High efficient corrosion inhibition of steel by nano-micro aggregates of Sapindus mukorossi Gaertn peel extracts

doi:10.11949/0438-1157.20200065

Abstract

Abstract:

To seek green, sustainable and natural plant extracts with the potential for large-scale application as corrosion inhibitors, this article selects the extracts of the Sapindus mukorossi Gaertn peels with surfactant properties as the research object. Hence, this article uses Sapindus mukorossi Gaertn peel extracts (SMGPE) with surfactant properties as the study candidate. This survey presents efficient extraction of Sapindus mukorossi Gaertn peels by simply refluxing ethanol solution. It is shown that SMGPE can process orderly nano-micro meters aggregation in DMF/HCl (volume ratio: 50/50, 1.0 mol/L HCl solution) mixed solution through self-organization at the room temperature.The results show that the predominantly strong chemical adsorption of formed SMGPE aggregates on the studied Q235 steel specimens is suggested through the detection of FT-IR, Raman as well as XPS spectroscopy. This study further determines the corrosion inhibition effect of the stable SMGPE aggregates for the studied steel specimens in 1.0 mol/L HCl aqueous solution based on electrochemical method. The results suggest that the SMGPE aggregates can inhibit corrosion of the steel specimens in HCl solution efficiently, and the greatest corrosion inhibition efficiency is over 90%.

Key words: self-aggregation, adsorption, steel, HCl solution, corrosion

摘要：

为寻求绿色、可持续与具备大规模应用潜能的天然植物提取物作为缓蚀剂，选择具有表面活性剂性质的无患子果皮提取物作为研究对象。通过简便乙醇回流萃取获得无患子果皮提取物。在室温条件下，无患子果皮提取物在DMF（N，N-二甲基甲酰胺）/HCl水溶液的混合溶液（体积比50/50，1.0 mol/L HCl 溶液）中能够发生自组装产生有序的纳微米聚集材料。傅里叶变换红外光谱（FT-IR）与X射线光电子能谱（XPS）研究表明了无患子果皮提取物聚集体能够对Q235钢表面产生化学吸附作用。利用电化学方法研究了无患子果皮提取物聚集体吸附在钢表面后，在1.0 mol/L盐酸水溶液中的缓蚀性能。结果表明无患子果皮提取物聚集体能够有效抑制钢被盐酸腐蚀，最大缓蚀效率达到90%以上。

关键词: 自聚集, 吸附, 钢, 盐酸溶液, 腐蚀

CLC Number:

TG 178

Xue LUO, Haijun HUANG, Ziping LUO, Zhiyong WANG, Xiaojing MU, Hongru LI, Xinchao WANG, Shengtao ZHANG, Fang GAO. High efficient corrosion inhibition of steel by nano-micro aggregates of Sapindus mukorossi Gaertn peel extracts[J]. CIESC Journal, 2020, 71(10): 4760-4772.

罗雪, 黄海军, 罗自萍, 王治永, 穆小静, 李红茹, 王新潮, 张胜涛, 高放. 无患子果皮提取物的纳微米聚集体对钢的高效缓蚀[J]. 化工学报, 2020, 71(10): 4760-4772.

Figures/Tables 20

Fig.1 Chemical structures of the main molecular constituents in Sapindus mukorossi Gaertn peel extract (SMGPE)

Fig.2 Diagrammatic drawing of the formation of SMGPE aggregates and the preparation of the stable SMGPE aggregates protection film on the studied steel specimen surface

Fig.3 OCP versus time curves in 1.0 mol/L HCl solutions for the investigated unmodified steel electrodes and the stable SMGPE aggregates of different concentrations covered steel electrodes

Fig.4 SEM images of SMGPE aggregates in DMF/HCl (vol ratio 50/50，1.0 mol/L HCl solution) mixed solution at different aggregation time

Fig.5 SEM images of SMGPE aggregates in DMF/HCl (vol ratio 50/50，1.0 mol/L HCl solution) mixed solution with different concentrations from 0.1 to 0.6 g/L at 10 h evolution time

Fig.6 FT-IR spectrum of original SME powder (a)； FT-IR spectrum of the stable SMGPE aggregates (aggregation concentration 0.5 g/L, aggregation time 10 h）adsorbed on the studied steel specimen surfaces (b)

Fig.7 Fe 2p XPS spectra from the surfaces of the investigated bare steel immersed in HCl solution for 1 h (a)； Fe 2p XPS spectra from the studied steel specimens treated by the stable SMGPE aggregates (aggregation concentration 0.5 g/L, aggregation time 10 h) immersed in HCl solution for 1 h (b)

样品	化学状态	结合能/eV	半峰宽/eV
空白钢片	Fe₂O₃/Fe₃O₄/FeOOH	710.38	3.45
空白钢片	FeCl₃	712.47	3.5
吸附稳定SMGPE聚集体的钢片	Fe⁰	707.31	1.75
	Fe₂O₃/ Fe₃O₄	709.10	2.00
	FeOOH	710.90	2.00

