Preparation of High Toughness Polymer Composites with Self-Healing Capacity via Non-Covalent Bonding
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摘要: 以鞣花酸（ELA）改性氧化石墨烯（EGO）作为“砖”、聚氨酯（PU）作为“泥”，并引入非共价键，通过蒸发诱导自组装制备了可修复仿珍珠层复合材料（PU-EGO）。利用红外光谱、电位分析仪、X射线衍射仪等对EGO结构进行表征，通过万能试验机对PU-EGO的力学性能进行测试。结果表明：ELA吸附于GO表面，且当PU与EGO质量比为3∶1时，PU-EGO的拉伸强度和韧性分别达到111.2 MPa和81.5 MJ/m3（相比PU分别提高了9.6倍和1.8倍）。此外，所制备的材料还具备良好的自修复性和重复加工性能。Abstract: Interfaces between nacreous tablets are crucial to the outstanding mechanical properties of nacre in natural shells and inspired by the “brick-and-mortar” structure and remarkable mechanical performance of nacre. Excellent research has been conducted to probe the effect of interfaces on strength and toughness of nacre, providing critical guidelines for the design of human-made laminated composites. Herein, a class of graphene oxide (GO) based artificial nacre composite material with self-healing capacity due to non-covalent bonding interactions was fabricated by functionalization of GO with ellagic acid through π-π stacking followed by evaporation-induced self assembling process between ellagic acid modified graphene oxide(EGO) and polyurethane(PU). The artificial nacre displays a strict “brick-and-mortar” structure, with EGO nanosheets as the brick and PU as the mortar. The structure of EGO was characterized by infrared spectroscopy, potential analyzer and X-ray diffraction, and the mechanical properties of PU-EGO were tested by universal testing machine. The results show that ellagic acid (ELA) is successfully adsorbed on GO surface, and when the mass ratio of PU to EGO is 3∶1, the tensile strength and toughness of the material reach 111.2 MPa and 81.5 MJ/m3, respectively (9.6 times and 1.8 times higher than that of PU), attributing to the interlayer slip of GO by breaking and recombing the π-π bond dynamically through which the energy can dissipate when PU-EGO is subjected to tensile stress. In addition, owning to the existence of non-covalent bonds, the resulting polymer composites display good recyclability. This work provides a pathway for the development of artificial nacre with self-healing capacity and recyclability.
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Key words:
- ellagic acid /
- graphene-oxide /
- polyurethane /
- high toughness /
- self-healing /
- "brick and mortar" structure
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图 3 (a) GO的透射电镜照片; (b) GO、PU、ELA和EGO的FT-IR谱图；(c)GO和EGO的Zeta电位图
Figure 3. (a) TEM image of GO; (b) FT-IR spectra of GO, PU, ELA and EGO; (c) Zeta potentials of GO and EGO
图 4 (a)GO、ELA和EGO的XRD谱图；(b)ELA和EGO的TGA曲线
Figure 4. (a) XRD patterns of GO, ELA and EGO; (b) TGA curves of ELA and EGO
图 5 (a) PU-EGO的SEM照片; (b) PU、EGO、PA、PU-GO和PU-EGO的红外谱图
Figure 5. (a) SEM image of PU-EGO; (b) FT-IR spectra of PU, EGO, PA, PU-GO and PU-EGO
图 6 (a)PU、PU-GO和PU-EGO的应力-应变曲线；(b)PU-EGO的受力示意图
Figure 6. (a) Stress-strain curves of PU, PU-GO and PU-EGO; (b) Schematic illustration of PU-EGO under stress
图 7 PU-EGO(a)回收前后及(b)修复前后应力-应变曲线; (c)水修复过程示意图
Figure 7. Stress-strain curves of PU-EGO before and after (a) recycled and (b) self-healed; (c) Schematic illustration of water-assisted self-healing process
表 1 样品的拉伸强度、断裂伸长率和韧性
Table 1. Stress, elongation at break and toughness of samples
Sample Stress/MPa Elongation at break/% Toughness/（MJ·m−3） PU 11.6 363 45.6 PU-GO(5∶1) 43.1 176 61.1 PU-EGO(5∶1) 63.5 262 123.1 PU-GO(3∶1) 63.3 45 19.7 PU-EGO(3∶1) 111.2 97 81.5 
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