Effect of powder painting procedures on the filiform corrosion of aluminium profiles

In this work, the filiform corrosion behaviour of powder painted aluminium profiles was studied, and the coating barrier properties together with adhesion to the substrate were analysed. Samples coated with a traditional painting procedure (one powder layer application followed by curing), and other samples coated using a special cycle to obtain wood grain effect were compared using accelerated filiform corrosion tests. Moreover, in order to better understand the degradation mechanisms of painted metal substrates, thermal stresses were applied to accelerate the natural weathering. The effects of the thermal aging were analysed by electrochemical impedance spectroscopy.     

Polyaniline inhibition of filiform corrosion on organic coated AA2024-T3

Dispersions of the polyaniline emeraldine salt (ES) of paratoluene sulphonic acid (PAni-pTS) effectively inhibit filiform corrosion (FFC) affecting polyvinyl butyral (PVB) coated AA2024-T3 aluminium alloy. An in-situ scanning Kelvin probe (SKP) technique is used to study the effect of systematically varying PAni-pTS volume fraction (?_pa) on FFC initiation and propagation. For ?_pa < 0.15, there is no evidence of FFC inhibition and E_corr values recorded for the intact coated aluminium (E_intact) remain similar to those measured for unpigmented PVB. At ?_pa ≥ 0.15, a marked rise in E_intact is observed, FFC propagation rates decrease and significant oxide growth is observed at the coating-metal interface. For emeraldine base (PAni-EB)-containing coatings, there is no evidence of interfacial oxide film formation, no ennoblement of E_intact and minimal inhibition of FFC. Conversely, when a PAni-pTS induced oxide covered surface is re-coated using unpigmented PVB and FFC is initiated as per normal, a substantial reduction in the rate of FFC propagation is observed. It is therefore proposed that inhibition of FFC by PAni-pTS arises principally as a result of the protective nature of the oxide film formed at the metal-coating interface.     

Influence of the curing temperature of a cataphoretic coating on the development of filiform corrosion of aluminium

Aluminium alloys are known to be particularly sensitive to filiform corrosion. The initiation of this particular type of corrosion is related to different parameters such as the presence of defects, the permeability of the coating to water and oxygen, the adherence of the paint system and the presence of salts.

In this work, the filiform corrosion resistance of Al 6016 substrates coated with a cataphoretic paint was studied. The curing of the coating was performed at different temperatures (185, 175, 165, 155 and 135 °C) in order to modify its mechanical properties and its permeability to oxygen.

The paint properties were studied by different techniques allowing the estimation of the degradation of the metal–primer system and giving some information about intrinsic paint properties.

The corrosion protection of the coating was evaluated by a normalized filiform corrosion test and by electrochemical impedance spectroscopy on scratched samples. The glass transition value and the internal stresses of the cataphoretic coatings obtained for different curing temperatures were determined by a stressmeter equipment.

This study enabled us to underline the influence of the curing temperature on the intrinsic properties of the coatings such as the glass transition temperature, the internal stresses, the adherence, the permeability and the corrosion protection properties.     

Silane sol–gel film as pretreatment for improvement of barrier properties and filiform corrosion resistance of 6016 aluminium alloy covered by cataphoretic coating

The aim of this study is to develop a newly silane sol–gel pretreatment on the barrier properties and filiform corrosion resistance of 6016 aluminium alloy covered by cataphoretic coating. The sol–gel coatings are used as coupling agent between aluminium substrate and cataphoretic paint. The pretreatment is an aqueous solution of three different silane compounds (glycidyloxypropyltrimethoxysilane (GPS), tetraethoxysilane (TEOS) and methyltriethoxysilane (MTES)) hydrolysed at two different pH (2 and 3.5). A system without pretreatment was studied as reference. The electrocoatings were cured between 155 °C and 195 °C in order to modify their mechanical properties.Polarisation curves, EIS and FT-IR measurements were used in order to characterize the silane layers. EIS measurements were used to follow the barrier properties and the water uptake evolution on intact coatings.The filiform corrosion protection of the coating was also evaluated by a normalized filiform corrosion test.     

Influence of crosslinking density of a cataphoretic coating on initiation and propagation of filiform corrosion of AA6016

The effect of curing temperature on initiation and propagation of filiform corrosion of an epoxy cataphoretic electrocoating deposited on aluminum alloy substrate was studied. EIS measurements were used to follow the evolution of the water uptake of the intact coatings. In addition, EIS was applied to determine the performances of the systems as a result of exposure to HCl vapours.     

