Corrosion protection of AA 2024-T3 by bis-[3-(triethoxysilyl)propyl]tetrasulfide in neutral sodium chloride solution. Part 1: corrosion of AA 2024-T3

This study consists of two parts. In the first part, the corrosion of 2024-T3 aluminum alloy (AA 2024-T3) was studied using scanning electron microscopy and energy-dispersive X-ray spectroscopy. The results showed that the anodic S phase (Al₂CuMg) particles dealloyed Al and Mg during the 3.5 h of immersion in a neutral 0.6 M sodium chloride (NaCl) solution; with the dealloying of Mg being the most severe. Simultaneously, a heavy dissolution was also observed for the surrounding Al matrix of the S phase particles. This Al dissolution is likely to be caused by a local alkalization resulting from the coupled cathodic reaction (water and/or oxygen reduction). Such corrosion in AA 2024-T3, however, can be inhibited efficiently after the treatment of bis-[3-(triethoxysilyl)propyl]tetrasulfide (bis-sulfur silane). The associated studies on bis-sulfur silane treated AA 2024-T3 will be presented in the second part.     

The corrosion resistance of hot dip galvanised steel and AA2024-T3 pre-treated with bis-[triethoxysilylpropyl] tetrasulfide solutions doped with Ce(NO3)3

The present work aims at evaluating the anti-corrosion behaviour of a novel pre-treatment based on bis-[triethoxysilylpropyl] tetrasulfide (BTESPT) doped with cerium nitrate for application on hot dip galvanised steel and AA2024-T3 substrates. The corrosion resistance was evaluated by electrochemical impedance spectroscopy (EIS) and by the scanning vibrating electrode technique (SVET), during immersion in NaCl solutions. The electrochemical results showed that the pre-treatment provides excellent corrosion protection to the substrates. Furthermore, the results evidenced improved protection comparatively to the use of undoped BTESPT pre-treatments, both for galvanised steel and AA2024-T3. This improvement is most likely due to enhanced barrier properties of the film and additional active corrosion protection originated from the inhibiting action of the cerium-based inhibitor impregnated in the silane matrix.     

Mechanisms of corrosion inhibition of AA2024-T3 by vanadates

The mechanisms of corrosion inhibition of AA2024-T3 by vanadates were studied using chronoamperometry, polarization curves and adsorption isotherms. The electrochemical behaviour of clear solutions containing metavanadates and orange solutions containing decavanadates was clearly distinctive. Metavanadates reduced the kinetics of oxygen reduction to an extent similar to chromates. Corrosion inhibition of AA2024-T3 by metavanadates was very rapid and it might occur by the formation of an adsorbed layer. Reduction of clear metavanadate solution was very slow. Approximately 35 min were required to develop a monolayer of a reduced vanadate species. The adsorption of the inhibitor likely blocked reactive sites on intermetallic particles, discouraging the oxygen reduction reaction (ORR). Adsorption of the inhibitor on the Al matrix could also displace Cl⁻ ions, increasing the stability of the passive film and reducing the breakdown of S-phase particles. In contrast, decavanadates were shown to be poor inhibitors of the ORR. A sharp current spike was observed after injection of decavanadates for both Cu and AA2024-T3 at various applied cathodic potentials. Integration of the current peaks suggested the formation of several monolayers of a reduced vanadate species. The formation of several monolayers was in line with the poor performance of decavanadates as inhibitors of AA2024-T3 corrosion.     

Preparation and electrochemical characterization of amoxicillin-doped cellulose acetate films for AA2024-T3 aluminum alloy coatings

Cellulose acetate films doped with amoxicillin were deposited onto AA2024-T3 aluminum alloy and the corrosion protection in 0.05 M NaCl was evaluated by Electrochemical Impedance Spectroscopy (EIS) and the Scanning Vibrating Electrode Technique (SVET). The doping of the cellulose acetate film with amoxicillin resulted in a significant increase in the high frequency resistance and a decrease in the capacitance of the material. The protective effect could be observed under anodic polarization by way of a marked decrease in the anodic current. These results show the promising potential for the deposition of cellulose acetate films doped with amoxicillin onto AA2024-T3.     

