Galvanic coupling between copper and aluminium in a thin-layer cell

The Al/Cu coupling was investigated in a thin-layer cell formed by a large Cu electrode and an Al microelectrode embedded in an insulator placed above the Cu electrode. By using a scanning electrochemical microscope (SECM) the thickness of the thin layer was perfectly controlled with a precision in the micrometer range. A copper deposit on an electrochemical quartz crystal microbalance (EQCM) was also used as SECM substrate to quantify the copper dissolution rate. It was shown that such an experimental set-up allows to mimic the galvanic corrosion of intermetallic particles embedded in the aluminium matrix of the 2XXX series aluminium alloys. The combination of the SECM and the EQCM permitted the evaluation of the corrosion rate of copper at the corrosion potential of the 2024 Al alloy, whereas cyclic voltammetry performed on the SECM tip indicated the enrichment in Cu²⁺ ions in the thin electrolyte layer.     

Corrosion behaviour of aluminium in copper containing environment

Corrosion behaviour of pure aluminium galvanically connected to metallic copper or in the presence of Cu²⁺ ions was investigated by electrochemical measurements in Na₂SO₄ and Na₂SO₄ + NaCl test solutions. It has been found that in aerated Cl⁻ ion containing solutions pitting corrosion of aluminium emerged immediately, while in the absence of oxygen this process was less violent. Effect of passivating pre-treatment of aluminium surface on corrosion behaviour Cu-Al bimetallic system is also demonstrated.     

Pitting corrosion in cast 7XXX aluminium alloys and fibre reinforced MMCs

The corrosion behaviour of cast and heat-treated Al-6%Zn-1%Mg and Al-6%Zn-1%Mg-1%Ag alloys and metal matrix composites (MMCs) were investigated using dynamic polarisation techniques, followed by scanning electron microscopy (SEM) and secondary ion mass spectrometry (SIMS). The addition of silver and the incorporation of continuous Altex fibres into the alloys have a positive effect on the materials’ corrosion resistance. It was observed that due to the presence of second phase particles and microsegregation, pitting occurs preferentially at the grain boundary and fibre/matrix interface regions in the cast alloys and composites, respectively.     

Influence of impurities in aluminium on surface treatment

The origin of grain orientation dependent textures on a surface treated aluminium Al-0.2% Mg alloy has been probed by atomic force microscopy, transmission electron microscopy and elemental depth profiling by radio frequency glow discharge optical emission spectroscopy. Magnesium cations are observed to act as a tracer species, assisting definition of the residual alumina film thickness, developed by pretreatment. Copper impurities, enriching in the alloy immediately below the alumina film, act as a marker, assisting definition of the alloy/film interface. Conversely, the absence of iron and silicon in the depth profiles, present in the alloy as impurities at similar levels to copper, suggests their role in the development of the texture. Such elements are considered to be present in the alloy as fine segregates; their location at alloy ridges defines the positions of cathodic sites, with the adjacent matrix undergoing dissolution through the residual alumina film during pretreatment.     

Influence of surface pre-treatments on disturbed rolled-in subsurface layers of aluminium alloys

Rolling is known to alter the surface properties of aluminium alloys and to introduce disturbed subsurface layers. These layers are characterised by a refined grain structure, rolled-in oxide particles, a fine distribution of intermetallic particles, various voids and cracks.In this study, the effects of some surface pre-treatments, i.e., alkaline etching at various temperatures and chemical cleaning with Nabuclean and CrO₃/H₃PO₄, on these rolled-in layers are investigated by means of surface analytical techniques. The changes in composition and morphology of the (sub)surface are studied with scanning electron microscopy/energy dispersive X-ray analysis and backscattered electron imaging (SEM/EDX + BEI). The presence of incorporated oxide particles is evaluated by measuring the total reflectance. The (re-)distribution of alloying, impurity and trace elements upon these surface treatments is investigated with radiofrequency glow discharge optical emission spectrometry (rf-GDOES).     

