Investigation of wear and corrosion resistance of nanocomposite coating formed on AZ31B Mg alloy by plasma electrolytic oxidation

Ceramic-WC coatings were prepared on AZ31 B Mg alloy by plasma electrolytic oxidation (PEO) from a phosphate based bath containing suspended tungsten carbide nanoparticles at various process times. Scanning electron microscope results indicated that increase of coating time and incorporation of tungsten carbide into the ceramic coating during the PEO process led to a decrease in the number and diameter of coating pores. Phase analysis showed that the nanocomposite coating was composed of MgO, Mg₃(PO₄)₂ and WC. Tribological properties and corrosion behaviour of uncoated AZ31 B Mg alloy and ceramic coatings were evaluated using a pin-on-disc tribometer and potentiodynamic polarisation technique in 3.5% NaCl solution, respectively. The wear and electrochemical tests showed that wear and corrosion resistance of ceramic-WC nanocomposite coatings were better than ceramic only ones. In addition, wear and corrosion behaviour of coatings improved with increasing the coating time.     

Characterization of plasma electrolytic oxidation coatings formed on Mg–Li alloy in an alkaline silicate electrolyte containing silica sol

We investigate the influence of silica sol addition on the ceramic coatings of Mg–Li alloy by plasma electrolytic oxidation (PEO) in an alkaline silicate electrolyte. Scanning electron microscopy, X‐ray diffraction, X‐ray photoelectron spectroscopy, and energy dispersive spectroscopy are employed to characterize the microstructure and composition of the ceramic coatings. The anti‐corrosion behavior of the ceramic coatings is evaluated by potentiodynamic polarization measurements in conjunction with electrochemical impedance analysis. The ceramic coating formed in the electrolyte containing silica sol contains SiO₂ and Mg₂SiO₄ phase and has more uniform morphology and higher corrosion resistance than that formed in the electrolyte without addition of silica sol.     

Effect of treatment time on a PEO-coated AZ31 magnesium alloy

Plasma electrolytic oxidation (PEO) coatings were formed in a phosphate–silicate-based electrolyte containing K₂ZrF₆ on an AZ31 Mg alloy. The physical and chemical properties of the coatings were investigated using scanning electron microscopy, atomic force microscopy, X-ray diffraction (XRD), potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS). The results showed that the thickness of the PEO coatings increased linearly with increased treatment times. Additionally, the micropores on the coating surfaces increased in size, but decreased in porosity with increased PEO treatment time. The XRD results showed that the coatings were mainly composed of MgO, MgF₂, MgSiO₃, and ZrO₂, and the electrochemical tests revealed that the corrosion resistance of the coatings increased with increased treatment time. Besides, the EIS results correlated well with the potentiodynamic polarization test results.     

Characterization of plasma electrolytic oxidation coatings formed on Mg–Li alloy in an alkaline polyphosphate electrolyte

Blue and white ceramic coatings have been successfully fabricated on the surface of Mg–Li alloys by plasma electrolytic oxidation (PEO) in an alkaline polyphosphate electrolyte with and without addition of titania sol. The influence of titania sol on the surface morphology, microstructure, phase composition, chemical composition, corrosion resistance, mechanical and tribological behavior of ceramic coatings was scrutinized by means of scanning electron microscopy (SEM), thin-film X-ray diffraction (TF-XRD), X-ray photoelectron spectroscopy (XPS), potentiodynamic polarization, nanoindentation measurements, and ball-on-cylinder friction testing. The blue ceramic coating containing MgO, TiO₂ and Ti₂O₃ phase exhibits better anticorrosion and tribological performance due to its higher nanohardness and lower friction coefficient.     

Preparation and characterization of duplex PEO/MoC coatings on Mg-Li alloy

A combined PEO and chemical conversion process was employed to fabricate duplex plasma electrolytic oxidation/molybdate conversion (PEO/MoC) coating on the surface of Mg-Li alloy. The microstructure and composition of the composite coatings were investigated by SEM, EDX, XRD and XPS. The anti-corrosion properties of duplex PEO/MoC coatings were evaluated by potentiodynamic polarization and EIS. The duplex PEO/MoC coating was composed of crystalline NaMgF₃, Mg₂SiO₄, MoO₃ and MgO. Spherical-like microparticles accumulated and dispersed uniformly on the surface of the PEO coating. The corrosion resistance for Mg-Li alloy was improved by using a combination of plasma electrolytic oxidation and chemical conversion.     

