In the present study, ex situ Fourier transform infrared (FTIR) chemical imaging and in situ electrochemical impedance spectroscopy (EIS) were combined to investigate the ageing process of a polyester/melamine coil-coated steel. The samples were first subjected to a QUV accelerated weathering test for 250 h up to 2000 h, followed by immersion in a 0.5 M NaCl solution to assess water uptake and polymer matrix plasticization. FTIR analyses revealed chemical degradation, including chain scission and the formation of polar groups, between 500 h and 2000 h of QUV exposure. Degradation effects were observed throughout the whole topcoat, with more significant degradation occurring near the surface. EIS measurements indicated greater water uptake with increasing QUV exposure, highlighting two regions of water sorption: an initial rapid Fickian diffusion region and a slower non-Fickian region. The time constant (τ) analysis, which was extracted from the EIS data and related to the dielectric manifestation of the glass transition, confirmed polymer matrix plasticization due to water uptake. Despite UV-induced degradation, the polymer maintained effective protective properties, as evidenced by the high low-frequency impedance unaffected by UV exposure or immersion duration (1 week). This methodology successfully identified ageing markers, providing a framework for studying UV degradation mechanisms, water uptake, and polymer mobility in anticorrosion coatings. 

Hot-dip Zn55Al-coated steel samples have been exposed for up to 6 years at 11 different weathering sites, including marine, marine-industrial, acid-rain and dry atmospheres. From the mass loss measurements, Zn55Al metallic coating showed globally long-term good corrosion resistance in all weathering conditions compared with hot-dip Zn-0.2Al-coated steel (Z). Yet, weaker performance was observed on Zn55Al in high SO2 polluted atmosphere, particularly when combined with seawater aerosols. This is explained by a more acidic surface condition linked to high SO2. Although the extent of corrosion in this phase was different at the different sites, the final corrosion products formed after 6 years were rather similar at all sites. This consists of hydrous aluminium sulphate or hydrous aluminium hydroxy sulphate and, probably also a smaller amount of sulphate-containing zinc corrosion products or Al/Zn products.

Local heterogeneities can have significant effects on the performance of anti-corrosion coatings. Even small features can act as initiation points for damage and result in corrosion of the substrate material. Analysis methods with high spatial resolution and the ability to collect information relevant to crosslinking and degradation behavior of these coatings are therefore highly relevant. In this work, we demonstrate the utility of nanomechanical AFM measurements and nano-FTIR in investigating the nanoscale mechanical and chemical properties of two polyester coil coating clearcoats before and after weathering. On the nanoscale, weathering led to a stiffer and less deformable coating with less variation in the nanomechanical properties. Chemical degradation was quantified using changes in band ratios in the IR-spectra. Macro and nano-scale measurements showed similar trends with the latter measurements showing larger heterogeneity. Our results demonstrate the usefulness of the described analysis techniques and will pave the way for future studies of local properties in other coating systems and formulations. © 2024 The Authors

The acid pickling of Al-3at.%Mg, Al-3at.%Cu, and aluminum alloy (AA) 7449-T651 in nitro-sulfuro-ferric acid was investigated using element-resolved electrochemistry (AESEC) in terms of their elemental dissolution kinetics. The influence of this acid pickling on the subsequent Zr-based conversion coating process was also demonstrated on these alloys by monitoring the dissolution rates of the alloying elements during conversion and the final elemental depth profiles from calibrated glow discharge-optical emission spectroscopy (GD-OES). The separate influence of fluoride (F−) and nitrate (NO3−) as additives on the dissolution kinetics was also investigated when added to the conversion coating bath solution. F− increased the dissolution rate of Al but no significant effect was seen on Cu, while NO3− enhanced the dissolution rates of both elements. Fourier-transform infrared reflection absorption spectroscopy (FT-IRRAS) data suggested a greater Zr-fluoride presence if the conversion coating was performed on a non-acid-pickled surface. 

An approach involving the quantification of microstructure characterized by different techniques such as SEM, EDS, and SKPFM is statistically treated to provide a deeper insight into the influence of recycling AA6063 on localized corrosion susceptibility. Particularly, the intermetallic particles and the two forms of localized corrosion – pitting and intergranular corrosion are systematically documented, measured, and analyzed. Even trace amounts of Cu and Zn introduced into the alloy from recycling had a remarkable effect on the localized corrosion susceptibility. The study found that the initiation and early evolution of the two localized corrosions are in competition, and the predominance of one over the other is closely linked to the composition of the alloy, and microstructure. Recycled variants with higher trace Cu made the alloy more susceptible to pitting attack whereas higher trace Zn is linked with greater IGC susceptibility. The trace amount of higher Zn addition has a particularly beneficial effect on pitting susceptibility as it reduces the likelihood of pitting even in alloys with a higher trace Cu content. The SKPFM results obtained in this study provided a basis for the circumferential pitting susceptibility around intermetallic particles, as a higher volta potential difference (∆V) implied a higher driving force for corrosion. ∆V differences between the different variants were further explained based on trace recycled element distribution in the microstructure. 

