Improvement in corrosion resistance of micro-arc oxidation coating on PVD Ti-coated aluminum alloy 7075

Surface treatments are always needed to enhance corrosion-resistant performance of aluminum (Al) alloys when they are used in seawater environments. The paper aimed to prepare the composite oxide ceramic coating on Al alloy 7075 by combining micro-arc oxidation (MAO) and magnetron sputtering technology. The Al substrate was precoated with titanium (Ti) layer by using the magnetron sputtering technology and then treated by MAO in the alkaline aluminate electrolyte, resulting in a composite MAO coating, which is composed of Al₂O₃ and TiO₂ along with the complex oxide (Al₂TiO₅). The potentiodynamic polarization and electrochemical impedance spectroscopy were carried out to evaluate the corrosion performance of the MAO coatings in 3.5 wt% NaCl solution. Better corrosion resistance was observed for composite oxide coating than the reference MAO coating on the bare Al, as evidenced by the higher corrosion potential of −0.664 V versus Ag/AgCl and the lower corrosion current density of 4.41 × 10^-6 A/cm².     

Wear resistance of alumina-coated oil casing steel N80 via MAO with rare earth additive

The wear resistance of oil casing steel N80 was improved by packing its aluminide prelayer at a relative low temperature. Then, an alumina coating was obtained through microarc oxidation (MAO), in which different La₂O₃ contents were added into the electrolyte. The chemical compositions and microstructures of the as-prepared coatings were characterized through scanning electron microscopy (SEM) equipped with energy-dispersive spectrometer (EDS). The wear resistance of the coated oil casing steel N80 under simulated oil and gas well condition was also investigated. With 1.5 g/L La₂O₃ addition, a denser alumina coating containing α-Al₂O₃ and γ-Al₂O₃ with 1750 HV microhardness value was obtained. Under the simulated oil and gas well wear condition, the oil casing steel N80 with an alumina ceramic coating, which was prepared by adding 1.5 g/L La₂O₃ in the electrolyte, showed a stable friction coefficient and low weight loss. Among the steel samples in this study, the oil casing steel N80 with an alumina ceramic coating exhibited the least wear debris and the shallowest groove. The influence mechanism of rare earth on the microstructure of the ceramic coating via MAO was discussed in detail.     

Effect of ultra accurate control of electrolyte temperature on the performance of micro arc oxidation ceramic coatings

The technique of micro arc oxidation (MAO) uses arc discharge and high-voltage breakdown to produce a ceramic layer on valve metal surfaces. However, the common method of MAO requires immersing the workpiece in an electrolyte solution, which can result in elevated temperatures due to the arc discharge, thus negatively affecting the coating's quality and performance. This article investigates the influence of electrolyte temperature on the performance of MAO ceramic coatings, with the assistance of a robotic arm enabling valve metal reaction without immersion in the electrolyte, and precise control of electrolyte temperature through a MAO temperature monitoring system. Various techniques, such as scanning electron microscopy (SEM), hardness testing, electrochemical corrosion experiments, and friction-wear experiments, were utilized to characterize the performance of the prepared coating. The results indicate a nonlinear correlation between the temperature of the electrolyte and the thickness and hardness of the ceramic coating. The corrosion and wear resistance of the MAO ceramic coatings initially improve with increasing electrolyte temperature but eventually deteriorate. At an electrolyte temperature of 40 °C, the MAO ceramic coating exhibits the optimal corrosion and wear resistance. The variation in electrolyte temperature affects the reactivity of the electrolyte ions, leading to changes in the morphology and properties of the resulting MAO ceramic coating. These findings offer valuable insights into the interaction mechanism between electrolyte temperature and the properties of the resulting MAO ceramic coating. This is of great significance in optimizing the MAO process for specific applications and improving the overall performance of ceramic coatings.     

Influences of electrolytes on tribocorrosion performance of MAO coating on AZ31B magnesium alloy in simulated body fluid

In this paper, the effects of electrolytes on the corrosion resistance and tribocorrosion performance of micro-arc oxidation (MAO) coatings on AZ31B magnesium (Mg) alloys in simulated body fluid (SBF) were studied. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) were utilized to explore the microstructure, surface morphology, and phase components of the MAO coatings. Corrosion and tribocorrosion performance of MAO coated Mg alloys were evaluated by using potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and a ball-on-disk tribotester. It was found that MAO coating produced in electrolyte containing both Na₂SiO₃ and Na₂B₄O₇ exhibited superior corrosion resistance and tribocorrosion performance in the SBF.     

