Localized corrosion mechanism associated with precipitates containing Mg in Al alloys

To clarify the localized corrosion mechanism associated with precipitates containing Mg in Al alloys, the simulated bulk precipitates of S and β were synthesized through melting and casting. Their electrochemical behaviors and coupling behaviors with α（Al） in NaCl solution were measured. Meanwhile, simulated Al alloys containing S and β particles were prepared and their corrosion morphologies were observed. It＇s found that there exist two kinds of corrosion mechanisms associated with precipitates containing Mg. The precipitate of β is anodic to the alloy base, resulting in its anodic dissolution and corrosion during the whole corrosion process. While, there exists a corrosion conversion mechanism associated with the S precipitate, which contains active element Mg and noble element Cu simultaneously. At an initial stage, S is anodic to the alloy matrix at its periphery and the corrosion occurs on its surface. However, during its corrosion process, Mg is preferentially dissolved and noble Cu is enriched in the remnants. This makes S become cathodic to a（Al） and leads to anodic dissolution and corrosion on the alloy base at its periphery at a later stage.     

Simulation on function mechanism of T1(Al2CuLi) precipitate in localized corrosion of Al-Cu-Li alloys

To clarify the corrosion mechanism associated with the precipitate of Tl(Al₂CuLi) in Al-Li alloys, the simulated bulk precipitate of T1 was fabricated through melting and casting. Its electrochemical behavior and coupling behavior with (Al) in 3.5% NaCl solution were investigated. Meanwhile, the simulated Al alloy containing T1 particle was prepared and its corrosion morphology was observed. The results show that there exists a dynamic conversion corrosion mechanism associated with the precipitate of T1. At the beginning, the precipitate of T1 is anodic to the alloy base and corrosion occurs on its surface. However, during its corrosion process, its potential moves to a positive direction with immersion time increasing, due to the preferential dissolution of Li and the enrichment of Cu. As a result, the corroded T1 becomes cathodic to the alloy base at a later stage, leading to the anodic dissolution and corrosion of the alloy base at its adjacent periphery. It is suggested that the localized corrosion associated with the precipitate of T1 in Al-Li alloys is caused by the alternate anodic dissolution of the T1 precipitate and the alloy base at its adjacent periphery.     

Study on localized corrosion mechanism of 2195 Al‐Li alloy in 4.0% NaCl solution (pH 6.5) using a three‐electrode coupling system

Localized corrosion morphologies of 2195 Al‐Li alloy with various heat treatment in 4.0% NaCl solution (pH 6.5) were investigated, and its corrosion mechanism was studied using a three‐electrode coupling system of α (Al) substituting for the precipitate‐free zone (PFZ), simulated bulk θ′ (Al₂Cu) and T1 (Al₂CuLi). θ′ acts as cathodic zone in the alloy. At the initial stage, T1 phase is active with respect to θ′ and α (Al), and endures the main anodic current, indicating that anodic dissolution occurs on T1. However, its potential moves to positive direction with immersion time, due to dealloying of Li from T1. As a result, the main anodic dissolution occurs on α (Al) at a later stage. At this stage, as only T1 and α (Al) are coupled, T1 is cathodic to α (Al). In real 2195 alloy, T1 phase is very tiny, and anodic dissolution of T1 and PFZ occurs alternately. These results show that its intergranular corrosion or intersubgranular corrosion is caused by alternate anodic dissolution of T1 phase and PFZ along grain and subgrain boundaries.     

Effect of heat treatment on corrosion behaviour of magnesium alloy AZ91D in simulated body fluid

The research explored ways of improving corrosion behaviour of AZ91D magnesium alloy through heat treatment for degradable biocompatible implant application. Corrosion resistance of heat-treated samples is studied in simulated body fluid at 37 °C using immersion and electrochemical testing. Heat treatment significantly affected microgalvanic corrosion behaviour between cathodic β-Mg₁₇Al₁₂ phase and anodic α-Mg matrix. In T4 microstructure, dissolution of the β-Mg₁₇Al₁₂ phase decreased the cathode-to-anode area ratio, leading to accelerated corrosion of α-Mg matrix. Fine β-Mg₁₇Al₁₂ precipitates in T6 microstructure facilitated intergranular corrosion and pitting, but the rate of corrosion was less than those of as-cast and T4 microstructures.     

