Effects of silicate concentration on anodic films formed on AZ91D magnesium alloy in solution containing silica sol

Anodic films were prepared on the AZ91D magnesium alloy in 1.0 M and 1.5 M Na₂SiO₃ with varied silica sol addition under the constant current density of 20 mA/cm² at 18 °C. The surface and cross-section morphologies of the anodic films were characterized by scanning electron microscopy (SEM) and energy dispersion spectrometry (EDS). The results showed that both the surface morphologies and the thickness of the anodic film were affected by the concentration of Na₂SiO₃ and the additions of silica sol. The effects of Na₂SiO₃ concentration and silica sol addition on the solution properties were also investigated. The results showed that the addition of silica sol into Na₂SiO₃ solution could decrease the surface energy and the conductivity of the solution. Moreover, the anodic film formed in 1.5 M Na₂SiO₃ with addition of silica sol was more uniform and compact than that formed in 1.0 M Na₂SiO₃ with addition of silica sol. And the electrochemical impedance spectroscopy (EIS) results also indicated that the anodic film formed in 1.5 M Na₂SiO₃ solution with 5 vol.% silica sol addition could provide higher corrosion resistance than that formed in 1.0 M Na₂SiO₃ with the same silica sol addition for the AZ91D Mg alloy substrate.     

Influence of silica sol particle behavior on the magnesium anodizing process with different anions addition

Combining the processes of colloid chemistry and electrochemistry the anodic films were made in electrolytes with silica sol addition. Two basic electrolytes 1 M NaOH + 10 vol.% silica sol and 1 M Na₂SiO₃ +10 vol.% silica sol were chosen to investigate the silica sol particle behavior during the anodizing process. The anodic films were prepared separately in the two basic electrolytes with various Na₂CO₃ or Na₃PO₄ additions at 2 A/dm², 20 °C for 10 min. The micro-images and element contents of the specimen were characterized by SEM and EDS. The results showed that some cracks appeared on the films by adding PO₄³⁻ in both of the two basic electrolytes. And the films became compact and uniform with the addition of CO₃²⁻ in Na₂SiO₃ basic solution. Moreover, the film average thickness decreased with adding anions. It can be confirmed that the sol particle adsorbing behavior in the solution was influenced by the amount of anions' charges, size and structure.     

Composite cerium oxide/titanium oxide thin films for corrosion protection of AZ91D magnesium alloy via sol–gel process

Anti‐corrosive composite cerium oxide/titanium oxide (CeO₂/TiO₂) thin films were successfully prepared on an AZ91D magnesium alloy substrate by applying cerium oxide (CeO₂) thin films as the inner layer with a sol–gel process. Composition and surface morphology of the thin films were analyzed using X‐ray diffraction (XRD) and scanning electron microscope (SEM). XRD showed that the composite films consisted of cerianite and anatase phases. The wettability of the thin films was evaluated by water contact angles measurements. Potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) tests were used to evaluate the corrosion behavior of the bare substrate and coated samples in 3.5 wt% sodium chloride solution (3.5 wt% NaCl). The results demonstrated that titanium oxide (TiO₂) thin film mainly dominated the corrosion resistance of samples and the composite films with excellent hydrophilicity could significantly improve the corrosion resistance of AZ91D magnesium alloy.     

The effect of phosphate on MAO of AZ91D magnesium using AC power source

A rapid and convenient anodization technology with AC power source to obtain the MAO films formed on magnesium alloy AZ91D in phosphate bath (base electrolyte + Na₃PO₄) with or without aluminate and silicate was studied. The corrosion resistance of the anodic films was studied by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization techniques and the microstructure and composition of films were examined by SEM and XRD. The results show that Na₃PO₄can promote the occurrence of sparking during the MAO process, while abundant heat generated by sparking might enhance the formation of the glassy phase of the compound when the electrolyte contains the additives of NaAlO₂and Na₂SiO₃simultaneously. The optimized MAO film is ivory‐white smooth by naked eye, while presents porous and microcracks in microscopic scale. The anodic film formed in the alkaline solution with optimized parameters possesses superior corrosion resistance by electrochemical test. The XRD pattern shows that the components of the anodized film consist of MgO, MgAlO₂, and MgSiO₃. No oxide crystal with P element can be found.     

Corrosion resistance of anodized AZ31 Mg alloy in borate solution containing titania sol

Anodic films were prepared on the AZ31 magnesium alloy in alkaline borate solution with or without addition of titania sol under the constant potential of 50 V (dc) for 10 min at room temperature. The morphology of the anodic films was observed by scanning electron microscope (SEM). The corrosion resistance of the anodic films was evaluated in 3.5% NaCl solution using fast anti-acid test, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The anodic film formed in borate solution with addition of 4% titania sol has superior uniform surface and higher corrosion resistance than in other conditions.     

