Enhancing corrosion resistance of plasma electrolytic oxidation coatings on AM50 Mg alloy by inhibitor containing Ba(NO_(3))_(2) solutions

To enhance the long-term corrosion resistance of the plasma electrolytic oxidation(PEO)coating on the magnesium(Mg)alloy,an inorganic salt combined with corrosion inhibitors was used for posttreatment of the coating.In this study,the corrosion performance of PEO-coated AM50 Mg was significantly improved by loading sodium lauryl sulfonate(SDS)and sodium dodecyl benzene sulf-onate into Ba(NO_(3))_(2) post-sealing solutions.Scanning electron microscopy,X-ray photoelectron spectroscopy,X-ray diffraction,Fourier transform infrared spectrometer,and ultraviolet-visible analyses showed that the inhibitors enhanced the incorporation of BaO_(2) into PEO coatings.Electrochemical impedance showed that post-sealing in Ba(NO_(3))_(2)/SDS treatment enhanced corrosion resistance by three orders of magnitude.The total impedance value remained at 926Ω·cm^(2)after immersing in a 0.5wt%NaCl solution for 768 h.A salt spray test for 40 days did not show any obvious region of corrosion,proving excellent post-sealing by Ba(NO_(3))_(2)/SDS treatment.The corrosion resistance of the coating was enhanced through the synergistic effect of BaO2 pore sealing and SDS adsorption.

NaF assisted preparation and the improved corrosion resistance of high content ZnO doped plasma electrolytic oxidation coating on AZ31B alloy

In the present research,the NaF assisted plasma electrolytic oxidation(PEO)is designed to fabricate the high-content ZnO nanoparti-cles doped coating on AZ31B alloy.The microstructure,phase constituents and corrosion behavior of the PEO coatings are investigated systematically.The results reveal that the introduction of NaF promotes the formation of MgF2 nanophases in the passivation layer on Mg alloy,decreasing the breakdown voltage and discharge voltage.As a result,the continuous arcing caused by high discharge voltage is alleviated.With the increasing of NaF content,the Zn content in the PEO coating is enhanced and the pore size in the coating is decreased correspondingly.Due to the high-content ZnO doping,the PEO coating protected AZ31B alloy demonstrates the better corrosion resistance.Compared with the bare AZ31B alloy,the high-content ZnO doped PEO coated sample shows an increased corrosion potential from-1.465 V to-1.008 V,a decreased corrosion current density from 3.043×10^(-5) A·cm^(-2) to 3.960×10^(-8) A·cm^(-2) and an increased charge transfer resistance from 1.213×10^(2) ohm·cm^(2) to 2.598×10^(5) ohm·cm^(2).Besides,the high-content ZnO doped PEO coated sample also has the excellent corrosion resistance in salt solution,exhibiting no obvious corrosion after more than 2000 h neutral salt spraying and 28 days’immersion testing.The improved corrosion resistance can be ascribed to the relative uniform distribution of ZnO in PEO coating which can transform to Zn(OH)2 and form a continuous protective layer along the corrosion interface.

Self-repairing Al_(2)O_(3)-TiO_(2)coatings fabricated through plasma electrolytic oxidation with various cathodic pulse parameters

The influence of cathodic pulse parameters was evaluated on plasma electrolytic oxidation(PEO)coatings grown on 7075 aluminum alloy in a silicate-based electrolyte containing potassium titanyl oxalate(PTO)using pulsed bipolar waveforms with various cathodic duty cycles and cathodic current densities.The coatings were characterized by SEM,EDS,and XRD.EIS was applied to investigate the electrochemical properties.It was observed that the increase of cathodic duty cycle and cathodic current density from 20%and 6 A/dm^(2) to 40%and 12 A/dm^(2) enhances the growth rate of the inner layer from 0.22 to 0.75μm/min.Adding PTO into the bath showed a fortifying effect on influence of the cathodic pulse and the mentioned change of cathodic pulse parameters,resulting in an increase of the inner layer growth rate from 0.25 to 1.10μm/min.Based on EDS analysis,Si and Ti were incorporated dominantly in the upper parts of the coatings.XRD technique merely detectedγ-Al_(2)O_(3),and there were no detectable peaks related to Ti and Si compounds.However,the EIS results confirmed that the incorporation of Ti^(4+)into alumina changed the electronic properties of the coating.The coatings obtained from the bath containing PTO using the bipolar waveforms with a cathodic duty cycle of 40%and current density values higher than 6 A/dm^(2) showed highly appropriate electrochemical behavior during 240 d of immersion due to an efficient repairing mechanism.Regarding the effects of studied parameters on the coating properties,the roles of cathodic pulse parameters and PTO in the PEO process were highlighted.

