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Journal of Chinese Society for Corrosion and protection  2018, Vol. 38 Issue (4): 381-390    DOI: 10.11902/1005.4537.2017.053
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Molecular Dynamics Simulation of Adsorption Behavior of Schiff Base Surfactants on Zn Surface in Aqueous Solution
Zheng LIU(), Haiying LI, Hao WANG, Yong ZHAO, Siwei XIE, Shufen ZHANG
Guangxi Key Laboratory of Electrochemical and Magneto-chemical Functional Materials, College of Chemical and Biological Engineering, Guilin University of Technology, Guilin 541004, China
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Abstract  

Three polyethylene glycol (400) lauric acid monoester Schiff base surfactants (M1, M2 and M3) were synthesized and characterized. The adsorption behavior and the effect of the group of surfactant molecules on the adsorption properties about M1, M2, M3 on the metal Zn surface were investigated by means of molecular dynamics simulation method. While the corrosion inhibition performance of the three surfactants on alkaline Zn-electrode was assessed by means of mass loss method, electrochemical impedance spectroscopy and scanning electron microscopy. It showed that M3 exhibited the best corrosion inhibition, and the corrosion inhibition efficiency was 92% when the concentration reached 1.0 mmol/L. The Schiff base surfactant molecules adsorbed on Zn surface parallelly to form a dense molecular adsorption film. What's more, the ranking of the adsorption energy of the three surfactants was M3>M2>M1, and that of the adsorption rate was M3>M2>M1. M3 had better corrosion inhibition performance for alkaline zinc electrode, and had better inhibition effect on zinc dendrite.
Key words:  surfactant      adsorption behavior      molecular dynamics simulation      zinc surface      corrosion inhibition performance     
Received:  13 April 2017     
ZTFLH:  O643.12  
Fund: Supported by National Natural Science Foundation of China (21266006), Natural Science Foundation of Guangxi (2016GXNSFAA380109) and Special Funds for Special Experts in Guangxi (NO2401007012)
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Zheng LIU
Haiying LI
Hao WANG
Yong ZHAO
Siwei XIE
Shufen ZHANG

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Zheng LIU, Haiying LI, Hao WANG, Yong ZHAO, Siwei XIE, Shufen ZHANG. Molecular Dynamics Simulation of Adsorption Behavior of Schiff Base Surfactants on Zn Surface in Aqueous Solution. Journal of Chinese Society for Corrosion and protection, 2018, 38(4): 381-390.

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https://www.jcscp.org/EN/10.11902/1005.4537.2017.053     OR     https://www.jcscp.org/EN/Y2018/V38/I4/381

Fig.1  Synthesis route of three Schiff base surfactants
Fig.2  Molecular structure models of M1 (a), M2 (b) and M3 (c)
Surfactant ConcentrationmmolL-1 ΔWg ηw% Dwg / m2h
Blank --- 3.6×10-2 --- ---
M1 0.4 1.4×10-2 62.0 1.89
0.7 7.7 ×10-3 79.0 1.06
1.0 6.3×10-3 82.0 0.87
1.3 6.1×10-3 82.8 0.85
1.6 6.0×10-3 83.3 0.82
M2 0.4 9.7×10-3 73.0 1.34
0.7 6.0×10-3 83.0 0.83
1.0 4.0×10-3 88.8 0.55
1.3 3.9×10-3 89.1 0.54
1.6 3.7×10-3 89.6 0.51
M3 0.4 8.3×10-3 77.0 1.15
0.7 5.0×10-3 86.0 0.69
1.0 2.8×10-3 92.2 0.38
1.3 2.5×10-3 93.0 0.34
1.6 2.3×10-3 93.6 0.31
Table1  Mass loss results of Zinc after corrosion in KOH solutions without and with different concentrations of the synthesized surfactants
Fig.3  Nyquist curves of Zn during corrosion in KOH solutions without and with different concentrations of M1 (a), M2 (b) and M3 (c), and corresponding equivalent circuit (d)
Surfactant Concentration / mmolL-1 R1 / Ωcm2 R2 / Ωcm2 Cd / Fcm-2 η / %
Blank --- 0.31 52.82 1.2×10-2 ---
M1 0.4 0.57 108.71 4.1×10-4 51.41
0.7 0.58 147.44 1.1×10-3 64.18
1.0 0.62 224.60 1.0×10-2 76.47
M2 0.4 0.51 271.48 8.4×10-3 80.54
0.7 0.53 316.92 7.8×10-3 83.33
1.0 0.59 412.02 6.6×10-3 87.18
M3 0.4 0.62 480.30 5.9×10-3 89.00
0.7 0.65 519.53 7.7×10-3 89.83
1.0 0.64 672.02 4.686×10-3 92.14
Table 2  Fitting electrochemical parameters of EIS and corrosion inhibition of zinc electrode in ZnO saturated KOH solutions with different concentrations of surfactants
Fig.4  SEM images of Zn electrode immersed for 50 h in 6 mol/L KOH solutions with saturated ZnO (a) as well as three kinds of 0.7 mmol/L surfactants of M1 (b), M2 (c) and M3 (d)
Fig.5  Temperature (a~c) and energy (d~f) equilibrium curves of M1 (a, d), M2 (b, e) and M3 (c, f) surfactants adsorbed on Zn (1 1 0) surface in aqueous solution
Fig.6  Configuration diagrams of three surfactants M1 (a, d), M2 (b, e), M3 (c, f) before (a~c) and after (d~f) adsorption on Zn (1 1 0) surface
Molecular Emolecule+surface / (kcalmol-1) Emolecule / (kcalmol-1) Esurface / (kcalmol-1) Eadsorption / (kcalmol-1)
M1 -34470 -38.19 -34023 -408.81
M2 -34484 -16.48 -34023 -444.52
M3 -34496 -16.93 -34023 -456.07
Table 3  Adsorption energies of three surfactants on Zn (1 1 0 ) surface
Fig.7  MSD of three surfactants adsorbed on Zn (1 1 0)
Fig.8  Distance variation between two groups of three surfactants M1 (a, d), M2 (b, e), and M3 (c, f) before (a~c) and after (d~f) adsorption, respectively
Fig.9  Variations of distance between the surface of zinc and feature groups of M1 (a), M2 (b) and M3 (c) surfactants and H2O
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