Role of cathodic half-cycle on AC etch process of aluminium

The AC etch process effectively expands the surface area of aluminium foil as compared with DC etch process. This study explored the effect of cathodic half-cycle. The cathodic half-cycle enhanced passivation of pits developed during the preceding anodic half-cycle, making pit nucleation random. Anodic pulse without cathodic half-cycle produced hollows, due to preferential pit nucleation on pits produced in the preceding anodic half-cycle. The open circuit before the cathodic half-cycle does not largely influence the etch factor, but etch film formation is largely suppressed. The precipitation of aluminium hydroxide may not have a crucial role in porous layer formation.     

Pit growth behaviour of aluminium under galvanostatic control

The pit growth process on (1 0 0) aluminium under anodic pulse current in a mixed solution of 1 M HCl and 0.1 M H₂SO₄ at 30 °C has been evaluated using potential transient measurements and pit size distributions obtained by scanning electron microscopy. Sustained pit growth is observed for all pits during the initial anodic potential rise before reaching a steady-state etch potential, whereas a substantial fraction of the pits passivate at the steady-state etch potential. The pit growth rate during the initial potential rise is 3.4 μm s⁻¹, which is similar to that at the steady-state etch potential. The growth rates of active pits are potential-independent.     

Effects of pretreatment on the aluminium etch pit formation

The effect of chemical pretreatments on the electrochemical etching behavior of aluminium was investigated with the topographic studies of surface and the analysis of initial potential transients. Two-step pretreatments with H₃PO₄ and H₂SiF₆ result in a high density of pre-etch pits on aluminium surface by the incorporation of phosphate ion inside the oxide film and the removal of surface layer by aggressive fluorosilicic acid solution. It generates a high density of etch pits during electrochemical etching and results in the capacitance increase of etched Al electrode by expanding the surface area, up to 61.3 μF/cm² with the pretreatment solution of 0.5 M H₃PO₄ at 65 °C and 10 mM H₂SiF₆ at 45 °C.     

Effect of placement of aluminium foil on growth of etch tunnels during DC etching

The tunnel growth behaviour of aluminium foil etched in different placement has been investigated. The limiting length of tunnel of specimens in increasing order is: face-down, vertical, and face-up placement. Many sub tunnels branch on the wall surface of the main tunnel when aluminium is etched in face-down placement, while much fewer sub tunnels are formed when aluminium is etched in face-up placement. A novel etching model has been proposed to interpret the phenomenon, by considering the electrocapillary effect. It reveals that the status and transport of hydrogen bubbles inside the tunnel has a great influence on the tunnel growth.     

Effect of microcrystallization on pitting corrosion of pure aluminium

A microcrystalline aluminium film with grain size of about 400 nm was prepared by magnetron sputtering technique. Its corrosion behaviour was investigated in NaCl containing acidic solution by means of potentiodynamic polarization curves and electrochemical noise (EN). The polarization results indicated that the corrosion potential of the sample shifted towards more positive direction, while its corrosion current density decreased compared with that of pure coarse-grain Al. The EN analysis based on stochastic model demonstrated that there existed two kinds of effect of microcrystallization on the pitting behaviour of pure aluminium: (1) the rate of pit initiation is accelerated, (2) the pit growth process was impeded. This leads to the enhancement of pitting resistance for the microcrystallized aluminium.     

Large-area self-ordered aluminium sub-micrometre dot arrays prepared by electropolishing on polycrystalline aluminium at constant current

The effects of electropolishing on the sub-micrometre structure pattern on the surface of polycrystalline aluminium were investigated. Under constant current, the electropolishing process results in large-area uniform sub-micrometre dot arrays despite the polycrystalline aluminium surface. Effects of temperature on the pattern of the surface structures were also investigated. Experimental temperature was shown to have a great influence on the structure pattern. When the electropolishing temperature increases, the structure of aluminium surface tends to transform from a dot pattern to stripe one and then to a corrosion structure.     