A super wear-resistant coating for Mg alloys achieved by plasma electrolytic oxidation and discontinuous deposition

Magnesium alloys are lightweight materials with great potential,and plasma electrolytic oxidation(PEO)is effective surface treatment for necessary improvement of corrosion resistance of magnesium alloys.However,the∼14µm thick and rough PEO protection layer has inferior wear resistance,which limits magnesium alloys as sliding or reciprocating parts,where magnesium alloys have special advantages by their inherent damping and denoising properties and attractive light-weighting.Here a novel super wear-resistant coating for magnesium alloys was achieved,via the discontinuous sealing(DCS)of a 1.3µm thick polytetrafluoroethylene(PTFE)polymer layer with an initial area fraction(A_(f))of 70%on the necessary PEO protection layer by selective spraying,and the wear resistance was exceptionally enhanced by∼5500 times in comparison with the base PEO coating.The initial surface roughness(Sa)under PEO+DCS(1.54µm)was imperfectly 59%higher than that under PEO and conventional continuous sealing(CS).Interestingly,DCS was surprisingly 20 times superior for enhancing wear resistance in contrast to CS.DCS induced nano-cracks that splitted DCS layer into multilayer nano-blocks,and DCS also provided extra space for the movement of nano-blocks,which resulted in rolling friction and nano lubrication.Further,DCS promoted mixed wear of the PTFE polymer layer and the PEO coating,and the PTFE layer(HV:6 Kg·mm^(−2),A_(f):92.2%)and the PEO coating(HV:310 Kg·mm^(−2),A_(f):7.8%)served as the soft matrix and the hard point,respectively.Moreover,the dynamic decrease of Sa by 29%during wear also contributed to the super wear resistance.The strategy of depositing a low-frictional discontinuous layer on a rough and hard layer or matrix also opens a window for achieving super wear-resistant coatings in other materials.

The mechanism for tuning the corrosion resistance and pore density of plasma electrolytic oxidation(PEO)coatings on Mg alloy with fluoride addition

Here we prepared PEO coatings on Mg alloys in silicate-NaOH-phosphate electrolyte containing different concentrations of NaF addition.The detailed microstructural characterizations combining with potentiodynamic polarization and electrochemical impedance spectra(EIS)were employed to investigate the roles of fluoride in the growth and corrosion properties of PEO coating on Mg.The result shows the introduction of NaF led to a fluoride-containing nanolayer(FNL)formed at the Mg/coating interface.The FNL consists of MgO nanoparticles and insoluble MgF_(2)nanoparticles(containing rutile phase and cubic phase).The increase in the NaF concentration of the electrolyte increases the thickness and the MgF_(2)content in the FNL.When anodized in the electrolyte containing 2 g/L NaF,the formed FNL has the highest thickness of 100-200 nm along with the highest value of x of∼0.6 in(MgO)_(1-x)(MgF_(2))x resulted in the highest corrosion performance of PEO coating.In addition,when anodized in the electrolyte containing a low NaF concentration(0.4-0.8 g/L),the formed FNL was thin and discontinuous,which would decrease the pore density and increase the coating's uniformness simultaneously.

