目的 咪唑啉缓蚀剂广泛使用在含氯腐蚀介质中,针对17烯基羟乙基咪唑啉（OEM）在含氯腐蚀介质中缓蚀效率较低的问题,通过研究小分子有机缓蚀剂与OEM复配机理提升缓蚀性能。方法 研究硫脲（TU）、苯并咪唑啉（BE）、2-巯基苯并咪唑（MBI）、5-胺基-2-巯基苯并咪唑啉（5AMBI）四种小分子有机物与OEM复配的缓蚀效果与机理。通过电化学测试、表面分析等方法研究复配缓蚀剂的腐蚀抑制性能,利用量子化学计算与分子动力学模拟探讨缓蚀剂的吸附行为、膜层性质及腐蚀控制机制。结果 利用电化学测试筛选OEM与四种小分子缓蚀剂复配比例,确定有机小分子与OEM的最优复配质量比为2∶3。进而通过电化学交流阻抗与极化曲线结合表面分析方法探索该复配比例下缓蚀剂浓度对L80钢的腐蚀抑制作用,不同复配缓蚀剂浓度下性能各有不同。量子化学计算与分子动力学模拟显示,有机小分子可有效嵌入OEM分子的直链间空隙,其N、S等活性原子与金属表面形成强吸附,提高膜层致密性与覆盖度,从而抑制Cl-等腐蚀介质的扩散,实现协同缓蚀效果。结论 OEM与小分子缓蚀剂在2∶3时具有最好的缓蚀效果。尽管不同浓度下缓蚀效果最优的复配缓蚀剂组分略有区别,但随缓蚀剂浓度上升缓蚀效果提升。
Abstract
Imidazoline (IM) corrosion inhibitors are widely used in chloride-containing corrosive environments to mitigate the corrosion of metal materials. The synergistic effect between different corrosion inhibitors is one of the most effective approaches to enhance the corrosion inhibition effect of organic inhibitors. The work aims to enhance the corrosion resistance performance of an imidazoline derivative, hydroxyethylimidazoline (OEM), by combining it with 4 kinds of organic inhibitors: thiourea (TU), benzimidazole (BE), 2-Mercaptobenzimidazole (MBI), 5-Amino-2-mercaptobenzimidazole (5AMBI). The synergistic effect and anti-corrosion efficiency of OEM and organic inhibitors were investigated through electrochemical measurements and surface analysis techniques. Quantum chemical calculations and molecular dynamics simulations were employed to understand the adsorption behavior and mechanism of the compound inhibitors. Electrochemical impedance spectroscopy (EIS) was used to screen for the optimal proportion of organic inhibitors and OEM at a total concentration of 50 mg/L. OEM exhibited good synergistic effects with the 4 organic inhibitors used in this work, and the BE+OEM combination showed the highest inhibition effect across various inhibitor mixing ratios. All inhibitor combinations performed the best inhibition effect at a weight ratio of 2∶3. Electrochemical measurements including EIS and potentiodynamic polarization curves were employed to investigate the effect of concentration on the corrosion inhibition efficiency of the compound inhibitors. Concentration variation had minimal impact on the inhibition efficiency of BE and OEM inhibitor group. While, for other compound inhibitor groups, the anti-corrosion performance improved significantly as the concentration increased. The compound inhibitors functioned as mixed-type inhibitors, predominantly affecting the cathodic reaction. The compound inhibitors could form an adsorption film on the steel surface, and the barrier effect and hydrophobic nature of this film reduced the kinetics of the cathodic reaction and inhibited the corrosion reactions. Surface morphology analysis of L80 steel treated with different inhibitors directly confirmed the inhibition effect of the hybrid inhibitors and the synergistic interaction between the tested organic inhibitors with OEM. The synergistic mechanism between the tested organic inhibitors and OEM was studied through quantum chemical calculations and molecular dynamics simulations. According to the optimal molecular configurations, TU and 5AMBI showed better electron donor capacity, indicating a better inhibition effect. The active atoms, such as N and S, in the corrosion inhibitor molecules formed strong adsorption with the metal surface, improving the density and coverage of the film layer. OEM molecules adsorb on Fe(110) crystal surface horizontally, which leads to a larger protection area of inhibitor. However, the steric-hindrance effect of OEM results in the significant voids in the inhibition film. The added organic molecules can effectively insert into the inter-chain gaps of OEM adsorption film, forming a more protective inhibitor layer. Based on molecular dynamics calculations, the compactness of the formed corrosion inhibitor film layer was explored by calculating the diffusion coefficient of the corrosion inhibitor film layer, thereby effectively inhibiting the diffusion of corrosive media, such as Cl- and O2, and achieving a synergistic corrosion inhibition effect. The combination of OEM and organic inhibitors achieves the best corrosion inhibition effect at a ratio of 2∶3. Although the optimal component of the corrosion inhibitor mixture varies slightly at different concentrations, the corrosion inhibition effect increases as the concentration of the corrosion inhibitor rises.
关键词
咪唑啉 /
复配缓蚀剂 /
含氯腐蚀介质 /
L80钢 /
协同机理
Key words
imidazolines /
compound corrosion inhibitors /
Cl--containing corrosive medium /
L80 steel /
synergistic mechanism
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基金
国家自然科学基金青年基金C类（52201088）
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