Corrosion Protection of Copper with Hybrid Sol-Gel Containing 1H-1, 2, 4-triazole-3-thiol

Document Type : Research Article


Department of Chemistry, Gandhigram Rural Institute-Deemed University, Gandhigram-624 302, Tamil Nadu, INDIA


To improve the corrosion protection of copper metal, 0.01M concentration of 1H-1,2,4-triazole-3-thiol (TAT) was incorporated into the hybrid sol-gel monolayers containing 3-glycidoxypropyltrimethoxysilane (GPTMS) and Tetraethoxysilane (TEOS). It was further subjected to hydrolysis and condensation reaction to form a sol-gel matrix. The TAT-doped hybrid sol-gel coating was applied over the copper surface by Self-Assembled Monolayer (SAM) method. The resultant coating was characterized by Fourier Transform Infrared (FT-IR), X- RayDiffraction (XRD) analysis, Scanning Electron Microscopy (SEM) and Energy-Dispersive X-ray (EDX) spectroscopy. The corrosion protection ability of these coatings was evaluated by Electrochemical Impedance Studies (EIS) and Potentiodynamic Polarization (PP) measurements in 3.5% NaCl medium. The EIS and PP results showed that TAT doped hybrid sol-gel coating exhibit better corrosion protection than the undoped hybrid coating alone. Thus these studies revealed the enhancement of corrosion protection of TAT doped hybrid sol-gel coating on the copper metal surface.


