Synergistic improvement of electrical conductivity and interlaminar toughness of carbon fiber resin matrix composites based on intercalation method
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摘要: 碳纤维增强树脂基复合材料(CFRP)因其低密度、高比强度等特点，在航空航天领域得到了广泛的应用，但其导电性和层间韧性的不足降低了CFRP作为飞机结构件的使用安全性。为了改善CFRP弱的导电性和层间断裂韧性，本文采用溶液浇铸法制备了多壁碳纳米管(MWCNTs)和石墨烯纳米片(GNPs)掺杂聚醚砜(PES)的导电热塑性薄膜(CTFs)。然后将CTFs交错放入碳纤维/环氧树脂(CF/EP)预浸料中制得复合材料层压板，并对其导电性和层间断裂韧性进行了探究。结果表明，相较于对照样品(CS)，在横向(Y)和厚度(Z)方向，层压板的电导率分别提高了474%和554%。采用双悬臂梁(DCB)和端口弯曲(ENF)法评估了Mode I和Mode II层间断裂韧性，当插入的CTF中纳米填料质量比为CNT∶GNP=2∶1时，复合材料层压板的Mode I层间断裂韧性(GIC)和断裂阻抗(GIR)分别提高了441%和165%，此外，纳米填料质量比CNT∶GNP=8∶1时，Mode II层间断裂韧性(GIIC)提高了79%。最后通过SEM观察了复合材料的微观结构形貌，并分析了复合材料的失效机制。
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关键词:
- 碳纤维/环氧树脂(CF/EP)复合材料 /
- 聚醚砜(PES) /
- 协同效应 /
- 电导率 /
- 层间断裂韧性
Abstract: Carbon fiber reinforced resin matrix composites (CFRP) are widely used in aerospace and is gradually replacing metal materials for aircraft structures as a result of their low density and high strength characteristics, while poor electrical conductivity and interlaminar shear fracture toughness could reduce their safety as structural components in use. In order to improve the poor electrical conductivity and interlaminar fracture toughness of CFRP, multi-walled carbon nanotubes (MWCNTs) and graphene nanoplatelets (GNPs) doped polyethersulfone (PES) conductive thermoplastic films (CTFs) were prepared by solution casting in this work. Then CTFs were interleaved into carbon fiber/epoxy resin (CF/EP) prepregs to prepare composite laminates. The electrical conductivity and interlaminar fracture toughness of the composite laminates were investigated. The results show that compared with the control sample (CS), the conductivity of the laminate increases by 474% and 554% in the transverse (Y) and thickness (Z) directions, respectively. The Mode I and Mode II interlaminar fracture toughness values were evaluated by double cantilever beam (DCB) and end-notched flexure (ENF) testing. The data show that when the nano-filler mass ratio of CNT∶GNP is 2∶1 in the interleaved CTF, the Mode I interlaminar fracture toughness and fracture impedance of the composite laminates are increased by 441% and 165%, respectively. Moreover, when the nano-filler mass ratio of CNT∶GNP is 8: 1, the Mode II interlaminar fracture toughness of the composite laminates is increased by 79%. In addition, the microstructural morphology of the composite material was observed by SEM and its failure mechanism was studied. -
图 1 导电热塑性薄膜(CTFs)和CTF交错CF/EP复合材料层压板的制作工艺：碳纳米管(CNT)/石墨烯纳米片(GNP)/聚醚砜(PES)膜 (a)、GNP/PES膜 (b) 和层压板的热压成型 (c)
MWCNTs—Multi-walled carbon nanotubes; DMF—N, N-dimethylformamide
Figure 1. Manufacturing process of conductive thermoplastic films (CTFs) and CTFs interlaced CF/EP composite laminates: Carbon nanotube (CNT)/graphene nanoplatelets (GNP)/ polyethersulfone (PES) film (a), GNP/PES film (b) and hot-press molding of laminate (c)
图 2 CF/EP预浸料固化工艺 (a)、Mode I 层间断裂韧性测试样品 (b)、Mode II层间断裂韧性测试样品 (c) 和层压板电性能测试样品 (d)
Figure 2. CF/EP prepreg curing process (a), Mode I interlayer fracture toughness test sample (b), Mode II interlayer fracture toughness test sample (c) and laminate electrical property test sample (d)
图 3 Mode I 断裂韧性测试装置 (a) 和Mode II 断裂韧性测试装置 (b)
