Thermal Reduced Graphene Oxide/Polyimide Nanocomposite Coating: Fabrication and Anticorrosive Property

doi:10.15541/jim20160699

Abstract

Abstract:

Thermal reduced graphene oxide (TRGO) was incorporated into polyimide (PI) matrix as two-dimensional nanofillers and TRGO/PI nanocomposite anticorrosive coatings were fabricated. Then AC impedance spectroscopy and dynamic potential polarization curves were adopted to evaluate the electrochemical corrosion behavior of the obtained coatings in simulated seawater (3.5wt% NaCl solution). The results show that the addition of TRGO significantly improves the coating resistance and corrosion protection efficiency compared with pure PI coating. Besides, the TRGO/PI composite coating with the addition of 0.3wt% TRGO shows the most excellent anticorrosive property, with the maximum coating resistance of 1.3176×10⁶ Ω and the highest corrosion protection efficiency of 99.65%. The enhanced anticorrosive property can be attributed to the physical barrier properties of the TRGO with lamellar structure.

Key words: graphene,, polyimide,, anticorrosive,, composite, coating

CLC Number:

TQ174

JIA Ying-Kun, CHEN Pei, ZHANG Qing-Hong, SUN Jing. Thermal Reduced Graphene Oxide/Polyimide Nanocomposite Coating: Fabrication and Anticorrosive Property[J]. Journal of Inorganic Materials, 2017, 32(12): 1257-1263.

Figures/Tables 12

Fig. 1 TEM (a) and AFM images (b-c) of GO sheets

Fig. 2 XRD patterns (a) and Raman spectra (b) of GO and thermal reduced graphene oxide (TRGO)

Fig. 3 Pictures of TRGO dispersions with varying concentrations^(a) 0.17 mg/mL; (b) 0.33 mg/mL; (c) 0.50 mg/mL; (d) 0.66 mg/mL; (e) 0.83 mg/mL

Fig. 4 SEM micrographs of fractured surfaces of (a,b) neat PI and (c,d) TRGO0.1/PI coatings

Fig. 5 (a) Bode phase plots, (b) Bode modulus plots and (c) Nyquist plots of different coatings

Fig. 6 Equivalent circuit used in the fitting process

Table 1 Fitting results for pure PI and TRGO/PI coatings

Samples	R_s/Ω	CPE_dl-T/F	CPE_dl-P/F	R_c/Ω
Pure PI	1279	2.7060×10^-6	0.7721	1.6081×10⁵
TRGO0.1/PI	1290	1.6952×10^-6	0.6325	5.6110×10⁵
TRGO0.2/PI	1064	6.2072×10^-7	0.7235	9.6912×10⁵
TRGO0.3/PI	1136	6.0883×10^-7	0.7442	1.3176×10⁶
TRGO0.4/PI	1249	2.3677×10^-6	0.7022	3.6245×10⁵
TRGO0.5/PI	1002	3.9181×10^-6	0.6605	3.0603×10⁵

Fig. 7 Comparison of experimental data and fitting curves for (a) TRGO0.1/PI, (b) TRGO0.4/PI composite coatings

Fig. 8 Coating resistance and Bode modulus at 0.1 Hz as a function of the SRGO content in TRGO/PI composite coating

Fig. 9 Tafel plots of bare steel, pure PI and TRGO/PI coatings

Fig. 10 Optical images of (a) TRGO0.1/PI and (b) TRGO0.5/PI coated 304SS after testing for adhesion

Table 2 Corrosion parameters of bare 304SS, pure PI, TRGO/PI-coated 304SS electrodes immersed in 3.5 wt% NaCl solution after 6 h

Sample	E_corr/V	I_corr/(A·cm^-1)	b_a/(mV·dec^-1)	b_c/(mV·dec^-1)	R_p/(kΩ·cm²)	Thickness/μm	P_EF/%
Bare steel	-0.53	1.319×10^-4	11	4423	0.744	-	-
Pure PI	-0.40	1.490×10^-6	1408	5960	36.931	1.30	98.87
TRGO0.1/PI	-0.31	8.513×10^-7	4312	5946	49.785	1.30	99.35
TRGO0.2/PI	-0.28	6.199×10^-7	1145	7123	108.823	1.30	99.53
TRGO0.3/PI	-0.24	4.616×10^-7	3036	8532	158.105	1.30	99.65
TRGO0.4/PI	-0.34	5.865×10^-7	2800	5227	96.969	1.30	99.56
TRGO0.5/PI	-0.36	1.070×10^-6	3463	5388	44.839	1.30	99.19

