Effects of inorganic additions on the performance of manganese-based conversion treatments

The electrochemical behaviour of permanganate-based no-rinse conversion coatings on AA3003-H14 aluminium alloy shows that they have promise as an alternative to toxic chromate-based coatings. A selection of inorganic additions has been made here to a simple 0.1 M KMnO₄ formulation investigated previously. The performance of the different coatings has been evaluated from potential-time and polarisation measurements in 0.5 wt % (0.085 M) NaCl solution for periods up to 3 days. The addition of fluoride ions produced no benefit, whereas Al(NO₃)₃ shows an improvement when added in small amounts. Tests with the individual ions reveal that it is Al³⁺ cations, rather than anions, which produce the greatest benefit.     

Effect of iron-containing intermetallic particles on the corrosion behaviour of aluminium

The effect of heat treatment on the corrosion behaviour of binary Al-Fe alloys containing iron at levels between 0.04 and 0.42 wt.% was investigated by electrochemical measurements in both acidic and alkaline chloride solutions. Comparing solution heat-treated and quenched materials with samples that had been subsequently annealed to promote precipitation of Al₃Fe intermetallic particles, it was found that annealing increases both the cathodic and anodic reactivity. The increased cathodic reactivity is believed to be directly related to the increased available surface area of the iron-containing intermetallic particles acting as preferential sites for oxygen reduction and hydrogen evolution. These particles also act as pit initiation sites. Heat treatment also causes depletion in the solute content of the matrix, increasing its anodic reactivity. When breakdown occurs, crystallographic pits are formed with {1 0 0} facets, and are observed to contain numerous intermetallic particles. Fine facetted filaments also radiate out from the periphery of pits. The results demonstrate that the corrosion of aluminium is thus influenced by the presence of low levels of iron, which is one of the main impurities, and its electrochemical behaviour can be controlled by heat treatment.     

Influence of electron beam liquid phase surface treatments on the corrosion resistance of AZ91D using different additive deposition techniques

Electron beam alloying (EBA) and electron beam cladding (EBC) were applied on AZ91D using Al-based additives. For EBA, additives were pre-deposited by atmospheric plasma spraying (APS) and cold gas spraying (CGS). In the case of EBC, a wire was used for in situ additive deposition. Polarisation test were carried out to investigate the corrosion behaviour of layers with Mg-rich (EBA) and Al-rich (EBC) layer matrices depending on the element contents of Mg, Al, and Si. In 0.001 M NaCl solution, the corrosion potential is significantly improved compared with the untreated AZ91D and corrosion current densities of the AlSi12 reference material are approached.     

Effect of rapid solidification on the microstructure and corrosion behaviour of Al-Zn-Mg based material

The corrosion behaviour of Al-5Zn-3Mg-0.6Cu-0.8Zr-0.25Cr-0.15Ni-0.15Ti alloys, produced by traditional and powder technologies, with similar thermo-mechanical treatments, in 3% sodium chloride solution, has been examined by electrochemical methods, scanning electron microscopy, transmission electron microscopy and X-ray microanalysis. The alloys reveal similar precipitation but of different shape, size and distribution; further, both alloys experience localized corrosion. Copper-rich precipitates initiate the dissolution of surrounding particles, enriched in Zn and Mg. As a result, the surface is enriched with other alloying elements after a full polarisation run. Cast material has lower corrosion properties because of the higher heterogeneity of the structure. The structure heterogeneity of the cast material involves a more non-uniform distribution of the precipitates, larger Zn- and Mg-rich particles, and depletion of the matrix and areas around the precipitates by alloying elements compared with the powder material.     

Effect of Mn/Mo incorporated oxide layer on the corrosion behavior of AA 2024 alloy

The oxide layer formed over AA 2024 using 10 wt.% H₂SO₄ (plain oxide, PO) was modified by Mn/Mo oxyanions (permanganate/molybdate modified oxide, PMMO) as an alternative to Cr(VI) ions to enhance the corrosion resistance. The corrosion current density values obtained for PMMO was found to be 2.8% and 1.4% of hydrothermal treated oxide (HTO) and PO respectively after 168 h immersion in 3.5% NaCl solution. The electrochemical studies showed the higher barrier layer resistance for PMMO. The improved corrosion behavior of PMMO was observed based on the damage function calculated. Similar observations were confirmed by continuous salt spray test.     

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.     

