Alkaline Silicate Electrolyte Research Articles

Plasma electrolytic oxidation of AMCs

Aluminum Matrix Composites (AMCs) consisting of high-strength alloys and ceramic reinforcement phases exhibit a high potential for security relevant lightweight components due to their high specific mechanical properties. However, their application as tribologically stressed components is limited because of their susceptibility against fatigue wear and delamination wear. Oxide ceramic protective coatings produced by plasma electrolytic oxidation (PEO) can solve these problems and extend the possible applications of AMCs. The substrate material was powder metallurgically processed using alloy EN AW 2017 and SiC or Al2O3 particles. The influence of material properties like particle type, size and volume fraction on coating characteristics is clarified within this work. An alkaline silicate electrolyte was used to produce PEO coatings with technically relevant thicknesses under bipolar-pulsed current conditions. Coating properties were evaluated with regard to morphology, chemical composition, hardness and wear resistance. The particle type proved to have the most significant effect on the coating properties. Whereas compactness and thickness are not deteriorated by the incorporation of thermodynamically stable alumina particles, the decomposition of silica particles during the PEO processes causes an increase of the porosity. The higher silica particle content decreases also the coating thickness and hardness, which leads in particular to reduction of the wear resistance of the PEO coatings. Finally, different approaches for the reduction of the coating porosity of silica reinforced AMCs are discussed.

The influence of current density on the morphology and corrosion properties of MAO coatings on AZ31B magnesium alloy

Micro-arc oxidation (MAO) coatings were prepared on AZ31B magnesium alloy using alkaline silicate electrolyte at different current densities (0.026, 0.046 and 0.067 A/cm2). Field Emission Scanning Electron Microscopy (FESEM) analysis of the coating revealed an irregular porous structure with cracked morphology. Compositional analysis carried out for MAO coating showed the presence of almost an equal amount of Mg and O (34 wt.%) apart from other elements such as F, Si and Al. The cross-sectional FESEM images clearly portrayed that the MAO coating was dense along with the presence of very few fine pores. The surface roughness (Ra) of the coatings increased with an increase in the current density. Potentiodynamic polarization and electrochemical impedance spectroscopic (EIS) studies were carried out for both the bare and MAO coated AZ31B Mg alloy in 3.5% NaCl solution. The corrosion potential (Ecorr) and corrosion current density (icorr) values obtained for the bare substrate were − 1.49 V and 46 μA/cm2, respectively. The coating prepared at 0.046 A/cm2 exhibited the lowest icorr value of 7.79 × 10− 10 A/cm2 and highest polarization resistance (41.6 MΩ cm2) attesting to the better corrosion resistance of the coating compared to other samples. EIS results also indicated almost similar corrosion behavior for the MAO coatings. Mott–Schottky analysis showed n-type and p-type semiconductor behavior for the oxide layer present on the bare magnesium alloy and MAO coatings respectively.

Effects of CH3OH Addition on Plasma Electrolytic Oxidation of AZ31 Magnesium Alloys**supported by National Natural Science Foundation of China (No. 21376088), the Project of Production, Education and Research, Guangdong Province and Ministry of Education (Nos. 2012B09100063, 2012A090300015), and Guangzhou Science and Technology Plan Projects of China (No. 2014Y2-00042)

Plasma electrolytic oxidation (PEO) films on AZ31 magnesium alloys were prepared in alkaline silicate electrolytes (base electrolyte) with the addition of different volume concentrations of CH3OH, which was used to adjust the thickness of the vapor sheath. The compositions, morphologies, and thicknesses of ceramic layers formed with different CH3OH concentrations were determined via X-ray diffraction (XRD), energy-dispersive spectroscopy (EDS), and scanning electron microscopy (SEM). Corrosion behavior of the oxide films was evaluated in 3.5 wt.% NaCl solution using potentiodynamic polarization tests. PEO coatings mainly comprised Mg, MgO, and Mg2SiO4. The addition of CH3OH in base electrolytes affected the thickness, pores diameter, and Mg2SiO4 content in the films. The films formed in the electrolyte containing 12% CH3OH exhibited the highest thickness. The coatings formed in the electrolyte containing different concentrations of CH3OH exhibited similar corrosion resistance. The energy consumption of PEO markedly decreased upon the addition of CH3OH to the electrolytes. The result is helpful for energy saving in the PEO process.

