不同石墨烯-碳纳米管杂化体系对热塑性聚氨酯复合材料力学和自修复性能的增强机制

doi:10.7503/cjcu20170384

摘要/Abstract

摘要：

采用溶液共混法, 设计不同的杂化方案, 制备了3种具有不同复合程度的石墨烯(G)和碳纳米管(CNT)三维空间结构材料, 并对G-CNT填充的热塑性聚氨酯(TPU)复合材料的力学性能及在微波诱导下的裂纹自修复特性进行了研究. 结果表明, G-CNT复合结构能改善增强相与基体间的界面结合及载荷传递, 且复合程度越高其对TPU力学增强效果越显著. 当采用预复合方法时G-CNT复合程度最高, 此时TPU复合材料的拉伸强度比纯TPU提高了37.6%, 比G/TPU提高了27.1%. TPU复合材料在微波场的诱导下可实现损伤裂纹的快速修复, 然而其修复效率并未随着G-CNT复合程度的增加而升高, 当采用超声复合时, G-CNT的复合程度低于预复合法的复合程度, 但其修复率却达到最高值(138%). 该自修复特性和G-CNT的空间构型及其异质界面与微波之间的耦合机制密切相关.

关键词: 自修复性能, 石墨烯, 碳纳米管, 微波, 拉伸强度, 热塑性聚氨酯, 力学性能

Abstract:

Three different hybridization degrees of the three dimensional structure of graphene-carbon nanotube(G-CNT) were prepared by the different experimental schemes. The research on the mechanical property of the thermoplastic polyurethane(TPU) composites reinforced by this three-dimensional hybrid structure of the G-CNT, and the behavior of self-healing of the damaged TPU composites was carried out. The results show that the three dimensional hybrid structure of G-CNT can effectively promote the load transfer between the reinforcing phase and the TPU matrix, and can improve the mechanical properties of the TPU composites. It also shows that the higher the hybridization degree of G-CNT, the more the enhancement effect will be. When the G-CNT was prepared by the pre-hybridization method, it achieved the highest hybridization degree. And the mechanical properties of the corresponding composite G-CNT/TPU achieved the highest value that equals to 61.95 MPa. It is about 37.6% higher than the pure TPU and 27.10% higher than the G/TPU composite. Meanwhile, it shows that these composites can realize the self-healing of the crack induced by the microwave electromagnetic fields. The tensile strength of these healed samples were even higher than that of their original samples. However, their healing efficiency does not increase as the hybridization degree of G-CNT increased. For example, as for the composite of G-CNT/TPU that prepared by the ultrasonic hybrid method, the hybridization degree of G-CNT is less than that prepared by the pre-hybrid method, but its healing efficiency achieved the highest that equals to 138%. This self-healing characteristic has important relationship with the spatial structure of the 3D G-CNT and the coupling mechanisms between microwave and the heterogeneous interface within G-CNT.

Key words: Self-healing property, Graphene, Carbon nanotube, Microwave, Tensile strength, Thermoplastic polyurethane, Mechanical property

中图分类号:

O631

TrendMD:

高飞龙, 李永存, 栾云博, 薛志成, 郭章新, 张祺, 吴桂英. 不同石墨烯-碳纳米管杂化体系对热塑性聚氨酯复合材料力学和自修复性能的增强机制. 高等学校化学学报, 2018, 39(4): 832.

GAO Feilong, LI Yongcun, LUAN Yunbo, XUE Zhicheng, GUO Zhangxin, ZHANG Qi, WU Guiying. Enhancement Mechanisms of Mechanical and Self-Healing Properties of Thermoplastic Polyurethane Composites Induced by Different G-CNT Hybridization Systems^†. Chem. J. Chinese Universities, 2018, 39(4): 832.

图/表 7

Fig.1 SEM images of G/TPU(A, A'), G/TPU+CNT/TPU(B, B'), G-CNT/TPU(C, C ') and G+CNT/TPU(D, D') with grapheme sheets(A), mechanical(B), ultrasonic(C) and pre-composite(D)(A')-(D') SEM images after loading and breaking.

Fig.2 Tensile strength(A) and stress-strain(B) of pure TPU(a), G/TPU(b), G/TPU+CNT/TPU(c),G-CNT/TPU(d) and G+CNT/TPU(e)

Fig.3 Mesoscopic model diagram and interface load transfer mechanism diagram of four kinds of TPU compositesRepresent representative elements of five kind of TPU materials: (A) pure TPU; (B) G/TPU; (C) G/TPU+CNT/TPU; (D) G-CNT/TPU; (E) G+CNT/TPU. Represent deformable diagram of four kinds of TPU composites under external load; (F) G/TPU; (G) G/TPU+CNT/TPU; (H) G-CNT/TPU; (I) G+CNT/TPU. Represent deformable diagram of half of the RVE model of four kinds of TPU composites under external load: (J) G/TPU; (K) G/TPU+CNT/TPU; (L) G-CNT/TPU; (M) G+CNT/TPU. Represent partial enlarged drawing of interface morphologies of four kinds of TPU composites: (N) G/TPU; (O) G/TPU+CNT/TPU; (P) G-CNT/TPU; (Q) G+CNT/TPU.

Fig.4 SEM images of damaged G-CNT/TPU composites before(A) and after(B) microwave healing

Fig.5 Tensile strength of different TPU composites before and after microwave healinga. Pure TPU; b. G/TPU; c. G/TPU+CNT/TPU; d. G-CNT/TPU; e. G+CNT/TPU.

