Effective corrosion protection of 8090 alloy by cerium conversion coatings

Conversion treatments based on immersion in Cr(VI) aqueous solutions are key technologies that combine low cost, easy application and high performance. However, they are environmentally problematic due to their carcinogenity and genotoxicity. Among the potential alternatives, treatments based on rare-earth compounds have drawn attention due to the stability of their oxides and their environmental acceptability. Despite the amount of work published, there is not yet an industrially suitable alternative treatment for aircraft aluminium alloys that is able to provide the required corrosion protection. A common feature of these alloys is the high level of copper in their chemical composition. Although the presence of copper in an alloy may enhance cerium deposition, high copper content alloys (AA2024, AA7075) have proven the most difficult to protect with Ce conversion coatings.In the present work, a commercial 8090-T8 aluminium alloy containing 1.15 weight percent (wt.%) Cu was coated with a Ce conversion coating at room temperature from a Ce bath without prior pretreatment of the specimens. Polarisation curves revealed that the presence of a cerium conversion coating (CeCC) reduces by two orders of magnitude the corrosion rate of the AA8090 alloy in a sodium chloride solution. Impedance measurements exhibited capacitive behaviour for the CeCC up to 216 h, showing that the cerium layer protects the bare alloy in the aggressive solution.Electrochemical tests have therefore revealed that these conversion layers afford long-lasting protection; withstanding up to 168 h in Salt Spray test.     

Structure,mechanical and corrosion properties of DC reactive magnetron sputtered aluminum nitride (AlN) hard coatings on mild steel substrates

Aluminum nitride (AlN) coatings of about 2 μm thick were deposited on mild steel (MS) by means of direct current (DC) reactive magnetron sputtering. AlN coatings were prepared in an Ar + N₂ gas mixture and their crystal structure, microstructure, and topography were analyzed by X-ray diffractometry (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM), respectively. XRD revealed that the films are polycrystalline in nature and have a hexagonal wurtzite structure with a predominant peak observed along the (002) plane. SEM and AFM images showed the presence of continuously covered pebble like spherical grains on the surface. These coatings showed lower coefficient of friction and excellent wear resistance compared to the bare MS substrate. The potentiodynamic polarization studies showed lower corrosion current density and higher polarization resistance for the AlN/MS structure than the uncoated MS substrate.     

Electropolymerised polyaniline films on AA 7075 alloy and its corrosion protection performance

Polyaniline has been electrodeposited on AA 7075 alloy and its corrosion protection ability has been studied by Tafel and impedance techniques in 1% NaCl. Pure polyaniline film is not found to protect the aluminium alloy due to galvanic interaction of polyaniline and aluminium surface exposed through pinholes and cracks. However, it is found that the corrosion resistance property of the polyaniline film can be substantially increased by post-treatment in cerium salt solution.     

On the corrosion protection properties of fluoropolymer coatings

Fluoropolymers have attained great importance as coating materials because of their excellent resistance to high temperature, chemicals and organic solvents. Electrochemical impedance spectroscopy was used to study the corrosion protection properties both on undamaged fluoropolymer coatings and on samples with an artificial defect. The experimental results were interpreted on the basis of a proposed equivalent electrical circuit which best fits the experimental impedance spectra. In this way we observed the high quality of the fluorinated coatings compared with that of the corresponding hydrogenated polymer used as a reference. The protective properties of the fluoropolymer coatings studied can be related to chemical (fluorine and chlorine functional groups) and physical (good order of the polymeric chains) characteristics of the resins.     

