Electropolishing of high-purity aluminium in perchloric acid and ethanol solutions

The electropolishing behaviour of high-purity aluminium with ultrasonic agitation was investigated in ethanol-perchloric acids by using anodic polarization measurement, electrochemical impedance spectroscopy (EIS), scanning electron microscope (SEM), and atomic force microscope (AFM). The results show that the electropolishing behaviour of the aluminium is under mass-transfer control and Al³⁺ is suggested as the governing species for the salt film mechanism during anodic dissolution in limiting current plateau.     

Corrosion inhibition of flaky aluminium powders prepared through sol–gel process

In order to prevent corrosion of aluminium pigment in water, coated flaky aluminium powder was prepared through the sol–gel process, in which tetraethoxysilane (TEOS) and tris(2-methoxyethoxy)vinylsilane (VTMOEO) were adopted as precursors. The influences of the dosage of precursors, ethylenediamine, water and ethanol, as well as the reaction temperature and reaction time on the corrosion inhibition efficiency were investigated. Under the optimum conditions, the corrosion inhibition efficiency reached 99.2% in alkaline media of pH 11. The analysis with SEM, FTIR, EDS and XPS showed that sol–gel coatings had successfully encapsulated on the surface of clear flaky aluminium powders.     

Influence of pre-treatment on the surface composition of Al-Zn alloys

The influences of pre-treatments on the composition of Al-Zn alloys, containing 0.6-1.9 at.%Zn, are investigated using scanning and transmission electron microscopies, glow discharge optical emission spectroscopy and ion beam analysis. Alkaline etching, anodic alkaline etching and electropolishing result in zinc enrichments, just beneath the oxide/hydroxide films on the alloy surfaces. The enriched alloy, about 4-5 nm thick, contains zinc in solid-solution with aluminium, up to about 18 at.%. The highest and lowest enrichments are produced by alkaline etching and electropolishing respectively. For a given pre-treatment, the enrichment increases with increase in zinc content of the bulk alloy.     

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.     

Diphenolic Schiff bases as corrosion inhibitors for aluminium in 0.1 M HCl: Potentiodynamic polarisation and EQCM investigations

The effects of novel synthesised two Schiff bases on the corrosion of aluminium in 0.1 M HCl were investigated using potentiodynamic polarisation and electrochemical quartz crystal microbalance measurements. Results show that inhibition efficiencies increase with increase in inhibitor concentration. This reveals that the inhibition occurs through adsorption of the inhibitor molecules on the metal surface. Adsorption of these inhibitors follows Temkin adsorption isotherm. The correlation between the inhibitor performances and their molecular structures has been investigated using quantum chemical parameters obtained by MNDO (modified neglect of diatomic overlap) semi-empirical method. Calculated quantum chemical parameters indicate that Schiff bases adsorbed on aluminium surface by chemical mechanism.     

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.     

Corrosion and electrochemical behavior of aluminium treated with high-temperature pulsed plasma in CsCl–NaCl–NaNO3 melt

Dense protective layers of aluminium corrosion products, whose composition depends on the oxidation temperature, are formed on the surface of aluminium treated with high-temperature pulsed plasma (HTPP) without visible remelting and then held in a chloride–nitrate melt in conditions of anodic polarization. Modification of aluminium treated with HTPP changes the properties of 20 μm layer under its surface and the oxide layer formed by such treatment has different morphology: it consists of smaller crystals and so has the other protective properties as compared with aluminium untreated by plasma.     

Corrosion resistance of lamellar aluminium pigments coated by SiO2 by sol–gel method

The aluminium pigments were coated with SiO₂ by sol–gel method to improve their stability. The effects of formulation factors, such as medium of reaction, adding sequence of catalyst and number of coating, were investigated. The stability of the coated aluminium pigments in acid was examined by measuring the hydrogen generation amount. It was found that the coating layer formation is due to the condensation of tetraethyl orthosilicate (TEOS) to form a dense 3D cross-linked layer on the surface of aluminium. The optimized sequence of adding catalysts would be hydrochloride first, then ammonia. Stability tests confirmed that the aluminium pigments have better corrosion resistance after coating with SiO₂.     

The application of ultramicrotomy to the electronoptical examination of surface films on aluminium

Ultramicrotomy has been used to produce thin sections of surface films on aluminium after different treatments and these have been examined by transmission electron microscopy. Films studied are those produced by electropolishing, outdoor exposure, a hydrothermal treatment, immersion in sodium hydroxide, a chemical conversion process, an a.c. treatment and cathodic polarization. Anodic films including porous and barrier-type films and the thick coating on a superplastic ZnAl alloy have been examined. It has been found that the application of ultramicrotomy enables observation of the thickness and morphology of both very thin and friable surface films on aluminium, and it is useful in the study of certain phenomena concerning thicker porous-type anodic films. Various novel features are visible that have not been observed previously, and it is apparent that ultramicrotomy may be used advantageously to examine surface films on aluminium.     

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.     