Fig.6 Schematic diagram of microwave healing mechanisms

Fig.7 Microwave healing mechanisms of G/TPU+CNT/TPU(A), G-CNT/TPU(B) and G+CNT/TPU(C)

参考文献 29

[1]	White S. R., Sottos N. R., Geubelle P. H., Moore J. S., Kessler M. R., Sriram S. R., Brown E. N., Viswanathan S., Nature,2001, 409(6822), 794-797
[2]	Ye X. J., Song Y. X., Zhu Y., Yang G. C., Rong M. Z., Zhang M. Q., Composites Science and Technology,2014, 104(104), 40-46
[3]	Dry C., Composite Structures, 1996, 35(3), 263-269
[4]	Chen X., Wudl F., Mal A. K., Shen H., Nutt S. R., Macromolecules,2003, 36, 1802-1807
[5]	Chen X., Dam M. A., Ono A., Mal A., Shen H., Nutt S. R., Sheran K., Wudl F., Science,2002, 295(5560), 1698-1702
[6]	Cordier P., Tournilhac F., Soulié-Ziakovic C., Leibler L., Nature,2008, 451(7181), 977-980
[7]	Kallista S. J., Ward T. C., Journal of the Royal Society Interface,2007, 4(13), 405-411
[8]	Burattini S., Colquhoun H. M., Fox J. D., Friedmann D., Greenland B. W., Harris P. J. F., Hayes W., Mackay M. E., Rowan S. J.,Chemical Communications, 2009, 6717-6719
[9]	Zhang M. M., Xu D. H., Yan X. Z., Chen J. Z., Dong S. Y., Zheng B., Huang F. H., Angewandte Chemie, 2012, 51(28), 7117-7121
[10]	Roy S., Srivastava S. K., Pionteck J., Mittal V., Macromolecular Materials and Engineering,2015, 300(3), 346-357
[11]	Kong L., Yin X., Yuan X., Zhang Y., Liu X., Cheng L., Zhang L., Carbon,2014, 73(73), 185-193
[12]	Zhang B., Asmatulu R., Soltani S. A., Le L. N., Journal of Applied Polymer Science,2014, 131(19), 453-461
[13]	Roumeli E., Pavlidou E., Bikiaris D., Chrissafis K., Carbon,2014, 67(2), 475-487
[14]	Cao N. N., Zheng Y. Y., Fan Z. M., Wang X.,Acta Polymerica Sinica, 2015, (8), 963-972
	(曹宁宁, 郑玉婴, 樊志敏, 王翔. 高分子学报, 2015, (8), 963-972 )
[15]	Liu Y. H., Lin Y. Y., Zhang D. G., Chen C. L., Wu G. Z., Zhang Y. Y., Luan W. L., Chem. J. Chinese Universities, 2016, 37(7), 1402-1407
	(刘尧华, 林摇宇, 张栋葛, 陈春蕾, 吴国章, 张摇衍, 栾伟玲. 高等学校化学学报, 2016, 37(7), 1402-1407)
[16]	Zhou T., Zha J. W., Hou Y., Wang D., Zhao J., Dang Z. M., ACS Applied Materials and Interfaces,2011, 3(12), 4557-4560
[17]	Li D., Muller M. B., Gilje S., Kaner R. B., Wallace G. G., Nature Nanotechnology, 2008, 3(2), 101-105
[18]	Yang S. Y., Lin W. N., Huang Y. L., Tien H. W., Wang J. Y., Ma C. C., Li S. M., Wang Y. S., Carbon,2011, 49(3), 793-803
[19]	Liu L. L., Zhao D. X., Yang Z. Z., Chem. Res. Chinese Universities, 2015, 31(5), 878-884
[20]	Zhang C., Ren L. L., Wang X. Y., Liu T. X., Chemical Physics, 2010, 114, 11435-11440
[21]	Romano M. S., Li N., Antiohos D., Razal J. M., Nattestad A., Beirne S., Advanced Materials, 2013, 25, 6602-6606
[22]	Gouda P. S. S, Kulkarni R., Kurbet S. N., Jawali D., Advanced Materials Letters, 2013, 4(4), 261-270
[23]	Wang P. N., Hsieh T. H., Chiang C. L., Shen M. Y., Journal of Nanomaterials, 2015, 2015, 1-9
[24]	Pradhan B., Srivastava S. K., Polymer International, 2014, 63(7), 1219-1228
[25]	Sadasivuni K. K., Ponnamma D., Kumar B., Strankowski M., Cardinaels R., Moldenaers P., Thomas S., Grohens Y., Composites Science and Technology,2014, 104, 18-25
[26]	Liu S., Tian M., Yan B. Y., Yao Y., Zhang L. Q., Nishi T., Ning N. Y., Polymer,2015, 56, 375-384
[27]	Gu Z. L., Mechanics of Short Fiber Composites, National Defense Industry Press, Beijing, 1987, 97-149
	(顾震隆. 短纤维复合材料力学, 北京: 国防工业出版社, 1987, 97-149)
[28]	Peng Z. H., Peng Y. F., Ning Y. T., Peng J. C., Guo Y. H., Henan Science, 2010, 12, 1526-1529
	(彭志华, 彭延峰, 宁艳桃, 彭景翠, 郭燕春. 河南科学, 2010, 12, 1526-1529)
[29]	Zhao D. L., Shen Z. M., Journal of Inorganic Materials, 2005, 20(3), 608-612
	(赵东林, 沈曾民. 无机材料学报, 2005, 20(3), 608-612)