Main Subjects

[1] Sherif E.M., Erasmus R.M., Comins J.D., Corrosion of Copper in Aerated Synthetic Sea Water Solutions and Its Inhibition by 3-Amino-1, 2, 4-Triazole, Journal of Colloid Interface Science, 309:470-477 (2007)
[2] Otmacic H, Telegdi J, Papp K, Stupnisek-Usac E., Protective Properties of an Inhibitor Layer Formed on Copper in Neutral Chloride Solution, J. Appl Electrochem, 34: 545-550 (2004)
[3] Sherif E.M, Park S.M., Electrochemical Behavior of Copper in Borax Buffer Solution in the Presence of l-Phenyl-5-Mercapto Tetrazole, J. Electrochem. Soc., 152: B428-B433 (2005)
[4] Curkovic H.O, Stupnisek-Lisac E, Takenouti H., The Influence of pH Value on the Efficiency of Imidazole Based Corrosion Inhibitors of Copper, Corros. Sci, 52: 398-405 (2010)
[5] Szocs E, Vastag G, Shaban A, Kalman E., Electrochemical Behviour of an Inhibitor Film Formed on Copper Surface, Corros. Sci, 38: 2019-2029 (1996)
[6] Sherif E.M, Park S.M., 2-Amino-5-ethyl-1, 3, 4-Thiadiazole as a Corrosion Inhibitor for Copper in 3.0% NaCl Solutions, Corros. Sci., 48: 4065-4079 (2006).
[7] Finsgar M, Milosev I, Pihlar B., Inhibition of Copper Corrosion Studied by Electrochemical and EQCN Techniques, Acta Chimica Slovenica, 54: 591-597 (2007).
[8] Amin M.A., Weight Loss, Polarization, Electrochemical Impedance Spectroscopy, J. Appl Electrochem, 36: 215-226 (2006).
[9] Ismail K.M., Electrochemical Preparation and Kinetic Study of Poly (o-Tolidine) in Aqueous Medium, Electrochim. Acta, 52: 3883-3888 (2007)
[11] Liang C, Wang P , Wu B, Huang N., Inhibition of Copper Corrosion by Self-Assembled Monolayers of Triazole Derivative in Chloride-Containing Solution, J. Solid State Electrochem, 14: 1391-1399 (2010).
[12] Sorensen P.A, Kiil S, Dam-Johansen K, Weinell C.E., Anticorrosive Coatings: A Review, J. Coat. Technol. Res., 6: 135-146 (2009).
[13] Huynh N., Bottle S.E., Notoya T., Schweinsberg D.P., Inhibitive Action of the Octyl Esters of 4-and
5-Carboxybenzotriazole for Copper Corrosion in Sulphate Solutions
, Corros. Sci., 42: 259-274 (2000).
[14] Antonijevic M.M, Milic S.M, Serbula S.M, Bogdanovic G.D., The Influence of Chloride Ions and Benzotriazole on the Corrosion Behavior of Cu37Zn Brass in Alkaline Medium, Electrochim. Acta., 50: 3693-3701 (2005).
[15] Ulman. A., “An Introduction to Ultrathin Organic Films, From Langmuir-Blodgett to Self Assembly”, Academic Press: Boston (1991).
[16] Swalen J.D., Allara D.L., Andrade J.D., Chandross E.A., Garof S., Israelachvili J., McCarthy T.J., Murray R., Pease R.F., Rabolt J.F., Wynne Y.H., Molecular Monolayers and Films. A Panel Report for the Materials Sciences Division of the Department of Energy, Langmuir, 3: 932-950 (1987).
[17] Zhang D.Q, Gao L.X, Cai Q.R, Lee K.Y., Inhibition of Copper Corrosion by Modifying Cysteine Self‐Assembled Film with Alkylamine/Alkylacid Compounds, Mater. Corros., 61: 16-21 (2010).
[18] Li G.Y., Ma H.Y., Jiao Y.L., Chen S.H., An Impedance Investigation of Corrosion Protection of Copper by Self-assembled Monolayers of Alkanethiols in Aqueous Solution, J. Serb. Chem. Soc., 69: 791-805 (2004). 
[20] Sherif E.M, Park S.M., Inhibition of Copper Corrosion in Acidic Pickling Solutions by N-Phenyl-1, 4-Phenylenediamine, Electrochim. Acta., 51: 4665-4673 (2006)
[21] Zucchi F., Trabanelli G., Fonsati M., Tetrazole Derivatives as Corrosion Inhibitors for Copper in Chloride Solutions, Corros. Sci., 38: 2019-2029 (1996).
[22] Antonijevic M.M, Petrovic M.B., Copper Corrosion Inhibitors. A Review, Int. J. of Electrochem. Sci., 3: 1-28 (2008).
[24] Zheng S.X, Li J.H., Inorganic–Organic Sol Gel Hybrid Coatings for Corrosion Protection of Metals, J. Sol-Gel Sci Technol., 54: 174-187 (2010).
[25] Zucchi F., Grassi V., Frignani A., Trabanelli G., Inhibition of Copper Corrosion by Silane Coatings, Corros. Sci., 46: 2853-2865 (2004).
[26] Laibinis P.E, Whitesides G.M, Allara D.L Tao Y.T, Parikh A.N, Nuzzo R.G., Comparison of the Structures and Wetting Properties of Self-Assembled Monolayers of n-Alkanethiols on the Coinage Metal Surfaces, Copper, Silver, and Gold , J. Am. Chem. Soc., 113:7 152-7167 (1991)
[27] Balaji J., Sethuraman M.G., Corrosion Protection of Copper with 3-Glycidoxypropyltrimethoxysilane-Based Sol–Gel Coating Through 3-Amino-5-Mercapto-1,2,4-Triazole Doping, Res. Chem. Intermed,  DOI: 10.1007/s11164-015-2087-1, (2015).
[30] Alvarez D., Colazzo A., Hernandez M., Nova X.R., Perez C., Characterization of Hybrid Sol–Gel Coatings Doped with Hydrotalcite-Like Compounds to Improve Corrosion Resistance of AA2024-T3 Alloys, Prog. Org. Coat., 68: 91-99 (2010).
[31] Krishnakumar V, Xavier R.J., FT Raman and FT–IR Spectral Studies of 3-Mercapto-1,2,4-Triazole, Spectrochimica Acta Part A, 60:709–714 (2004).
[32] Lu S., Chen Y., Xu W., Liu W., Controlled Growth of Superhydrophobic Films by Sol–Gel Method on Aluminum Substrate, Appl. Surf. Sci., 256: 6072-6075 (2010).
[33] Karthik N., Arunkumar V., Sethuraman M.G., Enhancement of Protection of Aluminum Through Dopamine Impregnation into Hybrid Sol–Gel Monolayers, J. Mater. Sci., 49: 7970-7978 (2014).
[34] Lamaka S.V., Zheludkevich M.L., Yasakau K.A., Serra R., Poznyak S.K., Ferreira M.G.S., Nanoporous Titania Interlayer as Reservoir of Corrosion Inhibitors for Coatings with Self-Healing Ability, Prog. Org. Coat., 58:127-135 (2007).
[35] Wang P, Liang C.H, Wu B, Huang N.B, Li J.L., Protection of Copper Corrosion by Modification of Dodecanethiol Self-Assembled Monolayers Prepared in Aqueous Micellar Solution, Electrochim. Acta, 55: 878-883 (2010).
[36] Ma H, Chen S, Niu L, Zhao S, Li S, Li D., Inhibition of Copper Corrosion by Several Schiff Bases in Aerated Halide Solutions, J. Appl. Electrochem., 32:65-72 (2002).
[37] Qin T.T., Li J., Qun Luo H., Li M., Bing Li N., Corrosion Inhibition of Copper by 2, 5-Dimercapto-1, 3, 4-Thiadiazole Monolayer in Acidic SolutionCorros. Sci., 53: 1072-1078 (2011).
[38] Zhou Y., Xu S., Guo L., Zhang S., Lu H., Gong Y., Gao F., Evaluating Two New Schiff Bases Synthesized on the Inhibition of Corrosion of Copper in NaCl Solutions, RSC Adv., 5, 14804-14813 (2015).
[39] Appa Rao B.V, Narsihma Reddy M., Self-Assembled 1-Octadecyl-1H-Benzimidazole Film on Copper Surface for Corrosion Protection, J. Chem. Sci., 125: 1325-1338 (2013).
[41] Kear G., Barker B.D., Walsh F.C., Electrochemical Corrosion of Unalloyed Copper in Chloride Media––a Critical Review, Corros. Sci., 46: 109-135 (2004).
[42] Otmacic H., Stupnisek-Lisac E., Copper Corrosion Inhibitors in Near Neutral Media, Electrochim. Acta, 48: 985-991 (2003).
[43] Innocenzi P., Kidchob T., Hybrid Organic-Inorganic Sol-Gel Materials Based on Epoxy-Amine Systems, J. Sol-Gel Sci. Technol., 35: 225-235 (2005).