Characterization of plasma electrolytic oxide formed on AZ91 Mg alloy in KMnO4 electrolyte

The aim of this work is to investigate microstructure, corrosion resistance characteristics and nanohardness of the oxide layer on AZ91 Mg alloy by applying different voltage with KMnO₄ contained solution. There are lots of closed pores that are filled with another oxide compound compared with the typical surface morphology with pore coated until 350 V of coating voltage. The thickness of oxide layer increases with increasing coating voltage. The oxide layer formed on AZ91 Mg alloy in electrolyte with potassium permanganate consists of MgO and Mn₂O₃. Corrosion potential of the oxide layer on AZ91 Mg alloy obtained at different plasma electrolytic oxidation(PEO) reaction stages increases with increasing coating voltage. The corrosion resistance of AZ91 Mg alloy depends on the existence of the manganese oxide in the oxide layer. The inner barrier layer composed of the MgO and Mn₂O₃ may serve as diffusion barrier to enhance the corrosion resistance and may partially explain the excellent anti-corrosion performance in corrosion test. Nanohardness values increase with increasing coating voltage. The increase in the nanohardness may be due to the effect of manganese oxide in the oxide layer on AZ91 Mg alloy coated from electrolyte containing KMnO₄.     

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.     

The effect of substrate composition on the electrochemical and mechanical properties of PEO coatings on Mg alloys

Plasma electrolytic oxidation (PEO) is a unique surface treatment technology which is based on anodic oxidation forming ceramic oxide coatings on the surface of light alloys such as Mg, Al and Ti. In the present study, PEO coatings prepared on AZ91D, AZ31B, AM60B and AM50B Mg alloys have been investigated. Surface morphology and elemental composition of coatings were determined using scanning electron microscope (SEM) equipped with energy dispersive spectrometer (EDS). SEM results showed that the coating exhibited a porous top surface layer and a subsequent dense layer with micro-pores and shrinkage cracks. Phase analysis of coatings was carried out by X-ray diffraction (XRD). XRD analyses indicated that PEO coatings on AZ alloys had higher amount of Periclase (MgO) followed by the presence of Spinel (MgAl₂O₄) e.g. on the AZ91D alloy compared to that on AM series alloys. In order to examine the effect of substrate composition on adhesion strength of PEO coating scratch tests were carried out. Electrochemical corrosion tests were undertaken by means of potentiodynamic polarization technique in 3.5% NaCl solution at room temperature (20 ± 2 °C). Corrosion test results indicated that the corrosion rates of coated Mg alloys decreased by nearly two orders of magnitude as compared to bare Mg alloys. PEO coatings on AZ series alloys showed better corrosion resistance and higher adhesion properties than AM series alloys. In addition to the PEO processing parameters, such are mainly attributes of the compositional variations of the substrate alloys which are responsible for the formation, phase contents and structural properties of the PEO coatings.     

Improving wear resistance and corrosion resistance of AZ31 magnesium alloy by DLC/AlN/Al coating

A novel protective coating, consisting of three layers (top: diamond-like carbon, middle: aluminum nitride, bottom: aluminum), was deposited on the surface of AZ31 magnesium alloy layer by layer. Nano-indenter, electrochemical system and tribological tester were performed to investigate the hardness, wear resistance and corrosion resistance of the coated AZ31 magnesium alloy, respectively. The DLC/AlN/Al coating improved the magnesium alloy's surface hardness and reduced its friction coefficient, which consequently induced a great improvement of the magnesium alloy's wear resistance. Furthermore, the corrosion resistance of the AZ31 magnesium alloy with the DLC/AlN/Al coating was also enhanced with the corrosion current density decreasing from 2.25 × 10⁻⁵ A/cm² to 1.28 × 10⁻⁶ A/cm² in a 3.5 wt.% NaCl solution.     

