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.     

Bioactivity,in-vitro corrosion behavior,and antibacterial activity of silver–zeolites doped hydroxyapatite coating on magnesium alloy

Mg-based alloys received significant attention for temporary implant applications while, their applications have been limited by high degradation rate. Therefore, silver–zeolite doped hydroxyapatite (Ag-Zeo-HAp) coating was synthesized on TiO₂-coated Mg alloy by physical vapour deposition (PVD) assisted electrodeposition technique to decrease the degradation rate of Mg alloy. X-ray diffraction (XRD) analysis and field emission scanning electron microscopy (FE-SEM) images showed the formation of a uniform and compact layer of Ag-Zeo-HAp with a thickness of 15 μm on the TiO₂ film with a thickness of 1 μm. The potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) tests indicated that corrosion resistance of Mg-Ca alloy was considerably increased by the Ag-Zeo-HAp coating. The bioactivity test in the simulated body fluid (SBF) solution showed that a dense and homogeneous bonelike apatite layer was formed on the Ag-Zeo-HAp surface after 14 d. Investigation of antibacterial activity via disk diffusion and spread plate methods showed that the Ag-Zeo-HAp coating had a significantly larger inhibition zone (3.86 mm) towards Escherichia coli (E. coli) compared with the TiO₂-coated Mg alloy (2.61 mm). The Ag-Zeo-HAp coating showed high antibacterial performance, good bioactivity, and high corrosion resistance which make it a perfect coating material for biomedical applications.     

Comparison of electrochemical corrosion behaviour of MgO and ZrO2 coatings on AM50 magnesium alloy formed by plasma electrolytic oxidation

Two types of PEO coatings were produced on AM50 magnesium alloy using pulsed DC plasma electrolytic oxidation process in an alkaline phosphate and acidic fluozirconate electrolytes, respectively. The phase composition and microstructure of these PEO coatings were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The corrosion behaviour of the coated samples was evaluated by open circuit potential (OCP) measurements, potentiodynamic polarization tests, and electrochemical impedance spectroscopy (EIS) in neutral 0.1 M NaCl solution. The results showed that PEO coating prepared from alkaline phosphate electrolyte consisted of only MgO and on the other hand the one formed in acidic fluozirconate solution was mainly composed of ZrO₂, MgF₂. Electrochemical corrosion tests indicated that the phase composition of PEO coating has a significant effect on the deterioration process of coated magnesium alloy in this corrosive environment. The PEO coating that was composed of only MgO suffered from localized corrosion in the 50 h exposure studies, whereas the PEO coating with ZrO₂ compounds showed a much superior stability during the corrosion tests and provided an efficient corrosion protection. The results showed that the preparation of PEO coating with higher chemical stability compounds offers an opportunity to produce layers that could provide better corrosion protection to magnesium alloys.     

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.     

Corrosion behaviour of Y2O3-ZrO2 coatings on IN713LC in a LiCl-Li2O molten salt

Hot corrosion studies were performed on superalloy specimens. The IN713LC superalloy were sprayed with an aluminized NiCrAlY-bond coat and then with an yttria-zirconia top coat. The bare superalloy reveals an obvious weight loss due to spalling of the scales by the rapid scale growth and thermal stress. The top coatings showed a much better hot corrosion resistance in the presence of LiCl-3 wt.% Li₂O molten salt when compared with those of the bare superalloy and the aluminized bond coatings. These coatings have been found to be beneficial for increasing hot corrosion resistance of structural materials for lithium molten salts.     

Structure and corrosion resistance of ZrO2 ceramic coatings on AZ91D Mg alloys by plasma electrolytic oxidation

The aim of this work is to study the structure and the corrosion resistance of the plasma electrolytic oxidation ZrO₂ ceramic coatings on Mg alloys. The ceramic coatings were prepared on AZ91D Mg alloy in Na₅P₃O₁₀ and K₂ZrF₆ solution by pulsed single-polar plasma electrolytic oxidation (PEO). The phase composition, morphology and element distribution in the coating were investigated by X-ray diffractometry, scanning electron microscopy and energy distribution spectroscopy, respectively. The results show that the coating thickness and surface roughness were increased with the increase of the reaction time. The ceramic coatings were of double-layer structure with the loose and porous outer layer and the compact inner layer. And the coating was composed of P, Zr, Mg and K, of which P and Zr were the main elements in the coating. P in the coating existed in the form of amorphous state, while Zr crystallized in the form of t-ZrO₂ and a little c-ZrO₂ in the coating. Electrochemical impedance spectra (EIS) and the polarizing curve tests of the coatings were measured through CHI604 electrochemical analyzer in 3.5% NaCl solution to evaluate the corrosion resistance. The polarization resistance obtained from the equivalent circuit of the EIS was consistent with the results of the polarizing curves tests.     

