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.     

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.     

Two-step plasma electrolytic oxidation of Ti-15V-3Al-3Cr-3Sn for wear-resistant and adhesive coating

Ti-15V-3Al-3Cr-3Sn (Ti-15-3) is one of the important practical titanium alloys with high cold deformability and high mechanical strength, but its wear resistance is poor. This paper reports the formation of wear-resistant and adhesive ceramic coatings on Ti-15-3 by two-step plasma electrolytic oxidation (PEO). The PEO of Ti-15-3 has been carried out first in alkaline aluminate electrolyte to form a wear-resistant oxide layer and then in acid electrolyte containing both phosphoric acid and sulfuric acid to improve adhesion of the coating. The coating formed in the alkaline aluminate electrolyte is more than 10 μm thick, and highly crystalline. The main phase is Al₂TiO₅. This coating shows high wear resistance, but is not adherent to substrate due to the development of a number of voids and pores in the oxide layer close to the substrate. A new oxide layer with amorphous structure is formed next to the substrate in the subsequent PEO in the acid electrolyte, during which the voids are filled with a new oxide formed in the acid electrolyte, reducing the porosity. As a consequence, the adhesion of the coating is markedly improved without deteriorating the high wear resistance.     

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.     

Small signal frequency response studies for plasma electrolytic oxidation

Plasma assisted electrochemical treatments provide new possibilities in surface modification of various materials including light weight alloys. However, their large-scale application is still restricted, mainly due to poor understanding of the process mechanisms and consequent limitations in process control and automation. This problem can be resolved if the frequency response (FR) of the system is known and applied for process diagnostics. Our previous work has shown the effectiveness of the large signal mode for FR studies of plasma electrolytic oxidation (PEO) of aluminium. This research is dedicated to FR measurements during PEO of Al in the small signal mode corresponding to small perturbations of voltage signal around large DC values. The study was carried out during PEO of Al at DC voltages which were varied from 450 to 600 V. The FR obtained is a frequency dependent admittance of the PEO electrolyser; this complex number is represented by a modulus and a phase angle. Under potentiostatic conditions, the modulus evolution strongly correlates with the average current value; therefore, it bears insufficient amounts of independent information. The FR phase angle measured within this study was never obtained before. Depending on the frequency, it varies between 0° and 70 ° in the capacitive domain. One of the most notable features of this characteristic is low values at 500-5000 Hz when microdischarges appear during PEO. The other feature is a correlation with the coating growth. As a result, a new diagnostic tool was developed and shown to be effective for evaluation of microdischarges and surface properties during the treatment, thus decreasing the uncertainty in the system.     

Development of a novel cathodic plasma/electrolytic deposition technique part 1: Production of titanium dioxide coatings

A new atmospheric pressure plasma electrolytic deposition process has been developed for the production of crystalline titanium dioxide films on metal substrates. The process occurs in a liquid precursor composed of titanium tetraisopropoxide and absolute ethanol. A plasma discharge is created and confined around the cathode in a superheated vapour sheath surrounded by the liquid phase, inducing the production of a nano-crystalline TiO₂ coating at the surface of the cathode. The analysis of the structure and composition of these TiO₂ coatings have been carried out by Scanning Electron Microscopy, Transmission Electron Microscopy, Raman and X-Ray Photoelectron Spectroscopies and X-Ray Diffraction. The produced crystalline titanium dioxide coatings are very adherent to the substrate and present a dendritic-like structure. We have moreover demonstrated that it is possible to adjust easily its composition by a post-processing calcination. Such characteristics make these films very interesting for photocatalysis, solar cells and gas sensing applications, and promise therefore some useful industrial benefits.     

Frequency response studies for the plasma electrolytic oxidation process

This paper introduces a methodology for obtaining a fundamental characteristic of the plasma electrolytic process — that is the frequency response (magnitude and phase angle). A methodology is developed for plasma electrolytic oxidation (PEO) of aluminium; however, it can be applied to any plasma electrolytic process. For PEO the frequency response was evaluated as a complex impedance of the electrolyser. It was found that the impedance magnitude decreases with frequency growth from 10³-10⁴ to 10-10² Ω and the phase angle decreases from 0 to − 70 − 80°. This fact appears to be consistent with a hypothesis of active-capacitive load behaviour for the PEO process. Evolution of the frequency response during PEO is consistent with that of the surface state; therefore, it can be used for process diagnostics and control. Frequency response adds a new dimension to the investigation of plasma assisted electrochemical processes. Major benefits of this approach are expected in the field of the process automation and the development of new pulsed plasma electrolytic technologies.     

Porous anodic oxides on titanium and on a Ti-W alloy

The growth of a nanoporous anodic oxide on titanium and a Ti-20 at.% W alloy, both deposited by magnetron sputtering, in a glycerol/phosphate electrolyte at 453 K is reported. The oxide formed on titanium is a mixture of amorphous titania and anatase. However, that on the alloy is amorphous only and forms at increased efficiency, about 27%. The amorphous structure is considered to be stabilized by incorporated units of WO₃, which are distributed uniformly throughout the anodic film. The growth of the porous oxides is suggested to be associated with loss of film species at the film/electrolyte interface at the base of pores, with new oxide forming exclusively at the metal/film interface by inward migration of O²⁻ ions.     

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.     

Effect of plasma electrolytic oxidation coating on joining metal to plastic

Abstract

Joining of magnesium alloy to polyethylene without adhesive using a newly developed friction lap welding technology was investigated. The polyethylene and magnesium alloy were hard to be joined together without surface premodification due to the lack of polar groups on polyethylene surfaces. Strong hybrid joints were achieved after the polyethylene was treated by corona discharge, and the magnesium alloy was subjected to plasma electrolytic oxidation treatment. Scanning electron microscope and high resolution transmission electron microscope observations demonstrated that the high joining strength was attributed to the development of both chemical bonds at the interface and micromechanical interlocking.     

