A comparative electrochemical and quantum chemical calculation study of BTAH and BTAOH as copper corrosion inhibitors in near neutral chloride solution

摘要

The inhibition of copper corrosion in 3% NaCl solution was studied by using a well-known inhibitor, benzotriazole (BTAH), and its not so extensively explored derivative, 1-hydroxybenzotriazole (BTAOH). Electrochemical methods, i.e., linear polarization, Tafel and potentiodynamic curve measurements and electrochemical quartz crystal microbalance (EQCM) measurements were used. Corrosion parameters and inhibition effectiveness were determined. Experimental results showed that benzotriazole is a more effective inhibitor of the corrosion of copper in chloride media than 1-hydroxybenzotriazole. Whereas in the presence of BTAH a protective Cu-BTA layer is formed on the Cu surface, in the presence of BTAOH a thick, poorly protective layer is formed, which readily dissolves in chloride solution. Kinetic parameters were calculated based on EQCM results. Adsorption of BTAOH follows a linear growth law, in contrast to BTAH, whose film growth can be best represented at first by a parabolic, and later by logarithmic, growth law. Different mechanisms of growth imply different mechanisms of inhibition and account for the different inhibition effectiveness. Density functional theory calculations were performed to characterize certain features of the molecular structures, including the electronic parameters related to the inhibition effectiveness of these inhibitors. Introduction of the -OH group into the benzotriazole molecules does not change their electronic parameters significantly neither in gas phase nor in the presence of water solvent. Other parameters, therefore, affect the inhibition effectiveness of these corrosion inhibitors. In particular, superior inhibition effectiveness of BTAH is attributed to interplay of planar molecular structure, physisorption and intermolecular H-bonding, which cooperatively may result in formation of thin and protective film on the surface.