Effect of Fe-Zn alloy layer on the corrosion resistance of galvanized steel in chloride containing environments

In this study, the effect of Fe-Zn alloy layer that is formed during galvanizing process on the corrosion behavior of galvanized steel has been investigated. The galvanostatic dissolution of galvanized steel was carried out in 0.5 M NaCl solution to obtain the Fe-Zn alloy layer on the base steel. The alloy layer was characterized to be composed of FeZn₁₃, FeZn₇ and Fe₃Zn₁₀ intermetallic phases, which constitute the zeta, delta1 and gamma layers of galvanized steel, respectively. It was observed that the alloy layer has similar cathodic polarization behavior but different anodic polarization behavior compared to galvanized steel. The anodic current plateau of alloy layer was up to 100 times lower than that of galvanized coating. Corrosion test performed in wet-dry cyclic condition has shown that the alloy layer has lower corrosion rate as compared to galvanized steel. From the results of corrosion test of alloy layer and base steel, it was concluded that Zn²⁺ has positive effect on the protectiveness of the zinc corrosion products. The measurement of surface potential over the alloy/steel galvanic couple has confirmed the galvanic ability of alloy layer to protect both the alloy layer itself and the base iron during initial stage of atmospheric corrosion.     

Mg_2Si及Si粒子在Al-Mg-Si合金晶间腐蚀中协同作用机理的多电极偶合研究

通过测定Al-Mg-Si合金晶界各组成相的极化曲线及不同Mg/Si比Al-Mg-Si合金晶界组成相(AlMg_2Si及Al-Mg_2Si-Si)间的动态电化学偶合行为,研究了不同Mg/Si比Al-Mg-Si合金的晶间腐蚀机理。研究表明,晶界Si电位比其边缘Al基体正,在整个腐蚀过程中作为阴极导致其边缘Al基体的阳极溶解。晶界Mg_2Si电位比其边缘Al基体负,在腐蚀初期将作为阳极而发生阳极溶解;由于Mg_2Si中活性较高元素Mg的优先溶解,不活泼元素Si富集,致使Mg_2Si电位正移,甚至与其边缘Al基体发生极性转换,导致其边缘Al基体的阳极溶解。Mg/Si1.73的Al-Mg-Si合金晶界只存在不连续分布的含Mg、Si的析出相,不能在晶界形成连续腐蚀通道,合金不表现出晶间腐蚀敏感性。Mg/Si1.73的Al-Mg-Si合金晶界同时析出含Mg、Si析出相和Si粒子;腐蚀首先萌生于Mg_2Si相;而后,Si粒子一方面导致其边缘无沉淀带严重的阳极溶解,另一方面通过加速Mg_2Si和晶界无沉淀带的极性转换,协同促进了Mg_2Si边缘无沉淀带的阳极溶解,即腐蚀沿晶界Si粒子及Mg_2Si粒子边缘的无沉淀带发展。Si粒子促进了腐蚀的发展,导致合金表现出严重的晶间腐蚀敏感性。     

Discontinuities in the porous anodic film formed on AA2099-T8 aluminium alloy

The anodizing behaviour of constituent particles (Al–Fe–Mn–Cu) and dispersoids (Al–Cu–Mn–Li and β′(Al₃Zr)) in AA2099-T8 has been investigated. Low-copper-containing Al–Fe–Mn–Cu particles anodized more slowly than the alloy matrix, forming a highly porous anodic oxide film. Medium- and high-copper-containing Al–Fe–Mn–Cu particles were rapidly dissolved, resulting in defects in the anodic film. The anodizing of Al–Cu–Mn–Li dispersoids is slightly slower than the alloy matrix, forming a less regular anodic oxide film. β′(Al₃Zr) dispersoids anodized at a similar rate to the alloy matrix. Further, the potential impact of the discontinuities in the resultant anodic films on the performance of the filmed alloy is discussed.     

