介孔SiO<sub>2</sub>对环氧树脂超低温力学性能及树脂/碳纤维界面性能的影响

陈汕; 孙杰; 李家亮; 谭添亮; 李梓睿; 顾海洋; 彭聪; 孙涛; 李世超; 武湛君

介孔SiO₂对环氧树脂超低温力学性能及树脂/碳纤维界面性能的影响

陈汕¹,
孙杰²,
李家亮³,
谭添亮¹,
李梓睿¹,
顾海洋¹,
彭聪¹,
孙涛¹,
李世超^{1, 2, ,},
武湛君¹

1.
江南大学纤维工程与装备技术学院先进复合材料实验室, 无锡214122
2.
苏州实验室, 苏州215009
3.
山东科技大学能源与矿业工程学院, 青岛 266590

基金项目: 中国科协青年人才托举工程(YESS20200084)；高校基本科研业务费专项资金资助(JUSRP123002)；国家自然科学基金重点支持项目“叶企孙”科学基金(U2341235)；国家自然科学基金面上项目(12372134)；山东省自然科学基金(ZR2022ME202)

详细信息

通讯作者:
李世超，博士，副研究员，硕士生导师，研究方向为耐极端环境树脂基复合材料　E-mail：Lsc1212@jiangnan.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2024-07-25
- 修回日期: 2024-08-26
- 录用日期: 2024-09-15
- 网络出版日期: 2024-10-12

Effect of mesoporous SiO₂on the mechanical properties of epoxy resin at ultra-low temperature and the interface properties of resin/carbon fiber

1.
Jiangnan University, Advanced Composite Materials Laboratory, School of Fiber Engineering and Equipment Technology, Wuxi 214122, China
2.
Suzhou Laboratory, Suzhou 215009, China
3.
Shandong University of Science and Technology, School of Energy and Mining Engineering, Qingdao 266590, China

Funds: China Association for Science and Technology Young Talent Lifting Project (YESS20200084); Special Fund for Fundamental Scientific Research Funds of Colleges and Universities (JUSRP 123002); National Natural Science Foundat Foundation of China (12372134); Natural Science Foundation of Shandong Province (ZR2022ME202) ion of China Key Support Project "Ye Qi sun" Science Foundation (U2341235)

摘要

摘要: 碳纤维增强环氧树脂基复合材料在超低温环境下的应用日益广泛。然而，由于环氧树脂基体与碳纤维之间的热膨胀系数不匹配，导致碳纤维复合材料在超低温环境下产生显著的温度应力，从而影响其服役性能。本文采用溶胶-凝胶法成功制备了粒径为100至160 nm、平均孔径为4.24 nm的介孔SiO₂，并通过三辊研磨法将其加入到环氧树脂中制备出介孔SiO₂/环氧树脂复合材料。测试结果表明：介孔SiO₂的添加有效降低了环氧树脂的热膨胀系数，并提高了其力学性能。具体来说，在室温和90 K下，添加10wt.%含量介孔SiO₂的环氧树脂抗拉强度分别达到约98 MPa和160 MPa，相比纯环氧树脂分别提高27.07%和26.02%。此外，随着介孔SiO₂含量的增加，环氧树脂的热膨胀系数逐渐降低，当添加20wt.%介孔SiO₂时，介孔SiO₂/环氧树脂复合材料的热膨胀系数相比于纯环氧树脂的热膨胀系数下降26.31%。TFBT测试结果表明：添加5wt.% 含量介孔SiO₂的环氧树脂的TFBT强度比纯环氧树脂提高了41.07%，这说明介孔SiO₂可以有效改善树脂/碳纤维的界面结合性能。
- 介孔SiO₂纳米粒子 /
- 环氧树脂 /
- 复合材料 /
- 热膨胀系数 /
- 界面强度
Abstract: Carbon fiber reinforced epoxy matrix composites are increasingly used in ultra-low temperature environments. However, due to the mismatch of the thermal expansion coefficient between the epoxy resin matrix and the carbon fiber, the carbon fiber composite material will produce significant temperature stress in the ultra-low temperature environment, which will affect its service performance. Mesoporous SiO₂ with a particle size of 100 to 160 nm and an average pore size of 4.24 nm was successfully prepared by sol-gel method, and mesoporous SiO₂/epoxy resin composites were prepared by adding them to epoxy resin by three-roller grinding method. The test results show that the addition of mesoporous SiO₂ effectively reduces the thermal expansion coefficient of epoxy resin and improves its mechanical properties. Specifically, at room temperature and 90 K, the tensile strength of epoxy resin with 10 wt.% mesoporous SiO₂ reached about 98 MPa and 160 MPa, respectively, which was 27.07% and 26.02% higher than that of pure epoxy resin, respectively. In addition, with the increase of mesoporous SiO₂ content, the thermal expansion coefficient of epoxy resin decreases gradually, and when 20wt.% mesoporous SiO₂ is added, the thermal expansion coefficient of mesoporous SiO₂/epoxy resin composites decreases by 26.31% compared with that of pure epoxy resin. The TFBT test results showed that the TFBT strength of epoxy resin with 5 wt.% mesoporous SiO₂ content was increased by 41.07% compared with that of pure epoxy resin, indicating that mesoporous SiO₂ could effectively improve the interfacial bonding properties of resin/carbon fiber.
- Mesoporous SiO₂ nanoparticles /
- Epoxy resin /
- composite material /
- Thermal expansion coefficient /
- Interfacial strength

