Preparation and properties of composite ceramic coating containing Al2O3–ZrO2–Y2O3 on AZ91D magnesium alloy by plasma electrolytic oxidation

A composite ceramic coating containing Al₂O₃–ZrO₂–Y₂O₃ was successfully prepared on AZ91D magnesium alloy by plasma electrolytic oxidation (PEO) technique in an alkaline aluminate electrolyte. The morphology, elemental and phase composition, corrosion behavior and thermal stability of the uncoated and coated samples were studied by environmental scanning electron microscopy (ESEM), energy dispersive X-ray spectrometer (EDS), X-ray diffractometer (XRD), electrochemical corrosion test, high temperature oxidation test and thermal shock test. The results showed that the composite ceramic coating was composed of Al₂O₃, c-ZrO₂, t-ZrO₂, Y₂O₃ and some magnesium compounds, such as MgO, MgF₂ and MgAl₂O₄. After PEO treatment, the corrosion potential of AZ91D alloy was increased and the corrosion current density was significantly reduced. Besides, the coated magnesium alloys also showed excellent high temperature oxidation resistance and thermal shock resistance at 500 °C environment.     

Effect of α-Al2O3 on the properties of cold sprayed Al/α-Al2O3 composite coatings on AZ91D magnesium alloy

Composite coatings using pure Al powder blended with α-Al₂O₃ as feedstock were deposited on AZ91D magnesium alloy substrates by cold spray (CS). The content of α-Al₂O₃ in the feedstock was 25 wt.% and 50 wt.%, respectively. The effects of α-Al₂O₃ on the porosity, microhardness, adhesion and tensile strength of the coatings were studied. Electrochemical tests were carried out in neutral 3.5 wt.% NaCl solution to evaluate the effect of α-Al₂O₃ on the corrosion behavior of the coatings. The results showed that the composite coatings possessed lower porosity, higher adhesion strength and tensile strength than cold sprayed pure Al coating. The corrosion current densities of the composite coatings were similar to that of the pure Al coating and much higher than that of bare AZ91D magnesium alloy.     

Investigation of plasma electrolytic oxidation process on AZ91D magnesium alloy

Ceramic coatings oxidized for different time periods were prepared to characterize the plasma electrolytic oxidation (PEO) process of AZ91D magnesium alloy. The coatings were analyzed using scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscope and potentiodynamic polarization measurement. The results show that the PEO coatings perform different growth behaviors at different PEO stages, and different morphologies are exhibited on α- and β-phase of Mg substrate. The corrosion resistance measurement predicates that within the first 30 min oxidation, coating oxidized for 20 min is the best corrosion resistant.     

A novel process of electroless Ni-P plating with plasma electrolytic oxidation pretreatment

A novel Ni based coating - plasma electrolytic oxidation (PEO) pre-treatment followed by electroless nickel (EN) plating - has been developed to produce pore free Ni coatings on AZ91 magnesium alloy. The application of the PEO film between the nickel coating and the substrate acts as an effective barrier and catalytic layer for the subsequent nickel plating. The potentiodynamic tests indicated that the corrosion current density of the PEO + EN plating on AZ91 decreased by almost two orders of magnitudes compared to the traditional EN coating. Salt fog spray testing further proved this improvement. More importantly, the new technique does not use Cr⁺⁶ and HF in its pretreatment, therefore is a much environmentally friendlier process.     

Solidification microstructure of AZ91D Mg alloy after laser surface melting

The solidification microstructure plays a critical role in determining the surface properties of laser-treated magnesium alloys. The purpose of this paper is to study the solidification microstructures of AZ91D Mg alloy following millisecond- and nanosecond-pulse Nd:YAG laser irradiation. The solidification microstructural evolution of laser-melt AZ91D Mg alloy was investigated using X-ray diffractometry, scanning electron microscopy, energy-dispersive X-ray spectrometer and transmission electron microscopy. Much refined α-Mg phase and β-Mg₁₇Al₁₂ intermetallics were observed in the microstructure after laser surface melting. Periodic and successive structure was observed in the millisecond irradiated surface and the melt depth was more than 100 μm. The solidification microstructure was mainly cellular/dendrite structures together with a large number of β-Mg₁₇Al₁₂ nano-particles. Micron holes were found in the nanosecond irradiated surface and the melt depth was shallow at 50 μm. Millisecond-pulse Nd:YAG laser was found to be more suitable for Mg alloy surface treatment due to sufficient melt depth.     

Composition design and laser cladding of Ni-Zr-Al alloy coating on the magnesium surface

The cluster line criterion was used for optimized design of a Ni-Zr-Al alloy used as coating on the AZ91HP magnesium alloy by laser cladding. Results show that the coating mainly consists of an amorphous, two ternary intermetallic phases with Ni₁₀Zr₇ and Ni₂₁Zr₈ type structures resulting in high hardness, good wear resistance and corrosion resistance. The interface between the clad layer and the substrate has good metallurgical bond.     

