热还原氧化石墨烯/环氧树脂复合涂层的防腐性能

doi:10.16085/j.issn.1000-6613.2022-1178

摘要/Abstract

摘要：

在市售溶剂型环氧树脂涂料（EPs）中添加少量的热还原氧化石墨烯（TRGO），以提高其防腐性能。本文以氧化石墨（GO）为前体，在不同热还原温度下制备了TRGO，表征了GO热还原反应前后的结构变化，对比了GO和TRGO在环氧树脂涂料稀释剂中的分散性；在Q345钢表面涂覆了TRGO/EPs复合涂层，通过塔菲尔极化曲线（Tafel）、电化学阻抗谱图（EIS）和腐蚀形貌考察了TRGO的制备温度和添加量对复合涂层防腐性能的影响，探讨了复合涂层的防腐机理。结果表明，高温热还原反应能够使GO剥离并成功制备TRGO，与GO相比，TRGO在溶剂型环氧树脂涂料的稀释剂中的分散性得到明显增强；TRGO的氧含量随热还原温度的升高而降低，但800℃下制备的TRGO（TRGO-800）具有最大的比表面积；不同热还原温度下制备的TRGO/EPs复合涂层均比纯EPs涂层具有更好的防腐性能，其中TRGO-800/EPs复合涂层的防腐效果最好，甚至还优于商用石墨烯/EPs复合涂层；当TRGO-800的添加量为0.1%，复合涂层的腐蚀电流密度为3.29×10^-8A/cm²，比纯EPs涂层降低了96.84%，极化电阻为1.38×10⁶Ω，比纯EPs涂层增大了28倍。TRGO/EPs复合涂层的防腐性能提升与TRGO的良好分散性和物理阻隔性有关。

关键词: 热还原氧化石墨烯, 环氧树脂涂料, 复合涂层, 分散性, 电化学, 腐蚀

Abstract:

A small amount of thermal reduced graphene oxide (TRGO) was added to commercial solvent-type epoxy resin coatings (EPs) to improve their anticorrosion performances. TRGO was prepared at different temperatures using graphite oxide (GO) as precursor. Structural changes before and after thermal reduction reaction of GO were characterized. The dispersion of GO and TRGO in the diluents of epoxy resin coatings were compared. The TRGO/EPs composite coatings were coated on the surface of Q345 steel. The influence of the preparation temperature and addition amount of TRGO on the anticorrosive performances of the composite coatings were investigated by Tafel polarization curves (Tafel), AC impedance spectra (EIS) and corrosion morphology. The anticorrosion mechanism of composite coating was discussed. The results indicated that high temperature thermal reduction reaction can strip GO and successfully prepare TRGO. Compared with the GO, TRGO showed significantly enhanced dispersion in diluents of solvent-based epoxy resin coatings. The oxygen content of TRGO decreased with increasing thermal reduction temperature, but the TRGO (TRGO-800) prepared at 800℃ had the maximum specific surface area. The TRGO/EPs composite coatings prepared at different thermal reduction temperatures all had better anticorrosion performances than the pure EPs coatings. Among them, the TRGO-800/EPs composite coating had the best anticorrosion effect, and even better than the commercial graphene/EPs composite coating. When the addition amount of TRGO-800 was 0.1%, the corrosion current density was 3.29×10^-8A/cm², which was 96.84% lower than the pure EPs coating, and the polarization resistance value of the composite coatings was 1.38×10⁶Ω, which was 28-fold greater than the pure EPs coating. The enhanced anticorrosive performance of TRGO/EPs composite coatings can be attributed to the good dispersion and physical barrier performance of the TRGO.

Key words: thermally reduced graphene oxide, epoxy resin coating, composite coating, dispersion, electrochemistry, corrosion

中图分类号:

TQ031.6

何阳, 李思盈, 李传强, 袁小亚, 郑旭煦. 热还原氧化石墨烯/环氧树脂复合涂层的防腐性能[J]. 化工进展, 2023, 42(4): 1983-1994.

HE Yang, LI Siying, LI Chuanqiang, YUAN Xiaoya, ZHENG Xuxu. Anticorrosion performance of thermal reduction graphene oxide /epoxy resin composite coating[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1983-1994.

图/表 23

图1 GO热还原反应及结构变化

图2 GO和TRGO的SEM图

图3 GO和TRGO的TEM图

图4 GO和TRGO的红外光谱图

图5 GO和TRGO的XPS谱图

表1 不同样品C 1s XPS光谱中碳组分的定量分析（原子分数） (%)

试验样品	C＝C/C—C	C—O	C＝O	O—C＝O
GO	47.79	42.61	3.05	6.55
TRGO-600	76.12	14.07	5.65	4.16
TRGO-800	84.16	10.32	3.65	1.87

图6 GO和TRGO的拉曼光谱

图7 GO和TRGO的热重分析图

图8 GO和TRGO的N2等温吸附脱附曲线和孔径分布

表2 TRGO、GO的比表面积和平均孔径

试验样品	比表面积/m²·g^–1	平均孔径/nm
GO	51.29	4.639
TRGO-600	307.14	11.557
TRGO-800	465.96	11.872
TRGO-1000	431.86	11.964

图9 GO和TRGO在环氧树脂涂料稀释液中的分散性

图10 复合涂层在质量分数3.5%NaCl溶液中浸泡48h后的极化曲线

表3 各种涂层在质量分数3.5%NaCl溶液中浸泡48h后的极化曲线参数

试验样品	E_corr/V	I_corr/A·cm^–2	R_p/Ω	P/%
Bare	–0.659	7.06×10^–5	8.63×10²	—
EPs	–0.547	8.493×10^–7	4.93×10⁴	98.80
Gr/EPs	–0.431	4.69×10^–7	1.01×10⁵	99.34
TRGO-600/EPs	–0.463	6.15×10^–7	7.20×10⁴	99.13
TRGO-800/EPs	–0.375	3.41×10^–7	1.26×10⁵	99.52
TRGO-1000/EPs	–0.474	7.84 ×10^–7	4.80×10⁴	98.89

图11 不同添加量的TRGO-800/EPs复合涂层在质量分数3.5%的NaCl溶液中浸泡后的数码照片

图12 不同添加量的TRGO-800/EPs复合涂层在质量分数3.5%的NaCl溶液中浸泡48h后的极化曲线

图13 不同添加量的TRGO-800/EPs复合涂层的腐蚀电流密度和极化电阻

图14 盐雾实验240h后涂层腐蚀情况

图15 纯EPs涂层和TRGO-800/EPs涂层的附着力测试

图16 复合涂层在质量分数3.5%的NaCl溶液中浸泡不同时间的Nyquist和Bode图

表4 复合涂层在质量分数3.5%的NaCl溶液中浸泡不同时间的等效电路拟合

浸泡时间/d	R_s/Ω	CPE-T	CPE-P	R_c/Ω·cm²	\|Z\|_(0.1Hz)/Ω·cm²
2	110	4.591×10^–8	0.6807	4.0292×10⁶	3.6063×10⁶
4	113	3.6051×10^–7	0.7105	2.5475×10⁶	1.8435×10⁶
6	116	2.6359×10^–7	0.6928	1.7997×10⁶	1.4586×10⁶
8	112	1.4536×10^–7	0.7100	1.3049×10⁶	1.2006×10⁶
10	123	2.6691×10^–7	0.6904	1.1973×10⁶	1.0041×10⁶

图17 等效电路图

图18 纯EPs涂层和TRGO/EPs复合涂层的SEM图

图19 纯EPs涂层和TRGO/EPs复合涂层的防腐机理示意图

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