Corrosion of AA2024-T3 Part I: Localised corrosion of isolated IM particles

Polished specimens of AA2024-T3 were immersed for various times up to 120 min in 0.1 M NaCl. The development of corrosion around isolated intermetallic particles was monitored using scanning electron microscopy with energy dispersive X-ray spectroscopy (EDXS). The earliest stages of attack started with localised corrosion of the S-phase particles resulting in dealloying which was followed by trenching around these particles. Subsequently, trenching was observed around cathodic particles where trenching started with AlCuFeMn particles with Cu/Fe ratios typically around 2.5 and then progressed to AlCuFeMnSi particles. This latter category of particles had a much lower Cu/Fe ratio, typically 0.5.     

Electrochemical study of modified non-functional bis-silane layers on Al alloy 2024-T3

In the last few years great efforts have been made in order to find and to develop environmentally friendly substitutes for Cr⁶⁺ pre-treatments applied on aluminium alloys used in the aircraft industry. Among the potential substitutes, silane layers have attracted considerable interest from researchers and from the industry. The present work investigates the anti-corrosion behaviour of (bis-1, 2-(triethoxysilyl) ethane (BTSE)) silane layers modified with Ce ions and/or silica nanoparticles applied on Al alloy 2024-T3 substrates. The corrosion behaviour was investigated in 0.1 M NaCl solution via d.c. polarization and electrochemical impedance spectroscopy (EIS). Contact angle measurements and XPS were used to assess information on the chemistry of the silane pre-treated surfaces. The results have shown that the introduction of additives improves the corrosion protection properties of the silane layer.     

Synergistic effect of pH and oxalate concentration on corrosion of aluminium alloy 2024-T3

This work aims at obtaining comprehensive information on the corrosion behaviour of AA2024-T3 in oxalic acid solutions under different concentrations (0.007–0.2?M) and pH (2–6). Various tests to characterise the corrosion behaviour are performed, including weight loss and electrochemical tests. Coupon surfaces are examined using infinite-focus microscopy, scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy, Raman spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy. Corrosion rates, anodic and cathodic reaction kinetics are detailed to provide a fundamental understanding of the electrochemical behaviour of AA2024-T3 as a function of pH and oxalate concentration. The synergistic effect of pH and oxalate concentration on corrosion of AA2024-T3 is evaluated for both AA2024-T3 matrix and main intermetallics (i.e. Al–Cu–Mg and Al–Cu–Fe–Mn) and the electrochemical behaviour of each constituent element in AA2024-T3 is systematically studied.     

Corrosion Protection of AA2024-T3 by Cerium Malate and Cerium Malate-Doped Sol-Gel Coatings

Cerium malate (CeMal) was tested as a corrosion inhibitor for AA2024-T3 in this work. Corrosion inhibition on bare AA2024-T3 indicated that the inhibiting effect was a result of the synergistic effect of cerium cations and maleic anions. The corrosion of AA2024-T3 was stagnated by greatly reducing the corrosion current when CeMal was present in NaCl solutions. CeMal was adsorbed on the surface of AA2024-T3 forming a protective film in the initial stage. Then, cerium cations transformed to cerium oxide/hydroxides, precipitating on the cathode sites to inhibit the further corrosion. The electrochemical impedance spectra results of the sol-gel coatings proved that CeMal was an effective corrosion inhibitor in the sol-gel coatings to provide corrosion protection for AA2024-T3.     