Investigation of Corrosion Protection Performance of Multiphase PEO (Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript>, MgO,MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript>) Coatings on Mg Alloy Formed in Aluminate-Silicate- based Mixture Electrolyte

Plasma electrolytic oxidation (PEO) coatings in the aluminate-silicate-based mixture electrolyte solution with different duty cycles were successfully applied on Mg alloy. The corrosion behavior of the samples was evaluated by water contact angle test, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and immersion tests. Hydrophobic PEO coating could be obtained by adjusting the duty cycle of the applied electric signal. This coating considerably diminished the Mg dissolution and could enhance the impedance values of Mg alloy in 3.5 wt % NaCl solution. However, the surface of other PEO coated samples showed more hydrophilic properties compared to that of the uncoated sample. Dense structure of the modified PEO multiphase (including Mg₂SiO₄, MgO and MgAl₂O₄ phases) coating and also its appropriate thickness provided an effective barrier to remarkably delay corrosive solution penetration into the PEO coating. This phenomenon led to major decrease in anodic current density of alloy in chloride solution.     

Ceria/stannate multilayer coatings on AZ91D Mg alloy

In this work, CeO₂/stannate multilayer coatings on AZ91D magnesium alloy were successfully obtained by chemical conversion and sol–gel dip coating. The stannate conversion coatings were prepared from a stannate aqueous bath containing Na₂SnO₃, CH₃COONa, Na₃PO₄ and NaOH at different temperatures and immersion times. Ceria films were produced on stannate/AZ91D starting from Ce(III) nitrate solutions in H₂O. In some cases, the PVA was added as chelating agent. Ceria top coatings were fired at 200 °C for 1 h. Coating microstructure was examined by FE-SEM. Finally, the corrosion resistance features of the coatings were tested by the electrochemical impedance spectroscopy (EIS) in 3 wt.% NaCl solution. The effect of PVA addition was evaluated in terms of microstructure and corrosion resistance features. CeO₂/stannate multilayer films, 3 μm thick, uniform, well adherent and nearly crack free were obtained. The formation of CeO₂ phase was confirmed by XRD and XPS analyses. The XPS depth profiles showed a limited diffusion of Mg towards the ceramic film. The EIS tests showed a significant improvement of corrosion resistance of the multilayer coatings (~ 16.6 kΩ after 48 h in NaCl solution) with respect to the blank alloy (~ 2.4 kΩ after 48 h in NaCl solution).     

An Investigation into the Corrosion Behavior of MgO/ZrO<Subscript>2</Subscript> Nanocomposite Coatings Prepared by Plasma Electrolytic Oxidation on the AZ91 Magnesium Alloy

Plasma electrolytic oxidation (PEO) of AZ91 Mg alloys was performed in ZrO₂ nanoparticles containing Na₂SiO₃-based electrolytes. The phase composition and the microstructure of PEO coatings were analyzed by x-ray diffraction and scanning electron microscopy followed by energy dispersive spectroscopy. Pitting corrosion properties of the coatings were investigated using cyclic polarization and electrochemical impedance spectroscopy tests in a Ringer solution. The results showed the better pitting corrosion resistance of the composite coating, as compared to the oxide one, due to the thickened inner layer and the decrease in the surface defects of the composite coating. Also, the PEO process decreased the corrosion current density from 25.06 µA/cm² in the Mg alloy to 2.7 µA/cm² in the oxide coating and 0.47 µA/cm² in the composite coating.     

Improving the corrosion performance of epoxy coatings by chemical modification with silane monomers

In this communication, commercial epoxy resins were chemically modified with various silane monomers under the catalysis of organotin compound, aiming to enhance the corrosion resistance of epoxy coatings on 2024-T3 aluminum substrates. Immersion studies conducted in 3.5 wt.% NaCl solution showed that the coating capacitance (C_c) decreases significantly after the silane modification, as measured by electrochemical impedance spectroscopy (EIS), indicating the higher resistance to water permeation. EIS measurements also indicated an enhancement in protectiveness of silane-modified epoxy coatings against substrate corrosion, which was characterized by higher charge transfer resistances (R_ct) and lower double layer capacitance (C_dl) at substrate/electrolyte interface. The adhesion of epoxy coatings was also found to improve after the modification with silane components. The best performance was observed for coating system modified by 3-glycidoxypropyltrimethoxy silane (GPTMS).     