Effect of rapid solidification on the microstructure and corrosion behaviour of Al-Zn-Mg based material

The corrosion behaviour of Al-5Zn-3Mg-0.6Cu-0.8Zr-0.25Cr-0.15Ni-0.15Ti alloys, produced by traditional and powder technologies, with similar thermo-mechanical treatments, in 3% sodium chloride solution, has been examined by electrochemical methods, scanning electron microscopy, transmission electron microscopy and X-ray microanalysis. The alloys reveal similar precipitation but of different shape, size and distribution; further, both alloys experience localized corrosion. Copper-rich precipitates initiate the dissolution of surrounding particles, enriched in Zn and Mg. As a result, the surface is enriched with other alloying elements after a full polarisation run. Cast material has lower corrosion properties because of the higher heterogeneity of the structure. The structure heterogeneity of the cast material involves a more non-uniform distribution of the precipitates, larger Zn- and Mg-rich particles, and depletion of the matrix and areas around the precipitates by alloying elements compared with the powder material.     

Corrosion behaviour of several aluminium alloys in contact with a thermal storage phase change material based on Glauber’s salt

This article presents the results of a study about the corrosion behaviour of four aluminium alloys (EN AW 2024, 3003, 6063, and 1050) in contact with a commercial thermal storage material based in the Glauber’s salt (Na₂SO₄·10 H₂O). Results indicate that the Al 2024 alloy is not compatible with this material due to the extense formation of NaAlCO₃·(OH)₂ in contact with air. The aluminium alloys 3003, 6063 and 1050 showed to be fully compatible with the material.     

A generic statistical methodology to predict the maximum pit depth of a localized corrosion process

This paper outlines a new methodology to predict accurately the maximum pit depth related to a localized corrosion process. It combines two statistical methods: the Generalized Lambda Distribution (GLD), to determine a model of distribution fitting with the experimental frequency distribution of depths, and the Computer Based Bootstrap Method (CBBM), to generate simulated distributions equivalent to the experimental one. In comparison with conventionally established statistical methods that are restricted to the use of inferred distributions constrained by specific mathematical assumptions, the major advantage of the methodology presented in this paper is that both the GLD and the CBBM enable a statistical treatment of the experimental data without making any preconceived choice neither on the unknown theoretical parent underlying distribution of pit depth which characterizes the global corrosion phenomenon nor on the unknown associated theoretical extreme value distribution which characterizes the deepest pits.Considering an experimental distribution of depths of pits produced on an aluminium sample, estimations of maximum pit depth using a GLD model are compared to similar estimations based on usual Gumbel and Generalized Extreme Value (GEV) methods proposed in the corrosion engineering literature. The GLD approach is shown having smaller bias and dispersion in the estimation of the maximum pit depth than the Gumbel approach both for its realization and mean. This leads to comparing the GLD approach to the GEV one. The former is shown to be relevant and its advantages are discussed compared to previous methods.     

Effect of temper on the distribution of pits in AA7075 alloys

A comparative study of pitting severity in T6 and T73 tempers of AA7075 in 0.1 M NaCl is reported here. Pitting was more severe for T6 tempers compared to T73 tempers. This could be attributed to higher pit nucleation sites in the former. The statistical distributions for pit areas indicated nucleation saturation in T73. The extreme value distributions showed differences for the two tempers. These differences in pit distribution are explained on the basis of the role of constituent as well as strengthening particles as well as the role of grain boundary η precipitates.     

Corrosion behaviour of sintered NdFeB deposited with an aluminium coating

A protective, pure Al coating was deposited by direct current (DC) magnetron sputtering onto sintered NdFeB magnets. Separated, single phases of sintered NdFeB (the Nd-rich phase, the B-rich phase and the matrix phase) were prepared by arc melting for open circuit potential (OCP) tests. The corrosion process of the sintered NdFeB magnets coated with Al (Al/NdFeB) was studied experimentally. It was found that the corrosion process can be divided into three different stages. The Al coating cannot provide complete sacrificial protection for the sintered NdFeB magnets.     

The corrosion of two aluminium sacrificial anode alloys in SRB-containing sea mud

Corrosion of two sacrificial anodes in marine sediment with and without sulphate-reducing bacteria (SRB) was performed. Weight loss experiments indicated that the corrosion rate of Al–Zn–In–Sn was 2–3 times higher than that of Al–Zn–In–Mg–Ti in the SRB-containing sediment. Electrochemical analysis suggested that the corrosion rates of the two anodes were enhanced substantially by SRB. Surface analysis revealed the localised corrosion of the two sacrificial anodes in abiotic and biotic sediments. The concentration of Al³⁺ in the surface of the samples immersed with SRB was lower than that of the samples without SRB.     

