CN111187076B - 一种超高温胶粘剂及其制备方法 - Google Patents

一种超高温胶粘剂及其制备方法 Download PDF

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CN111187076B
CN111187076B CN202010067896.0A CN202010067896A CN111187076B CN 111187076 B CN111187076 B CN 111187076B CN 202010067896 A CN202010067896 A CN 202010067896A CN 111187076 B CN111187076 B CN 111187076B
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史萌
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Abstract

本发明公开了一种超高温胶粘剂及其制备方法。关键是胶粘剂的组分构成按重量百分比计是：40～60％的液态酚醛树脂、20～40％的炭毡粉、5～20％的炭黑粉、10～25％的硅粉、5～15％的铝粉、0.1～0.5％的偶联剂、0.1～0.6％的正乙烷和10～20％的短炭纤维丝。本发明具有极佳的融合性，使大型炭/炭复合材料构件的热内应力极小，连接强度高，同时高温处理后形成的胶粘剂层自身也具有极佳的力学性能。

Description

一种超高温胶粘剂及其制备方法
技术领域：
本发明涉及一种胶粘剂，特别是指一种用于粘接炭/炭复合材料的耐超高温的胶粘剂。
背景技术：
C/C复合材料是当代最先进的高温结构/功能复合材料，具有比重轻，耐热，高强，抗烧蚀等优异的高温力学性能和热物理性能，在宇航领域获得广泛应用。但仅局限于中高温、形状简单的小型构件。然而随着航空航天技术的快速发展，迫切需要超高温(＞2200℃)，形状复杂，大型的C/C构件。例如，未来新型战略导弹要求C/C构件满足超高温(＞2200℃)使用条件。同时，空间技术的发展需要大型，超稳定的C/C构件，以满足太空长期热交变环境使用的要求。随着工程技术的发展，冶金、机械、化工等民用领域对C/C复合材料也有迫切的需求。现有的C/C复合材料生产工艺无法满足宇航领域和现代工业对超高温大型复杂C/C构件的需求。因此，解决超高温大型复杂C/C构件的制备方法，成为满足航空航天和现代工业对C/C复合材料迫切需求的重要课题。
发明内容：
本发明的发明目的是公开一种制备大型复杂结构的炭/炭构件使用的超高温胶粘剂及其制备方法，其将至少两件以上的炭/炭复合材料的预制体粘接为一个大尺寸、复杂异型结构预制体，经高温处理得到大尺寸、复杂结构的炭/炭复合材料构件。
实现本发明的技术解决方案是：超高温胶粘剂的组分构成按重量百分比计是：
Figure BSA0000201081110000021
所述的超高温胶粘剂的组分构成按重量百分比计是：
Figure BSA0000201081110000022
所述的炭毡粉的粒度为50～100目，炭黑粉的粒度为500目，硅粉的粒度为350目，铝粉的粒度为1600目，短炭纤维丝的长度为3～10mm。
所述的超高温胶粘剂的制备方法是：将炭毡粉、炭黑粉、硅粉、铝粉、偶联剂、正乙烷和短炭纤维丝依次加入液态酚醛树脂，每加入一种组分搅拌均匀后，再加入下一种组分，最后加入短炭纤维丝，再搅拌10～25分钟后，置入球磨机中碾磨20～40分钟，置入密闭容器中，静置12～24小时得所述的胶粘剂。
本发明的公开的超高温胶粘剂与炭/炭复合材料预制体具有极佳的融合性，且在高温处理后的胶粘层炭/炭复合材料构件之间有一相互渗入结构层，并且两者的密度基本相当，使大型炭/炭复合材料构件的热内应力极小，连接强度高，同时高温处理后形成的胶粘剂层自身也具有极佳的力学性能，特别是胶粘剂在经受超过2500℃高温的处理。
具体实施方式：
下面详细给出本发明的具体实施方式，需要说明的是本发明的具体实施方式的描述是为便于对本发明的技术内容的全面理解，而不应视为是对本发明的权利要求保护范围的限制。
