Effects of Additives on the Microstructure and Tribology Performance of Ta-12W Alloy Micro-Arc Oxidation Coating

Oxide ceramic coatings were fabricated on tantalum alloys by micro-arc oxidation (MAO) to improve their hardness and tribological properties. The MAO coatings were manufactured in a mixed silicatephosphate electrolyte containing NaF and/or EDTA (ethylene diamine tetraacetic acid). The surface morphology,cross-sectional view, chemical composition, hardness, and wear performance of the coatings were analysed. As revealed by the scanning electron microscopy, silica-rich nodules appear on the MAO coating obtained in the silicate-phosphate electrolyte, but the formation of nodules is inhibited with NaF and/or EDTA in the electrolyte.Also, they reduce the roughness and improve the compactness of the coatings, which are composed of Ta_(2)O_(5),(Ta, O), and TaO. A thick and hard coating is obtained in the NaF-containing electrolyte, and the tribology performance is effectively improved. With additives, the nodule structure is detached from the coating surface and dissolved in the electrolyte. By using NaF as an electrolyte additive, the abrasion performance of the MAO coating is enhanced by decreasing the nodule structure, increasing the size of micropores, and improving the coating hardness.

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.

Visualization of atomic scale reaction dynamics of supported nanocatalysts during oxidation and ammonia synthesis using in-situ environmental(scanning) transmission electron microscopy

Reaction dynamics in gases at operating temperatures at the atomic level are the basis of heterogeneous gas-solid catalyst reactions and are crucial to the catalyst function.Supported noble metal nanocatalysts such as platinum are of interest in fuel cells and as diesel oxidation catalysts for pollution control,and practical ruthenium nanocatalysts are explored for ammonia synthesis.Graphite and graphitic carbons are of interest as supports for the nanocatalysts.Despite considerable literature on the catalytic processes on graphite and graphitic supports,reaction dynamics of the nanocatalysts on the supports in different reactive gas environments and operating temperatures at the single atom level are not well understood.Here we present real time in-situ observations and analyses of reaction dynamics of Pt in oxidation,and practical Ru nanocatalysts in ammonia synthesis,on graphite and related supports under controlled reaction environments using a novel in-situ environmental(scanning) transmission electron microscope with single atom resolution.By recording snapshots of the reaction dynamics,the behaviour of the catalysts is imaged.The images reveal single metal atoms,clusters of a few atoms on the graphitic supports and the support function.These all play key roles in the mobility,sintering and growth of the catalysts.The experimental findings provide new structural insights into atomic scale reaction dynamics,morphology and stability of the nanocatalysts.

Surface modification of biomedical magnesium alloy wires by micro-arc oxidation

Magnesium alloy wires were processed by micro-arc oxidation （MAO） in a modified silicate-phosphate composite electrolyte containing hydroxyapatite （HA） nanopowders and NaOH. Effects of NaOH content in the composite electrolyte on the microstructure and properties of the MAO ceramic coatings on magnesium alloy wires were studied. It is found that the arc voltage of magnesium alloy wires in the micro-arc oxidation process is significantly reduced while the oxidation rate is accelerated. Addition of 2 g/L NaOH in the composite electrolyte is a better choice for improving corrosion resistance of magnesium alloy wires. During early simulated body fluids （SBF） immersion, the micro-arc oxidized magnesium alloy wires undergo a slow and stable degradation. After soaking for 28 d, the protective ceramic coating still shows no damage but significant degradation is observed for magnesium alloy wires after immersion for more than 60 d.

Microstructure and mechanical properties of ceramic coatings formed on 6063 aluminium alloy by micro-arc oxidation

The microstructure and mechanical properties of ceramic coatings formed on 6063 aluminium alloy obtained in silicate-,borate- and aluminate-based electrolyte without and with nanoadditive Al2O3 and TiO2 by micro-arc oxidation（MAO） were studied by scanning electron microscopy（SEM）,energy-dispersive X-ray spectroscopy（EDS）,X-ray diffraction（XRD）,microhardness and friction-abrasion tests,respectively.SEM results show that coatings with nanoadditive have less porosities than those without nanoadditive.XRD results reveal that nanoadditive-containing coatings contain more oxides compared with nanoadditive-free coatings in all cases,which are consistent with the EDS analysis.Mechanical properties tests show that nanoadditive Al2O3-containing coatings have higher microhardness values compared with the other coatings obtained in silicate-,borate- and aluminate-based electrolyte.On the other hand,nanoadditive has a positive effect on improving the wearing-resistance of MAO coatings in all cases.Furthermore,the borate-MAO coatings present an inferior anti-wearing property compared with the silicate- and aluminate-MAO coatings for both the nanoadditive-free and nanoadditive-containing coatings.

