Self-similar scaling of discharge events through PEO coatings on aluminium

Plasma electrolytic oxidation (PEO) typically involves hundreds to thousands of discharges per square millimetre per second. In the present work, the characteristics of individual discharges are measured and investigated through an experimental survey of over 3.7 million individual events. The parameters considered include the voltage at which a discharge event commences, the peak current to which it develops, the duration of the discharge, and the current-time profile of individual discharges. It is shown that there is a strong correlation between the voltage at which a discharge event commences and the peak current to which it subsequently develops. There are also strong correlations between these characteristics and the duration of the discharges. These correlations show no significant influence of the coating thickness. The current-time profile is similar for most discharges, scaling according to the initiation voltage, suggesting that all PEO discharge events, whether weak or powerful, all develop according to the same physical mechanisms.     

Study of the structure and corrosion behavior of PEO coatings on AM50 magnesium alloy by electrochemical impedance spectroscopy

In this work coatings were developed on the surface of AM50 magnesium alloy using four different electrolytes containing 10 wt.% each of K₃PO₄ and Na₃PO₄ in combination with either potassium or sodium hydroxides. Electrolyte conductivity and breakdown voltage were measured in order to correlate the property of the coating to the nature of electrolyte. Further, the coatings were examined using scanning electron microscopy for surface morphology and cross sectional investigation, X-ray diffraction for phase determination, and electrochemical impedance spectroscopy for corrosion resistance evaluation. The effect of employing different ions in the electrolytes results in different surface morphologies, chemical phases and, consequently, the corrosion resistance of the coatings. The EIS results indicate the presence of porous and compact layers in the structure of the PEO coatings, whilst the overall coating resistance mainly results from the compact layer, the role of the porous layer as a barrier against corrosion is negligible. Finally, a correlation between the passive current density of the bare alloy and the corrosion resistance of the PEO coating is proposed.     

Characterization of AC PEO coatings on magnesium alloys

Optical emission spectroscopy, fast video imaging and coating characterization are employed to investigate AC plasma electrolytic oxidation (PEO) of magnesium alloys. The findings revealed initiation and gradual increase in the number of discharges after 2-4 ms of each anodic pulse once a critical voltage was reached. No discharges were observed during the cathodic half-cycles. The lifetimes of discharges were in the range of 0.05-4 ms. A transition in the voltage-time response, accompanied by a change in the acoustic and optical emission characteristics of discharges, was associated with the development of an intermediate coating layer with an average hardness of 270-450 HV_0.05. The coatings grew at a rate in the range 4.0-7.5 µm min^− 1, depending on the substrate composition. Regardless of the substrate, the coatings consisted of MgO and Mg₂SiO₄, with incorporation of alloying element species. Electrolyte species were mainly present in a more porous layer at the coating surface, constituting 20-40% of the coating thickness. A thin barrier layer consisting of polycrystalline MgO was located next to the alloy. The corrosion rate of the magnesium alloys determined using potentiodynamic polarization in 3.5 wt.% NaCl was reduced by 2-4 orders of magnitude by the PEO treatment.     

Growth mechanism and corrosion behavior of ceramic coatings on aluminum produced by autocontrol AC pulse PEO

Ceramic coatings are produced on aluminum alloy by autocontrol AC pulse Plasma Electrolytic Oxidation (PEO) with stabilized average current. Transient signal gathering system is used to study the current, voltage, and the transient wave during the PEO process. SEM, OM, XRD and EDS are used to study the coatings evolution of morphologies, composition and structure. TEM is used to study the micro profile of the outer looser layer and inner compact layer. Polarization test is used to study the corrosion property of PEO coatings in NaCl solution. According to the test results, AC pulse PEO process can be divided into four stages with different aspects of discharge phenomena, voltage and current. The growth mechanism of AC PEO coating is characterized as anodic reaction and discharge sintering effect. PEO coating can increase the corrosion resistance of aluminum alloy by one order or two; however, too long process time is not necessarily needed to increase the corrosion resistance. In condition of this paper, PEO coating at 60 min is the most protective coating for aluminum alloy substrate.     

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.     

