石墨烯/聚乙烯醇/聚偏氟乙烯基纳米复合薄膜的介电性能

冯奇; 李梦凯; 唐海通; 王晓东; 高忠民; 孟繁玲

doi:10.7498/aps.65.188101

摘要

石墨烯由于具有良好的力学性能、高的电子传递能力以及相对较低的生产成本等优势而受到广泛关注，但现在多将其直接分散在聚合物中提高聚合物的介电性能. 本工作中，制备出了还原氧化石墨烯/PVA/聚偏氟乙烯（PVDF）的三相纳米复合薄膜. 首先把聚乙烯醇（PVA）和氧化石墨烯（GO）分散于二甲基亚砜（DMSO）中，得到PVA非共价键修饰的GO，再将PVDF溶于该混合液体中，通过溶液浇注以及低温加热过程得到三相纳米复合薄膜. 实验结果表明，在120 ℃ 下，GO可以被热还原成还原氧化石墨烯（RGO），且可以促进PVDF 的相向相转变. PVA修饰RGO比单纯RGO在PVDF基体中分散性要好，且使PVDF的球晶尺寸大大降低，复合薄膜的介电性能大幅提高. RGO/PVA/PVDF复合膜的渗流阈值fvol*约为8.45 vol.%，在102 Hz时RGO/PVA/PVDF复合膜的介电常数大约是纯PVDF的238倍. 本工作为制备介电性能高、生产成本低、操作简单的聚合物纳米复合材料提供了一种好的方法.

关键词:

Abstract

Graphene has been a superstar in the fields ranging from materials science to condensed-matter physics since 2004. Graphene possesses good thermal and mechanical properties, high electron transfer capability and relatively low production cost. As a consequence, graphene has been used in the areas of multi-functional advanced materials and electronics. A direct disperse method has been widely applied to polymers to improve their dielectric properties. Recently, graphene/polymer composites have received much attention. Graphene nanosheets can significantly improve the physical properties of the host polymer at a very low content of conductive filler loading. Poly vinylidene fluoride (PVDF) is a semicrystalline thermoplastic polymer with remarkably high piezo-/pyroelectric coefficient, and excellent thermal stability and chemical resistance. More efforts have been recently devoted to the preparations of high-' composites based on PVDF. In this work, a graphene/PVA/PVDF nanocomposite film composed of poly(vinyl alcohol) (PVA), reduced graphene oxide (RGO), and poly (vinylidene fluoride) (PVDF) is fabricated. First of all, graphene oxide (GO) is prepared by the modified Hummers method. GO and PVA are successively dissolved in the dimethyl sulfoxide (DMSO) solution, in order to obtain PVA functionalized GO which is formed via non-covalent bonds. Then PVDF is added into this solution to form a homogeneous three-phase aqueous mixture. According to the solution-casting and thermal reduction processes, the three-phase nanocomposite films are formed. The thickness values of the films are in a range of 0.3-0.4 mm. The square specimens are coated with a silver paste prior to electrical measurements. The obtained products are characterized using X-ray diffraction, UV Vis absorption spectrum, Fourier transform infrared absorption spectrum, and atomic force microscopy. The morphologies of PVDF and RGO/PVA/PVDF films are investigated by a scanning electron microscope. Electrical measurements are conducted in a frequency range from 102 to 104 Hz. Results suggest that GO can be reduced to RGO and phase transition of PVDF from to phases is effectively promoted at 120 ℃. The dielectric properties of the polymer matrix are improved. Furthermore, PVA modified RGO is easier to disperse in the PVDF substrate than the original one, which strongly reduces the spherulite size of PVDF and improves the dielectric property of the composite film. The percolation threshold (fvol*) of RGO/PVA/PVDF film is estimated to be 8.45 vol.%, and the dielectric constant of the film is 238 times as large as that of the pure PVDF films at 102 Hz. In addition, the dielectric constant increases rapidly near the percolation threshold and depends on frequency, which is mainly ascribed to the Maxwell-Wagner-Sillars polarization in the low frequency range. This study provides a low-cost and simple method of preparing polymer nanocomposites with high dielectric properties.

Keywords:

作者及机构信息

1.
吉林大学材料科学系, 教育部汽车材料重点实验室, 长春 130012;

2.
吉林省计量科学研究院, 长春 130103;

3.
吉林大学无机合成与制备化学国家重点实验室, 长春 130012

通信作者: 孟繁玲, mfl@jlu.edu.cn

基金项目: 国家重大科学仪器设备开发专项（批准号：2012YQ24026407）资助的课题.

Authors and contacts

1.
Key Laboratory of Automobile Materials of Ministry of Education, Department of Materials Science, Jilin University, Changchun 130012, China;

2.
Jilin Institute of Metrology and Research, Changchun 130103, China;

3.
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130012, China

Corresponding author: Meng Fan-Ling, mfl@jlu.edu.cn

Funds: Project supported by the National Key Scientific Instrument and Equipment Development Project of China (Grant No. 2012YQ24026407).

