含磷聚芳醚酮-双马来酰亚胺树脂(PAEK-P-BMI)及碳纤维/PAEK-P-BMI复合材料

胡晓兰; 刘文军; 余荣禄; 周川; 李伟东; 周玉敬; 刘刚; 益小苏

doi:10.13801/j.cnki.fhclxb.20200115.001

含磷聚芳醚酮-双马来酰亚胺树脂(PAEK-P-BMI)及碳纤维/PAEK-P-BMI复合材料

doi: 10.13801/j.cnki.fhclxb.20200115.001

胡晓兰^{1, 2, ,},
刘文军^1,,
余荣禄^1,,
周川^1,,
李伟东^2,,
周玉敬^3,,
刘刚^{2, 4,},
益小苏^2,

1.
厦门大学　材料学院　福建省防火阻燃材料重点实验室，厦门 361005
2.
中航复合材料有限责任公司　航空工业复合材料技术中心　先进复合材料重点实验室，北京 101300
3.
北京机科国创轻量化科学研究院有限公司　先进成型技术与装备国家重点实验室，北京 100083
4.
东华大学　先进低维材料中心，上海 201602

基金项目: 航空科学基金(2016ZF68011)；福建省科技创新平台建设计划(2014H2006)；厦门大学石墨烯工业技术研究院资助项目(2014I2005)

详细信息

通讯作者:
胡晓兰，博士，副教授，研究方向为高性能树脂基复合材料　E-mail：xlhu@xmu.edu.cn

中图分类号: TB332
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- 文章访问数: 906
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- 被引次数: 0
出版历程
- 收稿日期: 2019-10-30
- 录用日期: 2019-12-18
- 网络出版日期: 2020-01-15
- 刊出日期: 2020-09-15

Phosphorus-containing polyaryletherketone-bismaleimide resin (PAEK-P-BMI) and carbon fiber/PAEK-P-BMI composites

HU Xiaolan^{1, 2
, ,},
LIU Wenjun^1
,,
YU Ronglu^1
,,
ZHOU Chuan^1
,,
LI Weidong^2
,,
ZHOU Yujing^3
,,
LIU Gang^{2, 4
,},
YI Xiaosu^2
,

1.
Fujian Provincial Key Laboratory of Fire Retardant Materials, College of Materials, Xiamen University, Xiamen 361005, China
2.
National Key Laboratory of Advanced Composites, AVIC Composite Technology Center, AVIC Composite Corporation Ltd., Beijing 101300, China
3.
State Key Laboratory of Advanced Forming Technology & Equipment, Beijing Jike Guochuang Lightweight Science Research Institute Co. Ltd., Beijing 100083, China
4.
Center for Advanced Low-dimension Materials, Donghua University, Shanghai 201602, China

摘要

摘要: 为提高树脂传递模塑(RTM)复合材料的整体韧性，结合“离位”复合增韧技术和RTM制造技术，应用新型热塑性含磷聚芳醚酮(PAEK-P)对碳纤维/双马来酰亚胺树脂(CF/BMI)复合材料进行增韧改性，研究了PAEK-P-BMI复合树脂的流变性能、分相行为及PAEK-P对CF/BMI复合材料韧性的影响。结果表明，分子链的刚性结构使PAEK-P具有高的耐热性，玻璃化转变温度达到268.8℃，PAEK-P在BMI树脂中的溶解性较差，PAEK-P-BMI复合树脂凝胶时间和黏度急增拐点时间受PAEK-P含量的影响很小；PAEK-P-BMI复合树脂在110℃/300 min条件下未出现相分离，但在后期的高温固化过程形成了分相结构，并在CF/PAEK-P-BMI复合材料中保持了分相形貌；与CF/BMI复合材料相比，CF/PAEK-P-BMI复合材料的冲击后损伤投影面积降低了69%，冲击后压缩强度提高了16.6%，冲击凹坑深度减小了34.4%。
- 双马来酰亚胺树脂 /
- 碳纤维 /
- 复合材料 /
- 热塑性树脂 /
- 冲击后压缩性能 /
- 增韧
Abstract: In order to improve the toughness of resin transfer molding(RTM) composites, combining the “ex-situ” composite toughening technology and RTM processing, a novel thermoplastic phosphorus-containing polyaryletherketone(PAEK-P) was used to toughen the carbon fiber/bismaleimide resin(CF/BMI) composites. The rheological properties, phase separation behavior of the PAEK-P-BMI resin and the effect of PAEK-P upon the toughness of the CF/BMI composites were investigated. The results show that the PAEK-P resin has high heat resistance at the glass transition temperature of 268.8℃ for its rigid structure. The gel time and viscosity increase inflection point time of the PAEK-P-BMI composite resin are little affected by the PAEK-P content because of its poor solubility in BMI resin. The PAEK-P-BMI composite resin shows no phase separation at 110℃/300 min. However, the phase separation structure is formed in the late high temperature curing process, and the phase separation morphology is maintained in the cured CF/PAEK-P-BMI composites. Compared with CF/BMI composites, the CF/PAEK-P-BMI composites have a 69% reduction in damage area after impact, a 16.6% increase in compressive strength after impact, and a 34.4% reduction in impact pit depth.
- bismaleimide resin /
- carbon fiber /
- composites /
- thermoplastic resin /
- compressive performance after impact /
- toughening

