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.

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.

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.

Effect of the Oxidation Time on Properties of Ceramic Coatings Produced on Ti-6Al-4V by Micro-Arc Oxidation

Ceramic coatings were prepared on Ti-6AI-4V alloy using ac micro-arc oxidation (MAO) in silicate-hypophosphate solution. Growth regularity and formation mechanism of ceramic coatings were discussed. It was found that during the first stage the growth rate of coatings toward the external surface was larger than that toward substrate and then the coating began to grow mainly towards Ti alloy. When the total coating thickness reaches a certain value, it would no longer increase. In addition, the variations of the composition and microstructure of ceramic coatings according to the depositing time were also investigated with X-ray diffraction (XRD) and scanning electron microscope (SEM). The amount of rutile TiO2 gradually increased, whereas the amounts of the anatase TiO2 and amorphous phases first increased and then decreased slightly.

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.

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.

Wear resistance of ceramic coating on AZ91 magnesium alloy by micro-arc oxidation

The ceramic coating formed on AZ91 magnesium alloy by micro-arc oxidation (MAO) was characterized. The results show that the ceramic coating(3.4-23μm in thickness)on the surface of AZ91 alloy was attained under different micro-arc oxidation treatment conditions, which consist mainly of MgO, Mg2SiO4 and MgSiO3 phases. Nano-hardness in a cross-sectional specimen was determined by nano-indentation experiment. The MAO coatings exhibit higher hardness than the substrate. Dry sliding wear tests for the MAO coatings and AZ91 alloy were also carried out using an oscillating friction and wear tester in a ball-on-disc contact configuration. The wear resistance of the MAO coatings is improved respectively under different treatment time as a result of different structures of ceramic coatings formed on AZ91 alloy.

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.

Adhesive strength and structure of micro-arc oxidation ceramic coatings grown in-situ on LY12 aluminum alloy

The ceramic coatings containing zirconium dioxide were grown in-situ on LY12 aluminium alloy by micro-arc oxidation in mixed zirconate and phosphate solution. The phase composition and morphology of the coatings were studied by XRD and SEM. The adhesive strength of ceramic coatings was assessed by thermal shock test and tensile test. The results show that the coating is composed of m-ZrO2,t-ZrO2, and a littleγ-Al2O3. Along the section of the coating, t-ZrO2 is more on both sides than that in the middle, while m-ZrO2 is more in the middle than that on both sides. Meantime the coating is also composed of a dense layer and a loose layer. The coating has excellent thermal shock resistance under 550℃and 600℃. And tensile tests show the adhesive strength of the dense layer of the coating with the substrate is more than 17.5 MPa.

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.

Preparation and structure of microarc oxidation ceramic coatings containing ZrO2 grown on LY12 Al alloy

Ceramic coatings containing ZrO2 were prepared in situ on LY12 aluminum alloy by microarc oxidation（MAO） in the mixed solution of zirconate and phosphate solution.The phase composition and morphology of the coatings were studied by XRD and SEM,respectively.The growing mechanism of ceramic coatings was discussed in a preliminary manner.The results show that with an increase in MAO time,the compactness of the coating improved and the thickness increased.From the inner layer to the coating surface,the content of Zr increased,while the content of Al decreased.In addition,the coating was composed of m-ZrO2,t-ZrO2,and a little amount of γ-Al2O3.With an increase in reaction time,the relative content of t-ZrO2 within the coating sharply decreased while the relative content of m-ZrO2 sharply increased,and then both generally kept at a constant level after 60 min.

Microstructure and oxidation resistance of reactive plasma clad Cr_7C_3/γ-Fe ceramic composite coating

A new type oxidation resistance in situ Cr7 C3/γ-Fe ceramic composite coating was fabricated on hardened and tempered grade C steel by reactive plasma clad with Fe-Cr-C alloy powders. The oxidation resistance of the ceramic composite coating was investigated under the test condition of 900 ℃ and 50 hours. The results indicate that the coating has a rapidly solidified microstructure consisting of blocky primary Cr7 C3 and the inter-blocky Cr7 C3/γ-Fe eutectics and is metallurgically bonded to the hardened and tempered grade C steel substrate. The high temperature oxidation resistance of the coating is up to 1.9 times higher than that of grade C steel. The oxidation kinetics curve of the coating is conforming to the parabolic-rate law equation. The excellent oxidation resistance of the coating is mainly attributed to the continuous oxide films which consist of Cr203 and Fe203. The continuous oxide films can prevent the inner part of the coating from being further oxidized.

Salt spray corrosion test of micro-plasma oxidation ceramic coatings on Ti alloy

Ceramic coatings were prepared on Ti-6Al-4V alloy in NaAlO2 solution by micro-plasma oxidation （MPO）. The salt spray tests of the coated samples and the substrates were carded out in a salt spray test machine. The phase composition and surface morphology of the coatings were investigated by XRD and SEAM. Severe corrosion occurred on the substrate surface, while there were no obvious corrosion phenomena on the coated samples. The coatings were composed of Al2TiO5 and a little α-Al2O3 and mille TiO2, and the salt spray test did not change the composition of the coatings. The weight loss rate of the coatings decreased with increasing MPO time because of the increase in density and thickness of the coatings. The surface morphology of the coatings was influenced by salt spray corrosion test. Among the coated samples, the coating prepared for 2 h has the best corrosion resistance under salt spray test.

