In this work, in-situ ATR-FTIR in the Kretschmann configuration is proposed as an interfacial sensitive technique able to probe molecular processes at the buried interface of an industrial relevant polyester primer. Zinc, aluminium and magnesium oxide were used to represent oxides present at galvanized steel sheets used in coil coating. Two competing interactions with polyester resin and melamine-based crosslinker were shown to take place at metal hydroxide sites. This highlights the increased complexity of interfacial phenomena at metal–paint interfaces. Furthermore, in-situ ATR-FTIR was performed in deuterated water (D₂O) to study the evolution of interfacial carboxylate bond degradation, without overlap of dominant water signals. For the first time, interfacial bond formation of paints and its degradation in an aqueous environment is studied in-situ. It is shown that the introduction of D₂O at the interface initially increases the amount of interfacial carboxylate bonds, whereas upon longer exposure times bond degradation occurs. Significant delay of interfacial bond degradation on hexafluorozirconic acid treated oxides indicate successful stabilization of the metal-polymer interface by zirconium-based conversion coatings. Consequently, in-situ ATR-FTIR is able to demonstrate improved interfacial stability due to zirconium-based treatment in real-time and on a molecular level.

Integrated attenuated total reflection – Fourier transform infrared spectroscopy (ATR-FTIR) – Electrochemical impedance spectroscopy (EIS) measurements were used to simultaneously follow chemisorption mechanisms of organic inhibitors as well as their corrosion inhibition efficiency towards magnesium based substrates. Four carboxylic compounds, i.e. 2,5-pyridinedicarboxylic acid (PDC), 3-methylsalicylic acid (MSA), sodium salicylate (SS) and fumaric acid (FA), were selected based on their promising inhibiting capacities and were all shown to chemisorb at the MgO/Mg(OH)₂ surface by carboxylate bond formation. Orientation analysis using polarized infrared light showed that carboxylate bonds established using aliphatic carboxylate compound aligned perpendicular to the magnesium surface, whereas carboxylate bonds with aromatic compounds were oriented in plane with the magnesium surface. This different orientation is associated to the involvement of π-interactions in the MgO/Mg(OH)₂ – aromatic carboxylate adsorption. Additionally, DFT calculations revealed that the addition of hetero-atoms (i.e. N or OH) in the molecular structure contributes to increased adsorption energies, indicating that next to carboxylate groups also these hetero-atoms are involved in interfacial interactions. Integrating the ATR-FTIR setup with an electrochemical cell allowing for simultaneous EIS measurements lead to two surface phenomena determining the inhibition efficiency. Surface hydroxylation processes on one hand forming a MgO/Mg(OH)₂ layer on one hand, and the chemisorption of carboxylate compounds on the other hand. The inhibition efficiency was found to increase in following order: FA < PDC < MSA and was mainly associated to the formation of a MgO/Mg(OH)₂ layer. SS was shown to act as a corrosion accelerator rather than a corrosion inhibitor. Despite its high sensitivity for water, both surface processes could be followed in situ by means of ATR-FTIR. Simultaneously, protective properties of the formed films could be quantified by means of EIS. Consequently, integrated ATR-FTIR – EIS methodology has shown to be highly valuable for gaining in-situ insights in the inhibition mechanism, while quantifying the inhibition efficiency. This was even possible for highly active metal substrate as magnesium, although further developments are suggested if one aims to quantify electrochemical constants related to corrosion and other surface processes measured at the low frequencies (i.e. < 1 Hz).

The bonding properties of zirconium- and titanium-based conversion coatings were evaluated using model conversion solutions of H₂ZrF₆ and H₂TiF₆ with addition of various organic additives (PAA, PVA, PVP). Macroscopic testing techniques such as contact angle and pull-off adhesion measurements were performed on galvanized steel sheets. Complementary to this, molecular studies were performed on model zinc substrates using ATR-FTIR in the Kretschmann configuration. The macroscopic and molecular approaches showed a good correlation demonstrating ATR-FTIR in the Kretschmann configuration to be a valuable tool to gain fundamental insights in metal oxide-polymer interfacial phenomena. Zirconium-treated galvanized steel substrates were shown to have a higher bonding affinity for the polyester coil coat primer than titanium-treated galvanized steel substrates. The presence of organic additives did not further improve the bonding properties. Yet, organic additives initially improved the interfacial stability of titanium-treated substrates. However, on the long term, organic additives are shown to be detrimental for polyester coil coat adhesion. This adverse effect of organic additives on the long term was assigned to its selective dissolution during immersion and was most pronounced for titanium-treatments. The limited effect of organic additives in case of zirconium-treatments was attributed to the higher portion of chemical interfacial bonds, as well as its tendency for crosslinking reactions causing entanglement of polymeric compounds in the zirconium oxide structure.

The effect of zirconium-based conversion of thermally vaporized zinc, aluminium and magnesium on the chemisorption of dimethylsuccinate was studied using attenuated total reflection – Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) analysis. Two competing chemisorption mechanisms contribute to interfacial bond formation. Hydrogen interactions on one hand were shown to occur between metal hydroxides and non-hydrolysed ester-groups of the molecule. On the other hand, both native and zirconium-treated substrates were shown to form interfacial carboxylate bonds with dimethylsuccinate, evidencing their capability of hydrolysing ester groups towards more reactive acid groups. Both interactions were shown to correlate to the metal oxide acid-base properties.

In this paper, different macroscopic electrochemical techniques are applied to study the corrosion inhibitor efficiency, protection mechanism and stability of a calcium aluminum polyphosphate silicate hydrate inhibitor on hot-dip galvanized steel in the time-domain. Potentiodynamic polarization (PP) measurements are applied to study the anodic and cathodic mechanistic behavior as well as inhibitor efficiencies at discrete and single times of exposure. Open circuit potential (OCP) with superimposed linear polarization resistance (LPR) measurements are applied as a faster, non-invasive alternative to PP, characterizing the overall performance of the system in terms of the polarization resistance. Electrochemical impedance spectroscopy (EIS) measurements are applied to detail both the overall performance of the system as well as the corrosion inhibition mechanism related to the electrochemical system’s physicochemical representation over time. Electrochemical noise (EN) measurement are used to evaluate the inhibition efficiency as a function of exposure time, represented by the electrochemical noise resistance. Odd random phase electrochemical impedance spectroscopy (ORP-EIS) is selected as the electrochemical tool to study the system’s instability, by evaluation of the non-linearities and non-stationarities over time. The non-stationarities present in the inhibitor-containing electrochemical system are shown to cause the overall instability of the system and should be taken into account when interpreting results from the different techniques over time.