Corrosion characterization of Mg-8Li alloy in NaCl solution

The corrosion mechanism of Mg-8Li alloy in NaCl solution was investigated by electrochemical testing and SEM observation. The electrochemical results indicated that the corrosion resistance of Mg-8Li alloy in 0.1 M NaCl solution gradually deteriorated with increasing of immersion time expect for 2 h immersion, which was consistent with the SEM observation of corrosion morphology. Mg-8Li alloy exhibited filiform type of attack under significant anodic control of magnesium solution reaction. The cathodic reaction was driven by hydrogen evolution reaction. The presence of filiform corrosion also proved a resistant oxide film naturally formed on the surface of Mg-8Li alloy.     

Al-Mg-Si合金中Mg_2Si和Si粒子在晶间腐蚀过程中的作用机理

研究Al-Mg-Si合金晶界组成相（Al-Mg2Si及Al-Mg2Si-Si）间的电化学行为和动态电化学耦合行为,提出Al-Mg-Si合金的晶间腐蚀机理。研究表明,晶界Si的电位比其边缘Al基体的正,在整个腐蚀过程中作为阴极导致其边缘Al基体的阳极溶解;晶界Mg2Si的电位比其边缘Al基体的负,在腐蚀初期作为阳极发生阳极溶解,然而由于Mg2Si中活性较高的元素Mg的优先溶解,不活泼元素Si的富集,致使Mg2Si电位正移,甚至与其边缘Al基体发生极性转换,导致其边缘Al基体的阳极溶解。当n（Mg）/n（Si）〈1.73时,随着腐蚀的进行,合金晶界同时会有Mg2Si析出相和Si粒子,腐蚀首先萌生于Mg2Si相和Si边缘的无沉淀带,而后,Si粒子一方面导致其边缘无沉淀带严重的阳极溶解,另一方面加速Mg2Si和晶界无沉淀带的极性转换,从而促使腐蚀沿晶界Si粒子及Mg2Si粒子边缘向无沉淀带发展。     

FIB-SEM investigation on corrosion propagation of aluminium–lithium alloy in sodium chloride solution

Abstract

Microstructural characterisation of 2A97-T4 aluminium–lithium alloy was carried out using electron probe microanalysis and transmission electron microscopy (TEM). Scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy facilities has been employed to examine localised corrosion sites after immersion in sodium chloride solution. A dual beam microscope, which integrates a focused ion beam and an electron beam in one powerful instrument, has also been employed to investigate the development of intergranular corrosion from both surface and cross-section. It was found that localised corrosion is generally initiated at θ phase particles, which represents only 8.4% of the intermetallic (IM) particles in 2A97-T4 aluminium–lithium alloy. θ phase particles exhibit preferential dissolution of aluminium during corrosion testing, with trench formed at their periphery as well. Initiation of intergranular corrosion is relatively late with respect to the attack of IM particles. Owing to the presence of θ phase particles at intergranular corrosion sites and non-uniform distribution of T1 (Al₂CuLi) grain boundary precipitates, it is supposed that dealloyed θ phase particles and grain boundary precipitates cooperate to provide the driving force for grain boundary attack.     

Effect of low copper content and heat treatment on intergranular corrosion of model AlMgSi alloys

Certain 6000-series extrusions may develop susceptibility to intergranular corrosion (IGC) by improper heat treatment, especially if copper is present as an alloying element. Although occurrence of IGC in such cases is documented, the underlying mechanisms are not adequately explained. We present corrosion data for two model alloys, having different Cu content and Mg:Si ratio, showing that the susceptibility to IGC depended primarily on the Cu content and secondly on thermal processing. Low Cu samples (0.0005 wt.% Cu) were essentially resistant to IGC. High Cu samples (0.12 wt.% Cu), which were air cooled after extrusion, exhibited significant IGC. However, IGC susceptibility was reduced significantly as a result of artificial aging to peak strength. Water quenched high Cu samples were essentially resistant to IGC. However, slight IGC susceptibility was introduced after aging. Electron optical characterisation revealed Al₄Mg₈Si₇Cu₂ (Q-phase) grain boundary precipitates on all the variants susceptible to IGC. The susceptibility was attributed to microgalvanic coupling between Q-phase grain boundary precipitates (noble) and the adjacent depleted zone (active).     