Preparation and property of self-sealed plasma electrolytic oxide coating on magnesium alloy

Plasma electrochemical oxidation (PEO) is a surface modification technology to form ceramic coatings on magnesium alloys However,its application is limited due to its defects.This work reports a novel preparation of in-situ sealing of PEO coatings by four-layer voltage and sol addition.The morphology and structure were characterized by scanning electron microscopy (SEM),energy dispersive X-ray spectroscopy (EDS),and X-ray diffractometer (XRD).Image-Pro Plus 6.0 was used to determine the porosity of the coating,which was decreased from 8.53%to 0.51%.Simultaneously,the coating thickness was increased by a factor of four.The anti-corrosion performance of each sample was evaluated using electrochemical tests,and the findings revealed that the corrosion current density of coatings (i_(corr)) of the samples were lowered from 9.152×10^(-2) to 6.152×10^(-4) mA·cm^(-2),and the total resistance (R_(T)) of the samples were enhanced from 2.19×10^(4) to 2.33×10^(5)Ω·cm^(2).The salt spray test used to simulate the actual environment showed that corrosion points appeared on the surface of the coating only at the 336 h.In addition,the mechanism of PEO self-sealing behavior was described in this article.

A self-healing and bioactive coating based on duplex plasma electrolytic oxidation/polydopamine on AZ91 alloy for bone implants

Magnesium(Mg) alloys are well-known in biomedical materials owing to their elastic module near to bone, biocompatibility and biodegradation properties. Nevertheless, poor corrosion resistance hinders their biomedical applications. Besides, it is necessary to endow Mg alloys with bioactive property, which is crucial for temporary bone implants. Here, a self-healing, corrosion resistant and bioactive duplex coating of plasma electrolytic oxidization(PEO)/polydopamine(PDA) is applied on AZ91 substrate using PEO and subsequent electrodeposition process. Moreover, the role of different electrodeposition times(60 s, 120 s) and dopamine concentrations(1 and 1.5 mg/ml) to improve corrosion resistance, bioactivity, biocompatibility and self-healing property and its mechanism are investigated. The results indicate that the PEO coating is efficiently sealed by the PDA, depending on the electrodeposition parameters. Noticeably, electrodeposition for 120 s in dopamine concentration of 1 mg/ml(120T-1C) results in the formation of uniform and crack-free PDA coating. Duplex PEO/PDA coatings reveal high bioactivity compared to PEO coating, owing to electrostatic interaction between PDA top-layer and calcium and phosphate ions as well as high hydrophilicity of coatings. In addition, duplex PEO/PDA coatings also show improved and more stable protective performance than the PEO and bare alloy, depending on the PDA deposition parameters. Noticeably, the corrosion current density of the 120T-1C decreases one orders of magnitude compared to PEO. In addition, the presence of a broad passivation region in the anodic polarization branch shows durable self-healing property via Zipper-like mechanism, demonstrating the duplex coating could preserve promising corrosion resistance.Furthermore, the cytocompatibility of duplex coated samples is also confirmed via interaction with MG63 cells. In summary, the PEO/PDA coating with great corrosion protection, self-healing ability, bioactivity and biocompatibility could be a promising candidate for degradable magnesium-based implants.

Incorporation of LDH nanocontainers into plasma electrolytic oxidation coatings on Mg alloy

In-situ incorporation of layered double hydroxides(LDH)nanocontainers into plasma electrolytic oxidation(PEO)coatings on AZ91 Mg alloy has been achieved in the present study.Fumarate was selected as Mg corrosion inhibitor for exchange and intercalation into the nanocontainers,which were subsequently incorporated into the coating.It was found that the thickness and compactness of the coatings were increased in the presence of LDH nanocontainers.The corrosion protection performance of the blank PEO,LDH containing PEO and inhibitor loaded coatings was evaluated by means of polarization test and electrochemical impedance spectroscopy(EIS).The degradation process and corrosion resistance of PEO coating were found to be greatly affected by the loaded inhibitor and nanocontainers by means of ion-exchange when corrosion occurs,leading to enhanced and stable corrosion resistance of the substrate.