HTML全文

图 1 (a) 介孔SiO₂ (M-SiO₂)合成机制实验流程图，(b)实验流程图；(c)环氧树脂分子链嵌段固化示意图

Figure 1. (a) Mesoporous SiO₂ (M-SiO₂) synthesis mechanism, (b) Experimental flowchart; (c) schematic representation of epoxy resin molecular chain segmental curing

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图 2 介孔SiO₂：(a)SEM图像；(b) TEM图像；(c) XRD衍射图谱

Figure 2. Mesoporous SiO₂: (a) SEM image; (b) TEM image;(c) XRD diffraction pattern

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图 3 介孔SiO₂(a)氮气吸附/脱附曲线；(b)孔径分布曲线

Figure 3. Mesoporous SiO₂(a) nitrogen adsorption/desorption curve; (b) pore size distribution curve

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图 4 (a)不同介孔SiO₂/环氧树脂复合材料的热膨胀率随温度的变化关系；(b)不同介孔SiO₂/环氧树脂复合材料在不同温度区间的热膨胀系数

Figure 4. (a) The relationship between the thermal expansion rate of mesoporous SiO₂/epoxy resin composites with different mass fractions and temperature;(b) the thermal expansion coefficient of mesoporous SiO₂/epoxy resins with different mass fractions in different temperature ranges

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图 5 介孔SiO₂/环氧树脂复合材料在(a) RT和(b) 90 K下的应力-应变曲线；(c)抗拉强度随介孔SiO₂含量变化的趋势图；(d)断裂应变随介孔SiO₂含量变化的趋势图

Figure 5. RT(a) and 90 K(b) stress-strain curves; (c) tensile strength; (d) strain at break are added to the mesoporous SiO₂/epoxy resin composites with different contents

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图 6 添加(a)10 wt.%和(b)20 wt.%介孔SiO₂的环氧树脂复合材料的TEM图；RT下，(c) 纯环氧树脂和(d)添加10 wt.%介孔 SiO₂的环氧树脂复合材料断面SEM图；90 K下，(e) 纯环氧树脂和(f)添加10 wt.%介孔 SiO₂的环氧树脂复合材料断面SEM图

Figure 6. Transmission electron microscopy images of (a) solidified epoxy composites with 10.0 wt.% and (b) 20.0 wt.% mesoporous SiO₂;(c) Scanning electron microscopy of RT fracture sections of epoxy composites with 0 wt.% and (d) 10.0 wt.% mesoporous SiO₂; (e) Scanning electron microscopy of 90 K fracture cross-section of epoxy composites with 0 wt.% and (f) 10.0 wt.% mesoporous SiO₂

