The effect of illumination on passivity and the initiation of pitting
corrosion on pure iron in berate buffer pH 8.4 is studied. It is obser
ved that a monochromatic (325 nm) illumination of the sample leads to
a very strong increase in its pitting corrosion resistance-apparent fr
om pitting potential and incubation time measurements in chloride cont
aining electrolytes. This effect is strongly dependent on the light in
tensity. The cause for the decreased pitting susceptibility is not bas
ed on a change in the field distribution within the passive film but i
s much more associated with light induced changes in the passive film
properties during passivation. These changes can neither be attributed
to a film thickening nor to an altered temperature caused by illumina
tion. The electronic properties of the passive films were studied by M
ott-Schottky analysis and photocurrent transient measurements. The res
ults indicate that illumination during passivation leads to modificati
ons in the electronic properties of the passive films-specifically to
an increase of the bulk doping-and the surface state density. Further
it can be concluded that the electronic properties of the passive film
on iron can rather be described in terms of a semiconductor model tha
n by a dielectric approach.