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Journal of Chinese Society for Corrosion and protection  2021, Vol. 41 Issue (4): 517-522    DOI: 10.11902/1005.4537.2021.055
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Hybrid Corrosion Inhibitor for Anti-corrosion and Protection of Bronze Relics
ZHOU Hao1, WANG Shengli2, LIU Xuefeng2, YOU Shijie2()
1.Conservation Center, Shanghai Museum, Shanghai 200231, China
2.State Key Laboratory of Urban Water Resource and Environment, School of Environment, Harbin Institute of Technology, Harbin 150090, China
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Abstract  

The effect of a hybrid corrosion inhibitor, namely mixtures of benzotriazole (BTA) and sodium formate (SFA), on the corrosion behavior of bronze in 3% (mass fraction) NaCl solution was assessed by means of CHI760E electrochemical workstation and X-ray photoelectron spectroscopy (XPS) technique. The results demonstrated a satisfied anti-corrosion enhancement effect of SFA, indicated by increased film resistance and interfacial electron-transfer resistance on bronze surface measured by electrochemical impedance spectroscopy. The XPS analysis indicated a major impact of the type of the formed oxides on bronze surface to the formation of Cu-BTA complex. And in the presence of SFA, the corrosion product on bronze surface is dominated by Cu2O, which is more conductive to the adsorption of BTA and the formation of Cu (I)-BTA complex, thereby improving the corrosion resistance of bronze. This study not only provides a deeper insight into the theoretical basis for the anti-corrosion of bronze, but also suggests an effective approach to protect bronze cultural relics as well.

Key words:  bronze relic      hybrid corrosion inhibitor      anti-corrosion treatment     
Received:  18 March 2021     
ZTFLH:  TG174  
Fund: National Natural Science Foundation of China(51671117)
Corresponding Authors:  YOU Shijie     E-mail:  sjyou@hit.edu.cn
About author:  YOU Shijie, E-mail: sjyou@hit.edu.cn

Cite this article: 

ZHOU Hao, WANG Shengli, LIU Xuefeng, YOU Shijie. Hybrid Corrosion Inhibitor for Anti-corrosion and Protection of Bronze Relics. Journal of Chinese Society for Corrosion and protection, 2021, 41(4): 517-522.

URL: 

https://www.jcscp.org/EN/10.11902/1005.4537.2021.055     OR     https://www.jcscp.org/EN/Y2021/V41/I4/517