高强度铝合金微等离子体电解氧化陶瓷质膜层影响因素

微等离子体电解氧化是在阳极氧化基础上发展起来的直接在轻合金表面原位生成γ-Al2 O3和α-Al2 O3陶瓷质膜的一项表面工程新技术.α-Al2 O3对陶瓷质膜层的性能起决定性作用,最大限度地促进α-Al2 O3的形成,是改善铝合金表面综合性能的关键.经过对国内近20个单位的调研,发现该技术在军工、航空、航天、机械等领域有着迫切的需求和广泛的应用前景,有望部分替代硬质氧化膜实现大规模生产.本文从基体材料、溶液特性及电参数三方面分析铝合金微等离子体氧化膜层的影响因素,重点分析基体合金元素对陶瓷质膜层的影响.指出该技术在高强度铝合金应用领域的发展方向并对其前景进行了展望.     

Formation of corrosion resistant plasma electrolytic oxidation coatings on aluminium alloy with addition of sodium tungstate species

Plasma electrolytic oxidation (PEO) coatings were formed in silicate based electrolytes without and with the addition of sodium tungstate on AA?6063 aluminium alloy. Microstructure, composition and corrosion resistance of PEO coatings were investigated by scanning electron microscopy, X-ray diffraction and electrochemical impedance spectroscopy and potentiodynamic polarisation test respectively. The effects of additive sodium tungstate were examined. The results showed that the additive containing PEO coatings were of dense structure with additional phase (WO₃) and of less cracks than the additive free PEO coating. In addition, additive containing coatings were of better corrosion resistance than the additive free PEO coating, which was confirmed by electrochemical impedance spectroscopy and potentiodynamic polarisation tests. Furthermore, long time immersion test revealed that the PEO coated alloy with the addition of 12?g?L^??1 sodium tungstate maintained high impedance over 82?h in 3.5?wt-%NaCl, while the PEO coating without additive was unable to protect the substrate after such long time immersion.     

Amorphous coatings deposited on aluminum alloy by plasma electrolytic oxidation

Amorphous [Al-Si-O] coatings were deposited on aluminum alloy by plasma electrolytic oxidation (PEO). The process parameters, composition, micrograph, and mechanical property of PEO amorphous coatings were investigated. It is found that the growth rate of PEO coatings reaches 4.44μm/min if the current density is 0.9 mA/mm^2. XRD results show that the PEO coatings are amorphous in the current density range of 0.3 - 0.9 mA/mm^2. EDS results show that the coatings are composed of O, Si and A1 elements. SEM results show that the coatings are porous. Nano indentation results show that the hardness of the coatings is about 3 - 4 times of that of the substrate, while the elastic modulus is about the same with the substrate. Furthermore, a formation mechanism of amorphous PEO coatings was proposed.     

Wear and corrosion resistant coatings on surface of cast A356 aluminum alloy by plasma electrolytic oxidation in moderately concentrated aluminate electrolytes

Plasma electrolytic oxidation of a cast A356 aluminum alloy was carried out in aluminate electrolytes to develop wear and corrosion resistant coatings. Different concentrations of 2, 16 and 24 g/L NaAlO₂ solutions and a silicate electrolyte (for comparison) were employed for the investigation. Wear performance and corrosion resistance of the coatings were evaluated by WC (tungsten carbide) ball-on-flat dry sliding tests and electrochemical methods, respectively. The results show that the coating formed for a short duration of 480 s in 24 g/L NaAlO₂ solution generated the best protection. The coating sustained 30 N load for sliding time of 1800 s, showing very low wear rate of ～4.5×10^?7 mm³/(N·m). A low corrosion current density of ～8.81×10^?9 A/cm² was also recorded. Despite low α-Al₂O₃ content of the coating, the compact and nearly single layer nature of the coating guaranteed the excellent performances.     

Effects of electrolytes on properties of anodic coatings formed on AZ91HP magnesium alloy

In a basic solution containing 10 g/L NaOH, the thickness, morphology and corrosion resistance of anodic coatings formed in solutions without and with additions of Na2SiO3, Na2CO3, Na2B4O7 and Na2SnO3 were separately determined and evaluated. The results show that the electrolytes used above take part in the coating formation and the obtained anodic coatings contain elements from the electrolytes. These electrolytes, especially Na2SiO3 and Na2B4OT, contribute to the film thickness. The coating uniformity obtained by addition of Na2SiO3 is the best, while Na2CO3, Na2B4O7 and Na2SnO3 decrease the number of pores per area on the coatings surface though they worsen the uniformity of the anodic coatings. In addition, the anodic coatings formed in solutions with addition of Na2CO3 or Na2SnO3 exhibit loose and net-like structure. Na2SiO3 and Na2B4O7 can significantly improve the corrosion resistance of the anodic coatings while Na2CO3 and Na2SnO3 have minor effects on improving the coating corrosion resistance.     

