Corrosion resistance and mechanisms of smart micro-arc oxidation/epoxy resin coatings on AZ31 Mg alloy: Strategic positioning of nanocontainers

Smart micro-arc oxidation(MAO)/epoxy resin(EP) composite coatings were formed on AZ31 magnesium(Mg) alloy. Mesoporous silica nanocontainers(MSN) encapsulated with sodium benzoate(SB) corrosion inhibitors were strategically incorporated in the MAO micropores and in the top EP layer. The influence of the strategic positioning of the nanocontainers on the corrosion protective performance of coating was investigated. The experimental results and analysis indicated that the superior corrosion resistance of the hybrid coating is ascribed to the protection mechanisms of the nanocontainers. This involves two phenomena:(1) the presence of the nanocontainers in the MAO micropores decreased the distance between MSN@SB and the substrate, demonstrating a low admittance value(^5.18 × 10^(-8)Ω^(-1)), and thus exhibiting significant corrosion inhibition and self-healing function;and(2) the addition of nanocontainers in the top EP layer densified the coating via sealing of the inherent defects, and hence the coating maintained higher resistance even after 90 days of immersion(1.13 × 10^(10)Ω cm^(2)).However, the possibility of corrosion inhibitors located away from the substrate transport to the substrate is reduced, reducing its effective utilization rate. This work demonstrates the importance of the positioning of nanocontainers in the coating for enhanced corrosion resistance,and thereby providing a novel perspective for the design of smart protective coatings through regulating the distribution of nanocontainers in the coatings.

Improved Corrosion Behavior of Biodegradable Mg-4Zn-1Mn Alloy Modified by Sr/F co-doped CaP Micro-arc Oxidation Coatings

The Sr/F co-doped CaP(Sr/F-CaP)coatings were prepared by micro-arc oxidation(MAO)under different voltages to modify the microstructure and corrosion behavior of Mg-4Zn-1Mn alloy.The surface and interface characteristics investigated using scanning electron microscopy(SEM)and energy dispersive X-ray spectrometer(EDS)showed that the MAO coatings displayed uneven crater-like holes and tiny cracks under lower voltage,while they exhibited relatively homogeneous crater-like holes without cracks under higher voltage.The thickness of MAO coatings increased with increasing voltage.The corrosion behavior of Mg-4Zn-1Mn alloy was improved by the MAO coatings.The MAO coatings prepared under 450 V and 500 V voltages possessed the best corrosion resistance with regard to the electrochemical corrosion tests and immersion corrosion tests,respectively.The MAO coatings fabricated under 450-500 V could provide a better corrosion protection effect for the substrate.

Corrosion behavior of micro-arc oxidation coating on AZ91D magnesium alloy in NaCl solutions with different concentrations

Ceramic oxide coatings were prepared on AZ91D magnesium alloys in alkaline silicate solution using micro-arc oxidation（MAO） technique.The corrosion behavior of MAO coating on AZ91D magnesium alloys in NaCl solutions with different concentrations（0.1%,0.5%,1.0%,3.5% and 5.0% in mass fraction） was evaluated by electrochemical measurements and immersion tests.The results showed that the corrosion rate of the MAO coated AZ91D increased with increasing chloride ion concentration.The main form of corrosion failure was localized corrosion for the MAO coated AZ91D immersed in higher concentration NaCl solutions（1.0%,3.5% and 5.0%）,while it was general corrosion in dilute NaCl solutions（0.1% and 0.5%）.Two different stages of the failure process of the MAO coated AZ91D could be identified：1） occurrence of the metastable pits and 2） growth of the pits.Different equivalent circuits were also proposed based on the results of electrochemical impedance spectroscopy（EIS） for the MAO coated AZ91D immersed in different concentrations of NaCl solutions for 120 h.

Preparation and performance of coating on rare-earth compounds-immersed magnesium alloy by micro-arc oxidation