Antibacterial activity and corrosion resistance of Ta2O5 thin film and electrospun PCL/MgO-Ag nanofiber coatings on biodegradable Mg alloy implants

Biodegradable magnesium (Mg) alloys have drawn considerable attention for use in orthopedic implants, but their antibacterial activity and corrosion resistance still require improvement. In the present work, functional Ta₂O₅ (tantalum pentoxide) compact layers and PCL/MgO-Ag (poly (ε-caprolactone)/magnesium oxide-silver) nanofiber porous layers were subsequently deposited on Mg alloys via reactive magnetron sputtering and electrospinning, respectively, to improve anticorrosion and antibacterial performance. Sputter coating of the Ta₂O₅ resulted in a thick layer (～1?μm) with an amorphous structure and high adhesive strength. The nanostructure exhibited bubble-like patterns with no obvious nano-cracks, nano-porosities, or pinholes. The electrospun PCL/MgO-Ag nanofiber coating was porous, smooth, and plain with no obvious beads. In vitro corrosion tests demonstrated the PCL/MgO-Ag nanofiber-coated alloy had greater corrosion resistance than a Ta₂O₅ sputter-coated alloy or uncoated Mg alloy. The additional electrospun PCL/MgO-Ag nanofiber coating also had greater antibacterial behavior toward Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacteria than the Ta₂O₅-coated or uncoated alloy specimens. Increasing the MgO-Ag concentration of the nanofibers from 1 to 3?wt% increased antibacterial activity. The combination of Ta₂O₅ and PCL/MgO-Ag nanofiber coatings on Mg alloys may therefore have potential applications for reducing bone infection as related to orthopedic implants for bone repair.     

Polyaniline coatings on aluminium alloy 6061-T6: Electrosynthesis and characterization

The production of polyaniline films on aluminium alloy 6061-T6 in sulphuric acid was carried out by electrodeposition, using cyclic voltammetry and potentiostatic polarization. The films obtained were characterized by SEM and XPS analysis. Electrochemical techniques were also used to assess the anticorrosive properties of the coatings.The choice of the upper potential limits for potential cycling and of the fixed potential for potentiostatic production should take in consideration the balance between their effect on the minimum number of cycles (or time) needed to produce the film and on the rate of overoxidation.Polarization curves show a slight increase of the corrosion potential for polyaniline coated substrate as compared with bare metal, indicating that no significant protection is achieved by the polymer coating. The Bode diagrams show low impedance values for the alloy covered with polyaniline when compared with the results obtained for the bare metal. This can be attributed to the conductive character of the polyaniline films.     

Influence of amino functionalised POSS additive on the corrosion properties of (3-glycidoxypropyl)trimethoxysilane coatings on AA 2024 alloy

The influence of the addition of a mixture of POSS compounds substituted equally by 3-aminopropyl and isobutyl groups (AP₄IB₄ POSS) on sol-gel coatings prepared from (3-glycidoxypropyl)trimethoxysilane (GPTMS) was evaluated from the point of view of their anticorrosion properties. AP₄IB₄ POSS belong to a group of polyhedral oligomeric silsesquioxanes and their functionalisation with amino groups enables cross-linking with the epoxy groups of GPTMS. Additionally, GPTMS molecules react among themselves through hydrolysis and condensation processes of trimethoxysilane groups when catalysed by 0.1 M KF. The results of the Raman and IR measurements revealed that a molar ratio of GPTMS:H₂O = 1:3 is more beneficial than a molar ratio of 1:1.5 for the preparation of sol-gel coatings. The anticorrosion properties of the mixed GPTMS/POSS coatings deposited on AA 2024 aluminium alloy were tested using potentiodynamic electrochemical measurements and a salt-spray chamber test. It was found that the mixed GPTMS/POSS coatings showed improved corrosion protective properties vs. either pure GPTMS or POSS coatings.     

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.     

Sol-gel coatings for corrosion protection of 1050 aluminium alloy

The formation of organic-modified sol-gel coatings on 1050 aluminium alloy has been examined. The coatings were prepared by the combination of a completely hydrolysable precursor of tetra-n-propoxyzirconium (TPOZ), with a partly hydrolysable precursor of glycidoxypropyltrimethoxysilane (GPTMS). Influences of GPTMS/TPOZ ratio, withdrawal speed and curing temperature on the barrier-type corrosion protection of the alloy were examined. By control of process parameters and ratios of organic and inorganic moieties, crack-free sol-gel coatings with improved corrosion protection were produced on the alloy surface. Optimum protection was achieved by a coating formed with a GPTMS/TPOZ ratio of 2.7, a withdrawal speed of 180 mm/min and curing at 110 °C. The coating formed under the optimum conditions revealed good adhesion to the etched and desmutted alloy substrate. The pitting potential of the coated alloy increased significantly, indicative of an improved corrosion protection of the alloy.     