An investigation of (NaPO3)6 effects and mechanisms during micro-arc oxidation of AZ31 magnesium alloy

Micro-arc oxidation (MAO) in an environmentally friendly alkaline silicate electrolyte containing various concentrations of (NaPO3)6 has been used to produce oxide coatings on an AZ31 magnesium alloy. The variations of voltage, current and microdischarges with the treating time were recorded. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) were used to characterize microstructures and compositions of the coatings. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) in the 3.5wt.% NaCl solution were used to evaluate the corrosion behaviors of the coated samples. EIS conducted in the working electrolyte was used to test electrochemical properties of the passive films formed in the initial stage during the MAO process. The results show that (NaPO3)6 concentration significantly influences the initial passive film and hence the voltage rise rate and microdischarges. Further, the corrosion resistance of the samples decreases with increase of (NaPO3)6 concentration due to complex evolution in the microdischarges and the microstructures.

Effect of cathodic micro-discharges on oxide growth during plasma electrolytic oxidation (PEO)

Plasma electrolytic oxidation (PEO) of magnesium alloy is performed in NH4F and alkaline-silicate electrolytes within various waveforms of bipolar current pulses to investigate the role of the cathodic bias on both the growth mechanism of PEO layers and the behavior of micro-discharges. A particular attention is paid to cathodic micro-discharges and their ignition (or not) according to process conditions. Although cathodic micro-discharges have a detrimental effect on PEO layers, cathodic bias is necessary to improve the growth of oxide layers. Conditions that promote cathodic breakdown are discussed and a mechanism of layer cathodic breakdown is proposed. Cathodic micro-discharges, and to a greater extent the applied cathodic bias, influence the anodic breakdown coming immediately after, and therefore, the process behaviour during the anodic bias period.

Correlation between plasma electrolytic oxidation treatment stages and coating microstructure on aluminum under unipolar pulsed DC mode

Alumina coatings were deposited on 6061 aluminum alloy substrates using plasma electrolytic oxidation (PEO) in an alkaline silicate electrolyte. Different electrical parameters, including frequency, duty cycle, and current density were applied to obtain PEO coatings. Scanning electron microscopy (SEM) and microhardness tests were used to investigate the coating microstructure and properties. For each sample, the voltage–time response of the PEO process was obtained and compared with surface morphology, and coating cross sections and thicknesses. Special consideration was given to the connection between the electrical parameters, different stages of the PEO process, and the morphology and microstructure of the coatings. Applying different electrical parameters changed the duration and ratio of the PEO stages in the voltage–time response curve and affected the growth rate, surface morphology, microstructure and microhardness of the coatings. We report the new finding of a correlation between the stage of the PEO process and the microstructure and morphology of the coating.

Suggested mechanism for the MAO ceramic coating on aluminium substrates using bipolar current mode in the alkaline silicate electrolytes

Abstract 102 samples were treated by the micro arc oxidation at different bipolar pulsing periods in the alkaline silicate electrolyte. The obtained results demonstrated that the duty cycle has no correlation with the layer growth or the surface roughness. The results were analyzed by the multiple linear regression and then the proper diagrams for thickness and roughness were plotted. The growth mechanism of the ceramic coating was influenced by many complicated and interrelated factors. We suggested a new mechanism to describe the resultant coating phenomenon taking into account the different reactions during the four periods of bipolar pulsing mode. The plasma discharge generator, anodic period, affected significantly in the layer growth and the surface roughness. The cathodic period affected the growth by the etching-protection effect, and affected the surface morphology by the production of hydrogen gaseous sheath. The contribution of the anodic neutral period was caused by the internal etching. The cathodic neutral period significantly affected the surface roughness by releasing the cathodic-hydrogen gaseous sheath, and contributed in the layer growth. The phase formation was also described by the suggested mechanism.