Effect of Gd on microstructure and stress corrosion cracking of the AZ91-extruded magnesium alloy

AZ91 and AZ91–xGd (x = 0.5, 1.0, 1.5 wt%) magnesium alloys are extruded into plates. The addition of Gd promotes the formation of Al₂Gd, effectively reducing the volume fraction of the β-Mg₁₇Al₁₂ phase and making the banded structures of the extruded magnesium alloys thinner. The corrosion weight loss tests and electrochemistry analyses demonstrate that Gd significantly improves the pitting resistance of the AZ91 in 3.5-wt% NaCl solution saturated with Mg(OH)₂. Slow strain rate tensile tests show that in a corrosive environment, compared with AZ91, the elongation to failure of the AZ91–1.0Gd alloy is increased by 47%, and the alloy exhibits excellent stress corrosion resistance in this study. The fracture mode of AZ91 is changed from typical intergranular fracture to a mixture of transgranular and intergranular fracture in the corrosion solution by adding Gd. The mechanism of Gd to improve the stress corrosion resistance of the AZ91 magnesium alloy is that Gd increases the corrosion resistance, especially the pitting of AZ91.     

The effects of 8-hydroxyquinoline on corrosion performance of a Mg-rich coating on AZ91D magnesium alloy

A Mg-HQ-rich primer was prepared by adding 45% pure magnesium particles and 5% 8-hydroxyquinoline in epoxy coating. The Mg-HQ-rich primer showed obviously better protection for AZ91D alloy than 50% Mg-rich primer. The additive 8-HQ combines with Mg²⁺ in the coating, forming a insoluble complex, MgQ₂, instead of Mg(OH)₂ on Mg particles. The MgQ₂ layer may retard dissolution of magnesium particles and prolong the cathodic protection effect of Mg-HQ-rich primer. Additionally, the corrosion products may also block the defects in the primer and the active sites on the substrate surface, thereby further increase the corrosion resistance of the Mg-HQ-rich primer.     

An Investigation into the Corrosion Behavior of MgO/ZrO<Subscript>2</Subscript> Nanocomposite Coatings Prepared by Plasma Electrolytic Oxidation on the AZ91 Magnesium Alloy

Plasma electrolytic oxidation (PEO) of AZ91 Mg alloys was performed in ZrO₂ nanoparticles containing Na₂SiO₃-based electrolytes. The phase composition and the microstructure of PEO coatings were analyzed by x-ray diffraction and scanning electron microscopy followed by energy dispersive spectroscopy. Pitting corrosion properties of the coatings were investigated using cyclic polarization and electrochemical impedance spectroscopy tests in a Ringer solution. The results showed the better pitting corrosion resistance of the composite coating, as compared to the oxide one, due to the thickened inner layer and the decrease in the surface defects of the composite coating. Also, the PEO process decreased the corrosion current density from 25.06 µA/cm² in the Mg alloy to 2.7 µA/cm² in the oxide coating and 0.47 µA/cm² in the composite coating.     

Plasma-Sprayed Hydroxyapatite Coating for Improved Corrosion Resistance and Bioactivity of Magnesium Alloy

In the present study, the corrosion resistance and bioactivity of AZ91HP magnesium alloy were improved by plasma spraying hydroxyapatite (HA) coating. X-ray diffraction measurements indicated that the coating formed amorphous and little β-Ca₃ (PO₄)₂ besides of HA. The corrosion resistance and bioactivity of the coating and magnesium alloy in simulated body fluid were investigated using immersion test. The coating showed lower corrosion rate and better bioactivity than magnesium alloy. The coating significantly improved the hydrophilicity of Mg alloy. The prothrombin time of the coating was 18 s, and the prothrombin time of Mg alloy was 11 s, so the coating had better anticoagulant activity.     

