In previous work, the importance of taking the time-domain into account when studying corrosion inhibitor-containing electrochemical systems was highlighted. In this work, odd random phase electrochemical impedance spectroscopy (ORP-EIS) is applied as the electrochemical tool to study the time-effect by the evaluation of the non-stationarities per frequency decade over time for the screening of different silica- and phosphate- based corrosion inhibitors for hot-dip galvanized steel and possible corrosion inhibitor synergism. This serves as the basis for the interpretation of the results obtained from different macroscopic electrochemical techniques such as potentiodynamic polarization (PP), open circuit potential (OCP) with superimposed linear polarization resistance (LPR), electrochemical impedance spectroscopy (EIS) and electrochemical noise (EN) measurements. The analysis of the time-domain shows that all systems have a system-specific ‘stabilization’ time which affects the interpretation of the results obtained from the macroscopic electrochemical techniques. Furthermore, these results indicate that all corrosion inhibitors tested exhibit corrosion protective action and that the combination of both silica-based corrosion inhibitors show synergistic action on hot-dip galvanized steel.

Zirconium-based conversion treatment of zinc, aluminium and magnesium oxides have been studied in-situ using ATR-FTIR in a Kretschmann geometry. This set-up was coupled to an electrochemical cell, which allowed to obtain chemical and electrochemical information simultaneously as a function of conversion time. This elucidated the strong relation between physico-chemical surface properties and zirconium-based conversion kinetics. Whereas the surface hydroxyl density of zinc and aluminium increased during conversion, magnesium (hydr)oxide was shown to dissolve in the acid solution. Due to this dissolution, strong surface alkalization can be expected, explaining the rapid conversion kinetics. AES depth profiling was used to determine the final oxide thickness and elemental composition. This confirmed that magnesium is most active and forms a zirconium oxide layer approximately 10 times thicker than zinc. On the other hand, the presence of zirconium oxide on aluminium is very low and can be considered as not fully covering the metal oxide. Additionally, the converted oxide chemistry was related to the bonding mechanisms of amide functionalized molecules using ATR-FTIR and XPS. It was shown that inclusion of zirconium altered the acid-base properties, increasing the substrate proton donating capabilities in case of magnesium oxide and increasing hydrogen bonding and Bronsted interactions due to increased surface hydroxide fractions on zinc and aluminium substrates.