三乙醇胺在镁合金阳极氧化中的作用

在由KOH、Na₂SiO₃、Na₂B₄O₇ 和三乙醇胺等组成的电解液中,以恒电流方式对AZ91D镁合金进行阳极氧化处理,并研究了三乙醇胺浓度对AZ91D镁合金阳极氧化膜层性能的影响规律。利用电压-时间曲线,全浸腐蚀实验、动电势极化曲线和扫描电镜（SEM）等方法检测和观察阳极氧化膜层的性能和表面形貌。实验结果表明：三乙醇胺可以有效抑制火花放电,增加膜层的厚度,使表面孔隙变小,提高表面光洁度;当三乙醇胺浓度为30 g•dm^-3时,膜层耐蚀性能最好;在阳极氧化过程中,三乙醇胺化学吸附于镁合金表面,从而改变微弧氧化过程中氧气气泡在镁合金表面的吸附强度和氧气气泡的大小,降低了微弧氧化陶瓷层孔隙率,提高了阳极氧化膜的致密性和耐蚀性。     

Preparation of a thick sponge-like structured amorphous silica ceramic coating on 6061 aluminum alloy by plasma electrolytic oxidation in TEOS solution

Plasma electrolytic oxidation (PEO) was performed on 6061 aluminum alloy in organosilicon electrolyte using a stepwise constant potential control method for 23 min. The resulting coating was a sponge-like structured amorphous silica ceramic with a thickness of about 130 μm. Its exceptional wear resistance was attributed to the high hardness of the silica ceramic and the low elastic modulus of the sponge-like structure. The corrosion resistance was enhanced by a dense layer of approximately 2 μm between the coating and the substrate. Impressively, the indentation depth of the PEO coating during nano-indentation tests was only 50–60% of that of 6061 aluminium alloy under varying loads, while the recovery depth of the PEO coating after unloading was 2.5–3.1 times greater than that of 6061 aluminium alloy. Due to its special composition and structure, the PEO coating caused serious wear to the high hardness Si₃N₄ friction balls during the friction and wear test. In the electrochemical tests, the coating reduced the corrosion current density from 1.056 × 10⁻⁵A·cm⁻² to 1.239 × 10⁻⁷A·cm⁻², while extending the passivation region from 0.322 V to 1.032 V.     

Corrosion resistance of oxide layers formed on AZ91 Mg alloy in KMnO4 electrolyte by plasma electrolytic oxidation

The plasma electrolytic oxidation (PEO) process in AZ91 Mg alloy is studied using a solution containing KOH + KF + Na₂SiO₃ both with and without potassium permanganate (KMnO₄). The addition of potassium permanganate to the electrolyte influences coating thickness, surface morphology and the microstructure of oxide layers obtained by the PEO process. Oxide layers formed on AZ91 Mg alloy by the electrolyte containing KMnO₄ consists of MgO, MgF₂, Mg₂SiO₄ and Mn₂O₃. The corrosion resistance of the sample processed in bath containing KMnO₄ was superior to that of the sample processed in the bath without KMnO₄. It is suggested that enhancement of the corrosion resistance of AZ91 Mg alloy depends strongly on the presence of manganese oxide in the oxide layer.     

Influence of additives on microstructure and property of microarc oxidized Mg–Si–O coatings

Ceramic coatings were fabricated on ZK60 magnesium alloy substrate by microarc oxidation (MAO) in Na₂SiO₃–KOH base electrolyte with four kinds of additives (i.e. KF, NH₄HF₂, C₃H₈O₃ and H₂O₂). The effects of these additives on microstructure and property of coatings were investigated. The surface morphology, phase composition and corrosion resistance of the ceramic coatings were analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and simulation body fluid (SBF) immersion test respectively. It is found that different additives can change the spark discharge phenomenon during microarc oxidation. It is proved that both potassium fluoride (KF) and ammonium bifluoride (NH₄HF₂) promote discharge and accelerate reaction while the introduce of glycerol (C₃H₈O₃) leads to the refining of sparks and reduction of thermal effects. Results also demonstrate that the introduce of hydrogen peroxide (H₂O₂) contributes to the increase of coating surface roughness and enlargement of surface micropore size. XRD results indicate that the ceramic coatings are mainly composed of Mg₂SiO₄, MgSiO₃ and SiO₂. The introduce of H₂O₂ hinders the reaction between SiO₂ and MgO and creates favorable conditions for the formation of the MgO phase. The ceramic coatings formed in base electrolyte containing 7 g/L NH₄HF₂ and 5 mL/L C₃H₈O₃ exhibit the highest corrosion resistance.     

