Synchrotron infrared reflectance microspectroscopy study of film formation and breakdown on copper

This work demonstrates the utility of synchrotron infrared reflectance microspectroscopy in the far- and mid-IR for the determination of the composition of electrogenerated surface films formed during the general and localized corrosion of copper in alkaline and bicarbonate solutions. Back-reflection geometry has been employed to identify the anodic film formed on copper in 0.1 M NaOH solution at 0.3 V (versus a Ag/AgCl reference) to be mainly CuO. In 0.01 M NaHCO(3) solution general corrosion occurs with passive film formation below 0.2 V. The surface film at 0.2 V consisted mainly of bicarbonate, copper carbonate dihydroxide or malachite [CuCO(3).Cu(OH)(2)], Cu(OH)(2) and possibly some CuO. At higher potentials the passive film breaks down and localized corrosion occurs leading to the formation of pits. The composition of the surface films inside the pits formed at 0.6 V was found to be essentially the same as that outside but the relative amount of Cu(OH)(2) appears to be higher.