The Inhibition Of Copper Corrosion In Aqueous Environments With Heterocyclic Compounds

Benzotriazole (BTAH) has been used as a corrosion inhibitor for copper and copper-, based alloys for more than 40 years. It has been successfully employed for the, prevention of both atmospheric corrosion and particularly for the protection of, copper under immersed conditions. Whilst BTAH is an excellent inhibitor in alkaline, solution its efficiency drops off markedly as the pH decreases. It was hypothesized, that a possible way to increase surface adsorption and subsequent better inhibition, over a wide pH range might be through the preparation of derivatives, particularly, carboxybenzotriazoles and alkyl esters of these compounds. In this work the following techniques: weight loss measurements, potentiodynamic, polarisation, SERS spectroscopy, electrochemical impedance spectroscopy and, coulometry were employed to investigate the inhibition efficiency of 4- and 5-, carboxybenzotriazole and their alkyl ester for copper corrosion. Molecular modelling, was also investigated as a tool for inhibitor design. Studies on 4- and 5- carboxybenzotriazole (CBT) showed that the inhibition, efficiency for copper corrosion in aerated acidic sulphate solution of each isomer was, pH, concentration and time dependant. At lower pH the 5-isomer is the better, inhibitor and this behaviour continues at higher pH. The anti-tarnishing test showed, that whilst both isomers exhibited these properties, 5-CBT was once again the, superior inhibitor. It was found that a commercial mixture of the octyl esters of 4- and 5-, carboxybenzotriazole inhibits copper corrosion in sulphate environments open to air., The inhibition efficiency of the ester mixture at the lx10-4 M level (pH - 0) is 98%, which compares very favourably with that for BTAH (- 50%). With respect to other, alkyl esters of 4- and 5-carboxybezotriazole, hexyl, butyl and methyl, it was found, that all of these inlibited copper corrosion in sulphate environments open to air. In, each case the inhibition efficiency is concentration, pH and time dependent. Both, coupon tests and EIS measurements indicate that inhibition efficiency depends on the, length of the alkyl chain. At pH - 0 the inhibition efficiency decreased in the order, octyl >hexyl >butyl >methyl. At higher pH (- 8) the order is reversed. At the 1x104, M level (pH - 0) the inhibition efficiency of each of the alkyl esters is equal to or, better than that for BTAH. At higher pH (- 8) the inhibition efficiency in each case is, reduced in comparison to BTAH. but is still good enough for practical use ( 2 75%)., The inhibitive behaviour of the alkyl esters at low pH can be attributed to, chemisorption through an azole nitrogen of the protonated alkyl esters. The, hydrocarbon chain is also physically adsorbed and the increase in physical adsorption, as the chain is lengthened accounts for the improved inhibition efficiency. Dry films formed by immersing copper in solutions of alkyl esters of, carboxybenzotriazole also inhibit copper corrosion in both strongly acidic (pH - 0), and near neutral (pH - S) sulphate corrodents. The inhibition efficiency depends on, the solvents used to dissolve the esters, solution temperature and immersion time., Aqueous coating solutions furnish the most protective films. Films formed by, CBTAH-BU, CBTAH-HE and CBTAH-OE are more protective than that formed by, BTAH. The inhibition efficiency of the alkyl ester film increases as the alkyl chain is, made longer. Molecular modeling showed that the optimum crude binding energy (Eblnd), between each protonated ester molecule and the surface varied linearly with the alkyl, chain length. The resulting linear correlation between IE% and E bind for compounds, that are structurally similar suggested that the crude binding energy of a single, molecule with copper may be used to predict the inhibition performance of other, compounds constituting a series.