A composite ceramic coating containing Y2O3-ZrO2-MgO（YSZ-MgO） was prepared on AZ91D magnesium alloy,which was immersed in Y（NO3）3 aqueous solution as pretreatment,by micro-arc oxidation（MAO） process.The morphology,elemental and phase compositions,corrosion behavior and thermal stability of the coatings were studied by SEM,EDX,XRD,electrochemical corrosion test,high temperature oxidation and thermal shock test.The results show that the coating mainly consists of ZrO2,Y2O3,MgO,Mg2SiO4,and MgF2.Among these compounds,Y2O3 accounts for 26.7% of（Y2O3 ＋ ZrO2）.The thickness of YSZ-MgO coating is smaller than that of ZrO2-MgO coating,but its compactness and surface roughness are better than those of ZrO2-MgO coating.YSZ-MgO coating has a good corrosion resistance,and its corrosion rate in 5% NaCl aqueous solution is lower than that of ZrO2-MgO and only about 8.5% of that of AZ91D magnesium alloy.After oxidation at 410 °C,the mass gain of AZ91D magnesium alloy presents a linear increase with the oxidation time.The YSZ-MgO coating and ZrO2-MgO coating can remarkably decrease the oxidation mass gain.The oxidation mass gain of YSZ-MgO coating is lower than that of ZrO2-MgO coating,especially during a long oxidation period.The thermal shock resistance of YSZ-MgO coating is superior to ZrO2-MgO coating.

Micro-arc oxidation coatings on Mg-Li alloys

Micro-arc oxidation (MAO) method was used for the surface modification of an Mg-5wt.%Li alloy. Ceramic coatings were in-situ fabricated on the Mg-Li alloy. The morphology feature,phase composition,and corrosion-resistance of the formed ceramic coatings were studied by SEM,XRD,and electrochemical methods,respectively. The results showed that the coatings produced in a sodium silicate solution system were composed of MgO and Mg2SiO4. The ceramic coating became thicker and the content of Mg2SiO4 phase increase...

Effects of additives on corrosion and wear resistance of micro-arc oxidation coatings on TiAl alloy

Ceramic coating was deposited on TiAl alloy substrate by micro-arc oxidation(MAO)in a silicate-aluminate electrolyte solution with additives including sodium citrate,graphite and sodium tungstate.The microstructures and compositions were analyzed by SEM,EDX and XRD.The corrosion and wear properties of the coatings were investigated by potentiodynamic polarization and ball-on-disc wear test,respectively.The results show that the MAO coatings consist of WO3,Ti2O3,graphite and Al2O3 besides Al2TiO5 and Al2SiO5.With additives in the electrolyte,the working voltage at the micro-arc discharge stage decreases,and the ceramic coating gets smoother and more compact.The corrosion current density of MAO coating is much lower than that of TiAl substrate.It can be reduced from 9.81×10-8A/cm 2to 3.02×10-10A/cm 2 .The MAO coatings composed of hard Al2O3,WO3 and Ti2O3 obviously improve the wear resistance of TiAl alloy.The wear rate is-3.27×10-7g/(N·m).

Preparation technology and anti-corrosion performances of black ceramic coatings formed by micro-arc oxidation on aluminum alloys

In order to prepare ornamental and anti-corrosive coating on aluminum alloys, preparation technology of black micro-arc ceramic coatings on Al alloys in silicate based electrolyte was studied. The influence of content of Na2WO4 and combination additive in solution on the performance of black ceramic coatings was studied; the anticorrosion performances of black ceramic coatings were evaluated through whole-immersion test and electrochemical method in 3.5% NaCl solution at different pH value; SEM and XRD were used to analyze the surface morphology and phase constitutes of the black ceramic coatings. Experimental results indicated that, without combination additives, with the increasing of Na2WO4 content in the electrolyte, ceramic coating became darker and thicker, but the color was not black; after adding combination additive, the coating turned to be black; the black ceramic coating was multi-hole form in surface. There was a small quantity of tungsten existing in the black ceramic coating beside α-Al2O3 phase and β-Al2O3 phase. And aluminum alloy with black ceramic coating exhibited excellent anti-corrosion property in acid, basic and neutral 3.5% NaCl solution.

Preparation of micro-arc oxidation coatings on magnesium alloy and its thermal shock resistance property

In the NaAlO2-Na2SiO3 compound system, the ceramic coatings were prepared on magnesium alloy by micro-arc oxidation. The morphology, phase composition, and thermal shock resistance of the ceramic coatings were studied by scanning electron microscope, X-ray diffraction and thermal shock tests, respectively. The results showed that the ceramic coating contains MgO, MgAl2O4, as well as a little amount of MgESiO4. The thickness of the ceramic coatings increases with the current density increasing, when the current density is 12 A·dm^-2, the thermal shock resistance of the produced ceramic coating is the best. The hardness of the ceramic coating is up to 10 GPa or so.

