Microstructure and corrosion resistance of ceramic coating on carbon steel prepared by plasma electrolytic oxidation

Ceramic coating was prepared on Q235 carbon steel by plasma electrolytic oxidation (PEO). The microstructure of the coating including phase composition, surface and cross-section morphology were studied by X-ray diffraction (XRD), Fourier transform infrared spectroscope (FTIR) and scanning electron microscopy (SEM). The corrosion behavior of the coating was evaluated in 3.5% NaCl solution through electrochemical impedance spectra (EIS), potentiodynamic polarization and open-circuit potential (OCP) techniques. The bonding strength between Q235 carbon steel substrate and the ceramic coating was also tested. The results indicated that PEO coating is a composite coating composed of FeAl₂O₄ and Fe₃O_4. The coating surface is porous and the thickness is about 100 μm. The bonding strength of the coating is about 19 MPa. The corrosion tests showed that the corrosion resistance of Q235 carbon steel could be greatly improved with FeAl₂O₄-Fe₃O₄ composite coating on its surface.     

Structure and corrosion resistance of ZrO2 ceramic coatings on AZ91D Mg alloys by plasma electrolytic oxidation

The aim of this work is to study the structure and the corrosion resistance of the plasma electrolytic oxidation ZrO₂ ceramic coatings on Mg alloys. The ceramic coatings were prepared on AZ91D Mg alloy in Na₅P₃O₁₀ and K₂ZrF₆ solution by pulsed single-polar plasma electrolytic oxidation (PEO). The phase composition, morphology and element distribution in the coating were investigated by X-ray diffractometry, scanning electron microscopy and energy distribution spectroscopy, respectively. The results show that the coating thickness and surface roughness were increased with the increase of the reaction time. The ceramic coatings were of double-layer structure with the loose and porous outer layer and the compact inner layer. And the coating was composed of P, Zr, Mg and K, of which P and Zr were the main elements in the coating. P in the coating existed in the form of amorphous state, while Zr crystallized in the form of t-ZrO₂ and a little c-ZrO₂ in the coating. Electrochemical impedance spectra (EIS) and the polarizing curve tests of the coatings were measured through CHI604 electrochemical analyzer in 3.5% NaCl solution to evaluate the corrosion resistance. The polarization resistance obtained from the equivalent circuit of the EIS was consistent with the results of the polarizing curves tests.     

TEM analysis and wear resistance of the ceramic coatings on Q235 steel prepared by hybrid method of hot-dipping aluminum and plasma electrolytic oxidation

The hybrid method of PEO and hot-dipping aluminum (HDA) was employed to deposit composite ceramic coatings on the surface of Q235 steel. The composition of the composite coatings was investigated with X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. The cross-section microstructure and micro-hardness of the treated specimens were investigated and analyzed with scanning electron microscopy (SEM) and microscopic hardness meter (MHM), respectively. The wear resistance of the ceramic coatings was investigated by a self-made rubbing wear testing machine. The results indicate that metallurgical bonding can be observed between the ceramic coatings and the steel substrate. There are many micro-pores and micro-cracks, which act as the discharge channels and result of quick and non-uniform cooling of melted sections in the plasma electrolytic oxidation ceramic coatings. The phase composition of the ceramic coatings is mainly composed of amorphous phase and crystal Al₂O₃ oxides. The crystal Al₂O₃ phase includes κ-Al₂O₃, θ-Al₂O₃ and β-Al₂O₃. The grain size of the κ-Al₂O₃ crystal is quite non-uniform. The hardness of the ceramic coatings is about HV1300 and 10 times higher than that of the Q235 substrate, which was favorable to the better wear resistance of the ceramic coatings.     