Effect of tin modification on corrosion of AM70 magnesium alloy

In this study, AM70 magnesium alloys with and without 2 wt.% Sn addition are compared for their corrosion performance. They are found to have similar corrosion rates in the first 70 h in 5 wt.% NaCl solution, but in extended immersion test the Sn modified AM70 exhibits accelerated overall corrosion. Nevertheless, Sn modification significantly decreases the susceptibility of the alloy to localized corrosion attack. Polarization curve measurements further indicate that the Sn modified AM70 is likely to have worse galvanic corrosion than AM70 in terms of the loss of metal, but again the Sn modification makes the galvanic corrosion less localized, which is an improvement aspect of the galvanic corrosion performance. The effect of Sn addition on the corrosion behavior appears to be associated with the presence of Sn-containing particles and the solute Sn in the matrix phase, which may change the electrochemical anodic and cathodic polarization behavior of the 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.     

Effect of excimer laser surface melting on the microstructure and corrosion performance of the die cast AZ91D magnesium alloy

Excimer laser surface melting (LSM) of the die cast AZ91D alloy has been investigated in terms of microstructure and corrosion behaviour. Excimer LSM of the alloy resulted in a highly homogeneous and refined melted microstructure, which improved the corrosion resistance of the alloy. The latter was associated with the large dissolution of intermetallic phases and the enrichment of aluminium within the melted layer. An increased number of laser pulses resulted in thicker melted layers, but also in enhanced porosity and the formation of micro-cracks at the overlapping area. Both factors diminished the corrosion resistance of the laser-treated alloy.     

Relationship between microstructure and corrosion performance of AA2050-T8 aluminium alloy after excimer laser surface melting

Surface modification by excimer laser surface melting (LSM) has been performed with the aim to improve the corrosion resistance of the AA2050-T8 alloy. LSM produced melted surfaces, largely free of precipitates, with both microstructure and corrosion behaviour depending upon the number of laser pulses employed. Increased number of laser pulses resulted in thicker melted layers, but also in greater trapped porosity and formation of micro-cracks at the overlapping area. Nevertheless, the LSM-treated specimens exhibited enhanced corrosion resistance compared to the untreated alloy, which was associated with the formation of a relatively uniform melted layer and a diminished presence of precipitates.     

Influence of alloyed Nd content on the corrosion of an Al–5Mg alloy

The influence of neodymium (Nd) additions from 0 to 0.17 wt.% on the electrochemical response, corrosion, and hardness of a model 5xxx alloy (Al–5Mg) was studied. The combination of SEM, polarisation, constant immersion and nitric acid mass loss testing, followed by optical profilometry, revealed that Nd had no significant effect on pitting or general corrosion of Al–5Mg; however with Nd additions the extent of intergranular corrosion following sensitisation was decreased substantially. Nd additions also increased alloy hardness and thus microalloying with Nd was shown to improve the properties of Al–5Mg.     

Electrochemical behaviour of Cu-40Zn in 3% NaCl solution polluted by sulphides: Effect of aminotriazole

The electrochemical behaviour of Cu-40Zn alloy, in 3% NaCl medium pure and polluted by 2 ppm of S²⁻ ions, has been studied in the absence and presence of the 3-amino-1,2,4 triazole (ATA) as corrosion inhibitor. Electrochemical measurements (polarisation curves and electrochemical impedance spectroscopy) showed that sulphides accelerate the alloy corrosion. The studies revealed that ATA inhibits both cathodic and anodic reactions, indicating a mixed type of inhibition. The inhibiting effect was higher in presence of S²⁻ ions than in its absence. Scanning electron microscopy analysis showed that the inhibitor acts by preventing the adsorption of S²⁻ ions, and formation of Cu₂S at the alloy surface. The inhibition efficiency reaches 98% at a concentration of 5 × 10⁻³ M.     

Influence of silicon on the corrosion behaviour of Al–Zn–In–Mg–Ti sacrificial anode

The influence of Si on the corrosion behaviour of Al–5Zn–0.03In–1Mg–0.05Ti (wt.%) alloy was investigated by the microstructure observation and electrochemical measurements in order to improve its corrosion non-uniform and electrochemical properties. The main precipitates in Al–5Zn–0.03In–1Mg–0.05Ti–0.1Si (wt.%) alloy is Mg₂Si phase, which decrease the galvanic corrosion because the potential difference between Mg₂Si and a-Al is smaller than that between MgZn₂ and a-Al. The addition of Si improves the corrosion uniformity of the anode due to the fine equiaxed grains and grain boundaries where Mg₂Si particles uniformly distributed. The results indicate that the microstructure, electrochemical characteristics and corrosion uniformity can be improved significantly after adding 0.1 wt.% Si into Al–5Zn–0.03In–1Mg–0.05Ti (wt.%) alloy.     