Influence of the surface activation and local pitting susceptibility on the AC-electrograining of aluminium alloys

AC electrograining of aluminium is strongly influenced by the surface microstructure. The mechanical and electrochemical properties of the sub-surface present in aluminium alloys affect the electrochemical reactions that prevail during electrograining. Etching pre-treatment of aluminium removes intermetallics and rolled-in oxides; as a result, the attack on the aluminium substrate starts with the initial cycles of the electrograining process. Local electrochemical investigations show differences in corrosion and passivation properties between rolled-in oxides and clean surfaces. The interface between rolled oxides and aluminium matrix acts as a weak point for pit initiation.     

Electrochemical corrosion behaviour of microcrystalline aluminium in acidic solutions

The electrochemical corrosion behaviour of microcrystalline pure aluminium coating, fabricated by a magnetron sputtering technique, has been investigated in both 0.5 mol/l NaCl and 0.5 mol/l Na₂SO₄ acidic (pH = 2) aqueous solutions. The corrosion resistance of the microcrystalline Al coating has deteriorated more compared with that of the cast pure Al in Na₂SO₄ acidic solution. However, its oxide film has a higher pitting resistance in the NaCl acidic solution. Chloride ions play a big role in the formation of the oxide film on the microcrystalline Al coating. The higher pitting resistance was attributed to the more acidic isoelectric point which the oxide film achieved.     

Effect of trace elements on electrochemical properties and corrosion of aluminium alloy AA3102

The purpose of this work is to study the effect of heat treatment and chemical processing on the electrochemical behaviour of aluminium alloy AA3102. Aluminium alloy 3102 was electrochemically activated in chloride solution as a result of heat treatment for periods exceeding 10 min at temperatures higher than 400 °C. The electrochemical activation was determined by the presence of deep negative potential transients when exposed to an acidified chloride solution. Furthermore, the anodic current densities became large at a given potential relative to the as-extruded surface as a result of high temperature heat treatment. This activation phenomenon was attributed to enrichment of the surface by lead, which was present in the material as a trace element. Enrichment of lead at the metal-oxide interface was ascertained by GD-OES depth profiling. Chemical and structural changes occurring in the oxide as a result of heat treatment did not have a direct role in the activation process. It was also shown that enrichment of the surface by lead had a sacrificial effect in protecting the surface against pitting 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.     

Influence of 1,2-diaminoethane on the mechanism of aluminium corrosion in sulphuric acid solutions

The influence of 1,2-diaminoethane (DAE) on aluminium corrosion in H₂SO₄ solutions (pH 3) was investigated. In pure H₂SO₄, rapid uniform corrosion is followed by inhibition due to the formation of stable Al-sulphate binuclear bidentate metal bound surface complexes via a ligand exchange mechanism with two neighbouring sites. Metastable pitting is also observed. DAE acts as a strong corrosion inhibitor for both uniform and localised corrosion, due to the formation of Al-DAE monodentate hydrogen-bond surface complexes either by direct adsorption of the protonated molecule on Al-OH sites or via a ligand exchange mechanism with the proton of an site.     

Quantification of pitting in two tempers of 7075 aluminium alloy by non-destructive evaluation

An attempt was made to use the damage parameter, β obtained from non-linear ultrasonic assessment, to quantify pitting damage in 7075 aluminium alloy. β values were found to be different for the two tempers, T6 and T73. β reflected the pitting damage quite well in the initial stages of pitting, during which the non-linearity change in the lattice was mostly governed by the creation of free surfaces due to pitting. However, on prolonged pitting, the β values showed anomalous behaviour. The findings are explained by the operation of counteracting microstructural influences on lattice non-linearity.     

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.     

Temperature dependence of the pitting potential of high purity aluminium in chloride containing solutions

Slow scan anodic polarization experiments were conducted on high purity (99.99%) aluminium exposed to chloride containing solutions at temperatures ranging from 1 to 70 °C. The total anodic charge passed prior to stable pitting shifts towards higher values with increasing chloride concentration and there is a transition point at 30 °C above which a significantly greater amount of charge is involved. For all chloride concentrations, the pitting potential decreases with temperature according to a linear relationship, and also shows a transition at approximately 30 °C, with a much steeper decrease observed for the higher temperatures. Possible explanations for these two effects are discussed.