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.

Microstructural, corrosion and mechanical behavior of two-step plasma electrolyte oxidation ceramic coatings

Plasma electrolytic oxidation(PEO)is considered as a cost effective and environmentally friendly surface treatmentprocess for improving surface properties of light alloys.The formation of ceramic coatings on Ti6Al4V alloy was reported bytwo-step PEO process and its structural,electrochemical and mechanical properties with the coated samples were compared byone-step PEO process in an alkaline electrolyte.The structural properties were studied using field-emission scanning microscope(FESEM)and X-ray diffraction(XRD).Electrochemical studies were carried out using linear polarization method and in additionmechanical behaviors were investigated by means of Knoop microhardness and nanoindentation method.Results showed that thesecond step process resulted in an increase of both porosity percentage and average pore diameter on the surface.The two-stepprocess resulted in a small increase of thickness from about12.5to13.0μm.Electrochemical test results showed that applying thesecond step resulted in the decrease of both polarization resistance from1800.2to412.5kΩ/cm2and protection efficiency from97.8%to90.5%.Finally,the nanoindentation results indicated that the PEO coatings became softer but more ductile after applyingthe second processing step in acidic electrolyte.

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.

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.

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.

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.

Improving the wear resistance of plasma electrolytic oxidation(PEO)coatings applied on Mg and its alloys under the addition of nano-and micro-sized additives into the electrolytes:A review

As an efficient surface modification approach,the plasma electrolytic oxidation(PEO)technique can boost the capability of wear protection in Mg and its alloys by applying a hard and thick ceramic coating.In this procedure,more efficient protection can be acquired via adding additives(in the form of particle,powder,sheet,etc.)into solutions and producing composite coatings.These additives result in more efficient protection against wear via getting stuck in the cracks and pores of coatings and rising the thickness,hardness,and diminishing the porosity size and content.The efficiency of each additive can be changed owing to its intrinsic properties like melting point,size,participation type(reactive,partly reactive,or inert)and potential of zeta.In this review,the effects of distinct additives in nano-and micro-scale size on wear behavior of PEO coatings on Mg and its alloys is going to be reviewed.

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 NaOH on plasma electrolytic oxidation of A356 aluminium alloy in moderately concentrated aluminate electrolyte

Plasma electrolytic oxidation(PEO)of cast A356 aluminum alloy was carried out in 32 g/L NaAlO_(2) with the addition of different concentrations of NaOH.The stability of the aluminate solution is greatly enhanced by increasing the concentration of NaOH.However,corresponding changes in the PEO behaviour occur due to the increment of NaOH concentration.Thicker precursor coatings are required for the PEO treatment in a more concentrated NaOH electrolyte.The results show that the optimal NaOH concentration is 5 g/L,which improves the stability of storage electrolyte to about 35 days,and leads to dense coatings with high wear performance(wear rate:4.1×10^(−7) mm^(3)·N^(−1)·m^(−1)).

Plasma electrolytic oxidation behavior and corrosion resistance of brass in aluminate electrolyte containing NaH2PO4 or Na2SiO3

Plasma electrolytic oxidation(PEO) of brass was carried out in aluminate electrolytes with the addition of NaH2PO4(S1) and Na2SiO3(S2), respectively, with the aim to investigate the effect of additives on the coating formation and corrosion resistance. For the PEO in S1 electrolyte, a mixed layer of AlPO4and Al2O3is formed at the initial stage, which leads to fast plasma discharges and formation of black coatings with the compositions of Al2O3,CuO, Cu2O and ZnO. However, in S2 electrolyte, plasma discharges are delayed and the coatings show a reddish color due to more Cu2O. Mott-Schottky tests show that the S1 coatings are p-type semiconductors;while the S2 coatings can be adjusted between n-type and p-type. Potentiodynamic polarization and electrochemical impedance spectroscopy(EIS) tests show that the PEO treatment can significantly improve the corrosion resistance of brass, with protection efficiency up to 91.50% and the largest charge transfer resistance of 59.95 kΩ·cm^(2) for the S1 coating.

Effect of electrolyte temperature on the nano-carbonitride layer fabricated by surface nanocrystallization and plasma treatment on a γ-TiAl alloy

The distribution of nano-carbonitrides produced by the treatments of surface nanocrystallization and plasma electrolytic carbonitriding on a γ-TiAl was investigated by means of figure analysis. The skewness and kurtosis of Gaussian shape distribution curves were studied and the effect of electrolyte temperature was determined. The usage of lower temperatures of the electrolyte is more suitable for achieving lower sizes of complex nano-carbonitrides. The surface roughness of treated samples was measured and it was observed that there is an optimum level of electrolyte temperature for surface roughness increase （difference between two measured data）.

Effect of Various Additives on Performance of Plasma Electrolytic Oxidation Coatings Formed on AZ31 Magnesium Alloy in the Phosphate Electrolytes

Plasma electrolytic oxidation（PEO） coatings were prepared on AZ31 magnesium alloy using alkaline phosphate as base electrolyte system, and with the addition of sodium silicate（Na2SiO3）, sodium aluminate（NaAlO2） and potassium fluorozirconate（K2ZrF6） as additives. The microstructure, phase composition and element composition as well as surface profile of the PEO coatings were analyzed by means of scanning electron microscopy（SEM）, X-ray diffraction（XRD）, energy dispersive X-ray spectroscopy（EDS）, and threedimensional（3 D） optical profilometry. The corrosion and wear properties were evaluated by electrochemical potentiodynamic polarization in 3.5 wt% Na Cl solution and ball-on-disc wear tests, respectively. The results showed that the anions of the additives effectively participated in the coating formation influencing its microstructural features, chemical composition, corrosion resistance and tribological behaviour. It was observed that the sample treated by PEO in the electrolyte solution containing K2ZrF6 as an additive showed better corrosion and abrasive resistance.

Effect of electrolyte on mechanical properties of AZ31B Mg alloy in electrolytic plasma processing

Coatings on Mg alloys were prepared using NaOH + Na2SiO3 as basic electrolyte containing electrolyte of Na2SiF6 or NaF. EPP treatment was carried out on AZ31 Mg alloys matrix under a hybrid voltage of AC of 200 V combined with DC of 260 V for 30 min. Structural and morphological analyses of ceramic coatings were analyzed by XRD and SEM. Wear and hardness of coatings were measured by pin-on disk test and Vickers hardness test. The coatings formed in Na2SiF6 and NaF electrolytes were mainly composed of MgO and Mg2SiO4. The measured micro-hardness of coating formed in Na2SiF6 electrolyte was found to be over HV 1100, while, coating formed in NaF electrolyte possessed micro-hardness of HV ~900. These results show that the mechanical properties of AZ31 B Mg alloys can be enhanced by the proper selection of electrolyte agent.

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.