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.

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.

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.

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.

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.

The Effect of Plasma Surface Treatment on a Porous Green Ceramic Film with Polymeric Binder Materials

To reduce time and energy during thermal binder removal in the ceramic process, plasma surface treatment was applied before the lamination process.The adhesion strength in the lamination films was enhanced by oxidative plasma treatment of the porous green ceramic film with polymeric binding materials.The oxygen plasma characteristics were investigated through experimental parameters and weight loss analysis.The experimental results revealed the need for parameter analysis,including gas material,process time,flow rate,and discharge power,and supported a mechanism consisting of competing ablation and deposition processes.The weight loss analysis was conducted for cyclic plasma treatment rather than continuous plasma treatment for the purpose of improving the film’s permeability by suppressing deposition of the ablated species.The cyclic plasma treatment improved the permeability compared to the continuous plasma treatment.

Advancements in enhancing corrosion protection of Mg alloys:A comprehensive review on the synergistic effects of combining inhibitors with PEO coating

Magnesium(Mg)alloys are lightweight materials with excellent mechanical properties,making them attractive for various applications,including aerospace,automotive,and biomedical industries.However,the practical application of Mg alloys is limited due to their high susceptibility to corrosion.Plasma electrolytic oxidation(PEO),or micro-arc oxidation(MAO),is a coating method that boosts Mg alloys'corrosion resistance.However,despite the benefits of PEO coatings,they can still exhibit certain limitations,such as failing to maintain long-term protection as a result of their inherent porosity.To address these challenges,researchers have suggested the use of inhibitors in combination with PEO coatings on Mg alloys.Inhibitors are chemical compounds that can be incorporated into the coating or applied as a post-treatment to further boost the corrosion resistance of the PEO-coated Mg alloys.Corrosion inhibitors,whether organic or inorganic,can act by forming a protective barrier,hindering the corrosion process,or modifying the surface properties to reduce susceptibility to corrosion.Containers can be made of various materials,including polyelectrolyte shells,layered double hydroxides,polymer shells,and mesoporous inorganic materials.Encapsulating corrosion inhibitors in containers fully compatible with the coating matrix and substrate is a promising approach for their incorporation.Laboratory studies of the combination of inhibitors with PEO coatings on Mg alloys have shown promising results,demonstrating significant corrosion mitigation,extending the service life of Mg alloy components in aggressive environments,and providing self-healing properties.In general,this review presents available information on the incorporation of inhibitors with PEO coatings,which can lead to improved performance of Mg alloy components in demanding environments.

Effect of low concentration electrolytes on the formation and corrosion resistance of PEO coatings on AM50 magnesium alloy

In this paper,the formation process,morphology,and electrochemical performance of PEO coatings on AM50 magnesium alloy prepared in low concentration phosphate,aluminate,and phosphate-aluminate electrolytes were systematically studied.The results show that the coatings prepared from the phosphate electrolytes have a higher thickness and better corrosion resistance properties compared to the other electrolytes.The coatings prepared from low concentration phosphate-aluminate mixed electrolytes have slightly thinner thickness,a similar coating structure and an order of magnitude lower value of electrochemical impedance compared with phosphate electrolyte coatings.The Coatings prepared from low concentration aluminate electrolytes have the lowest thickness and the worst corrosion resistance properties which gets close to corrosion behavior of the bare AM50 under the same test conditions.Considering application,coatings prepared from single low concentration phosphate electrolytes and low concentration phosphate-aluminate electrolytes have greater potential than single low concentration aluminate coatings.However,reducing the electrolyte concentrations of coating forming ions too much has negative influence on the coating growth rate.

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.

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.

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.

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.

Hybrid electric discharge plasma technologies for water decontamination:a short review

Electric discharge plasma(EDP)can efficiently degrade aqueous pollutants by its in situ gen erated strong oxidative species(OH,0,H2O2.O.etc)“nd other physiochemical effects(UV irradiation,shockwaves,local high temperature,etc),but a high energy consumptions limit the application of EDP in water treatment.Some adsorbents,catalysts,and oxida nts have been employed for en hanci ng the degradation of pollutants by discharge plasma.These hybrid plasma technologies offer improved water treatment performance compared to dischai'ge plasma alone.This paper reviews the water decontamination performance and mechanisms of these hybrid plasma technologies,and some suggestions on future water treatment technologies based on discharge plasma are also proposed.

Investigation of mutual effects among additives in electrolyte for plasma electrolytic oxidation on magnesium alloys

Plasma electrolytic oxidation(PEO)coatings were prepared on AZ91D magnesium alloys in alkaline silicate-based electrolyte with and without additives.The mutual effects among additives including TiC particles,dispersant polyethylene glycol 6000(PEG6000)and anionic surfactant sodium dodecyl sulfate(SDS)were studied based on orthogonal experiment.The content and distribution of TiC deposited in the coatings were measured by EPMA and EDS.The thicknesses,phase compositions,microstructures and corrosion resistances of the codlings were cAarnined by using TT260 eddy current tuickncss gage,XRD,SEM and clcctrochcniical test,respectively.The results show that the experiment design of this study is the key to study the mutual effects among these additives.Each additive and their interactions all remarkably influence TiC content and corrosion resistance of the coatings.Smaller size TiC is much easier to migrate towards the anode,and the interaction between PEG6000 and SDS both effectively prevents its agglomeration and increases the number of its negative surface charges,which further increase the migration rate and the deposited uniformity of TiC and make TiC have more opportunity to deposit in the discharge channel.Thus,when smaller size TiC,PEG6000 and SDS are all added into the electrolyte,they could improve the anti-corrosion property of the coating to the largest extent attributed to higher TiC content and the densest microstructure of the coating.

