Micro-arc Oxidation Film Research Articles

Effects of electrolytic concentration on properties of micro-arc film on Ti6Al4V alloy

To study the effect of electrolytic concentration, bioactive ceramic films containing Ca and P on the surface of the Ti6Al4V alloy were prepared by micro-arc oxidation (MAO) in aqueous solutions of different concentrations. Composition, micro-morphology, wettability of the films and their corrosion behavior in a Hank's SBF were studied. Our experimental results show that the film is mainly composed of anatase, rutile and amorphous phases. With an increase in electrolytic concentration, the ratio of rutile in films enlarge and small amounts of calcium phosphate (Ca 3(PO 4) 2) and hydroxyapatite (HA) appear. The number of micropores in films increases but their dimensions decrease and their porosities increase slightly. As the surface roughness of MAO film increases with concentration, the wettablility of the oxide film improves continually, while micro-hardness increases at first and then decreases. MAO treatment clearly improves the corrosion resistance of substrates in a Hank's SBF.

Preparation and activation of micro-arc oxidation films on a TLM titanium alloy

In order to improve the biocompatibility and surface activity of a TLM alloy, a layer of a porous TiO2 film was prepared by the micro-arc oxidation method on the surface, and then the NH−2 active group was introduced on the film by an activation treatment in an aminated solution. The phase identification and surface characteristics of the micro-arc oxidation films were characterized by XRD, XPS, SEM and EDS. The in vitro blood compatibility of the TLM alloy samples with and without surface modification was evaluated by contact angle tests, hemolysis tests and electrochemical tests. The results indicate that the biocompatibility and surface activity of the TLM alloy could be remarkably improved by surface modification of micro-arc oxidation and activation treatment.

Preparation of bioceramic films containing hydroxyapatites on Ti–6Al–4V alloy surfaces by the micro-arc oxidation technique

The bioceramic films containing hydroxyapatite (HAP) were synthesized on Ti–6Al–4V alloy surfaces using the micro-arc oxidation technique. The influences of electric current density and treating time of micro-arc oxidation on the phase behavior of the bioceramic films were studied. XRD and SEM were utilized to characterize the phase formation and surface morphologies of the bioceramic films. The results revealed that electric current density and micro-arc oxidation time were two important factors for the formation of HAP, and the micro-arc oxidation films were composed of HAP, TiO 2, and Ca 3(PO 4) 2.

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, β-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 μm, 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.

Structure and apatite formation of microarc oxidized TiO 2-based films before and after alkali-treatment by various alkali concentrations

Alkali-treatment was performed to modify the surface of the TiO 2-based film containing Ca and P prepared by microarc oxidation (MAO) technique for improving the apatite-forming ability of the MAO film. Before alkali-treatment, in the MAO film amorphous and crystalline regions with main composition of Ti, Ca, P and Al both were observed; and in the latter TiO 2 nanocrystals were randomly distributed in Ca- and P-doped matrix. After alkali-treatment, the surfaces of the MAO films become rough, and the Ca and P concentrations decrease with increasing the concentration of NaOH solution (1, 3 and 5 mol/L). When 5 mol/L NaOH solution was used, amorphous calcium titanate hydrogel was formed on the surface, showing a nanoflake-like morphology. In vitro experiment indicates that the ability to induce apatite formation of the alkali-treated MAO films increase with increasing the concentration of NaOH solution, which is associated with the formation of Ti–OH groups during the incubation process in a simulated body fluid.

Microstructure and apatite-forming ability of the MAO-treated porous titanium

Porous titanium was treated by micro-arc oxidation (MAO) in the aqueous electrolytes containing 0.1 and 0.2 M NaOH. The microstructure (including morphology, phase component, element composition and chemical species) and in vitro apatite-forming ability of the oxidized films formed on the inner-pore walls of porous titanium were investigated. It is found that continuous thin films with pore sizes of 20–60 nm are formed in both electrolytes. The films consist of an amorphous TiO 2 outmost layer, a coexisted intermediate layer of amorphous TiO 2 and rutile, and a Ti 2O 3 bottom layer, and tightly bond to the titanium substrate without any cracks. In vitro bioactivity assessment shows that both MAO films possess high apatite-forming abilities. It is also found that, compared with the film formed in the 0.1 M NaOH-containing electrolyte, the film formed in the 0.2 M NaOH-containing electrolyte has a higher roughness and more nanopores which help shorten apatite induction time. It is expected the MAO-formed bioactive porous titanium will not only be beneficial to bone ingrowth into the porous structure, but also be beneficial to achieve a tough chemical bonding at the bone/implant interface.

