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.     

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.     

The behaviour of second phase particles during anodizing of aluminium alloys

Several model second phase particles and a practical alloy (AA7075-T6) have been anodized in chromic and sulphuric acid to disclose the relation between particle composition, electrolyte nature and oxidation behaviour. Generally, magnesium-containing second phases are readily oxidized, because the presence of sufficient magnesium hinders the formation of a stable oxide, while copper- and iron-containing particles oxidize at reduced rates and support a relatively stable oxide. At low potential, in chromic acid, the oxidation rate of magnesium-containing particles is reduced, due to passivation induced by chromate anions. Conversely, for particles containing only copper and/or iron, chromate anions increase the oxidation rate.     

Development of anodic coatings on aluminium under sparking conditions in silicate electrolyte

Spark anodizing of aluminium at 5 A dm⁻² in sodium metasilicate/potassium hydroxide electrolytes is studied, with particular emphasis on the mechanism of coating growth, using transmission electron microscopy and surface analytical techniques, with coatings typically 10 μm, or more, thick. Two-layered coatings develop by deposition of an outer layer based on amorphous silica, associated with low levels of alkali-metal species, at the coating surface and growth of an inner, mainly alumina-based, layer, with an amorphous region next to the metal/coating interface. Formation of crystalline phases in the inner layer, mainly γ-Al₂O₃, with some α-Al₂O₃ and occasional δ-Al₂O, is assisted by local heating, and possibly also by ionic migration processes, arising from the rapid coating growth at sites of breakdown. Due to local access of electrolyte species in channels created by breakdown events, the silicon content in the inner coating regions varies widely, ranging from negligible levels to about 10 at.%. Silica deposition at the coating surface and formation of Al₂SiO₅ and Al₆Si₂O₁₃ phases is promoted by increased time of anodizing and concentration of metasilicate in the electrolyte. However, at sufficiently high concentration of metasilicate and pH, when more extreme voltage fluctuations accompany breakdown, the two-layered nature of coatings is replaced by a mixture of aluminium-rich and silicon-rich regions throughout the coating thickness.     

Formation of micro-arc oxidation coatings on AZ91HP magnesium alloys

In a neutral solution, coating formation by micro-arc oxidation (MAO) on AZ91HP magnesium alloy was studied. The process involved the substrate dissolution and coating development. During the first 5 s, the sample mass decreased, indicating substrate dissolution dominating the process. After 5 s, the sample mass began to increase and the coating development began to predominate the process. The coating was firstly nucleated on α phase and sparks initially appeared mainly on the edges of the sample. With treating proceeded, the coating was becoming uniform; meanwhile, microscopic pores of anodic coatings increased in size and decreased in number.     

Film formation in the second step of micro-arc oxidation on magnesium alloys

Magnesium alloys were anodized firstly in a neutral solution and then in an alkaline solution by micro-arc oxidation (MAO). The second step of MAO was a competition between old film dissolution and new film formation. The curves of voltage and mass gain with time showed that in the initial stage, the old film was dissolved. Surface morphologies and EDX analyses indicated that a new film was formed after 1 min. The transition from the process dominated by old film dissolution to that by new film formation took place when the new film had completely covered the old film.     

Generation mechanism of microdischarges during plasma electrolytic oxidation of Al in aqueous solutions

The generation mechanism of microdischarges during plasma electrolytic oxidation (PEO) of aluminium was investigated at constant current densities in aqueous alkaline solutions. Microdischarges were generated only in weakly alkaline solutions under high applied voltages. The breakdown voltage of the anodic oxide film was not dependent on the applied anodic current density while it was strongly dependent on the OH⁻ concentration in the solution. The size and density of microdischarges became larger and lower, respectively, with increasing PEO treatment time. The mechanism of microdischarge generation could be explained based on the movement of ions in the oxide film and resistive property of the oxide film.     

