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).     

Development and analysis of frits for enamelling AA2024, AA6082 and AA7075 aluminium alloys

This study reports the development of frits with different composition, time, and firing temperature for mitigating the corrosion of AA2024, AA6082, and AA7075 aluminium alloys in chloride-containing solutions. The melting points of the frits were determined using a heating microscope, while the thermal expansion was measured using dilatometry. Several frits were prepared, of which seven were coated on AA2024, AA6082 and AA7075 aluminium alloys. The corrosion resistance of the coated samples was tested in 5 wt% NaCl solution at 25°C using potentiodynamic curve measurements. The corrosion resistance of the coated samples increased compared with the respective uncoated aluminium alloys. The composition and in-depth homogeneity of the best-performing coated samples were confirmed using a gas cluster ion beam sputtering source associated with X-ray photoelectron spectroscopy analysis. Furthermore, O₂⁺ sputtering was performed in association with time-of-flight secondary ion mass spectrometry to describe the three-dimensional composition of the frits.     

Influence of pre-treatments in cerium conversion treatment of AA2024-T3 and 7075-T6 alloys

The role of pre-treatment in the formation of a cerium conversion coating is investigated for the protection of AA2024-T3 and 7075-T6 alloys. The alloys were alkaline-etched and de-smutted in nitric acid, prior to cerium treatment in Ce(NO₃)₃ at 85 °C with H₂O₂ accelerator. Potentiodynamic polarization studies in 3.5% NaCl solution revealed a large shift of  300 mV of the corrosion potential below the pitting potential for the 7075-T6 alloy, which correlated with the development of a finely-textured, uniform coating. However, the formation of a uniform coating and protection was dependent upon the time of de-smutting, with non-uniform coatings resulting from extended times of de-smutting. In contrast, non-uniform coatings developed on the 2024-T3 alloy, with pitting potential at the corrosion potential, irrespective of the time of de-smutting. Findings for the 2024-T3 alloy indicate that extended de-smutting affects the enrichment of alloying elements.     

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.     

A morphological study of filiform corrosive attack on cerated AA2024-T351 aluminium alloy

SEM and EDS studies were carried out to characterise filiform attack on a cerated AA2024-T351 aluminium alloy with a polyurethane topcoat. The filiforms developed on AA2024-T351 were sectioned, stripped of corrosion product and etched to reveal the grain structure. Examination of sections through the filaments and the filaments themselves, revealed severe local attack in the form of pitting resulting in grain etch out, grain boundary attack and subsurface etch out. Chloride ions were detected deep within pits and the subsurface etch out. The observations were similar to those found with filiform corrosion on chromated and coated surfaces. The observations led to development of a filiform corrosion model naming the volume expansion of the corrosion product as the principal cause for delamination.     

In-situ investigation on the pitting corrosion behavior of friction stir welded joint of AA2024-T3 aluminium alloy

The surface corrosion behavior of an AA2024-T3 aluminium alloy sheet after friction stir welding was investigated by using an “in-situ observation” method. SEM observations showed that the density and degree of the pitting corrosion in the shoulder active zone were slightly larger compared to the other regions on the top surface. The origins of the pitting corrosion were in the regions between the S phase particles and the adjacent aluminium base. The effect of Al-Cu-Fe-Mn-(Si) intermetallic compounds on the pitting corrosion was attributed to their high self-corrosion potential which induced the anodic dissolution of the surrounding aluminium matrix.     

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.     

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.     

Comparison of the corrosion resistance of an Al–Cu alloy and an Al–Cu–Li alloy

ABSTRACT

In this study, the corrosion mechanisms of the AA2024-T3 and the AA2098-T351 were investigated and compared using various electrochemical techniques in 0.005?mol?L^?1 NaCl solution. The severe type of corrosion in the AA2098-T351 was intragranular attack (IGA) although trenching and pitting related to the constituent particles were seen. On the other hand, the AA2024-T3 exhibited severe localised corrosion associated with micrometric constituent particles, and its propagation was via grain boundaries leading to intergranular corrosion (IGC). Electrochemical techniques showed that the corrosion reaction in both alloys was controlled by diffusion. The non-uniform current distribution in both alloys showed that EIS was not a proper technique for comparing the corrosion resistance of the alloys. However, local electrochemical techniques were useful for the evaluation of the corrosion resistance of the alloys.     

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.     

Degradation of the corrosion resistance of anodic oxide films through immersion in the anodising electrolyte

The deterioration of AA2024, AA6061 and AA7475 anodised in an environmentally-compliant tartaric acid/sulphuric acid electrolyte has been examined as a function of the immersion time in the electrolyte after termination of anodising. By transmission electron microscopy and scanning electron microscopy, degradation of the porous oxide film was qualitatively observed on AA2024. Electrochemical impedance spectroscopy revealed that AA2024 and AA7075 were more sensitive to prolonged immersion in the anodising electrolyte compared with AA6061, due to increased barrier layer thinning rates and increased susceptibility to localized corrosion. Salt spray tests confirmed the previous, indicating decay of anticorrosion performance for AA2024 and AA7075.     

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.     

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.     

