Effect of sulfuric acid on pit propagation behaviour of aluminium under AC etch process

Pit propagation on high purity aluminium electrode in 2 M HCl solutions with and without H₂SO₄ under an alternating current (AC) has been examined. Pit development and potential transients were dependent on the H₂SO₄ concentration. In the sulfate-free etchant, most pits developed from the pretreated surface, with little tendency to form clusters of pits. With increasing H₂SO₄ concentration the size of the pit clusters increased. There is an optimal H₂SO₄ concentration, which is 0.01 M H₂SO₄ in this study, to form a deep etched layer of uniform thickness with high surface area. At H₂SO₄ concentrations higher than 0.01 M, the pit propagation proceeded on limited foil surface sites and deep etched regions were formed locally, since sulfate ions assisted passivation and reduced the number of pit nucleation sites on foil surface. Analysis of potential transients during the anodic half-cycle supports the hypothesis that sulfate ions retarded the pit nucleation.     

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.     

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 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.     

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.     

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.     

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.     

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.     

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.     

Hydrodynamic measurement of a single corrosion pit

The hydrodynamics of gas evolution plays an important role in the pitting corrosion of metals. A new technique for the measurement of the local hydrodynamics caused by corrosion processes, using the atomic force microscope, has been presented in this work. The hydrodynamics of hydrogen evolution on Al surface due to pitting corrosion was studied. The characteristic features of the hydrodynamics are discussed. To the best of our knowledge this is the first local measurement of pitting corrosion hydrodynamics.     

Effect of small amounts of alloyed tin on the electrochemical behaviour of aluminium in sodium chloride solution

Binary model AlSn alloys containing 30–1000 ppm (by weight) Sn were investigated by electrochemical polarization in 5 wt% chloride solution and subsequent characterization of corrosion morphology. In the homogenized and rolled condition, tin concentration only slightly affected electrochemical behaviour up to 500 ppm, and the pitting potentials were all about −0.8 V_SCE. However, alloy containing 1000 ppm Sn was significantly activated by lowering of the passivity-breakdown potential to −1.38 V_SCE. Annealing at 300 °C caused significant segregation of Sn to the metal surface, and all specimens, independent of bulk Sn concentration, became nearly similarly active with breakdown potentials around −1.2 V_SCE. Corrosion on 300 °C-annealed specimens was uniformly distributed by polarization below the bulk pitting potential of −0.76 V_SCE. Moreover, the activation effect was temporary, and corrosion was significantly reduced as the segregated Sn was etched away from the surface. Thick oxide, formed during water quenching on high Sn concentration samples, containing 500 and 1000 ppm Sn, introduced partial passivation during polarization test. Annealing at 600 °C caused increasing activation with increasing Sn concentration, caused by Sn enrichment at the metal surface by dealloying of aluminium during anodic polarization in chloride solution. Corrosion was localized in the form of grain boundary corrosion for alloyed Sn concentration less than and equal to 500 ppm and pitting following the triple grain boundaries for 1000 ppm.     

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.     

Relations between sample preparation and SKPFM Volta potential maps on an EN AW-6005 aluminium alloy

Quantitative measurements of the chemical composition and the local Volta potential contrast on metal surfaces can be performed with sub-micrometer resolution using a combination of scanning electron microscopy (SEM) and scanning kelvin probe force microscopy (SKPFM). Sample preparation techniques based on metal removal by mechanical and electrochemical polishing, OPS and ion-sputtering, may distort the local chemical composition or microstructure on the surface. Surfaces with insignificant mechanical and chemical distortions can be produced by ultramicrotomy. Ultramicrotomy gives quantitatively reliable SEM and SKPFM results when applied on extruded samples of an EN AW-6005 aluminium alloy.     

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.     

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.     

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.     

Corrosion inhibition by anionic surfactants of AA2198 Li-containing aluminium alloy in chloride solutions

This paper evaluates the inhibiting action of some anionic surfactants towards AA2198 corrosion in NaCl solutions; the effect of surfactant concentration in relation to chloride amount was determined.On separate electrodes, polarization curves were recorded after 1, 24 and 168 h immersion in the aggressive media, while EIS technique continuously monitored the alloy corrosion process.In general, these substances stifled both the cathodic and anodic processes and noticeably shifted the pitting potential (breakdown potential, E_BR) in the positive direction. The most efficient compounds were N-lauroylsarcosine sodium salt and sodium dodecyl-benzenesulfonate, able to withstand the effects of 0.1 M Cl⁻.     

Influence of reinforcement proportion and matrix composition on pitting corrosion behaviour of cast aluminium matrix composites (A3xx.x/SiCp)

The influence of silicon carbide (SiCp) proportion and matrix composition on four aluminium metal matrix composites (A360/SiC/10p, A360/SiC/20p, A380/SiC/10p, A380/SiC/20p) immersed in 1-3.5 wt% NaCl at 22 °C was investigated by potentiodynamic polarization. The kinetics of the corrosion process was studied on the basis of gravimetric measurements. The nature of corrosion products was analysed by scanning electron microscopy (SEM) and low angle X-ray diffraction (XRD). The corrosion damage in Al/SiCp composites was caused by pitting attack and by nucleation and growth of Al₂O₃ · 3H₂O on the material surface. The main attack nucleation sites were the interface region between the matrix and the reinforcement particles. The corrosion process was influenced more by the concentration of alloy elements in the matrix than by the proportion of SiCp reinforcement and saline concentration.     

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.     

In situ AFM detection of pit onset location on a 304L stainless steel

A set-up combining an AFM and an electrochemical cell has been used to study in situ the local corrosion of a 304L stainless steel in an aqueous chloride-containing solution. The focus was made on the sites where pits were initiated under controlled potential in order to establish whether or not the pits were randomly distributed at the nanoscale. Grain boundaries and surface stoichiometric inhomogeneities appeared to concentrate pit onsets significantly. The influence of the mechanical history of the material, especially soft surface strain hardening, on the location of the first pits has been shown. The study revealed that 70% of the pits initiated at strain hardened areas resulting from mechanical polishing. A plausible model has been suggested to explain such a behaviour.