Corrosion behavior of composite coatings containing hydroxyapatite particles on Mg alloys by plasma electrolytic oxidation: A review

Mg and its alloys have been introduced as promising biodegradable materials for biomedical implant applications due to their excellent biocompatibility, mechanical behavior, and biodegradability. However, their susceptibility to rapid corrosion within the body poses a significant challenge and restricts their applications. To overcome this issue, various surface modification techniques have been developed to enhance the corrosion resistance and bioactivity of Mg-based implants. PEO is a potent technique for producing an oxide film on a surface that significantly minimizes the tendency to corrode. However, the inevitable defects due to discharges and poor biological activity during the coating process remain a concern. Therefore, adding suitable particles during the coating process is a suitable solution. Hydroxyapatite(HAp)has attracted much attention in the development of biomedical applications in the scientific community. HAp shows excellent biocompatibility due to its similarity in chemical composition to the mineral portion of bone. Therefore, its combination with Mg-based implants through PEO has shown significant improvements in their corrosion resistance and bioactivity. This review paper provides a comprehensive overview of the recent advances in the preparation, characterization, corrosion behavior and bioactivity applications of HAp particles on Mg-based implants by PEO.

Electrochemical response of MgO/Co_(3)O_(4) oxide layers produced by plasma electrolytic oxidation and post treatment using cobalt nitrate

This work looked into the influence of the sealing treatment on the structural feature and electrochemical response of AZ31 Mg alloy coated via plasma electrolytic oxidation(PEO).Here,the inorganic layers produced by PEO in an alkaline-phosphate electrolyte were subsequently immersed for different periods in cold(60°C)and hot(100°C)aqueous solutions containing either 1 or 3 gr of cobalt nitrate hexahydrate in the presence of hydrogen peroxide as an initiator.The results showed that the sealing treatments in the hot solutions could trigger the hydration reactions of PEO coating which would largely assist the surface incorporation of Co_(3)O_(4)into the coating.In contrast,the sealing in cold solutions led to less compact coatings,which was attributed to the fact the hydration reactions would be restricted at 60°C.A nearly fully sealed coating with a porosity of~0.5%was successfully formed on the sample immersed in the hot solution containing 1 gr of cobalt nitrate hexahydrate.Thus,the electrochemical stability of this fully sealed coating was superior to the other samples as it had the lowest corrosion current density(4.71×10^(-10)A·cm^(-2))and the highest outer layer resistance(3.81×10^(7)Ω·cm^(2)).The composite coatings developed in this study are ideal for applications requiring high electrochemical stability.

Formation process of composite plasma electrolytic oxidation coating containing zirconium oxides on AM50 magnesium alloy

The formation processes of a composite ceramic coating on AM50 magnesium alloy prepared by plasma electrolytic oxidation （PEO） in a K 2 ZrF 6 electrolyte solution were studied by scanning electron microscope （SEM） and energy dispersive X-ray spectroscope （EDX）. Electrochemical impedance spectroscopy （EIS） tests were used to study the variation of the corrosion resistance of the coating during the PEO treatment. The results show that the coating formed on Mg alloy is mainly composed of MgO and MgF 2 when the applied voltage is lower than the sparking voltage, and zirconium oxides start to be deposited on Mg substrate after the potential exceeding the sparking voltage. The corrosion resistance of the coating increases with increasing the applied voltage.

Effects of current density on microstructure and properties of plasma electrolytic oxidation ceramic coatings formed on 6063 aluminum alloy

Plasma electrolytic oxidation (PEO) ceramic coatings were fabricated in a silicate-based electrolyte with the addition of potassium fluorozirconate (K2ZrF6) on 6063 aluminum alloy, and the effects of current density on microstructure and properties of the PEO coatings were studied. It was found that pore density of the coatings decreased with increasing the current density. The tribological and hardness tests suggested that the ceramic coating produced under the current density of 15 A/dm2showed the best mechanical property, which matched well with the phase analysis. Electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization curves proved that the coating obtained under 15 A/dm2 displayed the best anti-corrosion property, which was directly connected with morphologies of coatings.