Behaviour of copper during alkaline corrosion of Al–Cu alloys

Enrichment of copper beneath amorphous anodic films on relatively dilute, solid-solution Al–Cu alloys is necessary before copper can be oxidized and incorporated into the oxide layer. A similar enrichment arises during electropolishing, which also develops an amorphous oxide. In these cases, external polarization is applied, usually generating a relatively high oxidation rate. In contrast, enrichment behaviour at the corrosion potential has received less attention. The present study examines the corrosion of Al–Cu alloys, containing up to 6.7 at.% Cu, in 0.1 M sodium hydroxide solution at 293 K. Copper is again found to enrich in the alloy, similarly to behaviour with anodic polarization. However, following enrichment, discrete copper-rich particles appear to be generated in the corrosion product. These are suggested to be nanoparticles of copper, since the corrosion potentials of the alloys are low relative to that required for oxidation of copper. The corrosion rate increases with increase of both time and copper content of the alloy, probably associated with a greater cathodic activity due to an increasing number of nanoparticles. The corrosion proceeds with loss of aluminium species to the sodium hydroxide solution, but with retention of copper in the layer of hydrated alumina corrosion product.     

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).     

Behaviour of different bare and anodised aluminium alloys in the atmosphere

Exposure tests in natural atmospheres are an indispensable means for determining the behaviour and durability of metallic materials in the atmosphere. The corrosion behaviour of bare aluminium and anodised aluminium with three different coating thicknesses has been evaluated for two years' exposure in two natural atmospheres of very different corrosivities: one urban and the other marine. Several techniques have been used to evaluate changes in the specimens during exposure, but special attention is paid to the direct measurement of corrosion by gravimetry and its indirect estimation by the comparatively much more sensitive electrochemical impedance spectroscopy (EIS) technique. The results show that if no demands are placed on the conservation of its appearance, aluminium may be used without protection even in atmospheres of medium or high corrosivity. The anodising and sealing of aluminium alloys, above an ill-defined minimum thickness threshold, is an appropriate solution to prevent localised corrosion of aluminium and to conserve its appearance, even in aggressive atmospheres.     

Microstructure and phase composition of microarc oxidation surface layers formed on aluminium and its alloys 2214-T6 and 7050-T74

The influence of substrate on the microstructure and phase composition of surface layers synthesised by microarc oxidation (MAO) on aluminium and its alloys 2214-T6 and 7050-T74 is studied using scanning (SEM) and transmission electron microscopy (TEM) as well as cross-sectional X-ray diffraction. MAO layers are composed of three layers and are mainly made of gamma-Al₂O₃ and alpha-Al₂O₃ phases. The proportion of each phase depends on the substrate. The external porous layer is mainly composed of the gamma-Al₂O₃ phase. The internal dense layer can present two aspects according to the percentage of the alpha-Al₂O₃ phase. The so-called granular aspect indicates a high proportion of “dendrite” defect which results from discharge formation and implies a high percentage of the alpha-Al₂O₃ phase. The so-called columnar aspect indicates a high proportion of “small channels” associated with a very weak percentage in the alpha-Al₂O₃ phase. In the latter, it is believed that a Zn alloying element can inhibit the growth of alpha-Al₂O₃. During the MAO process, discharges likely occur in the vicinity of the MAO layer/substrate interface, probably in the spherical porosities that result from oxygen generated in the thin layer localised at the interface.     

Incorporation of transition metal ions and oxygen generation during anodizing of aluminium alloys

Enrichment of nickel at the alloy/film interface and incorporation of nickel species into the anodic film have been examined for a sputtering-deposited Al-1.2at.%Ni alloy in order to assist understanding of oxygen generation in barrier anodic alumina films. Anodizing of the alloy proceeds in two stages similarly to other dilute aluminium alloys, for example Al-Cr and Al-Cu alloys, where the Gibbs free energies per equivalent for formation of alloying element oxide exceeds the value for alumina. In the first stage, a nickel-free alumina film is formed, with nickel enriching in an alloy layer, 2 nm thick, immediately beneath the anodic oxide film. In the second stage, nickel atoms are oxidized together with aluminium, with oxygen generation forming gas bubbles within the anodic oxide film. This stage commences after accumulation of about 5.4 × 10¹⁵ nickel atoms cm⁻² in the enriched alloy layer. Oxygen generation also occurs when a thin layer of the alloy, containing about 2.0 × 10¹⁹ nickel atoms m⁻², on electropolished aluminium, is completely anodized, contrasting with thin Al-Cr and Al-Cu alloy layers on electropolished aluminium, for which oxygen generation is essentially absent. A mechanism of oxygen generation, based on electron impurity levels of amorphous alumina and local oxide compositions, is discussed in order to explain the observations.     

