CN111747753B - 一种碳纤维增强SiHfOC复合材料及其制备方法 - Google Patents

一种碳纤维增强SiHfOC复合材料及其制备方法 Download PDF

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CN111747753B
CN111747753B CN202010661429.0A CN202010661429A CN111747753B CN 111747753 B CN111747753 B CN 111747753B CN 202010661429 A CN202010661429 A CN 202010661429A CN 111747753 B CN111747753 B CN 111747753B
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郭蕾
马青松
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National University of Defense Technology
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Abstract

本发明公开了一种碳纤维增强SiHfOC复合材料及其制备方法，以碳纤维预制件为增强体，以含Hf的聚硅氧烷做先驱体，利用先驱体浸渍裂解法(PIP)通过反复浸渍‑固化‑裂解获得C/SiHfOC复合材料，该过程中采用的含Hf的聚硅氧烷先驱体是由无机铪盐与硅树脂通过溶胶‑凝胶过程获得，引入的Hf质量占硅树脂质量比的5‑25％。本发明解决了SiOC基体耐高温性能有限的问题，利用引入异质元素Hf对SiOC基体进行结构改性，工艺流程简单，对设备要求低，引入Hf后的C/SiHfOC复合材料具有较好的热稳定性。

Description

一种碳纤维增强SiHfOC复合材料及其制备方法
技术领域
本发明属于耐高温陶瓷基复合材料技术领域，具体涉及一种碳纤维增强SiHfOC复合材料及其制备方法。
背景技术
热防护技术是航天航空飞行器、载人飞船等重大战略需求的关键技术之一，轻量化、强韧化、耐高温、抗烧蚀是热防护系统研究的焦点。连续纤维增强陶瓷基复合材料(CFRCMC)因高比强度和比模量、高损伤容限、耐腐蚀、耐磨损等特点，成为飞行器推进系统和热防护系统热端部件高温结构材料的主流发展方向。
聚硅氧烷(Polysiloxane，PSO)衍生SiOC陶瓷是一种高性价比的轻质高温结构材料，以其为基体的碳纤维增强复合材料受到广泛关注和深入研究。目前，由于SiOC基体与C纤维在耐温能力上存在不匹配，C/SiOC复合材料在低压条件下只能在1250℃长寿命服役。
对SiOC陶瓷基体进行结构改性可提升其耐高温性能，主要有添加填料和引入异质元素两种途径：(1)添加填料是一类宏观调控结构的方法，存在分散不均匀的问题，对纤维增强陶瓷基复合材料的适用性不强；(2)引入异质元素，可以对原料聚硅氧烷(PSO)分子进行分子级甚至原子级水平的精细调控，实现SiOC陶瓷结构的改性，进而抑制碳热还原反应，达到提高SiOC陶瓷热稳定性的目的。
发明内容
针对现有技术的不足，本发明的目的在于提供一种碳纤维增强SiHfOC复合材料及其制备方法，即一种C/SiHfOC复合材料及其制备方法，是一种工艺方法简单、操作方便、成本较低，明显提升C/SiOC复合材料耐高温性能的C/SiHfOC复合材料的制备方法，在SiOC陶瓷基体中引入Hf元素可形成HfO2，在高温下可首先与SiOC分相产生的SiO2反应生成HfSiO4，从而阻碍SiO2的碳热还原反应，提高SiOC陶瓷基体的热稳定性，进而提升C/SiOC复合材料的耐高温性能
本发明所述的一种碳纤维增强SiHfOC复合材料的制备方法，包括以下步骤：
1)浸渍：准备碳纤维预制件并置于压力小于500Pa的真空条件下，用含Hf的聚硅氧烷先驱体溶液浸渍；所述的含Hf的聚硅氧烷先驱体溶液为铪溶胶与硅树脂乙醇溶液的混合溶胶，含Hf的聚硅氧烷中引入的Hf占硅树脂质量的5-25％，铪溶胶由HfOCl2·8H2O溶于乙醇并加入螯合剂后制得，HfOCl2·8H2O与乙醇的质量比为(1-4):4，螯合剂与HfOCl2·8H2O的物质的量比为(1-4):1，硅树脂乙醇溶液的质量浓度为20-60％；所述的螯合剂选自乙酰丙酮，所述的硅树脂选自小分子量的甲基硅树脂(MK)；
2)固化：将上步骤浸渍后的碳纤维预制件静置后形成凝胶，再将凝胶后的预制件在150-250℃交联固化；
