Interlaminar toughening of carbon fiber/epoxy composites with graphene oxide-carbon nanotube composite film
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摘要:
碳纤维增强环氧树脂基复合材料具有比强度高、比模量高、可设计性强等优异综合性能。但环氧树脂本征脆性较大，同时因复合材料层压板的层合结构特征，会带来层压板的耐冲击性和断裂韧性差、易分层破坏等性能缺陷。如何提高复合材料层合板结构的抗冲击损伤能力和抵抗分层破坏能力成为结构复合材料的研究难点和热点。氧化石墨烯优异的力学性能和其结构中丰富的含氧官能团，引起了树脂基复合材料研究人员的广泛兴趣。本文利用层间增韧技术，通过将氧化石墨烯(GO)和碳纳米管(CNT)制备了GO-CNT复合薄膜，将GO-CNT复合膜作为碳纤维/环氧树脂(CF/EP)的层间插层改性材料，制备了GO-CNT-CF/EP混杂复合材料。管状的CNT有效地抑制了GO片层间的紧密堆叠，使GO-CNT复合膜可以实现与树脂基体的良好浸润，GO和CNT结构中的羟基、羧基、环氧基等活性含氧基团增加了它们与EP的物理和化学作用，有利于复合材料层间GO-CNT/EP微区结构的强韧化。同时，利用CNT和GO片层形成的相互交叠的网络结构，实现了阻碍复合材料层间裂纹扩展、分散裂纹能量的作用。GO-CNT层间插层结构对复合材料的滑移型层间断裂韧性(GIIC)有显著的改善作用，使复合材料的GIIC从CF/EP的1855 J/m2提高到了GO-CNT-CF/EP的2720 J/m2，提高了47%，并且GO-CNT-CF/EP复合材料保持了与CF/EP复合材料同样优良的耐热性能。 GO-CNT复合膜SEM照片(a)和GO-CNT-CF/EP复合材料的滑移型层间断裂韧性GIIC载荷-位移曲线 (b) Abstract: The interlayer properties of carbon fiber reinforced resin matrix composites are always the weakness of composites. A composite film was designed and fabricated using graphene oxide (GO) and carbon nanotubes (CNT), which exhibited good permeability and resin wettability. A hybrid carbon fiber/epoxy (CF/EP) composite was prepared using the composite GO-CNT film by interlayer toughening method. The interlaminar toughness of the GO-CNT-CF/EP composites was investigated by open type interlaminar fracture toughness (GIC) and slip type interlaminar fracture toughness (GIIC). The interlayer toughening effect and toughening mechanism of the GO-CNT composite film on the GO-CN-CF/EP composites were analyzed based on the damage micro-morphology and damage/destruction characteristics of the composites. The results show that the composite GO-CNT film prepared with a mass ratio of GO to CNT of 3∶7 has good film-forming processability and resin wettability.The contact angle between EP and GO-CNT composite film is much lower than that between EP and pure GO film. Moreover, GO and oxygen-containing groups such as hydroxyl, carboxyl, and epoxy group in CNT increase their physical affinity and chemical interaction with EP, which is conducive to the toughening of GO-CNT/EP microzone structure between layers of composite materials. The GO-CNT composite film has no enhancement effect on the GIC of the composite. The GIC value of the GO-CNT-CF/EP composite even dropped slightly compared to the CF/EP composites. However, the GO-CNT composite film has a good effect on improving the GIIC of the GO-CNT-CF/EP composite. The GIIC of the composite increased from 1855 J/m2 for the CF/EP composite to 2720 J/m2 for the GO-CNT-CF/EP composite, which has an increase of 47%. This is attributed to the interpenetrating and overlapping network structure formed between the GO-CNT composite film and the resin, which inhibits the propagation of interlayer microcracks caused by slip-type loading.The glass transition temperature of GO-CNT/EP composites is similar to that of CF/EP composites.-
Key words:
- graphene oxide /
- carbon nanotube /
- interlaminar toughening /
- carbon fiber /
- composites
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图 1 氧化石墨烯(GO) (a)，碳纳米管(CNT) (b)、GO-CNT复合膜SEM图像((c)~(f)) (其中，GO∶CNT质量比2∶8 (c)、3∶7 ((d), (f))、4∶6 (e))，以及GO∶CNT为3∶7的复合膜的宏观照片(g)
Figure 1. SEM images of graphene oxide (GO) (a), carbon nanotube (CNT) (b), GO-CNT composite film ((c)-(f)) (GO∶CNT mass ratio 2∶8 (c), 3∶7 ((d), (f)), 4∶6 (e)), and its macro photo of GO∶CNT mass ratio 3∶7 (g)
图 2 环氧树脂胶液与薄膜的接触角：(a) GO膜；(b) CNT膜；(c) GO-CNT(3∶7)复合膜
Figure 2. Contact angle between epoxy resin glue and film: (a) GO film; (b) CNT film; (c) GO-CNT(3∶7) composite film
图 4 不同直径CNT制备的GO-CNT/EP浇铸体微观形貌SEM图像：(a) 10~20 nm；((b), (c)) 30~50 nm；(d) 大于50 nm
Figure 4. SEM images of GO-CNT/EP micro-structures with different CNT diameter: (a) 10-20 nm; ((b), (c)) 30-50 nm; (d) Greater than 50 nm
图 5 张开型层间断裂韧性GIC(a)和滑移型层间断裂韧性GIIC (b) 的测试原理图
Figure 5. Test schematic diagrams of open type interlaminar fracture toughness GIC (a) and slip type interlaminar fracture toughness GIIC (b)
图 7 GO-CNT-CF/EP复合材料的GIC载荷-位移曲线
Figure 7. GIC load-distance curves of GO-CNT-CF/EP composite
图 8 CF/EP ((a), (b))和GO-CNT-CF/EP ((c)-(f))的GIC测试后试样破坏面的SEM图像
Figure 8. SEM images of CF/EP ((a), (b)) and GO-CNT-CF/EP ((c)-(f)) composite after GIC test
图 9 CF/EP和GO-CNT-CF/EP复合材料的GIIC载荷-位移曲线
Figure 9. GIIC load-distance curves of CF/EP and GO-CNT-CF/EP composite
E54-DDS—E54 epoxy resin–4,4'-diaminodiphenylsulfone
图 10 CF/EP ((a), (b))和GO-CNT-CF/EP ((c)-(f))的GIIC测试试样破坏面的SEM图像
Figure 10. SEM images of damage surface of CF/EP ((a), (b)) and GO-CNT-CF/EP ((c)-(f)) composite after GIIC test
图 11 GO/E54-DDS (a)和CNT/E54-DDS (b)的DSC曲线
Figure 11. DSC curves of GO/E54-DDS (a) and CNT/E54-DDS (b)
表 1 CF/EP和GO-CNT-CF/EP的GIIC测试结果
Table 1. GIIC testing results of CF/EP and GO-CNT-CF/EP composite
Sample Critical load/N Critical load distance/mm GIIC/
(J·m−2)CF/EP 1453.81 2.18 1 894 1392.66 2.19 1 815 GO-CNT-CF/EP 1565.57 3.00 2801 1622.18 2.73 2638 
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