Characterization of bioactive ceramic coatings prepared on titanium implants by micro-arc oxidation

Micro-arc oxidation （MAO） is an enhanced chemical technology in an electrolyte medium to obtain coating structures on valve-metal surfaces. Titanium oxide films obtained by MAO in the sodium phosphate electrolyte were investigated. The films were composed mainly of TiO2 phases in the form of anatase and mille and enriched with Na and P elements at the surface. Their apafite-inducing ability was evaluated in a simulated body fluid （SBF）. When immersing in SBF for over 30 d, a preferential carbonated-hydroxyapatite was formed on the surfaces of the films, which suggests that the MAO-treated titanium has a promising positive biological response.

Evolution of Residual Stresses in Micro-arc Oxidation Ceramic Coatings on 6061 Al Alloy

Most researches on micro-arc oxidation mainly focus on the application rather than discovering the evolution of residual stresses. However, residual stresses in the surface coatings of structural components have adverse effects on their properties, such as fatigue life, dimensional stability and corrosion resistance, etc. The micro-arc oxidation ceramic coatings are produced on the surfaces of 6061 aluminum alloy by a homemade asymmetric AC type of micro-arc oxidation equipment of 20 kW. A constant current density of 4.4___0.1 A/dm2 and a self-regulated composite electrolyte are used. The micro-arc oxidation treatment period ranges from 10 min to 40 min, and the thickness of the ceramic coatings is more than 20 Bin. Residual stresses attributed to 7-A1203 constituent in the coatings at different micro-arc oxidation periods are analyzed by an X-ray diffractometer using the sin2~u method. The analysis results show that the residual stress in the ceramic coatings is compressive in nature, and it increases first and then decreases with micro-arc oxidation time increase. The maximum stress value is 1 667_＋20 MPa for period of 20 min. Through analyzing the coating thickness, surface morphology and phase composition, it is found that the residual stress in the ceramic coatings is linked closely with the coating growth, the phase composition and the micro cracks formed. It is also found that both the heat treatment and the ultrasonic action release remarkably the residual compressive stress. The heat treatment makes the residual compressive stress value decrease 1 378 MPa. The ultrasonic action even alters the nature of the residual stress, making the residual compressive stress change into a residual tensile stress.

Preparation and characterization of the micro-arc oxidation composite coatings on magnesium alloys

The magnesium alloys attract the light-weight manufacture due to its high strength to weight ratio,however the poor corrosion resistance limits the application in automobile industry.The Micro-arc Composite Ceramic(MCC)coatings on AZ91D magnesium alloys were prepared by Micro-arc Oxidation(MAO)and electrophoresis technologies.The microstructure,corrosion resistance,abrasion resistance,stone impact resistance and adhesion of MCC coatings were studied respectively.The cross section morphologies showed that the outer organic coating was filled into the hole on surface of MAO coating,and it acted as a shelter against corrosive products.The copper-accelerated acetic acid salt spray Test,abrasion resistance test,stone impact resistance test,thermal shock resistance test and adhesion test were used to evaluate the protective characterization by the third testing organization which approved by GM.The test results showed the composite coatings meet all the requirements.The MCC coating on Mg presents excellent properties,and it is a promising surface treatment technology on magnesium alloys for production vehicles.

Preparation and properties of a cerium-containing hydroxyapatite coating on commercially pure titanium by micro-arc oxidation

A porous cerium-containing hydroxyapatite coating on commercially pure titanium was prepared by micro-arc oxidation （MAO） in an electrolytic solution containing calcium acetate, p-glycerol phosphate disodium salt pentahydrate （β-GP）, and cerium nitrate. The thickness, phase, composition morphology, and biocompatibility of the oxide coating were characterized by X-ray diffraction （XRD）, electron probe microanalysis （EPMA）, scanning electron microscopy （SEM） with energy dispersive X-ray spectrometer （EDS）, and cell culture. The thickness of the MAO film is about 15-25 ~tm, and the coating is porous and uneven, without any apparent interface to the titanium substrates. The results of XRD and EDS show that the porous coating is made up of hydroxyapatite （HA） film containing Ce. The favorable osteoblast cell affinity makes the Ce-HA film have a good biocompatibility. The Ce-HA film is expected to have significant medical applications as dental implants and artificial bone joints.