3)裂解：将上步骤交联固化后的碳纤维预制件在惰性气氛下进行高温裂解，高温裂解温度为1000-1200℃，裂解时间为30-120min；
重复以上浸渍-固化-裂解周期10-16次，直至本周期结束时样品重量较上周期结束时样品重量增重不超过1％，完成制备，得到碳纤维增强SiHfOC复合材料。
本发明步骤1)所述的碳纤维预制件为2.5维编织物、平纹布叠层缝合预制件、三维针刺毡、三维四向编织物、三维五向编织物或三维六向编织物中的一种。
步骤1)所述的用含Hf的聚硅氧烷先驱体溶液浸渍，浸渍时间是1-5h。
步骤1)所述的小分子量的甲基硅树脂(MK)，MK是一种溶解在甲苯中的甲基硅树脂，该树脂有很高的SiO2含量，完全氧化后含有80％SiO2，按照固体树脂含量计算。
步骤2)所述的固化，是指：将上步骤浸渍后的碳纤维预制件静置8-20h后形成凝胶，再将凝胶后的预制件在150-250℃交联固化4-8h。
本发明还涉及采用上述一种碳纤维增强SiHfOC复合材料的制备方法得到的碳纤维增强SiHfOC复合材料，在制备工艺相同的情况下，本发明制备方法得到的C/SiHfOC复合材料能将C/SiOC复合材料在低压条件中的耐热温度提高100-200℃。因此，本发明制备得到的C/SiHfOC复合材料具有更好的耐高温性能。
与现有技术相比，本发明具有以下优点：
1、本发明采用硅树脂与无机铪盐为原料通过溶胶-凝胶技术合成含Hf的聚硅氧烷先驱体制备C/SiHfOC复合材料，将Hf元素引入SiOC陶瓷基体，在高温处理时形成HfO2和HfSiO4相可提高耐高温性能，此外，利用无机铪盐作为Hf源不仅能提高Hf元素的引入量，还能降低成本。
2、本发明引入Hf元素可形成HfO2，在高温下可首先与SiOC分相产生的SiO2反应生成HfSiO4，从而阻碍SiO2的碳热还原反应，提高SiOC陶瓷基体的热稳定性，进而提升C/SiOC复合材料的耐高温性能。
3、本发明工作方法简单，操作方便，成本低廉，制备的C/SiHfOC复合材料可将C/SiOC复合材料在低压条件下的服役温度提高100-200℃。
附图说明
图1是本发明实施例1制备得到的C/SiOC复合材料经不同温度真空高温热处理测试力学性能的载荷-位移曲线的图。
图2是本发明实施例1制备得到的碳纤维增强SiHfOC(C/SiHOC)复合材料经不同温度真空高温热处理测试力学性能的载荷-位移曲线的图。
具体实施方式
以下通过实施例进一步详细描述本发明，但这些实施例不应认为是对本发明的限制。
实施例1：
一种碳纤维增强SiHfOC复合材料的制备方法，包括以下步骤：
(1)浸渍：准备平纹布叠层缝合预制件并置于压力小于500Pa的真空条件下，用Hf的质量浓度10％的含Hf聚硅氧烷先驱体溶液浸渍1h；
所述的含Hf的聚硅氧烷先驱体溶液为铪溶胶与硅树脂乙醇溶液的混合溶胶，铪溶胶由HfOCl2·8H2O溶于乙醇并加入螯合剂后制得，HfOCl2·8H2O与乙醇的质量比为1:4，螯合剂是乙酰丙酮，螯合剂与HfOCl2·8H2O的物质的量比为1:1，硅树脂乙醇溶液的质量浓度为20％；所述的硅树脂是小分子量的甲基硅树脂(MK)；
(2)固化：将浸渍后的碳纤维预制件静置16h至凝胶，再将凝胶后的预制件在180℃交联固化8h；
(3)裂解：将交联固化后的碳纤维预制件在惰性气氛下进行高温裂解，高温裂解温度为1200℃，裂解时间为60min；
重复上述的浸渍-固化-裂解周期11次后，得到的样品较第10周期结束时的样品的增重只有0.81％，完成制备，得到C/SiHfOC复合材料。
对上述制得的C/SiHfOC复合材料与相同工艺制备的C/SiOC复合材料在低压条件下进行热处理并对比性能，结果表1所示，载荷-位移曲线图如图1(C/SiOC)，图2(C/SiHfOC)所示。
实施例2：
一种碳纤维增强SiHfOC复合材料的制备方法，包括以下步骤：
(1)浸渍：准备三维五向编织物并置于压力小于500Pa的真空条件下，用Hf的质量浓度25％的含Hf聚硅氧烷先驱体溶液浸渍2h；
所述的含Hf的聚硅氧烷先驱体溶液为铪溶胶与硅树脂乙醇溶液的混合溶胶，其中铪溶胶由HfOCl2·8H2O溶于乙醇并加入螯合剂后制得，HfOCl2·8H2O与乙醇的质量比为1:2，螯合剂是乙酰丙酮，螯合剂与HfOCl2·8H2O的物质的量比为2:1，硅树脂乙醇溶液的质量浓度为30％；所述的硅树脂是小分子量的甲基硅树脂(MK)；
(2)固化：将浸渍后的碳纤维预静置8h至凝胶，再将凝胶后的预制件在200℃交联固化5h；
(3)裂解：将交联固化后的碳纤维预制件在惰性气氛下进行高温裂解，高温裂解温度为1000℃，裂解时间为90min；