Analytical characterisation and corrosion behaviour of bis-[triethoxysilylpropyl]tetrasulphide pre-treated AA2024-T3

This work aims at studying the corrosion behaviour of AA2024-T3 pre-treated with bis-[triethoxysilylpropyl]tetrasulphide. Simultaneously, the work investigates the influence of the Cu-rich intermetallic particles on the formation of the silane film. The analytical characterisation of the silane films was performed by Auger electron spectroscopy and X-ray photoelectron spectroscopy. The corrosion performance of the pre-treated substrates was evaluated by electrochemical impedance spectroscopy. Atomic force microscopy associated with Kelvin probe was also used to determine the influence of the silane film on the Volta potential distribution on the alloy surface. The results show that copper present in the intermetallics plays an important role on the film formation.     

Corrosion protection of aluminium alloy 2024-T3 in 0.05 M NaCl by cerium cinnamate

The corrosion protection of AA 2024-T3 in 0.05 M NaCl by cerium cinnamate has been studied. Polarization measurements demonstrate that cerium cinnamate is markedly effective for suppressing anodic process of the alloy corrosion during the initial 72 h of immersion. The protection mechanism during the immersion period appears to involve two stages: the deposition of cerium cinnamate, and then hydrolysis of cerium ions forming a cerium oxide/hydroxide, prevailing over the foregoing deposition. This study also elucidates the inhibition effect of cerium cinnamate on the early corrosion attack occurred from the second phase particles by X-ray photoelectron spectroscopy and electron-probe microanalysis.     

Localized coating failure of epoxy-coated aluminium alloy 2024-T3 in 0.5 M NaCl solutions: Correlation between coating degradation, blister formation and local chemistry within blisters

The role of pH on the nature and rate of the degradation of epoxy coatings on AA2024-T3 panels and subsequent corrosion of the substrate during immersion in NaCl solutions was investigated. In acidic solutions both blister formation and growth are rapid. Blisters become very large (≈1 cm) and new blisters appear to form for a certain time after exposure. Often very small (∼0.1 mm) clear blisters surround these large blisters. Enhanced blister formation is due to irreversibly increased permeability of the coating for chloride ions and protons, the formation of more defect sites within the coating, and the weakening/dissolution of the oxide layer in low pH environments. In neutral pH solutions, coatings fail by forming one, or at most two, active blisters (red in color) within a few days of immersion with the time-to-failure dependent upon coating quality and thickness. Blister growth is a very slow process, and blister diameters rarely exceed a few millimeters even after several weeks. The accumulation of corrosion product within the blister slows down the corrosion rate and blister growth. The chloride concentration in the occluded solutions within the blister is significantly increased over the bulk concentration, and the pH is often in the acidic range. From electrochemical measurements it can be concluded that the anodic and cathodic reactions are confined to the blister and its immediate surroundings, rather than involving more of the surface over which the coating is intact. Based on corrosion morphology it is concluded that replated copper contributes to the overall cathodic reaction.     

Corrosion of AA2024-T3 Part II: Co-operative corrosion

Polished specimens of AA2024-T3 alloy were immersed for up to 120 min in 0.1 M NaCl. The development of corrosion was monitored using scanning electron microscopy with energy dispersive X-ray spectroscopy (EDXS) and particle induced X-ray emission spectroscopy (PIXE). Both techniques revealed the intermetallic (IM) particle distributions and attack sites as distinguished by detection of chloride species. The earliest stages of attack involved localized attack around isolated IM particles as reported in Part I. Additionally attack occurred on a larger scale developing rapidly with rings of corrosion product surrounding clusters of IM particles. There were significantly higher numbers of IM particles within the corrosion rings, indicating that local clustering played an important role in co-operative corrosion.     