Corrosion Behavior of AZ31 Magnesium Alloy with Microarc Oxidation Film Irradiated by High-Intensity Pulsed Ion Beam

The microarc oxidation (MAO) films on AZ31 magnesium alloy were modified by high-intensity pulsed ion beam (HIPIB) at an ion current density of 200 A/cm2 with 1-5 shots. The modified MAO films presented a corrosion resistance superior to that of the original films. Scanning electron microscopy (SEM) observation revealed that a sealing layer was formed on the MAO films by HIPIB irradiation. The corrosion behaviors of the MAO films in 3.5 % NaCl solution were characterized by using electrochemical impedance spectroscopy (EIS). The noticeable improvement in the corrosion resistance of MAO films is attributed to the blocking effect of the sealing layer that hinders the process of electrolyte penetrating the MAO films to the magnesium alloy.

The effect of chemical treatment on apatite-forming ability of the macroporous zirconia films formed by micro-arc oxidation

Macroporous and nano-crystalline zirconia film was prepared by micro-arc oxidation (MAO) of zirconium, and the effect of chemical treatment in H 2SO 4 or NaOH aqueous solutions on the microstructure and apatite-forming ability of the film was investigated. Compared with the MAO film, the chemically treated films do not exhibit apparent changes in phase component, morphology and grain size, however, have more abundant basic Zr–OH groups. The films treated with H 2SO 4 and NaOH solutions can induce apatite formation on their surfaces in simulated body fluids (SBF) within 1 day, whereas no apatite was detected on the untreated ZrO 2 surface by 30 days. It is believed that the enhanced apatite-forming ability of the chemically treated ZrO 2 films is related to the abundant basic Zr–OH groups on their surface.

Hydroxyapatite coatings produced on commercially pure titanium by micro-arc oxidation

A porous hydroxyapatite (HA) coating on commercially pure titanium was prepared by micro-arc oxidation (MAO) in electrolytic solution containing calcium acetate and β-glycerol phosphate disodium salt pentahydrate (β-GP). 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 an energy dispersive x-ray spectrometer (EDS) and cell culture. The thickness of the MAO film was about 20 µm, and the coating was porous and uneven without any apparent interface to the titanium substrates. The result of XRD showed that the porous coating was made up of HA film. The favorable osteoblast cell affinity gives HA film good biocompatibility. HA coatings are expected to have significant uses for medical applications such as dental implants and artificial bone joints.

Corrosion behavior of micro-arc oxidation film on titanium in simulated body fluid

To investigate the variation of the corrosion resistance of micro-arc oxidation film on titanium by electrochemical methods in simulated body fluid. Micro-arc oxidation film was formed on the titanium surface using micro-arc oxidation. The morphology was observed with scanning electron microscopy (SEM) and the phase composition was analyzed using X-ray diffraction (XRD). Polarization curves and electrochemical impedance spectroscopy (EIS) in simulated body fluid were examined with electrochemical methods. On the titanium surface with micro-arc oxidation, the film consisted of many volcanic micropores. The film formed was a titanium dioxide (TiO(2)) with peaks for both anatase and rutile phases. In addition, hydroxylapatite was also observed. The self-corrosion potential and self-corrosion current density of titanium with micro-arc oxidation film were -0.255 V and 0.80 microA/cm(2) respectively, while those of untreated titanium were -0.358 V and 0.55 microA/cm(2). Electrochemical impedance spectroscopy confirmed the model of equivalent circuits reasonable. The results of electrochemical examinations indicate that micro-arc oxidation film increases the corrosion resistance of titanium.

Thermal stability of titania films prepared on titanium by micro-arc oxidation

Micro-arc oxidation (MAO) is an effective technique to improve the properties of titanium and its alloy by forming a ceramic film on the materials surface. In high-temperature industrial applications, the thermal stability of the films plays a critical role. In order to evaluate the high-temperature stability of titania films synthesized on titanium substrates by MAO, we performed annealing at different temperatures. The composition, structure, and surface morphology of the annealed MAO films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and surface texture tests. Vickers indentation and pin-on-disc testing were also employed to investigate the micro-hardness and wear resistance of the films, respectively. The thermal stability of the MAO titania coatings remain very good up to 800 °C. The effects of post-annealing on the properties of the MAO TiO 2 films and the underlying mechanism are discussed.