Corrosion inhibition of 7000 series aluminium alloys with cerium diphenyl phosphate

Cerium diphenyl phosphate (Ce(dpp)₃) has previously been shown to be a strong corrosion inhibitor for aluminium-copper magnesium alloy AA2024-T3 and AA7075 in chloride solutions. Surface characterisation including SEM and ToF-SIMS coupled with electrochemical impedance spectroscopy (EIS) measurements are used to propose a mechanism of corrosion inhibition which appears to involve the formation of a complex oxide film of aluminium and cerium also incorporating the organophosphate component. The formation of a thin complex film consisting of hydrolysis products of the Ce(dpp)₃ compound and aluminium oxide is proposed to lead to the observed inhibition. SEM analysis shows that some intermetallics favour the creation of thicker deposits predominantly containing cerium oxide compounds.     

Corrosion resistance of cerium‐based chemical conversion coatings on AA5083 aluminium alloy

In this paper the effect of several parameters, such as temperature, time of immersion, cerium ions and hydrogen peroxide concentration, pH of the conversion solution, on the composition and morphology of the conversion layer are investigated as well as on its corrosion resistance in chloride environments. The cerium‐based chemical conversion coatings ennobles the corrosion potential and inhibits both the cathodic and anodic reactions rate. Using a cerium (III) chloride solution a not homogeneous coating is obtained and agglomerates with a “dry‐mud” morphology of mixed cerium‐aluminium oxide are deposited above the cathodic intermetallic particles, while using a cerium (III) nitrate solution the coating is more uniform but thinner than that obtained with cerium (III) chloride. Solution temperature below 50°C and time of immersion of 10 minutes produces a coating with better corrosion resistance.     

Effect of aluminium solids and chlorine on cold water pitting of copper

Both aluminium solids and chlorine are often present in potable water systems, but their effect on copper corrosion and pitting is not well understood. Circumstantial evidence from one system with copper pitting problems suggested that high chlorine residuals and aluminium solids might be contributing factors. To test this hypothesis, a series of experiments were conducted to examine their effect on copper corrosion under stagnant and flow conditions. Although chlorine alone impacted copper corrosion, a synergistic reaction was discovered between chlorine and aluminium solids when exposed to copper. Evidence for this effect was seen in increased chlorine decay rates, increased non-uniform copper corrosion, and rising corrosion potentials during exposure. It is likely this reaction is involved in copper pit initiation.     

Heat treatments for electroless nickel–boron plating on aluminium alloys

Electroless nickel–boron baths reduced with sodium borohydride can be stabilized with various agents such as thallium nitrate or lead tungstate with no fundamental modification of deposition rates and stability. To improve the mechanical properties of electroless nickel–boron deposits, various heat treatments are applied. At low temperatures, no fundamental changes in the deposit structure are observed, only an improvement of adhesion on aluminium substrate. The values of the Knoop microhardness obtained on these heat-treated deposits are near 600 hk₁₀₀. At higher temperatures, structural changes take place and the nickel–boron deposits crystallize. The microhardness rises until 1050 hk₅₀ for heat treatments at 350 °C for 4 h. A diffusion layer between the electroless nickel deposit and the aluminium substrate appears at high heat treatment temperatures. The results of scratch tests show that the Ni–B deposits, with or without heat treatments, have good tribological properties under external solicitations. They are hard, wear and abrasion resistant, and also have good adhesion to the aluminium substrate.     

The influence of surface treatment on filiform corrosion resistance of painted aluminium alloy sheet

Filiform corrosion of AA 5005 H14 aluminium alloy sheet has been investigated. Painted and scribed panels, with different surface treatments, were inoculated in HCl and exposed in a constant humidity cabinet maintained at 40 °C and 75-85% RH for 1000 h. After exposure, the panels were examined by optical and electron microscopy. It is evident that filiform corrosion susceptibility is determined largely by the near-surface microstructure. Heavily deformed layers, comprising oxide-decorated fine grains and dispersoids on as-rolled and mechanically ground alloy surfaces, are readily susceptible to filiform corrosion. Removal of these deformed layers, by caustic etching and acid cleaning, results in a high filiform corrosion resistance. On such surfaces, underfilm corrosion progresses by localized corrosion of the substrate; with comparatively slowly growing filaments propagating by repeated blistering of the overlying lacquer.     

