Influence of molybdate species on the tartaric acid/sulphuric acid anodic films grown on AA2024 T3 aerospace alloy

AA2024 T3 alloy specimens have been anodised in tartaric acid/sulphuric media and tartaric acid/sulphuric media containing sodium molybdate; molybdate species were added to the anodising bath to enhance further the protection provided by the porous anodic film developed over the macroscopic alloy surface. Morphological characterisation of the anodic films formed in both electrolytes was undertaken using scanning electron and transmission electron microscopies; the chemical compositions of the films were determined by Rutherford backscattering spectroscopy that was complemented by elemental depth profiling using rf-glow discharge optical emission spectrometry. The electrochemical behaviour was evaluated using potentiodynamic polarisations and electrochemical impedance spectroscopy; the corrosion performance was examined after salt spray testing. The porous anodic film morphology was little influenced by the addition of molybdate salt, although thinner films were generated in its presence. Chemical composition of the anodic film was roughly similar; however, addition of sodium molybdate in the anodizing bath resulted in residues of molybdate species in the porous skeleton and improved corrosion resistance measured by electrochemical techniques that was confirmed by salt spray testing.     

Study of the potential electrochemical noise during corrosion process of aluminum alloys 2024, 7075 and pure aluminum

Properties of the potential electrochemical noises (EN) generated during the corrosion process of aluminum alloys AA2024(T3), AA7075 (aged at 121°C/35 h + 160°C/20 h) and pure aluminum in 3wt% (mass fraction) NaCl solution were investigated in this study. During the initial stage of immersion, the EN amplitude of AA2024 is the largest while the EN amplitude of pure aluminum is negligible. The amplitude of the EN generated by these materials decreases with immersion time except the EN of AA2024 after extremely long immersion time (38 days in this study). Surface morphology corresponding to different stages of immersion and different types of EN were studied by scanning electron microscopy (SEM) coupled with energy dispersive spectrometry (EDS) analysis. The result shows that the micro‐galvanic cells formed by the constituent particles and the alloy matrix play an important role on the corrosion process of the aluminum alloys and the EN behaviors of AA2024, AA7075 and pure aluminum is proved to be strongly related to the type and intensity of corrosion process.     

Modelling the anodizing behaviour of aluminium alloys in sulphuric acid through alloy analogues

Anodic film morphologies on aluminium aerospace alloys are strongly influenced by alloying elements. The present study uses model alloys to interpret the early stages of anodizing of AA2024-T3 and AA7075-T6 aluminium alloys in 0.4 M sulphuric acid electrolyte. Further, coupled model alloys, representative of matrix and second phase regions, are employed as alloy analogues. The findings enable assignment of transient anodic currents during potentiodynamic polarization of the commercial alloys to oxidation of Al₂CuMg phase at 0 V SCE and of Al₂Cu, Al₇Cu₂Fe and Al–Cu–Fe phases at 5–6 V SCE. The phases that oxidize at the latter potential also cause voltage arrests during galvanostatic anodizing.     

Anodising of 2024-T3 aluminium alloy in electrolyte of sulphuric– boric–phosphoric mixed acid containing cerium salt as corrosion inhibitor

The effect of cerium salt as an inhibitor in anodising of the 2024-T3 aluminium alloy was studied. Scanning electron microscopy equipped with energy dispersive X-ray spectroscopy was used to study the surface composition of the alloy before and after surface preparation. A mixed electrolyte of 10% sulphuric acid, 5% boric acid and 2% phosphoric acid containing 0.1 mol/L cerium sulphate salt was used as the anodising electrolyte. Sealing treatment was also done in boiling water and molten stearic acid. Electrochemical impedance spectroscopy and salt spray techniques were performed in order to investigate the corrosion behaviour and durability of the oxide films, respectively. It was concluded that the presence of cerium ions in anodising electrolyte resulted in the increase in homogeneity, the rate of oxide film growth and also the thickness of the oxide layer, owing to the high oxidising power of cerium ion.     

