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.     

The adhesion properties and corrosion performance of differently pretreated epoxy coatings on an aluminium alloy

The influence of various blends of hexafluorozirconic-acid (Zr), polyacrylic-acid (PAA) and polyacrylamide (PAM) pretreatment on the performance of an epoxy coated aluminium substrate was investigated and compared to that of a so-called chromate/phosphate conversion coating (CPCC).Adhesive-strength of epoxy coated substrates was evaluated using pull-off and tape tests. Salt spray, humidity chambers and EIS were employed to characterize corrosion performance of coated substrates with different initial surface pretreatments. Among the Zr-based formulations, PAA/Zr and PAA/PAM/Zr showed the best adhesion strength, while the later revealed a good corrosion performance as well. However, CPCC pretreated sample was still superior in these aspects.     

Preparation and characterisation of aluminium pigments coated with silica for corrosion protection

Aluminium pigments with a layer of silica were prepared by a sol–gel method using tetraethoxysilane as precursor and ethylenediamine as catalyst. Under the optimum conditions, the corrosion protection factor can reach 99.3% and average grain almost remains the same size after coating, indicating that the coated aluminium pigments have excellent chemical stability and good dispersibility. FTIR and EDS analyses demonstrate that a layer of silica coating has been formed on the flaky aluminium particle. SEM, AFM and BET analyses show that a smooth and dense silica coating layer has been formed.     

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.     

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.     

Effects of pre-treatment on the growth rate and morphology of hard anodic films on aluminium (EN AW-6082)

For qualitative statements concerning influences of the substrate's surface on thickness and morphology of the films different surface states were prepared. Aluminium alloys (6000 series alloy) were applied as substrate for the hard anodization. The characterization (thickness, surface morphology) of the alumina films implies significant correlations between surface states of the substrate and film thickness. The results of the film thickness were confirmed with two investigation methods independently. Using Atomic Force Microscopy (AFM) the surface morphologies of both as-received and polished surface states were shown. The obtained roughness values correspond to the values by the conventional roughness measuring station.The comparison between the bare and the subsequently anodized surface morphologies implies an increasing film thickness growth rate with a decreasing roughness of the substrate. All experimental parameters for the hard anodizing process were maintained. Smooth surfaces of the substrate result in less rough anodized films. The effects of pre-treatment on the growth rate and morphology of hard anodized aluminium oxide films on AlSi1MgMn-alloy were summarized in a “hard anodization map”.     

Contradictory effect of chromate inhibitor on corrosive wear of aluminium alloy

The corrosive wear of D16T aluminium alloy in artificial acid rain was studied. A special tribometer with the linear reciprocating ball-on-flat geometry was used. The setup allows to measure simultaneously an open circuit potential, to carry out potentiostatic and potentiodynamic polarization studies of the alloy corrosion and to record the friction coefficient. It was established that the addition of strontium chromate inhibitor to the working environment decreases an electrochemical corrosion of the aluminium alloy under wear conditions, but in general accelerates its destruction due to insufficient wear resistance of a formed surface film.     

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.     

The role of silicon in the corrosion of AA6061 aluminium alloy laser weldments

The galvanic corrosion temporal increase observed on examination of the weld fusion zone (WFZ) of AA6061 laser weldments in 3.5 wt.% NaCl solution cannot be attributed to electron tunnelling as the surface oxide layer is too thick, or the presence of Cl⁻ within the surface layer as this element was not found to be present. Aluminium alloy and WFZ galvanic and surface analyses indicate that the cathodic WFZ corrosion characteristics are due to increases in silicate concentrations in the surface oxide layer, leading to increased ionic and/or p-type semi-conductor conductivity, intermetallic concentrations and surface area.     

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.     

The origin of weld seam defects related to metal flow in the hot extrusion of aluminium alloys EN AW-6060 and EN AW-6082

Longitudinal weld seams are an intrinsic feature in hollow extrusions produced with porthole dies. As these joins occur along the entire extruded length, it is desirable that these weld seams have a minimal impact on the structural integrity of the extrudate. In particular, defects associated with weld seam formation should be avoided. In this research, the occurrence of defects related to material flow inside the extrusion tooling is studied. In lab-scale experiments, EN AW-6060 and EN AW-6082 aluminium alloy billets are formed into strips by means of the direct hot extrusion process. By utilising model dies with an internal obstruction similar to the supports present in porthole dies, a strip with a central longitudinal weld seam is formed. The effects of different geometries of the weld-chamber and the processing conditions on the quality of the weld seam are investigated. Characterisation is performed through mechanical testing, focusing on the ability of the weld seam area to accommodate plastic deformation, and microstructural analysis provides insight into the defects related to unsound metal flow. Through computer simulations, conditions related to weld seam formation are modelled and correlated with the experimental results. The experimental results demonstrate that metal flow controlled by the die geometry causes defects leading to inferior mechanical performance of the extrudate. It is further argued that current weld seam formation criteria utilised in finite element modelling need enhancement to incorporate these flow related defects.     

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.     