The effect of welding parameters on the corrosion behaviour of friction stir welded AA2024-T351

The effect of welding parameters (rotation speed and travel speed) on the corrosion behaviour of friction stir welds in the high strength aluminium alloy AA2024-T351 was investigated. It was found that rotation speed plays a major role in controlling the location of corrosion attack. Localised intergranular attack was observed in the nugget region for low rotation speed welds, whereas for higher rotation speed welds, attack occurred predominantly in the heat-affected zone. The increase in anodic reactivity in the weld zone was due to the sensitisation of the grain boundaries leading to intergranular attack. Enhancement of cathodic reactivity was also found in the nugget as a result of the precipitation of S-phase. The results were compared with samples of AA2024-T351 that had been heat treated to simulate the thermal cycle associated with welding, and with samples that had been exposed to high temperatures for extended periods to cause significant over-ageing.     

A study of the corrosion of aluminum alloy 2024-T3 under thin electrolyte layers

The corrosion of aluminum alloy 2024-T3 (AA2024-T3) under thin electrolyte layers was studied in 3.0 wt% sodium chloride solutions by cathodic polarization and electrochemical impedance spectroscopy (EIS) method. The cathodic polarization measurements show that, when the electrolyte layer is thicker than 200 μm, the oxygen reduction current is close to that of the bulk solution. But in the range of 200-100 μm, the oxygen reduction current is inversely proportional to the layer thickness, which shows that the oxygen diffusion through the electrolyte layer is the rate-determining step for the oxygen reduction process. In the range of 100 μm to about 58 μm, the oxygen reduction current is slightly decreased probably due to the formation of aluminum hydroxide or the change of the diffusion pattern from 2-dimensional diffusion to one-dimensional diffusion. The further decrease in electrolyte layer thickness increase the oxygen reduction current to some extent again, because the diffusion of oxygen plays more important role in thin electrolyte layers.The EIS measurements show that the corrosion is controlled by the cathodic oxygen reduction at the initial stage, showing the largest corrosion rate at the electrolyte layer thickness of 105 μm. But at the later stage of corrosion, the anodic process begin to affect the corrosion rates and the corrosion rates show a maximum at 170 μm, which may be the thickness where the corrosion changes from cathodic control to anodic control. The corrosion rate under the very thin electrolyte layer (62 μm in this study) is even smaller than that in bulk solution, this is due to that the anodic process is strongly inhibited.     

Comparison of susceptibility to pitting corrosion of AA2024-T4, AA7075-T651 and AA7475-T761 aluminium alloys in neutral chloride solutions using electrochemical noise analysis

The susceptibility to pitting corrosion of AA2024-T4, AA7075-T651 and AA7475-T761 aluminium alloys was investigated in aqueous neutral chloride solution for the purpose of comparison using electrochemical noise measurement. The experimentally measured electrochemical noises were analysed based upon the combined stochastic theory and shot-noise theory using the Weibull distribution function. From the occurrence of two linear regions on one Weibull probability plot, it was suggested that there existed two stochastic processes of uniform corrosion and pitting corrosion; pitting corrosion was distinguished from uniform corrosion in terms of the frequency of events in the stochastic analysis. Accordingly, the present analysis method allowed us to investigate pitting corrosion independently. The susceptibility to pitting corrosion was appropriately evaluated by determining pit embryo formation rate in the stochastic analysis. The susceptibility was decreased in the following order: AA2024-T4 (the naturally aged condition), AA7475-T761 (the overaged condition) and AA7075-T651 (the near-peak-aged condition).     

The high throughput assessment of aluminium alloy corrosion using fluorometric methods. Part II - A combinatorial study of corrosion inhibitors and synergistic combinations

The discovery of new corrosion inhibition systems remains dependent on experimental methods for screening and characterization. This paper examines a new method to rapidly assess aluminium alloy corrosion and inhibitor performance through quantification of aluminium ion concentration using fluorometric probes. The fluorometric probes, lumogallion and morin, were used in conjunction with a plate reader to rapidly assess fourteen corrosion inhibitors and their combinations for AA2024-T3. AA2024-T3 wire electrodes were exposed to 3.4 mM total inhibitor concentration in 0.6 M NaCl adjusted to pH 2, 4, 7, 10, and 12 for 1-7 days. Corrosion inhibition provided by mixtures of lanthanum and molybdate, cerium and molybdate, and metavanadate with phosphate was found to be superior to the equivalent concentration of sodium chromate.     

