Influence of electrolyte on corrosion properties of plasma electrolytic conversion coated magnesium alloys

The synthesis of oxides in a low-temperature electrolytic plasma allows to cover surfaces of magnesium and its alloys with multifunctional protective oxide-ceramic coatings. The corrosion properties of these layers are strongly dependent on their porosity. In order to minimize the porosity and to optimize the corrosion properties of the layers, the electrolyte concentration and composition (addition of CrO₃ as corrosion inhibitor) were varied, and the influences on layer structure, composition, and properties with a main focus on corrosion behaviour were studied.The corrosion properties of various layers thus generated were studied in 5% NaCl solution by measuring electrochemical polarization curves and by electrochemical impedance spectroscopy (EIS) at pH 3 and 6. Using XRD, LM, SEM and EDX to evaluate the composition and microstructure of the modified surfaces, the corrosion results were related to the microstructure and composition of the specific layer. The better results were obtained for layers produced at higher electrolyte concentration, whereas the addition of CrO₃ had no significant beneficial effect.     

The corrosion performance of anodised magnesium alloys

The corrosion performance of anodised magnesium and its alloys, such as commercial purity magnesium (CP-Mg) and high-purity magnesium (HP-Mg) ingots, magnesium alloy ingots of MEZ, ZE41, AM60 and AZ91D and diecast AM60 (AM60-DC) and AZ91D (AZ91D-DC) plates, was evaluated by salt spray and salt immersion testing. The corrosion resistance was in the sequential order: AZ91D ≈ AM60 ≈ MEZ ? AZ91D-DC ? AM60-DC > HP-Mg > ZE41 > CP-Mg. It was concluded the corrosion resistance of an anodised magnesium alloy was determined by the corrosion performance of the substrate alloy due to the porous coating formed on the substrate alloy acting as a simple corrosion barrier.     

Effect of gelatin additions on the corrosion resistance of cerium based conversion coatings spray deposited on Al 2024-T3

The corrosion resistance of cerium based conversion coatings on Al 2024-T3 was improved by the addition of a water soluble gelatin to the coating solution. Auger electron spectroscopy depth profiling showed that coatings deposited from solutions containing 800-3200 ppm gelatin were ~ 400 nm thick, while coatings deposited from solutions with 0-200 ppm gelatin were ~ 850 nm thick. The thinner coatings exhibited reduced surface cracking and spalling. Open circuit potential measurements during deposition showed that adding gelatin to the coating solution resulted in a more negative and stable potential with increasing gelatin concentrations. Visually, increasing gelatin concentrations promoted the formation of stable bubbles that covered panel surfaces, which limited transport of cerium species to the surface and decreased the deposition rate. X-ray diffraction analysis revealed that only coatings deposited from solutions containing 400-3200 ppm gelatin could be converted to CePO₄H₂O during post-treatment, potentially improving the corrosion resistance compared to coatings deposited from solutions without gelatin.     

Formation and properties of stannate conversion coatings on AZ61 magnesium alloys

The effects of solution composition and temperature on the microstructure and corrosion resistance of stannate conversion coatings on AZ61 magnesium alloys were investigated. The conversion coating consisted of a porous layer as under layer intimately contacted with the magnesium plate and a hemispherical particle layer as major overlay formed right on top of the porous layer. During the coalescence of the hemispherical particles to form a complete coating on the magnesium alloy, some sites of discontinuity inevitably left and determined the corrosion resistance of the coating evaluated using a salt spray test. Increasing bath stannate ion concentration and lowering bath pH increased the population density of the hemispherical particles whose size was accordingly reduced. The corrosion resistance of the conversion coating was improved with finer particles, which were preferably formed at less alkaline solution with higher stannate ion contents. Furthermore, the conditions favoring the formation of finer particles also reduced the immersion time necessary for producing the conversion coating with optimal corrosion resistance.     

