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.     

Protective properties of cataphoretic epoxy coating on aluminium alloy AA6060 modified with electrodeposited Ce-based coatings: Effect of post-treatment

Ce-based conversion coatings (CeCCs) are a promising alternative to toxic chromate coatings on the metal substrates. In this work the CeCCs were electrodeposited on aluminium alloy AA6060 from aqueous solution of Ce(NO₃)₃ at different potentials (−0.95 V, −1.2 V and −1.4 V). Effect of deposition potential and post-treatment in the phosphate solution on morphology and protective properties of CeCCs with top cataphoretic epoxy coating was studied. To assess the differences between the protective systems, originating from the different CeCCs pre-treatments, electrochemical impedance spectroscopy (EIS), polarization measurements, AFM and SEM/EDS analysis were used. The EIS study was undertaken to follow the evolution of corrosion behaviour of epoxy coating/CeCCs protective systems over prolonged time of exposure to the chloride environment (3 wt.% NaCl). Results suggest significantly improved corrosion stability of epoxy coating on AA6060 with as-deposited CeCCs sub-layers with respect to the same epoxy coatings with phosphate post-treated CeCCs. The far best protective properties, i.e., the greatest value of pore resistance and the lowest value of corrosion current density were provided by the epoxy coating/CeCC protective system with CeCC deposited at −1.2 V and without post-treatment.     

Protective ability of hybrid nano-composite coatings with cerium sulphate as inhibitor against corrosion of AA2024 aluminium alloy

The corrosion protective ability of hybrid oxy silane nano-composite coatings deposited on AA2024 by sol-gel technique was studied. The coatings are developed as an environmentally friendly alternative of the toxic chromium containing coatings on aluminium. A cerium salt, Ce₂(SO₄)₃, was used as inhibitor of the corrosion process. Two methods were applied to introduce the salt in the hybrid matrix: directly in the matrix, or by porous Al₂O₃ nano-particles preliminary loaded by the salt. Atomic force microscopy (AFM) was used to evaluate the superficial morphology of the coatings, while their layer structure was studied by means of scanning electron microscopy (SEM). Linear voltammetry (LVA) and electrochemical impedance spectroscopy (EIS) were used for assessment of the barrier ability. The hybrid matrix was found to possess remarkable barrier ability which was preserved even after prolonged exposure of the coatings to a model corrosive medium of 0.05 M NaCl. In all cases, the cerium salt involved either directly or by Al₂O₃ nano-particles proved to deteriorate the protective properties of the coatings and to accelerate pitting nucleation. The experimental results have shown that cerium sulphate, introduced in the by the both manners in the hybrid matrix did not efficiently inhibit the corrosion of AA2024, unlike the reported inhibiting properties of other cerium salts.     

Stainless steel as new substrate for coil coating

Increasing needs of very high resistance to cosmetic corrosion, of more extended service life and reduced maintenance costs for infrastructures, civil and industrial buildings open new fields of application for coil coated stainless steel. This paper describes the adhesion and corrosion properties of new coil coated stainless steel materials produced in industrial coil coating lines. The use of an electrochemical test (electrochemical impedance spectroscopy) can give detailed information on the reactivity of the system and allow the performance of different substrates (AISI 409, 430, 316 and 304) coated with different polymers (polyvinylidene and polyester) to be compared. The results obtained show the interesting properties of this new class of coil coated products. The materials were tested for a long time (about 200 days) in an aggressive environment (3.5% sodium chloride solution) also in the presence of macrodefects. In particular, VIVINOX 430, 304 and 316 revealed no reactivity, corrosion or disbonding, thus supporting the expectancy of very long trouble free exposure also in very aggressive natural environments. (VIVINOX is the brand name of the AST (Acciali Speciali Terni) line of coil coated stainless steel.)     

Adhesion characteristics and corrosion stability of epoxy coatings electrodeposited on phosphated hot-dip galvanized steel

The influence of hot-dip galvanized steel (HDG) surface pretreatment with phosphate coatings on the corrosion stability and adhesion characteristics of epoxy coatings electrodeposited on HDG steel was investigated. Phosphate coatings were deposited on hot-dip galvanized steel from baths with different concentrations of NaF (0.1, 0.5 and 1.0 g dm⁻³) and at different temperatures (50, 65 and 80 °C). The influence of fluoride ion concentration in the phosphating bath, as well as the deposition temperature of the bath, on the adhesion characteristics and corrosion stability of epoxy coatings on phosphated HDG steel was investigated. The dry and wet adhesions were measured by a direct pull-off standardized procedure, as well as indirectly by NMP test, while corrosion stability was investigated by electrochemical impedance spectroscopy (EIS).     