A mechanistic model of atmospheric bimetallic corrosion with a simplified empirical approach to the onset of localized corrosion attacks is presented. The model was built for a typical bimetallic sample containing aluminum alloy 1050 and stainless steel 316L sheets. A strategy was developed that allowed the model to be calibrated against the measured galvanic current, geometrical corrosion attack properties, and corrosion products. The pitting-onset simplification sets all pits to be formed at a position near the nobler metal and treated all pits as being of the same shape and size. The position was based on the location of the highest pitting events and the pit attributes on an average of the deepest pits. For 5 h exposure at controlled RH (85%, 91%, and 97%) and salt load (86 μg NaCl/cm2), the model was shown to be promising: both for analysis of local bimetallic corrosion chemistry, such as pH and corrosion products, and for efficient assessment of pitting damage by computing a single largest pit depth. Parametric studies indicated that the pitting-onset approximation deviated the most at the beginning of exposure and when RH was below 91%. © 2023 by the authors.

The initial atmospheric corrosion of ZM (ZnAlMg)-coated steel in humid air (85% RH) and humid argon (85% RH) containing 320 ppb SO2 was studied using in situ infrared reflection absorption spectroscopy (IRRAS), FTIR-ATR focal plane array (FPA) imaging and SEM-EDS. The corrosion products formed in humid air containing SO2 are mainly composed of magnesium sulphites and sulphates, with sulphite-containing corrosion products formed initially while the contribution from sulphates increased with exposure time. The results from FTIR-FPA imaging and SEM-EDS showed that the magnesium sulphite and sulphate are formed mainly on eutectic phases with a higher quantity of corrosion products formed on the binary eutectic (Zn-MgZn2 ) phases. This is due to presence of microgalvanic elements with the zinc-rich phases as the main sites for the cathodic oxygen reduction while the anodic reactions take place on the eutectic areas. Sulphate content is the highest on the binary eutectic phases, due to the microgalvanic effects and the production of oxidants by the cathodic reaction, which increases the oxidation of sulphite to sulphate.

Improved methods to assess the degradation of coil coatings to approximate lifetime have been an area of academic and industrial interest for decades. This work aims to elucidate the differences in the degradation behavior of two coil coating systems: one standard commercial formulation and one formulation with a significant addition of biorenewable reactive diluents. Depth-resolved degradation behavior of samples exposed to accelerated and natural field weathering is assessed. Focal plane array attenuated total reflection-Fourier transform infrared spectroscopy was used to acquire high-resolution chemical data from a sloping cross section. The results agreed with conventional photoacoustic spectroscopy. Degradation profiles for the two coatings were significantly different, with the biobased samples showing a more durable behavior. This study provides a method for detailed assessment of coating degradation, giving a good estimation of its durability. This is both a way to compare the performance of coating systems and to improve the understanding of the impact of exposure conditions, paving the way for the development of more sustainable coil coatings.

Spectroscopic imaging of water at the substrate / polymer interface was demonstrated by a new experimental set-up based on FTIR-ATR focal plane array (FPA) imaging and simultaneous electrochemical impedance spectroscopy measurements. The local distribution of water at the substrate / polymer interfacial region could be imaged with a lateral resolution in the micrometer range. The kinetics of local water uptake vs exposure time on polymer coated Ge as well as on polymer coated and NaCl pre-contaminated Ge surfaces was obtained. The set-up can also be used to study interfacial processes at polymer coated thin film metallic or metal oxide surfaces.

There are many potential causes of corrosion in animal buildings. Animals exhale large quantities of moisture into the air creating high relative humidity in the building if the moisture is not properly vented. High humidity increases the potential for condensation. In addition, ammonia may be found in large quantities in animal buildings. Ammonia is released from manure and urine. In addition, ammonium chloride is used as a nitrogen source in fertilisers. In this study, the atmospheric corrosion of hot-dip-galvanised steel and zinc alloy-coated steel such as zinc–aluminium and zinc–aluminium–magnesium has been studied in atmospheres containing different levels of ammonia. Investigations have also been conducted at different levels of ammonium chloride. The results are discussed in view of the mechanisms of corrosion of zinc and zinc alloy-coated steel in ammonia and ammonium chloride-containing environments.