Development of HA-CNTs composite coating on AZ31 magnesium alloy by cathodic electrodeposition. Part 1: Microstructural and mechanical characterization

Magnesium alloys are considered as a new class of biodegradable alloys having many favorable properties to overcome the problems of currently used biomedical materials. Hydroxyapatite (HA) containing carbon nano-tubes (CNTs), with concentration ranging from 0 to 1.5?wt.%, coated on AZ31 magnesium alloy by direct and pulse cathodic electrodeposition methods. The coating properties including phase analysis, chemical bonding, morphology, and thickness were characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and field emission scanning electron microscopy (FESEM), respectively. Nano-indentation, micro-hardness and adhesion tests were also used to evaluate the mechanical properties of the coatings. The results showed that a dense and fine coating structure was obtained by pulse deposition method. Moreover, the presence of carbon nanotubes in composite coating increased crystallization, presumably due to the increase in nucleation sites affecting the growth direction of hydroxyapatite crystals. The optimum condition having high crystallinity (71.2%) along with an uniform structure was the pulse deposited hydroxyapatite coating containing 1?wt.% CNTs. The elastic modulus and hardness of this sample increased by approximately 42% and 130% compared to the pure HA coating, respectively. Furthermore, the fracture toughness of pulse deposited HA–1wt % CNTs on AZ31 alloy reaches 1.96 ± 0.72MPa/m^0.5 which is in the range of compact bone.     

Corrosion protection behavior of AZ31 magnesium alloy with cathodic electrophoretic coating pretreated by silane

As an alternative process to phosphate and chromate conversion coatings, silane pretreatment was used to improve the performance of cathodic electrophoretic coating (E-coat) on AZ31 Mg alloy in this study. The galvanic corrosion behavior of AZ31 Mg alloy with E-coat coupled with Q235 steel was investigated. Compared to bare Mg alloy and Mg alloy with conventional painting, the corrosion properties of the AZ31 Mg alloy pretreated with silane and subsequently E-coated were studied during salt solution immersion and salt spray testing. The surface morphologies of the Mg alloy were examined in detail after immersion in NaCl solution for different times using digital photography and scanning electron microscopy (SEM). The corrosion current density of the specimens was characterized by DC polarization tests. It was found that silane pretreatment of AZ31 Mg alloy followed by subsequent E-coat led to much better corrosion protection than that without silane treatment. The silane pretreatment and E-coat delayed the galvanic corrosion of Mg alloy coupled with 235 steel bolts.     

Hydroxyapatite-carboxymethyl cellulose-graphene composite coating development on AZ31 magnesium alloy: Corrosion behavior and mechanical properties

In this study, hydroxyapatite (HA) coatings containing carboxymethyl cellulose (CMC) and graphene (Gr) were developed on AZ31 magnesium alloy through two-step electrophoretic deposition method. The morphology and chemical bonding of coatings were characterized and also the phase identification was done using scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction, respectively. Moreover, the corrosion behavior of the applied coatings was compared with the bare AZ31 Mg alloy substrate in the simulated body fluid by the means of potentiodynamic polarization test and electrochemical impedance spectroscopy. Obtained results revealed that the novel HA-CMC-Gr coating possesses the highest corrosion resistance compared to the HA, HA-CMC, and HA-Gr coatings due to its uniform and compact structure. To investigate the mechanical properties and to elucidate the effect of CMC on the adhesion of coating-alloy interface, pull-off test was employed, where results demonstrated that the addition of CMC increases the adhesion force from 1.06 MPa to 1.62 MPa. Besides, the modulus of elasticity and the hardness of HA and HA-Gr composite coatings were compared by applying nanoindentation test. Interestingly, it is detected that the presence of Gr has considerably increased the elastic modulus of the coating by approximately 30% in comparison to the pure HA coating.     

