Preparation and lightning strike protection properties of lightweight high conductive metallized carbon nanotube film
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摘要: 碳纤维增强树脂基复合材料(CFRP)导电性差，无法满足飞机航行过程中的雷击防护需求。金属化碳纳米管薄膜具备轻质、高导电、高载流的特点，可应用于复合材料雷击防护。采用电化学沉积工艺成功制备了一种碳纳米管(CNT)/Cu复合薄膜，并对其微观结构、电学性能及载流失效行为进行了表征分析。结果表明，CNT/Cu复合薄膜柔性较好，具有明显的梯度结构，铜的含量在薄膜厚度方向上逐渐递减。复合薄膜电导率与Cu同一量级，比电导率为Cu的2倍，载流量及比载流量分别为商用铜网的1.4倍和7倍。复合薄膜中的CNT抑制了Cu在大载流作用下电迁移的发生，进而延长其载流失效时间。基于CNT/Cu复合薄膜制备了CFRP雷击防护试样，进行人工模拟雷击试验及高精度损伤分析，评估雷击防护效果。与商用铜网雷击防护材料相比，CNT/Cu复合薄膜质量减轻61%，且表现出更为优异的雷击防护性能。Abstract: Due to the poor conductivity, carbon fiber reinforced resin matrix composites (CFRP) cannot meet the lightning strike protection requirement of aircrafts. The metallization of carbon nanotube (CNT) films are lightweight, and possess high conductivity and high current-carrying capacity, making them promising for lightning strike protection of composite materials. CNT/Cu composite films were successfully prepared by electrochemical deposition process, and its microstructure, electrical properties and current-carrying failure behavior were characterized and analyzed. The results show that CNT/Cu composite films are flexible and have gradient microstructures, where the content of Cu gradually decreases from one side to another. The electrical conductivity of the composite films is 2.16×107 S/m, and their specific conductivity is 2 times of pure Cu, and the current carrying capacity and specific current carrying capacity are 1.4 times and 7 times of copper mesh, respectively. CNTs in the composite film can inhibit the electromigration of Cu, thus prolonging its current-carrying failure time. CFRPs for lightning strike protection testing were prepared by using CNT/Cu composite films, and the lightning strike protection performance was evaluated by artificial simulation lightning test and damage analysis. Compared with copper mesh, CNT/Cu composite films are 61% lighter and showed more excellent lightning protection performance.
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Key words:
- CNT/Cu /
- composite materials /
- electrical properties /
- metallized /
- lightning strike protection /
- non-destructive examination /
- CFRP
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图 1 (a) 浮动催化化学气相沉积法(FCCVD)制备的碳纳米管(CNT)薄膜；(b) 电化学沉积装置示意图
Figure 1. (a) Carbon nanotube (CNT) film prepared by floating catalytic chemical vapor deposition (FCCVD); (b) Schematic diagram of electrochemical deposition device
图 2 (a) 人工模拟雷击测试装置；(b) 飞行器雷电效应2A区电流分量B波形；(c) 电流分量D波形；(d) 电流分量C*波形
Figure 2. (a) Artificial simulation lightning strike test device; (b) Waveform of current component B of aircraft lightning effect zone 2A; (c) Waveform of current component D; (d) Waveform of current component C*
图 3 (a) 电化学沉积法制备的CNT/Cu复合薄膜试样；CNT/Cu复合薄膜上表面 (b) 及下表面 (c) 的SEM图像；复合薄膜截面微观形貌 (d) 及对应EDS元素表征 (e)；(f) 复合薄膜截面Cu元素分布示意图
Figure 3. (a) CNT/Cu composite film sample prepared by electrochemical deposition; SEM images of upper (b) and lower surfaces (c) of CNT/Cu composite film; Micromorphology of CNT/Cu composite film section (d) and its elemental analysis by EDS (e); (f) Schematic diagram of Cu element distribution of composite film section
图 4 CNT/Cu复合薄膜与铜网的电导率比较
Figure 4. Comparison of electrical conductivity between CNT/Cu composite film and Cu mesh
图 5 CNT/Cu复合薄膜与铜网的载流量比较
Figure 5. Comparison of ampacity between CNT/Cu composite film and Cu mesh
CCC—Current-carrying capacity
图 6 CNT/Cu复合薄膜 ((a)~(d)) 及铜网 ((e)~(h)) 载流失效时的电迁移
Figure 6. Electromigration of CNT/Cu ((a)-(d)) and Cu mesh ((e)-(h)) current-carrying failure