镁合金微弧氧化陶瓷膜的制备及耐蚀性能

利用微弧氧化技术在AZ91D镁合金表面原位生成含有钙、磷元素的陶瓷膜层.用SEM、XRD、EDS等研究陶瓷膜微观形貌、相组成及元素含量,利用Tafel和EIS技术来评价陶瓷膜的腐蚀性能.结果表明,所制备的陶瓷膜层成功地引入了钙和磷元素,陶瓷膜层主要由Mg2SiO4和MgO相组成.增加钙盐浓度,可以使膜层内的钙元素含量增多,微孔增加并且出现了微裂纹.电化学测试表明陶瓷膜使得镁合金在0.9%NaCl生理盐水中的耐蚀性提高了1～2个数量级,当钙盐浓度为0.3 g/L时,陶瓷膜层的耐蚀性最好.     

Corrosion and wear resistance of AZ31 Mg alloy treated by duplex process of magnetron sputtering and plasma electrolytic oxidation

In order to improve the wear and corrosion resistance of AZ31 magnesium alloy, a magnetron-sputtered Al layer with a thickness of 11 μm was firstly applied on the alloy, and then treated by plasma electrolytic oxidation (PEO) in an aluminate and silicate electrolytes, respectively. The performance of PEO coatings was investigated by dry sliding wear and electrochemical corrosion tests. The aluminate coating exhibits excellent wear resistance under both 10 and 20 N loads. The silicate coating only shows low wear rate under 10 N, but it was destroyed under 20 N. Corrosion tests show that the Al layer after magnetron sputtering treatment alone cannot afford good protection to the Mg substrate. However, the duplex layer of PEO/Al can significantly improve the corrosion resistance of AZ31 alloy. Electrochemical tests show that the aluminate and silicate coatings have corrosion current densities of ∼1.6×10⁻⁶ and ∼1.1×10⁻⁶ A/cm², respectively, which are two orders lower than that of the un-coated AZ31 alloy. However, immersion tests and electrochemical impedance spectroscopy (EIS) show that the aluminate coating exhibits better long-term corrosion protection than silicate coating.     

The effect of interlayer on corrosion resistance of ceramic coating/Mg alloy substrate in simulated physiological environment

Ceramic coatings are deposited on biodegradable magnesium alloys by physical vapor deposition to reduce the electrochemical activity in the simulated physiological environment. Although an interlayer is generally used to reduce the mismatch between the hard coating and soft substrate, the effects of the interlayer on the electrochemical corrosion behavior have seldom been explored. In this work, AlO_xN_y ceramic coatings were deposited on AZ31 magnesium alloys with Al or Ti interlayers. Polarization tests and electrochemical impedance spectroscopy (EIS) were conducted to evaluate the corrosion resistance in the cell culture medium. The AlO_xN_y ceramic coating significantly improved the bio-corrosion resistance of the magnesium alloy, but the Ti interlayer accelerated the corrosion rate. In comparison, although the addition of an Al interlayer led to smaller enhancement in the surface mechanical properties of the AlO_xN_y coating, corrosion could be impeded effectively. Our results indicate that an Al interlayer is preferred over Ti and the corrosion failure mechanism is discussed from the perspective of defects.     

The effect of substrate composition on the electrochemical and mechanical properties of PEO coatings on Mg alloys