Corrosion of hot extrusion AZ91 magnesium alloy. Part II: Effect of rare earth element neodymium (Nd) on the corrosion behavior of extruded alloy

The corrosion behavior of extruded Nd-free AZ91 and extruded AZ91 + 1.5Nd alloy was investigated by weight loss and electrochemical measurements. The results showed that the extruded AZ91 + 1.5Nd alloy had higher corrosion resistance compared to the extruded Nd-free AZ91 alloy, which could been explained from point of view of microstructure changes: (1) the significant decrease of twins and dislocation decreased the anodic dissolution rate; (2) the micro-galvanic corrosion was inhibited by the formation of Al₃Nd phase; and (3) Nd not only increased the percent of Non-Faraday process, but also led to anisotropic feature on the corrosion mechanism.     

A correlation between phosphorous impurity in stainless steel and a second anodic current maximum in H2SO4

Phosphorous as a minor element (0.03%) in AISI 304 austenitic stainless steel greatly affects the polarization and corrosion behavior in sulfuric acid solution. The presence of P in stainless steel created a second current maximum in the anodic polarization curve and the current increased with increasing aging in the solution. An adhesive corrosion surface layer, rich with phosphate, formed on the surface of a P-containing steel during active dissolution. The layer lowered the cathodic Tafel slope at low current densities, and is likely, due to a change in hydrogen evolution mechanism. Phosphorous increases the H-adsorbed (and/or absorbed) atoms on the surface, leading to the appearance of a second anodic current peak that is interpreted as re-oxidation of hydrogen atoms. Also, P shifted the corrosion potential to the noble side, decreased effectively the active anodic dissolution, and lowered the corrosion rate.     

Effect of surface finishing of a Zr-based bulk metallic glass on its corrosion behaviour

Zr-based metallic glasses passivate spontaneously, but exhibit also a certain pitting susceptibility. On the example of the Zr₅₉Ti₃Cu₂₀Al₁₀Ni₈ alloy studied in 0.01 M Na₂SO₄ + x M NaCl (x = 0-0.1) electrolytes it is demonstrated that the surface finishing state and the pre-exposure conditions can significantly influence the free corrosion and anodic polarisation behaviour. Mechanical fine-polishing procedures can lead to extremely smooth topographies but also to Cu enrichment at the surface. This yields a pronounced Cu dissolution at low anodic polarisation prior to stable passivity and increases the pitting initiation susceptibility as compared to mechanically ground surface states.     

Effect of iron-containing intermetallic particles on the corrosion behaviour of aluminium

The effect of heat treatment on the corrosion behaviour of binary Al-Fe alloys containing iron at levels between 0.04 and 0.42 wt.% was investigated by electrochemical measurements in both acidic and alkaline chloride solutions. Comparing solution heat-treated and quenched materials with samples that had been subsequently annealed to promote precipitation of Al₃Fe intermetallic particles, it was found that annealing increases both the cathodic and anodic reactivity. The increased cathodic reactivity is believed to be directly related to the increased available surface area of the iron-containing intermetallic particles acting as preferential sites for oxygen reduction and hydrogen evolution. These particles also act as pit initiation sites. Heat treatment also causes depletion in the solute content of the matrix, increasing its anodic reactivity. When breakdown occurs, crystallographic pits are formed with {1 0 0} facets, and are observed to contain numerous intermetallic particles. Fine facetted filaments also radiate out from the periphery of pits. The results demonstrate that the corrosion of aluminium is thus influenced by the presence of low levels of iron, which is one of the main impurities, and its electrochemical behaviour can be controlled by heat treatment.     

Variation of Aging Precipitates and Mechanical Strength of Al-Cu-Li Alloys Caused by Small Addition of Rare Earth Elements

The effect of small rare earth (RE) addition of 0.11%Ce, 0.2%Er and 0.082%Sc on aging precipitates and mechanical strength of an Al-(3.3-4.2)Cu-1.2Li-X alloy were investigated. It is found that Cu-rich residual particles containing RE element exist in the solutionized alloy, which leads to a decrease of dissolved Cu concentration in the solutionized matrix. Like RE-free alloy, the main aging precipitate types in RE-containing alloy are T1 (Al₂CuLi) and θ′ (Al₂Cu), but their fraction is decreased. The strength of the corresponding alloys is therefore lowered by the small RE addition. Combined with the analysis of some reported references, it is proposed that the effect of small RE addition on Al-Cu-Li alloy strength is also associated with the Cu and Li concentrations and their ratio.     