Study on wear behavior of plasma electrolytic oxidation coatings on aluminum alloy

Thick and hard ceramic coatings were fabricated on A356 aluminum alloy by using plasma electrolytic oxidation(PEO) technique.The microstructure and phase composition of the PEO coatings were examined by using SEM and XRD method.It is found that the PEO coatings are mainly composed of crystalline α-Al2O3 and mullite.The dry sliding wear test of PEO coatings were carried out on a ring-on-ring wear machine.Results shows that there is hardly no wear loss of polished PEO coatings while the wear rate of uncoated aluminum alloy is 4.3×10-5 mm3·(N·m)-1 at a speed of 0.52 m·s-1 and a load of 40 N.     

Effects of alloying elements on microstructure and protective properties of Al2O3 coatings formed on aluminum alloy substrates by plasma electrolysis

Hard alumina coatings were formed on three typical Al alloys using a plasma electrolytic oxidation (PEO) process. The microstructure and protective behavior of the coatings were characterized in the context of the elements alloyed in the substrates. The substrates investigated were three commercial aluminum alloys (Al 6061, 2024, 7075) and various Al − x–Mg binary alloys with x = 0.6–4.6 wt.%. The major portion of all coating films consisted of a mixture of γ- and α-alumina on top of a very thin amorphous substrate-based layer. Examination of the coatings on the commercial alloys reveals that the ratio of α- to γ-alumina is inversely proportional to the total concentration of residual Mg, Cu, and Zn ions in the coatings. Additional experiments on Al − x–Mg binary alloy substrates suggest that Mg ions play the most important role in suppressing the transition of γ- to α-alumina. Our results suggest that Mg content ≥ 3 wt.% yields only the γ-alumina. We propose a mechanism that correlates the residual elements in the coatings to the alumina phase transition. A higher content of the dense α-alumina in the coatings yielded greater hardness as well as improved wear tolerance and crack resistance of the coating layers.     

Tribological and corrosion behavior of PEO coatings with graphite nanoparticles on AZ91 and AZ80 magnesium alloys

The effect of the addition of graphite nanoparticles into the electrolyte used to produce plasma electrolytic oxidation (PEO) coatings on AZ91 and AZ80 magnesium alloys was studied. The corrosion and wear resistances of the obtained coatings were investigated. A solution that contained both phosphates and silicates was used as electrolyte. Moreover, two different PEO treatment times were studied. The corrosion resistance was analyzed with potentiodynamic polarization and EIS tests; the wear resistance was investigated with a flat on ring tribometer. The results were related to the morphology, microstructure, elemental composition and thickness evaluated with SEM analysis. The presence of the graphite nanoparticles increased the thickness, produced a densification of the coating and sealed the pores on the surface, thus improving both the corrosion and wear resistance. The increase in the corrosion and wear resistances was more evident for AZ91 than for AZ80 due to the higher aluminum content.     

锆-4合金的直流等离子电解氧化及膜层的性能(英文)

在硅酸盐、磷酸盐、焦磷酸盐或其混合电解液中对锆-4 合金进行等离子电解氧化。通过实验确定合适的工艺参数,并运用电化学技术、显微硬度、SEM、XRD 等技术对膜层性能进行表征。结果表明:在纯的硅酸盐电解液中得到的膜层很不均匀,且在添加磷酸盐后,膜层均匀性仍然很差。在焦磷酸盐体系中得到的膜层比较均匀,但硬度低。在焦磷酸盐体系中添加硅酸盐后,膜层的均匀性和硬度都得到改善。XRD 结果表明,膜层的主要成分为单斜氧化锆和四方氧化锆。添加硅酸盐后,有利于四方氧化锆的形成。极化曲线结果表明,在焦磷酸盐以及焦磷酸盐与硅酸盐混合体系中得到的膜层具有较强的耐蚀性。     

Electrochemical performance of microarc oxidation films formed on AZ91D alloy in two group electrolytes

The phase composition and electrochemical performances of microarc oxidation（MAO） films prepared on AZ91D alloy by using step-down current method in a phosphate electrolyte（P-film） and silicate electrolyte（Si-film） were studied. The results show that P-film is mainly composed of Mg, MgAl2O4 and MgO, and Si-film is composed of Mg2SiO4 and MgO. There clearly exists a fluoride-enriched zone with the thickness of about 1 - 2 μm for P-film and 0.7 - 1μm for Si-film at the MAO coating/substrate interface. The electrochemical tests show that both P-film and Si-film can enhance the corrosion resistance of AZ91D magnesium alloy significantly. The corrosion failure process of the two films in 5% （mass fraction） NaCl solution is quite different.     