Structure and Properties of Microarc Oxidation Films on Zinc-Containing Aluminum Alloy

The wear and corrosion protective films were synthesized on the LC4 Al-Zn-Mg-Cu alloy by microarc oxidation (MAO) technique in an alkali-silicate electrolyte. The microstructure and composition profiles were investigated by scanning electron microscopy and energy dispersive spectroscopy, and the phase structure was performed by X-ray diffraction. The corrosion resistance of coated LC4 alloy was evaluated using potentiodynamic polarization curves. The MAO film consists of γ-Al2O3, α-Al2O3 and amorphous SiO2 phases. The film up to 210 μm contains two layers. The Si element from electrolyte enriched in the outer layer film. After microarc oxidation treatment, the microhardness and corrosion resistance of LC4 alloy were improved significantly.

Structure and In Vitro Bioactivity of Si Enriched Hydroxyapatite/TiO<sub>2</sub> Coatings on Pure Titanium by Micro-Arc Oxidation

The effect of Si doping on the bioactivity and characteristics of hydroxyapatite/TiO2 composite films was investigated. Pure titanium plates were treated to form Ca, P and Si enriched titania-based films by using micro-arc oxidation (MAO). Then, some specimens were undergone a further hydrothermal treatment to produce a thin outermost layer of hydroxyapatite (HA). Experiments revealed that that the film, which was about 10μm thick, was composed of amorphous silicon dioxide, amorphous calcium phosphate, rutile and anatase. The film was porous and uneven, with the pore size of 1-4μm. No obvious cracks exist on the surface. In order to investigate the cytocompatibility of the films, periodontal ligament (PDL) cells were seeded onto the surface of the films. It was concluded that the Si ion did not influence the characters of MAO film but Si enriched hydroxyapatite/ TiO2 composite coatings exhibited an effect on cell attachment.

Preparation of hydroxyapatite-containing titania coating on titanium substrate by micro-arc oxidation

Hydroxyapatite-containing titania coatings on titanium substrates were formed by micro-arc oxidation (MAO) in electrolyte containing calcium acetate monohydrate (CH 3COO) 2Ca·H 2O) and sodium phosphate monobasic dihydrate (NaH 2PO 4·2H 2O) using a pulse power supply. Scanning electron microscopy (SEM) with Energy dispersive X-ray spectrometer (EDX) and X-ray diffraction (XRD) were employed to characterize the microstructure, elemental composition and phase components of the coatings. The coatings were rough and porous, without apparent interface to the titanium substrates. All the oxidized coatings contained Ca and P as well as Ti and O, and the porous coatings were made up of anatase, rutile and hydroxyapatite. Such MAO films are expected to have significant applications as artificial bone joints and dental implants.

Corrosion behaviors and galvanic studies of microarc oxidation films on Al–Zn–Mg–Cu alloy

Corrosion-resistant films were fabricated by the microarc oxidation technique on the LC4 zinc-containing aluminum alloy in silicate electrolyte. The electrochemical corrosion behaviors of LC4 alloy, with and without films, were evaluated using potentiodynamic polarization curves. Galvanic currents and galvanic potentials of bare and coated alloys coupled with copper were measured using the zero-resistance technique. Scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX) was used to analyze the microstructure of films and the corrosion morphology before and after corrosion testing. After microarc discharge treatment, the corrosion potential was increased and the corrosion current was significantly reduced. For a thin film sample, the galvanic current is similar to that of the bare alloy. However, a thick film can protect the LC4 alloy against galvanic corrosion.

Preparation and properties of hydroxyapatite-containing titania coating by micro-arc oxidation

A porous hydroxylapatite-containing titania film was prepared by a electrochemical oxidation method, i.e. micro-arc oxidation (MAO). During the oxidation treatment, the titanium sample was immersed in electrolytic solution containing calcium acetate monohydrate and sodium biphosphate dihydrate by using a pulse power supply. The thickness, phase, composition and morphology of the oxide coating were monitored with X-ray diffraction (XRD) and scanning electron microscopy (SEM) with energy dispersive X-ray spectrometer (EDS). The thickness of the MAO film was about 20 μm and the coating was porous and uneven, without apparent interface to the titanium substrates. The coating formed in the Ca- and P-containing solution with MAO contained Ca and P along with Ti and O. The Ca / P ratio on the surface is 1.63, while that in the interface is 0.51. XRD showed that the porous coating was made up of anatase, rutile and hydroxyapatite. Such MAO films are expected to have significant medical applications as dental implants and artificial bone joints.