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图 7 (a) 横向纤维束(TFBT)试样拉伸测试过程实物图；(b) 图a中红色箭头区域处TFBT试样光学照片

Figure 7. (a) The mechanical tensile test process of the TFBT model; (b) the red arrow in Figure a points to the lateral optical microscope magnification of the transverse fiber bundle (TFBT) model

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图 8 (a)未处理和(b)50次热循环处理后TFBT试样拉伸应力-应变曲线图

Figure 8. TFBT tensile stress-strain curves (a) were tested in RT environment without treatment; and (b) were tested in RT environment after 50 thermal cycles

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图 9 纯环氧树脂TFBT试样经50次热循环处理后的表面光学照片：(a)试样侧向，(b)试样正向

Figure 9. Magnification of optical fiberscope on the surface of pure epoxy/carbon fiber TFBT sample after 50 thermal cycles: (a) the specimen is sideways, (b) the specimen is forward

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图 10 未经热循环处理的介孔 SiO₂/环氧树脂复合材料TFBT样品断面SEM图：(a) 0 wt.%介孔SiO₂ ；(b) 5 wt.%介孔SiO₂； (c) 10 wt.%介孔SiO₂ ；(d) 20 wt.%介孔SiO₂

Figure 10. Cross-sections of mesoporous SiO2 modified epoxy/carbon fiber TFBT samples: (a) 0 wt.% mesoporous SiO₂; (b) 5 wt.% mesoporous SiO₂; (c) 10 wt.% mesoporous SiO₂; (d) 20 wt.% mesoporous SiO₂

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表 1 介孔SiO₂/环氧复合材料制备配比

Table 1. Preparation ratio of mesoporous SiO₂/epoxy composites

Sample name	M-SiO₂/ g	830 epoxy/g	DETDA/ g
Pure epoxy resin	0	80	20
5 wt.%M-SiO₂/Epoxy composite	4	80	20
10 wt.%M-SiO₂/Epoxy composite	8	80	20
15 wt.%M-SiO₂/Epoxy composite	12	80	20
20 wt.%M-SiO₂/Epoxy composite	16	80	20

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表 2 制备的介孔SiO₂比表面积、孔容孔径分布参数

Table 2. The specific surface area and pore size distribution parameters of mesoporous SiO₂

M-SiO₂	Specific surface area/(m²·g)	Pore volume/(cm³·g)	The most pore size distribution/nm	Average pore size distribution/nm
MCM-41	758.54	0.64	2.61	4.24

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表 3 添加不同含量介孔SiO₂/环氧树脂复合材料RT和90 K抗拉强度以及断裂应变。

Table 3. Tensile strength and breaking strain of mesoporous SiO₂/epoxy composites with different amounts of RT(a) and 90 K(b) are added.

Temperature	RT		90 K
Mesoporous SiO₂ content/wt.%	Tensile strength/MPa	Strain at break/%	Tensile strength/MPa	Strain at break/%
0	77.56±1.92	3.57±0.39	127.09±2.89	2.01±0.30
5	88.86±1.16	4.46±0.22	138.05±3.62	2.15±0.18
10	98.56±2.26	5.80±0.55	160.97±2.24	2.26±0.31
15	90.64±2.02	4.89±0.34	140.01±3.72	1.74±0.10
20	89.05±1.27	3.63±0.39	132.04±4.61	1.58±0.04

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表 4 添加不同含量介孔SiO₂的TFBT试样热循环处理前后的强度

Table 4. Strength of mesoporous SiO₂TFBT with different contents before and after thermal cycling

	Before thermal cycling treatment	50 thermal cycles
Mesoporous SiO₂ content/wt.%	TFBT Strength/MPa	TFBT Strength/MPa
0	9.30±0.23	7.63±0.41
5	12.72±0.51	11.1±0.47
10	11.72±0.17	11.3±0.15
15	11.21±0.13	10.78±0.17
20	10.31±0.39	10.24±0.12

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