Plasma electrolytic oxidation of zircaloy-4 alloy with DC regime and properties of coatings

The plasma electrolytic oxidation（PEO） coatings on zircaloy？4 alloy were prepared in silicate,phosphate and pyrophosphate electrolyte systems or their combination by DC current regime.The proper processing parameters were determined and the coatings were evaluated by electrochemistry technique,micro-hardness,SEM and XRD.The results show that the coating prepared in pure silicate system is uneven and after the addition of phosphate solution,the homogeneity of the coating is still poor.The coating prepared in pure pyrophosphate electrolyte system is homogeneous,but its hardness value is low.After the addition of silicate into the pyrophosphate electrolytic system,both the uniformity and hardness of the coating are improved.The XRD results show that the phase compositions are m-ZrO2 and t-ZrO2,the addition of silicate is beneficial to the formation of t-ZrO2.The results of polarization curves show that the coatings prepared in pyrophosphate and the mixture of pyrophosphate and silicate have better corrosion resistance.

Wear and corrosion resistant coatings on surface of cast A356 aluminum alloy by plasma electrolytic oxidation in moderately concentrated aluminate electrolytes

Plasma electrolytic oxidation of a cast A356 aluminum alloy was carried out in aluminate electrolytes to develop wear and corrosion resistant coatings. Different concentrations of 2, 16 and 24 g/L NaAlO2 solutions and a silicate electrolyte （for comparison） were employed for the investigation. Wear performance and corrosion resistance of the coatings were evaluated by WC （tungsten carbide） ball-on-flat dry sliding tests and electrochemical methods, respectively. The results show that the coating formed for a short duration of 480 s in 24 g/L NaAlO2 solution generated the best protection. The coating sustained 30 N load for sliding time of 1800 s, showing very low wear rate of -4.5×10^-7 mm3/（N· m）. A low corrosion current density of -8.81×10^-9 A/cm2 was also recorded. Despite low α-Al2O3 content of the coating, the compact and nearly single layer nature of the coating guaranteed the excellent performances.

Plasma electrolytic oxidation of magnesium and its alloys:Mechanism,properties and applications

Plasma Electrolyte Oxidation(PEO)process has increasingly been employed to improve magnesium surface properties by fabrication of an MgO-based coating.Originating from conventional anodizing procedures,this high-voltage process produces an adhesive ceramic film on the surface.The present article provides a comprehensive review around mechanisms of PEO coatings fabrication and their different properties.Due to complexity of PEO coatings formation,a complete explanation regarding fabrication mechanisms of PEO coatings has not yet been proposed;however,the most important advancements in the field of fabrication mechanisms of PEO coatings were gathered in this work.Mechanisms of PEO coatings fabrication on magnesium were reviewed considering voltage–time plots,optical spectrometry,acoustic emission spectrometry and electronic properties of the ceramic film.Afterwards,the coatings properties,affecting parameters and improvement strategies were discussed.In addition,corrosion resistance of coatings,important factors in corrosion resistance and methods for corrosion resistance improvement were considered.Tribological properties(important factors and improvement methods)of coatings were also studied.Since magnesium and its alloys are broadly used in biological applications,the biological properties of PEO coatings,important factors in their biological performance and existing methods for improvement of coatings were explained.Addition of ceramic based nanoparticles and formation of nanocomposite coatings may considerably influence properties of plasma electrolyte oxidation coatings.Nanocomposite coatings properties and nanoparticles adsorption mechanisms were included in a separate sector.Another method to improve coatings properties is formation of hybrid coatings on PEO coatings which was discussed in the end.

Effects of electrical parameters and their interactions on plasma electrolytic oxidation coatings on aluminum substrates

Based on orthogonal experiments,the effects of voltage,frequency,duty ratio and their interactions on the thickness and corrosion resistance of coatings prepared by plasma electrolytic oxidation(PEO)on aluminum in an alkaline silicate-containing electrolyte were investigated.The thicknesses of these coatings were obtained by measuring their cross-section using Image J software.Their corrosion resistances were evaluated in HCl and NaCl media through spot test and electrochemical test.The results show that the experimental design of this study is the key to investigate the interactions among these electrical parameters.Additionally,not only each independent factor,but also their interactions exhibit a remarkable influence on the coatings.The combination of high voltage,low frequency and large duty ratio significantly increases the coating thickness and content of the corrosion resistance phase,and thus improves the corrosion resistance of the coating in HNO3 medium.Conversely,the coating possessing the densest microstructure and best corrosion resistance in NaCl medium is obtained when low voltage and high frequency match with a small duty ratio.