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.

Effects of nano-additive TiO_2 on performance of micro-arc oxidation coatings formed on 6063 aluminum alloy

Ceramic coatings were fabricated on aluminum doped with different concentrations of TiO2 nano-additive. alloy substrates by micro-arc oxidation （MAO） in silicate electrolytes Effects of nano-additive concentration on the structural and mechanical properties of the MAO coatings were analyzed. The results revealed that some nano-particle were incorporated into the resulting coating during the MAO process, while there was a reasonable concentration for the TiO2 nano-additive. With increasing the nano-additive concentration to 3.2 g/L, the adhesion value increased, while mean friction coefficient and mass loss decreased. A further increase of nano-additive deteriorated the adhesion and mean friction coefficient values, which was consistent with the micro-hardness tests.

Optimization of dual electrolyte and characteristic of micro-arc oxidation coating fabricated on ZK60 Mg alloy

Micro-arc oxidation （MAO） process was carried out in a dual electrolyte system of NaAlO 2 and Na 3 PO 4 to develop compact, smooth and corrosion-resistant coatings on ZK60 Mg alloy by single factor experiments. The microstructural characteristics of coatings were investigated by X-ray diffractometry （XRD） and scanning electron microscopy （SEM） coupled with energy dispersive X-ray spectroscopy （EDS）. Test of mass loss was conducted at a 3.5% NaCl solution to assess the resistance to corrosion. The effect of every element in the dual electrolyte system on voltage—time responses during MAO process and the coating characteristic were also analyzed and discussed systematically via single factor experiments. The results reveal that the main components of NaAlO 2 and Na 3 PO 4 as well as additives of NaOH, NaB4O7 and C6H5Na3O7 demonstrate different effects on MAO process and coating characteristics. By means of single factor experiments, an optimized dual electrolyte system was developed, containing 17.5 g/L NaAlO 2, 5.0 g/LNa3 PO4, 5.0 g/L NaOH, 3.0 g/L NaB4O7 and 4.2g/LC6H5Na3O7 .

Preparation and characterization of ZrO_2/TiO_2 composite photocatalytic film by micro-arc oxidation

ZrO2/TiO2 composite photocatalytic film was produced on the pure titanium substrate using in-situ Zr（OH）4 colloidal particle by the micro-arc oxidation technique and characterized by scanning electron microscope （SEM）, energy dispersive X-ray （EDX）, X-ray diffraction （XRD） and ultraviolet-visible （UV-Vis） spectrophotometer. The composite film shows a lamellar and porous structure which consists of anatase, futile and ZrO2 phases. The optical absorption edge of film is shifted to longer wavelength when ZrO2 is introduced to TiO2. Furthermore, the photocatalytic reaction rate constants of degradation of rhodamine B solution with ZrO2/TiO2 composite film and pure TiO2 film under ultraviolet irradiation are measured as 0.0442 and 0.0186 h 1, respectively.

Structure and corrosion resistance of modified micro-arc oxidation coating on AZ31B magnesium alloy

A hydrophobic surface was fabricated on a micro-arc oxidation (MAO) treated AZ31 Mg alloys via surface modification with myristic acid. The effects of modification time on the wettability of the coatings were investigated using the contact angle measuring device. The surface morphologies and structure of the coatings were evaluated using SEM, XRD and FT-IR. The corrosion resistance was investigated by potentiodynamic polarization curves and long-term immersion test. The results showed that the water contact angle (CA) increases gradually with modification time from 0 to 5 h, the highest CA reaches 138° after being modified for 5 h, and the number and size of the micro pores are decreased. The modification method hardly alters crystalline structure of the MAO coating, but improves the corrosion resistance based on the much positive potential and low current density. Moreover, the corrosion resistance and hydrophobicity can be enhanced with increasing the alkyl chain. The wetting and spreading for the alkylcarboxylate with low surface energy become easier on the micro-porous surface, and alkylcarboxylate monolayer will be formed through bidentate bonding, which changes the surface micropores to a sealing or semi-sealing structure and makes the MAO coating dense and hydrophobic. All the results demonstrate that the modification process improves the corrosion protection ability of the MAO coating on AZ31B Mg alloy.

Preparation and osteoinduction of active micro-arc oxidation films on Ti-3Zr-2Sn-3Mo-25Nb alloy

A layer of porous film containing Ca and P was prepared by the micro-arc oxidation method on the surface of a novel near β biomedical Ti-3Zr-2Sn-3Mo-25Nb alloy, and then NH2- active group was introduced to the films by activation treatment. The phase composition, surface micro-topography and elemental characteristics of the micro-arc oxidation films were investigated with XRD, SEM, EDS and XPS, and the osteoinduction of the micro-arc oxidation films was tested using the simulated body fluid immersion, the in-vitro osteoblast cultivation test and animal experiment. The results show that the oxide layer is a kind of porous ceramic intermixture and contains Ca and P. The films in the simulated body fluid can induce apatite formation, resulting in excellent bioactivity. The cell test discovers that osteoblasts can grow well on the surface of micro-arc oxidation films. And the Ti-3Zr-2Sn-3Mo-25Nb biomedical alloy coated with active porous calcium-phosphate films shows better osteoinduction in vivo.