Plasma electrolytic oxidation (PEO) is a unique surface treatment technology which is based on anodic oxidation forming ceramic oxide coatings on the surface of light alloys such as Mg, Al and Ti. In the present study, PEO coatings prepared on AZ91D, AZ31B, AM60B and AM50B Mg alloys have been investigated. Surface morphology and elemental composition of coatings were determined using scanning electron microscope (SEM) equipped with energy dispersive spectrometer (EDS). SEM results showed that the coating exhibited a porous top surface layer and a subsequent dense layer with micro-pores and shrinkage cracks. Phase analysis of coatings was carried out by X-ray diffraction (XRD). XRD analyses indicated that PEO coatings on AZ alloys had higher amount of Periclase (MgO) followed by the presence of Spinel (MgAl₂O₄) e.g. on the AZ91D alloy compared to that on AM series alloys. In order to examine the effect of substrate composition on adhesion strength of PEO coating scratch tests were carried out. Electrochemical corrosion tests were undertaken by means of potentiodynamic polarization technique in 3.5% NaCl solution at room temperature (20 ± 2 °C). Corrosion test results indicated that the corrosion rates of coated Mg alloys decreased by nearly two orders of magnitude as compared to bare Mg alloys. PEO coatings on AZ series alloys showed better corrosion resistance and higher adhesion properties than AM series alloys. In addition to the PEO processing parameters, such are mainly attributes of the compositional variations of the substrate alloys which are responsible for the formation, phase contents and structural properties of the PEO coatings.     

Corrosion behavior in boiling dilute HCI solution of different ceramic coatings fabricated by plasma spraying

An Al₂O₃ ceramic coating (A), a 13 wt.% TiO₂-Al₂O₃ (13TA) composite ceramic coating, and a Ni-Al-13wt.%TiO₂-Al₂O₃ (NA-13TA) gradient composite ceramic coating were prepared on Q235 steel by plasma spraying. The corrosion behavior of samples sprayed with these coatings in a boiling 5% HCl solution was investigated. It was shown that an A ceramic coating and a 13TA composite ceramic coating were destroyed after immersion for 17 and 23 h, respectively. The NA-13TA gradient composite ceramic coating was still sound after 14 days of immersion. The corrosion resistance of samples with the NA-13TA gradient composite ceramic coating was sharply improved due to the decreased amount of connected pores in the coating. The corrosion of the sample sprayed with the gradient ceramic coating included the partial corrosion of the surface ceramic coating and the interlayer coatings. The corrosion weight loss depended on the degree of open porosity.     

Microstructure and corrosion behavior of plasma electrolytic oxidation coated magnesium alloy pre-treated by laser surface melting

An AZ91D magnesium alloy was treated using duplex techniques of laser surface melting (LSM) and plasma electrolytic oxidation (PEO). The microstructure, composition and corrosion behavior of the laser melted surface, PEO coatings, LSM–PEO duplex coatings as well as the as-received specimen were characterized by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD) and electrochemical corrosion tests, respectively. Especially, the effect of LSM pre-treatment on the microstructure, composition and corrosion resistance of the PEO coatings was investigated. Results showed that the corrosion resistance of AZ91D alloy was marginally improved by LSM due to the refinement of grains, redistribution of β-phase (Mg₁₇Al₁₂) and increase of Al on the surface. Both the PEO and duplex (LSM–PEO) coatings improved significantly the corrosion resistance of the AZ91D alloys, while the duplex (LSM–PEO) coating exhibited better corrosion resistance compared with the PEO coating.     

Mechanistic interpretation of electrochemical behaviour of galvannealing coating in saline environment

A comparative study on galvannealed (GA) and galvanised plain-skin passed (GP-SP) coatings was carried out to evaluate coating microstructures, the corrosion resistance and electrochemical behaviour in 3.5% NaCl solution. The corrosion resistance behaviour of GA coating was found to be superior compared to GP-SP coating. The Fe-Zn intermetallic phases formed in GA coating provided galvanic protection i.e., a cell reaction between Fe and Zn within a single phase. This gives rise to protective potential plateau and are believed to be responsible for the electrochemical polarisation resulting in sluggish corrosion reaction kinetics, thereby reducing the corrosion rate significantly after prolonged exposure in saline environment. It was also observed from the electrochemical impedance spectroscopy (EIS) study that the coating capacitance (C_c) decreased and polarisation resistance (R_p) increased with exposure time indicating a continuous charge transfer reaction across the coating and electrolyte interface. Although the corrosion potential of both coatings increased towards more noble direction with exposure time, it was observed that the potential for GA coatings was always nobler than GP-SP coating as E_corr shifted towards more positive potential corresponding to a flat potential band of −850 ± 20 mV.     