Figure 3. Mode I fracture toughness test device (a) and Mode II fracture toughness test device (b)
图 4 掺杂不同质量比的CNT/GNP的CTFs的电导率
Figure 4. Electrical conductivity of CTFs containing different mass ratios of CNT/GNP
图 5 不同质量比的CTFs的SEM图像：((a), (b)) CNT；((c), (d)) CNT∶GNP=8∶1；((e), (f)) CNT∶GNP=2∶1；((g), (h)) GNP
Figure 5. SEM images of CTFs with different mass ratios: ((a), (b)) CNT; ((c), (d)) CNT∶GNP=8∶1; ((e), (f)) CNT∶GNP=2∶1; ((g), (h)) GNP
图 6 加载不同质量比的CNT/GNP的CTF插层的复合材料层压板和对照样品(无插页)在X、Y和Z三个方向上的电导率
Figure 6. Conductivity in X, Y, and Z directions of composite laminates loaded with CTF interlayers of CNT/GNP with different mass ratios and control samples (Without interleaf)
图 7 插入质量比CNT∶GNP=2∶1的CTF插层复合材料导电层压板的SEM图像：((a), (b)) 低放大倍数；((c), (d)) 高放大倍数
Figure 7. SEM image of CTFs (CNT∶GNP=2∶1) intercalated composite laminate: ((a), (b)) Low magnification; ((c), (d)) High magnification
图 8 CNT和GNP通过协同增强作用改善复合材料的导电路径示意图((a)无CTF插层的复合材料层压板；(b)有CTF插层的复合材料层压板)
Figure 8. Schematic diagram of CNT and GNP improving the conductive path of composites through synergistic reinforcement ((a) Composite laminates without CTF intercalation; (b) Composite laminates with CTF intercalation)
图 9 不同插层CNT/GNP复合材料的典型双悬臂梁(DCB)荷载-位移曲线
Figure 9. Typical double cantilever beam (DCB) load-displacement curves of different interlayers CNT/GNP composite materials
图 10 不同插层CNT/GNP复合材料的Mode I断裂韧性-(a−a0)曲线
Figure 10. Mode I fracture toughness-(a−a0) curves obtained for CNT/GNP composites with different interlayers
图 11 不同插层的复合材料的Mode I断裂韧性和断裂阻抗
GIC—Mode I interlaminar fracture toughness; GIR—Fracture resistance
Figure 11. Mode I fracture toughness and fracture resistance of composite materials with different interlayers
图 12 通过端口弯曲(ENF)试验得到的层间含有不同插层CNT/GNP复合材料的典型荷载-位移曲线
Figure 12. Typical load–displacement curves obtained by end-notched flexure (ENF) tests for CNT/GNP composites with interlayers
图 13 含有不同插层的CNT/GNP复合材料层压板的Mode II 断裂韧性
Figure 13. Mode II fracture toughness of CNT/GNP composite laminates with different interlayers
图 14 DCB测试后对照样品 ((a), (b)) 和分别插入CNT ((c), (d))、CNT/GNP=2∶1 ((e), (f)) 和GNP ((g), (h)) 的CTFs 制得的CNT/GNP复合材料层压板断裂面的SEM图像
Figure 14. SEM images of fracture surface control samples ((a), (b)) and CNT/GNP composite laminates obtained by interleaving CTFs with CNT ((c), (d)), CNT/GNP=2∶1 ((e), (f)) and GNP ((g), (h)) after DCB test
图 15 裂纹在基体界面中的扩展示意图：无CTF插层的CF/EP复合材料层压板 (a) 和有CTF插层的CNT/GNP复合材料层压板 (b)
Figure 15. Diagram of crack propagation in matrix interface: CF/EP composite laminates without CTF intercalation (a) and CNT/GNP composite laminates with CTF intercalation (b)
图 16 ENF测试后对照样品 ((a), (b)) 和分别插入CNT ((c), (d))、CNT∶GNP=8∶1 ((e), (f)) 和GNP ((g), (h)) 的导电热塑性薄膜制得的CNT/GNP复合材料层压板的断裂面SEM图像
Figure 16. SEM images of fracture surface control samples ((a), (b)) and CNT/GNP composite laminates obtained by interleaving CTFs with CNT ((c), (d)), CNT/GNP=8:1 ((e), (f)) and GNP ((g), (h)) after ENF test
表 1 单向碳纤维/环氧树脂(CF/EP)预浸料规格参数
Table 1. Specifications of unidirectional carbon fiber/epoxy resin (CF/EP) prepreg
Specification parameter Value Carbon fiber model T700 Fiber mass per unit area/(g·m−2) 132±4 Resin content/wt% 35±2 Monolayer prepreg thickness/mm 0.125 Epoxy resin model E1010 Tensile strength in fiber direction/MPa 2500 Bending strength/MPa 1650 
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