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.     

Enhancing Biocompatibility and Corrosion Resistance of Ti-6Al-4V Alloy by Surface Modification Route

Titanium (Ti) and its alloys are widely used as candidate materials for biomedical implants. Despite their good biocompatibility and corrosion resistance, these materials suffer from corrosion after implantation in biological environments. The aim of this research work is to study the effect of two coatings on biocompatibility and corrosion behavior of Ti-6Al-4V biomedical implant material. Hydroxyapatite (HA) and hydroxyapatite/titanium dioxide (HA/TiO₂) coatings were thermal-sprayed on Ti-6Al-4V substrates. In the latter case, TiO₂ was used as a bond coat between the substrate and HA top coat. The corrosion behavior of coated and un-coated samples in Ringer’s solution was studied by potentiodynamic and linear polarization techniques. Before and after corrosion testing, XRD and SEM/EDS techniques were used for the analysis of phases formed and to investigate microstructure/compositional changes in the coated specimens. The cellular response was analyzed by the MTT (microculture tetrazolium) assay. The results showed that both the HA, as well as, the HA/TiO₂ coatings significantly increased the corrosion resistance of the substrate material. The HA coating was found to be more biocompatible as compared to the un-coated and HA/TiO₂-coated Ti-6Al-4V alloy.     

In vitro corrosion resistance and antibacterial properties of layer-by-layer assembled chitosan/poly-L-glutamic acid coating on AZ31 magnesium alloys

Surface functionalization of magnesium (Mg) alloys is desired to obtain the surfaces with both improved corrosion resistance and antibacterial property. A corrosion-resistant and antimicrobial coating was prepared on Mg alloy surface by layer-by-layer (LbL) assembly of chitosan (CHI) and poly-L-glutamic acid (PGA) by electrostatic attraction. The functionalized surfaces of the Mg alloys were characterized by field-emission scanning electron microscopy (FE-SEM), Fourier transform infrared (FT-IR) spectroscopy and electrochemical tests. The bactericidal activity of the samples against Staphylococcus aureus was assessed by the zone of plate-counting method. The obtained coating on the Mg alloy substrates exhibits good corrosion resistance and antibacterial performance.     

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.     

Influence of potassium pyrophosphate in electrolyte on coated layer of AZ91 Mg alloy formed by plasma electrolytic oxidation

The effect of potassium pyrophosphate in the electrolyte on plasma electrolytic oxidation (PEO) process for AZ91 Mg alloy was investigated. The morphologies and chemical compositions of the coating layer on the AZ91 Mg alloy were evaluated and corrosion resistance was also estimated by potentiodynamic polarization analysis. The coating layer on AZ91 Mg alloy coated from the Bath 2 containing 0.03 mol/L of potassium pyrophosphate for 360 s exhibited considerably dense structure and contained 11%–18% (mass fraction) of phosphorous. The higher content of phosphorous of coating layer coated from Bath 2 could be detected at the bottom of oxide layer, which strongly implied that the phosphorous ion might be concentrated at the barrier layer. Corrosion potential of coating layer of AZ91 Mg alloy increased and corrosion current density decreased with increasing the concentration of potassium pyrophosphate. The polarization resistance (R_p) of coating layer of AZ91 Mg alloy coated from Bath 2 was 4.65×10⁷ Ω/cm², which was higher than that (R_p=3.56×10⁴ Ω/cm²) of the sample coated from electrolyte without potassium pyrophosphate. The coating layer coated from Bath 2 containing 0.03 mol/L potassium pyrophosphate exhibited the best corrosion resistance.     

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.     

Microstructure,anticorrosion, biocompatibility and antibacterial activities of extruded Mg−Zn−Mn strengthened with Ca

To find suitable biodegradable materials for implant applications, Mg?6Zn?0.3Mn?xCa (x=0, 0.2 and 0.5, wt.%) alloys were prepared by semi-continuous casting followed by hot-extrusion technique. The microstructure and mechanical properties of Mg?6Zn?0.3Mn?xCa alloys were investigated using the optical microscope, scanning electron microscope and tensile testing. Results indicated that minor Ca addition can slightly refine grains of the extruded Mg?6Zn?0.3Mn alloy and improve its strength. When 0.2 wt.% and 0.5 wt.% Ca were added, the grain sizes of the as-extruded alloys were refined from 4.8 to 4.6 and 4.2 μm, respectively. Of the three alloys studied, the alloy with 0.5 wt.% Ca exhibits better combined mechanical properties with the ultimate tensile strength and elongation of 334 MPa and 20.3%. The corrosion behaviour, cell viability and antibacterial activities of alloys studied were also evaluated. Increasing Ca content deteriorates the corrosion resistance of alloys due to the increase of amount of effective cathodic sites caused by the formation of more Ca₂Mg₆Zn₃ phases. Cytotoxicity evaluation with L929 cells shows higher cell viability of the Mg?6Zn?0.3Mn?0.5Ca alloy compared to Mg?6Zn?0.3Mn and Mg?6Zn?0.3Mn? 0.2Ca alloys. The antibacterial activity against Staphylococcus aureus is enhanced with increasing the Ca content due to its physicochemical and biological performance in bone repairing process.     

