Corrosion Inhibition of Q235 Steel by Ionic Liquid Based on the 2-(Dimethylamino)ethyl Methacrylate †

doi:10.7503/cjcu20190370

Abstract

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

CLC Number:

O647

TrendMD:

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]. Chem. J. Chinese Universities, 2019, 40(12): 2556.

Figures/Tables 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

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 ℃

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

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

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

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

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

References 32

[1]	Zou C., Qin Y., Yan X., Zhou L., Luo P ., Ind. Eng. Chem. Res., 2014,53(33), 12901— 12910 doi: 10.1021/ie501569d URL
[2]	Barmatov E., Hughes T., Nagl M ., Corros. Sci., 2015,92, 85— 94 doi: 10.1016/j.corsci.2014.11.038 URL
[3]	Xiong D. Z., Zhang G. Y ., Oilfield Chem., 1991,8(4), 310— 313
	( 熊德珍, 张功亚 . 油田化学, 1991,8(4), 310— 313)
[4]	Finšgar M., Jackson J ., Corros. Sci., 2014,86(3), 17— 41 doi: 10.1016/j.corsci.2014.04.044 URL
[5]	Abdallah M., Helal E. A., Fouda A. S ., Corros. Sci., 2006,48(7), 1639— 1654 doi: 10.1016/j.corsci.2005.06.020 URL
[6]	Abdallah M., Meghed H. E., Sobhi M ., Mater. Chem. Phys., 2009,118(1), 111— 117 doi: 10.1016/j.matchemphys.2009.07.013 URL
[7]	Dehri İ., Özcan M ., Mater. Chem. Phys., 2006,98(2), 316— 323 doi: 10.1016/j.matchemphys.2005.09.020 URL
[8]	Verma C., Ebenso E. E., Quraishi M. A ., J. Mol. Liq., 2017,233, 403— 414 doi: 10.1016/j.molliq.2017.02.111 URL
[9]	Likhanova N. V., Domínguez-Aguilar M. A., Olivares-Xometl O., Nava-Entzana N., Arce E., Dorantes H ., Corros. Sci., 2010,52(6), 2088— 2097 doi: 10.1016/j.corsci.2010.02.030 URL
[10]	Luo Y. J., Zhang X. S., Wang Z. L ., Speciality Petrochem., 2004,2, 58— 60
	( 罗娅君, 张新申, 王照丽 . 精细石油化工, 2004,2, 58— 60)
[11]	Zhang G. H., Dong Q. C., Zhang W. B., Wang S ., Chem. J Chinese Universities, 2019,40(1), 130— 137
	( 张光华, 董秋辰, 张万斌, 王爽 . 高等学校化学学报, 2019,40(1), 130— 137)
[12]	Dong Q. C., Zhang G. H., Zhang W. B., Liu Y ., Fine Chem., 2019,36(5), 1005— 1011
	( 董秋辰, 张光华, 张万斌, 刘瑜 . 精细化工, 2019,36(5), 1005— 1011)
[13]	Hanza A. P., Naderi R., Kowsari E., Sayebani M ., Corros. Sci., 2016,107, 96— 106 doi: 10.1016/j.corsci.2016.02.023 URL
[14]	Sığırcık G., Yildirim D., Tüken T ., Corros. Sci., 2017,120, 184— 193 doi: 10.1016/j.corsci.2017.03.003 URL
[15]	Wang T. Y., Zou C. J., Li D. X., Chen Z. L., Liu Y., Li X. K., Li M ., Acta Phys. Chim. Sin., 2015,31(12), 2294— 2302
[16]	Wang X., Yang H., Wang F ., Corros. Sci., 2010,52(4), 1268— 1276 doi: 10.1016/j.corsci.2009.12.018 URL
[17]	Qiang Y., Zhang S., Tan B., Chen S ., Corros. Sci., 2018,133, 6— 16 doi: 10.1016/j.corsci.2018.01.008 URL
[18]	Guo R., Li Y. P., Tu R. X., Song B., Guo Y ., Chem. J Chinese Universities, 2018,39(5), 1018— 1025
	( 郭睿, 李云鹏, 土瑞香, 宋博, 郭煜 . 高等学校化学学报, 2018,39(5), 1018— 1025)
[19]	Cao S., Liu D., Ding H., Wang J., Lu H., Gui J ., Corros. Sci., 2019,153, 301— 313 doi: 10.1016/j.corsci.2019.03.035 URL
[20]	Khaled K. F., Hackerman N ., Electrochim. Acta, 2003,48(19), 2715— 2723 doi: 10.1016/S0013-4686(03)00318-9 URL
[21]	Fan B. M., Hao H., Yang B., Ma Z., Feng Y. H ., Surf. Technol., 2018,47(10), 22— 29
	( 樊保民, 郝华, 杨彪, 马震, 冯云皓 . 表面技术, 2018,47(10), 22— 29)
[22]	Ahamad I., Prasad R., Quraishi M. A ., Corros. Sci., 2010,52(4), 1472— 1481 doi: 10.1016/j.corsci.2010.01.015 URL
[23]	Tian H., Li W., Liu A., Gao X., Han P., Ding R., Yang C., Wang D ., Corros. Sci., 2018,131, 1— 16 doi: 10.1016/j.corsci.2017.11.010 URL
[24]	Liu Z., Li B. R., Pan Y. X., Shi K., Wang W. C ., Chem. J Chinese Universities, 2017,38(4), 669— 677
	( 刘志, 李炳睿, 潘艳雄, 石凯, 王伟财 . 高等学校化学学报, 2017,38(4), 669— 677)
[25]	Zarrouk A., Zarrok H., Ramli Y., Bouachrine M., Hammouti B., Sahibed-Dine A ., J. Mol. Liq., 2016,222, 239— 252 doi: 10.1016/j.molliq.2016.07.046 URL
[26]	Abdallah M ., Corros. Sci., 2002,44(4), 717— 728 doi: 10.1016/S0010-938X(01)00100-7 URL
[27]	Hu S. Q., Hu J. C., Gao Y. J., Jia X. L., Guo W. Y ., CIESC. J., 2011,62(1), 147— 155
	( 胡松青, 胡建春, 高元军, 贾晓林, 郭文跃 . 化工学报, 2011,62(1), 147— 155)
[28]	Khalil N ., Electrochim. Acta, 2003,48(18), 2635— 2640 doi: 10.1016/S0013-4686(03)00307-4 URL
[29]	Hu S. Q., Hu J. C., Fan C. C., Mi S. Q., Zhang J., Guo W. Y ., Acta Phys. Chim. Sin., 2010,26(8), 2163— 2170
[30]	Ansari K. R., Quraishi M. A ., J. Ind. Eng. Chem., 2014,20(5), 2819— 2829 doi: 10.1016/j.jiec.2013.11.014 URL
[31]	Yurt A., Balaban A., Ustün Kandemir S., Bereket G., Erk B ., Mater. Chem. Phys., 2004,85(2), 420— 426 doi: 10.1016/j.matchemphys.2004.01.033 URL
[32]	Singh A., Gajra A., Cardiovasc. Hematol . Agents Med. Chem., 2011,9(1), 7— 13