Fig.1  SEM images of original sample surface (a) and polished sample surface (b)
SampleBTA / mol·L-1SFA / mol·L-1
#000
#10.050
#20.040.01
#30.030.02
#40.020.03
#50.010.04
#600.05
Table 1  Proportion of BTA and SFA
Fig.2  Curves of open circuit potential (EOCP) vs time of bronzes in 3%NaCl solution
Fig.3  Surface corrosion of bronze samples in 3%NaCl after immersed for 24 h
Fig.4  Potentiodynamic polarization curves of bronze samples in 3%NaCl solution
SampleEcorr / mVIcorr / μA·cm-2η / %
#0-25157.38---
#1-3473.5893.76
#2-3453.8493.31
#3-3803.2594.34
#4-3282.9194.93
#5-3623.0694.67
#6-223141.77-147.07
Table 2  Fitted parameters of potentiodynamic polarization curves
Fig.5  EIS comparison of bronze samples in 3%NaCl solution
Fig.6  Electrical equivalent circuit model used to fit the impedance data: (a) #0 and #6; (b) #1~#5
ParameterRs / Ω·cm2Y1 / S·Secn·cm-2n1R1 / Ω·cm2Y2 / S·Secn·cm-2n2R2 / Ω·cm2Zw / Ω·cm2Rp / Ω·cm2η / %
#01.994.9×10-60.8014.5---------0.000714.5---
#12.222.9×10-50.7529.126.4×10-60.61166.20---195.3289.85
#22.991.5×10-60.8271.652.6×10-50.91478.98---550.6396.40
#31.641.3×10-60.7381.351.4×10-40.78753.79---835.1497.38
#43.264.01×10-50.851212.685.1×10-50.4634043.04---35255.7299.95
#52.708.1×10-60.90734.123.2×10-40.521373.41---2107.5399.01
#63.947.7×10-70.960.65---------0.00060.65-180.66
Table 3  Electrical equivalent circuit parameters obtained for bronze samples
Fig.7  XPS spectra of the surface film of bronzes (a) and Cu 2p (b)
SampleCOPbClNSnCu
#070.3518.230.381.463.130.745.71
#178.7312.760.31.55.370.271.07
#477.3211.640.210.848.010.261.72
#663.4524.862.520.892.662.453.16
Table 4  Surface film composition of bronze sample treated with corrosion inhibitor
Fig.8  Percentage of Cu (II) and Cu (I) on bronze surfaces
1 Wang Z C, Li Y, Jiang X D, et al. Research progress on ancient bronze corrosion in different environments and using different conservation techniques: A review [J]. MRS Adv., 2017, 2: 2033
2 Shamnamol G K, Sreelakshmi K P, Ajith G, et al. Effective utilization of drugs as green corrosion inhibitor-a review [J]. AIP Conf. Proc., 2020, 2225: 070006
3 Verma C, Verma D K, Ebenso E E, et al. Sulfur and phosphorus heteroatom-containing compounds as corrosion inhibitors: an overview [J]. Heteroat. Chem., 2018, 29: e21437
4 Liu L, Lu S, Wu Y Q, et al. Corrosion inhibition behavior of four benzimidazole derivatives and benzotriazole on copper surface [J]. Anti-Corros. Methods Mater., 2020, 67: 565
5 Lv X H, Zhang Y, Yan Y L, et al. Performance evaluation and adsorption behavior of two new mannich base corrosion inhibitors [J]. J. Chin. Soc. Corros. Prot., 2020, 40: 31
吕祥鸿, 张晔, 闫亚丽等. 两种新型曼尼希碱缓蚀剂的性能及吸附行为研究 [J]. 中国腐蚀与防护学报, 2020, 40: 31
6 Chugh B, Singh A K, Thakur S, et al. An exploration about the interaction of mild steel with hydrochloric acid in the presence of N-(Benzo [d]thiazole-2-yl)-1-phenylethan-1-imines [J]. J. Phys. Chem., 2019, 123C: 22897
7 Lu S, Ren Z B, Xie J Y, et al. Investigation of corrosion inhitibion behavior of 2-aminobenzothiazole and benzotriazole on copper surface [J]. J. Chin. Soc. Corros. Prot., 2020, 40: 577
卢爽, 任正博, 谢锦印等. 2-氨基苯并噻唑与苯并三氮唑复配体系对Cu的缓蚀性能 [J]. 中国腐蚀与防护学报, 2020, 40: 577
8 Salvadori B, Cagnini A, Galeotti M, et al. Traditional and innovative protective coatings for outdoor bronze: Application and performance comparison [J]. J. Appl. Polym. Sci., 2018, 135: 46011
9 Neodo S, Carugo D, Wharton J A, et al. Electrochemical behaviour of nickel-aluminium bronze in chloride media: influence of pH and benzotriazole [J]. J. Electroanal. Chem., 2013, 695: 38
10 Mezzi A, Angelini E, De Caro T, et al. Investigation of the benzotriazole inhibition mechanism of bronze disease [J]. Surf. Interface Anal., 2012, 44: 968
11 Cho B J, Shima S, Hamada S, et al. Investigation of cu-BTA complex formation during Cu chemical mechanical planarization process [J]. Appl. Surf. Sci., 2016, 384: 505
12 Monticelli C, Balbo A, Esvan J, et al. Evaluation of 2-(salicylideneimino) thiophenol and other Schiff bases as bronze corrosion inhibitors by electrochemical techniques and surface analysis [J]. Corros. Sci., 2019, 148: 144
13 Brunoro G, Frignani A, Colledan A, et al. Organic films for protection of copper and bronze against acid rain corrosion [J]. Corros. Sci., 2003, 45: 2219
14 Peng J, Chen B L, Wang Z C, et al. Surface coordination layer passivates oxidation of copper [J]. Nature, 2020, 586: 390
15 Hu G, Lv G C, Xu C C, et al. Synergistic effect of corrosion inhibition on bronze by benzotriazole and sodium molybdate [J]. Corros. Sci. Prot. Technol., 2008, 20: 25
胡钢, 吕国诚, 许淳淳等. BTA和钼酸钠对青铜的协同缓蚀作用研究 [J]. 腐蚀科学与防护技术, 2008, 20: 25
16 Chavez K L, Hess D W. A novel method of etching copper oxide using acetic acid [J]. J. Electrochem. Soc., 2001, 148: G640
17 Van Ingelgem Y, Tourwé E, Vereecken J, et al. Application of multisine impedance spectroscopy, FE-AES and FE-SEM to study the early stages of copper corrosion [J]. Electrochim. Acta, 2008, 53: 7523
18 Venkatesh R P, Cho B J, Ramanathan S, et al. Electrochemical impedance spectroscopy (EIS) analysis of BTA removal by TMAH during post Cu CMP cleaning process [J]. J. Electrochem. Soc., 2012, 159: C447
19 Manivannan R, Cho B J, Hailin X, et al. Characterization of non-amine-based post-copper chemical mechanical planarization cleaning solution [J]. Microelectron. Eng., 2014, 122: 33
20 Nyrkova L I, Polyakov S H, Osadchuk S O, et al. Determination of the rate of atmospheric corrosion of metal structures by the method of polarization resistance [J]. Mater. Sci., 2012, 47: 683
21 Cohen S L, Brusic V A, Kaufman F B, et al. X‐ray photoelectron spectroscopy and ellipsometry studies of the electrochemically controlled adsorption of benzotriazole on copper surfaces [J]. J. Vac. Sci. Technol., 1990, 8A: 2417
22 Kokalj A, Peljhan S. Density functional theory study of adsorption of benzotriazole on Cu2O surfaces [J]. J. Phys. Chem., 2015, 119C: 11625
23 Finšgar M, Milošev I. Inhibition of copper corrosion by 1,2,3-benzotriazole: A review [J]. Corros. Sci., 2010, 52: 2737
[1] Zhanshi Zhang; Shaohua Chen; Zhangru Chen; Yuemiao Liu. SIMULATION STUDY ON THE CORROSION PROCESSES OF UNEARTHED BRONZE RELICS[J]. 中国腐蚀与防护学报, 2006, 26(2): 94-99 .
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