Abstract
X‐ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM) were combined to investigate the thickness, chemical composition, and structure of passive films formed in 0.5 M 
on (100)Fe‐18Cr‐13Ni. The XPS measurements show that aging under polarization at +500 mV/SHE causes a dehydration reaction of the outer chromium hydroxide layer of the passive film. This reaction results in a thickening of the mixed Cr(III) and Fe(III) inner oxide layer and increases the 
enrichment. This reaction consumes, in addition to chromium hydroxide of the outer layer, chromium from the metallic phase underneath the passive film. Only traces of nickel (hydroxide) are detected in the passive film, whereas Ni enrichment is observed in the alloy underneath the passive film. High‐resolution STM images reveal that aging under polarization causes a crystallization of the inner 
oxide layer in epitaxy with the substrate. The epitaxial relationship is 
with 
. The crystallization proceeds with a faster kinetics than on (110) Fe‐22Cr in the same conditions. The crystallization rate is modified by the presence of Ni in the alloy, which is enriched in the metallic phase underneath the film and slows down the formation of 
in the inner part of the film. This favors a more complete process of crystallization. Aging under polarization is beneficial to the further stability of the passive film in air.