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.

In situ synchrotron far-infrared spectromicroscopy of a copper electrode at grazing incidence angle.

Synchrotron far-infrared spectroscopy in situ was successfully carried out on a copper microelectrode using a grazing-angle objective attached to a Bruker IRscope II microscope. The thin-layer spectroelectrochemical cell was constructed out of Teflon and fitted with a 20 microm-thick Mylar window; the copper electrode was 500 microm in diameter. Measurements were carried out in 0.1 M NaOH solution as a function of applied potential between -1.4 and 0 V versus a Hg/Hg2SO(4) reference electrode. Results demonstrate that with the present technique it is possible to obtain in situ spectra with excellent signal-to-noise ratio for surface oxide films formed electrochemically with less than 1 nL of active solution volume. The surface film on copper at 0 V consisted mainly of CuO with possibly some Cu(OH)2 also present. This interpretation is consistent with previous works and thermodynamic calculations.