Surface modification of die casting mold steel by a composite technique of hot-dipping and plasma electrolytic oxidation

The hot dipping process of pure aluminum on H13 steel substrates followed by plasma electrolytic oxidation（PEO） was studied to form alumina ceramic coatings for protective purpose.H13 steel bars were first dipped in pure aluminum melts,and then,a reactive iron-aluminum intermetallic layer grew at the interface between the melt and the steel substrate.The reactive layer was mainly composed of intermetallic Fe-Al（Fe₂Al₅）;the thickness of aluminum layer and Fe-Al intermetallic layer were mainly influenced by dipping time（1.5～12.0 min） and dipping temperature（710～760 ℃）.After PEO process,uniform Al₂O₃ ceramic coatings were deposited on the surface of aluminized steel.The element distribution,phase composition and morphology of the aluminized layer,and the ceramic coatings were characterized by SEM/EDS and XRD.The distribution of hardness across the composite coating is demonstrated,and the maximum value reaches 1864 HV.The thermal shock resistance of the coated sample is also well improved.     

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.     

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.     

Characterization of the surface layers formed on titanium by plasma electrolytic oxidation

This paper is concerned with the surface modification of titanium by the PEO method (plasma electrolytic oxidation) in the solutions which contain Ca, P, Si and Na. The chemical composition of the thus formed surface layers was examined by XPS and EDS. The morphology of the surface was observed by SEM. The phase composition was determined by X-ray diffraction (XRD). The adhesive strength of the oxide layers was evaluated by the scratch-test. The corrosion resistance was determined in a simulated body fluid (SBF) at a temperature of 37 °C by electrochemical methods for various exposure times.The oxide layers obtained were porous and enriched with Ca, P, Si and Na and their properties depended on the electrolyte solution and the parameters of the oxidation process. The results of the electrochemical examinations show that the surface modification by PEO does not worsen the corrosion resistance of titanium after a 13 h exposure in SBF. The electrochemical impedance spectroscopy (EIS) results indicate that the surface layers have a complex structure and that their electric properties undergo changes during long-term exposures in SBF.     

微弧电解氧化新进展

铝合金的微弧电解氧化处理起源于上世纪50年代中期,现在包括俄罗斯在内的世界各主要国家与地区都在对此技术进行研发,在推广应用方面取得了一定的成效.微弧氧化处理膜具有硬度高、抗磨性强、耐腐蚀性强、耐热冲击、介电性强等一系列优点,但处理时的电压高、电流大,能耗高,如不在节能降耗方面有所突破,很难大面积推广应用.微弧氧化处理槽液不含铬等重金属,处理时也不排放温室气体及其他污染物,是一种环境友好型表面处理工艺.     

H13热作模具钢微弧氧化复合陶瓷层的组织和性能

通过热浸镀铝/微弧氧化复合工艺对H13模具钢进行表面改性以提高模具表面质量。在热浸镀铝过程中,将H13钢基体浸入710℃纯铝液6 min,得到了以Fe2Al5为主中间合金层,使得镀层与基体紧密结合。经过微弧氧化处理后,镀铝试样表面铝层转化为氧化铝陶瓷,主要由α-Al2O3和γ-Al2O3相组成。用带有能谱分析装置(EDX)的扫描电镜(SEM)、X射线衍射(XRD)分析了膜层的形貌、成分和相组成。微弧氧化陶瓷层主要由Al、O、Si元素组成,其中O、Si主要来源于硅酸盐电解液。     