Effect of carbonate additive on the microstructure and corrosion resistance of plasma electrolytic oxidation coating on Mg-9Li-3Al alloy

Carbonate was added to the silicate system electrolyte to improve the corrosion resistance of the plasma electrolytic oxidation coating on Mg-9Li-3Al(wt%,LA93)alloy.The influences of carbonate on the morphology,structure,and phase composition of the coating were investigated by scanning electron microscopy,energy dispersive spectrometry,X-ray diffraction,and X-ray photoelectron spectroscopy.The corrosion resistance of the coating was evaluated by electrochemical experiment,hydrogen evolution,and immersion test.The results showed that the addition of carbonate resulted in a denser coating with increased hardness,and the corrosion-resistant Li_(2)CO_(3) phase was formed.Electrochemical experiments showed that compared with the coating without carbonate,the corrosion potential of the carbonate coating positively shifted(24 mV),and the corrosion current density was reduced by approximately an order of magnitude.The coating with carbonate addition possessed a high corrosion resistance and long-term protection capability.

Surface characterization and corrosion behavior of calcium phosphate(Ca-P)base composite layer on Mg and its alloys using plasma electrolytic oxidation(PEO):A review

Magnesium has been known as an appropriate biological material on account of its good biocompatibility and biodegradability properties in addition to advantageous mechanical properties.Mg and its alloys are of poor corrosion resistance.Its high corrosion rate leads to its quick decomposition in the corrosive ambiance and as a result weakening its mechanical properties and before it is repaired,it will vanish.The corrosion and degradation rate must be controlled in the body to advance the usage of Mg and its alloys as implants.Different techniques have been utilized to boost biological properties.Plasma electrolytic oxidation(PEO)can provide porous and biocompatible coatings for implants among various techniques.Biodegradable implants are generally supposed to show enough corrosion resistance and mechanical integrity in the body environment.Much research has been carried out in order to produce PEO coatings containing calcium phosphate compounds.Calcium phosphates are really similar to bone mineral composition and present great biocompatibility.The present study deals with the usage of calcium phosphates as biocompatible coatings applied on Mg and its alloys to study the properties and control the corrosion rate.

Optimization of plasma electrolyte oxidation process parameters for corrosion resistance of Mg alloy

Plasma electrolyte oxidation(PEO)is a surface treatment method with high dependency on the process parameters.This paper focuses on maximizing the corrosion resistance of PEO coatings applied on Mg-5Zn-0.4Ca(ZX504)alloy by optimizing the process parameiers.For this purpose,the Taguchi method based on LI8 orthogonal array with mixed level design was used for optimization and determining effective parameters.Main process factors including electrolyte concentration,current density,frequency and duty cycle were considered at different levels.The corrosion resistance,as the performance indicator,was obtained using electrochemical impedance spectroscopy technique.Surface characteristics were also evaluated using SEM(scanning electron microscopy),EDS(energy dispersive spectroscopy),profilometer and contact angle goniometer.The statistical analysis showed that the optimum condition could be obtained at a current density of 200 mA/cm^2,frequency of 500Hz and at a duty cycle of 30%,in an electrolyle containing 15 g/L NazPO·12H2O and 10g/L KF.

Characteristics of a multi-component MgO-based bioceramic coating synthesized in-situ by plasma electrolytic oxidation

Plasma electrolytic oxidation(PEO)has held great potential for the advancement of biodegradable implants,as it helps in developing porous bioceramic coatings on the surface of magnesium alloys.In this research work,MgO-based bioceramic coatings containing the Si,P,Ca,Na,and F elements have been successfully fabricated on an AZ31 magnesium alloy plate utilizing the PEO method.The characteristic current-voltage behavior of the samples during the process was surveyed in an electrolyte containing Ca(H_(2)PO_(4))_(2),Na_(2)SiO_(3)·9H_(2)O,Na_(3)PO_(4)·12H_(2)O,NaF,and KOH with a pH of 12.5 and electrical conductivity of 20 mS/cm^(-1).The results revealed that applying a voltage of 350-400 V(that is 50-100 V higher than the breakdown limit)could greatly facilitate the synthesis of a PEO ceramic coating with fewer defects and more uniform morphology.The resulting coating was a compositionally graded bioceramic layer with a thickness in the range of 3.5±0.4 to 6.0±0.7µm,comprising the above-mentioned elements as promising bioactive agents.The synthesized ceramic features were investigated in terms of the elemental distribution of components through the thickness,which indicated a gradual rise in the Si and P contents and,conversely,a decline in the F content towards the outer surface.The growth mechanism of the PEO coating has been discussed accordingly.