Trimethylsilane-based pretreatments in a Mg-rich primer corrosion prevention system

A trimethylsilane-based coating was investigated as a pretreatment for Al-2024 T3 in a novel Mg-rich primer corrosion prevention system. SiC-based thin films were deposited onto Al substrates by plasma-enhanced chemical vapor deposition (PECVD). A screening study of the pressure (P) dependence of films deposited at 350 °C showed an increase in growth rate from 0.6 to 1.9 Torr. A second screening study where P was fixed at 1.9 Torr and temperature (T) was varied from 125 to 550 °C showed decreasing growth rates with increasing temperature with an apparent transition around 300 °C. Electrochemical impedance spectroscopy (EIS) of the SiC-based films on Al-2024 after exposure to a corrosive environment (i.e., dilute Harrison solution) indicated that samples coated using SiC-based films exhibit higher low frequency impedance (i.e., 100–1000× higher) than bare Al-2024 with open circuit potential remaining 0.1 V higher for the former suggesting the SiC-based films slow the corrosion process. A Mg-rich primer was coated onto the SiC on Al-2024 with the galvanic function of the system determined by EIS. As compared to SiC on Al-2024, a similar behavior for the low frequency impedance was observed for the Mg-rich primer-coated samples with some films exhibiting 1E + 8 Ω at 0.1 Hz indicating a strong barrier property. Initial gas jet erosion using acrylic media indicates the Mg-rich primer coatings are removed in preference to the Si–C films—the first step toward demonstrating a permanent pretreatment. When successfully developed and optimized, the value of such a hard, protective coating is the reduction of a three-component coatings system (i.e., pretreatment, primer, and topcoat) to a two-component system (i.e., primer and topcoat).     

Effect of nano-sized calcium carbonate on cure kinetics and properties of polyester/epoxy blend powder coatings

Today's strict environmental laws pose significant challenges for coating's formulators to look for eco-friendly products. Powder coatings, particularly polyester/epoxy blends have demonstrated their ability as alternatives to traditional solvent-borne coatings. Recently, the use of nanoparticles such as nano-CaCO₃ (nCaCO₃) has been suggested as a beneficial strategy towards powder coating application with improved properties. Here, we study the effect of nCaCO₃ on morphology, cure behavior, adhesion and hardness of polyester/epoxy systems. The nanoparticles shape, size and dispersion state were investigated through X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) methods. Furthermore, isothermal cure characterization of the neat and filled systems was performed using a torque rheometer. The most important finding based on the rheological studies was the catalytic effect of nCaCO₃ on cure reaction of polyester/epoxy, leading to the shorter curing time. Moreover, the kinetic analyses of rheograms revealed a marked decrease in the activation energy of the cure process upon raising nCaCO₃ content. Interestingly, pull-off adhesion and hardness tests showed that the hardness and adhesion strength were dramatically increased by the addition of nCaCO₃ into the polyester/epoxy system compared to pure blend resin. Therefore, considering the strong competition in powder coating market, the use of nCaCO₃ as a commercial and inexpensive nanofiller is necessary not only to reduce the dwell time which has benefits in terms of the energy consumption and economics, but also to improve the performance of final polyester/epoxy coating.     

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.     

Real time mapping of corrosion activity under coatings

Current accelerated testing of aircraft coating systems for corrosion protection relies heavily on salt spray methods. Electrochemical techniques such as electrochemical impedance spectroscopy (EIS) and electrochemical noise methods (ENM) provide insight into the global properties of a coating system, and both techniques are being used on a limited basis. However, there is a need to investigate corrosion events with greater spatial resolution under coatings at the metal/coating interface. Such corrosion activity may be related to coating defects and variations in the surface chemistry of the underlying metal.

The scanning vibrating electrode technique (SVET) has been developed to allow high spatial resolution investigation of localized corrosion activity that may be associated with coating defects or galvanic coupled regions of the metal surface. The SVET offers high resolution in current measurements of the order of 0.5 μA/cm² and is able to detect in-situ initiation and progress of corrosion activity under a protective coating. Using the SVET, minute variations in d.c. current associated with localized corrosion activity are detected and used to map both anodic and cathodic corrosion activities in a localized area. The difference in initial corrosion activity under various coatings can be correlated to the performance life of the coatings. The application of SVET to aircraft coatings and corrosion is reported to demonstrate the utility of this important new electrochemical tool.