Effect of Y2O3 on acid resistance of alumina ceramic

This work aimed to improve the acid resistance of an alumina ceramic. Acid corrosion of alumina ceramic composed of Al₂O₃-CaCO₃-SiO₂-MgO-Y₂O₃ (ACSMY) was investigated in a hydrochloric-hydrofluoric acid solution at 65 °C for 30 min. The effect of Y₂O₃ content on sintering temperature, density, and acid solubility were discussed. The composition and microstructure of this material were analyzed. The acid solubilities of minor crystal phases (Y₃Al₅O₁₂, CaAl₁₂O₁₉, Ca₂Al₂SiO₇, and CaAl₂Si₂O₈) and the effect of them on acid resistance of this alumina ceramic were studied. The results showed that Y₂O₃ additive can enhance density and change the type of phases. Phases with good acid resistance and dense structure lead to a crust formed on the surface of ceramic during acid corrosion. The crust can effectively protect the interior structure of the sample from acid solution, and then improve the acid resistance of the material.     

Effects of graphene content in alkaline silicate electrolyte on AA1060 pure aluminum micro-arc oxidation coating

Ceramic coatings were obtained by micro-arc oxidation (MAO) on the surface of AA1060 pure aluminum in alkaline silicate electrolyte with the addition of graphene. The effects of graphene contents in the range of 0–.30 g/L in the electrolyte on surface morphology, corrosion resistance, and wear resistance of the ceramic coatings were investigated. The outer surface structure, outer surface element content, coating cross-section structure, coating cross-section element content, coating/substrate interface structure, and coating phase were characterized by scanning electron microscope and X-ray diffraction. Potentiodynamic polarization and electrochemical impedance spectroscopy were used to evaluate the corrosion behavior of MAO samples in a 3.5-wt% NaCl solution. In addition, the resistance to sliding and abrasive wear of the oxide coating were studied experimentally. The results show that the alkaline silicate electrolyte with the addition of graphene has a significant effect on the characteristics of MAO coating. The performance of micro-arc oxide coatings is best when the graphene content in the electrolyte is .15 g/L, the average thickness of the film is 7.24 μm, the average pore size is 6.07 μm, the impedance value is approximately 4.01 × 106 Ω, and its friction coefficient is .55.     

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.     

Role of rare-earth Y addition on formation and anticorrosion properties of MAO coating on 2024 aviation aluminum alloy

Different ceramic coatings were prepared on the surface of 2024 aviation aluminum alloy using micro-arc oxidation process in silicate based electrolyte combined with the rare earth based compound Y(NO₃)₃·6H₂O. The thickness, hardness of the coating and conductivity of electrolyte were tested using relative devices, morphology and chemical composition were studied by scanning electron microscope and energy dispersive spectroscope, respectively. The phase composition of the coatings was characterized by X-ray diffraction and X-ray photoelectron spectroscopy. Furthermore, the corrosion resistance of the coating was evaluated by an electrochemical workstation. The results showed that the addition of Y(NO₃)₃·6H₂O could improve the thickness and hardness of the coating. The morphological observation of the coating showed that Y(NO₃)₃·6H₂O was successfully incorporated into the ceramic layer and that the coating had the smallest porosity at 1.5 g/L Y(NO₃)₃. The phase composition of the coating was mainly γ-Al₂O₃, α-Al₂O₃, SiO₂, Y₂O₃, and AlPO₄. The corrosion resistance of coating in simulated seawater with the addition of Y(NO₃)₃·6H₂O was significantly improved, and the values of |Z|_0.01 Hz and corrosion rate of the coating reached the maximum and minimum at 1.5 g/L Y(NO₃)₃, which were 5.63 × 10⁵ Ω cm² and 7.444 × 10⁻⁴ mm/a, respectively.     

