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.     

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.     

Microstructural characteristics and corrosion property of non‐chromate surface treatments on AZ91D magnesium alloy

Chromate conversion coatings can be successfully used for corrosion protection of magnesium alloys. However, the environmental laws have imposed severe restrictions on chromate use in many countries. In this study, a novel protective environmental‐functionally gradient coating was formed on AZ91D magnesium alloy by non‐chromate surface treatments, which consisted of pre‐etching followed by cerium‐based chemical conversion before applying the sol–gel CeO₂ film. It was determined by the analysis of X‐ray diffraction that the gradient coating was mainly composed of CeO₂. The calculation, based on the Scherrer formula, further revealed the formation of nanocrystalline structure in the coating. Scanning electron microscopy (SEM) observations showed that the coating was homogeneous and compact, no obvious cracked structure occurred. According to the immersion tests, potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) tests, the corrosion resistance of AZ91D magnesium alloy was found to be greatly improved by means of this novel environmental‐functionally gradient coating.     

Influences of NH4 + ions and thin electrolyte layers (TEL) thickness on the corrosion behavior of AZ91D magnesium alloy

In this study, the influences of NH₄ ⁺ ions and the thin electrolyte layer (TEL) thickness on the corrosion behavior of the AZ9D magnesium alloy in NH₄⁺‐containing environments were investigated by electrochemical measurements and surface characterization. The experimental results indicate that NH₄⁺ greatly accelerates the corrosion of AZ91D magnesium alloy whether in a bulk solution or in a TEL. As the TEL thickness decreasing, the corrosion resistance of the AZ91D magnesium alloy is strengthened. According to the corrosion morphology, electrochemical analysis, and characterization analysis of corrosion products, the corrosion mechanism of AZ91D under TELs with different thicknesses is divided into three stages: (a) uniformly distributed corrosion pits with deep depth and large size when TEL thickness is higher than or equal to 500 μm; (b) slightly corrosion with randomly distributed corrosion pits and the accumulation of small amount of corrosion product when TEL thickness is between 100 μm and 200 μm; (c) no corrosion pit with only deposition of corrosion product when TEL thickness is lower than or equal to 100 μm. Among which, the roles of NH₄⁺, TEL thickness, and corrosion product are emphasized and discussed in the corrosion process of AZ91D magnesium alloy under TEL with different thicknesses.     

Effect of sintering temperature on corrosion properties of sol–gel based Al2O3 coatings on pre-treated AZ91D magnesium alloy

A novel anti-corrosion sol–gel based Al₂O₃ coating was developed on the AZ91D magnesium alloy. The morphology, microstructure and composition of the coatings were investigated by scanning electron microscope coupled with energy dispersive spectroscopy, Fourier transform infrared spectrum analysis, X-ray diffraction, thermo-gravimetric and differential thermal analysis. The corrosion resistance of the coatings in 3.5 NaCl wt.% solution was studied using electrochemical measurements. The results demonstrated that a homogeneous Al₂O₃ coating could be obtained and the sol–gel coated samples sintered at 380 °C had the best corrosion resistance properties as compared to the specimens sintered at 120 and 280 °C.     

Enhanced corrosioon resistance by sol‐gel‐based ZrO2‐CeO2 coatings on magnesium alloys

The physical, chemical and mechanical properties of magnesium alloys make them attractive materials for automotive and aerospace applications. However, these materials are susceptible to corrosion and wear. This work discusses the potential of using sol‐gel based coatings consisting of ZrO₂ and 15 wt.% of CeO₂. The CeO₂ component provides enhanced corrosion protection, while ZrO₂ impart corrosion as well as wear resistance. Coating deposition was performed by the dip coating technique on two magnesium alloy substrates with different surface finishes: AZ91D (as‐casted, sand‐blasted, and machined) and AZ31 (rolled and machined). All as‐deposited coatings (xerogel coatings) were then subjected to 10 h annealilng: a temperature of 180°C was applied to the AZ91D alloy and 140°C to the AZ31 alloy. Morphological and structural properties of the annealed coatings were investigated by scanning electron microscopy, atomic force microscopy and transmission electron microscopy. Coating composition was examined using energy dispersive X‐ray analysis. Adhesion of the annealed ZrO₂‐CeO₂ coatings on the substrates, assessed by scratch tests, showed critical loads indicative of coating perforation of up to 32 N. Hardness and elasticity, measured using depth‐sensing nanoindentation tests, gave a hardness and elastic modulus of 4.5 GPa and 98 GPa, respectively. Salt spray corrosion tests performed on these coatings showed superior corrosion resistance for AZ91D (as‐casted and machined) and AZ31 (machined), while severe corrosion was observed for the AZ31 (rolled) and AZ91D (sand‐blasted) magnesium alloy substrates.     

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.     