A morphological study of filiform corrosive attack on chromated and alkaline-cleaned AA2024-T351 aluminium alloy

In order to characterise filiform corrosion on a commercial AA2024-T351 aluminium alloy, a detailed microscopical study using SEM and EDS was performed. One set of AA2024-T351 aluminium alloy samples was alkaline-cleaned and deoxidised and chromate conversion coated. Another set was alkaline-cleaned only. Both samples were similarly spray coated with a 42 μm clear polyurethane topcoat. Filaments were subjected to a range of specimen preparation techniques. Sections and top views examined by SEM revealed varying degrees of attack ranging from generalised etching without local attack to severe local attack in the form of pitting, resulting in grain etchout, grain boundary attack and subsurface etchout. EDS revealed the presence of chloride deep into the pits and the subsurface etchout.     

纳米SiC颗粒强化7075铝合金在NaCl溶液中的电化学腐蚀行为

研究了纳米SiC颗粒强化7075铝合金(SiC_p/7075A1)经T6处理后在3.5%NaCl中性水溶液中的腐蚀特性及腐蚀机理.结果表明,适量纳米SiC颗粒的加入,可提高AA7075-T6的自腐蚀电位和击穿电位,降低腐蚀速率,增强其耐蚀性.SEM观察表明,SiC_p/7075Al-T6的腐蚀以点蚀为主,主要发生在晶界及近晶界区域,没有大的点蚀坑,而未经强化的AA7075-T6则呈现出严重的点蚀和晶间腐蚀的特征,这与EIS特征相符,浸泡实验也得到了同样的结果.TEM观察证实SiC颗粒在晶界的存在分割了η相;阻断了晶界阳极性的η相与其边缘合金组成的腐蚀电偶形成的活性通道;阻碍了蚀孔的长大,提高了腐蚀抗力.     

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.     

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.     

Stable pit formation on AA2024-T3 in a NaCl environment

Scanning vibrating electrode (SVE), particle induced X-ray emission spectroscopy (PIXE) and standard electrochemical measurements were used to study the establishment of stable pits on AA2024-T3 in neutral sodium chloride solution (0.1 M NaCl). Pits were allowed to develop until hydrogen evolution was observed. Typical current at the mouth of the pits were in the vicinity of 1 mA. PIXE maps revealed the intermetallic (IM) particle distributions in the surface as well as significant chloride buildup around the pits. A significant fraction of the small selection of pits examined here appeared to have an S-phase particle (or remnant) within 20 μm of a AlCuFeMn type IM particle suggesting a coupling between the two. The electrochemistry of the coupling between different IM particle types was further investigated using potentiodynamic scans in 0.1 M aqueous NaCl solution of macroscopic electrodes made according to the IM particle compositions. Current densities at the open circuit potential of AA2024-T3 were largest, typically (0.2 up to 1 mA/cm²) for phases that were anodic with respect to AA2024-T3. Coupling of the IM particles was examined by comparing the degree of clustering around chloride attack sites to the average particle density for each map. There were significantly higher number of IM particles surrounding pit sites than the average IM particle densities indicating that local clustering played an important role in pit initiation.     

Electrochemical behavior and localized corrosion associated with Al7Cu2Fe particles in aluminum alloy 7075-T651

Initiation of localized corrosion upon high strength aluminum alloys is often associated with cathodic intermetallic particles within the alloy. Electrochemical measurements and metallurgical characterization have been made to clarify and quantify the physical properties of Al₇Cu₂Fe particles in AA7075-T651. Prior studies regarding either the stereology or electrochemical properties of Al₇Cu₂Fe are scarce. Quantitative microscopy revealed a significant population of Al₇Cu₂Fe in the alloy; comprising up to 65% of the constituent particle population and typically at a size of 1.7 ± 1.0 μm. It was determined that Al₇Cu₂Fe may serve as a local cathode in the evolution of localized corrosion of AA7075-T651 and is capable of sustaining oxygen reduction reactions at rates of several hundreds of μA/cm² over a range of potentials typical of the open circuit potential (OCP) of AA7075-T651 in NaCl solution of various concentrations and pH. The presence of Al₇Cu₂Fe leads to the development of pitting at the particle–matrix interface.     

On the first breakdown in AA7075-T6

The first breakdown in AA7075-T6 was studied by an in situ observation system in which a combination of a magnified image of the surface and the instantaneous polarization curve allowed determination of the corrosion process as a function of potential. As-polished (to 1 μm) AA7075-T6 clearly exhibited dissolution of a thin surface layer corresponding to a sharp increase of current just above the first breakdown potential. No surface layer dissolution was observed for samples that were either ion milled or chemically etched to remove the effects of polishing. This susceptible surface layer was apparently the result of the mechanical polishing process. The surface microstructure of an as-polished sample was analyzed by TEM and several distinct features were found: (1) a unique thin layer with thickness of 100 nm on average; (2) many fewer fine hardening particles in the thin surface layer than in the bulk matrix, which suggests that the fine particles were destroyed and eliminated by polishing; (3) high aspect ratio nano-grains elongated along the final polishing direction; (4) a high concentration of Zn and Mg at the nano-grain boundaries. The attack of the surface layer might initiate at the active nano-grain boundary followed by nano-grain dissolution.