Baking treatment effect on materials characteristics and electrochemical behavior of anodic film formed on AZ91D magnesium alloy

The composition and microstructure of the anodic films formed on AZ91D Mg alloy, with or without baking, were investigated. The associated corrosion behavior of the anodized alloy in 3.5 wt% NaCl solution was also examined using electrochemical impedance spectroscopy (EIS). The results show that MgO was the main component in the anodic film which also contained some Mg(OH)₂, Al₂O₃, Al(OH)₃, and MgAl₂O₄. Both the amorphous and crystalline forms of anodic film were identified. The degree of crystallinity depended on baking temperature, which increased with increasing temperature in the range of 50-250 °C. The amounts of MgO and Al₂O₃ increased as a result of a dehydration reaction. The polarization resistance of anodized Mg alloy was improved significantly by increasing the oxide content in the anodic film. An optimum value of polarization resistance of anodic film was obtained for the alloy baked at 150 °C for 2 h followed by air cooling.     

Characterization of anodic films formed on AZ91D magnesium alloy

Anodization of die-casted AZ91D magnesium alloy was performed in 3 M KOH+0.21 M Na₃PO₄+0.6 M KF base electrolyte with and without Al(NO₃)₃ addition. The anodic film was characterized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The corrosion resistance of the various anodized alloys was then evaluated in 3.5 wt % NaCl solution using electrochemical impedance spectroscopy (EIS) and immersion testing. The results showed that the anodic film was mainly composed of MgO. The addition of Al(NO₃)₃ into the base electrolyte results in the formation of Al₂O₃ and Al(OH)₃ in the anodic film. The maximum amount of Al₂O₃ was found in the anodic film when the alloy was anodized in the electrolyte containing 0.15 M Al(NO₃)₃. The results of EIS analysis and morphological examination showed that the MgO anodic film modified with Al₂O₃ exhibited the superior corrosiom resistance for AZ91D Mg alloy.     

2-Hydroxy-4-methoxy-acetophenone as an environment-friendly corrosion inhibitor for AZ91D magnesium alloy

The inhibition behavior of 2-hydroxy-4-methoxy-acetophenone (paeonol) as an environment-friendly corrosion inhibitor for AZ91D magnesium alloy was investigated in 0.05 wt.% NaCl solution by means of polarization curve, AC impedance, weight loss measurement, scanning electron microscopy, Fourier transformation infrared spectroscopy, ultraviolet analysis, and computer molecular simulation. The results show that paeonol can inhibit the corrosion of AZ91D. The maximum inhibition efficiency is achieved when paeonol concentration is 50 ppm by weight in this study. It is proposed that paeonol chelates with Mg to form a paeonol-Mg complex mixing with the original Mg(OH)₂ film on the surface to inhibit the anodic dissolution of AZ91D.     

Development of anodic film on Mg alloy AZ91D

At constant applied current, the evolution of morphology, structure and composition of anodic film on Mg alloy AZ91D with anodizing time was investigated using SEM, EDX and XRD. The development of anodic film on the Mg alloy was similar to that on high-purity Mg except that, attributed to alloying effect, hunch-like resultants replaced volcano-like ones to become predominant initial products at transitional stage of anodization. The black cicatrices at the anode surface were related with the inhomogeneous activation and dissolution under strong polarization conditions. The evolution of micropores in shape, size and number was associated with anodizing mechanism. The main elements in anodizing products were Mg, O, Al and Si, indicating that both alloy substrate and electrolyte solution were involved in anodization. Anodic film developed early was mainly comprised of periclase MgO and forsterite Mg₂SiO₄. However, amorphous compounds became dominant with treatment time increasing. In anodizing products, the element Al existed primarily in the form of amorphous compound.     

Effects of Na2SiO3 on anodization of Mg-Al-Zn alloy in 3 M KOH solution

The anodic behavior of Mg-Al-Zn alloy (AZ91D) under low potential electrolysis in 3 M KOH solutions was studied with and without addition of 0.5-5 M Na₂SiO₃. Anodic films incorporating silicon were formed during electrolysis, and the films formed under constant potential electrolysis at 4 V in 3 M KOH solution with Na₂SiO₃ were uniform and thicker than the films formed without Na₂SiO₃. A few at% of silicon was present as Mg₂SiO₄ in the films, although the main compound was Mg(OH)₂. The corrosion resistance of the films formed in solutions with Na₂SiO₃ increased in an anodic polarization test in 0.1 M KCl solution.     