Scanning Kelvin probe force microscopy for the in situ observation of the direct interaction between active head and intermetallic particles in filiform corrosion on aluminium alloy

This article presents for the first time an in situ high-resolution study of the interaction between the active head in filiform corrosion (FFC) and intermetallic particles within an aluminium alloy. For the first time direct evidence will be provided that the intermetallic particles directly determine the so far seemingly random course of the filaments. Both the segments of active filaments and the intermetallic particles (IMPs) were successfully imaged in a humid air (ca. 85% RH) environment by scanning Kelvin probe force microscopy (SKPFM) through a plasma polymer coating of about 340 nm thickness. In order to be able to do that, the experimental parameters need to be adjusted in such a way, that the width of the filaments is small enough to be well within the scan window of SKPFM (100 μm × 100 μm). Also it is important that the small IMPs can still be mapped by SKPFM through the coating. This was successfully achieved by use of a HDMSO plasma polymer film. Surface potential values in the head region of the propagating filaments were found to be 200 mV lower than the interface between intact plasma polymer and the aluminium alloy, indicating the active region. On the other hand, the surface potential values in the trailing filament tail are found to be about 250 mV higher than background, pointing out the cathodic site and superpassivation due to the accumulated corrosion products in this region. It was found that the direction of the filament is determined by the location of the IMPs nearest to the active head.     

Investigation by electrochemical impedance spectroscopy of filiform corrosion of electrocoated steel substrates

This work aims at studying by electrochemical impedance spectroscopy (EIS) the susceptibility to filiform corrosion of low carbon steel covered by cataphoretic coating. The determination of the exposed metallic area variations of scratched samples during ageing test is an estimation of the disbonding of the coating and/or the filiform corrosion. This area can be evaluated by electrochemical impedance spectroscopy (EIS). A simplified electrical equivalent model used to estimate the exposed metallic area is valid if the corrosion products are correctly dissolved before characterization. Furthermore the steel is a very complex substrate and thus many parameters must be optimized in order to remove the corrosion products before EIS measurements.     

The influence of aluminium surface pretreatment on the corrosion stability and adhesion of powder polyester coating

One of the most important factors in corrosion prevention by protective coatings is the coating adhesion loss under environmental influence. Thus, adhesion strength is often used when characterizing protective properties of organic coatings on a metal substrate. In order to improve the adhesion of organic coating the metal substrate is often pretreated in some way. In this work, the adhesion of polyester coatings on differently pretreated aluminium surface (by anodizing, with and without sealing, by phosphating and by silane film deposition) was examined. The dry and wet adhesion of polyester coatings were measured by a direct pull-off standardized procedure, as well as indirectly by NMP test. It was shown that under dry test conditions all polyester coatings showed very good adhesion, but that aluminium surface pretreated by silane film showed superior adhesion. The overall increase of wet adhesion for polyester coating on aluminium pretreated by silane film was maintained throughout the whole investigated time period. The different trends in the change of adhesion of polyester coatings were observed for different aluminium pretreatments during exposure to the corrosive agent (3% NaCl solution). The highest adhesion reduction was obtained for polyester coating on aluminium pretreated with phosphate coating. The corrosion stability of polyester coated aluminium was investigated by electrochemical impedance spectroscopy in 3% NaCl solution. The results confirmed good protective properties of polyester coating on aluminium pretreated with silane film, i.e. greater values of pore resistance and smaller values of coating capacitance were obtained in respect to other protective systems, whereas charge-transfer resistance and double-layer capacitance were not measurable during 2 months of exposure to a corrosive agent.     

Investigation of the first stages of the localized corrosion of pure copper combining EIS, FE-SEM and FE-AES

During the first 48 h that pure copper is submerged in a chloride containing solution, an oxide layer is formed that acts as a barrier layer between the aggressive solution and the substrate, offering some protection to the material. This barrier layer itself is subsequently attacked and localized corrosion is observed. The study of the corrosion behavior was based on open circuit potential (OCP) measurements. The evolution of this value was concurrent with the evolution of the state of the oxide layer. Furthermore the surface state was evaluated by taking impedance spectra every 2 h. This method proved to be insufficient to elucidate the surface evolution and additional techniques were employed. The thickness and the composition of the oxide layers as well as the different composition of the corrosion products in and around the zones of localized attack were determined by means of an FE-AES equipped with an ion gun. The scanning electron microscope (SEM) allowed us to visually discriminate between the three stages the surface passes through during the first 48 h. Mathematically the equivalent circuit used in literature fits the impedance data very well. The observations in this work are however in contradiction with the different physical meanings attributed to the circuit elements found in literature. Further research is necessary to reveal the real mechanism of copper corrosion in this sort of systems.     