Evaluation of corrosion resistance of magnesium alloys in radiator coolants

Abstract

Coolant corrosion is a major drawback for the use of magnesium alloys in engine and cooling system, but the coolant is not normally intended to prevent corrosion of magnesium alloys. This research assessed the corrosion performance of two magnesium alloys, AZ91D and AM50A, in two newly formulated radiator coolants using immersion test, potentiodynamic polarisation test, and corroded surface analysis. Two coolants were named as Irgacool Plus L and Irgacool Plus S. C7, C8-organic acids and polycarboxylic acid were the main inhibitor species in Irgacool Plus L while Irgacool Plus S was formulated with C7, C8-organic acids and sebacic acid inhibitors. Corrosion rates of magnesium alloys decreased twice in Irgacool Plus L compared with Irgacool Plus S. AZ91D alloy had better corrosion resistance than AM50A alloy in both radiator coolants. Both alloys suffered corrosion due to microgalvanic coupling between cathodic β-Mg₁₇Al₁₂ intermetallic and anodic α-Mg matrix, and the presence of Al₈Mn₅ and Al₁₁Mn₄ intermetallics in AM50A led to further microgalvanic corrosion. A continuous network of β-Mg₁₇Al₁₂ phase and higher Al content α-Mg matrix accounted for better corrosion resistance of AZ91D alloy.     

Characterization and corrosion studies of fluoride conversion coating on degradable Mg implants

Fluoride conversion coating was synthesized on magnesium (Mg) by immersion treatment in hydrofluoric acid (HF) at room temperature, with the aim of improving the corrosion resistance of Mg in applications as degradable implant material. After an immersion period of 24 h in 48% HF, the samples carried a bronze color, and the conversion coating was dense and free of cracks. Field-emission scanning-electron microscopy (FE-SEM) of the cross-section revealed a coating thickness of about 1.5 μm. Atomic-force microscopy (AFM) recorded an average surface roughness of ∼ 21 nm for the coated sample, similar to that of the untreated one (∼ 17 nm). The coating was mainly composed of magnesium fluoride (MgF₂) as identified by thin-film X-ray diffractometry (TF-XRD), consistent with compositional analysis using X-ray photoelectron spectroscopy (XPS). The MgF₂ was in the form of crystallites of a few nm. A small amount of oxygen was present inside the coating, suggesting that some F⁻ ions are replaced by hydroxyl (OH⁻) ions in the MgF₂ structure, or that a small amount of Mg(OH)₂ was present. The corrosion resistance of untreated and conversion coated Mg in Hanks' solution was studied using electrochemical impedance spectroscopy (EIS), potentiodynamic polarization tests, and immersion tests. EIS results showed a polarization resistance of 0.18 kΩ cm² for the untreated Mg and 5.2 kΩ cm² for the coated sample, giving an improvement of about 30 times. Polarization tests also recorded a reduction in corrosion current density from 400 μA/cm² to 10 μA/cm², showing an improvement of about 40 times. The galvanic effect between untreated and fluoride-coated Mg samples was small. Immersion tests in Hanks' solution also resulted in a much milder and more uniform corrosion damage on the fluoride-coated samples. The results of the present study showed that fluoride coating by conversion treatment is a simple and promising way of enhancing the corrosion resistance of Mg in Hanks' solution, or that it may be employed as a pretreatment step for subsequent coating.     

Stannate and permanganate conversion coatings on AZ31 magnesium alloy

The formation of stannate and permanganate–phosphate conversion coatings on AZ31 magnesium alloy was investigated in situ by EIS measurements and their protective performances were studied by different electrochemical techniques in diluted (0.05 M) sodium sulphate solution.The influence that short or long treatment times exert on the performances of such conversion coatings is discussed. While permanganate–phosphate baths always built layers characterized by penetrating cracks, long stannate baths produced layers without interconnected porosity, but were defective. This accounted for the initial greater protectiveness achieved with the stannate treatment; nevertheless, the easy penetration of the electrolytic solution through such a layer quickly decreased its corrosion resistance.     

Corrosion resistance of cerium‐based chemical conversion coatings on AA5083 aluminium alloy

In this paper the effect of several parameters, such as temperature, time of immersion, cerium ions and hydrogen peroxide concentration, pH of the conversion solution, on the composition and morphology of the conversion layer are investigated as well as on its corrosion resistance in chloride environments. The cerium‐based chemical conversion coatings ennobles the corrosion potential and inhibits both the cathodic and anodic reactions rate. Using a cerium (III) chloride solution a not homogeneous coating is obtained and agglomerates with a “dry‐mud” morphology of mixed cerium‐aluminium oxide are deposited above the cathodic intermetallic particles, while using a cerium (III) nitrate solution the coating is more uniform but thinner than that obtained with cerium (III) chloride. Solution temperature below 50°C and time of immersion of 10 minutes produces a coating with better corrosion resistance.     