In the current study, the SVET was used to discriminate the corrosion protection performance of selected sol–gel based coating systems. Sol–gel based surface treatments are being developed as part of an environmentally compliant coating system alternative to the currently used chromate-based systems. The SVET results are compared with data obtained from chromium inhibition coating systems. The SVET analyses are compared with electrochemical impedance measurements. The comparison of such data will provide the basis to adopt SVET measurements as an early performance discriminator for newly developed coating systems.     

Influence of rare earth Y on the corrosion behavior of as-cast AZ91 alloy

The influence of different contents of rare earth Y on the corrosion resistance of AZ91 alloy was investigated by the salt spray test and electrochemical measurements. It was found that the proper amount of Y was effective on improving the corrosion resistance of AZ91 alloy. The optimal modification effect was obtained when the Y content in the alloys was 0.3 wt.%. However, with the increase of rare earth Y, the corrosion rate became bigger slightly, and further addition of Y content over 0.3 wt.% resulted in the increment of the corrosion rate. It is suggested that the excessive rare earth Y can reduce the corrosion resistance of AZ91 alloy.     

Characterization of structure and corrosion resistivity of polyurethane/organoclay nanocomposite coatings prepared through an ultrasonication assisted process

In this study, a series of castor oil based polyurethane/organically modified montmorillonite (OMMT) clay nanocomposite coatings have been successfully prepared by effective dispersing of OMMT nano-layers in polyurethane matrix through an ultrasonication assisted process. Effectiveness of ultrasonication process in de-agglomeration of clay stacks in castor oil dispersions was evaluated by optical microscopy and sedimentation test. Structure of nanocomposite coatings was investigated by wide angle X-ray diffraction (WAXD) and Fourier-transform infrared spectroscopy (FT-IR). The anticorrosive properties of nanocomposite coatings were characterized by electrochemical impedance spectroscopy (EIS), Tafel polarization study, water absorption and pull-off adhesion tests. The experimental results showed that PU/OMMT nanocomposite coatings were superior to the neat PU in corrosion protection effects. Also, it was observed that the corrosion protection of polyurethane organoclay nanocomposite coatings is improved as the clay loading is increased up to 3 wt.%.     

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.     

Effects of carbon nanotube content on adhesion strength and wear and corrosion resistance of epoxy composite coatings on AA2024-T3

The effects of multiwalled carbon nanotube (MWCNT) content on the adhesion strength and wear and corrosion resistance of the epoxy composite coatings prepared on aluminum alloy (AA) 2024-T3 substrates were evaluated using atomic force microscopy (AFM), blister test, ball-on-disk micro-tribological test and electrochemical impedance spectroscopy (EIS). The adhesion strength of the epoxy composite coatings improved with increasing MWCNT content. Increased MWCNT content also decreased the friction coefficient and increased the wear resistance of the epoxy composite coatings due to improved solid lubricating and rolling effects of the MWCNTs and the improved load bearing capacity of the composite coatings. Finally, EIS indicated that increased MWCNT content increased the coating pore resistance due to a decreased porosity density, which resulted in an increase in the total impedance of the coated samples.     

Corrosion resistance properties of Ormosil coatings on 2024-T3 aluminum alloy

The corrosion resistance behavior of organically modified silane (Ormosil) thin films on 2024-T3 aluminum alloy substrates was investigated using electrochemical impedance spectroscopy (EIS) and accelerated salt spray analysis techniques. Coatings were prepared containing 0–16.6 vol.% alkyl-modified silane, X_n---Si(OR)_4−n, where X=methyl, dimethyl, n-propyl, n-butyl, i-butyl, n-hexyl, n-octyl, or i-octyl. Coating thicknesses were measured to be in the 6–16 μm range, with the thickest coatings being observed for the highest concentrations of alkyl-modified silane. Contact angle measurements showed an enhancement in hydrophobicity of the Ormosil film imparted by increasing size and concentration of the alkyl-modifiers in the coating. In general, corrosion resistance characteristics, as determined using EIS and salt spray techniques, were found to increase with increasing alkyl-modified silane concentration and alkyl chain length. The best overall corrosion resistance was observed for coating systems containing ≥10.4 vol.% alkyl-modified silane; the hexyl-modified films exhibited corrosion resistance properties superior to the other Ormosil coatings. Immersion studies conducted in 0.5 M K₂SO₄ indicated that coating degradation occurs via hydration of the dense linear chain silicate network leading to the formation of porous cyclic structures.     

