宇航级T800碳纤维复合材料界面调控

李天舒; 王绍凯; 武清; 顾轶卓; 李庆辉; 李敏

doi:10.13700/j.bh.1001-5965.2021.0619

宇航级T800碳纤维复合材料界面调控

doi: 10.13700/j.bh.1001-5965.2021.0619

1.
北京航空航天大学材料科学与工程学院，北京 100191
2.
陕西科技大学材料科学与工程学院，西安 710016
3.
北京航空航天大学前沿科学技术创新研究院，北京 100191

详细信息

通讯作者:
E-mail：leemy@buaa.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2021-10-21
- 录用日期: 2022-01-02
- 网络出版日期: 2022-01-29
- 整期出版日期: 2023-08-31

Interface adjustment of aerospace-grade T800 carbon fiber composite material

1.
School of Materials Science and Engineering，Beihang University，Beijing 100191，China
2.
School of Materials Science and Engineering，Shaanxi University of Science & Technology，Xi’an 710016，China
3.
Research Institute for Frontier Science，Beihang University，Beijing 100191，China

More Information

Corresponding author: E-mail：leemy@buaa.edu.cn

摘要

摘要:
上浆剂对高性能碳纤维（CF）表面的修饰作用及对其复合材料界面性能的调制作用至关重要。以湿法制备的宇航级T800碳纤维为研究对象，分析上浆前后纤维表面微结构、化学组成和化学反应特性的变化规律，并对其复合材料的宏微观界面性能进行表征评价。采用X射线光电子能谱（XPS）、差式扫描量热法（DSC）、傅里叶变换红外光谱（FTIR）等表征方法，分析上浆剂的反应性及其与环氧树脂（EP）、双马来酰亚胺树脂（BMI）的化学反应行为。结果表明：在树脂固化温度条件下上浆剂与纤维表面基团发生化学反应，使得纤维上浆剂提取量及纤维表面活性碳元素含量降低，并且上浆剂与EP、BMI工艺具有良好的化学反应性。经过高温处理后CF表面的上浆剂失活，CF/EP的界面剪切强度发生一定变化，CF/BMI的界面剪切强度下降13%。综上可见：具有化学活性的环氧类上浆剂可明显改善CF表面特性，进而对复合材料的界面性能产生影响，其中上浆剂与树脂体系的反应性对界面亦有影响。
- 上浆剂 /
- 碳纤维 /
- 化学反应 /
- 界面调控 /
- 复合材料
Abstract:
The effect of the sizing agent on the surface modification of high-performance carbon fiber (CF) and the modulation effect on the interface performance of its composite is very important. In this paper, the aerospace-grade T800 carbon fibers prepared by the wet method are used, and the changes in the surface microstructure, chemical composition, and chemical reaction characteristics of the fiber before and after sizing are analyzed, and the macro and micro interface properties of the composites are characterized. In addition, the reactivity of the sizing agent and its chemical reaction behavior with epoxy resin (EP) and bismaleimide resin (BMI) were examined using X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and other characterization techniques. The results show that the sizing agent reacts chemically with the groups on the fiber surface under the curing temperature of the resin so that the extraction amount of the sizing agent and the content of active carbon atoms on the fiber surface is reduced. The sizing agent has good chemical reaction characteristics with EP and BMI. The surface of CF sizing agent is rendered inactive after the high-temperature treatment, which also results in a little change in the interface shear strength between CF and EP but a 13% reduction between CF and BMI. In conclusion, the epoxy sizing agent with chemical activity can significantly improve the surface properties of carbon fiber, and then affect the interface properties of composites, in which the reactivity between the sizing agent and resin also affects the interface performance.
- sizing agent /
- carbon fiber /
- chemical reaction /
- interface adjustment /
- composite material

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图 1 F4纤维上浆前后的表面形貌

Figure 1. Surface morphologies and roughness of F4 fiber before and after sizing

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图 2 F1~F4纤维上浆前后的表面粗糙度

Figure 2. Surface roughness of F1~F4 fibers before and after sizing

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图 3 F1~F4纤维表面上浆剂的红外光谱图

Figure 3. FTIR of F1-F4 fibers surface sizing agents

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图 4 F4纤维在不同热处理工艺制度下提取上浆剂的含量

Figure 4. Content of sizing agent extracted from F4 fibers that treated by different heat processes

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图 5 F4纤维在不同工艺制度热处理后纤维表面粗糙度

Figure 5. Surface roughness of F4 fibers that treated by different heat processes

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图 6 不同工艺处理后的F4纤维提取上浆剂的红外光谱

Figure 6. IR of sizing agents extracted from F4 fibers that treated by different processes