Influence of intermetallic Al-Mn particles on in-situ steam Mg-Al-LDH coating on AZ31 magnesium alloy

The influence of intermetallic Al-Mn particles on the corrosion behavior of in-situ formed Mg-Al layered double hydroxide (Mg-Al-CO₃^2--LDH) steam coating on AZ31 Mg alloy was investigated. The alloy was pretreated with H₃PO₄, HCl, HNO₃ or citric acid (CA), followed by hydrothermal treatment, for the fabrication of Mg-Al-LDH coating. The microstructure, composition and corrosion resistance of the coated samples were investigated. The results showed that the surface area fraction of Al-Mn phase exposed on the surface of the alloy was significantly increased after CA pretreatment, which promotes the growth of the Mg-Al-LDH steam coating. Further, the LDH-coated alloy pretreated with CA possessed the most compact surface and the maximum coating thickness among all the coatings. The corrosion current density of the coated alloy was decreased by three orders of magnitude as compared to that of the bare alloy.     

Wear and corrosion resistance of AZ91 magnesium alloy coated by pulsed current electrodeposited Ni–Al2O3 nanocomposite

In this work, Ni and Ni–Al₂O₃ nanocomposite coatings were applied on AZ91 magnesium alloy using a pulse plating process and the corrosion resistance of coated samples was evaluated by means of the potentiodynamic polarisation method in 3.5?wt-% NaCl solution. Field emission scanning electron microscopy was employed to identify microstructure and morphology of the coatings. Vickers microhardness and pin-on-disc wear tests were also used to investigate mechanical properties of the coatings. The polarisation test revealed that the pure Ni coating on AZ91 along with the presence of nanoparticles were key factors leading to a reduction in the corrosion current density and the improvement of corrosion resistance so that the corrosion current density of 210.45?µA?cm^?2 for the substrate (AZ91) decreases to 31.92 and 1.54?µA?cm^?2 by applying pure Ni and Ni–Al₂O₃ nanocomposite coatings, respectively. Furthermore, Ni–Al₂O₃ nanocomposite coating increased the microhardness and wear resistance compared to the substrate up to 435 and 340%, respectively.     

Electrolytic MgO/ZrO2 duplex-layer coating on AZ91D magnesium alloy for corrosion resistance

By a two-step fabrication process of electrolytic deposition and annealing treatment, an MgO/ZrO₂ duplex-layer coating has been prepared on AZ91D magnesium alloy as a protective film against corrosion. Owing to the chemical bonding formed after the condensation of precursory hydroxides, the adhesion strength, thickness and compactness of MgO coating on the substrate are significantly enhanced by the intermediate ZrO₂ layer which prevents the formation of corrosion product Mg₂(OH)₃Cl·4H₂O. As a result, the MgO/ZrO₂ duplex-layer coated specimen reveals relatively high corrosion resistance and superior stability in 3.5 wt% NaCl solution with respect to the MgO single-layer coated specimen.     

Formation of an aluminum-alloyed coating on AZ91D magnesium alloy in molten salts at lower temperature

An aluminum-alloyed coating was formed on an AZ91D magnesium alloy in molten salts containing AlCl₃ at a lower temperature of 380 °C. The microstructure and phase constitution of the alloyed layer were investigated by optical microscopy, scanning electron microscopy, energy dispersive spectrum and X-ray diffraction. The nano-hardness of the coating was studied by nanoindentation associated with scanning probe microscopy. The corrosion resistance of the coated specimen was evaluated in a 3.5 wt.% NaCl solution by electrochemical impedance spectroscopy and cyclic potentiodynamic polarization. The results show that the aluminum-alloyed coating consists of Mg₂Al₃ and Mg₁₇Al₁₂ intermetallic layers. The formation of the coating is dictated by the negative standard free energy of the reaction: 2AlCl₃ + 3 Mg = 3MgCl₂ + 2Al. This process is associated with a displacement reaction mechanism and diffusion process that takes place during the molten salt treatment. High activity of Al elements in molten salts contributes to the lower temperature formation of the Al-alloyed coating. The alloyed coating markedly improves the hardness as well as the corrosion resistance of the alloy in comparison with the untreated AZ91D magnesium alloy, which is attributed to the formation of the intermetallic compounds.     

