CIESC Journal ›› 2020, Vol. 71 ›› Issue (10): 4733-4749.doi: 10.11949/0438-1157.20191318

• Surface and interface engineering • Previous Articles     Next Articles

Study on highly efficient corrosion inhibition of copper by regular self-aggregates of organic molecule

Xue LUO1(),Chuan JING1(),Haijun HUANG1,Hongru LI1,Zhiyong WANG1,Zhenqiang WANG1,2,Fang GAO1(),Shengtao ZHANG1   

  1. 1.School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China
    2.College of Chemistry, Chongqing Normal University, Chongqing 401331, China
  • Received:2019-11-11 Revised:2020-03-28 Online:2020-10-05 Published:2020-04-22
  • Contact: Fang GAO E-mail:xueluo1994@163.com;493753698@qq.com;fanggao1971@gmail.com

Abstract:

This study presents synthesis of target ionic bistriazole rings-based molecule, 4,4'-{benzene-1,3-diylbis[(1E)-3-oxoprop-1-ene-1,3-diyl]}bis[2-(2H-benzotriazol-2-yl)phenolate] dipotassium (BDBD), through multi-step preparation route. At room temperature, the target molecule can self-assemble to produce nano-micron self-aggregates in a 3.5%(mass) NaCl / DMSO (dimethyl maple) mixed solution (volume ratio, 40/60). It is shown that the predominantly strong chemical adsorption of the formed molecular self-aggregates on the studied copper specimen leads to the yield of self-assembly film on copper surface, which is characterized by FT-IR, Raman and XPS spectroscopy. The corrosion inhibition performance of the stable self-aggregates adsorbed-copper specimens in 3.5%(mass) brine solution based on electrochemical method is surveyed. The results show that the target molecular self-aggregates can effectively inhibit copper corrosion in NaCl solution.

Key words: self-aggregation, adsorption, copper, NaCl solution, corrosion, repair

CLC Number: 

  • TG 178

Fig.1

Chemical structure and synthesis route of the target molecule BDBD"

Fig.2

Schematic diagram of the formation of the target molecular BDBD aggregates efficiently adsorbed on copper surface"

Fig.3

SEM images of BDBD aggregates at 5×10-4 mol/L in the mixed 3.5% NaCl solution/DMSO (40% volume ratio of DMSO) at aggregation time course of 20 min (a), 1 h (b), 2 h (c), respectively"

Fig.4

SEM images of the BDBD aggregates in the mixed 3.5% NaCl DMSO aqueous solution (40% DMSO volume ratio) at 2 h evolving time with diflerent BDBD concentration: 1.0×10-4 mol/L (a), 3.0×10-4 mol/L (b), 5.0×10-4 mol/L (c), 7.0×10-4 mol/L (d)"

Fig.5

SEM micrographs of the studied Cu specimen surfaces: before the immersion in the 3.5% NaCl/DMSO aqueous solution containing the stable BDBD aggregates (a); after the immersion in the 3.5% NaCl/DMSO aqueous solution with 3.0×10-4 mol/L of the stable BDBD aggregates for 3 h (b); after the immersion in the 3.5% NaCl/DMSO aqueous solution with 5.0×10-4 mol/L of the stable BDBD aggregates for 3 h (c); after the immersion in the 3.5% NaCl/DMSO aqueous solution with 7.0×10-4 mol/L of the stable BDBD aggregates for 3 h (d)"

Fig.6

SEM micrographs of the studied Cu specimen surface absorbed with 5.0×10-4 mol/L of the stable BDBD aggregates for 3 h in 3.5% NaCl/ DMSO, which was take out and immersed in the 3.5% NaCl for 14 d"

Fig.7

FT-IR spectrum of the BDBD powder (a); FT-IR spectrum of the stable BDBD aggregates adsorbed on the studied copper specimen surfaces (b); Raman spectra of stable BDBD aggregates adsorbed on the studied copper specimen surfaces (c)"

Fig.8

Cu 2p (a), O 1s (b), C 1s (c) XPS spectra and the fitted curves measured on the studied copper specimens that were immersion in the mixed 3.5% NaCl DMSO aqueous solution for 3 h (DMSO/H2O: 40/60, volume ratio)"

Fig.9

Cu 2p (a), C 1s (b); O 1s (c), N 1s (d) XPS spectra and the fitted curves measured on the studied copper specimens after 3 h of immersion in the mixed 3.5% NaCl DMSO aqueous solution (DMSO/H2O: 40/60, volume ratio) containing the stable BDBD aggregates of 5.0 ×10-4 mol/L"

Fig.10

Potentiodynamic polarization curves in 3.5 % NaCl solution for the studied naked copper electrodes, and for the studied stable BDBD-aggregates of different concentrations covered copper electrodes"

Table 1

Polarization parameters for the studied copper specimens covered without and with the stable BDBD aggregates of different concentrations in 3.5% NaCl solution"

缓蚀剂极化曲线参数
c (mol/L)Ecorr(SCE)/ Vjcorr/(A/cm2)βc/(V/dec)βa/(V/dec)ηj /%
空白-0.2215.233×10-6-0.16670.04305
BDBD自聚集体1.0×10-4-0.2371.349×10-6-0.13310.115374.22
3.0×10-4-0.2659.35×10-7-0.13820.119282.14
5.0×10-4-0.2692.22×10-7-0.14710.202595.76
7.0×10-4-0.2514.78×10-7-0.14250.139390.87

Fig.11

Nyquist plots for the studied naked copper electrodes and the stable BDBD aggregates of different concentrations covered copper electrodes in 3.5% NaCl solution"

Fig.12

Equivalent circuit models fitting the EIS experimental data in 3.5% NaCl solution"

Table 3

Thermodynamic parameters for the adsorption of stable BDBD aggregates in 3.5% NaCl solution at 298 K"

方法Kads/ (L/mol)吸附能/ (J/mol)
Polarization4.9×104-6730
EIS4.5×104-36510

Fig.A1

Representative 1H NMR spectrum of target molecule BDBD"

Fig.A2

SEM images of the BDBD aggregates of 5.0×10-4 mol/L in the mixed 3.5% NaCl DMSO aqueous solution (40% DMSO volume ratio) at 6 h evolving time"

Fig.A3

SEM micrographs of the studied blank Cu specimen surface immersed in the 3.5% NaCl for 14 d"

Fig.A4

Langmuir adsorption isotherms of the stable BDBD aggregates covered on the studied copper specimen surfaces in 3.5 % NaCl solution (yp to potentiodynamic polarization and yE to electrochemical impedance spectroscopy"

Fig.A5

Optimized geometric structure, electron cloudy density distribution of HOMO and LUMO and Mulliken charge of the target molecule BDBD"

Fig.A6

The possible chemical coordination mechanism of the target molecule BDBD with Cu (I)"

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