Fault-tolerant hybrid epoxy-silane coating for corrosion protection of magnesium alloy AZ31

In this work, a hybrid epoxy-silane coating was developed for corrosion protection of magnesium alloy AZ31. The average thickness of the film produced by dip-coating procedure was 14 μm. The adhesion strength of the epoxy-silane coating to the Mg substrate was evaluated by pull-off tests and was found to be higher than 16 MPa both in dry and wet conditions. The hybrid epoxy-silane coating showed high corrosion resistance both when intact and when punched through by a needle. The low frequency impedance of intact coating was higher than 1 GΩ cm² after one month of immersion in 3.5% NaCl solution. Both, artificially induced defects and corrosion sites that appeared on the metal surface did not propagate. Their passivation behavior, that we call fault-tolerance, was observed by EIS, SVET-SIET and SEM-EDS. It was ascribed to the good adhesion, high coating integrity and corrosion inhibiting effect provided by diethylenetriamine used as epoxy hardener.     

Corrosion behaviors of Zn/Al-Mn alloy composite coatings deposited on magnesium alloy AZ31B (Mg-Al-Zn)

After being pre-plated a zinc layer, an amorphous Al-Mn alloy coating was applied onto the surface of AZ31B magnesium alloy with a bath of molten salts. Then the corrosion performance of the coated magnesium alloy was examined in 3.5% NaCl solution by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The results showed that the single Zn layer was active in the test solution with a high corrosion rate while the Al-Mn alloy coating could effectively protect AZ31B magnesium alloy from corrosion in the solution. The high corrosion resistance of Al-Mn alloy coating was ascribed to an intact and stable passive film formed on the coating. The performances of the passive film on Al-Mn alloy were further investigated by Mott-Schottky curve and X-ray photoelectron spectroscopy (XPS) analysis. It was confirmed that the passive film exhibited n-type semiconducting behavior in 3.5% NaCl solution with a carrier density two orders of magnitude less than that formed on pure aluminum electrode. The XPS analysis indicated that the passive film was mainly composed of AlO(OH) after immersion for long time and the content of Mn was negligible in the outer part of the passive film. Based on the EIS measurement, electronic structure and composition analysis of the passive film, a double-layer structure, with a compact inner oxide and a porous outer layer, of the film was proposed for understanding the corrosion process of passive film, with which the experimental observations might be satisfactorily interpreted.     

Electrochemical study of modified bis-[triethoxysilylpropyl] tetrasulfide silane films applied on the AZ31 Mg alloy

This work investigates the protective behaviour of bis-[triethoxysilylpropyl] tetrasulfide silane pre-treatments on the AZ31 Mg alloy. The silane solution was modified by the addition of cerium nitrate or lanthanum nitrate in order to introduce corrosion inhibition properties in the silane film.The corrosion behaviour of the pre-treated AZ31 magnesium alloy was studied during immersion in 0.005 M NaCl solution, using electrochemical impedance spectroscopy and the scanning vibrating electrode technique (SVET). The electrochemical experiments showed that the presence of cerium ions or lanthanum ions improve the protective behaviour of the silane film. The SVET experiments evidenced that the presence cerium in the silane film led to an important reduction of the corrosion activity.The results demonstrate that either cerium ions or lanthanum ions can be used as additives to the silane solutions to improve the performance of the pre-treatments for the AZ31 magnesium alloy.     

Preparation and corrosion resistance of a self-sealing hydroxyapatite- MgO coating on magnesium alloy by microarc oxidation

An ideal self-sealing hydroxyapatite (HA)-MgO coating was designed on an AZ31 Mg alloy by one-step microarc oxidation (MAO) with the addition of HA nanoparticles into a base electrolyte. The formation mechanism of the self-sealing HA-MAO coating was discussed. The effect of the nano-HA addition on the corrosion resistance of the MAO coating was evaluated by corrosion tests in Hank's solution. The results show that HA nanoparticles inertly incorporated into the MAO coating during the process of coating growth. HA and MgO were the main constituents of the HA-MAO coating. The HA nanoparticles were absent in the inner barrier layer but concentrated in the outer porous layer. In addition, HA nanoparticles accumulated much more inside coating defects than in the other zones, which resulted in the nearly ideal sealing of micropores on the coating surface. By forming a denser and more stable outer layer, the incorporation of HA nanoparticles greatly enhanced the anti-corrosion properties of the MAO coating.     