Effect of current frequency on coating properties formed on aluminised steel by plasma electrolytic oxidation

In the present study, plasma electrolytic oxidation process was carried out on aluminised steel with a pulsed bipolar electrical source at different frequencies, namely, 50, 300, 600 and 1500 Hz with constant 50% duty cycle for 10 min in an alkaline silicate electrolyte. Morphology, wear behaviour and corrosion resistance of the coatings were investigated by scanning electron microscopy, pin on disc and potentiodynamic polarisation experiment in 3·5 wt-%NaCl solution. The results showed that with increasing the pulse frequency, the density of the residual pores increases, but their size as well as the coating thickness decreases. The corrosion current density of the coating processed at 1500 Hz was 1·14×10−8 A cm−2, which exhibited superior corrosion resistance compared with the bare substrate. Lower friction coefficient of the specimen processed at 600 Hz in comparison with that of the specimens prepared at lower frequencies was due to the formation of a less rough coating.

Non-destructive methods to control the properties of MAO coatings on the surface of 2024 aluminium alloy

The kinetic aspects of the coating formation on the 2024 aluminium alloy at different time intervals of the microarc oxidation process (MAO) in an alkaline–silicate electrolyte under the AC current are investigated. Moreover the main reasons of modifications in the MAO coating properties (corrosion resistance, microhardness) and phase composition during the process are shown. Finally, non-destructive control methods of MAO coating properties are worked out.

Morphology and performances of the anodic oxide films on Ti6Al4V alloy formed in alkaline-silicate electrolyte with aminopropyl silane addition under low potential

Oxide films on Ti6Al4V alloy are prepared using sodium hydroxide–sodium silicate as the base electrolyte with addition of aminopropyl trimethoxysilane (APS) as additive by potentiostatic anodizing under 10V. APS is incorporated into the films during anodizing and the surface morphology of the oxide films is changed from particle stacked to honeycomb-like porous surfaces as shown by scanning electron microscopy (SEM) with Energy Disperse Spectroscopy (EDX). The surface roughness and aminopropyl existence on the oxide films result in their differences in wettability as tested by the surface profile topography and contact angle measurements. The anti-abrasive ability of the anodic films is improved with the addition of APS due to its toughening effects and serving as lubricants in the ceramic oxide films as measured by ball-on-disk friction test. Also, potentiodynamic corrosion test proves that their anticorrosive ability in 3.5wt.% NaCl is greatly improved as reflected by their much lower corrosion current (Icorr) and higher corrosion potential (Ecorr) than those of the substrate.

Influence of voltage waveform on anodic film of AZ91 Mg alloy via plasma electrolytic oxidation: Microstructural characteristics and electrochemical responses

Abstract The present study investigated how the voltage waveform influenced the microstructural characteristics and electrochemical responses of the anodic film on AZ91 Mg alloy coated by plasma electrolytic oxidation (PEO). PEO coatings of AZ91 Mg alloy were performed for 600 s in an alkaline silicate electrolyte with respect to the voltage waveform such as half-sine and asymmetric-sine waveforms. Microstructural observations on cross section of the anodic film utilizing scanning electron microscope revealed that the anodic film formed via asymmetric-sine wave was much denser in structure than that via half-sine counterpart since the occurrence of the cathodic breakdown between the anodic pulses could effectively suppress the formation of the micro-pores and discharge channels in the anodic films. Thereby, the hardness and corrosion properties of the anodic film formed by asymmetric-sine wave were found to be superior to those by half-sine wave. In addition, electrochemical responses were interpreted in relation to the equivalent circuit model consisting of resistor and capacitor elements within an electrical cell.