Fig.8 C 1s XPS spectra from surfaces of the investigated bare steel immersed in HCl solution (1.0 mol/L HCl) for 1 h (a); C 1s XPS spectra from surfaces of the studied steel specimens treated by stable SMGPE aggregates (aggregation concentration 0.5 g/L, aggregation time 10 h) immersed in 1.0 mol/L HCl solution for 1 h (b)

样品	化学状态	结合能/eV	半峰宽/eV
空白钢片	C—C/CC	284.90	1.62
	C—O	285.79	1.55
	CO	288.43	2.00
吸附稳定SMGPE聚集体的钢片	C—C/CC	284.98	2.06
	C—O	287.03	1.90
	CO	288.68	2.30

Fig.9 O 1s XPS spectra from surfaces of the investigated bare steel immersed in 1.0 mol/L HCl solution for 3 h; O 1s XPS spectra from surfaces of the studied steel specimens treated by stable SMGPE aggregates (aggregation concentration 0.5 g/L, aggregation time 10 h) immersed in HCl solution for 1 h

Table 3 De-convolution parameters including chemical states, binding energies and FWHMs of O 1s XPS spectra peaks obtained from surfaces of the studied bare steel specimen and the studied steel specimens treated by stable SMGPE aggregates immersed in 1.0 mol/L HCl solution for 1 h (aggregation concentration, 0.5 g/L, aggregation time, 10 h)

样品	化学状态	结合能/eV	半峰宽/eV
空白钢片	Fe₂O₃/ Fe₃O₄	530.92	2.00
空白钢片	FeOOH	531.61	1.80
吸附稳定SMGPE聚集体的钢片	Fe₂O₃/ Fe₃O₄	530.24	1.90
	FeOOH	531.55	1.75
	CO/C—O	533.41	1.60

Fig.10 SEM micrographs of the studied steel specimen surfaces

Fig.11 Potentiodynamic polarization curves in 1 mol/L HCl solutions for the investigated unmodified steel electrodes and the stable SMGPE aggregates of different concentrations (aggregation time 10 h) covered steel electrodes

Table 4 Polarization parameters for the studied unmodified and modified steel specimens by different concentrations of stable SMGPE aggregates (aggregation time 10 h) in 1.0 mol/L HCl solution

电极	极化参数
电极	C/(g/L)	E_corr (vs. SCE) /V	I_corr/(A/cm²)	β_c/(V/dec)	β_a/(V/dec)	η_j/%
空白钢电极	—	-0.480	4.387×10^-7	-0.1278	0.1068	—
稳定SMGPE聚集体吸附的钢电极	0.1	-0.447	1.004×10^-7	-0.1146	0.0585	77.11
	0.2	-0.442	4.957×10^-8	-0.1175	0.0508	88.7
	0.3	-0.437	4.549×10^-8	-0.1233	0.0515	89.63
	0.5	-0.430	2.820×10^-8	-0.1226	0.0424	93.57
	0.6	-0.440	3.767×10^-4	-0.1212	0.0524	91.41

Fig.12 Nyquist curves for the studied naked steel electrodes and SMGPE aggregates (aggregation time 10 h) of various concentrations covered steel electrodes(a)； Bode plots for the studied naked steel electrodes (b) and SMGPE aggregates (aggregation time 10 h) of various concentrations covered steel electrodes (c)

Fig.13 Equivalent circuit models fitting the EIS experimental data in this study

Table 5 Electrochemical impedance parameters for the studied unmodified and different concentrations of stable SMGPE aggregates (aggregation time 10 h) modified steel specimens in 1.0 mol/L HCl solution

电极	C/ (g/L)	电化学参数					χ²
电极	C/ (g/L)	R_s/ (Ω·cm²)	R_ct/ (Ω·cm²)	C_dl/ (F/cm²)	n	η_E/%	χ²
空白钢电极	—	0.6096	44.36	1.408×10^-7	0.9551	—	4.81×10³
SMGPE聚集体吸附的钢电极	0.1	0.8946	182.0	6.34×10^-8	0.8832	75.63	2.41×10³
	0.2	0.9725	315.4	5.48×10^-8	0.8829	85.94	1.52×10³
	0.3	0.9667	451.2	4.49×10^-8	0.8707	90.17	4.65×10³
	0.5	0.8991	635.0	3.98×10^-8	0.8928	93.01	1.95×10³
	0.6	1.2320	484.4	4.46×10^-8	0.8867	90.92	7.48×10³

Fig.14 Langmuir adsorption isotherm of stable SMGPE aggregates on the studied steel specimen surfaces in 1.0 mol/L HCl solution at 298 K (yP to Tafel curves, yE to electrochemical impedance spectroscopy)

Table 6 Thermodynamic parameters for the adsorption of SMGPE aggregates at 298 K

测试方法	吸附能 $Δ G a d s 0$ /(J/mol)
Polarization	-26790
EIS	-26430

Table 6 Thermodynamic parameters for the adsorption of SMGPE aggregates at 298 K

测试方法	吸附能 $Δ G a d s 0$ /(J/mol)
Polarization	-26790
EIS	-26430

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