An electrochemical framework to explain the intergranular stress corrosion behavior in two Al-Cu-Mg-Ag alloys as a function of aging

A modified version of the Cu-depletion electrochemical framework was used to explain the metallurgical factor causal to intergranular stress corrosion cracking (IGSCC) susceptibility in two Al-Cu-Mg-Ag alloys (i.e., Al-5.0%Cu-0.8%Mg-0.5%Ag and Al-5.4%Cu-0.5%Mg-0.5%Ag). This framework was also used to explain the specific cases of IGSCC susceptibility in the under-aged condition and increased IGSCC resistance with over-aging. Susceptibility in the under-aged and T8 (peak-aged) conditions is consistent with the grain boundary Cu-depletion mechanism and high concentrations of Cu in solid solution in grain interiors. Improvement in resistance to IGSCC of the over-aged T8+ condition (i.e., T8 temper followed by an additional thermal exposure of 5000 h at 107.2 °C) can be explained by elimination of the differential Cu concentration adjacent to the grain boundary compared to that of the grain interior. The resultant leveling of Cu concentration leads to the suppression of a preferential dissolution path at the grain boundaries associated with IGSCC.     

Corrosion of aluminium in copper-aluminium couples under a marine environment: Influence of polyaniline deposited onto copper

In this study, we examined how aluminium corrosion in Al-Cu/PANI galvanic couples in a marine environment is influenced by deposition of polyaniline (PANI) on copper. Polarization curves and immersion assays in 0.1 M NaCl were performed. The morphologies of etched Al and corrosion products were observed by SEM, and the Al ions in solution were quantified by atomic absorption spectroscopy. A reduction in aluminium damage due to galvanic corrosion was observed as a result of decreased effective area for the oxygen reduction reaction on Cu/PANI electrode. Furthermore, an electrochemical reduction of PANI from leucoemeraldine to emeraldine base is proposed.     

Optimal modifying and refining processes for A356 aluminium alloys

M illions of alum inium alloy com ponents are produced using A356 alum inium alloys, which provide high fluidity, good 'castability'and m echanical properties. A356 alloys are widely used to fabricate structural castings for autom otive and other industrial applications. For α (Al) refining,A356 alum inium alloys usually apply Al-Tim aster alloys in the range 0.08-0.20% Ti, resulting in high consum ption of Al-Ti m aster alloys and higher production cost.M odification ofthe Al-Sieutectic …     

High temperature oxidation mechanism of dilute copper aluminium alloys

Dilute copper-aluminium alloys were oxidized in air from 700 to 1000 °C. Two distinctive behaviours were observed: alloys with at least 3 wt% aluminium showed excellent oxidation resistance in the whole temperature range. Alloys with 2 wt% or less aluminium exhibited good oxidation resistance up to 800 °C; but as the temperature was further increased, the oxidation rate of these alloys increased and became comparable to that of pure copper. A kinetic model was developed to explain the oxidation behaviour and indirectly determine the amount of dissolved oxygen in the alloys tested. It was found that the oxygen dissolved in alloys with up to 2 wt% Al exceeded its solubility limit in copper, whereas the dissolved oxygen in alloys with higher aluminium contents was below the solubility limit. This difference may account for the significantly different oxidation resistance.     

Combinatorial corrosion study of the passivation of aluminium copper alloys

An Al_96.1–Cu_3.9 to Al_51.4–Cu_48.6 material library was obtained by thermal co-deposition and characterized by EDX and XRD. The crystallographic data reveals the presence of Al₂Cu and pure aluminium depending on the film composition and following the stoichiometry. Utilizing a scanning droplet cell setup, the zero current potential for anodization, the oxide formation factor and the dielectric constant of the oxide formed are presented with high resolution along the composition gradient.While the dielectric constant of the oxide formed remains nearly unaffected by the increasing copper content of the base material along the composition gradient, the zero current potential shows well defined steps between 6.9 and 8.5 at.% as well as between 20.9 and 26.7 at.% copper indicating an increased thickness of the native oxide present on the film. Additionally, starting around 25 at.% copper, oxygen evolution gradually superimposes the oxide growth and in turn significantly reduces the current efficiency for anodization. The formation of the intermetallic phase Al₂Cu was linked to both phenomena as it promotes the growth of native oxides and current leakage by oxygen evolution.