Effects of Yttrium Ion on Formation Mechanism of ZrO_2-Y_2O_3 Ceramic Coatings Formed by Plasma Electrolytic Oxidation on Al-12Si Alloy

ZrO2-Y2O3 ceramic coating was produced by plasma electrolytic oxidation （PEO） on ZAlSil2Cu3Ni2 alloy. The microstructure and phase composition of the coating were investigated by SEM and XRD.： The results show that adding an appropriate amount of yttrium ion can improve the growing rate of ceramic coating at different oxidation stages and decrease arc voltage. The thickness of ZrO2-Y2O3 coating is 16 μn thicker than that of ZrO2 coating and the maximum oxidation rate improves by 0.6 μm/min. In addition, the arc voltage decreases from 227 to 172 V. It can be seen that the rate of oxidation firstly increases to some extent and then decreases with the content of yttrium ion increasing. The growth rate reaches the maximum while the content of yttrium ion is 0.05 g-L-1The maximum thickness is 90 μm.Compared to ZrO2 coating, the micropores of ZrO2-Y2O3 coating are less and the ceramic layer is repeatedly deposited by ZrO2 and Y2O3 ceramic particles. Meanwhile, the binding force between coating and substrate is better and the coating is uniform and compact. The ceramic layer is mainly composed of c-Y0.15Zr0.85O1.93□0.07, m-ZrO2, α-Al2O3, ,γ-Al2O3 and Y2O3. It is indicated that ZrO2 has beert fully stabilized by yttrium ion through the formation of solid solution.

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.

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.

Compound Ceramic Coatings Grown by Micro-plasma Oxidation on Ti-6Al-4V Alloy

Compound ceramics coatings on the Ti-6Al-4V alloy were prepared by the direct current micro-plasma oxidation （MPO） in NaAlO2 solution. The composition and morphology of the coatings were studied with the X-ray diffraction （XRD） and the scanning electron microscopy （SEM）, respectively. Inductively coupled plasma atomic emission spectrometer technique was used to analyze the solution features of Ti-6Al-4V alloy in the process of preparation. The results reveal that Al2TiO5 forms in the coatings at the initial stages of MPO reaction, and its content changes rapidly with the reaction continuing： after 20 min, the ceramics coatings are composed of α-Al2O3, 7-Al2O3 and Al2TiO5, but after 40 min, its main composition is of α-Al2O3. The content of Ti in the solution will increase when the MPO time extends, and as will Al in the anode area until, after 30 min, it reaches the maximum and keeps constant from then on. Both substrata of Ti and Al in the electrolyte join the MPO reaction at the initial stage, where the formation of Al2TiO5 happens; but as the MPO reaction prolongs, more and more Al in the electrolyte will take part in the reaction, leading to the appearance of a large amount ofAl2O3.

Compound Ceramic Coatings on Ti-6Al-4V by Micro-Plasma Oxidation in NaAlO_2 Solution

Micro-plasma oxidation (MPO) technique is a new technique by which compound ceramic coating can be grown in situ on Al, Ti, Mg and many other valve-metals. Compound ceramic coatings on Ti-6Al-4V alloy were prepared for different time by pulsed bi-polar MPO in NaAlO2 solution. The phase composition, morphology and the element distribution of the coatings were studied by XRD, SEM and JEOL SUPERPROBE 733 electric probe, respectively. Electrochemical Impedance Spectra (EIS) of the coatings were measured to study the structure character of the coatings. Through the proper EIS interpreting software, the "equivalent circuit" of the coatings was established, and the fitting values of equivalent element were calculated. The coating is mainly composed of Al2TiO5, a-A12O3 and rutile TiO2. The content of Ti element in the coating is less than that of substrate; its distribution is relatively uniform, and Ti in the outer layer is less than that in the inner layer. The content of Al in the coating is more than that of substrate, and its distribution is not even: Al in the middle part is more than that on both sides of the coating; And the EIS analysis has illustrated the double-layer structure of the coatings, and the outside layer is loosen and the inner layer compact; with the increase of the oxidizing time, the surface roughness of the coatings, and the porosity of the outer layer of the coating are increased while the compactness of the inner layer of the coatings are improved.

Structure and tensile/wear properties of microarc oxidation ceramic coatings on aluminium alloy

Thick and hard ceramic coatings were prepared on the Al-Cu-Mg alloy by microarc oxidation in alkali-silicate electrolytic solution. The thickness and microhardness of the oxide coatings were measured. The influence of current density on the growth rate of the coating was examined. The microstructure and phase composition of the coatings were investigated by means of scanning electron microscopy, energy dispersive spectroscopy, and X-ray diffraction. Moreover, the tensile strength of the Al alloy before and after microarc oxidation treatment were tested, and the fractography and morphology of the oxide coatings were observed using scanning electron microscope. It is found that the current density considerably influences the growth rate of the microarc oxidation coatings. The oxide coating is mainly composed of α-Al2O3 and γ-Al2O3, while high content of Si is observed in the superficial layer of the coating. The cross-section microhardness of 120 μm thick coating reaches the maximum at distance of 35 μm from the substrate/coating interface. The tensile strength and elongation of the coated Al alloy significantly decrease with increasing coating thickness. The microarc oxidation coatings greatly improve the wear resistance of Al alloy, but have high friction coefficient which changes in the range of 0.70.8. Under grease lubricating, friction coefficient is only 0.15 and wear loss is less than 1/10 of the loss under dry friction.