功能化Al2O3@SiO2/酚醛环氧-双马树脂复合材料的微观结构及性能

陈宇飞; 赵辉; 董磊

doi:10.13801/j.cnki.fhclxb.20210316.002

功能化Al₂O₃@SiO₂/酚醛环氧-双马树脂复合材料的微观结构及性能

doi: 10.13801/j.cnki.fhclxb.20210316.002

陈宇飞^{1, 2, ,},
赵辉¹,
董磊¹

1.
哈尔滨理工大学　材料科学与工程学院，哈尔滨 150040
2.
哈尔滨理工大学　工程电介质及应用技术教育部重点实验室，哈尔滨 150080

基金项目: 哈尔滨创新人才专项(2015RAXXJ029); 哈尔滨理工大学创新项目(201910214126)

详细信息

通讯作者:
陈宇飞，博士，教授，硕士生导师，研究方向为介电复合材料、高性能航空材料结构与性能　E-mail：chenyufei@hrbust.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2021-01-26
- 修回日期: 2021-03-01
- 录用日期: 2021-03-09
- 网络出版日期: 2021-03-17
- 刊出日期: 2022-01-15

Microstructure and properties of functionalized Al₂O₃@SiO₂/phenolic epoxy-bismaleimide composites

CHEN Yufei^{1, 2
, ,},
ZHAO Hui¹,
DONG Lei¹

1.
College of Materials Science and Engineering, Harbin University of Science and Technology, Harbin 150040, China
2.
Key Laboratory of Engineering Dielectrics and its Application, Ministry of Education, Harbin University of Science and Technology, Harbin 150080, China

摘要

摘要: 采用溶胶-凝胶法(Sol-gel)分别制备Al₂O₃和SiO₂，同时以KH560为架桥剂制得SiO₂包覆Al₂O₃(KH560-Al₂O₃@SiO₂)的增强体。以双马来酰亚胺树脂和酚醛环氧树脂(MBMI-EPN)为基体、4’4-二氨基二苯甲烷(DDM)为固化剂，采用原位聚合法制备了KH560-Al₂O₃@SiO₂/MBMI-EPN复合材料；表征KH560-Al₂O₃@SiO₂的微观结构及该增强体对复合材料性能的影响。结果表明：Al₂O₃@SiO₂粒子微观结构清晰，核壳结构完整，内核为短纤维状Al₂O₃，外壳为无定形SiO₂，二者通过化学键方式相连；Al₂O₃@SiO₂表面成功接枝上KH560基团，粒子堆积现象减弱。KH560-Al₂O₃@SiO₂/MBMI-EPN复合材料的微观形貌显示：KH560-Al₂O₃@SiO₂在MBMI-EPN基体中形成多相结构、分散性较好、界面作用稳定且断面形貌呈鱼鳞状，并未发现Al₂O₃@SiO₂粒子团聚体，整体结构完整。当KH560-Al₂O₃@SiO₂含量为1.5wt%时，复合材料的弯曲强度与冲击强度分别为126 MPa和14.7 kJ/m²，比树脂基体分别提高了21.2%和27.8%；材料的热分解温度为392.3℃，比树脂基体提高了14.5℃，力学性能和耐热性得到明显改善。
- 酚醛环氧树脂 /
- 双马来酰亚胺 /
- 三氧化铝 /
- 二氧化硅 /
- 力学性能 /
- 耐热性
Abstract: The Al₂O₃ and SiO₂ were obtained by sol-gel method and the KH560-Al₂O₃@SiO₂ were prepared with KH560 as the coupling agent. The KH560-Al₂O₃@SiO₂/MBMI-EPN composites were prepared by in-situ polymerization, using bismaleimide resin and phenolic epoxy resin (MBMI-EPN) as matrix, KH560-Al₂O₃@SiO₂ as the reinforcement and 4’4-diaminodiphenylmethane (DDM) as curing agent. The micro-structure of KH560-Al₂O₃@SiO₂ were characterized and the effect of the reinforcement on properties of composites were studied. The results show that the Al₂O₃@SiO₂ particles have clear core-shell structure. The short-fiber Al₂O₃ is inner core, and the amorphous SiO₂ is outer shell, which are connected by chemical bonds. The KH560 is successfully grafted onto the surface of Al₂O₃@SiO₂, and the particles packing phenomenon is weakened. The micro-structure of the composites shows that KH560-Al₂O₃@SiO₂ forms a multi-phase structure in the MBMI-EPN matrix with good dispersion and stable interface. The cross-sectional shape is fish scale, and there are no Al₂O₃@SiO₂ nanoparticle agglomerates and the overall structure is regular. When the content of KH560-Al₂O₃@SiO₂ is 1.5wt%, bending strength and impact strength of the composites are 126 MPa and 14.7 kJ/m², which are 21.2% and 27.8% higher than resin matrix, respectively. And the thermal decomposition temperature of the composites is 392.3℃, which is 14.5℃ higher than that of resin matrix.
- phenolic epoxy resin /
- bismaleimide /
- alumina, silicon oxide /
- mechanical properties /
- heat resistance /

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图 1 Al₂O₃@SiO₂(a)、KH560-Al₂O₃@SiO₂(b)和Al₂O₃(c)的FTIR图谱

Figure 1. FTIR spectra of Al₂O₃@SiO₂(a), KH560-Al₂O₃@SiO₂(b) and Al₂O₃(c)

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图 2 Al₂O₃(a)、SiO₂(b)和Al₂O₃@SiO₂((c)~(e))的XRD衍射图谱

Figure 2. XRD diffraction spectra of Al₂O₃(a), SiO₂(b) and Al₂O₃@SiO₂((c)~(e))

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图 3 Al₂O₃@SiO₂和KH560-Al₂O₃@SiO₂的SEM图像

Figure 3. SEM images of Al₂O₃@SiO₂ and KH560-Al₂O₃@SiO₂

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图 4 Al₂O₃@SiO₂的TEM图像

Figure 4. TEM images of Al₂O₃@SiO₂

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图 5 MBMI-EPN基体和KH560-Al₂O₃@SiO₂/MBMI-EPN复合材料的SEM图像

Figure 5. SEM images of MBMI-EPN matrix and KH560-Al₂O₃@SiO₂/MBMI-EPN composites

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图 6 KH560-Al₂O₃@SiO₂/MBMI-EPN复合材料的冲击强度(a)和弯曲强度(b)

Figure 6. Impact strength (a) and bending strength (b) of KH560-Al₂O₃@SiO₂/MBMI-EPN composites

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图 7 KH560-Al₂O₃@SiO₂/MBMI-EPN的热失重曲线

Figure 7. TGA curves of KH560-Al₂O₃@SiO₂/MBMI-EPN

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表 1 KH560-Al₂O₃@SiO₂/双马来酰亚胺树脂-酚醛环氧树脂(MBMI-EPN)复合材料样品的名称及组分含量

Table 1. Sample name and content of KH560-Al₂O₃@SiO₂/bismaleimide resin and phenolic epoxy resin (MBMI-EPN) composites

Sample	KH560-Al₂O₃@SiO₂ mass ratio/wt%
MBMI-EPN	0
0.5wt% KH560-Al₂O₃@SiO₂/MBMI-EPN	0.5
1.0wt% KH560-Al₂O₃@SiO₂/MBMI-EPN	1.0
1.5wt% KH560-Al₂O₃@SiO₂/MBMI-EPN	1.5
2.0wt% KH560-Al₂O₃@SiO₂/MBMI-EPN	2.0
2.5wt% KH560-Al₂O₃@SiO₂/MBMI-EPN	2.5

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