Synthesis and evaluation of corrosion resistance of molybdate-based conversion coatings on electroplated zinc

Three molybdate-based conversion coatings on electroplated zinc have been prepared and the composition, morphology, and structure of these coatings are measured by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and X-ray diffraction (XRD), respectively. It was found that these coatings with ‘meshwork’ surface were complex coatings composed of multiple compounds. Molybdenum species were present in the conversion coating as Mo (VI) and Mo (IV) compounds. The results of neutral salt spray test showed that molybdate-based conversion coatings with the addition of H₃PO₄, SiO₂ and TiOSO₄ in the passivation baths possess higher corrosion resistance compared with chromate conversion coatings, which was due to the compactness and anti-corrosion essence of the conversion coating.     

Preparation of MgO coatings on magnesium alloys for corrosion protection

MgO coating is formed on magnesium alloy by anodic electrodeposition in 6 M KOH solution, whereas Mg(OH)₂ coating is produced by anodization in 10 M KOH solution, which could be successively converted to MgO by calcination in air at 450 °C. The evolution of morphology, structure and composition of anodic film obtained on Mg alloy is investigated using scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDX) and X-ray diffraction (XRD). Potentiodynamic polarization measurements show that the as-grown MgO protective coatings are very effective in improving the corrosion resistance of magnesium alloy compared to bare metallic magnesium.     

Characterization of calcium-modified zinc phosphate conversion coatings and their influences on corrosion resistance of AZ31 alloy

Two kinds of phosphate conversion coatings, including zinc phosphate coating and zinc-calcium phosphate coating, were prepared on the surface of AZ31 alloy in phosphate baths. The morphologies of these coatings were observed using scanning electron microscopy. Their chemical compositions and structures were characterized using energy-dispersive X-ray spectrum, X-ray photoelectron spectroscopy and X-ray diffraction. The corrosion resistance of the coatings was evaluated by potentiodynamic polarization technique. The results show that the flowerlike Zn-Ca phosphate conversion coatings are mainly composed of hopeite (Zn₃(PO₄)₂·4H₂O). They have a quite different morphology from the dry-riverbed-like Zn phosphate coatings that consist of MgO, MgF₂, Zn or ZnO and hopeite. Both of the zinc and zinc-calcium phosphate coatings can remarkably reduce the corrosion current density of the substrates. The Zn-Ca coating exhibits better corrosion resistance than the Zn coating. Introduction of calcium into the phosphate baths leads to the full crystallinity of the Zn-Ca coating.     

Electroless Ni-Sn-P coating on AZ91D magnesium alloy and its corrosion resistance

An electroless Ni-Sn-P coating was deposited on AZ91D magnesium alloy in an alkaline-citrate-based bath where nickel sulphate and sodium stannate were used as metal ion sources and sodium hypophosphite was used as a reducing agent. The phase structure of the coating was amorphous. SEM and attached EDS observation revealed the presence of dense and uniform nodules in the ternary coating and the content of tin was 2.48wt.%. Both the electrochemical analysis and the immersion test in 10% HCl solution proved that the ternary Ni-Sn-P coating exhibited better corrosion resistance than the Ni-P coating in protecting the magnesium alloy substrate.     

Formation of subsurface crevices in aluminum alloy 2024-T3 during deposition of cerium-based conversion coatings

The processing variables that contributed to the formation of subsurface crevices under cerium-based conversion coatings on AA 2024-T3 were investigated. Focused ion beam milling revealed the presence of subsurface crevices underneath a small fraction (∼ 10%) of coated areas, typically in areas with large cracks through the coatings. A solution of sodium chloride and H₂O₂ etched AA 2024-T3 and produced features similar to subsurface crevices, which confirmed that crevices formed during deposition due to the composition of the coating solution. Using sodium nitrate in place of sodium chloride resulted in no etching of the substrate. Thus, coatings free of subsurface crevices could be produced by using cerium nitrate instead of cerium chloride in the coating solution. Electrodeposited coatings, even those deposited from solutions containing chloride ions and H₂O₂, were also free of subsurface crevices. As a result, subsurface crevices are not inherent to cerium-based conversion coatings, but rather were formed due to certain process parameters, specifically the presence of chloride ions and hydrogen peroxide in the coating solution.     