Enhanced corrosion protection for MAO coating on magnesium alloy by the synergism of LDH doping with deposition of 8HQ inhibitor film

The inherent micropores of micro-arc oxidation (MAO) coatings on magnesium alloy often cause poor long-term corrosion resistance. Herein, a low-porosity and high corrosion-resistant 8HQ/LDH/MAO composite coating, comprising a layered double hydroxide (LDH)-doped MAO primer and a top layer of 8-hydroxyquinoline (8HQ) inhibitor film, was deposited onto the magnesium alloy surface. Characterizations such as high-resolution field-emission transmission electron microscopy were performed to observe the synthesized nanoparticles’ morphology, size, composition, and structure. Results confirmed the successful synthesis of nitrate ion intercalated MgAl-LDH nanosheets and demonstrated the increase in thickness and denseness of the MAO coating after LDH doping. Based on electrochemical impedance spectroscopy and Tafel curves, the corrosion current density (j_corr) of the newly fabricated 8HQ/LDH/MAO composite coating was reduced by about three orders of magnitude. The low-frequency impedance modulus (|Z|_ƒ=0.1 Hz) increased by nearly four orders of magnitude compared with that of bare Mg alloy. After 14 days of exposure to the corrosive electrolyte, the composite coating maintained a low j_corr, showing significantly enhanced corrosion resistance compared with single MAO coating. These findings demonstrated the synergism of LDH doping with 8HQ sealing to enhance the corrosion protection of MAO coating on magnesium alloy.     

Electrochemical behavior of AZ91D magnesium alloy in phosphate medium—part I. Effect of pH

The influence of pH on the corrosion behavior of Mg-based AZ91D alloy was investigated in a constant composition phosphate medium using various electrochemical techniques, complemented with surface analysis data. The studied solutions were 0.1 M H₃PO₄, NaH₂PO₄, Na₂HPO₄ and Na₃PO₄ having pH values of 1.8, 4.5, 9.1 and 11.8, respectively. Spontaneous passivation was substantiated from monitoring the continuous positive shift of the open circuit corrosion potential with both immersion time and solution pH. The impedance data indicated more improvement in the insulating properties of the corrosion products formed on the alloy surface with increase in pH. The electrolyte pH plays a determinant influence on surface film properties, as films formed in phosphate solutions with higher pH values are thicker, thus affording better protection for the alloy than those formed in acidic solutions. Good agreement was observed between the results obtained from electrochemical techniques and those from EDX and XRD examinations. The alloy is more susceptible to corrosion in acidic phosphate solutions than in the alkaline ones. Crystalline magnesium (Mg), magnesium hydride (MgH₂) and magnesium oxide (MgO) were found to be the main constituents of the surface film after holding for 2 h in the acidic phosphate medium.     

Effect of La2O3 on the oxidation resistance of SiC ceramic at 1973 K: Experimental and theoretical study

The effect of La₂O₃ on the oxidation resistance of SiC ceramic at 1973 K was investigated using isothermal oxidation test and first-principles calculations. The SiC ceramic with La₂O₃ shows a better oxidation resistance compared with that without La₂O₃ due to the in situ formed La₂Si₂O₇ in SiO₂ glass layer after oxidation at 1973 K. First-principles calculations based on density functional theory were applied to analyze the solution behaviors of La atom in the surface of SiO₂ and La₂Si₂O₇. The solution energy of La atom in SiO₂ (0 1 1) is −19.05 eV, which is far less than −4.19 eV in La₂Si₂O₇ (2 0 1) with a La vacancy, thus resulting in that La atom in La₂Si₂O₇ (2 0 1) diffuses into SiO₂ (0 1 1). The SiO₂ lattice with an interstitial La atom is more stable than that with a substitutional La atom and the interstitial La breaks the nearest Si–O bond to form La–O and La–Si bonds, which is beneficial to improving the high-temperature stability of SiO₂. Experimental and theoretical results indicate that the formation of refractory La₂Si₂O₇ phase enhances the stability of SiO₂ glass layer, so as to protect SiC ceramic from further oxidation at 1973 K.     