Effect of doping by corrosion inhibitors on the morphological properties and the performance against corrosion of polypyrrole electrodeposited on AA6061-T6

This paper describes the electrosynthesis of polypyrrole (PPy) onto AA6061-T6 aluminum alloy from a sulfuric acid solution doped with molybdate anions (MoO₄²⁻) or 8-hydroxyquinoline (8HQ) species. These dopant compounds were chosen as they have been proven to be effective in mitigating the corrosion in chloride medium. The protectiveness of PPy coatings incorporating these corrosion inhibitors within the polymer matrix is discussed. The coatings were morphologically characterized via scanning electron microscopy (SEM) and evaluated electrochemically via polarization in 0.5 M NaCl. The results show that doping PPy with molybdates or 8HQ changes its morphological properties and its effectiveness in preventing passivity loss for AA6061-T6 in chloride media.     

Electro-assisted preparation of dodecyltrimethoxysilane/TiO2 composite films for corrosion protection of AA2024-T3 (aluminum alloy)

Thin films of organosilanes have been successfully used as the alternative to toxic chromate coatings for surface pretreatment of metals and alloys. To further improve their corrosion performance, in the present work nano-scaled TiO₂ particles were added to the dodecyltrimethoxysilane (DTMS) films coated onto AA2024-T3 substrates, by using either the dip-coating or the cathodically electro-assisted deposition process. The obtained composite films were investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM), water contact angle measurements, Fourier transform reflection-absorption IR (FTRA-IR) and electrochemical impedance spectroscopy (EIS). The results show that these two techniques (nanoparticles incorporation and the electro-assisted deposition) both facilitate the deposition process of silane films, giving thicker deposit and higher coverage surface along with higher roughness and hydrophobicity, and thereby improve their corrosion resistance. Moreover, the corrosion performance of silane films is further improved by the combined use of nanoparticles modification and electro-assisted deposition.     

Electrodeposition of silane films on aluminum alloys for corrosion protection

In this paper, three types of protective silane films, methyltrimethoxysilane (MTMS), vinyltrimethoxysilane (VTMS) and dodecyltrimethoxysilane (DTMS) were prepared on aluminum alloys AA 2024-T3 by electrodeposition technique. The Reflection-Absorption Fourier Transform IR (FTRA-IR) measurements showed that, the silane films were successfully deposited through chemical bonding between silane agents and Al alloys. Electrochemical impedance spectroscopy (EIS) tests indicated that in comparison with those by conventional “dip-coating” method, silane films electrochemically prepared at cathodic potentials exhibited obviously higher corrosion resistances. “Critical potential” was all observed for each silane system. Silane films prepared at this potential performed the highest corrosion resistance. The scanning electron microscopy (SEM) images indicated a potential dependence of surface morphology of silane films. The highest compactness was obtained at the “critical potential”. Due to the presence of long hydrophobic dodecyl chain in bone structure, DTMS films displayed the highest barrier properties.     

Mechanism of corrosion protection of aluminum alloy substrate by hybrid polymer nanocomposite coatings