Structures of ceramics coatings on steel fabricated by hot-dipping and micro-arc oxidation

Firstly, an aluminum coating was produced metallurgically on mild steel by hot-dipping, then an aluminum oxide coating was formed self-growingly from the aluminum coating by micro-arc oxidation treatment. The structures of the composite coatings were investigated by means of SEM, TEM and XRD. The results show that the composite coating consists of three layers which are Fe-Al alloy, aluminum coating and aluminum oxide orderly outward from the steel substrate. There are amorphous phases, k-Al2O3 and θ-Al2O3 mainly in the aluminum oxide.

Corrosion resistance of micro-arc oxidized ceramic coating on cast hypereutectic alloy

The corrosion resistance of the micro-arc oxidation(MAO) ceramic coating on a cast Al-13Si-5Cu alloy was investigated using various electrochemical methods including electrochemical impedance spectroscopy(EIS) and polarization curves.Microstructures of MAO ceramic coating were studied by SEM,and the influence of microscopic patterns on corrosion resistance was analyzed.The corrosion resistance of the aluminum alloy can be improved significantly by MAO process owing to increasing impedance and corrosion potential and decreasing corrosion current,and the ceramic coatings are composed of loose layer,compact layer and transition layer,which improve the corrosion resistance.The corrosin resistance is determined by the thickness of the compact layer and is not proportional to the total thickness of MAO,though the latter is one of the important factors influencing the corrosin resistance.

Comparative Study of the Effects of Nano ZnO and CuO on the Biodegradation,Biocompatibility,and Antibacterial Properties of Micro-arc Oxidation Coating of Magnesium Alloy

This research systematically examined the degradation,antibacterial effects,and biocompatibility of micro-arc oxidation(MAO)coatings with nano CuO and ZnO on extruded Mg alloys.Both copper(Cu)and Zinc(Zn)possess antibacterial properties.The findings demonstrated that adding ZnO will appreciably reduce the degradation rate of MAO-coating alloy due to the self-sealing micro holes.CuO+MAO coating exhibited excellent antibacterial performance,with an antibacterial rate of over 90%within 6 h co-cultured with Staphylococcus aureus.Similarly,the antibacterial rate of ZnO+MAO coating reached 90%after 12 h co-culture.Cytotoxicity test using MG63 cell indicated that the incorporation of CuO and ZnO did not notably affect the cell viability rate of the coating.Moreover,after 14 days of culture,the CuO+MAO and ZnO+MAO coated samples exhibited higher alkaline phosphatase(ALP)activity than the MAO-coated and uncoated samples,suggesting favorable osteogenic properties.

Corrosion and antimicrobial property of TiO_(2)/Cu_(2)O and TiO_(2)/Cu_(2)O@CeO_(2)micro-arc oxidation coatings on Ti-6Al-4V alloys in natural seawater

Microarc oxidation is an effective surface treatment for improving certain properties of metals and their alloys.In this paper,TiO_(2)/Cu_(2)O and TiO_(2)/Cu_(2)O@CeO_(2)coatings were prepared on Ti-6Al-4V by microarc oxidation.Thecoatings exhibited good corrosion resistance and antimicrobial properties.X-ray diffraction(XRD),scanning electronmicroscopy(SEM),and 3D laser confocal were used to characterize the coatings.The properties of TiO_(2)/Cu_(2)O and TiO_(2)/Cu_(2)O@CeO_(2)coatings were analyzed,including microstructure,surface roughness,corrosion resistance,andantimicrobial properties.The electrochemical results showed that the coatings prepared by microarc oxidation hadenhanced corrosion resistance compared to the substrate.The antibacterial properties of TiO_(2)/Cu_(2)O and TiO_(2)/Cu_(2)O@CeO_(2)coating against Pseudomonas aeruginosa were evaluated by fluorescence microscopy and plate counting.The antibacterial rate of TiO_(2)/Cu_(2)O@CeO_(2)coating was up to 99.70%.In summary,the TiO_(2)/Cu_(2)O and TiO_(2)/Cu_(2)O@CeO_(2)coatings prepared by microarc oxidation have a potential application background in the field of marine corrosionprotection and biofouling.