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 properties of Nd:YAG laser-GMA hybrid welded AA6061 Al alloy and its microstructure

The paper presents the corrosion behaviour of the Nd:YAG laser-gas metal arc (GMA) welds of AA6061-T6 alloy. The laser-GMA hybrid welding enhances the corrosion susceptibility of AA6061 alloy. The surface morphology observation and composition analysis were investigated by the scanning electron microscopy (SEM) with energy dispersive X-ray (EDX) spectroscopy. An increasing of the precipitate phase is observed in the weld fusion zone (WFZ). The WFZ suffers more severe pitting and cracks are associated with pitting. It is proposed that the increased precipitate phase increases the galvanic corrosion couples and results in the aggravation of pitting and cracking in the WFZ.     

Interpretation of the anodic and cathodic potential variations during the AC-graining of aluminium in hydrochloric acid

The variations of the anodic and cathodic amplitudes during the AC-graining of aluminium in hydrochloric acid electrolyte were investigated in this work in order to combine the amplitude variations with the electrochemical reactions that take place in the electrograining process. Aluminium samples were galvanostatically grained in 0.34 M hydrochloric acid and the signal of the applied potential versus a reference electrode was recorded by a high frequency acquisition system. The potential variation during the AC-graining of the aluminium alloy AA1050 and of pure aluminium (99.99%) was examined as well as the influence on the potential variation of the applied pre-treatments. In addition, scanning electron microscopy and backscattering electron micrographs were also used to examine the aluminium samples. The smut layer formation at the initial stages of graining was investigated by X-ray photoelectron spectroscopy. It was concluded that the variations of the anodic and cathodic amplitudes were divided into three different regions. An interpretation of these regions was achieved by the combination of the potential measurements of the different example substrates with the subsequent observations of the grained surfaces. By using this interpretation of the potential variations, interesting information can be obtained about the influence on the electrograining process of the aluminium substrate, the applied pre-treatments and the electrograining conditions.     

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.     

FIB/SEM study of AA2024 corrosion under a seawater drop: Part I

The role of metallic microstructure in 0.5 μl seawater droplet corrosion of aluminium alloy 2024 (AA2024) has been investigated. Focussed ion beam/scanning electron microscopy (FIB/SEM) was used to determine the relationships between the corrosion products formed at specific sites at the surface and the underlying attack mechanisms. Dealloying of S-phase particles, matrix/particle interfacial attack and grain boundary attack were the predominant attack modes. Cooperative behaviour between IM particles was made possible by networks of etched grain boundaries, which provided a connecting path.     

Effect of solution heat treatment on galvanic coupling between intermetallics and matrix in AA7075-T6

Susceptibility to localised corrosion is strongly affected by heat treatments performed on Al-Zn-Cu-Mg alloys. In order to study how galvanic coupling between intermetallics and matrix is affected by solution heat treatment, AA7075-T6 and solution heat treated AA7075 have been characterised by means of scanning electron microscopy and scanning Kelvin probe force microscopy. Solution heat treatment strongly increased the Volta potential difference between the intermetallics and the surrounding matrix showing a strong increase in galvanic coupling. This is explained by Zn and Mg enrichment of the matrix caused by dissolution of strengthening particles during solution heat treatment.     

Co-operative corrosion phenomena

The corrosion of aluminium alloy 2024-T3 (AA2024-T3) was studied as a function of immersion time from 2.5 to 120 min in 0.1 M aqueous NaCl solution. At immersion times as short as 5 min, rings of corrosion product of 100 to 200 μm diameter, containing smaller domes of corrosion product, were observed using SEM. The domes of corrosion product had greater chloride concentrations than elsewhere on the surface and represented sites of anodic attack. As the immersion time was increased, significant grain boundary attack was observed within the rings of corrosion product. Analyses of Particle Induced X-ray Emission (PIXE) maps of the corroded surfaces showed a significantly higher number of IM particles around the chloride attack sites than the average particle density for the maps, indicating clustering of IM particles. These results suggest a co-operative corrosion effect as a result of clustering of the IM particles. A mechanism for the generation of the corrosion rings is discussed.     

