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Unravelling the Fe Effect on the Corrosion of Chromium Coatings: Chemical Composition and Semiconducting Properties


 A model trivalent chromium-based electroplating bath doped with different concentration of Fe was used to obtain the different metallic coatings. The impact of the Fe was investigated on the Cr layer and on its native passive film by a detailed characterisation using X-ray Photoelectron Spectroscopy (XPS), Angle Resolved XPS and Auger Electron Spectroscopy. Moreover, the semiconducting properties of their oxide layers were explored by Mott-Schottky and the corrosion performance by the linear polarisation resistance and kinetics of the oxide formation. Results revealed not only a homogeneous Fe distribution into the Cr layer but also the presence of an iron-chromium duplex oxide layer for concentrations ≥ 100 mg/L Fe in the bath. The Mott-Schottky analysis showed a p-n junction for such coatings due to the presence of an iron oxide layer on the top of a chromium oxide one which increases the total amount of point defects (charge carrier density) and drastically affects their corrosion resistance (the polarisation resistance decreased by one order of magnitude and their oxide layer showed slower kinetics and a higher passivation current). In contrast, coatings with a single chromium oxide layer showed a p-type semiconducting behaviour as well as the best corrosion performance.