Production of ceramic layers on aluminum alloys by plasma electrolytic oxidation in alkaline silicate electrolytes

Plasma electrolytic oxidation (PEO) of aluminum alloy 5052 in alkaline-silicate electrolytes having different SiO2/Na2O ratios (silicate indexes) was studied. For all the electrolytes 20–90μm thick technological layer was obtained; composition, structure and properties of the oxidized layer were studied. For each sample, the oxidized layer consists of a denser internal and looser external sublayer. While for “n=1 electrolytes” the oxidized layer is mainly formed by several kinds of alumina, the principal constituent of the oxidized layer for “n=3 electrolytes” is mullite.Measurements of microhardness evidenced that it is apparently not influenced by the kind of silicate (n=1 or n=3) and by its concentration in the electrolyte. Electrolytes with silicate index n=3 ensure better corrosion protection than those with n=1. Corrosion protection parameters are significantly better for all PEO oxidized samples than for the untreated Al5052 alloy.

The influences of microdischarge types and silicate on the morphologies and phase compositions of plasma electrolytic oxidation coatings on Zircaloy-2

Plasma electrolytic oxidation coatings were formed in alkaline silicate electrolyte on Zircaloy-2. The evolution of the types of discharges, the microstructures, phase compositions and the corrosion resistance of the coatings were studied by real time imaging, SEM, XRD, and electrochemical tests. Characteristic solidification structures were revealed in the PEO coatings, the formation of the solidification structures is related to the long lasting discharges during the PEO process and the very low thermal conductivity of zirconium oxide. Thermal effect in the coatings and silicate content in the electrolyte affect the phase compositions of the coatings.

Improving Corrosion Resistance of MRI 230D Mg Alloy by Hybrid Coating of Laser Surface Alloying and Plasma Electrolytic Oxidation

A permanent mould cast creep resistant MRI 230D Mg alloy was laser surface alloyed (LSA) with Al and Al2O3 in order to improve its wear and corrosion resistance. However, this treatment was successful only in improving wear resistance but not corrosion resistance due to the presence of micro−cracks in the coated layer, which has been discussed in an earlier paper. The LSA coated Mg alloy has been further subjected to plasma electrolytic oxidation (PEO) treatment in alkaline silicate electrolyte in order to cover those micro−cracks and improve corrosion resistance, which is discussed in the present manuscript. For comparison, the PEO coating has also been applied on the as−cast MRI 230D Mg alloy. The microstructural characterization of coatings and corroded surfaces was carried out by scanning electron microscope and X−ray diffraction. Electrochemical corrosion tests were conducted in 3.5 wt% NaCl solution having neutral pH to investigate the corrosion behavior. The LSA coatings consisted mainly of β (Mg17Al12) phase, the coatings produced by PEO treatment on MRI 230D Mg alloy consisted mainly of Mg2SiO4 phase, and hybrid coatings of PEO on LSA consisted of Mg2SiO4 and MgAl2O4 phases in the PEO layer. Scanning electron micrographs of the cross−section revealed that the PEO treatment covered the micro−cracks present in the LSA and corrosion tests revealed that it improved the corrosion resistance, though not to the extent of the corrosion resistance of the PEO coated MRI 230D Mg alloy. All the samples exhibited localized form of corrosion.

Study of the growth kinetics, microhardness and morphology of PEO coatings formed on Al 2024 alloy in alkaline-silicate electrolytes using different current waveforms

Study of the growth kinetics, microhardness and morphology of PEO coatings formed on Al 2024 alloy in alkaline-silicate electrolytes using different current waveforms

Cathodic pulse breakdown of anodic films on aluminium in alkaline silicate electrolyte – Understanding the role of cathodic half-cycle in AC plasma electrolytic oxidation

Sequential anodic and cathodic pulse voltages were applied on anodised Al micro-electrodes in alkaline silicate electrolyte to explore the role of cathodic pulse in AC or bipolar plasma electrolytic oxidation (PEO) process. SEM observation was carried out to observe the sites of anodic and cathodic breakdown and their morphologies. The prior anodic breakdown accelerated the cathodic breakdown at −50V, and the acceleration was associated with the preferential cathodic breakdown at the anodic breakdown sites. However, the succeeding anodic breakdown during applying anodic pulse of 420V for 2ms was highly suppressed at the cathodic breakdown sites. This would randomise the anodic breakdown sites. Such role may contribute to the formation of rather uniform coatings on aluminium in this electrolyte without large discharge channels when larger cathodic current is applied with respect to the anodic current in AC PEO.