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 behaviour of second phase particles during anodizing of aluminium alloys

Several model second phase particles and a practical alloy (AA7075-T6) have been anodized in chromic and sulphuric acid to disclose the relation between particle composition, electrolyte nature and oxidation behaviour. Generally, magnesium-containing second phases are readily oxidized, because the presence of sufficient magnesium hinders the formation of a stable oxide, while copper- and iron-containing particles oxidize at reduced rates and support a relatively stable oxide. At low potential, in chromic acid, the oxidation rate of magnesium-containing particles is reduced, due to passivation induced by chromate anions. Conversely, for particles containing only copper and/or iron, chromate anions increase the oxidation rate.     

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.     

Effect of tantalum film on corrosion behaviour of AA6061 aluminium alloy in hydrochloric acid- and chloride-containing solutions

ABSTRACT

The present work is concerned with the corrosion resistance of AA6061 aluminium alloys with tantalum films in hydrochloric acid- and chloride-containing solutions. The tantalum films were produced by magnetron sputtering at different sputtering times (50 and 120 min). The films’ morphologies were observed by metallographic microscope and scanning electron microscope with energy dispersion spectrum. It is shown in this paper that with longer sputtering time, the film’s thickness increased, but it became less dense. The corrosion behaviour was characterised by potentiodynamic polarisation, scanning electrochemical microscopy analysis and an immersion experiment. These investigations revealed that the corrosion resistance of AA6061 aluminium alloy in chloride ions medium and hydrochloric acid was significantly improved after deposition of a tantalum film. Specifically, samples deposited for 50 min exhibited the best corrosion resistance in hydrochloric acid, while samples deposited for 120 min showed best corrosion resistance in sodium chloride solution.     

Galvanic compatibility of corrosion protective coatings with AA7075 aluminum alloy

The galvanic compatibility of aerospace aluminum alloy AA7075 with cadmium (Cd), zinc (Zn), and zinc–cobalt–iron (Zn–Co–Fe, 32–37%Co and 1%Fe) alloys was investigated. A comparison of open circuit potential [OCP vs. saturated calomel electrode (SCE)] measurements in 0.6 mM NaCl showed that all coatings would act anodically to AA7075 with an exception of Zn–Co–Fe (37%Co + 1%Fe) alloy which was electropositive to AA7075. During the zero resistance ammetry (ZRA) measurement in 0.6 M NaCl electrolyte the coupled OCP and current density were measured during 7 days of immersion and both Zn and Cd acted anodic and thus sacrificial to AA7075. Galvanic coupling of AA7075 with (37%Co + 1%Fe) Zn–Co–Fe alloy resulted in the consequent dissolution of the AA7075 aluminum alloy. In contrast, Zn–Co–Fe (32%Co + 1%Fe) alloy was found to be anodic to AA7075 during the first 26 h of immersion but after dezincification and cobalt enrichment at the surface became cathodic to the AA7075 aluminum alloy. During coupling with Zn, some pitting was also observed on AA7075.     

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.     

High-throughput channel arrays for inhibitor testing: Proof of concept for AA2024-T3

A high-throughput test has been developed for screening aqueous corrosion inhibitors on aluminium AA2024-T3. The method adapts basic microfluidic technology to create multiple channels in polydimethylsiloxane, which allow solutions to flow over the surface of the alloy, causing severe corrosion within hours if no inhibitor is present. In three-channel experiments under various channel conditions, corrosion rates were accelerated up to 15 times when compared to standard immersion tests. In addition, 10-channel experiments were conducted to simultaneously test 10 different inhibitors, and the results were compared visually and to actual corrosion results obtained quantitatively via solution analyses.     

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.     

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.