Effects of ring substituents on the protective properties of self-assembled benzenethiols on copper

The self-assembled monolayers (SAMs) of a series of substituted benzenethiol (BT) molecules, X–C6H4–SH (where X = meta-NH2, ortho-NH2, para-NH2, para-NHCOCH3, para-F, para-CH3 and para-CH(CH3)2), have been prepared by adsorption from a solution onto a fresh copper (Cu) surface pretreated by a nitric acid etch. The corrosion inhibition efficiency of the modified Cu surfaces in a sulfuric acid solution was investigated by electrochemical characterization. The protection afforded by the substituted functional groups on BT is strongly influenced by the type and the position of the substituent on the benzene ring. BT molecules without any substituent group on the ring are ineffective corrosion inhibitors, indicating that the chemical configuration is the key factor in determining the efficacy of the SAMs as barriers to electrochemically corrosive ions. It is further proposed that the steric hindrance offered by the substituted group in the SAMs plays a very important role in determining its barrier properties.