The corrosion protection of polymer clay nanocomposite, PCN coatings consisting of polyurea, siloxanes, epoxy ester and montmorillonite clay was determined. Corrosion resistance of the coating, was assessed by monitoring the polarization resistance and impedance of coated aluminum alloy, Al 2024-T3, coupons immersed in 3.5 wt.% of sodium chloride, NaCl, solution. Direct current polarization and electrochemical impedance spectroscopic techniques were used to measure polarization resistance and impedance of the samples, respectively. Diffusion of saturated salt solution into free-standing PCN films was measured gravimetrically and diffusivity of the nanocomposites was determined. The presence of clay decreases diffusivity and increases corrosion resistance of the non-scribed coatings containing up to 10 wt.% of clay. A correlation between polarization resistance and diffusivity was made. It was shown that for non-scribed coatings, polarization resistance increases with decreasing diffusivity. A relationship between coating's diffusivity and weight fraction of clay was established. Increasing clay concentration also resulted in decreasing diffusivity. The scribed nanocomposite coatings show slightly decreasing polarization resistance with increasing weight fraction, however, the polarization resistance of scribed coatings containing low clay weight fraction in the range between 0.5 and 2.0 wt.% was higher than that for the matrix. A barrier mechanism of corrosion prevention of the coated substrate is proposed for non-scribed coatings. The viscoelastic property of the nanocomposites was determined by using dynamic mechanical spectrometer. A correlation between polarization resistance of the coatings and the rubbery plateau modulus on the one hand and polarization resistance and tan δ peak area for α-transition of the nanocomposites is made. Decreasing tan δ peak area for α-transition and increasing rubbery plateau modulus resulted in increasing coatings polarization resistance.     

Improving the corrosion protection properties of organically modified silicate–epoxy coatings by incorporation of organic and inorganic inhibitors

Organically modified silicate (ORMOSIL)–epoxy coatings were formed on aluminium alloy 2024-T3 in order to protect the substrates from corrosion. Organic and inorganic compounds, all known for their corrosion inhibition ability, were incorporated into the polymer matrix for the improvement of the corrosion resistance. The ORMOSIL–epoxy coatings were deposited via the dip-coating process. The properties of the coatings were investigated after 24 h of curing at 90 °C. The morphology of the coatings was examined by scanning electron microscopy (SEM). Their composition and structure were investigated by Fourier transform infrared spectroscopy (FT-IR) and energy dispersive X-ray analysis (EDX). The corrosion resistance of these coatings was investigated using electrochemical impedance spectroscopy (EIS). The results showed that the most effective corrosion protection ability was provided by the inorganic inhibitors and that an important role can be attributed to the cation in the nitrate salt.     

Electrodeposition and characterization of polypyrrole films on aluminium alloy 6061-T6

Polypyrrole films on aluminium alloy 6061-T6 were prepared by electropolymerization of pyrrole in sulphuric acid using two different processes - cyclic voltammetry and potentiostatic polarization - and assessed through SEM observation and voltammetry. The anticorrosive properties of these films were studied by polarization curves and electrochemical impedance spectroscopy.The polypyrrole films formed by both methods are homogeneous and present a globular structure. However, it was found that the films produced by cyclic voltammetry are thicker than those produced potentiostatically at a potential equal to the upper limit of the cyclic voltammetry (E_λa). It was also found that there is an optimum value for the formation potential (E_appl, in the case of the potentiostatic method or E_λa for cyclic voltammetry). Above this value, overoxidation of the polymer occurs, which is found to be deleterious to the coated system behaviour.From polarization curves no major differences were detected between the PPy-coated alloy and the bare material, indicating that no significant protection is achieved by the polymer coating. On the other hand, Bode diagrams are typical of a system undergoing pitting corrosion and show lower impedance values for the alloy covered with polypyrrole than for the bare metal. This can be attributed to the conductive character of the polypyrrole films.     

Corrosion protection of iron by benzoate doped polyaniline containing coatings

Polyaniline containing organic coatings based on vinyl and acrylic resins are found to protect iron in acid and neutral media. Since dopants play an important role in forming salts with iron, a study has been made on the effect of benzoate doped polyaniline on the corrosion protection of iron by polyaniline–vinyl coatings in acid and neutral media. EIS studies have been made on the corrosion protection performance of vinyl coating on steel with 1% polyaniline in 0.1N HCl and 3% NaCl up to 100 days of exposure. It has been found that benzoate doped polyaniline containing coating has found to offer more protection in neutral media than that in acidic media due to passivating ability of benzoate ions in neutral solution, along with iron–polyaniline complex.     

