A graphene/polyurea composite with both thermal conduction and self-healing functions based on dual dynamic networks
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摘要: 开发能够快速修复的导热材料引起了越来越多的关注。然而，材料的导热性能与自修复性能一直难以平衡，制备具有自愈性的导热聚脲复合材料具有挑战性。为了解决这一难题，本论文提出利用氢键和动态亚胺键的双动态网络构筑自修复聚脲(D-PUA)柔性膜。氢键和亚胺键的动态断裂和重构不断耗散能量，使D-PUA具有良好的弹性和自修复性。实验结果表明，在短时间内(60 ℃、8 min) D-PUA膜上的划痕可完全修复，切断愈合72 h后拉伸强度的修复效率为84.62%。在动态聚脲基体中填充石墨烯(GNP)制备得到兼具自修复、导热性和可回收性的GNP/D-PUA复合膜。基于GNP本身的高导热性，负载量为10 wt%时，复合膜的面内导热系数为2.57 W·m−1·K−1，相对于本征膜提升了571%。GNP10/D-PUA在90 ℃，60 min能够使划痕愈合，切断愈合72 h后拉伸强度的修复效率为83.94%。此外，由于动态键的存在复合膜经过五次热压重塑后，没有明显的机械损失，且面内热导率的回复率均在80.93%以上。Abstract: The development of thermal conductivity materials that can be quickly repaired has attracted increasing attention. However, due to the trade-off between thermal conductivity and self-healing properties of materials, it is challenging to prepare thermal conductivity polyurea composites with self-healing properties. To solve this problem, this paper proposes to construct self-healing polyurea (D-PUA) flexible membrane by using the double dynamic network of hydrogen bonds and dynamic imine bonds. The dynamic breaking and reconstruction of hydrogen bonds and imine bonds dissipates energy continuously, which makes D-PUA have good elasticity and self-repair. The experimental results demonstrate that scratches on the D-PUA film can be completely repaired in a short time (60 ℃, 8 min), and the repair efficiency of tensile strength reaching 84.62% after 72 h of cutting and healing. The GNP/D-PUA composite membrane with self-healing, thermal conductivity and recyclability was prepared by incorporating graphene (GNP) as a filler. Due to the high thermal conductivity of graphene itself, the in-plane thermal conductivity of the composite film is 2.57 W·m−1·K−1 when the GNP content is 10 wt%, which is 571% higher than that of the pure film. GNP10/D-PUA can also heal scratches at 90 ℃ for 60 min, and the repair efficiency of tensile strength after 72 h of cutting and healing is 83.94%. Additionally, due to the presence of dynamic bonds, there is no significant mechanical loss after five hot pressing remodeling of the composite film, and the repair rate of in-plane thermal conductivity is above 80.93% in all cases.
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Key words:
- Polyurea /
- Self-healing /
- Hydrogen bonds /
- Imine bonds /
- Heat conduction /
- Composite materia
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图 1 (a) 自修复聚脲(D-PUA)的合成路线图; (b) D-PUA薄膜的制备过程示意图; (c) D-PUA双动态网络结构示意图，包含氢键和动态亚胺键
Figure 1. (a) The synthetic route of self-healing polyurea (D-PUA); (b) Schematic demon-stration of the preparation process of the D-PUA films; (c) D-PUA dual dynamic network structure diagram, including hy-drogen bonds and dynamic imine bonds
图 2 D-PUA的 (a) 核磁共振氢谱图 (b) 衰减全反射红外光谱图 (c) 变温红外光谱图
Figure 2. (a) The 1 H NMR (b) ATR-FTIR and (c) variable-temperature FTIR spectra of D-PUA
图 3 (a) D-400/D-2000不同配比下的应力-应变曲线; (b) 不同静息时间下D-PUA的拉伸-回缩循环曲线; (c) D-PUA加载-卸载的数码照片
Figure 3. (a) Stress-strain curves of D-400/D-2000 at different proportions; (b) D-PUA stretch-shrink cycle curves at different resting times; (c) D-PUA load - unload digital photos
图 4 (a) PUA和D-PUA划痕自修复的光学显微镜图像; (b) 染色和未染色D-PUA样品在60℃下修复72 h的数码照片; (c) D-PUA切断后在60℃下不同愈合时间的应力-应变曲线; (d) D-PUA切断后在60℃下不同愈合时间的韧性及修复效率; (e) D-PUA自修复机制图
Figure 4. (a) Optical microscope images of PUA and D-PUA scratch self-healing; (b) Digital photos of dyed and undyed D-PUA samples repaired at 60 ° C for 72 h; (c) Stress-strain curves of D-PUA after cutting at different healing times at 60℃; (d) Toughness and repair efficiency of D-PUA after cutting at different healing time at 60℃; (e) Self-healing mechanism diagram of D-PUA
图 5 (a) 具有不同质量分数石墨烯(GNP)复合材料的应力-应变曲线；(b) GNP10/D-PUA划痕自修复的光学显微镜图像；(c) GNP10/D-PUA切断后在90℃下不同愈合时间的应力-应变曲线；(d) GNP10/D-PUA切断后在90℃下不同愈合时间的韧性及修复效率
Figure 5. (a) Stress-strain curves of composites with different mass fractions graphene (GNP); (b) Optical microscope images of GNP10/D-PUA scratch self-healing; (c) Stress-strain curves of GNP10/D-PUA after cutting at different healing times at 90℃; (d) Toughness and repair efficiency of GNP10/D-PUA after cutting at different healing time at 90℃
图 6 具有不同填料负载量的GNP/D-PUA在90℃下划痕自修复的光学显微镜图像
Figure 6. Optical microscope images of GNP/D-PUA with different filler loadings scratch self-healing at 90℃
图 7 (a) D-PUA和 (b) GNP10/D-PUA热压回收前后的数码照片和 (c) D-PUA和 (d) GNP10/D-PUA热压回收前后的应力-应变曲线
Figure 7. Digital photos of (a) D-PUA and (b) GNP10/D-PUA before and after hot pressing recovery; stress-strain curves of (c) D-PUA and (d) GNP10/D-PUA before and after hot pressing recover
图 8 (a, b) D-PUA 和 (c, d) GNP10/D-PUA 复合材料的断面扫描电子显微镜图片
Figure 8. The fracture surface SEM images of (a, b) D-PUA and (c, d) GNP10/D-PUA
图 9 (a) 不同填料含量的GNP/D-PUA平面内导热系数; (b) GNP/D-PUA 的传热机制图; (c) 放置在加热板边缘的GNP/D-PUA复合材料的热红外图像; (d) GNP/D-PUA在散热器的LED间通电前后的红外热像图和 (e)不同时间点对应的表面温度
Figure 9. (a) The in-plane thermal conductivity of GNP/D-PUA with different stuffing contents; (b) Heat transfer mechanism diagram of GNP/D-PUA composite; (c) Thermal infrared images of GNP/D-PUA composites placed on the edge of a heating plate; (d) Infrared thermal images of GNP/D-PUA before and after power is applied between the LED of the radiator and (e) corresponding surface temperature at different time points
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