Electrodeposition of high corrosion resistance Cu/Ni-P coating on AZ91D magnesium alloy

High corrosion resistance Cu/Ni-P coatings were electrodeposited on AZ91D magnesium alloy via suitable pretreatments, such as one-step acid pickling-activation, once zinc immersion and environment-friendly electroplated copper as the protective under-layer, which made Ni-P deposit on AZ91D Mg alloy in acid plating baths successfully. The pH value and current density for Ni-P electrodeposition were optimized to obtain high corrosion resistance. With increasing the phosphorous content of the Ni-P coatings, the deposits were found to gradually transform to amorphous structure and the corrosion resistance increased synchronously. The anticorrosion ability of AZ91D Mg alloy was greatly improved by the amorphous Ni-P deposits, which was investigated by potentiodynamic polarization curve and electrochemical impedance spectroscopy (EIS). The corrosion current density (I_corr) of the coated Mg alloy substrate is about two orders of magnitude less than that of the uncoated.     

Corrosion and wear properties of PEO coatings formed on AM60B alloy in NaAlO2 electrolytes

Coatings with a thickness of 22-32 μm were formed on an AM60B magnesium alloy by plasma electrolytic oxidation (PEO) in electrolytes containing 12.0-24.0 g/l NaAlO₂ and other additives. SEM analyses of the coated samples showed that the coatings were compact with relatively low porosity. X-ray diffraction revealed that the coatings consisted of mainly MgAl₂O₄ and MgO phases. The relative amount of MgAl₂O₄ in the coating increased with increasing NaAlO₂ concentration. The relatively compact and thick coatings provide good corrosion protection for magnesium, as indicated by the results of potentiodynamic polarization tests. In addition, the PEO treatment also significantly improved the wear resistance of the alloy. Pin-on-disk wear tests showed that the PEO treatment reduced the wear volume loss by a factor of 10.     

Electroless Ni-P/Ni-B duplex coatings for improving the hardness and the corrosion resistance of AZ91D magnesium alloy

The Ni-P/Ni-B duplex coatings were deposited on AZ91D magnesium alloy by electroless plating process and their structure, morphology, microhardness and corrosion resistance were evaluated. The duplex coatings were prepared using dual baths (acidic hypophosphite- and alkaline borohydride-reduced electroless nickel baths) with Ni-P as the inner layer. The coatings were amorphous in as-plated condition and crystallized and produced nickel borides upon heat-treatment. SEM observations showed that the duplex interface on the magnesium alloy was uniform and the compatibility between the layers was good. The Ni-P/Ni-B coatings microhardness and corrosion resistance of having Ni-B coating as the outer layer was higher than Ni-P coatings. The Ni-P/Ni-B duplex coatings on AZ91D magnesium alloy with high hardness and good corrosion resistance properties would expand their scope of applications.     

Studies on influence of zinc immersion and fluoride on nickel electroplating on magnesium alloy AZ91D

The effect of zinc immersion and the role of fluoride in nickel plating bath were mainly investigated in nickel electroplating on magnesium alloy AZ91D. The state of zinc immersion, the composition of zinc film and the role of fluoride in nickel plating bath were explored from the curves of open circuit potential (OCP) and potentiodynamic polarization, the images of scanning electron microscopy (SEM) and the patterns of energy dispersive X-ray (EDX). Results show that the optimum zinc film mixing small amount of Mg(OH)₂ and MgF₂ is obtained by zinc immersion for 30-90 s. The corrosion potential of magnesium alloy substrate attached zinc film will be increased in nickel plating bath and the quantity of MgF₂ sandwiched between magnesium alloy substrate and nickel coating will be reduced, which contributed to produce nickel coating with good performance. Fluoride in nickel plating bath serves as an activator of nickel anodic dissolution and corrosion inhibitor of magnesium alloy substrate. 1.0-1.5 mol dm⁻³ of F⁻ is the optimum concentration range for dissolving nickel anode and protecting magnesium alloy substrate from over-corrosion in nickel plating bath. The nickel coating with good adhesion and high corrosion resistance on magnesium alloy AZ91D is obtained by the developed process of nickel electroplating. This nickel layer can be used as the rendering coating for further plating on magnesium alloys.     

