Complete protection of a passive film on iron from breakdown in a borate buffer containing 0.1 M of Cl− by coverage with an ultrathin film of two-dimensional polymer

An ultrathin film of two-dimensional polymer was prepared on a passivated iron electrode by modification of a 16-hydroxyhexadecanoate ion HO(CH2)15CO2- self-assembled monolayer with 1,2-bis(triethoxysilyl)ethane (C2H5O)3Si(CH2)2Si(OC2H5)3 and octadecyltriethoxysilane C18H37Si(OC2H5)3. This film prevented passive film breakdown examined by potentiodynamic anodic polarization of the coated electrode in the borate buffer solution containing 0.1 M of Cl−. Neither current spikes nor the pitting potential was observed in the passive and transpassive regions of polarization curve. The anodic current density was decreased in these regions markedly, implying hindrance to permeation of Cl− and water through the film. Structure of the film was clarified by X-ray photoelectron and FTIR reflection spectroscopies and contact angle measurement with a drop of water. Electron-probe microanalysis of the passivated surface coated with the film after anodic polarization scanning up to the transpassive region revealed that the polymer film prevents pit initiation by an attack on the passive film with Cl−.