环氧豆油树脂涂层的防腐性能研究

doi:10.11949/0438-1157.20200842

摘要/Abstract

摘要：

以环氧大豆油（ESO）为主要原料，四亚乙基五胺为固化剂，在碳钢基底表面制备了环氧豆油树脂（ESOR）涂层。利用场发射扫描电镜、傅里叶红外变化光谱仪、纳米压痕仪、热重分析仪、接触角测量仪、电化学阻抗谱等技术对ESOR涂层的性能进行了表征。结果发现，原料中ESO的含量有助于提高ESOR涂层的耐水性；而当原料中ESO的含量逐渐增加时，ESOR涂层的硬度、弹性模量和耐蚀性都会随之增强；根据拟合的等效电路，ESO与四亚乙基五胺的摩尔比为2的ESOR涂层的涂层电阻R_c能达到8.22×10¹¹ Ω·cm²，电荷转移电阻R_ct能达到1.32 $\times$ 10¹⁰ Ω·cm²，表现出了优异的防腐性能。

关键词: 碳钢, 环氧大豆油, 涂层, 电化学阻抗谱, 腐蚀

Abstract:

Using epoxy soybean oil (ESO) as the main raw material and tetraethylenepentamine as the curing agent, epoxy soybean oil resin (ESOR) coatings were prepared on the surface of carbon steel. Field emission scanning electron microscope, Fourier infrared change spectrometer, nano-indenter, thermogravimetric analyzer, contact angle measuring instrument, electrochemical impedance spectroscopy and other techniques were used to characterize the performance of the ESOR coatings. It was found that the content of ESO in the raw materials helps to improve the water resistance of the ESOR coating. When the content of ESO in the raw material gradually increases, the hardness, elastic modulus and corrosion resistance of the ESOR coating will also increase. According to the fitted equivalent circuit, the coating resistance R_c of ESOR coating with a molar ratio of epoxy soybean oil to tetraethylenepentamine equal to 2 can reach 8.22×10¹¹ Ω·cm², and the charge transfer resistance R_ct can reach 1.32×10¹⁰ Ω·cm², which shows excellent anti-corrosion performance.

Key words: carbon steel, epoxidized soybean oil, coating, electrochemical impedance spectroscopy, corrosion

中图分类号:

TQ 050.9

何吉喆, 刘明言, 徐杨书函. 环氧豆油树脂涂层的防腐性能研究[J]. 化工学报, 2021, 72(2): 1067-1077.

HE Jizhe, LIU Mingyan, XU Yangshuhan. Study on anticorrosive properties of epoxy soybean oil resin coating[J]. CIESC Journal, 2021, 72(2): 1067-1077.