参考文献

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施引文献

[1]	Zhang T, Xue Q Z, Zhang S, Dong M D 2012 Nano Today 7 180
[2]	Naber R C G, Tanase C, Blom P W M, Gelinck G H, Marsman A W, Touwslager F J, Setayesh S, Leeuw D M D 2005 Nat. Mater. 4 243
[3]	Zheng W, Lu X, Wang W, Wang Z, Song M, Wang Y, Wang C 2010 Phys. Status Solidi A 207 1870
[4]	Li J C, Wang C L, Zhong W L, Xue X Y, Wang Y X 2002 Acta Phys. Sin. 51 776 (in Chinese) [李吉超, 王春雷, 钟维烈, 薛旭艳, 王渊旭 2002 物理学报 51 776]
[5]	Wang X D, Wang P, Wang J L, Hu W D, Zhou X H, Cuo N, Huang H, Sun S, Shen H, Lin T, Tang M H, Liao L, Jiang A Q, Sun J L, Meng X J, Chen X S, Lu W, Chu J H 2015 Adv. Mater. 27 6575
[6]	Zheng D S, Wang J L, Hu W D, Liao L, Fang H H, Guo N, Wang P, Gong F, Wang X D, Fan Z Y, Wu X, Meng X J, Chen X S, Lu W 2016 Nano Lett. 16 2548
[7]	Dang Z M, Lin Y H, Nan C W 2003 Adv. Mater. 15 1625
[8]	Dang Z M, Wang L, Yin Y, Zhang Q, Lei Q Q 2007 Adv. Mater. 19 852
[9]	Novoselov K S, Jiang Z, Zhang Y, Morozov S V, Stormer H L, Zeitler U, Maan J C, Boebinger G S, Kim P, Geim A K 2007 Science 315 1379
[10]	Zhang H J, Shen P 2013 Physics 42 456(in Chinese) [张海婧, 沈平2013 物理42 456]
[11]	Yang S D, Chen L 2015 Chin. Phys. B 24 118104
[12]	Hirata M, Gotou T, Horiuchi S, Fujiwara M, Ohba M 2004 Carbon 42 2929
[13]	Zhang G, Huang S Y 2013 Physics42 100 (in Chinese)[张刚, 黄少云2013 物理42 100]
[14]	Ding G W, Liu S B, Zhang H F, Kong X K, Li H M, Li B X, Liu S Y, Li H 2015 Chin. Phys. B 24 118103
[15]	Chae H K, Siberio-Prez D Y, Kim J, Go Y, Eddaoudi M, Matzger A J, O'Keeffe M, Yaghi O M 2004 Nature 427 523
[16]	Berger C, Song Z M, Li T B, Li X B, Ogbazghi A Y, Feng R, Dai Z T, Marchenkov A N, Conrad E H, First P N, Heer W A D 2004 J. Phys. Chem. B 108 19912
[17]	Ansari S, Giannelis E P 2009 J. Polym. Sci. Pol. Phys. 47 888
[18]	Wang D R, Bao Y R, Zha J W, Zhao J, Dang Z M, Hu G H 2012 ACS Appl. Mater. Interfaces 4 6273
[19]	Chu L Y, Xue Q Z, Sun J, Xia F J, Xing W, Xia D, Dong M D 2013 Compos. Sci. Technol. 86 70
[20]	Cho S H, Lee J S, Jang J 2015 ACS Appl. Mater. Interfaces 7 9668
[21]	Tang H X, Ehlert G J, Lin Y R, Sodano H A 2012 Nano Lett. 12 84
[22]	Liu H Y, Zheng Y L, Peng S G, Liu J C, Zhang Y Q 2014 New Chem. Mater. 42 1 (in Chinese) [刘红宇, 郑英丽, 彭淑鸽, 刘继纯, 张玉清2014 化工新型材料42 1]
[23]	Daniela C M, Kosynkin D V, Berlin J M, Sinitskii A, Sun Z Z, Slesarev A, Alemany L B, Lu W, Tour J M 2010 ACS Nano 4 4806
[24]	Zhao X, Zhang Q H, Hao Y P, Li Y Z, Fang Y, Chen D J 2010 Macromolecules 43 9411
[25]	Li D, Muller B M, Gilje S, Kaner R B, Wallace G G 2008 Nat. Nanotechnol. 3 101
[26]	Salimi A, Youseli A A 2003 Polym. Test. 22 699
[27]	Gregorio R, J R, Uneo E M 1999 J. Mater. Sci. 34 4489
[28]	Li J C, Wang C L, Zhong W L 2003 Acta Phys. -Chim. Sin. 19 1010 (in Chinese) [李吉超, 王春雷, 钟维烈 2003 物理化学学报 19 1010]
[29]	He F, Lau S T, Chan H L, Fan J T 2009 Adv. Mater. 21 710
[30]	Nan C W 1993 Prog. Mater. Sci. 37 1
[31]	Li Y J, Xu M, Feng J Q, Dang Z M 2006 Appl. Phys. Lett. 89 072902

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