|
|
- 2018
改性石墨烯/聚(偏二氟乙烯-共-六氟丙烯)复合材料薄膜的制备与性能
|
Abstract:
采用改进Hummers法对天然鳞片石墨进行氧化和超声剥离处理制备氧化石墨烯（GO），将十三氟辛基三乙氧基硅烷（FAS）与GO反应并还原得到FAS修饰的还原氧化石墨烯（FAS-RGO）。利用溶液涂覆成膜工艺制得FAS-RGO/聚（偏二氟乙烯-共-六氟丙烯）（P（VDF-HFP））复合材料。采用FTIR、XPS、XRD、Raman和TEM表征了FAS-RGO的结构与形貌，同时研究了FAS-RGO用量对FAS-RGO/P（VDF-HFP）介电性能的影响。结果表明：FAS包覆在RGO的表面，有效解决了RGO容易团聚的问题，并且FAS的引入提高了RGO与P（VDF-HFP）的界面结合，改善了RGO在P（VDF-HFP）中的分散性，FAS-RGO还能提高P（VDF-HFP）的结晶性，促进形成β晶型。当FAS-RGO的体积分数为1.6vol%、在100 Hz频率时，FAS-RGO/P（VDF-HFP）复合材料的介电常数为62，较纯P（VDF-HFP）提高了5.2倍，同时FAS-RGO/P（VDF-HFP）复合材料的介电损耗较低。 Graphene oxide (GO) was synthesized through a modified Hummers method from graphite flakes. Then tridecafluorooctyl triethoxysilane modified reduced graphene oxide (FAS-RGO) was obtained by reducing the GO functioned with FAS. And the composite films of poly(vinylidene fluoride-co-hexafluoropropylene)(P(VDF-HFP)) incorporating FAS-RGO were prepared by a solution-cast method. FTIR, XRD, XPS, Raman and TEM were employed to characterize the structure of FAS-RGO. Meanwhile, the effect of FAS-RGO content on the dielectric property of FAS-RGO/P(VDF-HFP) was discussed. The results show that FAS layer is coated on RGO surface, which can solve the problem of accumulation of RGO effectively. FAS layer also increases interfacial combination of the FAS-RGO/P(VDF-HFP) composite films and improves the dispersion of RGO in the matrix. The FAS-RGO could nucleate the P(VDF-HFP) crystallization and induce the formation of β phase. A dielectric constant of FAS-RGO/P(VDF-HFP) is up to 62 at 100 Hz, which is 5.2 times that of pure P(VDF-HFP) film. In this case, FAS-RGO/P(VDF-HFP) composite films show low dielectric loss when the concentration of FAS-RGO is 1.6vol%. 国家自然科学基金（51273157；51773163）；湖北省自然科学基金创新群体项目（2016CF008）
| [1] | DANG Z M, YUAN J K, ZHA J W, et al. Fundamentals, processes and applications of high-permittivity polymer-matrix composites[J]. Progress in Materials Science, 2012, 57(4):660-723. |
| [2] | NAN C W, SHEN Y, MA J. Physical properties of composites near percolation[J]. Annual Review of Materials Research, 2010, 40:131-151. |
| [3] | WU C, HUANG X, WU X, et al. Graphene oxide-encapsulated carbon nanotube hybrids for high dielectric performance nanocomposites with enhanced energy storage density[J]. Nanoscale, 2013, 5(9):3847-3855. |
| [4] | KOHLMEYER R R, JAVADI A, PRADHAN B, et al. Electrical and dielectric properties of hydroxylated carbon nanotube elastomer composites[J]. The Journal of Physical Chemistry C, 2009, 113(41):17626-17629. |
| [5] | ZHANG Q M, BHARTI V, ZHAO X. Giant electrostriction and relaxor ferroelectric behavior in electron-irradiated poly (vinylidene fluoride-trifluoroethylene) copolymer[J]. Science, 1998, 280(5372):2101-2104. |
| [6] | ZHOU X, ZHAO X, SUO Z, et al. Electrical breakdown and ultrahigh electrical energy density in poly (vinylidene fluoride-hexafluoropropylene) copolymer[J]. Applied Physics Letters, 2009, 94(16):162901. |
| [7] | NING N, BAI X, YANG D, et al. Dramatically improved dielectric properties of polymer composites by controlling the alignment of carbon nanotubes in matrix[J]. RSC Advances, 2014, 4(9):4543-4551. |
| [8] | SHEHZAD K, DANG Z M, AHMAD M N, et al. Effects of carbon nanotubes aspect ratio on the qualitative and quantitative aspects of frequency response of electrical conductivity and dielectric permittivity in the carbon nanotube/polymer composites[J]. Carbon, 2013, 54:105-112. |
| [9] | FENG Q, DANG Z, LI N, et al. Preparation and dielectric property of Ag-PVA nano-composite[J]. Materials Science and Engineering B, 2003, 99(1):325-328. |
| [10] | 樊玮, 张超, 刘天西. 石墨烯/聚合物复合材料的研究进展[J]. 复合材料学报, 2013, 30(1):14-21. FAN W, ZHANG C, LIU T X. Recent progress in graphene/polymer composites[J]. Acta Materiae Compositae Sinica, 2013, 30(1):14-21(in Chinese). |
| [11] | ZHANG Y, XU D, XU W, et al. Influence of the existence of a phthalocyanine phase on the dielectric properties of ternary composites:Carbon nanotubes/phthalocyanine/poly(vinylidene fluoride)[J]. Composites Science and Technology, 2014, 104:89-96. |