图/表 15

图1 环氧豆油树脂涂层厚度

Fig.1 Thickness of ESOR coatings

图2 ESOR涂层的DSC图

Fig.2 DSC curves of ESOR coatings

图3 ESOR涂层的固化度α

Fig.3 Curing degree α of ESOR coatings

图4 ESOR涂层的载荷-位移曲线

Fig.4 Load-displacement curves of ESOR coatings

图5 ESOR涂层的静态力学性能

Fig.5 Static mechanical properties of ESOR coatings

图6 ESOR涂层的TG-DTG曲线

Fig.6 TG-DTG curves of ESOR coatings

图7 环氧大豆油与环氧豆油树脂涂层的傅里叶红外变换光谱

Fig.7 FTIR of ESO and ESOR coatings

图8 20#碳钢和ESOR涂层的微观形貌

Fig.8 Microscopic of 20# carbon steel and ESOR coatings

图9 ESOR涂层在3.5%NaCl溶液中浸泡30 d后的微观形貌

Fig.9 Microscopic of ESOR coating soaking in 3.5% NaCl solution for 30 d

图10 纯水在样片表面的润湿行为

Fig.10 Wetting behaviors of pure water on samples surface

图11 ESOR涂层表面的接触角

Fig.11 Contact angle of ESOR coatings

图12 ESOR涂层的Bode图

Fig.12 Bode diagram of ESOR coatings

图13 ESOR涂层的Nyquist图

Fig.13 Nyquist diagram of ESOR coatings

图14 用于EIS拟合的等效电路模型

Fig.14 Equivalent circuits model for EIS fitting

表1 ESOR涂层的等效电路模拟数据

Table 1 Simulation data of equivalent circuits of ESOR coatings

涂层	Q_c/ (s^-ⁿ/(cm²·Ω))	R_c/ (Ω·cm²)	Q_dl/ (s^-ⁿ/(cm²·Ω))	R_ct/ (Ω·cm²)
E0.5-0d	2.18 $\times$ 10^-11	5.60 $\times$ 10⁹	—	—
E0.5-1d	3.34 $\times$ 10^-11	9.87 $\times$ 10⁸	—	1.31 $\times$ 10⁹
E0.5-15d	1.21 $\times$ 10^-10	1.12 $\times$ 10⁸	7.43 $\times$ 10^-11	4.11 $\times$ 10⁸
E0.5-30d	7.76 $\times$ 10^-9	1.67 $\times$ 10⁷	4.88 $\times$ 10^-10	1.88 $\times$ 10⁷
E1.0-0d	2.03 $\times$ 10^-11	4.81 $\times$ 10¹¹	—	—
E1.0-1d	2.80 $\times$ 10^-11	1.34 $\times$ 10¹¹	—	—
E1.0-15d	9.61 $\times$ 10^-11	2.11 $\times$ 10⁹	3.15 $\times$ 10^-11	1.57 $\times$ 10⁹
E1.0-30d	3.21 $\times$ 10^-10	5.13 $\times$ 10⁸	4.33 $\times$ 10^-11	4.57 $\times$ 10⁸
E1.5-0d	2.07 $\times$ 10^-11	5.43 $\times$ 10¹¹	—	—
E1.5-1d	2.41 $\times$ 10^-11	1.78 $\times$ 10¹¹	—	—
E1.5-15d	8.14 $\times$ 10^-11	2.86 $\times$ 10¹⁰	3.09 $\times$ 10^-11	7.66 $\times$ 10⁹
E1.5-30d	4.65 $\times$ 10^-10	1.23 $\times$ 10⁹	4.09 $\times$ 10^-11	1.36 $\times$ 10⁹
E2.0-0d	1.77 $\times$ 10^-11	8.22 $\times$ 10¹¹	—	—
E2.0-1d	1.76 $\times$ 10^-11	5.57 $\times$ 10¹¹	—	—
E2.0-15d	5.13 $\times$ 10^-11	3.09 $\times$ 10¹⁰	1.43 $\times$ 10^-11	1.32 $\times$ 10¹⁰
E2.0-30d	1.46 $\times$ 10^-10	2.57 $\times$ 10⁹	2.11 $\times$ 10^-11	3.17 $\times$ 10⁹

表1 ESOR涂层的等效电路模拟数据

Table 1 Simulation data of equivalent circuits of ESOR coatings

涂层	Q_c/ (s^-ⁿ/(cm²·Ω))	R_c/ (Ω·cm²)	Q_dl/ (s^-ⁿ/(cm²·Ω))	R_ct/ (Ω·cm²)
E0.5-0d	2.18 $\times$ 10^-11	5.60 $\times$ 10⁹	—	—
E0.5-1d	3.34 $\times$ 10^-11	9.87 $\times$ 10⁸	—	1.31 $\times$ 10⁹
E0.5-15d	1.21 $\times$ 10^-10	1.12 $\times$ 10⁸	7.43 $\times$ 10^-11	4.11 $\times$ 10⁸
E0.5-30d	7.76 $\times$ 10^-9	1.67 $\times$ 10⁷	4.88 $\times$ 10^-10	1.88 $\times$ 10⁷
E1.0-0d	2.03 $\times$ 10^-11	4.81 $\times$ 10¹¹	—	—
E1.0-1d	2.80 $\times$ 10^-11	1.34 $\times$ 10¹¹	—	—
E1.0-15d	9.61 $\times$ 10^-11	2.11 $\times$ 10⁹	3.15 $\times$ 10^-11	1.57 $\times$ 10⁹
E1.0-30d	3.21 $\times$ 10^-10	5.13 $\times$ 10⁸	4.33 $\times$ 10^-11	4.57 $\times$ 10⁸
E1.5-0d	2.07 $\times$ 10^-11	5.43 $\times$ 10¹¹	—	—
E1.5-1d	2.41 $\times$ 10^-11	1.78 $\times$ 10¹¹	—	—
E1.5-15d	8.14 $\times$ 10^-11	2.86 $\times$ 10¹⁰	3.09 $\times$ 10^-11	7.66 $\times$ 10⁹
E1.5-30d	4.65 $\times$ 10^-10	1.23 $\times$ 10⁹	4.09 $\times$ 10^-11	1.36 $\times$ 10⁹
E2.0-0d	1.77 $\times$ 10^-11	8.22 $\times$ 10¹¹	—	—
E2.0-1d	1.76 $\times$ 10^-11	5.57 $\times$ 10¹¹	—	—
E2.0-15d	5.13 $\times$ 10^-11	3.09 $\times$ 10¹⁰	1.43 $\times$ 10^-11	1.32 $\times$ 10¹⁰
E2.0-30d	1.46 $\times$ 10^-10	2.57 $\times$ 10⁹	2.11 $\times$ 10^-11	3.17 $\times$ 10⁹

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