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.     

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.     

The effect of atmospheric corona treatment on AA1050 aluminium

The effect of atmospheric corona discharge on AA1050 aluminium surface was investigated using electrochemical polarization, SEM-EDX, FIB-SEM, and XPS. The corona treatment was performed with varying time (1, 5, and 15 min) in atmospheric air. A 200 nm oxide layer was generated on AA1050 after the 15 min air corona treatment. A significant reduction in anodic and cathodic reactivities was observed starting from 1 min exposure, which further decreased with prolonged exposure (15 min) and after delayed testing (after 30 days). The reduction in surface reactivity is due to the formation of thicker and denser oxide film.     

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.     

Modelling the anodizing behaviour of aluminium alloys in sulphuric acid through alloy analogues

Anodic film morphologies on aluminium aerospace alloys are strongly influenced by alloying elements. The present study uses model alloys to interpret the early stages of anodizing of AA2024-T3 and AA7075-T6 aluminium alloys in 0.4 M sulphuric acid electrolyte. Further, coupled model alloys, representative of matrix and second phase regions, are employed as alloy analogues. The findings enable assignment of transient anodic currents during potentiodynamic polarization of the commercial alloys to oxidation of Al₂CuMg phase at 0 V SCE and of Al₂Cu, Al₇Cu₂Fe and Al–Cu–Fe phases at 5–6 V SCE. The phases that oxidize at the latter potential also cause voltage arrests during galvanostatic anodizing.     

Current oscillations during the anodic dissolution of copper in trifluoroacetic acid

A phenomenon of current oscillators was characterized crosswise active-passive potential region during the electrodissolution of copper electrode in trifluoroacetic acid (TFA). The current density-potential curves show two transition points. A potential region of current oscillations was found as a part of limiting current region. The Cu|TFA electrochemical oscillator was found to displaying rich dynamical response on varying the temperature and the applied potential. The Cu|TFA system display current oscillation behaviour from the mono-periodic to the mixed-mode (relaxation type). Changes of the electrode surface structure and morphology were investigated by X-ray diffraction spectroscopy, atomic forced microscopy and optical microscopy.     

Surface oxide formation during corona discharge treatment of AA 1050 aluminium surfaces

Atmospheric plasmas have traditionally been used as a non-chemical etching process for polymers, but the characteristics of these plasmas could very well be exploited for metals for purposes more than surface cleaning that is presently employed. This paper focuses on how the corona discharge process modifies aluminium AA 1050 surface, the oxide growth and resulting corrosion properties. The corona treatment is carried out in atmospheric air. Treated surfaces are characterized using XPS, SEM/EDS, and FIB-FESEM and results suggest that an oxide layer is grown, consisting of mixture of oxide and hydroxide. The thickness of the oxide layer extends to 150–300 nm after prolonged treatment. Potentiodynamic polarization experiments show that the corona treatment reduces anodic reactivity of the surface significantly and a moderate reduction of the cathodic reactivity.     

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.     

Effect of the aluminium content of AlxCrFe1.5MnNi0.5 high-entropy alloys on the corrosion behaviour in aqueous environments

High-entropy alloys (HEAs) are a newly developed family of multi-component alloys. The potentiodynamic polarization and electrochemical impedance spectroscopy of the Al_xCrFe_1.5MnNi_0.5 alloys, obtained in H₂SO₄ and NaCl solutions, clearly revealed that the corrosion resistance increases as the concentration of aluminium decreases. The Al_xCrFe_1.5MnNi_0.5 alloys exhibited a wide passive region, which extended >1000 mV in acidic environments. The Nyquist plots of the Al-containing alloys had two capacitive loops, which represented the electrical double layer and the adsorptive layer. SEM micrographs revealed that the general and pitting corrosion susceptibility of the HEAs increased as the amount of aluminium in the alloy increased.     

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.     

Dielectric breakdown and healing of anodic oxide films on aluminium under single pulse anodizing

Single pulse anodizing of aluminium micro-electrode has been employed to study the behaviour of dielectric breakdown and subsequent oxide formation on aluminium in alkaline silicate and pentaborate electrolytes. Current transients during applying pulse voltage have been measured, and surface has been observed by scanning electron microscopy. Two types of current transients are observed, depending on the electrolyte and applied voltage. There is a good correlation between the current transient behaviour and the shape of discharge channels. In alkaline silicate electrolyte, circular open pores are healed by increasing the pulse width, but such healing is not obvious in pentaborate electrolyte.     

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.     