Effect of postreatment on the corrosion behaviour of tartaric-sulphuric anodic films

Unclad and clad AA2024 T3 specimens were anodised in a chromium-free tartaric-sulphuric acid bath (TSA) and subsequently postreated by different processes including impregnation in a cold, concentrated chromate solution, Cr-free hot-water sealing, and dichromate hot-water sealing. The purpose of this work is to evaluate the effectiveness of the classical postreatments used in the aircraft industry on the TSA-anodic films and their corrosion resistance behaviour. TSA-anodic films were characterised by scanning electron microscopy (SEM) and their thicknesses were measured by SEM and the eddy current method. Electrochemical impedance spectroscopy (EIS) was used to characterise the barrier and porous layers, and jointly with potentiodynamic polarisation allowed the evaluation of corrosion resistance parameters with immersion time in NaCl solution for anodised and postreated specimens. In all cases the postreatments increased the resistance of the barrier layer against degradation. However, the NaCl electrolyte easily penetrated TSA-anodised porous layers when they were not postreated, while penetration was slightly more difficult in cold-postreated specimens. The effective pore plugging was observed in the sealed TSA specimens resulting in an improved corrosion resistance. On the other hand, unsealed clad AA2024 specimens showed a self-sealing process of the TSA-anodic layer, which was slower for the cold chromate solution-postreated specimens.     

Influence of microstructure and composition on the corrosion behaviour of Mg/Al alloys in chloride media

The influence of the microstructure and aluminium content of commercial AZ31, AZ80 and AZ91D magnesium alloys was evaluated in terms of their corrosion behaviour in an aerated 3.5 wt.% NaCl solution at 25 °C. The corrosion process was monitored by electrochemical impedance spectroscopy (EIS). The surface was characterized by scanning electron microscopy (SEM), scanning Kelvin probe force microscopy (SKPFM) and low-angle X-ray diffraction (XRD). The extent of corrosion damage was strongly dependent on the aluminium content and alloy microstructure. Two key factors were observed for the lowest corrosion rates, which occurred for the AZ80 and AZ91D two-phase alloys: the aluminium enrichment on the corroded surface for the AZ80 alloy, and the β-phase (Mg₁₇Al₁₂), which acted as a barrier for the corrosion progress for the AZ80 and AZ91D alloys. Surface potential maps suggested that, between the β-phase and the α-matrix, the galvanic coupling was not significant.     

The role of chromate in filiform corrosion inhibition

This paper is part of a study on filiform corrosion (FFC) on aluminum alloy 2024-T3 and focuses on the surface characterization of corroded samples. Untreated samples were used as well as samples which had undergone pretreatments including polishing, surface etching and chromated conversion coatings (CCC). These samples were coated with both pigmented and non-pigmented epoxy-based coatings. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectroscopy (TOF-SIMS) analysis was used to investigate the nature of the surface as well as optical images to gauge the rate of FFC advancement. FFC corrosion rates decreased on samples which had received a surface etching pretreatment and a chromate conversion coating. Pigmented coatings reduced the rate of FFC further and led to two different types of corrosion surface morphology. On pretreated samples, the corrosion appeared deeper and pit-like, possibly due to an enhanced polymer-substrate bond. On untreated samples, widespread FFC developed. SEM and EDX analysis of various intermetallic particles (IMPs) on all samples, inside and outside of corroded regions, revealed that Cr from pigments was found deposited on Cu-containing intermetallics in corroded areas while Fe/Mn-containing particles were free from all pigment traces. These results suggest that the Cr deposition on Cu particles hinders the cathodic reduction of oxygen necessary for FFC advancement. For this reason, the coating pigments proved, under FFC conditions, to be a more effective inhibitor than the Cr originating from a chromate conversion coating.     