Formation, structure and composition of anodic films on AM60 magnesium alloy obtained by DC plasma anodising

Anodising of AM60 magnesium alloy (6% Al + 0.27% Mn) was studied in a solution containing 1.5 M KOH + 0.5 M KF + 0.25 M Na₂HPO₄ · 12H₂O with addition of various NaAlO₂ concentrations. The experiments were carried out in DC current galvanostatic mode. Observations of phenomena occurring at the sample surface plus voltage monitoring revealed three stages: traditional anodising, followed by microarc anodising and finally arcing. The film was porous and cracked, with poor bonding to the substrate. It was composed of magnesium and aluminium oxide, and contained all the elements present in the electrolyte. The aluminium concentration in the film was dependent on the concentration of aluminate ions in the electrolyte. The transition from microarc to arcing stage took place when the alloy surface was completely covered by the anodic film.     

TEM analysis and tribological properties of Plasma Electrolytic Oxidation (PEO) coatings on a magnesium engine AJ62 alloy

In order to reduce the fuel consumption and pollution, automotive companies are developing magnesium-intensive components. However, due to the low wear resistance of the magnesium (Mg) alloys, Mg cylinder bores are vulnerable to the sliding wear attack. In this paper, a Plasma Electrolytic Oxidation (PEO) process was used to produce oxide coatings on a Mg alloy AJ62 (MgAl6Mn0.34Sr2), developed for Mg engine block, to battle against the wear attack. The surface morphology, coating thickness and tribological properties were tailored by adjusting the PEO process parameters. TEM analysis demonstrated that the PEO coatings had a nanocrystalline structure in the inner dense layer next to the substrate. The PEO coatings exhibited a much better wear resistance and a smaller friction coefficient than the uncoated AJ62 substrate. The tribological performance of the PEO-coated Mg alloy was even better than that of a hypereutectic Al-Si alloy currently used for engine applications under a high contact load.     

电解质对镁合金微弧氧化表面膜组织与腐蚀性能的影响

采用SEM、TEM、EDX、XRD、AUTOLAB电化学工作站分析比较两种电解质（硅酸盐体系和有机胺体系）直流微弧氧化处理AZ91D合金表面涂层的成分、组织结构和涂层的动电位极化曲线。虽然两种电解质体系涂层元素成分和组成相相同,均为金属相、MgO相和Mg2SiO3相,但有机胺电解质体系的涂层中非金属相（MgO、Mg2SiO4）相对含量高于硅酸盐处理体系,有机胺体系获得的涂层表面均匀致密性也优于硅酸盐体系。有机胺体系获得的涂层在3.5%NaCl中性介质中的腐蚀电流密度、腐蚀电压分别为0.29μA/cm^2和522 mV,与硅酸盐体系处理涂层相比,前者的抗腐蚀能力有很大幅度的提高。     

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.     

Na_2SiO_3浓度对6063铝合金微弧氧化层组织与性能的影响

采用X射线衍射仪(XRD)、扫描电镜(SEM)、显微硬度计、摩擦磨损试验机等手段研究了不同电解液浓度对6063铝合金微弧氧化陶瓷涂层的相组成、微观结构、显微硬度、耐磨性能等的影响。结果表明:电解液浓度对涂层的性能有着较大的影响。电流密度和处理时间一定的条件下,当Na2SiO3的浓度小于9 g/L时,随着电解液浓度的增大,成膜速率有所提高,涂层中α-Al2O3与γ-Al2O3相的衍射峰明显增强,涂层与基体的结合力增大,且涂层的硬度和耐磨性也有很大的提高;但是当Na2SiO3的浓度大于9g/L时,涂层的硬度等性能基本不再变化,甚至有所下降。