Crystalline and amorphous PEO based ceramic coatings on AA6061: Nanoindentation and corrosion studies

Present study reports the detailed nanomechanical and corrosion behaviours of crystalline and amorphous plasma electrolytic oxidation (PEO) coatings developed on Aluminium alloy-6061. The concentration of sodium silicate in the electrolyte is tailored to achieve crystalline and amorphous natures of the PEO coatings. X-ray diffraction (XRD), scanning electron microscopy (SEM) and nanoprofilometry techniques are utilized to investigate microstructural and morphological properties of the PEO coatings. XRD studies confirmed that crystalline ceramic phases are obtained at lower silicate concentration while amorphous nature occurred for comparatively higher concentration of silicate in the electrolyte. Nanoindentation technique is utilized to study the mechanical properties such as hardness (H) and Young's modulus (E) of the PEO coatings. The scatter of the data is treated with well-established Weibull statistical method. Finally, in depth corrosion behaviour of the coatings are investigated by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization techniques. Amorphous coatings exhibited superior mechanical properties compared to the crystalline coatings. This is possibly linked with the presence of aluminosilicate phases and difference in silicon content in the coatings. However, as expected crystalline PEO coatings offer better corrosion resistance than the amorphous coatings and this behaviour is explained in terms of porosity contents of the coatings.     

EIS characterisation of new zinc-rich powder coatings

A zinc-rich powder coating, applied onto steel substrate, was studied using electrochemical impedance spectroscopy (EIS). Before immersion when coating is dry, EIS spectra revealed that the percolation threshold was reached. Then, an equivalent circuit including a transmission line was applied to model electrochemical response. In this model, which considers isolated and semi-isolated zinc particles within the binder, it was found that both phases were equally distributed in the coating.     

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.     

Evaluation of barrier coatings by cycling testing

A variety of methodology which are supposed to accelerate and/or simulate the effects of time and environment, weathering, on organic coatings degradation are under development since long time. Taking into account that no test can duplicate all of the variables associated with a coatings environment, two modern accelerated tests were carried out and their investigation capabilities were compared: the Norwegian Norsok M 501 and the thermal cycling in electrolyte immersion. The first test highlighted the adhesion performances of coatings and the importance of the zinc-rich primers on the scratch protection. The thermal cycling test has lead to a very rapid loss of film properties. Electrochemical impedance measurements associated to this test have shown the relative importance of electrical resistance and capacitance in predicting corrosion protective performance in presence of very thick coatings.     

Plasma interface engineered coating systems for magnesium alloys

In this study, a dc low-temperature plasma technique, including plasma treatment and plasma polymerization, was used to create interface engineered coating systems with a structure of Mg/plasma interlayer/cathodic electrocoating (E-coat) for machined AZ31B magnesium (Mg) alloy panels. The plasma interlayer deposited from trimethylsilane (TMS) precursor had a nano-scale thickness of ∼65 nm and well-controlled surface properties through subsequent plasma treatments in order to achieve different level of interfacial adhesion between the E-coat and the Mg substrates. The surface wettability of the plasma interlayer was monitored by water surface contact angle measurement. The interface adhesion of the coating system was evaluated using N-methylpyrrolidinone (NMP) paint removal test and ASTM tape test conducted under dry and wet conditions. Electrochemical impedance spectroscopy (EIS) was employed to investigate the effects of plasma interlayer properties including surface wettability and adhesion enhancement on corrosion protection properties of the coating systems. It was found that a more wettable interface enhanced the electrolyte penetration through the coating and thus reduced the corrosion resistance of the coating system. On the other hands, the improved interface adhesion had little effects on EIS results mainly due to the high chemical reactivity of the Mg alloy substrates.     

Electrochemical impedance spectroscopic investigation of the role of alkaline pre-treatment in corrosion resistance of a silane coating on magnesium alloy, ZE41

The protective performance of the coatings of bis-1,2-(triethoxysilyl) ethane (BTSE) on ZE41 magnesium alloy with different surface pre-treatments were evaluated using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) in 0.1 M sodium chloride solution. Electrical equivalent circuits were developed based upon hypothetical corrosion mechanisms and simulated to correspond to the experimental data. The morphology and cross section of the alloy subjected to different pre-treatments and coatings were characterized using scanning electron microscope. A specific alkaline pre-treatment of the substrate prior to the coating has been found to improve the corrosion resistance of the alloy.