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.     

Corrosion of AA2024-T3 Part III: Propagation

Optical and electron microscopies and EBSD were used to study the early stages of corrosion propagation during stable pit formation on AA2024-T3. Polished AA2024-T3 developed large scale rings of corrosion product, typically a few hundred microns in diameter, within 2 h of exposure to 0.1 M NaCl at room temperature. These features were sectioned using diamond ultramicrotomy and substantial subsurface attack, in the form of intergranular corrosion was observed beneath these sites with virtually no grain etchout. A model is proposed for the mechanism of stable pit progression which involves extensive grain boundary attack, followed by grain etchout leading to open pit formation.     

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.     

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 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 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 study of intergranular corrosion in aircraft aluminium alloys using X-ray tomography

Atmospheric corrosion is one of the leading causes of structural damage to aircraft. Of particular importance is pitting and intergranular corrosion, which can develop into fatigue cracks, stress corrosion cracks, or exfoliation. Therefore it is of interest to the Australian Defence Force (ADF) to understand how corrosion ensues in susceptible aircraft aluminium alloys, such as AA2024-T351 and 7050-T7451. However, there are many difficulties in measuring the extent of intergranular corrosion, since it is predominantly hidden below the surface. Traditionally, cross-sectioning has been used to view and measure the depth of attack. In the present work, 2 mm diameter pin specimens were contaminated with a droplet of 3.5% NaCl and exposed to constant humidity that resulted in intergranular corrosion. X-ray computed tomography was then used to non-destructively assess the depth and volume of corrosion both as a function of time in 97% relative humidity, and as a function of relative humidity after 168 h exposure. Both corrosion depth and volume increased with time, but there was evidence for a limiting depth in AA2024. Depth and volume also increased with relative humidity of the environment, for which the time-of-wetness and oxygen concentration of the droplets were considered the important factors in driving the corrosion process.     

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.     

Study of localized corrosion in AA2024 aluminium alloy using electron tomography

SEM based tomography of localized corrosion has been achieved using selective detection of backscattered electrons. The high resolution tomography provides direct evidence that links the surface appearance of corroded alloy, the alloy microstructure and the corrosion propagation path. Stable localized corrosion of AA2024-T351 aluminium alloy was initiated at locations where large clusters of S phase particles were buried beneath the surface. Propagating away from the initiation sites, corrosion developed preferentially along the grain boundary network. The grain boundary attack started beneath the alloy surface, proceeded along preferred grain boundaries and may emerge at the alloy surface.     

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.     

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.     

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).     

基于晶格储存能的航空铝合金腐蚀行为研究

采用多种电子显微技术对AA2024-T3航空铝合金的局部腐蚀行为进行研究。结果表明:AA2024-T3铝合金的局部腐蚀主要以晶间腐蚀的形式出现,相对于晶界沉淀相,晶格储存能更为显著地影响晶间腐蚀的发展,促使其优先发生在晶格储存能更高的晶粒周围。研究结果有助于提高对航空铝合金晶间腐蚀机理的认识,并为航空铝合金的设计提供理论指导,对保障航空安全具有重要意义。     

Corrosion Evolution of High-Strength Aluminum Alloys in the Simulated Service Environment of Amphibious Aircraft in the Presence of Chloride and Bisulfite

The corrosion evolution of 2024-T351 and 7075-T651 aluminum alloys in the thin electrolyte layer (TEL) and wet-dry alter-nating cycle (WDAC) environment is studied in this work.The results show that in the TEL environment,the competitive effect between H+ that accelerates corrosion reactions and deposition of aluminum sulfate that impedes corrosion attacks exists during the corrosion exposure.The difference is that with increasing HSO3-,subsurface intergranular corrosion on 2024-T351 is promoted to form exfoliation corrosion eventually and the degree of exfoliation corrosion begins to decrease because the blocking effect of aluminum sulfate exceeds the expediting effect of H+.For 7075-T651,the corrosion area and the corrosion diameter decrease gradually,which is attributed to the HSO3-enhanced deposition of corrosion products and their blocking effect.In the WDAC environment,the corrosion processes of 2024-T351 and 7075-T651 are the acidic dissolution of the matrix during the soaking phase.When the HSO3-concentration is high enough (0.1 M),the inhibiting effect of aluminum sulfate becomes the dominant factor.     

Corrosion pathways in aluminium alloys

The corrosion pathways in AA2024-T3, AA5083-O and AA6082-T6 alloys have been investigated. The objective of the investigation is to further the understanding of the complex localised corrosion mechanism in aluminium alloys. The investigation was carried out by examining the corroded surfaces of the alloys after potentiodynamic polarization tests in a 3.5% NaCl solution with the aid of a scanning electron microscope, and by analysing the flow of anolyte solution using the scanning vibrating electrode technique. The results revealed that the overall corrosion pathways in the alloys are distinctively different and are influenced by the flow of anolyte solution. Also revealed, was the fact that corrosion propagates in two ways (particularly in the AA5083-O and AA6082-T6 alloys): an overall pathway in the corrosion front (filiform-like pathway in the AA5083 alloy and organized linear pathways in AA6082 alloy); and the crystallographic channelling along the 〈100〉 directions. These are dependent on the grain distinct features of the AA5083-O and AA6082-T6 alloys and are not influenced by the presence of coarse second phase particles in these alloys, compared with the AA2024-T3 alloy, where the corrosion pathways are more dependent on the presence of second phase particles and grain boundary character.     

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.     

Effects of testing variables on stress corrosion cracking susceptibility of Al 2024-T351

In the present study, the effects of testing variables on stress corrosion cracking (SCC) susceptibility of Al 2024-T351 in 3.5% NaCl solution were examined using slow strain rate test (SSRT) method with controlled applied potentials and a constant load test (CLT) method. The SSRTs were conducted at various strain rates and applied potential, while the CLTs were performed with different exposure time, with different grain directions of ST (short-transverse) and L (longitudinal) to understand how the testing parameters affected on the SCC susceptibility of Al 2024-T351. The percent reductions in tensile elongation in an SCC-causing environment over those in air tended to express the SCC susceptibility of Al 2024-T351 most properly for both SSRT and CLT. The present fractographic examination suggested that both anodic dissolution and hydrogen embrittlement played a role in the SCC process of Al 2024-T351 in 3.5% NaCl solution at both anodic and cathodic applied potentials, and the contribution of each mechanism could vary with different testing variables. It was also found that the SCC susceptibility of Al 2024-T351 obtained from the CLT result could provide the similar SCC evaluation result obtained by SSRT with a proper selection of testing variables. The metallurgical aspect of SCC behaviour of Al 2024-T351 was also discussed based on the microstructural and fractographic examinations.     

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.     

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.     

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.