High efficiency corrosion inhibitor 8-hydroxyquinoline and its synergistic effect with sodium dodecylbenzenesulphonate on AZ91D magnesium alloy

The inhibition effects of sodium dodecylbenzenesulphonate (SDBS) and 8-hydroxyquinoline (8HQ) on the corrosion of AZ91D magnesium alloy in ASTM D1384-87 corrosive solution were investigated by the electrochemical impedance spectroscopy and potentiodynamic polarization tests. For SDBS, the inhibition effect was not significant. For 8HQ, a monotonic increase in inhibition efficiency was observed as a function of the immersion time, and the component of the film was Mg(8HQ)₂, which was characterized by three spectra methods. Upon mixing 8HQ and SDBS inhibitors, a synergistic inhibition behavior was observed, and a proper synergistic inhibition mechanism was proposed.     

Ceria/stannate multilayer coatings on AZ91D Mg alloy

In this work, CeO₂/stannate multilayer coatings on AZ91D magnesium alloy were successfully obtained by chemical conversion and sol–gel dip coating. The stannate conversion coatings were prepared from a stannate aqueous bath containing Na₂SnO₃, CH₃COONa, Na₃PO₄ and NaOH at different temperatures and immersion times. Ceria films were produced on stannate/AZ91D starting from Ce(III) nitrate solutions in H₂O. In some cases, the PVA was added as chelating agent. Ceria top coatings were fired at 200 °C for 1 h. Coating microstructure was examined by FE-SEM. Finally, the corrosion resistance features of the coatings were tested by the electrochemical impedance spectroscopy (EIS) in 3 wt.% NaCl solution. The effect of PVA addition was evaluated in terms of microstructure and corrosion resistance features. CeO₂/stannate multilayer films, 3 μm thick, uniform, well adherent and nearly crack free were obtained. The formation of CeO₂ phase was confirmed by XRD and XPS analyses. The XPS depth profiles showed a limited diffusion of Mg towards the ceramic film. The EIS tests showed a significant improvement of corrosion resistance of the multilayer coatings (~ 16.6 kΩ after 48 h in NaCl solution) with respect to the blank alloy (~ 2.4 kΩ after 48 h in NaCl solution).     

Corrosion protection of magnesium alloys by cerium, zirconium and niobium-based conversion coatings

A new Ce, Zr and Nb-based conversion coating was designed for AZ91 and AM50 magnesium alloys. The corrosion protection provided by this coating was evaluated by electrochemical measurements (polarization curves, electrochemical impedance spectroscopy) in Na₂SO₄ electrolyte, and accelerated atmospheric corrosion tests (humid, SO₂ polluted air, and salt spray). Its chemical composition was characterized by X-ray photoelectron spectroscopy (XPS). Electrochemical measurements showed that Mg alloys treated during 24 h in the Ce-Zr-Nb conversion bath exhibit: (i) increased corrosion potential, (ii) decreased corrosion and anodic dissolution current densities, and (iii) increased polarization and charge transfer resistances. The accelerated corrosion tests revealed excellent atmospheric corrosion resistance for all Ce-Zr-Nb-treated samples, with or without an additional layer of epoxy-polyamide resin lacquer or paint. XPS analysis showed that the coating includes CeO₂, Ce₂O₃, ZrO₂, Nb₂O₅, MgO, and MgF₂ as main components. No significant modification of the chemical composition was observed after cathodic and anodic polarization in Na₂SO₄. This new coating provides improved corrosion resistance, and excellent paint adhesion. It offers an alternative to the chromate conversion coating for magnesium alloys.     

Effect of magnesium hydride on the corrosion behavior of an AZ91 magnesium alloy in sodium chloride solution

The effect of magnesium hydride on the corrosion behavior of an as-cast AZ91 alloy in 3.5 wt.% NaCl solution was investigated using gas collection method and potentiostatic test. The Pourbaix diagram of Mg–H₂O system was built using thermodynamic calculation. It was possible that magnesium hydride could form in the whole pH range in theory. The experimental results showed that at cathodic region, magnesium hydride formed on surface, which was the controlling process for the corrosion behavior of AZ91 alloy; at anodic region and free corrosion potential, magnesium hydride model and partially protective film model, monovalent magnesium ion model and particle undermining model were responsible for the corrosion process of AZ91 alloy.     

Microstructure and corrosion behavior of plasma electrolytic oxidation coated magnesium alloy pre-treated by laser surface melting

An AZ91D magnesium alloy was treated using duplex techniques of laser surface melting (LSM) and plasma electrolytic oxidation (PEO). The microstructure, composition and corrosion behavior of the laser melted surface, PEO coatings, LSM–PEO duplex coatings as well as the as-received specimen were characterized by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD) and electrochemical corrosion tests, respectively. Especially, the effect of LSM pre-treatment on the microstructure, composition and corrosion resistance of the PEO coatings was investigated. Results showed that the corrosion resistance of AZ91D alloy was marginally improved by LSM due to the refinement of grains, redistribution of β-phase (Mg₁₇Al₁₂) and increase of Al on the surface. Both the PEO and duplex (LSM–PEO) coatings improved significantly the corrosion resistance of the AZ91D alloys, while the duplex (LSM–PEO) coating exhibited better corrosion resistance compared with the PEO coating.     

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.     

