高效双咪唑啉季铵盐对Q235的缓蚀性能及机理分析

doi:10.19965/j.cnki.iwt.2023-1112

摘要/Abstract

摘要：

为进一步提高酸洗环境中的缓蚀效率并降低使用成本，以油酸、三乙烯四胺和溴代正丁烷为原料，制备出一种高效的双咪唑啉季铵盐化合物SMZB。通过失重实验、电化学实验、表面形貌和理论计算等方法，研究了SMZB在1.0 mol/L HCl溶液中对Q235的缓蚀性能及其缓蚀机理。结果表明，SMZB浓度为2.0 mmol/L时，通过失重实验、电化学阻抗谱（EIS）、动电位极化曲线（Tafel）测试得到的缓蚀效率分别为98.88%、98.15%、99.62%；电化学实验可进一步证明SMZB能够吸附在Q235表面形成稳定的保护膜，并进一步降低腐蚀体系内的电荷转移速率；SMZB是一种抑制阴极为主的混合型缓蚀剂，且遵循Langmuir等温吸附方程；理论计算表明SMZB的吸附位点主要位于咪唑环和Br^-，且能够自发地吸附在Q235表面。SMZB能够在1.0 mol/L HCl溶液中发挥优异的缓蚀性能，主要是在Q235表面形成稳定保护膜并降低体系内的电荷转移速率，从而具有优异的缓蚀性能。

关键词: 咪唑啉季铵盐, 腐蚀, 电化学

Abstract:

To further improve the corrosion inhibition efficiency in acid washing environments and reduce costs, an efficient bis-imidazoline quaternary ammonium salt(SMZB) compound was synthesized by using oleic acid, triethylenetetramine,and bromo-n-butane as raw materials. The corrosion inhibition performance and mechanism of SMZB on Q235 in 1.0 mol/L HCl solution were studied through methods such as weight loss experiments, electrochemical experiments, surface morphology, and theoretical calculations. The results showed that when the concentration of SMZB was 2.0 mmol/L, the inhibition efficiencies by weight loss experiment, EIS, and Tafel corrosion were 98.88%,98.15%, and 99.62%, respectively. Electrochemical experiments further proved that SMZB could adsorb on the surface of Q235 to form a stable protective film and further reduced the charge transfer rate within the corrosion system. SMZB was a mixed corrosion inhibitor that mainly suppresses the cathode and follows the Langmuir isotherm adsorption equation. Theoretical calculations indicated that the adsorption sites of SMZB were mainly located in the imidazole ring and Br^-, and could spontaneously adsorb on the surface of Q235. SMZB exhibited excellent corrosion inhibition performance in a 1.0 mol/L HCl solution, which was mainly due to the formation of a stable protective film on the surface of Q235 and the reduction of the charge transfer rate within the system, thus providing excellent corrosion inhibition performance.

Key words: imidazoline quaternary ammonium salt, corrosion, electrochemical

中图分类号:

TG174.42

王鹏杰, 宋昱灏, 樊林, 邓宽海, 李忠慧, 梅宗斌, 郭雷, 林元华. 高效双咪唑啉季铵盐对Q235的缓蚀性能及机理分析[J]. 工业水处理, 2024, 44(12): 166-174.

Pengjie WANG, Yuhao SONG, Lin FAN, Kuanhai DENG, Zhonghui LI, Zongbin MEI, Lei GUO, Yuanhua LIN. Corrosion inhibition performance and mechanism analysis of high-efficiency imidazoline quaternary ammonium salt on Q235[J]. Industrial Water Treatment, 2024, 44(12): 166-174.

https://www.iwt.cn/CN/Y2024/V44/I12/166

图/表 15

图1 SMZB的合成路线和分子结构

Fig.1 Synthesis route and molecular structure of SMZB

图2 SMZB的结构表征

Fig.2 Structural characterization of SMZB

图3 试样在不同浓度SMZB中的腐蚀参数

Fig.3 Corrosion parameters of specimen in different concentrations of SMZB

图4 Langmuir吸附等温线

Fig.4 Langmuir adsorption isotherms

图5 试样在不同浓度SMZB中的Nyquist图

Fig.5 Nyquist plot of specimen in different concentrations of SMZB

表1 试样在不同浓度SMZB中的EIS参数

Table 1 EIS parameters of specimen in different concentrations of SMZB

C/ （mmol·L^-1）	R _s/ （Ω·cm²）	Y _0.f/ （Ω^-1·cm^-2·s ⁿ ）	n _f	R _f/ （Ω·cm²）	Y _0.rct/ （Ω^-1·cm^-2·s ⁿ ）	n _rct	R _ct/ （Ω·cm²）	χ ²	η _p/%
0	8.59	2.45×10^-5	0.99	1.48	1.246×10^-4	0.81	17.14	0.001 5	—
0.2	2.67	1.962×10^-4	0.84	294.40	2.683×10^-4	0.81	166.9	0.005 0	94.13
0.5	2.91	1.746×10^-4	0.75	499.00	1.864×10^-4	0.81	152.0	0.006 4	95.85
1.0	2.68	1.822×10^-4	0.72	589.40	1.273×10^-4	0.79	167.9	0.006 4	96.42
2.0	2.98	1.652×10^-4	0.69	1 016.00	3.69×10^-5	0.74	448.3	0.000 9	98.15

图6 试样在不同浓度SMZB中的动电位极化曲线

Fig.6 Polarization curves of specimen in different concentrations of SMZB

表2 动电位极化曲线参数及缓蚀效率

Table 2 Parameters of dynamic potential polarization curve and corrosion inhibition efficiency

C/ （mmol·L^-1）	E _corr/V	i _corr/ （mA·cm^-2）	β _c/ （mV·dec^-1）	β _a/ （mV·dec^-1）	η/%
0	-0.460	1.602	182.25	181.29	—
0.2	-0.482	0.084	160.17	153.30	94.75
0.5	-0.467	0.048	157.82	133.94	97.00
1.0	-0.468	0.035	157.72	126.40	97.81
2.0	-0.473	0.022	152.62	119.64	99.62

图7 2.0 mmol/L SMZB中失重后的试样表面形貌和EDS能谱

Fig.7 Surface morphology and EDS spectrum of specimen after weight loss of 2.0 mmol/L SMZB

图8 失重后试样表面和SMZB的IR

Fig.8 Infrared spectra of specimen surface after weight loss and SMZB

图9 SMZB的分子结构、HOMO、LUMO和ESP

Fig.9 SMZB structure，HOMO，LUMO and ESP

表3 SMZB量子化学参数

Table 3 Quantum chemical parameters of SMZB

E _HOMO/eV		E _LUMO/eV		ΔE _SMZB/eV	E _LUMO，SMZB-E _HOMO，Fe/eV	E _LUMO，Fe-E _HOMO，SMZB/eV
SMZB	Fe^〔23〕	SMZB	Fe^〔23〕	ΔE _SMZB/eV	E _LUMO，SMZB-E _HOMO，Fe/eV	E _LUMO，Fe-E _HOMO，SMZB/eV
-4.503	-7.810	-2.857	-0.250	1.628	4.953	4.253

图10 SMZB在Fe（110）面的最佳平衡吸附形态

Fig.10 Optimal equilibrium adsorption morphology of SMZB on Fe（110）

图11 SMZB的保护膜动力学模拟后的晶胞

Fig.11 Cell dynamics simulation of protective film of SMZB

图12 缓蚀剂膜中Cl^-和H₃O⁺的MSD曲线

Fig.12 MSD curve of Cl^- and H₃O⁺ in corrosion inhibitor film

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