| [12] | YAO S H, YUAN J K, ZHOU T, et al. Stretch-modulated carbon nanotube alignment in ferroelectric polymer composites:Characterization of the orientation state and its influence on the dielectric properties[J]. The Journal of Physical Chemistry C, 2011, 115(40):20011-20017. |
| [13] | XU X, YANG C, YANG J, et al. Excellent dielectric properties of poly(vinylidene fluoride) composites based on partially reduced graphene oxide[J]. Composites Part B:Engineering, 2017, 109:91-100. |
| [14] | HE F, LAU S, CHAN H L, et al. High dielectric permittivity and low percolation threshold in nanocomposites based on poly(vinylidene fluoride) and exfoliated graphite nanoplates[J]. Advanced Materials, 2009, 21(6):710-715. |
| [15] | FAN P, WANG L, YANG J, et al. Graphene/poly(vinylidene fluoride) composites with high dielectric constant and low percolation threshold[J]. Nanotechnology, 2012, 23(36):365702. |
| [16] | WANG D, BAO Y, ZHA J W, et al. Improved dielectric properties of nanocomposites based on poly(vinylidene fluoride) and poly(vinyl alcohol)-functionalized graphene[J]. ACS Applied Materials & Interfaces, 2012, 4(11):6273-6279. |
| [17] | 王明路, 宁南英, 张静, 等. 氧化石墨烯核-壳杂化粒子/硅橡胶介电弹性体复合材料的制备与性能[J]. 复合材料学报, 2016, 33(6):1192-1197. WANG M L, NING N Y, ZHANG J, et al. Preparation and property of graphene oxide core-shell hybrid particles/silicone rubber dielectric elastomer composites[J]. Acta Materiae Compositae Sinica, 2016, 33(6):1192-1197(in Chinese). |
| [18] | FERRARI A C, BASKO D M. Raman spectroscopy as a versatile tool for studying the properties of graphene[J]. Nature Nanotechnology, 2013, 8(4):235-246. |
| [19] | CHU L, XUE Q, SUN J, et al. Porous graphene sandwich/poly(vinylidene fluoride) composites with high dielectric properties[J]. Composites Science and Technology, 2013, 86:70-75. |
| [20] | TANG H, EHLERT G J, LIN Y, et al. Highly efficient synthesis of graphene nanocomposites[J]. Nano Letters, 2011, 12(1):84-90. |
| [21] | TONG W, ZHANG Y, YU L, et al. Novel method for the fabrication of flexible film with oriented arrays of graphene in poly(vinylidene fluoride-co-hexafluoropropylene) with low dielectric loss[J]. The Journal of Physical Chemistry C, 2014, 118(20):10567-10573. |
| [22] | TOMER V, MANIAS E, RANDALLl C A. High field properties and energy storage in nanocomposite dielectrics of poly (vinylidene fluoride-hexafluoropropylene)[J]. Journal of Applied Physics, 2011, 110(4):044107. |
| [23] | AN N, LIU S, FANG C, et al. Preparation and properties of β-phase graphene oxide/PVDF composite films[J]. Journal of Applied Polymer Science, 2015, 132(10):41577. |
| [24] | WANG Y, LIU J, LIU L, et al. High-quality reduced graphene oxide-nanocrystalline platinum hybrid materials prepared by simultaneous co-reduction of graphene oxide and chloroplatinic acid[J]. Nanoscale Research Letters, 2011, 6(1):241. |
| [25] | HAN K, LI Q, CHEN Z, et al. Suppression of energy dissipation and enhancement of breakdown strength in ferroelectric polymer-graphene percolative composites[J]. Journal of Materials Chemistry C, 2013, 1(42):7034-7042. |
| [26] | HUANG L, LU C, WANG F, et al. Piezoelectric property of PVDF/graphene composite films using 1H, 1H, 2H, 2H-Perfluorooctyltriethoxysilane as a modifying agent[J]. Journal of Alloys and Compounds, 2016, 688:885-892. |
| [27] | HUMMERS J W S, OFFEMAN R E. Preparation of graphitic oxide[J]. Journal of the American Chemical Society, 1958, 80(6):1339. |
| [28] | HERMANSON G T. Bioconjugate techniques[M]. San Diego:Academic Press, 1996. |
| [29] | LI W, TANG X Z, ZHANG H B, et al. Simultaneous surface functionalization and reduction of graphene oxide with octadecylamine for electrically conductive polystyrene com-posites[J]. Carbon, 2011, 49(14):4724-4730. |
| [30] | 黄文斌. 聚苯乙烯接枝石墨烯及其聚合物复合材料的制备与性能研究[D]. 成都:西南交通大学, 2016. HUANG W B. Study on preparation of polystyrene grafted graphene and properties of its polymer composites[D]. Chengdu:Southwest Jiaotong University, 2016(in Chinese). |