Recent advances in energy efficient PEO processing of aluminium alloys

Plasma electrolytic oxidation (PEO) coatings developed under voltage-controlled mode on various commercial wrought, gravity cast and rheocast aluminium alloys were discussed with respect to enhancement of their tribological and corrosion performance and minimization of the PEO energy consumption. It is demonstrated that use of conventional porous anodic film precursors reduces the PEO energy consumption by up to 50%. The wear of 6082 alloy with PEO coatings with added α-Al₂O₃ particles is two times lower compared with electrolytic hard chrome. The long-term corrosion resistance of the PEO-coated A356 rheocast alloy is enhanced via use of a precursor and hydrophobic post-treatment.     

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.     

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.     

In-situ layered double hydroxides on Mg−Ca alloy: Role of calcium in magnesium alloy

Mg?Al layered double hydroxides (LDHs), produced on cast Mg?xCa (x=0.5, 0.8, 2.0, wt.%) alloys by an in-situ growth method, showed good corrosion resistance compared to the bare magnesium substrate. The influence mechanism of the second phase (Mg₂Ca) on LDHs production was investigated. Increasing Ca content increased the amount of Mg₂Ca, decreasing the grain size and the corrosion rate of the alloys. The increased amount of the second phase particles and the grain refinement promoted the growth of LDHs, and thus led to the decreasing of corrosion rate of the Mg?xCa alloys with LDHs. A higher Mg₂Ca amount resulted in forming fluffy LDHs. Due to the dual effects of the second phase (Mg₂Ca) for LDHs growth and microgalvanic corrosion, LDHs/Mg?0.8Ca showed the lowest corrosion rate.     

Investigation of hybrid PEO coatings on AZ31B magnesium alloy in alkaline K<Subscript>2</Subscript>ZrF<Subscript>6</Subscript>–Na<Subscript>2</Subscript>SiO<Subscript>3</Subscript> electrolyte solution

Detail study of the PEO coatings produced on AZ31B magnesium alloy in Na₂SiO₃–K₂ZrF₆-based electrolyte solution was carried out in this work. ZrO₂, MgF₂, MgO and Mg₂SiO₄ were observed as the major phases in the coatings. Electrolytic decomposition and then the severe thermochemical environment provoked various Zr–F–Mg based complexes in the coatings. From the surface analysis, various structures e.g, nano-grains, pores and volcano shape sintered material were evidenced. Using Vicker hardness test, maximum hardness was recorded as ~1280 HV. Potentiodynamic polarization technique in 3.5 wt % NaCl solution was used to predict the corrosion performances of the specimens. Among the coated samples, highest corrosion resistance was recorded to be ~223.5 × 10³ kΩ/cm² for 15 min coatings.     

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.     

Effects of bond coat preoxidation on the properties of ZrO2-8wt.% Y2O3/Ni-22Cr-10Al-1Y thermal-barrier coatings

Plasma-sprayed thermal barrier coatings (TBCs) consist of an intermediate MCrAlY bond coat to protect the substrate superalloy from oxidation/hot corrosion and a thermal insulating zirconia-based ceramic top coat. This system is developed for advanced turbine-engine, hot-section components. In this study the as-sprayed Ni-22Cr-10Al-1Y bond coat was subjected to preoxidation treatment at 1000° C for 1, 50, 100, and 200 hr, also at 1100°C, 1200°C and 1300°C for 1 hr to form an oxide scale before subsequent deposition of a ZrO₂-8wt.% Y₂O₃ top coat. The oxidation kinetics were measured, and the phase constitution and morphology of pregrown oxides on the Ni-22Cr-1Y bond coat were analyzed by x-ray diffractometer and SEM/EDS to elucidate the improvement and degradation mechanisms of the new system. The results of the experiments in this study showed that the tentative ZrO₂-8wt.% Y₂O₃ TBC specimens with preoxidized Ni-22Cr-10Al-1Y bond coat, when properly processed, exhibited lower oxidation rates and generally longer lifetime compared with traditional TBC specimens.