Effect of heat treatment on anodic activation of aluminium by trace element indium

The presence of trace elements in Group IIIA-VA is known to activate aluminium anodically in chloride environment. The purpose of this paper is to investigate the surface segregation of trace element In by heat treatment and resulting surface activation. Model binary AlIn alloys, containing 20 and 1000 ppm by weight of In, were characterized after heat treatment at various temperatures by use of glow discharge optical emission spectroscopy, electron microscopy and electrochemical polarization. Heat treatment for 1 h at 300 °C gave significant segregation of discrete In particles (thermal segregation), which activated the surface. Indium in solid solution with aluminium, obtained by 1 h heat treatment at 600 °C, also activated by surface segregation of In on alloy containing 1000 ppm In, resulting from the selective dissolution of the aluminium component during anodic oxidation (anodic segregation). The effect of anodic segregation was reduced by decreasing indium concentration in solid solution; it had negligible effect at the 20 ppm level. The segregated particles were thought to form a liquid phase alloy with aluminium during anodic polarization, which in turn, together with the chloride in the solution destabilized the oxide.     

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.     

Liquid metal embrittlement of aluminium by segregation of trace element gallium

The effect of small amounts of gallium on liquid metal embrittlement of model binary AlGa alloys containing 50–1000 ppm² Ga is studied. Ga segregation did not occur by annealing in the temperature range 300–600 °C because of the high solid solution solubility of Ga in aluminium. Alkaline etching caused significant enrichment of Ga at the surface by dealloying. Diffusion of Ga from the surface into the grain boundaries caused liquid metal embrittlement of samples containing at least 250 ppm Ga. Segregated Ga dissolved back into aluminium by annealing for 1 h at 600 °C after etching, eliminating the grain boundary embrittlement.     

Surfactant inhibition of aluminium pigments for waterborne printing inks

Micrometre-sized aluminium particles are used as pigments in silver inks and for environmental reasons it is desirable to develop water-based formulations of such pigments. In waterborne coatings, however, aluminium is prone to react with water, with subsequent hydrogen gas evolution and loss of the silvery lustre. The protection against water of aluminium pigments by adsorption of either a nonionic or an anionic surfactant has been evaluated. Phosphate esters with different lengths of the hydrocarbon tail have been synthesised and tested, and were found to provide very effective protection of the pigments. Sodium dodecyl sulphate (SDS), on the other hand, was completely ineffective as inhibitor, even though the adsorption isotherm was about the same as for the structurally similar sodium dodecyl phosphate (SDP). This difference may be explained by formation of different types of complexes with the aluminium oxide surface. Outer-sphere complexes are suggested for SDS, whilst SDP can form more stable inner-sphere complexes. Tests with the non-surface active methyl phosphate as inhibiting agent gave insufficient protection, indicating that surface activity is crucial for the inhibition, and that the use of the phosphates as such is not enough to give proper protection. The work shows that amphiphilic compounds having phosphate as anchoring group are efficient in providing water resistance to aluminium pigments.     

Corrosion behaviour of magnesium/aluminium alloys in 3.5 wt.% NaCl

Corrosion behaviour of commercial magnesium/aluminium alloys (AZ31, AZ80 and AZ91D) was investigated by electrochemical and gravimetric tests in 3.5 wt.% NaCl at 25 °C. Corrosion products were analysed by scanning electron microscopy, energy dispersive X-ray analysis and low-angle X-ray diffraction. Corrosion damage was mainly caused by formation of a Mg(OH)₂ corrosion layer. AZ80 and AZ91D alloys revealed the highest corrosion resistance. The relatively fine β-phase (Mg₁₇Al₁₂) network and the aluminium enrichment produced on the corroded surface were the key factors limiting progression of the corrosion attack. Preferential attack was located at the matrix/β-phase and matrix/MnAl intermetallic compounds interfaces.     

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.     

Quantitative topography measurements of rolled aluminium surfaces by atomic force microscopy and optical methods

We have compared the results of quantitative topography measurements on typical industrial, rolled or etched aluminium surfaces, using three different methods that can measure surface features in the 10-μm to sub-micrometre range. The methods used, atomic force microscopy (AFM), white-light interferometry, and confocal laser scanning microscopy (LSM), utilize very different mechanisms of image formation. We find good agreement between data measured by AFM and by white-light interferometry. The two techniques complement each other. AFM is not limited to reflecting samples, it has a better resolution than interferometry, and it can measure steeper slopes. White-light interferometry is faster and allows larger areas to be analysed, and data from neighbouring areas can be spliced more easily. When used on strongly reflecting, rolled or etched aluminium surfaces, LSM yields results that deviate strongly from those of the other two methods and from the true sample surface topography.     

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.     

Electrochemical behaviour of microcrystalline aluminium in neutral fluoride containing solutions

The electrochemical behaviour of microcrystalline pure aluminium coating (mc-Al), fabricated by a magnetron sputtering technique, has been investigated in NaF as well as NaF + NaCl aqueous solutions. Results indicate that the anodic polarization characteristic changes with NaF concentration. F⁻ anions promote the formation of a passive film, whose semiconducting properties were investigated. When the F⁻ concentration is high ([F⁻] ? 0.03 mol/L) the passive film is mainly composed of aluminium fluoride, which is an n-type semiconductor on mc-Al and a p-type semiconductor on polycrystalline Al (pc-Al). In NaF + NaCl aqueous solutions, Cl⁻ and F⁻ ions compete in affecting the type of semiconducting passive films formed on mc-Al.     

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.