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图 1 含磷聚芳醚酮(PAEK-P)和酚酞聚芳醚酮(PAEK-C)的化学结构

Figure 1. Chemical structures of phosphorus-containing polyaryletherketone(PAEK-P) and polyether-ether ketone(PAEK-C)

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图 2 PAEK-P和PAEK-C的DSC曲线

Figure 2. DSC curves of PAEK-P and PAEK-C

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图 3 BMI树脂的黏度-温度曲线(a)及恒温110℃下黏度-时间曲线(b)

Figure 3. Viscosity-temperature curve of BMI resin (a) and viscosity-time curve of BMI resin at constant temperature of 110℃(b)

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图 4 不同PAEK-P含量(质量比)的PAEK-P-BMI复合树脂的凝胶特性曲线

Figure 4. Gel characteristic curves of PAEK-P-BMI resin with different PAEK-P contents (mass ratio)

G'—Storage modulus; G''—Loss modulus

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图 5 恒温110℃下不同PAEK-P含量的PAEK-P-BMI复合树脂(a)及BMI树脂、3%PAEK-C-BMI复合树脂和3%PAEK-P-BMI复合树脂(b)的黏度曲线

Figure 5. Viscosity curves of PAEK-P-BMI composite resins with different PAEK-P contents(a) and BMI resin, 3%PAEK-C-BMI composite resin, 3%PAEK-P-BMI composite resin(b) at constant temperature of 110℃

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图 6 110℃时PAEK-P-BMI复合树脂的形貌演变

Figure 6. Morphological evolution of PAEK-P-BMI composite resin at 110℃((a) 110℃/2 min; (b) 110℃/6 min; (c) 110℃/60 min; (d) 110℃/300 min)

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图 7 PAEK-P-BMI复合树脂浇铸体的SEM图像(DMF刻蚀72 h)

Figure 7. SEM images of PAEK-P-BMI resin castings (DMF etching 72 h)

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图 8 碳纤维(CF)/PAEK-P-BMI复合材料的SEM图像

Figure 8. SEM images of carbon fiber(CF)/PAEK-P-BMI composites

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图 9 CF/BMI、CF/PAEK-P-BMI和CF/PAEK-C-BMI复合材料冲击前后C扫描图像

Figure 9. C-scan images of CF/BMI, CF/PAEK-P-BMI, CF/PAEK-C-BMI composites before and after impact

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表 1 PAEK-P和PAEK-C的溶解性能

Table 1. Solubility properties of PAEK-P and PAEK-C

Thermoplastic resin	THF	DMF	BMI (110℃)
PAEK-C	Rapid dissolution	Rapid dissolution	Transparent
PAEK-P	Insoluble	Slow dissolution	Large amount of precipitation
Notes: THF—Tetrahydrofuran; DMF—N,N-dimethyformamide; BMI—Bismaleimide resin.

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表 2 PAEK-P-BMI复合树脂的凝胶特性

Table 2. Gel properties of PAEK-P-BMI composite resin

Mass ratio of PAEK-P/%	G' /Pa	G''/Pa	Gel point modulus/Pa	Gel point time/s
1	0.438	0.80	95.48	3 910
3	0.601	2.50	149.24	3 747
5	1.390	3.59	108.85	3 477
7	9.730	20.68	175.53	3 472

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表 3 CF/BMI、CF/PAEK-P-BMI和CF/PAEK-C-BMI复合材料冲击后损伤情况及冲击后压缩强度

Table 3. Damage and compressive strength of CF/BMI, CF/PAEK-P-BMI and CF/PAEK-C-BMI composites after impact

Composite	Surface density/(g·m⁻²)	Pit depth/mm	Compressive strength after impact/MPa	Damage area/mm²
CF/BMI	0	0.90	162.1	3 750
CF/PAEK-P-BMI	11.4	0.59	189.0	1 156
CF/PAEK-C-BMI	12.2	0.60	210.8	660

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