Corrosion resistance of plasma-anodized AZ91D magnesium alloy by electrochemical methods

Anodic coatings formed on magnesium alloys by plasma anodization process are mainly used as protective coatings against corrosion. The effects of KOH concentration, anodization time and current density on properties of anodic layers formed on AZ91D magnesium alloy were investigated to obtain coatings with improved corrosion behaviour. The coatings were characterized by scanning electron microscopy (SEM), electron dispersion X-ray spectroscopy (EDX), X-ray diffraction (XRD) and micro-Raman spectroscopy. The film is porous and cracked, mainly composed of magnesium oxide (MgO), but contains all the elements present in the electrolyte and alloy. The corrosion behaviour of anodized Mg alloy was examined by using stationary and dynamic electrochemical techniques in corrosive water. The best corrosion resistance measured by electrochemical methods is obtained in the more concentrated electrolyte 3 M KOH + 0.5 M KF + 0.25 M Na₃PO₄·12 H₂O, with a long anodization time and a low current density. A double electrochemical effects of the anodized layer on the magnesium corrosion is observed: a large inhibition of the cathodic process and a stabilization of a large passivation plateau.     

Influence of nanocrystallization on passive behavior of Ni-based superalloy in acidic solutions

The electrochemical corrosion behaviors of Ni-based superalloy nanocrystalline coating (NC) fabricated by a magnetron sputtering technique have been investigated in comparison with cast alloy in 0.25 M Na₂SO₄ + 0.05 M H₂SO₄ and 0.5 M NaCl + 0.05 M H₂SO₄ solution, respectively. Compared with cast alloy, the NC coating had a little higher passive current density in Na₂SO₄ acidic solution, while it had superior resistance to pitting corrosion in NaCl acidic solution. The semiconductive type of passive film of the NC coating was p-type in both acidic solutions, while, that of cast alloy changed from p-type in Na₂SO₄ acidic solution to n-type in NaCl acidic solution. XPS results indicated that Cr₂O₃ was the main component for the passive films of the NC coating as well as those of the cast alloy. No chloride ion was found in the passive film of NC coating while it was in the passive film of cast alloy. The chloride ions adsorbing on the surface of cast alloy incorporated into the passive film, which induced the formation of n-type oxide film. The nanocrystallization of Ni-base superalloy obviously weakened the adsorption of chloride ions on surface, which decreased the susceptibility of pitting corrosion in acidic solution.     

医用镍钛合金表面微弧氧化膜层的显微结构及耐蚀性

采用由NaAlO2和NaH2PO2组成的电解液,以微弧氧化技术在医用镍钛合金表面制备Al2O3陶瓷膜层,以减少合金表面Ni含量,并进一步提高其耐腐蚀性能,使其具有良好的生物相容性.随微弧氧化过程中处理时间的延长,试样表面的游动火花由白色逐渐向橙色转变,火花数减少但尺寸增大.所得陶瓷膜层由γ-Al2O3晶相组成,随着处理...     

Sol-enhanced electroplating of nanostructured Ni-TiO2 composite coatings—The effects of sol concentration on the mechanical and corrosion properties

Novel sol-enhanced Ni-TiO₂ nano-composite coatings were electroplated by adding a transparent TiO₂ sol into the traditional electroplating Ni solution. It was found that the structure, mechanical properties and corrosion resistance of the nano-composite coatings were largely determined by the sol concentration. The higher sol concentration in the plating electrolyte led to a higher content of TiO₂ nano-particles in the coating matrix. The coating prepared at the sol concentration of 12.5 mL/L had the best microhardness, wear resistance and corrosion resistance. Adding excessive sol to the electrolyte changed the surface microstructure, caused cracking on the coating surface and deteriorated the properties. It was demonstrated that the corrosion resistance of the composite coatings is determined by two factors: surface microstructure and incorporation of TiO₂ nano-particles.     

Mixed modifier effects on structural,mechanical, chemical,and mechanochemical properties of sodium calcium aluminosilicate glass

Glass properties are governed by the interplay between network formers and network modifiers; for a given composition of network formers, the ratio of different cationic modifiers compensating the anionic species in the network has a profound effect, which is often nonlinear, called a mixed modifier effect (MME). We have investigated the MME of sodium (Na) and calcium (Ca) in an aluminosilicate (NCAS) glass series following the formula [Na₂O]_30−x [CaO]_x [Al₂O₃]₁₀ [SiO₂]₆₀, where x = 0, 7.5, 15, 22.5, and 30. A nonadditive trend was observed in hardness and indentation toughness, with aqueous corrosion resistance exhibiting a shift from incongruent to congruent corrosion, whereas the network structure determined by molecular dynamics simulations revealed no significant trend with composition. Additionally, the NCAS glass containing both [Na₂O] and [CaO] within an intermediate range exhibited superior resistance to wear at high humidity, a clear MME phenomenon previously only observed in soda–lime silica.