Broad-beam laser cladding of Al-Cu alloy coating on AZ91HP magnesium alloy

The resistance to wear and corrosion of AZ91HP Mg alloy was improved by laser cladding Al-Cu alloy. It was found that the clad layer was characterized by AlCu₄ and Mg₁₇Al₁₂ grains embedded in a AlMg matrix. The bonding zone exhibited a white-light planar crystal band with thickness of 10-13 μm. The heat-affected zone formed a eutectic structure due to the Mg diffusion. The microhardness and wear resistance of the coating were improved due to the formation of the hard phases AlCu₄ and Mg₁₇Al₁₂. Owing to the formation of dense Al₂O₃ oxide film, the coating exhibited better corrosion resistance in 3.5 wt.% NaCl solution.     

Chemical nature of phytic acid conversion coating on AZ61 magnesium alloy

Phytic acid (PA) conversion coating on AZ61 magnesium alloy was prepared by the method of deposition. The influences of pH, time and PA concentration on the formation process, microstructure and properties of the conversion coating were investigated. Scanning electron microscopy (SEM) was used to observe the microstructure. The chemical nature of conversion coating was investigated by energy dispersive X-ray spectroscopy (EDS) and Fourier transform infrared spectroscopy (FTIR) techniques. The corrosion resistance was examined by means of potentiodynamic polarization method. The adhesive ability was tested by score experiments. The results showed that the growth and microstructure of the conversion coatings were all obviously affected by pH, time and PA concentration. In 0.5 mg/ml PA solution with a pH of 5, an optimization conversion coating formed after 20 min immersion time by deposition of PA on AZ61 magnesium alloy surface through chelating with Al³⁺. It made the corrosion potential E_corr of sample shifted positively about 171 mV than that of the untreated sample, and the adhesive ability reached to Grade 1 (in accordance with GB/T 9286).     

Correlation between the surface chemistry and the atmospheric corrosion of AZ31, AZ80 and AZ91D magnesium alloys

X-ray photoelectron spectroscopy (XPS) was used in order to investigate the correlation between the surface chemistry and the atmospheric corrosion of AZ31, AZ80 and AZ91D magnesium alloys exposed to 98% relative humidity at 50 °C. Commercially pure magnesium, used as the reference material, revealed MgO, Mg(OH)₂ and tracers of magnesium carbonate in the air-formed film. For the AZ80 and AZ91D alloys, the amount of magnesium carbonate formed on the surface reached similar values to those of MgO and Mg(OH)₂. A linear relation between the amount of magnesium carbonate formed on the surface and the subsequent corrosion behaviour in the humid environment was found. The AZ80 alloy revealed the highest amount of magnesium carbonate in the air-formed film and the highest atmospheric corrosion resistance, even higher than the AZ91D alloy, indicating that aluminium distribution in the alloy microstructure influenced the amount of magnesium carbonate formed.     

Bi，Sb及稀土元素对AZ91镁合金高温性能影响机理研究

利用大角重位点阵概念建立了AZ91镁合金基体(α相)和镁［0001］对称倾斜晶界原子结构模型,应用实空间的连分数方法计算了体系的结构能,环境敏感镶嵌能以及相互作用能.结果发现,在镁合金基体中,Al和稀土形成团簇时比较稳定,Al,Bi或Sb与稀土形成团簇时不稳定.Bi或Sb和稀土元素同时存在于AZ91镁合金中时,一方面Bi或Sb将可与RE结合形成RE₂Bi(RE₂Sb)或RE-Bi(RE-Sb)化合物弥散分布于晶界,另一方面镁合金基体中会形成Al_{11关键词： 电子理论 晶界偏聚 合金元素 高温性能}     

Characterization of ceramic PVD thin films on AZ31 magnesium alloys

Ceramic thin films have been widely used to protect the metal substrate as coatings in the past years. In order to improve the poor corrosion resistance of AZ31 magnesium alloy, the study in this paper used the electron beam evaporation method to prepare ceramic PVD films on its surface with TiO₂ and Al₂O₃ as donors, respectively. Atomic force microscopy (AFM), scanning electron microscope (SEM), energy dispersive X-ray spectrometer (EDS), Auger electron spectroscopy (AES) and X-ray diffraction (XRD) were used to investigate the surface morphology, composition and microstructure of the thin films. Both films deposited on AZ31 took on compact top surface morphologies and grew as amorphous structures on substrate. AES test not only showed that films compositions deviated the standard stoichiometric ratios, but also found that element Mg diffused into films and existed as magnesium oxide in the TiO_x film as well as the AlO_x film. In the electrochemical corrosion test, the AlO_x coating on AZ31 exhibited the largest electrochemical impedance in a 3.5% NaCl solution. But it did not show better corrosion resistance than others for the poorer adhesion. Even if its thickness was small, the TiO_x coating on AZ31 exhibited the best corrosion resistance in this study. According to the observation and analysis, the damage of these films on AZ31 in aggressive solutions was mainly due to the existence of pores, microcracks, vacancies and poor adhesion between coating and substrate.     