Electrochemical impedance behavior of graphite-dispersed electrically conducting acrylic coating on AZ31 magnesium alloy in 3.5 wt.% NaCl solution

The paper deals with understanding the electrochemical impedance behavior of (a) chromate coating (b) electrically conducting polymer coating and (c) polyurethane coating under different combinations applied over AZ31 magnesium alloy in an effort to develop a conducting organic coating that can offer corrosion protection as well as electrical conductivity. The study indicates that dispersion of graphite in acrylic coating though significantly brings down the electrical resistance; application of such a coating on the magnesium alloy does not offer good resistance against corrosion. In order to gain both the corrosion resistance as well as electrical conductivity an intermediate coating such as polyurethane needs to be provided. The paper discusses the electrochemical impedance behavior of the above coatings.     

Deposition temperature effect on sputtered hydroxyapatite coatings prepared on AZ31B alloy substrate

The corrosion of Mg alloys is a provocative topic and it is still a challenge to find a solution for the improvement of their degradation rate into solution found in human body (Simulated Body Fluid, SBF). The aim of the present paper is to coat AZ31B alloy by hydroxyapatite (HAp) as a possible solution in order to change its degradation behaviour for medical implants. Since the Mg alloy is sensible to temperature while the HAp properties depend on the deposition temperature, in this study, the effect of deposition temperature on the properties of the AZ31Balloy was evaluated. The HAp coatings were prepared using the RF magnetron sputtering technique, ranging the temperature from the room one to 400 °C. It was found that the grain size of the investigated Mg alloy increased more than 100% when the deposition temperature was increased. By increasing the temperature, the hardness level was reduced of about 15%. All HAp coatings revealed corrosion behaviour much better than the uncoated AZ31B alloy; in particular, the coating deposited at 200 °C exhibited the best corrosion behavior. Moreover, the best protection to the corrosive attack of SBF was found for the HAp coating deposited at 200 °C (97.3%), which was also characterized by the lowest porosity. To conclude, HAp coatings can be used to improve the properties of AZ31B alloys, but just up to 200 °C; beyond this temperature, the mechanical and the anticorrosion properties are lost.     

Preparation and characterization of a double-layer coating on magnesium alloy AZ91D

A double-layer coating was prepared on AZ91D alloy by plasma electrolytic oxidation (PEO) plus electroless plating (EP). The plasma eletrolytic oxidation film was prepared in a silicate bath as an inner layer of the coating. Electroless plated Ni-P layer grew from the pores of the PEO film in a nickelous acetate bath and formed as the outer layer of the coating. The microstructure and crystallographic structure was observed with FESEM and XRD. The corrosion resistance of the double-layer coating was evaluated by means of chronopotentiometric (E-t), potentiodynamic polarization (E-i), neutral salt spray test and electrochemical impedance spectroscopy (EIS) test. Compared with the data of as-cast AZ91D magnesium, the open circuit potential of the double-layer coated AZ91D alloy increased by 1.1815 V, while the self-corrosion current density decreased by two orders of magnitude. E-i, EIS result showed that the corrosion resistance of magnesium alloy AZ91D was improved by the double-layer coating. The salt spray test and polarization test results show that the pitting corrosion resistance of AZ91D alloy was improved greatly. An equivalent circuit was proposed to fit the impedance diagrams of AZ91D alloy with the coating.     

Localized electrochemical study of corrosion inhibition in microdefects on coated AZ31 magnesium alloy

In the present work corrosion inhibition in microdefects of protective coatings on magnesium alloy was studied by SVET (scanning vibrating electrode technique) and SIET (scanning ion-selective electrode technique) in 0.05 M NaCl. Mg²⁺- and pH-selective microelectrodes were developed to be used by SIET. The microelectrodes were characterized from the standpoint of properties important for corrosion applications, aiming at the reliable functioning during measurements. The combination of SVET and SIET demonstrated to be a useful approach to investigate the inhibition of corrosion processes in microdefects on coated AZ31. In this paper the corrosion inhibiting properties of 1,2,4,-triazole, F⁻ and Ce³⁺ on AZ31 alloy were analyzed. According to the results, 1,2,4-triazole in concentration of 0.01 M showed the highest inhibition efficiency among the studied inhibitors and was able to prevent the increase of pH in the corroding defects, by keeping the corrosion activity on a very low level during the tested immersion period.     