Anodising as pre-treatment before organic coating of extruded and cast aluminium alloys

Anodising has been investigated as a replacement for chromating as pre-treatment prior to organic coating of aluminium. Both AC and DC anodising gave filiform corrosion properties that were comparable to chromated samples. A correlation between filiform corrosion performance and cathodic properties of converted surface was found. Chromating and hot AC anodising gave significant reduction in cathodic current density. The reduction is due to chromium oxide covering intermetallic particles after chromating, while iron rich intermetallics normally acting as cathodic sites were removed by hot AC anodising.     

Corrosion behavior of the composite ceramic coating containing zirconium oxides on AM30 magnesium alloy by plasma electrolytic oxidation

The deterioration process of a plasma electrolytic oxidation (PEO) coating containing zirconium oxides on AM30 magnesium alloy in 3.5 wt.% NaCl solution have been investigated. The coating consists of an outer porous layer and an inner dense layer. The content of MgF₂ is high in the pores and an MgO-rich layer is evident in the inner layer. The corrosion resistance of the outer layer gradually decreases in the initial immersion stage (96 h) due to the decomposition of MgO, and the deterioration of the inner layer is delayed by the blocking effect of the outer layer.     

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.     

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.     

Comparison of electrochemical corrosion behaviour of MgO and ZrO2 coatings on AM50 magnesium alloy formed by plasma electrolytic oxidation

Two types of PEO coatings were produced on AM50 magnesium alloy using pulsed DC plasma electrolytic oxidation process in an alkaline phosphate and acidic fluozirconate electrolytes, respectively. The phase composition and microstructure of these PEO coatings were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The corrosion behaviour of the coated samples was evaluated by open circuit potential (OCP) measurements, potentiodynamic polarization tests, and electrochemical impedance spectroscopy (EIS) in neutral 0.1 M NaCl solution. The results showed that PEO coating prepared from alkaline phosphate electrolyte consisted of only MgO and on the other hand the one formed in acidic fluozirconate solution was mainly composed of ZrO₂, MgF₂. Electrochemical corrosion tests indicated that the phase composition of PEO coating has a significant effect on the deterioration process of coated magnesium alloy in this corrosive environment. The PEO coating that was composed of only MgO suffered from localized corrosion in the 50 h exposure studies, whereas the PEO coating with ZrO₂ compounds showed a much superior stability during the corrosion tests and provided an efficient corrosion protection. The results showed that the preparation of PEO coating with higher chemical stability compounds offers an opportunity to produce layers that could provide better corrosion protection to magnesium alloys.     

Corrosion behaviour of a magnesium matrix composite with a silicate plasma electrolytic oxidation coating

The corrosion behaviour of AZ92 magnesium alloy reinforced with various volume fractions of silicon carbide particles (SiCp) and treated by alternating current (AC) plasma electrolytic oxidation (PEO) was investigated in humid and saline environments. For untreated composites, corrosion attack started around the Al-Mn inclusions and gradually developed into general corrosion without significant galvanic coupling between the matrix and the SiCp. PEO coatings consisted mainly of MgO and Mg₂SiO₄, and revealed increased hardness, reduced thickness and slightly higher corrosion resistance with increasing proportion of reinforcement. Pit formation and hydration of the outer layer were the main mechanisms of corrosion of PEO-treated specimens.     

Stability of aluminium in 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid and ethylene glycol mixtures

The stability of electrochemically passivity aluminium has been investigated in mixtures of ethylene glycol, 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid, Na₂B₄O₇.10H₂O and NaH₂PO₄. The effects of (i) borax and sodium dihydrogen phosphate salts presence, (ii) water absorption and (iii) ethylene glycol content are studied by electrochemical impedance spectroscopy (EIS). The results show a decrease in the polarization resistance and an increase in the capacitance associated with the passive oxide dielectric properties with an increase in the water and/or ethylene glycol content in the mixtures. The presence of Na₂B₄O₇.10H₂O and NaH₂PO₄ salts stabilize the oxide layer.     