Growth behaviour of low-energy plasma electrolytic oxidation coatings on a magnesium alloy

Plasma electrolytic oxidation(PEO),a promising surface treatment method to improve the corrosion and wear resistance of magnesium and its alloys,operates at high voltages,resulting in a relatively high energy cost.To make the PEO process more economically viable,its energy efficiency needs to be improved.This study investigates the growth behaviour and microstructural characteristics of low-energy PEO coatings on an AM50 magnesium alloy in a concentrated electrolyte containing sodium tetraborate.The surface morphology of the coatings was different from typical PEO coating morphologies and a large voltage oscillation was observed during treatment.Using different characterisation techniques,and based on a micro-discharge model,a correlation was made between the voltage-time behaviour,microdischarge characteristics and the composition and microstructure of the coated samples.The results suggest electrolyte chemistry can somewhat control discharge behaviour,which plays an important role in PEO coating growth.

Effect of particles addition to solution of plasma electrolytic oxidation(PEO)on the properties of PEO coatings formed on magnesium and its alloys:A review

The plasma electrolytic oxidation(PEO)procedure is utilized in order to amend the surface properties of Mg and its alloys.This procedure creates a ceramic coating on the surface applying high-voltage.The presence of deep pores and porosities in the surface that affect the corrosion resistance of the coatings is one of the PEO procedure limitations.One of the useful methods to decrease porosities of coating and improve its final properties is changing electrolyte conditions based on the presence of micro-and nanoparticles.The present paper reviews the mechanisms of particle adsorption and composition in PEO thin films in addition to the effect of particle addition on the microstructure,composition and corrosion behavior of coatings that were applied on magnesium alloys.

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 11μm 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/cm^(2),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.

Plasma electrolytic oxidation of AZ31 and AZ91 magnesium alloys:Comparison of coatings formation mechanism

The growth kinetics of PEO coatings on AZ31 and AZ91 magnesium alloys were studied and correlated with their structure,compositions(phase and elemental)and corrosion resistance.It was established that the coatings have a two-(outer and anodic)or three-layer structure(outer,inner and anodic)depending on the treatment time.Briefly,at short treatment time only an anodic layer and outer layer exists.Growth of the outer PEO layer takes place due to the micro discharges,which occur in vertical pores and voids with spherical cross-section.If the time is increasing,and electrolyte inside of the pores is heating-up,etching of the Mg substrate and oxide film becomes more dominant and horizontal pores in the interface between coating and metal are formed.In the pores new anodic layer will form and at this time the formation of the third inner layer starts.The growth of the inner layer happens via the anodic film as a result of micro discharge ignition in the horizontal pores,accompanied by formation of plasma in numerous micro-voids of this layer.The coatings formed on AZ91 alloy are denser,than those on AZ31,which is related to the difference in the rates of inner layer growth and dissolving of oxides which are located at the bottom of the horizontal pores.Because of the lower Al content,the AZ31 substrate itself and the also the oxide films are less stable and tend to dissolve at a higher rate compared to AZ91.Thus,it was demonstrated that a good corrosion resistance of the coatings was only obtained on AZ91 and if the average thickness of the coating is around 50μm,correlating with the formation of a sufficiently dense inner laye-Knowing this mechanism,a new two-step treatment was suggested,combining the standard PEO treatment with a subsequent PEO process in an electrolyte supporting the inner film formation.The concept was successfully applied and a further improved corrosion resistance was obtained compared to the single stage PEO process.This improvement of corrosion resistance was related to the better sealing of porosity and formation of a denser inner layer.