Structure and mechanical properties of ceramic coatings fabricated by plasma electrolytic oxidation on aluminized steel

Ceramic coatings were formed by plasma electrolytic oxidation (PEO) on aluminized steel. Characteristics of the average anodic voltages versus treatment time were observed during the PEO process. The micrographs, compositions and mechanical properties of ceramic coatings were investigated. The results show that the anodic voltage profile for processing of aluminized steel is similar to that for processing bulk Al alloy during early PEO stages and that the thickness of ceramic coating increases approximately linearly with the Al layer consumption. Once the Al layer is completely transformed, the FeAl intermetallic layer begins to participate in the PEO process. At this point, the anodic voltage of aluminized steel descends, and the thickness of ceramic coating grows more slowly. At the same time, some micro-cracks are observed at the Al₂O₃/FeAl interface. The final ceramic coating mainly consists of γ-Al₂O₃, mullite, and α-Al₂O₃ phases. PEO ceramic coatings have excellent elastic recovery and high load supporting performance. Nanohardness of ceramic coating reaches about 19.6 GPa.     

Laser (a pulsed Nd:YAG) cladding of AZ91D magnesium alloy with Al and Al2O3 powders

The laser surface cladding of an AZ91D magnesium alloy with Al and Al₂O₃ powders was investigated using a pulsed Nd:YAG laser. The optimum ratio of Al to Al₂O₃ and the suitable range of laser processing parameters were identified. The resulting microstructure in the modified surface layer was examined and the wear resistance property was evaluated. The results show that the wear resistance of the laser treated samples was much superior to that of the untreated samples.     

The microstructure, mechanical and friction properties of protective diamond like carbon films on magnesium alloy

Protective hard coatings deposited on magnesium alloys are believed to be effective for overcoming their poor wear properties. In this work, diamond-like carbon (DLC) films as hard protective films were deposited on AZ91 magnesium alloy by arc ion plating under negative pulse bias voltages ranging from 0 to −200 V. The microstructure, composition and mechanical properties of the DLC films were analyzed by scanning electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and nanoindentation. The tribological behavior of uncoated and coated AZ91 magnesium alloy was investigated using a ball-on-disk tribotester. The results show that the negative pulse bias voltage used for film deposition has a significant effect on the sp³ carbon content and mechanical properties of the deposited DLC films. A maximum sp³ content of 33.3% was obtained at −100 V, resulting in a high hardness of 28.6 GPa and elastic modulus of 300.0 GPa. The DLC films showed very good adhesion to the AZ91 magnesium alloy with no observable cracks and delamination even during friction testing. Compared with the uncoated AZ91 magnesium alloy, the magnesium alloy coated with DLC films exhibits a low friction coefficient and a narrow, shallow wear track. The wear resistance and surface hardness of AZ91 magnesium alloy can be significantly improved by coating a layer of DLC protective film due to its high hardness and low friction coefficient.     

The resistance to wear and corrosion of laser-cladding Al2O3 ceramic coating on Mg alloy

The paper presents a study on the preparation of Al₂O₃ ceramic coating on AZ91HP Mg alloy by laser remelting plasma-sprayed coating. It was found that after laser remelting, the coating exhibited obvious layer-like characteristics due to influence of temperature distribution, thermophysical parameters and layer thickness. According to the microstructural difference, the coating can be divided into the melted zone with the α-Al₂O₃ column-like crystal, the sintered zone with flock-like structure, the residual plasma-sprayed zone with loosened structure. Because of the dense column-like crystal, the hardness, wear and corrosion resistance of the laser remelted coating are much higher than those of the plasma-sprayed coating and as-received Mg alloy.     

Characterization of calcium containing plasma electrolytic oxidation coatings on AM50 magnesium alloy

An attempt was made to produce calcium containing plasma electrolytic oxidation (PEO) coatings on AM50 magnesium alloy using an alkaline electrolyte. This study was performed in three alkaline electrolytes containing calcium hydroxide and sodium phosphate with three different mass ratios viz., 1:2.5, 1:5 and 1:7.5. All the three coatings produced were found to contain Ca and P in appreciable amounts. The concentration of P was found to be higher in the coatings obtained in the electrolytes with higher concentration of phosphate ions. Even though all the three coatings were found to be constituted with magnesium oxide and magnesium phosphate phases, X-ray diffraction analyses revealed that the phase composition was influenced by the phosphate ion concentration/conductivity of the electrolyte. Further, the PEO coating obtained in the 1:7.5 ratio electrolyte was found to contain di-calcium phosphate (monetite) and calcium peroxide phases, which were absent in the other two coatings. Potentiodynamic polarization studies performed in 0.1 M NaCl solution showed that the coatings obtained from the 1:5 ratio electrolyte possessed a superior corrosion resistance, which is attributed to the combined effect of thickness, compactness and phase/chemical composition of this coating.