二次电压对AZ91D镁合金微弧氧化封孔的影响

目的提高镁合金微弧氧化膜层的耐蚀性。方法在锆盐体系电解液中对AZ91D镁合金进行微弧氧化处理,通过调节二次电压对AZ91D镁合金微弧氧化膜层的孔隙进行封闭,采用XRD、SEM和电化学测试分别对微弧氧化膜层的物相、表面形貌和耐蚀性进行了研究。结果二次电压对膜层的相成分没有影响,主要相组成为MgO、MgF_2、ZrO_2、Mg_2Zr_5O_(12)。随着二次电压的升高,膜层表面放电微孔孔径先减小后增大,孔隙率先降低后升高。与没有二次电压相比,施加二次电压的腐蚀电流降低2~3个数量级,极化电阻升高1~2个数量级,耐蚀性明显提高,且当二次电压为160 V时,膜层的极化电阻最高,耐蚀性最好。结论二次电压能够对AZ91D镁合金微弧氧化膜层的孔隙进行封闭,进而阻止腐蚀液通过微孔进入基体,提高膜层的耐蚀性。     

Corrosion of hot extrusion AZ91 magnesium alloy. Part II: Effect of rare earth element neodymium (Nd) on the corrosion behavior of extruded alloy

The corrosion behavior of extruded Nd-free AZ91 and extruded AZ91 + 1.5Nd alloy was investigated by weight loss and electrochemical measurements. The results showed that the extruded AZ91 + 1.5Nd alloy had higher corrosion resistance compared to the extruded Nd-free AZ91 alloy, which could been explained from point of view of microstructure changes: (1) the significant decrease of twins and dislocation decreased the anodic dissolution rate; (2) the micro-galvanic corrosion was inhibited by the formation of Al₃Nd phase; and (3) Nd not only increased the percent of Non-Faraday process, but also led to anisotropic feature on the corrosion mechanism.     

Corrosion behavior of AZ91D magnesium alloy in sodium sulfate solution

The corrosion behavior of as‐cast AZ91D magnesium alloy in 0.1M sodium sulfate solution at the corrosion potential (E_corr) was investigated by using electrochemical impedance spectroscopy (EIS), environmental scanning electron microscopy (ESEM), energy dispersive X‐ray spectroscopy (EDS) and X‐ray diffraction (XRD). The results showed that the corrosion of AZ91D started at both the primary α‐Mg and the eutectic α‐Mg. The surface first was covered by a film (MgO, Mg(OH)₂) which became thicker with time. Due to the dissolution of the eutectic α‐Mg, the concentration of aluminum increased, MgAl₂(SO₄)₄ · 2H₂O precipitated at the primary α‐Mg and progressively spread to the eutectic α‐Mg areas. The surface film changed from two‐layer to three‐layer structure with the increase of immersion time.     

Corrosion behaviour of magnesium/aluminium alloys in 3.5 wt.% NaCl

Corrosion behaviour of commercial magnesium/aluminium alloys (AZ31, AZ80 and AZ91D) was investigated by electrochemical and gravimetric tests in 3.5 wt.% NaCl at 25 °C. Corrosion products were analysed by scanning electron microscopy, energy dispersive X-ray analysis and low-angle X-ray diffraction. Corrosion damage was mainly caused by formation of a Mg(OH)₂ corrosion layer. AZ80 and AZ91D alloys revealed the highest corrosion resistance. The relatively fine β-phase (Mg₁₇Al₁₂) network and the aluminium enrichment produced on the corroded surface were the key factors limiting progression of the corrosion attack. Preferential attack was located at the matrix/β-phase and matrix/MnAl intermetallic compounds interfaces.     

Effect of alternating voltage treatment on corrosion resistance of AZ91D magnesium alloy

AZ91D magnesium alloy was treated by the alternating voltage (AV) treatment technique. The optimal AV‐treatment parameters of the alloy were determined by orthogonal experiments. Polarization curve, electrochemical impedance spectroscopy (EIS), and scanning electrochemical microscopy (SECM) were used to understand the effect of AV‐treatment on the corrosion resistance of the alloy. AFM, contact angle, and XPS were employed to investigate further the influence of AV‐treatment on the properties of the surface film formed on the alloy after AV‐treatment. The results showed that a uniform and stable film was formed and the corrosion resistance of AZ91D magnesium alloy was significantly improved after AV‐treatment. This was caused by the noticeable change of the chemical structure and semi‐conducting properties of the surface film after AV‐treatment.     

Electrodeposition of zinc on AZ91D magnesium alloy pre‐treated by stannate conversion coatings

A stannate chemical conversion process followed by an activation procedure was employed as the pre‐treatment process for AZ91D magnesium alloy substrate. Zn was electroplated onto the pre‐treated AZ91D magnesium alloy surface from pyrophosphate bath to improve the corrosion resistance and the solderability. The surface morphologies of conversion coating and zinc coating were examined with scanning electron microscope (SEM). The phase composition of conversion coating was investigated by X‐ray diffraction (XRD). The electrochemical corrosion behavior of the coatings in the corrosive solution was investigated by potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS). The experimental results showed that the activated stannate chemical conversion coating provided a suitable interface between zinc coating and the AZ91D magnesium alloy substrate. The corrosion resistance of the AZ91D substrate was improved by the zinc coating.     

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.