Initial stages of plasma electrolytic oxidation of titanium

The initial stages of oxide growth on titanium are examined in a recently developed commercial alkaline pyrophosphate/aluminate electrolyte of interest for plasma electrolytic oxidation of light metal alloys. Constant current anodizing was employed, with resultant films examined by scanning and transmission electron microscopies and Rutherford backscattering spectroscopy. The initial film is relatively uniform and composed of TiO₂, with low concentrations of aluminium and phosphorus species incorporated from the electrolyte. With increase in voltage the film breaks down locally, and regions of original and modified film develop simultaneously, with the latter occupying more of the surface as the voltage rises. Porous regions due to dielectric breakdown also become increasingly evident. At 240 V, sparking commences, and the surface reveals extensive, relatively uniform porosity, with the coating now containing much enhanced concentrations of aluminium and phosphorus species compared with the coating at lower voltages. The films develop at low efficiency due to generation of oxygen. The oxygen is produced within the original film material and at sites of dielectric breakdown. The former type of film develops a two-layered morphology, with an outer layer of amorphous TiO₂ and an inner layer with numerous fine and course cavities. The cavities are due to the generation of oxygen that may be associated with the formation of anatase in the inner layer.     

Characterisation of discharge events during plasma electrolytic oxidation

A study has been made of the electrical characteristics and optical emission spectra exhibited when discharge events take place during plasma electrolytic oxidation processing. Both conventional and small area experimental arrangements have been employed, allowing detailed measurement of durations, and temporal distributions, as well as such characteristics as charge transfer, and power. Individual discharges are of short duration, typically tens to hundreds of microseconds, but there is a strong tendency for them to occur in cascades that commonly last between several ms and several tens of ms. The composition, temperature and electron density of the plasma formed during PEO processing are inferred from characteristics of the emission spectra. This confirms that there are two distinct regions of plasma; a lower density peripheral region at ~ 3500 K, and a higher density core at ~ 16,000 ± 3500 K. The implications of these results are considered in terms of the interpretation of different types of experimental measurement, and attention is also briefly given to how such behaviour might relate to the mechanisms of growth.     

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.     

Investigation of the discharge mechanism of plasma electrolytic oxidation using Ti tracer

The study focused on the discharge mechanism of plasma electrolytic oxidation (PEO). Titanium with a layer of aluminum deposited on it (Ti-Al) was used as the substrate. When PEO process for Ti-Al substrate developed for a period of time, by analyzing the distribution of Ti element in oxide coatings, the existence of oxide film dielectric breakdown in discharge process was testified and the general shapes of discharge channels were also obtained. From the study on discharge channels' shapes we found that: in most of discharge locations, the coatings were broken down partly, while there also existed some discharge places in which the coatings were broken down thoroughly. Moreover, it was found that the oxide films grew toward the outer as well as the interior of PEO coatings, through analyzing the distributions of Si and Ti elements in discharge channels.     

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.     

Deposition, characterization and performance evaluation of ceramic coatings on metallic substrates for supercritical water-cooled reactors

A series of ceramic coatings have been prepared on P91 substrates by spray pyrolysis processes and on Zr-2.5Nb substrates by a plasma electrolytic oxidation process. Preliminary results show that coatings obtained with different solution compositions and procedures can reduce the oxidation weight gain of P91 samples by factors of 2-10 for exposure times up to 500 h in deaerated supercritical water at 500 °C and 25 MPa. Results also show that the weight gain of a P91 sample with an alumina (Al₂O₃) coating is about nine times less than that of uncoated P91 after exposures for 400 h in deaerated supercritical water at 650 °C and 25 MPa. These results indicate that the Al₂O₃ coating shows promising results for preventing oxidation of P91 under supercritical water conditions. The samples with ceramic coatings on Zr-2.5Nb substrates show marginally improved corrosion resistance compared to the bare substrates.     

电解液成分对TA1纯钛等离子电解氧化陶瓷膜生长与组织的影响

钛合金长期植入体内依然存在磨损和腐蚀的问题,因此钛合金表面改性的目的就是提高其表面耐蚀性、耐磨性并赋予生物活性.本文在3种不同的电解液中,采用等离子电解氧化技术在TA1纯钛表面制备含有Ca、P的氧化钛多孔复合陶瓷层.研究了不同电解液中,改变工艺参数对纯钛表面陶瓷层平均厚度和生长机制的影响.采用扫描电镜和能谱分析了电流密度改变时,3种不同电解液中生成复合陶瓷膜的表截面形貌以及成分.结果表明,相同的电流密度,在电解液B中,陶瓷膜初始击穿电位最大,电解液C中陶瓷膜初始击穿电位值最小.正向电流为16 A/dm2时,在电解液A中陶瓷膜表面出现粉末状团聚物,在电解液B和C中,没有粉末状团聚物出现.无论是工艺参数还是电解液成分,对纯钛生物陶瓷膜的生长过程与组织结构都产生很大的影响,适当控制可制备所需的功能陶瓷膜.     