Structure and properties of micro-arc calcium phosphate coatings on pure titanium and Ti-40Nb alloy

The microstructure, physical and mechanical, and chemical properties of micro-arc calcium phosphate （CAP） coatings deposited under different process voltages in the range of 150-400 V on the commercially pure titanium （Ti） and Ti-40%Nb （Ti-40Nb） （mass fraction） alloy were investigated by the SEM, TEM, XRD and EDX methods. The coating thickness, roughness, and sizes of structural elements were measured and showed similar linear character depending on the process voltage for the coatings on both substrates. SEM results showed the porous morphology with spherical shape structural elements and rough surface relief of the coatings. XRD and TEM studies exhibited the amorphous structure of the CaP coating. With increasing the process voltage to 300-400 V, the crystalline phases, such as CaHPO4 and β-Ca2P207, were formed onto the coatings. The annealing leads to the formation of complex poly-phase structure with crystalline phases： CaTi4（PO4）6, β-Ca2P2O7, TiP2O7, TiNb（PO4）3, TiO2, NbO2, and Nb2O5. The applied voltage and process duration in the ranges of 200-250 V and 5-10 min, respectively, revealed the coating formed on Ti and Ti-40Nb with optimal properties： thickness of 40-70μm, porosity of 20%-25%, roughness （Ra） of 2.5-5.0 μm, adhesion strength of 15-30 MPa, and Ca/P mole ratio of 0.5-0.7.

Investigation of anti-corrosion property of hybrid coatings fabricated by combining PEC with MAO on pure magnesium

Novel hybrid coatings on pure magnesium were prepared by combining plasma electrolytic carburizing(PEC)with micro-arc oxidation(MAO)to further enhance the anti-corrosion property in this paper.Scanning electron microscopy(SEM)was used to observe the microstructure of the coatings,meanwhile,energy dispersive spectrometry(EDS)and X-ray diffraction(XRD)were separately used to investigate the elemental as well as phase compositions of the coatings.The anti-corrosion property of the coatings was evaluated by potentiodynamic polarization curves as well as electrochemical impedance spectroscopy(EIS).The results show that PEC process is closely related with the effects of adsorption as well as diffusion of the activated carbon atoms,and it can provide a favorable pretreatment surface with predesigned chemical composition to obtain a new kind of phase,namely Si C with superior corrosion resistance and chemical stability,in the following PEC+MAO hybrid coatings.Meanwhile,PEC preprocessing also can afford an excellent micro-structure to increase the coating thickness as well as to improve the compactness of the PEC+MAO hybrid coatings.During the fabrication process of the PEC+MAO hybrid coatings,an overlapping phenomenon in regard to coating thickness can be observed instead of heaping up layer by layer.Compared with both single PEC surface modification layers as well as single MAO coatings,the PEC+MAO hybrid coatings exhibit more superior anti-corrosion property.Especially,the EIS data reveal that the PEC+MAO hybrid coatings can act as an effective protection system to provide relatively excellent long-range anti-corrosion protection.Note also that employing same MAO technique for both single MAO treatment as well as PEC+MAO combining procedure is the key to this research.

Corrosion and tribocorrosion resistance of MAO-based composite coating on AZ31 magnesium alloy

In this paper, a multi-functional composite coating with low friction coefficient, high wear resistance and excellent tribocorrosion resistance is fabricated on AZ31 Mg alloys by micro-arc oxidation and spray-coating methods. The microstructure, and composition of the coating are characterized by SEM, EDS, XRD, and FT-IR. Potentiodynamic polarization and EIS tests are conducted to evaluate the corrosion resistance of the composite coating. The tribocorrosion property is also studied using pin-on-disk tribometer in 3.5 wt.% Na Cl solution. It is found that the composite coating possesses better long-term corrosion resistance than the single MAO coating. The tribocorrosion tests prove that the composite coating exhibits much better wear and tribocorrosion resistance than the single MAO coating and can protect the substrate from corrosion under a sliding condition.

Comparison of the corrosion behavior of AM60 Mg alloy with and without self-healing coating in atmospheric environment

Coatings on the surface of Mg alloys are inevitably damaged during their practical applications,and corrosion can easily initiate from the damaged areas to accelerate the failure of Mg parts.A dual self-healing coating has already been developed to solve this problem in our previous work.Considering the practical application of this coating,it is necessary to investigate its service behavior in atmospheric environment.Thus,the corrosion behavior of AM60 Mg substrate with and without the self-healing coating was compared in Shenyang industrial atmospheric environment.The results show that the enrichment of sediments and rainwater on the scratch areas can accelerate the corrosion of the exposed Mg substrate.The inhibitors can be released from the damaged coating to inhibit corrosion.The dual self-healing coating shows better inhibition ability to narrow scratches due to the higher inhibitor concentration and less resumption.Also,the coating with wide scratches displays enough inhibition ability as well.The dual self-healing coating is a good alternative for Mg alloy parts in the practical applications.