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

doi:10.11949/0438-1157.20191318

Abstract

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

摘要：

通过多步法合成了离子型含双苯并三氮唑环的目标分子，4，4'-{苯-1，3-二基二[(1E)-3-羰基丙-1-烯-1，3-二基]}二[2-(2H-苯并三唑-2-基)苯醇酸]二钾。在室温条件下，目标分子在3.5%（质量）NaCl/DMSO（二甲基亚枫）混合溶液（体积比：40/60）中能够发生分子自组装产生纳-微米级的自聚集体。通过傅里叶变换红外光谱（FT-IR）、拉曼光谱和X射线光电子能谱（XPS）的表征，证实了所形成的目标分子自聚集体能够对铜表面产生强烈的化学吸附作用，在铜表面形成自组装膜。利用电化学方法测定了目标分子自聚集体吸附在铜表面形成自组装膜后，在3.5%（质量）NaCl溶液中的缓蚀性能。结果表明目标分子自聚集体在NaCl溶液中能高效地抑制铜腐蚀。

关键词: 自聚集, 吸附, 铜, NaCl溶液, 腐蚀, 修复

CLC Number:

TG 178

Xue LUO, Chuan JING, Haijun HUANG, Hongru LI, Zhiyong WANG, Zhenqiang WANG, Fang GAO, Shengtao ZHANG. Study on highly efficient corrosion inhibition of copper by regular self-aggregates of organic molecule[J]. CIESC Journal, 2020, 71(10): 4733-4749.

罗雪, 荆川, 黄海军, 李红茹, 王治永, 王震强, 高放, 张胜涛. 规整有机分子自聚集体对铜的高效缓蚀的研究[J]. 化工学报, 2020, 71(10): 4733-4749.

Figures/Tables 20

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
缓蚀剂	c (mol/L)	E_corr(SCE)/ V	j_corr/(A/cm²)	β_c/(V/dec)	β_a/(V/dec)	η_j/%
空白	—	-0.221	5.233×10^-6	-0.1667	0.04305	—
BDBD自聚集体	1.0×10^-4	-0.237	1.349×10^-6	-0.1331	0.1153	74.22
	3.0×10^-4	-0.265	9.35×10^-7	-0.1382	0.1192	82.14
	5.0×10^-4	-0.269	2.22×10^-7	-0.1471	0.2025	95.76
	7.0×10^-4	-0.251	4.78×10^-7	-0.1425	0.1393	90.87

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	K_ads/ (L/mol)	吸附能/ (J/mol)
Polarization	4.9×10⁴	-6730
EIS	4.5×10⁴	-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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