Corrosion characterization of microarc oxidation coatings formed on Mg–7Li alloy

Ceramic coatings with thickness of 27 µm were fabricated on Mg–7Li alloy in Na₂SiO₃–C₆H₁₈O₂₄P₆ solution by microarc oxidation (MAO). The morphology and phase composition of MAO coatings were characterized by scanning electron microscopy (SEM) and X‐ray diffraction (XRD). The corrosion behavior of the bare and MAO coated Mg–7Li alloy was investigated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). Results showed that the MAO coatings were composed of MgO, Li₂O, and Mg₂SiO₄, and there existed some micropores on the coating surface with a diameter of 3–20 µm. The corrosion potential (E_corr) and corrosion current density (I_corr) of the MAO coated alloy were about ?1.4761 V and 7.204 × 10^?7 A/cm², respectively. The E_corr of the MAO coated alloy increased by 109.6 mV and its I_corr decreased by three orders compared with that of the bare Mg–7Li alloy. The EIS plots indicated that the impedance of the MAO coated alloy was 15 times higher than that of the bare alloy. The fitting parameters showed that the resistance of the MAO coatings was far greater than that of the bare alloy. The dense intermediate layer and the transition layer of the MAO coatings acted as a barrier to hinder the proceeding of solution permeation, remarkably improving the corrosion resistance of the Mg–7Li alloy.     

Electric field assisted chemical conversion process of AZ91D magnesium alloy in HCO3−/CO32− solution

A new method for synthesizing Mg–Al hydrotalcite conversion coating on AZ91D Mg alloy was developed by the application of electric field (EF). By using EF technique, the formation time of the coating can be significantly reduced. The SEM results indicate that a continuous and compact Mg–Al hydrotalcite coating is formed on the surface of Mg alloy after short time EF treatment. However, a long time treatment would make the coating partially exfoliate. The corrosion current density (J_corr) of the coated sample (EF1+1 h) is approximately two orders of magnitude lower than that of Mg alloy substrate. The test of electrochemical impedance spectroscopy (EIS) and immersion corrosion also suggest that the coating can effectively protect Mg alloy against corrosion.     

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.     

AZ91D镁合金表面激光熔覆Al-TiC涂层组织和性能的研究

目的研究Al-TiC涂层组织和性能的特性,以提高镁合金涂层的硬度和耐蚀性能。方法采用Nd:YAG固体激光器,在AZ91D镁合金表面通过激光熔覆制备Al-TiC涂层,采用光学显微镜、X射线衍射仪、显微硬度计、电化学工作站,对熔覆层的组织形貌、物相结构、显微硬度和耐蚀性能进行测定和分析。结果 Al-TiC涂层的主要组成相有AlTi_3(C,N)_(0.6),Al_3Mg_2,Mg_2Al_3,Al和TiC等。激光熔覆层的厚度约为0.35 mm,表面成型良好,结合层晶粒细小,熔覆层与镁合金基体之间结合良好,呈大波浪形。熔覆层试样的平均显微硬度为224HV,约为基体显微硬度(62HV)的4倍,由此表明熔覆层对镁合金硬度有明显的增强作用。镁合金基体的自腐蚀电位为-1.475 V,自腐蚀电流密度为7.556×10~(–5) A/cm~2,熔覆层试样的自腐蚀电位为-1.138V,自腐蚀电流密度为4.828×10~(–5) A/cm~2,与镁合金基体相比,熔覆层的腐蚀电位值增加,腐蚀电流密度值变小,熔覆层的耐蚀性能得到提高。结论采用激光熔覆技术,能够在AZ91D镁合金基体表面制备Al-TiC涂层,由于硬质相AlTi_3(C,N)_(0.6),Al_3Mg_2,Mg_2Al_3,TiC等的存在,熔覆层的显微硬度和耐蚀性能显著提高。     