Characterization of the plasma electrolytic oxidation of aluminium in sodium tungstate

Morphology, composition and microhardness of oxide coatings formed during DC plasma electrolytic oxidation (PEO) of aluminium in sodium tungstate were investigated. Oxide coatings were characterized by optical emission spectroscopy, AFM, SEM-EDS and XRD. Oxide coatings morphology is strongly dependent on process duration, while microhardness decreases with extended PEO time. The microdischarges characteristics were studied as well and it is shown that size of microdischarges becomes larger, while the surface density of microdischarge sites becomes lower, with increasing PEO time. Optical emission spectrum of microdischarges has several intensive band peaks caused by electronic transition in Al, W, Na, O, H atoms.     

Formation and characterisation of a chromate conversion coating on AA6060 aluminium

AA6060-T6, an AlMg0.5Si0.4 model alloy and α-Al(Fe,Mn)Si phase electrodes have been subjected to chromate treatment in a commercial chromate-fluoride based solution. The coated surfaces were subsequently examined by use of field emission SEM, TEM, AES and electrochemical measurements in 0.1 M NaCl solution in order to study the effect of substrate microstructure on coating formation and properties. Non-uniform growth of the chromate conversion coating (CCC) on AA6060-T6 resulted in a porous morphology, with cracks extending down to the base metal. Poor coverage was particularly observed at the grain boundaries. The thickness of the CCC after completed treatment was about 150-200 nm, while significantly thinner films were formed on the α-Al(Fe,Mn)Si particles. AlMg0.5Si0.4 in the artificially aged (T6) condition exhibited a coating morphology similar to AA6060-T6, while CCC formation on homogenised AlMg0.5Si0.4 was characterised by growth of localised oxide particles and filaments, resulting in poor coverage. These observations indicated that precipitation of Mg₂Si particles due to heat treatment promoted nucleation of the CCC. Chromate treatment caused a significant reduction of cathodic activity on AA6060 during subsequent polarisation in chloride solution. This was attributed to rapid formation of a thin chromium oxide film on the α-Al(Fe,Mn)Si particles during the chromate treatment, resulting in significant cathodic passivation of the phase. Inhibition of the oxygen reduction reaction at cathodic intermetallic particles is suggested as an important factor contributing to the high performance of chromate pre-treatments on aluminium.     

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.     

Pitting corrosion of rheocast A356 aluminium alloy in 3.5 wt.% NaCl solution

In this study, the microstructure and corrosion behaviour of rheocast and gravity-cast A356 aluminium alloys were examined and compared. Scanning Kelvin probe force microscopy (SKPFM) results proved that large potential differences between iron-containing intermetallics and the α-Al matrix were responsible for the initiation of the attack at the intermetallics/α-Al interfaces. For longer immersion times, corrosion attack proceeded through the eutectic areas. Semisolid processing refined the eutectic silicon and iron-intermetallics and reduced the potential difference between secondary phases and the matrix. This resulted in improved pitting corrosion resistance of the rheocast A356 aluminium alloy.     

Corrosion evaluation of microarc oxidation coatings formed on 2024 aluminium alloy

Dense alumina ceramic coatings of 7 μm thickness were fabricated on 2024 aluminium alloy by microarc oxidation (MAO). The corrosion behaviour of the MAO coated alloys was evaluated using potentiodynamic polarisation and EIS measurements. The results show that the corrosion process of the coated alloy can be divided into three stages: (1) the initial stage (the first 2-6 h of immersion): penetration of corrosion medium into the aluminium alloy was inhibited by coating; (2) the second stage (after 24 h of immersion), corrosion medium penetrated to attack the interface between the substrate and the coating; (3) the final stage (after about 96 h): corrosion process was controlled by the diffusion of corrosion products.     

Electrochemical behaviour of aluminium/steel rivet joints

The galvanic corrosion behaviour of a rivet joint of two sheets of the aluminium alloys EN AW-6014-T4 and EN AW-6082-T5 joined by an electrogalvanized steel blind rivet was investigated. The potentiodynamic polarization curves in a 5 wt.% NaCl solution show a potential reversion of the anodic and cathodic regions of the rivet joint. The surface potential was investigated with a capillary electrode before and after corrosion. From the measurements by the capillary electrode and SEM-observations an improved resistance against galvanic corrosion is expected after the dissolution of the zinc layer of the blind rivet.     

Electrochemical etching of AA5083 aluminium alloy in trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)amide ionic liquid

Trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)amide ([P_6,6,6,14][NTf₂]) ionic liquid is shown to react with AA5083 aluminium alloy under a two-step anodic polarisation, leading to partial passivation of the surface. Surface characterisation established that an electrochemical etching process had occurred, comparable to acid etching of aluminium. Energy dispersive X-ray spectroscopy (EDXS) and X-ray photoelectron spectroscopy (XPS) results indicated that magnesium de-alloyed from Mg₂Si intermetallic particles and metal fluorides were deposited onto the remaining Mg₂Si sites, leading to a decrease in the anodic corrosion kinetics (to one third of that of the control) as well as a 100 mV vs. SCE increase in the corrosion and pitting potentials.