Corrosion and tribocorrosion behaviour of thermally sprayed ceramic coatings on steel

This research aims at investigating the corrosion and tribocorrosion behaviour of thermally sprayed ceramic coatings deposited on steel specimens and exposed to a 3.5% NaCl solution. The coatings have been prepared by plasma spraying Cr₂O₃ and Al₂O₃/13% TiO₂ powders on a Ni/20% Cr bond coating. Combined wear-corrosion conditions have been achieved by sliding an alumina antagonist on the lateral surface of coated steel cylinders, during their exposure to the aggressive solution.Polarization resistance values monitored during 3 days exposures and polarization curves recorded at the end of the immersion period show that both coatings only partially protect steel substrate from corrosion. Sliding conditions (under 2 N load and 20 rpm or 10 N and 100 rpm) induce a limited increase of the substrate corrosion rates, likely as a consequence of an increase in the defect population of the ceramic coatings.On Cr₂O₃-coated specimens, tribocorrosion is more severe at 10 N and 100 rpm, while on Al₂O₃/13% TiO₂-coated specimens, a stronger corrosion attack is achieved at 2 N and 20 rpm. Profilometer analysis and wear track observations by optical and scanning electron microscopes evidence that on both coatings abrasion of the surface asperities produce both a surface polishing effect and, at high loads, the formation of a tribofilm, more continuous on Al₂O₃/13% TiO₂. On this coating the tribofilm reduces the amount of surface defects and limits the corrosion attack to a certain extent.     

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.     

Effects of addition of Al(NO3)3 to electrolytes on alumina coatings by plasma electrolytic oxidation

Alumina coatings were prepared by plasma electrolytic oxidation (PEO) on Al alloys using NaAlO₂ electrolytes with added Al(NO₃)₃ to enhance the mechanical properties of the coatings. Electrolytes (0.1 M NaAlO₂) with small amounts of Al(NO₃)₃ ranging from 1.0 to 5.3 mM were employed at a fixed current density (10 A/dm²). With the added Al(NO₃)₃, the onset of spark discharges was delayed, which is associated with the dissolution and oxidation of Al alloys in the nitrates. X-ray diffraction results showed that the obtained coatings consisted of both the α-Al₂O₃ and γ-Al₂O₃ phases. The maximum α-Al₂O₃ content of the coatings was obtained with the addition of 1.6 mM Al(NO₃)₃ to the electrolytes. The hardness of the coatings was significantly enhanced by increasing their α-Al₂O₃ content, which could be achieved by adding suitable amounts of Al(NO₃)₃ to the electrolytes.     

Plasma electrolytic oxidation of a zirconium alloy under AC conditions

The microstructures of zirconia coatings formed by plasma electrolytic oxidation of a zirconium alloy, Zirlo, under AC conditions in an alkaline silicate electrolyte have been examined by scanning and transmission electron microscopies. The coatings are shown to consist of three layers. The innermost barrier layer is relatively thin, up to 500 nm in a 100 µm-thick coating formed for 3600 s. The intermediate layer, constituting the main part of the coatings, consists primarily of monoclinic and tetragonal zirconia. The outer, loose layer is rich in silicon species and constitutes a reduced proportion of the coating thickness at increased time of treatment. The porous intermediate and outer layers are readily permeated by the electrolyte. The formation of the coating accounts for < 27% of the anodic charge passed during the treatment.