Heat exchangers corrosion protection by using organic coatings

Corrosion phenomena in aluminium heat exchangers represent a problem in terms of durability and efficiency of thermal exchange. This work evaluates the barrier properties of two coatings that represent the state of the art for the protection in the heat, ventilating, air conditioning/refrigerating field (HVAC/R): electrophoretic coating (E-coating) using epoxy resin and spraying of polyurethane coating with addition of metallic pigments. The ability of the coatings to cover the surface of heat exchanger has been evaluated by means of optical microscopy in order to highlight critical zones of the system for the application of the coatings. The electrochemical behaviour of coated heat exchangers has been studied by means of electrochemical impedance spectroscopy in 3.5% NaCl solution. The local electrochemical behaviour of coating defects has been investigated using the electrochemical micro-cell, which enables to perform potentiodynamic polarization measurements on single defects. E-coatings evidenced difficulties to provide uniform thickness of the coating at the extremities of the fins. Spraying of the polyurethane coating containing pigments require particular care in order to fully cover zones of the heat exchanger with difficult accessibility. The electrochemical behaviour of coated heat exchangers is affected by the existence of defects in the coatings.     

The investigation of the tribocorrosion properties of DLC coatings deposited on Ti6Al4V alloys by CFUBMS

Various machine components produced from titanium alloys used in various industries are subject to a combination of electrochemical and mechanical effects. The science of surface transformations resulting from the interaction of mechanical loading and chemical reactions that occur between elements of a tribosystem exposed to corrosive environments is described as tribocorrosion. This research focuses on the tribocorrosion behaviour of Ti6Al4V alloys after coated by using closed field unbalance magnetron sputtering (CFUBMS). The structural analyses of the coatings were performed using Raman spectroscopy and scanning electron microscopy (SEM). Tribocorrosion experiments were performed in a pin-on-disc tribotester under electrochemical polarisation in NaCl 1 wt.% solution. This study shows that the Ti-DLC coating is protecting the Ti6Al4V alloy and having good performance in corrosion and tribocorrosion conditions. The OCP values for Ti6Al4V substrate and Ti-DLC protective coatings during tribocorrosion tests were measured as −560 V and −330 V, respectively. These results showed that Ti-DLC protective coating on Ti6Al4V substrates increased the tribocorrosion resistance by acting as a barrier layer.     

The formation and corrosion behavior of a zirconium-based conversion coating on the aluminum alloy AA6061

To understand the mechanism of the coating formation, the formation process of a zirconium-based conversion coating on aluminum alloy 6061 has been studied by means of AFM in PeakForce Kelvin Probe Force Microscope (PF-KPFM) mode which could provide direct evidence for the existence of driving force for the film formation. In addition, various techniques including SEM, XPS, EIS, salt spray test, and scanning electrochemical microscope were used to investigate the surface state and corrosion behavior of the conversion film. The direct driving force for the coating formation is the Volta potential difference between the intermetallic particles and matrix. That difference produces an ocean of micro electrochemical cells in which the intermetallic particles act as cathodic sites for the film deposition. However, the precipitation of the layer is a self-limited process in which the driving force gradually decreases as the conversion layer covers the surface of the aluminum alloys. The anti-corrosion performance of the film is unfavorable compared to the conventional chromate conversion coatings due to the pitting corrosion that occurs when exposed to harsh environment containing chloride. Furthermore, the zirconium-based conversion coating possesses no self-healing ability leading to the continuous degradation of the film until it completely lose efficacy.     

Evaluation of the protection against corrosion of a thick polyurethane film by electrochemical noise

This paper focuses on the study of protection against corrosion by means of a thick polyurethane film. Noise resistance, R_n, calculated from a series of potential and current noise measurements, shows that electrochemical noise (EN) technique was able to monitor corrosion under coated metals even when applied at high thicknesses. By using spectral analysis, the nature of the attack on the metallic surface was determined; indeed, the characteristics of the corrosion process were determined even from the beginning of the phenomenon when the surface was exposed in a Salt Fog Chamber. It was possible to determine both how the continuous protection was given by the polyurethane film as a barrier and when the corrosion process was controlled by the appearance of pores on the barrier film. This paper seeks to establish a methodology to study highly resistant coatings.