A room temperature cured sol–gel anticorrosion pre-treatment for Al 2024-T3 alloys

The inherent reactivity of the Al–Cu alloys is such that their use for structural, marine, and aerospace components and structures would not be possible without prior application of a corrosion protection system. Historically these corrosion protection systems have been based upon the use of chemicals containing Cr(VI) compounds. Organic–inorganic hybrid silane coatings are of increasing interest in industry due to their potential application for the replacement of current toxic hexavalent chromate based treatments. In the present study, a hybrid epoxy–silica–alumina coating with or without doped cerium nitrate has been prepared using a sol–gel method. The hybrid coatings were applied by a dip-technique to an Al–Cu alloy, Al 2024-T3, and subsequently cured at room temperature. The anticorrosion properties of the coatings within 3.5% NaCl were studied using electrochemical impedance spectroscopy (EIS), and conventional DC polarisation. An exfoliation test method involving immersion in a solution of 4 M NaCl, 0.5 M KNO₃ and 0.1 M HNO₃ was also used. The cerium nitrate doped sol–gel coating exhibited excellent anticorrosion properties providing an adherent protection film on the Al 2024-T3 substrate. The resistance to corrosion of the sol–gel coating was also evaluated by analysing the morphology of the coating before and after corrosion testing using scanning electron microscopy.     

Investigation of the corrosion behaviour of AA 2024-T3 in low concentrated chloride media

Aluminium alloy (AA) 2024-T3 is an important engineering material due to its widespread use in the aerospace industry. However, it is very prone to localized corrosion attack in chloride containing media, which has been mainly associated to the presence of coarse intermetallics (IMs) in its microstructure. In this work the corrosion behaviour of AA 2024-T3 in low concentrated chloride media was investigated using microscopy and electrochemical methods. TEM/EDS observations on non-corroded samples evidenced the heterogeneous composition within the IMs. In addition, SEM observations showed that intermetallics with the same nominal composition present different reactivity, and that both types of coarse IMs normally found in the alloy microstructure are prone to corrosion. Moreover, EDS analyses showed important compositional changes in corroded IMs, evidencing a selective dissolution of their more active constituents, and the onset of an intense oxygen peak, irrespective to the IM nature, indicating the formation of corrosion products. On the other hand, the results of the electrochemical investigations, in accordance with the SEM/EDS observations, evidenced that IMs corrosion dominates the electrochemical response of the alloy during the first hours of immersion in the test electrolyte.     

The effect of inhibitor structure on the corrosion of AA2024 and AA7075

A range of structurally-related compounds were tested for their capacity to inhibit corrosion on aluminium alloys AA2024-T3 and AA7075-T6 in 0.1 M NaCl solution. It was found that the thiol group, positions para- and ortho- to a carboxylate, and substitution of N for C in certain positions strongly inhibited corrosion. The hydroxyl group was slightly inhibitive, while the carboxylate group provided little or no corrosion inhibition on its own. In several cases, different activities were found on the different alloys, with some compounds (particularly thiol-containing compounds) being more effective on AA2024 than on AA7075.     

Corrosion protection of AA7449-T7951 friction stir welds by laser surface melting with an Excimer laser

The corrosion protection afforded by laser surface melting (LSM) AA7449-T7951 friction stir welds was investigated. LSM produced melting of the constituent particles and formation of a homogeneous 3–5 μm thick layer. Electrochemical tests showed a reduction in cathodic reactivity after LSM. The breakdown potentials, however, did not change significantly, indicating an anodically reactive surface. In situ and ex situ observation after immersion in 0.1 M NaCl showed that LSM reduced the depth attack in the weld region (particularly the HAZ), affording sacrificial protection to the substrate. Delamination of the treatment can occur during corrosion propagation.