Correlation between the corrosion resistance and the semiconducting properties of the oxide film formed on AZ91D alloy after solution treatment

The corrosion resistance and semiconducting properties of the oxide film formed on the AZ91D alloy were evaluated. The alloy was tested in the as-cast condition and after a solution annealing treatment. Electrochemical impedance spectroscopy measurements and potentiodynamic polarization curves were obtained in a H₃BO₃ (0.05 M) + Na₂B₄O₇⋅10H₂O (0.075 M) solution with pH = 9.2 at room temperature. The semiconducting properties of the oxide film were evaluated using Mott–Schottky plots. The corrosion resistance of the AZ91D was reduced after the solution treatment while the semiconducting properties of the passive films were little affected.     

High resistivity magnesium-rich layers and current instability in anodizing a Mg/Ta alloy

Strikingly different morphologies of amorphous anodic films on a Mg/40 at.%Ta alloy are shown to result from single-stage and sequential anodizing procedures. The alloy, prepared by magnetron sputtering, was anodized galvanostatically in ammonium pentaborate (pH 8.3) and sodium silicate (pH 12.6) electrolytes at 293 K and studied by transmission electron microscopy, Rutherford backscattering spectroscopy, glow discharge optical emission spectroscopy and X-ray photoelectron spectroscopy. For one-step anodizing in the pentaborate electrolyte, a single-layered film, of approximate composition Ta₂O₅ · MgO, forms at a ratio of ∼1.8 nm V⁻¹. In the silicate electrolyte, an outer, magnesium-rich layer, containing silicon species, also forms, with a ratio of 0.8 nm V⁻¹. The outer layer can develop due to relatively fast migration of magnesium ions in the inner layer and the stabilization of the pH at the film surface, probably linked to generation of a silica gel that also limits loss of magnesium species to the electrolyte. Further thickening of the anodic film, in ammonium pentaborate electrolyte, produces fingers of low resistivity, inner oxide that penetrate the pre-existing, high resistivity outer layer, with a bi-modal distribution of finger sizes. When fingers reach the film surface, magnesium ions are ejected to the electrolyte. The absence of fingers in films grown in sodium silicate electrolyte is possibly due to prevention, by the silica gel, of their initiation.     

Corrosion resistance of WE43 and AZ91D magnesium alloys with phosphate PEO coatings

The corrosion performance of WE43-T6 and AZ91D magnesium alloys with and without treatment by plasma electrolytic oxidation (PEO) was investigated by electrochemical measurements in 3.5 wt.% NaCl solution. For untreated WE43-T6 alloy, formation of a uniform corrosion layer (Mg(OH)₂) was accompanied by initial pits around magnesium-rare earth intermetallic compounds. The AZ91D alloy disclosed increased corrosion susceptibility, with localized corrosion around the β-phase, though the β-phase network phase acted as a barrier for corrosion progression. PEO treatment in alkaline phosphate electrolyte improved the corrosion resistance of WE43-T6 alloy only at the initial stages of immersion in the test solution. However, PEO-treated AZ91D alloy revealed a relatively high corrosion resistance for much increased immersion times, contrary to the relative corrosion resistances of the untreated alloys. The improved performance of the PEO-treated AZ91D alloy appears to be related to the formation of a more compact coating.     

Improvement of corrosion resistance of AZ31 Mg alloy by anodizing with co-precipitation of cerium oxide

Anodizing of AZ31 Mg alloy in NaOH solution by co-precipitation of cerium oxide was investigated. The chemical composition and phase structure of the coating film were determined via optical microscopy, SEM and XRD. The corrosion properties of the anodic film were characterized by using potentiodynamic polarization curves in 17 mmol/L NaCl and 0.1 mol/L Na₂SO₄ solution at 298 K. The corrosion resistance of AZ31 magnesium alloy is significantly improved by adding cerium oxide to alkaline solution. In addition, the surface properties are enhanced and the film contains no crack.     

Corrosion Performance of Anodized AZ91D Magnesium Alloy: Effect of the Anodizing Potential on the Film Structure and Corrosion Behavior

Die-cast AZ91D magnesium alloy samples have been submitted for anodizing at different potentials. Anodizing was conducted in an environmentally friendly solution which comprised 3 M KOH + 1 M Na₂SiO₃ at room temperature. The surface treatment was performed electrolytically at four different potentials: 3, 5, 8, and 10 V. The corrosion resistance was evaluated by electrochemical impedance spectroscopy and potentiodynamic polarization curves obtained after 7 days of immersion in a 3.5 wt.% NaCl solution at room temperature. The porosity of the anodic films was estimated by means of the linear polarization method. SEM images revealed that the surface oxide was thicker for the anodic films obtained at 3 and 5 V. The films obtained at these potentials were more porous than those formed at 8 and 10 V. The results showed that the thickness of the anodic film had a significant effect on the corrosion behavior of the AZ91D, whereas the influence of the initial porosity was not significant.     

