Cathodic electrodeposition of cerium-based oxides on carbon steel from concentrated cerium nitrate solutions

In this work the elaboration by cathodic electrodeposition of cerium-based oxides on carbon steel from relatively concentrated cerium nitrate solutions is investigated. In particular, the study presented here (Part I) focuses on the electrochemical and analytical characterisation of the films and on the correlations between the electrochemical features and the characteristics of the layers. The effect of other parameters such as concentration, temperature, pH and additives to improve the behaviour of the film against corrosion will be investigated in part II of the study. The electrochemical characterisation will reveal that Ce(IV)-steel interactions can be responsible for some weak electrochemical waves appearing in the cyclic voltammograms that often are attributed to oxygen or nitrates reduction. This results from the oxidation of Ce(III) solutions to Ce(IV) in contact with air. Furthermore, the deposits strongly depend on the applied current density. Low current densities do not render fully covering deposits on the steel and a carbonated green rust will appear. On the contrary, the increase of the current density leads to denser layers of relatively small crystallite size that readily covers the steel surface. The deposits have a needle-like morphology and the Ce content achieves a plateau of about 20-22 at.%. However, a significant network of cracks appears probably occurring during the deposition process itself. The differential scanning calorimetry (DSC) results indicate that the deposits are not fully crystalline after 550 deg. C in contrast with the X-ray diffraction (XRD) patterns that unambiguously show a fluorite-type CeO2 phase whose crystallite size decreases with increasing the current density. The rinsing medium also brings about different features of the films. Rinsing with water allows to incorporate more nitrates and to adsorb CO2 than when rinsing with ethanol. However, R-OH bonds will be trapped in the latter