EIS study of a self-repairing microarc oxidation coating

The self-repairing microarc oxidation (MAO) coating consisting of a bottom nanocrystalline layer covered by a top conversion ceramic coating was fabricated on 2024 Al alloy by a duplex process with surface mechanical attrition (SMAT) prior to microarc MAO treatment. A 20 μm thick nanocrystalline layer with average grain size of 52.8 nm was fabricated by SMAT, and on which covered by a top MAO coating of 5 μm. The self-repairing property caused by the formation of a dense passive film at the damaged regions contacting the bottom nanocrystalline layer enhances the corrosion reisitance of the SMAT-MAO coating.     

Effect of plasma electrolytic oxidation coating on the stress corrosion cracking behaviour of wrought AZ61 magnesium alloy

An attempt was made to understand the effect of silicate based plasma electrolytic oxidation (PEO) coating on the stress corrosion cracking (SCC) behaviour of an AZ61 wrought magnesium alloy. The SCC behaviour of untreated and PEO coated specimens was assessed using slow strain rate tensile tests at two different nominal strain rates, viz. 1 × 10⁻⁶ s⁻¹ and 1 × 10⁻⁷ s⁻¹, in ASTM D1384 test solution at ambient conditions. The PEO coating was found to improve the general corrosion resistance to a significant extent; however, the improvement in the resistance to stress corrosion cracking was only marginal.     

Influence of pH on the deterioration of plasma electrolytic oxidation coated AM50 magnesium alloy in NaCl solutions

The corrosion deterioration process of plasma electrolytic oxidation (PEO) coatings on AM50 magnesium alloy prepared from two different based electrolytes, i.e., an alkaline phosphate electrolyte and an acidic fluozirconate electrolyte, were investigated using electrochemical impedance spectroscopy (EIS) in a 0.1 M NaCl solution with pH of 3, 7 and 11, respectively. It was found that the PEO coating formed in alkaline phosphate electrolyte, which was composed mainly of MgO, suffered from rapid chemical dissolution and lost its protection capability very quickly in acidic NaCl solution (pH 3). The chemical dissolution of this PEO coating was retarded in neutral NaCl solution (pH 7) and the corrosion damage was localized in this environment. On the other hand, in the alkaline NaCl solution (pH 11), the MgO coating underwent only slight degradation. The PEO coating produced in acidic fluozirconate electrolyte, the failure was marked by the flaking-off of the large areas of coating in acidic NaCl solution (pH 3). However, in the neutral and alkaline NaCl solutions, the coating underwent only a slight degradation without any observable corrosion damage in the 50 h test. The results showed that the deterioration process of PEO coated magnesium alloy was governed mostly by the pH of NaCl solution and it was also strongly related to the microstructure and composition of the PEO coatings.     

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.     

Investigation of the mechanism of plasma electrolytic oxidation of aluminium using O tracer

¹⁸O is used as a tracer to investigate the mechanism of plasma electrolytic oxidation of aluminium under AC conditions, with distributions of ¹⁸O species in the coatings determined by imaging SIMS. The transport of the oxygen species to the inner part of the coating occur through short-circuit paths, leading to formation of fresh alumina within the coating material near to the substrate. With increased times of PEO treatment the coating growth rate declines substantially, and concentration of ¹⁸O tracer is much reduced in the coating, either due to dispersal of the tracer in the coating or loss of coating material.     

The role and effect of residual stress on pore generation during anodization of aluminium thin films

The role and effect of residual stress on pore generation of anodized aluminium oxide (AAO) have been investigated into anodizing the various-residual-stresses aluminium films. The plane stresses were characterised by X-ray diffraction with sin²ψ method. The pore density roughly linearly increased with residual stress from 64.6 (−132.5 MPa) to 90.5 pores/μm² (135.9 MPa). However, the average pore size around 40 nm was not changed significantly except for the rougher film. The tensile residual stress lessened the compressive oxide growth stress to reduce AAO plastic deformation for higher pore density. The findings provide new foundations for realizing AAO films on silicon.