实现本发明的超高温胶粘剂的具体实施例的技术解决方案是：所述的胶粘剂的组分构成按重量百分比计是：40～60％的液态酚醛树脂、20～40％的炭毡粉、5～20％的炭黑粉、10～25％的硅粉、5～15％的铝粉、0.1～0.5％的偶联剂、0.1～0.6％的正乙烷和10～20％的短炭纤维丝。前述的炭/炭复合材料预制体为一种已固化的炭/炭复合材料，但还未经高温处理，上述的胶粘剂使用时置于两件炭/炭复合材料预制体的接触部分之间，并使两件炭/炭复合材料预制体粘接构成一个更大尺寸的预制体，或使三件或更多件所述的预制体构成一个大尺寸并具有复杂结构的预制体，由于上述的预制体为炭/炭复合材料，为使胶粘剂与预制体能够相互融合，并且在后续的高温烧制过程能够反应结合，经过反复多次的调节胶粘剂的组分构成和配比、大量的试验与成品检测得出上述的胶粘剂的组分与配比。为达到上述的融合与结合，胶粘剂中含有多种不同类型的炭材料，正是由于多种不同类型的炭材料即与胶粘剂中的短炭纤维丝形成结合，又与预制体中的炭材料结合，同时胶粘剂粘接预制体后，胶粘剂还渗透入预制体表面的内部，并且不同的炭材料还与硅粉和铝粉反应，生成碳化硅和复杂结构的金属陶瓷；上述的胶粘剂在高温处理后与预制体烧结为一体，烧结后的胶粘剂层由于上述的特定配方与配比使之具有与烧结后的预制体的密度和膨胀系数接近，这样大型复杂结构的炭/炭复合材料构件在高温状态下使用时，不会产生因膨胀系数的差异而导致的热应力和构件内产生微小裂纹。
为进一步提高所述的胶粘剂与炭/炭复合材料构件的结合性能，所述的胶粘剂的组分构成按重量百分比计是：45～55％的液态酚醛树脂、20～32％的炭毡粉、5～15％的炭黑粉、6～15％的硅粉、8～12％的铝粉、0.3～0.4％的偶联剂、0.3～0.4％的正乙烷和12～16％的短炭纤维丝。上述的胶粘剂的配比的优化使胶粘剂具有更好的渗透预制体的性能、更佳的结合能力，并且进一步提高了自身的力学性能，经过测试，前述的胶粘剂在高温处理后，其力学性能可达到层间剪切强度≥12MPa，弹性模量≥20GPa，压缩强度≥150MPa，拉伸强度≥60Mpa。
为更进一步提高前述的胶粘剂的性能，所述的胶粘剂中的炭毡粉的粒度优选为50～100目，炭黑粉的粒度为500目，硅粉的粒度为350目，铝粉的粒度为1600目，短炭纤维丝的长度为3～10mm；上述的胶粘剂中的组分粒度的优化是建立在大量的试验与检测基础得出的，上述的各组分粒度的配合使混合后的胶粘剂具有较佳的密度，也就是说各组分粒子之间相互嵌合，达到较佳的空间主体的相互嵌入，使胶粘剂达到尽可能高的密度，同时胶粘剂的各组分粒子达到空间主体的尽可能高的相互配合对高温烧结时的反应速度和结晶也有益处。
前面已介绍了本发明的胶粘剂的组成，上述的胶粘剂制备方法是：将炭毡粉、炭黑粉、硅粉、铝粉、偶联剂、正乙烷和短炭纤维丝依次加入液态酚醛树脂中，每加入一种组分搅拌均匀后，再加入下一种组分，最后加入短炭纤维丝，再搅拌10～25分钟后，置入球磨机碾磨20～40分钟，置入密闭容器中，静置12～24小时得所述的胶粘剂。通过上述的依次添加组分、反复多次的搅拌和最后的球磨过程，使胶粘剂的各组分得到充分的混合，达到各组分的粒子的最佳空间的相互嵌入，使胶粘剂各组分粒子之间空间间隙最小，使胶粘剂达到尽可能的致密性。
前述的胶粘剂将多件炭/炭复合材料预制体粘接为一个更大尺寸、并且复杂结构的大预制体后，置入高温炉，经高温处理得到炭/炭复合材料的构件。
需要说明的是上述的胶粘剂的各组分均为市场采购，液态的酚醛树脂的商品名为PF-51，偶联剂的商品名为KH-792，正乙烷为工业纯，炭黑粉为工业纯。

Claims (4)

1.一种超高温胶粘剂，其特征在于胶粘剂的组分构成按重量百分比计是：
Figure FSB0000196509810000011
以上组分的重量百分比之和为百分之一百。
2.按权利要求1所述的超高温胶粘剂，其特征在于所述的胶粘剂的组分构成按重量百分比计是：
Figure FSB0000196509810000012
以上组分的重量百分比之和为百分之一百。
3.按权利要求1或2所述的超高温胶粘剂，其特征在于所述的炭毡粉的粒度为50～100目，炭黑粉的粒度为500目，硅粉的粒度为350目，铝粉的粒度为1600目，短炭纤维丝的长度为3～10mm。
4.按权利要求1或2或3所述的超高温胶粘剂的制备方法，其特征在于所述的胶粘剂的制备方法是：将炭毡粉、炭黑粉、硅粉、铝粉、偶联剂、正乙烷和短炭纤维丝依次加入液态酚醛树脂，每加入一个组分搅拌均匀后，再加入下一个组分，最后加入短炭纤维丝，再搅拌10～25分钟后，置入球磨机中碾磨20～40分钟，置入密闭容器中，静置12～24小时得所述的胶粘剂。
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