高温热还原氧化石墨烯/聚酰亚胺复合涂层的制备及防腐蚀性能研究

doi:10.15541/jim20160699

摘要/Abstract

摘要：

将高温热还原氧化石墨烯(TRGO)作为二维纳米填料添加到聚酰亚胺(PI)聚合物基质中, 制备了不同质量分数的TRGO/PI纳米复合耐蚀涂层, 采用交流阻抗谱和动电位极化曲线评估了涂层在模拟海水(3.5wt%NaCl溶液)中的电化学腐蚀行为。结果表明: 与纯PI涂层相比, 添加TRGO可以显著提高涂层的电阻和腐蚀防护效率; 当TRGO的添加量为0.3wt%时, 对涂层耐蚀性能的增强效果最好, 最大涂层电阻为1.3176×10⁶Ω, 最高腐蚀防护效率可达到99.65%, 其防蚀增益与片层结构TRGO的物理阻隔性能有关。

关键词: 石墨烯, 聚酰亚胺, 耐腐蚀, 复合涂层

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

中图分类号:

TQ174

贾营坤, 陈培, 张青红, 孙静. 高温热还原氧化石墨烯/聚酰亚胺复合涂层的制备及防腐蚀性能研究[J]. 无机材料学报, 2017, 32(12): 1257-1263.

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.

图/表 12

图1 GO纳米片的(a)TEM和(b-c)AFM照片

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

图2 氧化石墨烯和高温还原氧化石墨烯的 (a)XRD图谱和 (b)拉曼光谱图

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

图3 不同浓度的TRGO分散液的照片

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

图4 (a,b)纯PI涂层和(c,d)TRGO0.1/PI复合涂层的SEM断面照片

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

图5 不同涂层的Bode相位角图(a), Bode模值图(b)和复平面图(c)

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

图6 拟合过程采用的等效电路图

Fig. 6 Equivalent circuit used in the fitting process

表1 不同样品涂层的等效电路拟合结果

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

图7 (a)TRGO0.1/PI和(b)TRGO0.4/PI两种涂层的拟合结果示意图

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

图8 TRGO/PI的涂层电阻和0.1 Hz处对应的阻抗模值对TRGO含量的变化

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

图9 各涂层样品的Tafel极化曲线

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

图10 (a)TRGO0.1/PI和(b)TRGO0.5/PI两种涂层粘附力测试后的光学照片

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

表2 不同样品涂层的电化学腐蚀参数

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

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