Corrosion electrochemical characteristics of red iron oxide pigmented epoxy coatings on aluminum alloys

Red iron oxide pigmented epoxy coatings were prepared on aluminum alloys and were characterized by electrochemical impedance spectroscopy (EIS) immersed in NaCl solution. The evolutions of impedance models of coated metals were obtained by the fitting analysis of experimental data using suitable equivalent electrical circuits (EEC). The results indicated that the composite electrode system could be fitted by three impedance models. At the initial immersion stage, coatings acted as a barrier layer and only performed a simple circuit consisting of a coating resistance (R_c) parallel to a coating capacitance (C_c). After a certain time of exposure, water and (or) oxygen arrived at the metal surface through the coating, leading to the formation of electrochemical corrosion sites at metal interface and thereby the appearance of double-layer capacitance (C_dl) and charge transfer resistance (R_ct). After intensive attacking of metal substrates, the mass transfer of corrosion products was in difficulty. In this case, the diffusion elements were added to the EEC. It was found that due to the presence of inert pigment particles, the mass transfer behaviors were interestingly different from those of the varnish polymer coatings. Electrical parameters were also obtained from the EIS data. lnC_c-time curve showed a Case II water sorption kinetics, typical non-Fickian diffusion for water uptake.     

Electrochemical corrosion behavior of plasma sprayed Al2O3‐13%TiO2 coatings in aqueous hydrochloric acid solution

One kind of conventional and two kinds of nanostructured Al₂O₃‐13%TiO₂ coatings were prepared by plasma spray process. The phase composition and microstructure of coatings were examined by means of scanning electron microscopy (SEM) and X‐ray diffraction (XRD). The potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) were used to investigate the corrosion behavior of coatings in aqueous hydrochloric acid solution. The results showed that nanostructured coatings had superior corrosion resistance compared to conventional Metco 130 coating. The corrosion resistance of coatings was mainly related to their microstructure and defects density. The EIS measurement for long time immersion in hydrochloric acid solution revealed that the corrosion resistance of coatings decreased with the increasing of immersion time. During the immersion period, electrochemical corrosion mainly occurred on the carbon steel substrate under NiCrAl coatings. In addition, the Al₂O₃‐13%TiO₂ coatings were also failed during corrosion in aqueous hydrochloric acid solution.     

Corrosion and surface study of sputtered Al–W coatings with a range of tungsten contents

The corrosion behaviour of sputter-deposited, Al–W coatings with three different concentrations of tungsten (0.6, 3.5 and 11 at.% W) on AA7075 aluminium alloy substrates was investigated in chloride media using EIS, salt-fog tests and surface analyses. The surface analyses were performed with XPS/AES, SEM/EDS and TEM microscopy. The presence of W reduces the thickness of the oxide layer formed after the EIS test, as proved by the compositional depth profile. From the EIS data of the investigated Al–W_x coatings, the polarisation resistance (R_p) and the capacitive behaviour as a function of the immersion time were obtained. A small increase in R_p suggested improved corrosion properties over time. However, the extent of the improvement depends on the content of W and the coating-surface morphology (the presence of growth defects on the coating surface). The capacitive behaviour observed at high frequencies was related to the dielectric properties and the thickness of the barrier oxide film formed. The salt-fog tests to some extent supported the results from the EIS measurements. However, there was a difference between the corrosion EIS and salt-fog test results in the case of the Al₈₉W₁₁ coatings. The thickest oxide layer and the “layering” into the three regions (porous, semi-porous and intact) were observed when the salt-fog corrosion test was performed on the Al₈₉W₁₁ coating. Galvanic corrosion, probably due to the local compositional and structural inhomogeneities, takes place. However, this was not unambiguously observed during the EIS corrosion test.     

AM50镁合金表面含氧化锆的微弧氧化复合涂层的形成过程(英文)

采用扫描电镜(SEM)和电子衍射能谱(EDX)研究在含K2ZrF6的溶液中AM50镁合金表面复合微弧体氧化涂层的形成过程。采用电化学阻抗谱(EIS)研究在微弧体氧化制备膜层过程中膜层耐腐蚀性能的变化。结果表明:当电压小于起弧电压时,合金表面膜层的主要成分为MgO和MgF2;当施加电压超过起弧电压时,锆氧化物开始在合金表面沉积,且膜层的耐腐蚀性随着电压的升高而提高。