Electrochemical corrosion behavior of composite coatings of sealed MAO film on magnesium alloy AZ91D

Protective composite coatings were prepared on magnesium alloy AZ91D by micro-arc oxidation (MAO) treatment plus a top coating with sealing agent using multi-immersion technique under low-pressure conditions. The corrosion resistance of AZ91D alloy with composite coatings was superior evidently to that with merely MAO film. SEM observations revealed that the sealing agent was integrated with MAO film by physically interlocking; therewith covered uniformly the surface as well as penetrated into pores and micro-cracks of MAO film. The anti-corrosion properties in 3.5% NaCl solution of the composite coatings were evaluated by using electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements. Based on the results of chronopotentiometric (E ∼ t) and EIS measurements for long time immersion in 3.5% NaCl solution, appropriate equivalent circuits for the composite coatings system were proposed. It follows that due to the blocking effect of the sealing agent in pores and cracks in MAO film, the composite coatings can suppress the corrosion process by holding back the transfer or diffusion of electrolyte and corrosion products between the composite coatings and solution during immersion.     

Influence of rare earth Y on the corrosion behavior of as-cast AZ91 alloy

The influence of different contents of rare earth Y on the corrosion resistance of AZ91 alloy was investigated by the salt spray test and electrochemical measurements. It was found that the proper amount of Y was effective on improving the corrosion resistance of AZ91 alloy. The optimal modification effect was obtained when the Y content in the alloys was 0.3 wt.%. However, with the increase of rare earth Y, the corrosion rate became bigger slightly, and further addition of Y content over 0.3 wt.% resulted in the increment of the corrosion rate. It is suggested that the excessive rare earth Y can reduce the corrosion resistance of AZ91 alloy.     

Enhanced corrosion resistance of hydroxyapatite/magnesium-phosphate-composite-coated AZ31 alloy co-deposited by electrodeposition method

Magnesium-phosphate-doped hydroxyapatite (HAMP, Mg₃(PO₄)₂-Ca₁₀(PO₄)₆(OH)₂) and magnesium-hydrogen-phosphate-doped dicalcium-phosphate-dehydrate (DCPD-MHP, MgHPO₄-CaHPO₄) composite coatings were successfully electrodeposited onto an AZ31 alloy, and their corrosion behaviour was evaluated via electrochemical and in vitro degradation tests. In addition, the stability of the coatings was evaluated via these electrochemical tests. The results showed that the corrosion resistance and stability of the composite coatings were both significantly higher than those of single coatings; this greater resistance and stability resulted from the denser and more uniform structures of the composite coatings.     

Corrosion protection of AZ91D magnesium alloy with sol–gel coating containing 2-methyl piperidine

Sol–gel coatings were prepared using 3-glycidoxypropyltrimethoxysilane (GPTMS) and tetraethoxysilane (TMOS) as precursors, diethylentriamine as curing agent. Inhibition effect of 2-methyl piperidine on AZ91D in 0.005%, 0.05% and 0.5% (wt.%) NaCl solution is investigated. Potentiodynamic polarization tests revealed that 2-methyl piperidine significantly decreased the anodic activity of AZ91D especially at high concentration. Corrosion behaviors of sol–gel coatings incorporated with 2-methyl piperidine on AZ91D in the Harrison's solution were analyzed using electrochemical impedance spectroscopy (EIS). EIS results showed the corrosion resistance of sol–gel coatings and sol–gel sealed phosphate conversion coating on AZ91D were significantly improved through addition of 2-methyl piperidine. Fourier transform infrared spectra (FT-IR) confirmed that the 2-methyl piperidine was compatible with sol–gel matrix.     

Novel hybrid sol-gel coatings for corrosion protection of AZ31B magnesium alloy

This work aims to develop and study new anticorrosion films for AZ31B magnesium alloy based on the sol-gel coating approach.Hybrid organic-inorganic sols were synthesized by copolymerization of epoxy-siloxane and titanium or zirconium alkoxides. Tris(trimethylsilyl) phosphate was also used as additive to confer additional corrosion protection to magnesium-based alloy. A sol-gel coating, about 5-μm thick, shows good adhesion to the metal substrate and prevents corrosion attack in 0.005 M NaCl solution for 2 weeks. The sol-gel coating system doped with tris(trimethylsilyl)-phosphate revealed improved corrosion protection of the magnesium alloy due to formation of hydrolytically stable Mg-O-P chemical bonds.The structure and the thickness of the sol-gel film were characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The corrosion behaviour of AZ31B substrates pre-treated with the sol-gel derived hybrid coatings was tested by electrochemical impedance spectroscopy (EIS). The chemical composition of the silylphosphate-containing sol-gel film at different depths was investigated by X-ray photoelectron spectroscopy (XPS) with depth profiling.     

