Preparation and toughening mechanism of glass fiber/epoxy composites toughened by carbon nanotube sprayed layers
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摘要: 玻璃纤维增强树脂基复合板(GFRP)由于价格便宜、力学性能优异、耐疲劳等优点，广泛应用于风电叶片、运动器材等领域。但是上浆剂和树脂间的不良配合易导致层间分层破坏。本文通过在玻璃纤维织物表面喷涂碳纳米管(CNT)喷涂层，在不破坏面内性能的情况下，使双酚F型和双酚A型环氧树脂基体的玻璃纤维/树脂复合材料的层间I型断裂韧性分别提高了71.7%和23.4%。结果表明：CNT/丙酮分散液喷涂工艺在玻璃纤维上稳定地负载了CNT，成功改变了玻璃纤维表面形态，并通过机械锁合、拔出耗能、延长裂纹扩展路线和触发纤维桥接等机制，成功对不同树脂基体的GFRP实现增韧。Abstract: Glass fiber reinforced polymer (GFRP) composites are widely used in the fields of wind turbine blades and sports equipment due to their low cost, excellent mechanical performance and fatigue resistance. However, poor compatibility between sizing agent and resin can easily lead to interlaminar delamination. In this paper, the mode I interlaminar fracture toughness of GFRP with bisphenol F and bisphenol A epoxy resin matrices is improved by 71.7% and 23.4% through spraying a carbon nanotube (CNT) spray layer on the surface of fiberglass fabrics without sacrificing in-plane properties. Experimental results show that the CNT/acetone dispersion spray process stably loads CNTs on fiberglass and successfully changes the surface morphology of fiberglass. Through mechanisms such as mechanical interlocking, pull-out energy consumption, extension of crack propagation path as well as triggering of fiber bridging, the GFRP with different resin matrices is successfully toughened.
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图 1 碳纳米管(CNT)喷涂层及增韧玻璃纤维增强树脂基复合材料(GFRP)板材制备过程
Figure 1. Preparation process of carbon nanotube (CNT) spray coating toughened glass fiber reinforced plastic (GFRP) sheet
图 2 双悬臂梁试样测试示意图
Figure 2. Schematic diagram of double cantilever beam specimen testing
图 3 ((a), (b)) CNT/丙酮改性前后玻璃纤维(GF)的表面元素；(c) CNT/丙酮改性前后GF的表面粗糙度(Ra)变化；(d) CNT/水分散和CNT/丙酮分散液超声前后状态；(e) CNT在GF表面的状态
Figure 3. ((a), (b)) Surface elements of glass fiber (GF) before and after CNT/acetone modification; (c) Surface roughness (Ra) changes of GF before and after CNT/acetone modification; (d) State of CNT/water dispersion and CNT/acetone dispersion before and after ultrasound; (e) State of CNT on GF surface
图 4 不同树脂基体的CNT/GFRP的I型层间断裂韧性测试过程与结果：(a) I型层间断裂韧性测试过程；((b), (c)) A-Baseline和A-CNT的I型断裂韧性力-位移曲线及R曲线；(d) 两种树脂复合材料I型层间断裂韧性扩展值对比；((e), (f)) F-Baseline和F-CNT的I型断裂韧性力-位移曲线及R曲线
GIc—Mode I interlaminar fracture toughness propagation value
Figure 4. Mode I testing process and results of CNT/GFRP with different resin matrices: (a) Process of mode I interlaminar fracture toughness testing;((b), (c)) A-Baseline and A-CNT mode I fracture toughness force-displacement curves and R-curves; (d) Comparison of the results of mode I interlaminar fracture toughness extension for two resin composite materials; ((e), (f)) Force-displacement curves andR-curves of F-Baseline and F-CNT mode I fracture toughness
图 5 引入CNT前后复合材料层间裂面状态和力-位移曲线
Figure 5. State of interlayer crack surface and force-displacement curves of composite materials before and after the introduction of CNT
图 6 A-Baseline、A-CNT、F-Baseline、F-CNT这4种样品的Ⅰ型裂纹扩展的超景深显微镜图像
Figure 6. Super-depth microscopic images of mode I crack propagation in four samples of A-Baseline, A-CNT, F-Baseline and F-CNT
The yellow arrow indicates the location where the crack is relatively smooth; The red arrow indicates the location wherefiber nesting bridging may occur
图 7 双酚F环氧树脂基体GFRP的Ⅰ型断裂侧面形态：(a) F-Baseline层间光滑脱粘；(b) F-CNT层间的纤维桥接；(c) F-CNT样品的分层和“桥接”
Figure 7. Type I fracture profile of bisphenol F epoxy resin matrix GFRP: (a) F-Baseline smooth inter layer debonding;(b) Fiber bridging between F-CNT interlayers; (c) Layering and "bridging" of F-CNT samples
图 8 A-Baseline、A-CNT、F-Baseline、F-CNT这4种样品的I型断裂面的SEM图像
Figure 8. SEM images of mode I fracture surfaces of A-Baseline, A-CNT, F-Baseline and F-CNT samples
表 1 样品标记
Table 1. Sample marking
Resin matrix With or without CNT Abbreviation Bisphenol A type epoxy resin and curing agent (R0221A+R0221B) — A-Baseline Bisphenol A type epoxy resin and curing agent (R0221A+R0221B) CNT A-CNT Bisphenol F type epoxy resin and curing agent (Epon862+D230) — F-Baseline Bisphenol F type epoxy resin and curing agent (Epon862+D230) CNT F-CNT 
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