Heat-transfer corrosion behaviour of cast Al alloy

Heat-transfer corrosion behaviour of an ISO 2379 cast Al alloy was studied in antifreeze radiator coolant under heat-rejecting condition. Extensive analyses of microstructures and corroded surfaces were carried out under the optical microscope, scanning electron microscope equipped with energy dispersive spectroscopy and X-ray diffractometer. Heat-rejecting condition led to a cavitation process and cavities were observed within the α-Al matrix. Crevice corrosion was predominant at oxygen depleted regions in heat-transfer corrosion cell. Al₂Cu, Al₁₅(Fe,Mn)₃Si₂ dendrites, Al₄Cu₂Mg₈Si₇ and Si phases served as the effective cathodes resulting microgalvanic corrosion at the anodic site of α-Al matrix.     

Effect of high temperature heat treatment on intergranular corrosion of AlMgSi(Cu) model alloy

Copper containing 6000-series aluminium alloys may become susceptible to intergranular corrosion (IGC) as a result of improper thermomechanical processing. Effect of cooling rate after solution heat treatment on the corrosion behaviour of a model AlMgSi(Cu) alloy of nominal composition (wt%) 0.6 Mg, 0.6 Si, 0.2 Fe, 0.2 Mn and 0.1 Cu was investigated. Slow cooling rates were simulated by isothermal treatment for predetermined times in lower temperature baths immediately after solution heat treatment. Treatment for 10-100 s at temperatures below 400 °C introduced susceptibility to IGC. Longer heat treatment at the same temperatures introduced susceptibility to pitting. A corrosion resistant time zone was found between the zones of IGC and pitting at temperatures lower than 350 °C. Quenching in water after solution heat treatment prevented IGC. IGC was related to microgalvanic coupling between the noble Q-phase (Al₄Mg₈Si₇Cu₂) grain boundary precipitates and the adjacent depleted zone. Pitting was attributed to coarse particles in the matrix. Possible mechanisms causing the corrosion resistant intermediate zone are discussed. The results indicate possible methods for obtaining increased corrosion resistance of similar alloys by proper thermal processing.     

Stress corrosion cracking study of microalloyed pipeline steels in dilute NaHCO3 solutions

Studies were carried out to evaluate the stress corrosion cracking (SCC) behavior of a X-70 microalloyed pipeline steel, with different microstructures by using the slow strain rate testing (SSRT) technique at 50 °C, in NaHCO₃ solutions. Both anodic and cathodic potentials were applied. Additionally, experiments using the SSRT technique but with pre-charged hydrogen samples and potentiodynamic polarization curves at different sweep rates were also carried out to elucidate hydrogen effects. The results showed that the different microstructures in conjunction with the anodic applied potentials shift the cracking susceptibility of the steel. In diluted NaHCO₃ solutions cathodic potentials close to their rest potential values decreased the SCC susceptibility regardless the microstructure, whereas higher cathodic potentials promote SCC in all steel conditions. Certain microstructures are more susceptible to present anodic dissolution corrosion mechanism. Meanwhile concentrated solution did not promotes brittle fracture.     

Galvanic corrosion of laser weldments of AA6061 aluminium alloy

Galvanic corrosion of laser welded AA6061 aluminium alloy, arising from the varying rest potentials of the various weldment regions, was examined. The weld fusion zone is found to be the most cathodic region of the weldment while the base material is the most anodic region. The rate of galvanic corrosion, controlled by the cathodic process at the weld fusion zone, increases with time until a steady state maximum is reached. On galvanic corrosion the corrosion potential of the weld fusion zone shifts in the positive direction and the free corrosion current increases. It is proposed that the cathodic process at the weld fusion zone causes a local increase in pH that in turn causes dissolution of the surface film resulting in the loss of Al to solution and the increase of intermetallic phases. The increase in galvanic corrosion may result from either the build up of the intermetallic phases in the surface layer and/or significant increase in surface area of the weld fusion zone due to the porous nature of the surface layer.