纤维预制体层和所述下纤维预制体层各自独立地由石英纤维、氧化铝纤维、莫来石纤维、硅酸铝纤维、高硅氧纤维和碳化硅纤维中的一种或者多种耐高温纤维制得;
所述中间纤维基体层由氧化锆纤维、氧化铝纤维、石英纤维、高硅氧纤维和莫来石纤维中的一种或者多种耐高温纤维制得;
所述缝合线材料由氧化铝纤维、莫来石纤维、氧化锆纤维和碳化硅纤维中的一种或者多种耐高温纤维制得。
5.根据权利要求1所述的制备方法,其特征在于:
所述烧蚀复合材料由以质量百分比计为19.9~99.8%的烧蚀树脂、0.1~10%的凝胶固化剂和0.1~80%的烧蚀填料组成;
所述烧蚀树脂选自由硼酚醛树脂、钡酚醛树脂和高残炭酚醛树脂组成的组;
所述凝胶固化剂选自由六次甲基四胺、苯胺、三聚氰胺、对甲苯磺酸、对甲苯磺酰氯和石油磺酸组成的组;
所述烧蚀填料为有机硅树脂,所述有机硅树脂选自由甲基硅树脂、乙基硅树脂、甲基乙基硅树脂、甲基苯基硅树脂和低聚倍半硅氧烷组成的组。
6.根据权利要求1所述的制备方法,其特征在于:
所述高温粘结剂与所述抗冲刷预制体的质量比为(1~10):100。
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