The influence of Ce-based coatings as pretreatments on corrosion stability of top powder polyester coating on AA6060

Cerium-based conversion coatings (CeCCs) are one of the most prospective alternatives to the widely used chromate conversion coatings (CCCs) due to their anticorrosion efficiency, environmentally friendly nature and low cost. In this work, the CeCCs on AA6060 were prepared by immersion into aqueous cerium salt solutions at room temperature, and subsequently post-treated in heated phosphate solution. The effect of counter ion (nitrate and chloride) on the coating properties was studied testing CeCCs as sole or conversion layers for the top polyester coating. Since the 60 μm thick polyester coating was applied, an artificial defect of 0.8 mm hole was introduced to faster assess the differences between pretreatments. The system with CCC pretreatment was used as reference. Corrosion properties were investigated in 0.5 M NaCl solution by electrochemical impedance spectroscopy while the adhesion strength was measured by NMPR (N-methyl-2-pyrrolidone) and pull-off tests. As shown, the post-treated chloride-based CeCC offered better protection than crack-free thin nitrate-based CeCC, when used as sole coatings. On the other hand, it was brought to evidence that in combination with top powder polyester coating, the CeCC deposited from nitrate solution exhibited better protection compared to protective system pretreated with chloride-based one. Excellent polyester coating adhesion was found independently on aluminium surface pretreatment.     

Electrochemical noise and impedance study of aluminium in weakly acid chloride solution

The electrochemical noise (EN) characteristics of pure aluminium in unbuffered potassium chloride solution and with acetic acid/sodium acetate buffer at pH 5.4 and 4.3 have been analysed to throw light on the influence of pH and of the presence of buffer at the aluminium surface on chloride ion-induced corrosion. Comparison has been made with results obtained by electrochemical impedance spectroscopy (EIS) and quantitative deductions made concerning the values of the noise resistance and the magnitude of the electrochemical impedance. Deviations between results obtained by the two experimental techniques are discussed.     

Comparative EIS study of pretreatment performance in coated metals

Various coated metal samples with different pretreatments were investigated by electrochemical impedance spectroscopy (EIS). Variables were the substrate (cold-rolled steel and hot-dipped galvanized steel), phosphate system (iron and zinc phosphate), post rinse (chromate and silane/zirconium rinse) and paint systems. The corrosion performance was determined on the basis of coating degradation, water uptake and interface delamination of the tested samples. The zinc phosphate performed better than iron phosphate on CRS. The silane/Zr rinse did not perform well in the CRS/iron-phosphate system. However, it showed a better performance than the chromate when used as a post rinse of zinc phosphate. Salt spray test (SST) and adhesion test results of the same samples are also reported in this paper and compared to the EIS data. The correlation among three test methods was poor.     

Estimation of kinetic and transport parameters by quantitative evaluation of EIS and XPS data

The relatively large number of adjustable parameters often precludes the unambiguous interpretation of electrochemical impedance spectra in terms of a unique kinetic model. In the present paper, the possibilities offered by a combination between in situ electrochemical impedance spectroscopic data and ex situ surface analytical information to improve the credibility of the estimates of the kinetic and transport parameters are discussed. Two electrode systems in which passive oxide films are formed—stainless steel in simulated pressurised water reactor coolant and tungsten in sulphate-fluoride solutions—are used as representative examples to demonstrate the different approaches taken to analyse the experimental data in terms of the Mixed-Conduction Model. Ways to extract information on the rate-limiting steps of the process of passive film formation, growth and restructuring by quantitative comparison of the model equations to electrochemical impedance and X-ray photoelectron spectroscopic data are described and the significance of the obtained parameters for the kinetics of the overall process of metal and alloy dissolution in the passive state is discussed.     

Electrochemical and spectroscopic evidences of corrosion inhibition of bronze by a triazole derivative

The electrochemical behavior of the bronze (Cu-8Sn in wt%) was investigated in 3% NaCl aqueous solution, in presence and in absence of a corrosion inhibitor, the 3-phenyl-1,2,4-triazole-5-thione (PTS). The inhibiting effect of the PTS was evidenced for concentrations higher than 1 mM for the cathodic process whereas its effect was clearly seen with a concentration as low as 0.1 mM for the anodic process. A significant positive shift of the corrosion potential was also observed, and its inhibiting effect increased with both its concentration and the immersion time of the sample. From voltammetry and electrochemical impedance spectroscopy experiments, the inhibiting efficiency of the PTS was found to be in the 94-99% range for 1 mM concentration. Scanning electron microscopy and X-ray energy dispersion analysis of the specimen surface show the presence of sulphur on the surface. Raman micro-spectrometry study confirms the protective effect of the PTS in aqueous solution through three types of interactions with the electrode, namely the adsorption of the inhibitor in a flat configuration, the formation of copper-thiol molecules, and when copper is released, the formation of a polymeric complex.     

