甲基丙烯酸二甲氨基乙酯类离子液体对Q235钢的缓蚀性能

doi:10.7503/cjcu20190370

摘要/Abstract

摘要：

以甲基丙烯酸二甲氨基乙酯为母体、对氯甲基苯乙烯为季铵化试剂, 合成了一种具有疏水结构的甲基丙烯酸二甲氨基乙酯型离子液体(DEMA). 通过失重实验、电化学分析、原子力显微镜(AFM)、接触角测试和量子化学计算等研究了DEMA在1 mol/L盐酸中对Q235钢的缓蚀性能, 并揭示了其在Q235钢表面的吸附行为和吸附机理. 失重实验结果表明, DEMA在盐酸中对Q235钢具有优异的缓蚀效果, 且在较高温度(60 ℃)下也能保持高效吸附; 电化学实验结果与失重测试结果一致; 接触角测试结果表明, DEMA可明显增强Q235钢表面的疏水性; 分析热力学参数可知, DEMA在Q235钢表面的吸附为自发、放热过程, 符合Langmuir等温式, 且以化学吸附为主; 量子化学计算结果证实DEMA的结构中包含大量吸附活性位点.

关键词: 缓蚀剂, 离子液体, 吸附, 量子化学, 缓蚀机理

Abstract:

A 2-(dimethylamino)ethyl methacrylate type ionic liquid with hydrophobic structure(DEMA) was prepared from 2-(dimethylamino)ethylmethacrylate and 4-vinylbenzyl chloride. The corrosion inhibitory property of DEMA on Q235 steel in 1 mol/L hydrochloric acid solution and their adsorption behavior on Q235 steel surface were studied by means of mass loss measurement, electrochemical technique, force microscopy(AFM), contact angle measurement and quantum chemical calculation. The mass loss results show that DEMA has good corrosion inhibition effect on Q235 steel in hydrochloric acid, and it can maintain strong adsorption at higher temperature(60 ℃). The results of electrochemical tests are consistent with that of mass loss test. Contact angle test results show that DEMA can significantly enhance the hydrophobicity of the surface of Q235 steel. Thermodynamic and activation energy parameters show that the adsorption of DEMA on Q235 steel surface is spontaneous and exothermic, conforming to the Langmuir’s adsorption isotherm and mainly based on chemical adsorption. Quantum chemical calculation results show that the entire structure of DEMA contains a large number of adsorbed active sites. Thermogravimetric analysis(TGA) shows that DEMA has good thermostability. DEMA has the advantages of mild preparation condition, good thermal stability and excellent corrosion inhibition performance, thus it has important industrial application value and theoretical reference. At the same time, the studies also provide a new idea for the structural design of corrosion inhibitor.

Key words: Corrosion inhibitor, Ionic liquid, Adsorption, Quantum chemical, Inhibition mechanism

中图分类号:

O647

董秋辰,张光华,张万斌,张雪,刘晶. 甲基丙烯酸二甲氨基乙酯类离子液体对Q235钢的缓蚀性能[J]. 高等学校化学学报, 2019, 40(12): 2556-.

Qiuchen DONG,Guanghua ZHANG,Wanbin ZHANG,Xue ZHANG,Jing LIU. Corrosion Inhibition of Q235 Steel by Ionic Liquid Based on the 2-(Dimethylamino)ethyl Methacrylate ^†[J]. Chemical Journal of Chinese Universities, 2019, 40(12): 2556-.

图/表 18

Scheme 1 Synthetic route of DEMA

Fig.1 FTIR spectrum of DEMA

Fig.2 1H NMR spectrum of DEMA

Fig.3 TG-DTG curves of DEMA

Table 1 Corrosion rate of Q235 steel and inhibition efficiency of various concentrations of DEMA in 1 mol/L HCl at different temperatures obtained from mass loss measurements

Temp./℃	c(DEMA)/ (mg·L^-1)	v/(mg· cm^-2·h^-1)	θ	η_w(%)	Temp./℃	c(DEMA)/ (mg·L^-1)	v/(mg· cm^-2·h^-1)	θ	η_w(%)
30	0	2.7016	—	—	50	0	6.7581	—	—
	20	0.0824	0.9695	96.95		20	0.3899	0.9423	94.23
	40	0.0686	0.9746	97.46		40	0.3393	0.9498	94.98
	60	0.0546	0.9798	97.98		60	0.2879	0.9574	95.74
	80	0.0413	0.9847	98.47		80	0.2467	0.9635	96.35
	100	0.0394	0.9854	98.54		100	0.2041	0.9698	96.98
40	0	4.3276	—	—	60	0	10.5565	—	—
	20	0.1878	0.9566	95.66		20	0.6957	0.9341	93.41
	40	0.1580	0.9635	96.35		40	0.5510	0.9478	94.78
	60	0.1389	0.9679	96.79		60	0.5035	0.9523	95.23
	80	0.1207	0.9721	97.21		80	0.4518	0.9572	95.72
	100	0.1021	0.9764	97.64		100	0.4085	0.9613	96.13