Oxidation behaviour of molten magnesium and AZ91D magnesium alloy in 1,1,1,2-tetrafluoroethane/air atmospheres

The oxidation rates, the morphologies and compositions of the surface films on molten magnesium and AZ91D alloy in covering gas of 1,1,1,2-tetrafluoroethane/air at 760 °C were investigated using thermogravimetric techniques, SEM, XRD and XPS. The oxidation rates of the two melts followed parabolic law in the atmosphere of high concentrate 1,1,1,2-tetrafluoroethane, and obeyed linear law in the atmosphere of low concentrate 1,1,1,2-tetrafluoroethane. But the oxidation rates of molten magnesium and AZ91D alloy presented a certain difference. The oxidation products on its surface films were composed of MgF₂ which played an import role to prevent the molten oxidation and other compounds.     

Effects of low temperature thermal treatment on zinc and/or tin plated coatings of AZ91D magnesium alloy

A new method was investigated to obtain composite coatings on the AZ91D magnesium alloy by electrodeposition and low temperature thermal treatment. Zinc and tin were introduced to AZ91D Mg alloy surface by electroplating firstly. And a succedent thermal treatment was carried out at 190 ± 10 °C for 12 h. The surface and cross-section morphologies of the plated coatings with and without thermal treatment were studied by scanning electron microscopy (SEM). And the microstructure was determined by X-ray diffraction (XRD). The results reveal that it was difficult to obtain good adhesion plated Sn coating but easy to get well-adherent plated Zn coating. And the thermal treatment promoted the formation of Mg₂Sn in the plated Sn coating and the recrystallization in the plated Zn coating. The plated double Zn-Sn coating owned good adhesion and uniform surface. Furthermore, when the plated double Zn-Sn coating was treated at 190 ± 10 °C for 12 h, a three-layer structure coating was formed due to the diffusion of tin. The results of the anodic polarization behaviors in 5 wt.% NaCl solution show that the three-layer structure coating could provide better protection for AZ91D substrate than the plated Zn-Sn coating.     

XRD studies of electrochemically hydrided–dehydrided thin films of the alloy AZ31 and AZ31 with Ti

A magnetron sputtered thin films of the AZ31 alloy and AZ31 alloy with Ti capped with Pd were electrochemically hydrogenated and dehydrogenated in a 3 M KOH solution. A phase composition and structure of the films were studied by XRD. It has been determined that the behaviour of magnetron sputtered alloy AZ31 during electrochemical charging with hydrogen was alike that of pure Mg. The shift of the XRD peak Mg (0 0 0 2) to lower angles indicates that a hydrogen solid solution in the AZ31 alloy was formed along with MgH₂. When the AZ31 alloy with 18 at.% of Ti was electrochemically hydrogenated the whole film was transformed into hydride. The minor part of the hydride was in the nanocrystalline state with a structure of rutile and a major part of the hydride was in the amorphous state. After dehydrogenation only a part of the alloy recovered and the rest remained in the state of amorphous hydride. A positive shift of peak Pd (1 1 1) was observed in all of the XRD patterns for hydrogenated films. At least partially the shift should be associated with the compressive stresses in the top-cap layer of Pd, which arose due to the hydrogenation of the AZ31 alloy.     

Corrosion of AZ91D magnesium alloy with a chemical conversion coating and electroless nickel layer

A chemical conversion treatment and an electroless nickel plating were applied to AZ91D alloy to improve its corrosion resistance. By conversion treatment in alkaline stannate solution, the corrosion resistance of the alloy was improved to some extent as verified by immersion test and potentiodynamic polarization test in 3.5 wt.% NaCl solution at pH 7.0. X-ray diffraction patterns of the stannate treated AZ91D alloy showed the presence of MgSnO₃ · H₂O, and SEM images indicated a porous structure, which provided advantage for the adsorption during sensitisation treatment prior to electroless nickel plating. A nickel coating with high phosphorus content was successfully deposited on the chemical conversion coating pre-applied to AZ91D alloy. The presence of the conversion coating between the nickel coating and the substrate reduced the potential difference between them and enhanced the corrosion resistance of the alloy. An obvious passivation occurred for the nickel coating during anodic polarization in 3.5 wt.% NaCl solution.     

Anodization of Mg-alloy AZ91 in NaOH solutions

Anodic oxide films were grown on the Mg-Al-Zn alloy AZ91 in NaOH-solution and examined by electron microscopy, X-ray diffraction and micro-Raman spectroscopy. The anodic film consists of an inner barrier layer and an outer porous layer. The thin barrier layer is hydrated or contains Mg(OH)₂. The porous layer was identified as crystalline MgO (periclase) and contains tunnels formed by breakdown/repair events, which involve plasma-electrolytic reactions. The micro-Raman-spectrum indicates the formation of a highly disordered zone around the tunnels. Applied current density, potential limit, electrolyte concentration and alloy phase were identified as parameters which have an influence on density and diameter of the tunnels.