重复上述的浸渍-固化-裂解周期16次后，得到的样品较第15周期结束时的样品的增重只有0.92％，完成制备，得到C/SiHfOC复合材料。
对上述制得的C/SiHfOC复合材料与相同工艺制备的C/SiOC复合材料在低压条件下进行热处理并对比性能，结果如表2所示。
实施例3：
一种碳纤维增强SiHfOC复合材料的制备方法，包括以下步骤：
(1)浸渍：准备2.5维编织物并置于压力小于500Pa的真空条件下，用Hf的质量浓度15％的含Hf聚硅氧烷先驱体溶液浸渍5h；
所述的含Hf的聚硅氧烷先驱体溶液为铪溶胶与硅树脂乙醇溶液的混合溶胶，铪溶胶由HfOCl2·8H2O溶于乙醇并加入螯合剂后制得，HfOCl2·8H2O与乙醇的质量比为3:4，螯合剂是乙酰丙酮，螯合剂与HfOCl2·8H2O的物质的量比为3:1，硅树脂乙醇溶液的质量浓度为45％；所述的硅树脂是小分子量的甲基硅树脂(MK)；
(2)固化：将浸渍后的碳纤维预制件静置12h至凝胶，再将凝胶后的预制件在250℃交联固化4h；
(3)裂解：将交联固化后的碳纤维预制件在惰性气氛下进行高温裂解，高温裂解温度为1000℃，裂解时间为30min；
重复上述的浸渍-固化-裂解周期12次后，得到的样品较第11周期结束时的样品的增重只有0.87％，完成制备，得到C/SiHfOC复合材料。
对上述制得的C/SiHfOC复合材料与相同工艺制备的C/SiOC复合材料在低压条件下进行热处理并对比性能，结果如表3所示。
实施例4：
一种碳纤维增强SiHfOC复合材料的制备方法，包括以下步骤：
(1)浸渍：准备三维针刺毡并置于压力小于500Pa的真空条件下，用Hf的质量浓度5％的含Hf聚硅氧烷先驱体溶液浸渍3h；
所述的含Hf的聚硅氧烷先驱体溶液为铪溶胶与硅树脂乙醇溶液的混合溶胶，铪溶胶由HfOCl2·8H2O溶于乙醇并加入螯合剂后制得，HfOCl2·8H2O与乙醇的质量比为1:1，螯合剂是乙酰丙酮，螯合剂与HfOCl2·8H2O的物质的量比为4:1，硅树脂乙醇溶液的质量浓度为60％；所述的硅树脂是小分子量的甲基硅树脂(MK)；
(2)固化：将浸渍后的碳纤维预制件静置20h至凝胶，再将凝胶后的预制件在150℃交联固化6h；
(3)裂解：将交联固化后的碳纤维预制件在惰性气氛下进行高温裂解，高温裂解温度为1100℃，裂解时间为120min；
重复上述的浸渍-固化-裂解周期10次后，得到的样品较第9周期结束时的样品的增重只有0.91％，完成制备，得到C/SiHfOC复合材料。
对上述制得的C/SiHfOC复合材料与相同工艺制备的C/SiOC复合材料在低压条件下进行热处理并对比性能，结果如表4所示。
对比例：实施例1相比，没有添加螯合剂，其他同实施例1；
(1)浸渍：准备平纹布叠层缝合预制件并置于压力小于500Pa的真空条件下，用Hf的质量浓度10％的含Hf聚硅氧烷先驱体溶液浸渍1h；
所述的含Hf的聚硅氧烷先驱体溶液为铪溶胶与硅树脂乙醇溶液的混合溶胶，铪溶胶由HfOCl2·8H2O溶于乙醇制得，HfOCl2·8H2O与乙醇的质量比为1:4，所述的硅树脂乙醇溶液的质量浓度为20％，硅树脂是小分子量的甲基硅树脂(MK)；
(2)固化：将浸渍后的碳纤维预制件静置22h至凝胶，再将凝胶后的预制件在180℃交联固化8h；
(3)裂解：将交联固化后的碳纤维预制件在惰性气氛下进行高温裂解，高温裂解温度为1200℃，裂解时间为60min；
重复上述的浸渍-固化-裂解周期13次后，得到的样品较第12周期结束时的样品的增重只有0.89％，完成制备，得到C/SiHfOC复合材料。
对上述制得的C/SiHfOC复合材料与相同工艺制备的C/SiOC复合材料在低压条件下进行热处理并对比性能，结果如表5所示。
实验结果：
表1：
Figure BDA0002578723200000051
表2：
Figure BDA0002578723200000052
表3：
Figure BDA0002578723200000061
表4：
Figure BDA0002578723200000062
表5：
Figure BDA0002578723200000063
结果分析：
1、实施例1-4表明本发明引入Hf元素可形成HfO2，在高温下可首先与SiOC分相产生的SiO2反应生成HfSiO4，从而阻碍SiO2的碳热还原反应，提高SiOC陶瓷基体的热稳定性，进而提升C/SiOC复合材料的耐高温性能。
2、对比例表明，在缺少螯合剂的情况下，得到的C/SiOC复合材料和添加了螯合剂的实施例1得到的C/SiOC复合材料相比其耐高温性能存在明显差距。
以上仅是本发明的优选实施方式，本发明的保护范围并不局限于上述实施例，与本发明构思无实质性差异的各种工艺方案均在本发明的保护范围内。