RESEARCH STATUS ABOUT SURFACE MODIFICATION OF BIOMEDICAL Ti AND ITS ALLOYS BY MICRO-ARC OXIDATION

Ti and its alloys are considered to be very promising in biological material field. But their biological activity and corrosion resistance in body fluid still need to be improved. As a novel technique for surface treatment, Micro-arc oxidation (MAO) is attracting interest from those who want to improve their implant properties through surface modification. This paper reviewed the application of MAO on biomedical Ti -alloys. The structure characteristic such as surface and cross-section micrographs, phase components, and element distribution were analyzed. The mechanical and biological properties of MAO films were further discussed on this basis. The effects of current density, voltage, and electrolyte on the structure and properties of the films were summarized.

Electrochemical corrosion behavior of composite coatings of sealed MAO film on magnesium alloy AZ91D

Protective composite coatings were prepared on magnesium alloy AZ91D by micro-arc oxidation (MAO) treatment plus a top coating with sealing agent using multi-immersion technique under low-pressure conditions. The corrosion resistance of AZ91D alloy with composite coatings was superior evidently to that with merely MAO film. SEM observations revealed that the sealing agent was integrated with MAO film by physically interlocking; therewith covered uniformly the surface as well as penetrated into pores and micro-cracks of MAO film. The anti-corrosion properties in 3.5% NaCl solution of the composite coatings were evaluated by using electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements. Based on the results of chronopotentiometric ( E ∼ t) and EIS measurements for long time immersion in 3.5% NaCl solution, appropriate equivalent circuits for the composite coatings system were proposed. It follows that due to the blocking effect of the sealing agent in pores and cracks in MAO film, the composite coatings can suppress the corrosion process by holding back the transfer or diffusion of electrolyte and corrosion products between the composite coatings and solution during immersion.

Electrochemical performance of microarc oxidation films formed on AZ91D magnesium alloy in silicate and phosphate electrolytes

This paper reports on studies of the phase composition and electrochemical performances of microarc oxidation (MAO) films formed on AZ91D alloy using step-down current method in phosphate electrolytes (P-film) and silicate electrolytes (Si-film). The results showed that the P-film was mainly composed of Mg, MgAl 2O 4, MgO and the Si-film was composed of Mg 2SiO 4, MgO. There clearly existed a fluoride-enriched zone of about 1∼2 μm for P-film and 0.7∼1 μm for Si-film at the MAO coating/substrate interface. The electrochemical tests showed that both P-film and Si-film could enhance the corrosion resistance of AZ91D magnesium alloy significantly; the corrosion failure processes of the two films in 5 wt.% NaCl solution were quite different.

Photoexcited formation of bone apatite‐like coatings on micro‐arc oxidized titanium

A novel method to rapidly deposit bone apatite-like coatings on titanium implants in simulated body fluid (SBF) is proposed in this article. The processing was composed of two steps; for example, micro-arc oxidation (MAO) of titanium to form titania films, and UV-light illumination of the titania-coated titanium in SBF. The morphology, crystalline structure, and bond strength of the MAO films were investigated as a function of the applied voltage (in the range of 250-400 V) by using scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectrometry, Fourier transform infrared spectroscopy, adhesion-tensile test, and scratch test. Results showed that the MAO films were porous and nanocrystalline with pore sizes varying from 1 to 3 microm and grain sizes varying from 10-20 to 70-80 nm; the predominant phase in titania films changed from anatase to rutile, and the bond strength of the films decreased from 43.4 to 32.9 MPa as the applied voltage increased from 250 to 400 V. After UV-light illumination of the films in SBF for 2 h, bone apatite-like coating was deposited on the MAO film formed at 250 V. The bond strength of the apatite/titania bilayer was about 44.2 MPa. However, no apatite was observed on the MAO film formed at 400 V after UV-light illumination.