Pitting corrosion of spray formed Al-Li-Mg alloys

The pitting corrosion behaviour of two new spray formed alloys, designated OX24 and OX27, has been compared with spray formed AA7034 and more corrosion resistant AA5083 by polarisation tests. The new alloys have been designed for use in the aerospace industry where good corrosion resistance and specific mechanical properties are required. OX24 and AA5083 had good corrosion resistance; OX27 pitted immediately showing poor corrosion resistance. However, both OX24 and OX27 show better corrosion resistance than AA7034. Scanning electron microscopy showed that corrosion was associated with intermetallic particles, except in OX24 where initiation appeared not to be associated with the Zr-rich intermetallics.     

Effect of common water contaminants on the corrosion of aluminium alloys in ethylene glycol-water solution

The effects of common water contaminants of chloride (Cl⁻), cupric (Cu²⁺) and ferric (Fe³⁺) ions, in four different mixture combination of Fe³⁺ + Cu²⁺, Cl⁻ + Fe³⁺, Cl⁻ + Cu²⁺ and Cl⁻ + Fe³⁺ + Cu²⁺, were examined on the corrosion behaviour of aluminium alloys in ethylene glycol-water solution, using mass loss technique. The highest material losses were recorded for the two alloys in ethylene glycol solution containing the combination of the chloride and the two heavy metal ions. The corrosivity of the solution in the presence of the combination of ions was in the order of Cl⁻ + Fe³⁺ + Cu²⁺ > Cl⁻ + Cu²⁺ > Cl⁻ + Fe³⁺ > Fe³⁺ + Cu²⁺. The results gave first-order kinetics with respect to aluminium in ethylene glycol solution-ion systems. Alloy 3SR exhibits maximum corrosion in all the solutions. It is concluded that the two commercial alloys in the solution polluted with all the three ions would not be able to survive for reasonable period of time without corrosion inhibitor.     

Effect of second phases on the corrosion behaviour of wrought Mg-Zn-Y-Zr alloy

The corrosion behaviour of wrought Mg-Zn-Y-Zr alloy was investigated by corrosion morphology observation and electrochemical measurement. The results indicate that the corrosion process can be divided into three stages, corresponding to three types of corrosion features. At the initial stage, corrosion occurred surrounding the second phases, which was driven by galvanic couple effect; at the middle stage, filiform corrosion was found in the central regions of α Mg matrix; at the final stage, pitting corrosion presented around the second phases. The second phases have a great effect on the corrosion process of Mg-Zn-Y-Zr alloy.     

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.     

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.     

Effect of antimony, bismuth and calcium addition on corrosion and electrochemical behaviour of AZ91 magnesium alloy

This study investigated the effect of antimony, bismuth and calcium addition on the corrosion and electrochemical behaviour of AZ91 magnesium alloy in 3.5% NaCl solution. Techniques including constant immersion, electrochemical potentiodynamic polarisation, scanning electron microscopy (SEM), energy dispersed spectroscopy (EDS) and X-ray diffraction (XRD) were used to characterise electrochemical and corrosion properties and surface topography. It was found that corrosion attack occurred preferentially on Mg₃Bi₂ and Mg₃Sb₂ particles while Mg₁₇Al₈Ca_0.5 and Mg₂Ca phases showed no detrimental effect on corrosion. Combined addition of small amounts of bismuth and antimony to the AZ91 alloy resulted in significant increase in corrosion rate.     

An investigation on corrosion behaviour of pressure infiltrated Al-Mg alloy/SiCp composites

In this study, effect of Mg alloying addition (2-8 wt.%) on corrosion behaviour of Al matrix composites, in 3.5 wt.% NaCl environment, has been investigated. Composites were produced by pressure infiltration technique at 750 °C and had a SiC particle (SiC_p) volume fraction of ∼60%. Results were evaluated by using potentiodynamic polarisation measurements, immersion tests, SEM, EDS and XRD analysis. Compared to the pure Al matrix, mass loss of the composites decreased with increasing Mg content. Experimental results revealed that intermetallics as a result of reaction between Al-Mg alloy and SiC particle has beneficial effect on corrosion resistance of the composites due to interruption of the continuity of the matrix channels within the pressure infiltrated composites.