Fig.4 Nyquist(A), phase angle(B) and bode(C) plots for Q235 steel in 1 mol/L HCl solution without and with different concentrations of DEMA at 30 ℃

Table 2 Impedance parameters of Q235 steel with various mass concentrations of DEMA

c(DEMA)/(mg·L^-1)	R_s/(Ω·cm²)	R_ct/(Ω·cm²)	CPE		η_e(%)
c(DEMA)/(mg·L^-1)	R_s/(Ω·cm²)	R_ct/(Ω·cm²)	C_dl/(μF·cm^-2)	n	η_e(%)
0	0.89	17.3	343.1	0.90
20	1.13	245.7	168.7	0.84	92.96
40	1.02	256.7	166.4	0.86	93.26
60	0.95	275.0	159.2	0.83	93.71
80	1.17	300.9	150.2	0.91	94.25
100	0.88	364.2	136.7	0.84	95.25

Table 3 Electrochemical parameters for the corrosion of Q235 steel in 1 mol/L HCl containing different concentrations of DEMA at 30 ℃

c(DEMA)/(mg·L^-1)	E_corr/mV(vs. SCE)	i_corr/(μA·cm^-2)	β_a/(mV·dec^-1)	β_c/(mV·dec^-1)	η_p(%)
0	-483.4	52.2	85.4	-131.0
20	-445.5	3.8	86.2	-132.8	92.72
40	-437.8	3.3	75.6	-126.9	93.68
60	-432.8	2.3	79.8	-126.2	95.59
80	-430.6	2.0	82.6	-127.4	96.17
100	-426.4	1.6	88.3	-122.3	96.93

Fig.5 Potentiodynamic polarization curves for Q235 steel in 1 mol/L HCl with different concentrations of DEMA at 30 ℃

Fig.6 Langmuir absorption isotherm fitting for DEMA at Q235 steel surface

Table 4 Adsorption parameters obtained from mass loss tests for DEMA in 1 mol/L HCl at different temperatures

Temperature/℃	K_ads/(L·mol^-1)	Δ $G ads 0$ /(kJ·mol^-1)	Δ $H ads 0$ /(kJ·mol^-1)	Δ $S ads 0$ /(J·mol^-1·K^-1)
30	558659	-43.45	-17.27	86.4
40	452489	-44.34	-17.27	86.5
50	358423	-45.13	-17.27	86.3
60	302115	-46.05	-17.27	86.4

Table 4 Adsorption parameters obtained from mass loss tests for DEMA in 1 mol/L HCl at different temperatures

Temperature/℃	K_ads/(L·mol^-1)	Δ $G ads 0$ /(kJ·mol^-1)	Δ $H ads 0$ /(kJ·mol^-1)	Δ $S ads 0$ /(J·mol^-1·K^-1)
30	558659	-43.45	-17.27	86.4
40	452489	-44.34	-17.27	86.5
50	358423	-45.13	-17.27	86.3
60	302115	-46.05	-17.27	86.4

Fig.7 Relationship between lnKads and 1/T for DEMA inhibiting Q235 steel

Fig.8 Arrhenius plots for Q235 steel in 1 mol/L HCl with different concentrations of DEMA

Fig.9 Contact angle for Q235 steel after 4 h immersion in 1 mol/L HCl with different concentrations of DEMA

Fig.10 AFM images of Q235 steel surface after immersion in 1 mol/L HCl at 30 ℃ for 1 h (A1, A2) Before immersion; (B1, B2) without DEMA; (C1, C2) with 80 mg/L DEMA. (A1—C1) Plane graphs; (A2—C2) three-dimensional images.

Fig.11 Optimized structure(A), HOMO(B) and LUMO(C) distributions of DEMA

Table 5 Frontier orbital energies of DEMA

E_HOMO/eV		E_LUMO/eV		E_LUMO-E_HOMO,Fe/eV	E_LUMO,Fe-E_HOMO/eV	ΔE/eV
DEMA	Fe	DEMA	Fe	E_LUMO-E_HOMO,Fe/eV	E_LUMO,Fe-E_HOMO/eV	ΔE/eV
-8.022	-7.810^[29]	-4.622	-0.250^[29]	3.188	7.772	3.40

Fig.12 Corrosion inhibition mechanism of [DEMA]x+ on Q235 steel surface

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