Numerical modelling of the galvanic coupling in aluminium alloys: A discussion on the application of local probe techniques

A discussion is proposed on the determination of the input values and the experimental validation of finite element modelling of the galvanic coupling in aluminium alloys by local probe techniques such as the Scanning Vibrating Electrode Technique (SVET) and the microcapillary electrochemical cell (microcell). Polarization curves obtained by the microcell were introduced as input conditions in the model based on Laplace or Nernst-Planck equation. SVET measurements were performed to determine the coupling current distribution on an Al/Al4%Cu bimetallic system. Agreement was found between simulated and experimental current distributions depending on the input conditions and the solved equation.     

Behaviour of a fast migrating cation species in porous anodic alumina

The behaviour of Nd³⁺ ions is examined in porous anodic alumina films formed at 5 mA cm⁻² in 0.4 M phosphoric acid at 293 K on aluminium substrates that contain a buried 5 nm-thick tracer band of Al-Nd alloy. The Nd³⁺ ions migrate outward in the barrier region about twice as fast as Al³⁺ ions. The neodymium was located in the anodic film by transmission electron microscopy and scanning electron microscopy, and quantified by Rutherford backscattering spectroscopy. The Nd³⁺ ions migrated to the cell walls and to pore base, depending upon their location in the substrate relative to the alumina cells and pores. Nd³⁺ ions that reached the pore base were lost to the electrolyte. The outward transport of the Nd³⁺ ions was greatest beneath the pores and least at the cell boundaries, resulting in transformation of the planar tracer layer of the substrate to a roughly hemispherical shape in the film. The behaviour contrasts with that of a tracer band of slowly migrating W⁶⁺ ions, which reveals an approximately inverse distribution, while W⁶⁺ ions are retained within the film.     

Formation of barrier-type anodic films on sputtering-deposited Al-Ti alloys

The formation of amorphous anodic films at constant current is investigated for sputtering-deposited Al-Ti alloys containing from 3-30 at.% Ti. The films were grown at high efficiency in a borate electrolyte and comprised a main region containing units of Al₂O₃ and TiO₂, with a thin surface region enriched in titanium species. The formation ratios of the films increased with increase of titanium content of the alloys. The presence of the outer region is explained by the faster migration of Ti⁴⁺ ions relative to that of Al³⁺ ions through the films.     

Electrochemical aspects of exfoliation corrosion of aluminium alloys: The effects of heat treatment

Electrochemical approaches are used to investigate the exfoliation corrosion (EFC) of a 7XXX series aluminium alloy that has undergone different tempering treatments. EFC was produced under an artificial crevice at open circuit potential in neutral chloride solutions, and is found to be associated to current and potential transients. EFC was also produced under galvanostatic control conditions. Observations made through Scanning Electron Microscopy (SEM) suggest that these transients result from the progression of inter-granular cracks. Last, over-ageing heat treatments that are known to decrease both metal hardness and EFC sensitivity were found to decrease the number of transients.     

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.     

Electrochemical response of AlNiLa amorphous and devitrified alloys

The electrochemical response of Al_94−xNi₆La_x alloys (x = 4, 5, 6, 7) after different stages of devitrification was studied in 0.05 M Na₂SO₄ as well as in different concentrations [0.001 M, 0.01 M and 0.1 M] NaCl solutions. Complementary crystallization studies were carried out to elucidate the composition dependent phase evolution in these alloys. It was observed that the primary crystallization did not cause any deterioration in the corrosion resistance of the alloys as compared to the amorphous alloys. In the case of Al₈₇Ni₆La₇, there was actually an improvement in the passivating ability in benign media. The various primary crystalline phases in the different alloys investigated did not cause different electrochemical responses. However, the onset of secondary crystallization caused a reduction in the corrosion resistance in the NaCl media through a loss in passivating ability of all the alloys. This is due to increased galvanic activity as well as the loss of the amorphous phase.     

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⁻.     

Inhibition by tetradecylpyridinium bromide of the corrosion of aluminium in hydrochloric acid solution

The inhibition effect of tetradecylpyridinium bromide (TDPB) on the corrosion of aluminium in 1.0 M HCl solution was studied by weight loss, potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS) methods. The results show that TDPB is a very good inhibitor at little concentrations, and the adsorption of TDPB on aluminium surface obeys Langmuir adsorption isotherm. Polarization curves reveal that TDPB behaves as a cathodic inhibitor. EIS spectra consist of large capacitive loop at high frequencies followed by a large inductive one at low frequency values, and confirm the inhibitive ability.