Chemical conversion coating on AZ31B magnesium alloy and its corrosion tendency

The morphology change of the magnesium matrix after pre-treatment and the mor-phology as well as the phase composition of chemical conversion coating formed by phosphate were studied using scanning electron microscope and X-ray diffraction. The corrosion resistance of the coating was studied by salt spray and damp test, and the corrosion tendency during salt immersion test was analyzed. The results show that the phase composition before and after pre-treatment is almost change- less, and the deep microflaw appears between α and β phases during acidic pickling. The phosphate conversion coating is mainly composed of Mg, MgO, and some amor-phous phase, and it can provide a good protection for the AZ31B alloy. Results from corrosive morphology indicate that the growth and the corrosion resistance of the phosphate conversion coating are related to the forming process of the AZ31B matrix.     

The characterization and corrosion resistance of cerium chemical conversion coatings for 304 stainless steel

A golden yellow-colored cerium conversion coating was obtained on 304 stainless steel surface by immersing the steel into a solution containing cerium (III), KMnO₄ and sulfuric acid. The corrosion resistance of the coatings was evaluated by electrochemical methods, potentiodynamic polarization experiments and electrochemical impedance spectrum. The experimental results indicated that the corrosion resistance for the conversion coated 304SS in 3.5% NaCl solution increased markedly. The corrosion potential of the treated steel increased to a more noble level, the pitting corrosion potential increased also, the passive potential range was enlarged markedly and the passive current density decreased about one order compared to that of the untreated steel. The cathodic and anodic reaction were both inhibited to some extent. The chemical state of the elements in the coatings was investigated by XPS. The cerium element was in the form of tetravalent state. And AES depth profile analysis suggested that the thickness of the conversion coatings was less than 66 nm. The mechanisms of coatings formation and corrosion resistance are discussed.     

Chromate conversion coatings on aluminium-copper alloys

The study compares the formation of chromate/fluoride conversion coatings, composed mainly of amorphous hydrated chromia, on model, solid-solution, binary Al-Cu alloys, of a range of compositions, and on 2014-T6 aluminium alloy. The model alloys, produced by magnetron sputtering, reveal the importance of copper in limiting the thickness of the coatings by promoting loss of coating material. This occurs at an earlier time in the treatment with increasing copper content of the alloy. The coating loss follows closely upon the achievement of the required level of copper enrichment for incorporation of copper into the coating, with a thin alumina film beneath the hydrated chromia sustaining the enrichment process. The coating on the 2014-T6 alloy is of non-uniform thickness, with much thinner coating developing at copper-rich second phases, consistent with the results of model alloys.     

Enhancement of corrosion resistance of Mg-9 wt.% Al-1 wt.% Zn alloy by a calcite (CaCO3) conversion hard coating

A calcite (CaCO₃) coating on Mg alloy, formed by chemical conversion treatment, was investigated. Aqueous with Ca²⁺ concentration of ∼220 ppm was employed in the chemical conversion treatment. Cross-sectional microstructures of the coated sample after 2 h of treatment revealed a two-layer coating structure. The corrosion current density (I_corr) of the coated sample was approximately two orders of magnitude lower than that of the untreated sample. Electrochemical impedance spectroscopy (EIS) and an appropriate equivalent circuit suggested that each of the layers of the two-layer coating effectively protects Mg alloy against corrosion.     

Polyoxadiazole-based coating for corrosion protection of magnesium alloy

In this study, polyoxadiazole-based coatings were molecularly designed by attaching two different functional groups, i.e., diphenyl-ether and diphenyl-hexafluoropropane, in the main polymer chain for the purpose of low water permeability and eventually for high corrosion protection of AM50 magnesium alloy. Potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS) were used to evaluate the coating performance of the two polymers. Electrochemical experiments showed that POD-6FP (poly(4,4′-diphenyl-hexafluoropropane-1,3,4-oxadiazole)) coated alloy exhibited 3-4 orders of magnitude higher corrosion resistance as compared to the POD-DPE (poly (4,4′-diphenyl-ether-1,3,4-oxadiazole)) coated alloy. The high coating performance of the POD-6FP polymer can be attributed to the hydrophobic group attached to the polyoxadiazole chain.     

Cerium-based conversion coatings on aluminium alloys: a process review

Abstract

Rare earths are among the most promising options for replacing chromate conversion coatings on aluminium. In nearly three decades of research, several hundred papers have been published in the area, the bulk of which has never been reviewed. This paper reviews the literature on rare earth coating processes, with particular emphasis on those based on cerium. It is concluded that several process areas are poorly understood, some of which are critical to further progress in the field. These include the development of industrially suitable pretreatments, technologies for coating non-aerospace alloys and seals to enhance corrosion performance and paint adhesion.