Microstructure and properties of Nb2O5/Mg gradient coating on AZ31 magnesium alloy by magnetron sputtering

A Nb₂O₅/Mg gradient coating was synthesized on AZ31 magnesium alloy through the magnetron sputtering technique. The microstructure and properties of the coating were investigated by SEM, AFM, EDS and XPS, scratch tester, nanoindenter, friction tester, and electrochemical workstation, with a Nb₂O₅ monolayer coating as a control. The results show that all the as-disposed films have an amorphous columnar structure, and can improve the mechanical, anti-wear and anti-corrosion properties of AZ31 magnesium alloy. The Nb₂O₅/Mg gradient coating shows a gradual change in chemical composition through its depth, decreasing the residual stress of the coating/substrate system, thus reducing the risk of film cracking, and increasing compactness of the coating. Compared with a Nb₂O₅ single-layer film of the same thickness, the gradient coating exhibits increased adhesion, H/E and H³/E² increased by about 16 times, 7.8% and 100% respectively, and a wear rate reduced by more than an order of magnitude. In addition, the gradient coating has better corrosion resistance, having a two orders of magnitude lower current density and one order of magnitude higher polarization resistance. This study provides a workable strategy for improving the performance of ceramic coatings on magnesium alloy, for medical applications.     

Electrochemical deposition and characterization of ZnCo alloys and corrosion protection by electrodeposited epoxy coating on ZnCo alloy

ZnCo alloys electrochemically deposited on steel under various deposition conditions were investigated. The influence of deposition current density, temperature and composition of deposition solution on the phase structure and corrosion properties of ZnCo alloys were studied. It was found that ZnCo alloy obtained from chloride solution at 5 A dm⁻² showed the best corrosion properties, so this alloy was chosen for further examination. Epoxy coating was electrodeposited on steel and steel modified by ZnCo alloy using constant voltage method. The effect of ZnCo alloy on the corrosion behavior of the protective system based on epoxy coating is interpreted in terms of electrochemical and transport properties, as well as of thermal stability.     

聚苯胺涂层对AZ91D镁合金防护性能的研究

在镁合金表面用循环伏安法制备了聚苯胺涂层,并对其防护性能进行了深入研究。考察了制备工艺对涂层性能的影响,如:扫描电位区间、扫描速率、循环圈数等。研究结果表明,聚苯胺涂层制备工艺对其防护性能影响较大。在0.2 M苯胺+0.5 M水杨酸钠溶液中,采用循环电位区间为-0.2~1.8 V,扫速为30 m V/s,连续扫描10圈的工艺参数,有利于得到与镁合金基材结合良好、均匀致密的聚苯胺膜层。红外光谱和扫描电镜测试结果表明,该涂层为均匀片状结构的聚苯胺。     

Corrosion resistance and chemical stability of super-hydrophobic film deposited on magnesium alloy AZ31 by microwave plasma-enhanced chemical vapor deposition

A super-hydrophobic film was successfully deposited on magnesium alloy AZ31 by the microwave plasma-enhanced chemical vapor deposition (MPECVD) process. The film surface showed a static water contact angle of more than 150°. The hydrophobicity and root mean square roughness of the film surface increased with an increase in deposition time. The anticorrosion resistance of the deposited film was estimated by electrochemical impedance spectroscopy (EIS) measurements. The EIS measurements and appropriate equivalent circuit models revealed that the super-hydrophobic film considerably improved the anticorrosion resistant performance of magnesium alloy AZ31. The anticorrosion mechanism of the super-hydrophobic film was also considered. Moreover, the chemical stability of the super-hydrophobic film in acidic, neutral, and alkaline aqueous solutions was investigated. The super-hydrophobic film showed high chemical stability in acidic and neutral aqueous solutions.