图 7 CNT/Cu复合薄膜载流失效断口形貌及元素分析：((a), (b)) 复合薄膜断口处SEM图像；((c), (d)) 图7(b)中对应位置元素线扫描及面扫描结果
Figure 7. Fracture morphology and elemental analysis of current carrying failure of CNT/Cu composite films: ((a), (b)) SEM images of composite film fracture; ((c), (d)) Line scan and map scan results of corresponding position elements in Fig. 7(b)
图 8 CFRP试样截面形貌及界面形态：((a), (d), (g)) 商用铜网防护(Cu mesh-CFRP)；((b), (e), (h)) 磁控溅射CNT/Cu复合薄膜防护(MS CNT/Cu-CFRP)；((c), (f), (i)) 电沉积 CNT/Cu 复合薄膜防护(EP CNT/Cu-CFRP) (由上至下分别为3D共聚焦显微图、金相图、SEM图像)
Figure 8. Section morphology and interface morphology of CFRP samples: ((a), (d), (g)) Commercial copper mesh (Cu mesh-CFRP); ((b), (e), (h)) CNT/Cu composite films produced by magnetron sputtering (MS CNT/Cu-CFRP); ((c), (f), (i)) CNT/Cu composite films produced by electrodeposition (EP CNT/Cu-CFRP ) (From top to bottom are 3D confocal micrograph, metallographic diagram, SEM images)
图 9 人工模拟雷击测试后试样表面损伤形貌：(a) NP-CFRP；(b) Cu mesh-CFRP；(c) MS CNT/Cu-CFRP；(d) EP CNT/Cu-CFRP
Figure 9. Surface damage morphologies after artificial simulated lightning strike tests: (a) NP-CFRP; (b) Cu mesh-CFRP; (c) MS CNT/Cu-CFRP; (f) EP CNT/Cu-CFRP
图 10 雷击中心点形貌表征：((a), (d)) Cu mesh-CFRP；((b), (e)) MS CNT/Cu-CFRP；((c), (f)) EP CNT/Cu-CFRP
Figure 10. Morphological characterization of lightning strike center point: ((a), (d)) Cu mesh-CFRP; ((b), (e)) MS CNT/Cu-CFRP; ((c), (f)) EP CNT/Cu-CFRP
图 11 试样雷击试验后计算机断层(CT)扫描整体形貌：(a) NP-CFRP；(b) Cu mesh-CFRP；(c) MS CNT/Cu-CFRP；(d) EP CNT/Cu-CFRP；随深度变化10%、20%、40%的剖面损伤形貌： ((a1)~(a3)) NP-CFRP；((b1)~(b3)) Cu mesh-CFRP；((c1)~(c3)) MS CNT/Cu-CFRP；((d1)~(d3)) EP CNT/Cu-CFRP
Figure 11. Computed tomography (CT) scanning of samples overall damage morphology after lightning strike test: (a) NP-CFRP; (b) Cu mesh-CFRP; (c) MS CNT/Cu-CFRP; (d) EP CNT/Cu-CFRP; Profile damage morphology varies by 10%, 20% and 40% with depth: ((a1)-(a3)) NP-CFRP; ((b1)-(b3)) Cu mesh-CFRP; ((c1)-(c3)) MS CNT/Cu-CFRP; ((d1)-(d2)) EP CNT/Cu-CFRP
图 12 试样雷击试验后CT扫描截面图
Figure 12. CT scanning cross-section of samples after lightning strike test
D—Thickness of the undamaged area after lightning strike
图 13 试样雷击防护机制示意图
Figure 13. Schematic diagram of lightning strike protection mechanism for samples
IH—Horizontal current; IV—Vertical current
表 1 商用铜网参数
Table 1. Commercial copper mesh parameters
Project Parameter Long intercept 2.54 mm±5% Short intercept 1.40 mm±6% Areal density (245±20) g/m2 Long intercept direction resistance ≤2.10 mΩ Short intercept direction resistance ≤6.30 mΩ 
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表 2 雷击防护CFRP试样电导率测试结果
Table 2. Conductivity test results of CFRP samples for lightning strike protection
Direction Sample Conductivity/(S·m−1) X NP-CFRP 23.14±3.47 Cu mesh-CFRP 31.02±2.88 MS CNT/Cu-CFRP 55.82±6.55 EP CNT/Cu-CFRP 99.81±7.13 Y NP-CFRP 8.57±0.61 Cu mesh-CFRP 19.62±2.36 MS CNT/Cu-CFRP 32.19±2.66 EP CNT/Cu-CFRP 62.87±9.47 Z NP-CFRP 0.79±0.06 Cu mesh-CFRP 1.30±0.07 MS CNT/Cu-CFRP 1.65±0.25 EP CNT/Cu-CFRP 2.38±0.35 Notes: NP-CFRP—Completely unprotected carbon fiber reinforced composite；MS—Magnetron sputtering; EP—Electrodeposition.
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表 3 4组CFRP试样雷击测试后损伤深度分析
Table 3. Analysis of damage depth of four groups of CFRP samples after lightning strike test
Sample Total thickness/mm Protective layer thickness/mm Total damage thickness/mm Total damage rate/% Damage rate of carbon
fiber structural layer/%NP-CFRP 3.837 0 1.456 37.95 37.95 Cu mesh-CFRP 4.372 0.218 0.671 15.35 10.91 MS CNT/Cu-CFRP 3.870 0.055 0.370 9.56 8.26 EP CNT/Cu-CFRP 3.850 0.050 0.050 1.30 0
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