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图 7 不同纤维/树脂界面剪切强度对比

Figure 7. Comparison of interface shear strength of different fibers/resins

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图 8 树脂、F4上浆剂及其混合物的DSC曲线

Figure 8. DSC curves of resins, F4sizing agents and their mixtures

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图 9 EP和BMI固化前后的红外光谱

Figure 9. FTIR of EP and BMI resins before and after curing

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图 10 树脂与上浆剂混合物的原位红外光谱

Figure 10. In-situ FTIR of resin and sizing agent mixture

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图 11 不同树脂与热处理前后F4纤维的界面剪切强度

Figure 11. IFSS of different resins and F4 fibers before and after heat treatment

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表 1 不同T800级CF上浆前后的表面元素

Table 1. Surface element content of different T800 grade CF before and after sizing

纤维类型	C/%	O/%	N/%	Si/%	S/%	Na/%	O/C
F1	74.12	16.83	2.2	6.01	0.84	0	0.23
F1-US	78.72	16.24	2.43	2.62	0	0	0.21
F2	74.35	19.4	1.73	4.52	0	0	0.26
F2-US	79.74	14.05	2.99	3.22	0	0	0.18
F3	76.32	16.39	2.98	3.39	0.73	0.2	0.21
F3-US	78.16	17.12	2.28	2.44	0	0	0.22
F4	76.1	16.99	2.28	3.71	0.91	0	0.22
F4-US	77.58	16.85	2.36	3.21	0	0	0.22

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表 2 不同CF XPS的C1s分峰拟合结果

Table 2. XPS C1s peak fitting results of different CF %

纤维类型	参比基团含量	−C−C−； −C−H−含量	−C−OH−C−O−； −C−NH₂含量	C−O−C=O；环氧基团含量	−C=O− C=N含量	−O−C=OHO− C=O含量	活性碳元素含量
纤维类型	（Peak1，能量284.8 eV）	（Peak2，能量285.0 eV）	（Peak3，能量286.1 eV）	（Peak4，能量286.6 eV）	（Peak5，能量287.7 eV）	（Peak6，能量289.4 eV）	活性碳元素含量
F1	38.54	26.05	10.92	16.35	6.45	1.69	35.41
F1- US	70.22	11.65	0.00	6.02	7.15	4.96	18.13
F2	36.67	12.59	20.59	17.49	3.31	9.35	50.74
F2- US	37.09	18.02	24.05	0.00	11.35	9.49	44.89
F3	44.20	13.92	16.36	12.29	6.40	6.85	41.90
F3- US	59.81	20.80	1.53	3.75	6.79	7.31	19.38
F4	24.61	13.73	27.97	22.03	4.90	6.77	61.67
F4- US	73.21	7.38	2.84	4.43	6.66	5.49	19.42

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表 3 不同工艺制度处理后F4纤维表面元素

Table 3. Surface element content of F4 fiber after different heat treatment processes

纤维类型	C/%	O/%	N/%	Si/%	S/%	O/C
F4	76.1	16.99	2.28	3.71	0.91	0.22
F4+EP工艺	82.03	15.93	2.04	0	0	0.19
F4+BMI 工艺	89.98	10.02	0	0	0	0.11

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表 4 不同工艺处理后F4纤维XPS的C1s分峰拟合结果

Table 4. XPS C1s peak fitting results of F4 fiber after different heat treatment processes %

纤维类型	参比基团含量	−C−C−； −C−H−含量	−C−OH−C−O−； −C−NH₂含量	C−O−C=O；环氧基团含量	−C=O− C=N含量	−O−C=OHO− C=O含量	活性碳元素含量
纤维类型	（Peak1，能量284.8 eV）	（Peak2，能量285.0 eV）	（Peak3，能量286.1 eV）	（Peak4，能量286.6 eV）	（Peak5，能量287.7 eV）	（Peak6，能量289.4 eV）	活性碳元素含量
F4	24.61	13.73	27.97	22.03	4.90	6.77	61.67
F4+EP工艺	45.05	26.66	20.52	7.76	0	0	28.28
F4+BMI工艺	37.24	48.29	11.38	3.09	0	0	14.47

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表 5 不同树脂/上浆剂的DSC峰值温度与放热

Table 5. DSC peak temperature and heat of different resins/sizing agents

树脂/上浆剂	第1峰值温度/℃	第2峰值温度/℃	第3峰值温度/℃	放热/(J·g⁻¹)
EP		229.2	264.7	421.5
F4			282.7	246.8
EP和F4		224.2	282.7	360.4
BMI	156.3	258.1	176.6	482.8
F4			282.7	246.8
BMI和F4	126.6		277.7	316.1

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