Electrophoretic deposition of 3YSZ coating on AZ91D using an aluminum interlayer

The zirconia stabilized by 3 mol % Y₂O₃ (3YSZ) was applied onto the surface of the magnesium alloy AZ91D using electrophoretic deposition (EPD) from a non- aqueous solvent. An interlayer of aluminum between the substrate and YSZ coating was also prepared by EPD. The preparation, microstructure and corrosion resistance of the coatings were investigated. The surface morphologies of the coatings were studied by scanning electron microscopy (SEM) and their compositions were determined by X-ray diffraction (XRD). The corrosion resistance of the coatings was evaluated by electrochemical impedance spectroscopy (EIS) in 3.5% NaCl solution. The results indicate that the aluminum interlayer has a favorable effect on the densification of the coating by formation of aluminum oxide. In addition, the corrosion resistance of coated AZ91D alloy in chloride solution is significantly improved because of the aluminum interlayer and an increase in charge-transfer resistance of the AZ91D surface in chloride solution was observed which was attributed to YSZ.     

Crystallization of a chemical conversion layer that forms on AZ91D magnesium alloy in carbonic acid

This investigation studied the crystallization of a chemical conversion layer that formed on AZ91D Mg alloy in carbonic acid. The layer was an amorphous precursor to a crystalline Mg–Al layered double hydrotalcite, which improved the corrosion resistance of the alloy. The precursor must be treated with a strongly alkaline solution, causing the leaching out of amphoteric Al³⁺. The leaching step evidently caused crystallization from an amorphous precursor layer to a crystalline coating. Nuclear magnetic resonance analysis indicated that Al³⁺, which was originally randomly coordinated with surrounding OH⁻ in the precursor, coordinated octahedrally with OH⁻ groups in the crystalline conversion coating.     

Corrosion and wear resistance of AZ31 Mg alloy treated by duplex process of magnetron sputtering and plasma electrolytic oxidation

In order to improve the wear and corrosion resistance of AZ31 magnesium alloy, a magnetron-sputtered Al layer with a thickness of 11 μm was firstly applied on the alloy, and then treated by plasma electrolytic oxidation (PEO) in an aluminate and silicate electrolytes, respectively. The performance of PEO coatings was investigated by dry sliding wear and electrochemical corrosion tests. The aluminate coating exhibits excellent wear resistance under both 10 and 20 N loads. The silicate coating only shows low wear rate under 10 N, but it was destroyed under 20 N. Corrosion tests show that the Al layer after magnetron sputtering treatment alone cannot afford good protection to the Mg substrate. However, the duplex layer of PEO/Al can significantly improve the corrosion resistance of AZ31 alloy. Electrochemical tests show that the aluminate and silicate coatings have corrosion current densities of ∼1.6×10⁻⁶ and ∼1.1×10⁻⁶ A/cm², respectively, which are two orders lower than that of the un-coated AZ31 alloy. However, immersion tests and electrochemical impedance spectroscopy (EIS) show that the aluminate coating exhibits better long-term corrosion protection than silicate coating.     

Effect of cerium addition on microstructure and corrosion resistance of die cast AZ91 magnesium alloy

A novel AZ91 Ce containing magnesium alloy characterized by excellent corrosion resistance is fabricated by adding rare earth Ce (cerium) in the form of a Mg‐Ce master alloy. The metallographic investigation shows that Ce added to AZ91 can obviously decrease the size of β‐Mg₁₇Al₁₂ and forms Al₁₁Ce₃ intermetallic compounds in the shape of fine needles. The corrosion tests and electrochemical measurements indicate that the corrosion resistance of AZ91 Ce containing magnesium alloy is obviously higher than that of AZ91. Furthermore, increasing the content of Ce in the magnesium alloy can further enhance the corrosion resistance. X‐ray photoelectron spectroscopy (XPS) reveals that Ce can be incorporated into corrosion products in the form of CeO₂ in the course of corrosion. Based on the preliminary analysis, the addition of Ce can improve the corrosion resistance of AZ91 by decreasing the size of β‐Mg₁₇Al₁₂ and enhancing the protective effectiveness of corrosion products.