References 31

[1]	NINE M J, COLE M A, TRAN O N H, et al. Graphene: a multipurpose material for protective coatings. J. Mater. Chem. A, 2015, 3(24): 12580-12602.
[2]	KUANG D, HU W.Research progress of graphene composites. J. Inorg. Mater., 2013, 28(3): 235-246.
[3]	ZHU Y, MURALI S, CAI W, et al.Graphene and graphene oxide: synthesis, properties, and applications. Adv. Mater., 2010, 22(35): 3906-3924.
[4]	LEENAERTS O, PARTOENS B, PEETERS F M. Graphene: a perfect nanoballoon. Appl. Phys. Lett., 2008, 93(19): 193107-1-4.
[5]	BUNCH J S, VERBRIDGE S S, ALDEN J S, et al.Impermeable atomic membranes from graphene sheets. Nano Lett., 2008, 8(8): 2458-2462.
[6]	NAIR R R, WU H A, JAYARAM P N, et al.Unimpeded permeation of water through helium-leak-tight graphene-based membranes. Science, 2012, 335(6067): 442-444.
[7]	CHEN S, BROWN L, LEVENDORF M, et al.Oxidation resistance of graphene-coated Cu and Cu/Ni alloy. ACS Nano, 2011, 5(2): 1321-1327.
[8]	PRASAI D, TUBERQUIA J C, HARL R R, et al.Graphene: corrosion-inhibiting coating. ACS Nano, 2012, 6(2): 1102-1108.
[9]	SCHRIVER M, REGAN W, W J GANNETT, et al. Graphene as a long-term metal oxidation barrier: worse than nothing. ACS Nano, 2013, 7(7): 5763-5768.
[10]	COMPTON O C, KIM S, PIERRE C, et al.Crumpled graphene nanosheets as highly effective barrier property enhancers. Adv. Mater., 2010, 22(42): 4759-4763.
[11]	YANG Y H, BOLLING L, MORGAN A, et al.Super gas barrier and selectivity of graphene oxide-polymer multilayer thin films. Adv. Mater., 2013, 25(4): 503-508.
[12]	KIM H, MIURA Y, MACOSKO C W.Graphene/polyurethane nanocomposites for improved gas barrier and electrical conductivity.Chem. Mater., 2010, 22(11): 3441-3450.
[13]	YOUSEFI N, GUDARZI M M, ZHENG Q, et al.Highly aligned, ultralarge-size reduced graphene oxide/polyurethane nanocomposites: mechanical properties and moisture permeability. Compos. Part A-Appl. S., 2013, 49(6): 42-50.
[14]	李雅雅. 石墨烯增强水性聚氨酯复合涂层及其对钢铁表面的腐蚀防护. 上海: 上海理工大学硕士学位论文, 2013.
[15]	LI Y, YANG Z, QIU H, et al.Self-aligned graphene as anticorrosive barrier in waterborne polyurethane composite coatings. J. Mater. Chem. A, 2014, 2(34): 14139.
[16]	CHANG C H, HUANG T C, PENG C W, et al.Novel anticorrosion coatings prepared from polyaniline/graphene composites. Carbon, 2012, 50(14): 5044-5051.
[17]	YU Y H, LIN Y Y, LIN C H, et al.High-performance polystyrene/ graphene-based nanocomposites with excellent anti-corrosion properties. Poly. Chem., 2014, 5(2): 535-550.
[18]	CHEN S, ZHU J, WU X, et al.Graphene oxide MnO2 nanocomposites for supercapacitors. ACS Nano, 2010, 4(11): 2822-2830.
[19]	SU C Y, XU Y, ZHANG W, et al.Electrical and spectroscopic characterizations of ultra-large reduced graphene oxide monolayers. Chem. Mater., 2009, 21(23): 5674-5680.
[20]	LI M X, ZHU J E, ZHANG L L, et al.Facile synthesis of NiAl-layered double hydroxide/graphene hybrid with enhanced electrochemical properties for detection of dopamine. Nanoscale, 2011, 3(10): 4240-4246.
[21]	LI H, ZHU G, LIU Z H, et al.Fabrication of a hybrid graphene/layered double hydroxide material. Carbon, 2010, 48(15): 4391-4396.
[22]	LUO D, ZHANG G, LIU J, et al.Evaluation criteria for reduced graphene oxide. J. Phys. Chem. C, 2011, 115(23): 11327-11335.
[23]	TAI Z, YAN X, XUE Q.Shape-alterable and -recoverable graphene/ polyurethane bi-layered composite film for supercapacitor electrode. J. Power Source, 2012, 213: 350-357.
[24]	JI Z Y, SHEN X P, ZHU G X, et al.Reduced graphene oxide/nickel nanocomposites: facile synthesis, magnetic and catalytic properties. J. Mater. Chem., 2012, 22(8): 3471-3477.
[25]	曹楚南; 张鉴清. 电化学阻抗谱导论. 北京: 科学出版社, 2002.
[26]	CHI M, LI F, ZHOU M, et al.Synthesis and anticorrosive properties of a novel electroactive polyurea containing oligoaniline pendants. Colloid Polym. Sci., 2015, 293(8): 2217-2227.
[27]	SCULLY J R.Electrochemical impedance of organic-coated steel: correlation of impedance parameters with long-term coating deterioration. J. Electro. Chem. Soc., 1989, 136(4): 979-990.
[28]	GU L, LIU S, ZHAO H, et al.Facile preparation of water¬dispersible graphene sheets stabilized by carboxylated oligoanilines and their anticorrosion coatings. ACS Appl. Mater. Interfaces, 2015, 7(32): 17641-17648.
[29]	AMIRUDIN A, THIENY D.Application of electrochemical impedance spectroscopy to study the degradation of polymer-coated metals. Prog. Org. Coat., 1995, 26(1): 1-28.
[30]	LIU J, GONG G, YAN C, et al.EIS study of corrosion behaviour of organic coating/Dacromet composite systems. Electrochim. Acta, 2005, 50(16): 3320-3332.
[31]	CHANG K C, HSU C H, LU H I, et al.Advanced anticorrosive coatings prepared from electroactive polyimide/graphene nanocomposites with synergistic effects of redox catalytic capability and gas barrier properties. Express Polym. Lett., 2014, 8: 243-255.