Claims (2)

1.一种碳纤维增强SiHfOC复合材料的制备方法，其特征在于：包括以下步骤：
1）浸渍：准备碳纤维预制件并置于压力小于500Pa的真空条件下，用含Hf的聚硅氧烷先驱体溶液浸渍1-5h；
所述的含Hf的聚硅氧烷先驱体溶液为铪溶胶与硅树脂乙醇溶液的混合溶胶，含Hf的聚硅氧烷中引入的Hf占硅树脂质量的5-25%，铪溶胶由HfOCl2•8H2O溶于乙醇并加入螯合剂后制得，HfOCl2•8H2O与乙醇的质量比为1-4:4，螯合剂与HfOCl2•8H2O的物质的量比为1-4:1；
所述的碳纤维预制件为2.5维编织物、平纹布叠层缝合预制件、三维针刺毡、三维四向编织物、三维五向编织物或三维六向编织物中的一种；
所述的螯合剂是乙酰丙酮；
所述的硅树脂乙醇溶液的质量浓度为20-60%，所述的硅树脂是甲基硅树脂；
2）固化：将上步骤浸渍后的碳纤维预制件静置8-20h后形成凝胶，再将凝胶后的预制件在150-250℃交联固化4-8h；
3）裂解：将上步骤交联固化后的碳纤维预制件在惰性气氛下进行高温裂解，高温裂解温度为1000-1200℃，裂解时间为30-120min；
重复以上浸渍-固化-裂解周期10-16次，直至本周期结束时样品重量较上周期结束时样品重量增重不超过1%，完成制备，得到碳纤维增强SiHfOC复合材料。
2.一种碳纤维增强SiHfOC复合材料，其特征在于：采用权利要求1所述的一种碳纤维增强SiHfOC复合材料的制备方法得到。
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