Influence of the curing temperature of a cataphoretic coating on the development of filiform corrosion of aluminium

Aluminium alloys are known to be particularly sensitive to filiform corrosion. The initiation of this particular type of corrosion is related to different parameters such as the presence of defects, the permeability of the coating to water and oxygen, the adherence of the paint system and the presence of salts.In this work, the filiform corrosion resistance of Al 6016 substrates coated with a cataphoretic paint was studied. The curing of the coating was performed at different temperatures (185, 175, 165, 155 and 135 °C) in order to modify its mechanical properties and its permeability to oxygen.The paint properties were studied by different techniques allowing the estimation of the degradation of the metal–primer system and giving some information about intrinsic paint properties.The corrosion protection of the coating was evaluated by a normalized filiform corrosion test and by electrochemical impedance spectroscopy on scratched samples. The glass transition value and the internal stresses of the cataphoretic coatings obtained for different curing temperatures were determined by a stressmeter equipment.This study enabled us to underline the influence of the curing temperature on the intrinsic properties of the coatings such as the glass transition temperature, the internal stresses, the adherence, the permeability and the corrosion protection properties.     

Electrochemical studies of the inhibition of the cathodic delamination of organically coated galvanised steel by thin conversion films

Scanning Kelvin Probe (SKP) measurements of thin amorphous conversion film coated galvanised steel in combination with current density-potential curves and electrochemical impedance spectroscopy (EIS) were performed with the aim to improve the understanding of electrode potentials at the coating/metal interface and their influence on corrosive de-adhesion. The thin hybrid conversion films contained Zn-phosphates, titanates and also complexing organic compounds and led to an inhibition of the cathodic oxygen reduction and anodic zinc dissolution. In the polymer coated area the conversion film leads to a cathodic shift of the potential as measured by means of the SKP. This cathodic potential shift is explained by the substitution of the n-semiconducting Zn-oxide with an insulating inorganic layer. When the SKP detects the potential of freely corroding iron at a defect, where no protective coating layer is, the interfacial potential for the conversion film coated zinc layer is more negative than the defect potential. This leads to a diminished driving force for an oxygen reduction induced delamination process which is of relevance for the understanding of cut-edge corrosion.     

Role of KOH and NaNO2 on the structural and corrosion properties of anodic spark electrolysis coatings produced on aluminium

Doping light elements into ceramic coatings on different metal substrates by anodic-spark electrolysis (ASE) to improve their properties, such as wear and corrosion resistance, has recently attracted a lot of attention. In this study, nitrogen-doped Al₂O₃ composite ceramic coatings had been fabricated in eco-friendly KOH–NaNO₂ electrolytes using the anodic-spark electrolysis (ASE) method after 9 min at a fixed applied ASE voltage (75 V higher than the breakdown voltages). To deposit a nitrogen-doped coating with high amounts of oxynitride phases possible, we thoroughly studied the ASE coatings deposited in different total variable salts concentrations (KOH+NaNO₂) and NaNO₂/KOH ratios of ASE electrolytes. The coating properties were investigated using X-ray diffraction (XRD), scanning electron microscope (SEM), Fourier-transform infrared spectroscopy (FT-IR), and the electrochemical impedance spectroscopy (EIS) tests. The results indicated that the coating produced in the KOH–NaNO₂ electrolyte with a low total variable salts concentration (2 gr.L⁻¹) and a high NaNO₂/KOH ratio value (3) is optimum in the investigated conditions. It has the highest percentage of nitrogen-doped phases, such as N-doped γ-Al₂O₃ and γ-AlON (γ-Al_2.78O_3.65N_0.35), and a homogeneous morphology of surface with the smallest average size of pores (<14 μm²). This coating showed the significantly higher corrosion resistance with a 4.101104 × 10⁶ Ω cm² value compared to the uncoated aluminium substrate with a corrosion resistance value of 0.094195 × 10⁶ Ω cm² after 48 h of immersion in the 3.5 wt% NaCl solution. The approach presented herein provides an attractive way to modify the surface of aluminium alloys to improve corrosion behaviour.