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.

Enhanced corrosion resistance of micro-arc oxidation coated magnesium alloy by superhydrophobic Mg-Al layered double hydroxide coating

To further enhance the corrosion resistance of the porous micro-arc oxidation(MAO) ceramic layers on AZ31 magnesium alloy, superhydrophobic Mg-Al layered double hydroxide(LDH) coating was fabricated on MAO-coated AZ31 alloy by using in-situ growth method followed by surface modification with stearic acid. The characteristics of different coatings were investigated by XRD, SEM and EDS. The effect of the hydrothermal treatment time on the formation of the LDH coatings was studied. The results demonstrated that the micro-pores and cracks of MAO coating were gradually sealed via in-situ growing LDH with prolonging hydrothermal treating time. Electrochemical measurement displayed that the lowest corrosion current density, the most positive corrosion potential and the highest impedance modulus were observed for superhydrophobic LDH/MAO coating compared with those of MAO coating and LDH/MAO coating. Immersion experiment proved that the superhydrophobic LDH/MAO coating with the active anti-corrosion capability significantly enhanced the long-term corrosion protection for MAO coated alloy.

Investigation of a novel self-sealing pore micro-arc oxidation film on AM60 magnesium alloy

Micro-arc oxidation(MAO)is one of the promising methods to improve the corrosion resistance of magnesium alloys.However,there are plenty of micro-pores in the traditional MAO films,deteriorating their protection property.A novel self-sealing pore MAO film was developed in this paper.The morphologies and chemical composition of the film were detected by scanning electron microscopy(SEM)and energy dispersive X-ray spectroscopy(EDX).The corrosion behavior was investigated by electrochemical and salt spray tests.The possible film formation and corrosion mechanisms were proposed.The self-sealing pore film presents a blue appearance.Most of the micro-pores in the surface of the film are sealed during the film formation process.The chemical composition of the film mainly contains Mg,O,Ti,F and P.The self-sealing pore film exhibits better corrosion resistance compared with the traditional silicate film.Especially,the self-sealing pore film keeps intact after salt spray test for 2000 h,which can be attributed to its high compactness.

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.

Corrosion and wear properties of micro-arc oxidation treated Ti6Al4V alloy prepared by selective electron beam melting

In order to analyze the effect of voltage during micro-arc oxidation(MAO)on corrosion and wear properties of Ti6Al4V(TC4),the MAO technology was employed to treat TC4 samples fabricated by selective electron beam melting(SEBM)at the voltages of 400,420 and 450 V.The results show that the metastable anatase phase gradually transforms to rutile phase with oxidation time and temperature increasing.The surface morphology of coating contains numerous micropores with uniform size distribution.Cracks and pores over 10μm are found on MAO-TC4 sample with applied voltage of 450 V.The thickness of MAO coating is positively correlated with the voltage.The corrosion resistance and wear resistance are related to phase composition,micropore size distribution on the surface and film thickness.When the voltage is 420 V,the coating shows the smallest corrosion current density(0.960×10^-7 A/cm^2)and the largest resistance(7.17×10^5Ω·cm^2).Under the same load condition,the coating exhibits larger friction coefficient and wear loss than the TC4 substrate.With the increase of voltage,the wear mechanism of the coating changes from abrasive wear to adhesive wear,and the adhesive wear is intensified at applied voltage of 450 V,with a maximum friction coefficient of 0.821.

Research of growth mechanism of ceramic coatings fabricated by micro-arc oxidation on magnesium alloys at high current mode

Micro-arc oxidation(MAO)coatings of ZK60 magnesium alloys were formed in a self-developed dual electrolyte composed of sodium silicate and phosphate at the high constant current of 1.8 A(15 A/dm^(2)).The MAO process and growth mechanism were investigated by scanning electron microscopy(SEM)coupled with an energy dispersive spectrometer(EDS),confocal laser scanning microscopy and X-ray diffraction(XRD).The results indicate that the growth process of MAO coating mainly goes through“forming→puncturing→rapid growth of micro-arc oxidation→large arc discharge→self-repairing”.The coating grows inward and outward at the same time in the initial stage,but outward growth of the coating is dominant later.Mg,Mg_(2)SiO_(4) and MgO are the main phases of ceramic coating.