Ceramic Coatings of LA141 Alloy Formed by Plasma Electrolytic Oxidation for Corrosion Protection

Superlight Mg-Li alloy is a promising structural materials in aerospace, automobile, and electronics because of its excellent properties such as low density, high ductility, superior strength-to-weight ratio, and good damping ability. The fabrication of compact plasma electrolytic oxidation coatings with excellent corrosion resistance is valuable for the widespread application of Mg-Li alloy. Here we present a ceramic coating on the surface of Mg-14Li-1Al (LA141) alloy for corrosion protection via plasma electrolytic oxidation (PEO) in an alkaline silicate electrolyte with tungstate as an additive. X-ray photoelectron spectroscopy and thin film-X-ray diffraction analysis of coatings show that the surface coating is mainly comprised of Mg(2)SiO(4), MgO and WO(3). Scanning electron microscopy observations have revealed that the dense and compact coating formed in the presence of tungstate has less structural imperfections in comparison to the control one fabricated without use of tungstate. The effect of oxidation time on the morphology and phase composition of coatings is also examined in detail.

Characterization of plasma electrolytic oxidation coatings on Zircaloy-4 formed in different electrolytes with AC current regime

Plasma electrolytic oxidation was undertaken on Zircaloy-4 in alkaline silicate and pyrophosphate electrolytes, with a square waveform AC current regime. The resultant coatings were examined using scanning electron spectroscopy, X-ray diffraction and nanoindentation. The coatings formed in silicate electrolyte comprised mainly a porous inner layer and a more compact outer layer, with characteristic solidification structures being evident following prolonged treatment. The coatings contained monoclinic and tetragonal ZrO 2, the latter being mainly present in the outer layer, which was of hardness up to ∼8 GPa. In contrast, extensively cracked coatings resulted from use of pyrophosphate electrolyte; the coating integrity was improved by the addition of silicate to the pyrophosphate electrolyte. The different morphologies of the coatings appeared to be related to the differing nature of the microdischarges and to the incorporation of silicon species that enhanced the formation of t-ZrO 2.

Dielectric breakdown and healing of anodic oxide films on aluminium under single pulse anodizing

Single pulse anodizing of aluminium micro-electrode has been employed to study the behaviour of dielectric breakdown and subsequent oxide formation on aluminium in alkaline silicate and pentaborate electrolytes. Current transients during applying pulse voltage have been measured, and surface has been observed by scanning electron microscopy. Two types of current transients are observed, depending on the electrolyte and applied voltage. There is a good correlation between the current transient behaviour and the shape of discharge channels. In alkaline silicate electrolyte, circular open pores are healed by increasing the pulse width, but such healing is not obvious in pentaborate electrolyte.

An electrochemical analysis of AZ91 Mg alloy processed by plasma electrolytic oxidation followed by static annealing

In this study, the effect of subsequent annealing on the electrochemical response of AZ91 Mg alloy coated via plasma electrolytic oxidation (PEO) was investigated. PEO coating was carried out on the Mg alloy under AC condition in an alkaline silicate electrolyte, and the PEO-coated samples underwent several subsequent annealing treatments at three different temperatures of 100, 150, and 200 °C. The surface morphologies of the coating layers were observed via a scanning electron microscope (SEM) and their constituent compounds were characterized by qualitative observation based on X-ray photoelectron spectroscopy (XPS). In addition, the corrosion protection properties of the PEO-coated sample were examined by electrochemical impedance spectroscopy (EIS) in a 3.5 wt% NaCl solution with a focus on exploring the effect of subsequent annealing on the electrochemical response in a quantitative manner. SEM and XPS observations evidenced that the subsequent annealing at temperatures higher than 150 °C resulted in significant morphological changes due to the dehydration reaction of Mg(OH) 2 to form MgO. Thus, it was found that the sample annealed at 150 °C exhibited a better corrosion resistance than the other samples, which were analyzed by taking an equivalent circuit model into account.