Spectroscopic characterization of plasma during electrolytic oxidation (PEO) of aluminium

We present results of an optical emission spectroscopic study of Plasma during Electrolytic Oxidation (PEO) of aluminium in citric acid and in sodium-tungstate water solutions. The line shape analysis of the first two hydrogen Balmer lines indicates presence of two PEO processes characterized by relatively low electron number densities N_e ≈ 0.8 × 10¹⁵ cm^− 3 and at 2.5 × 10¹⁶ cm^− 3. Apart from these two N_e values, N_e ≈ 6.0 × 10¹⁶ cm^− 3 is determined from the width of the Al II 704.2 nm line. Three considerably different N_e values imply presence of three types of discharge during PEO of aluminium. The electron temperature T_e is determined from relative line intensities of the O II (T_e ≈ 38,300 K) and W I (T_e ≈ 3300 K) lines. The use of two databases of transition probabilities for O II lines introduces systematic difference of reported T_e results.     

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.     

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.     

阳极氧化处理对钛表面粗糙度和亲水性的影响

本文通过阳极氧化处理技术在钛表面制备出具有不同粗糙度和亲水性的纳米表面。采用扫描电镜观察表面特征,原子力显微镜检测表面粗糙度,接触角仪测量亲水性。实验结果表明,表面形貌随着氧化电压和时间的改变有较大变化。在优化的电解液和氧化条件下,可以在钛表面制备规则排列的纳米管阵列。粗糙度随着氧化时间的延长而增大,在几十到几百纳米之间变化,而氧化电压对粗糙度的影响不大。表面亲水性随着氧化时间的延长先增加,再降低。钛表面结构形貌、粗糙度与亲水性的变化可用阳极氧化过程中表面发生的反应进行解释。     

Unipolar plasma electrolytic oxidation: Waveform optimisation for corrosion resistance of commercially pure titanium

This study deals with the anodisation of titanium grade 2 in 0.5-M sulphuric acid using a pulsed signal in a unipolar regime. The electrical parameters investigated are voltage, frequency and duty cycle. The use of duty cycles with a high percentage of anodic polarisation (90%), combined with high frequencies (1000 Hz) and the higher voltage tested (220 V), favoured the establishment of a plasma regime involving strong dielectric discharges, allowing the growth of thicker oxides but with rough architecture. The corrosion resistance of the formed film has been characterised by potentiodynamic tests in 0.5-M NaBr for localised corrosion resistance and by immersion tests in 10% v/v sulphuric acid solution for a uniform corrosion assessment. Current–time curves, visual observations and electron microscope analysis (scanning electron microscopy, energy-dispersive X-ray spectroscopy) were the tools selected to provide a correlation between technological parameters and oxide growth mechanism. For localised and uniform corrosion, anodisation at 220 V with a high level of anodic polarisation (90%) and frequency (1000 Hz) was verified to be particularly advantageous.     

Environmentally assisted cracking behaviour of plasma electrolytic oxidation coated AZ31 magnesium alloy

Abstract

A wrought AZ31 magnesium alloy was plasma electrolytic oxidation (PEO) coated in phosphate and silicate based alkaline electrolytes. The effect of these PEO coatings on the stress corrosion cracking (SCC) behaviour of the alloy was investigated by slow strain rate tensile (SSRT) tests in ASTM D1384 solution. The untreated and PEO coated AZ31 magnesium alloy specimens were found to be susceptible to SCC, despite the fact that the PEO coatings offered an excellent general corrosion resistance. The results of the polarisation tests on the untreated AZ31 alloy specimen after prolonged immersion in ASTM D1384 electrolyte suggested the formation of a film on the surface constituted by the corrosion products. The cracking of this film and the evolution/ingress of hydrogen at these defective sites during the SSRT tests in the corrosive environment was believed to be responsible for the SCC of the untreated alloy. Similarly, the cracking of the PEO coatings during the SSRT test, the consequent exposure of the underneath magnesium alloy substrate and the associated electrochemical reactions were attributed as reasons for the SCC of the PEO coated specimens. The transgranular mode of fracture in all the cases avowed that the hydrogen induced cracking was the mechanism of SCC.     

TC21钛合金微弧氧化涂层微动磨损行为研究

采用球盘接触形式,在50 μm和150 μm位移振幅条件下,研究了载荷(60 N、40 N和20 N)对TC21钛合金及其表面微弧氧化(PEO)涂层切向微动磨损性能的影响。结果显示,随着位移振幅的增大和载荷的减小,TC21钛合金和PEO涂层的微动区域均由部分滑移区向滑移区转变。在部分滑移区,两种材料沿微动方向的磨痕宽度随载荷的减小而减小。虽均未出现明显的材料损失,但TC21钛合金边缘微滑区存在微裂纹的萌生和扩展,其程度随载荷的减小而加重,而微动对PEO涂层只起到了平滑作用。在滑移区,两种材料的磨痕宽度随载荷的减小而增大,且均存在局部磨损。磨损程度随振幅的增大和载荷的减小而加深。其中,PEO涂层的最大磨痕深度小于TC21钛合金,显示出更好的抗微动磨损性能。     

Optical emission spectroscopy studies of discharge mechanism and plasma characteristics during plasma electrolytic oxidation of magnesium in different electrolytes

The discharge mechanism of the plasma electrolytic oxidation (PEO) process in different electrolytes was investigated by examining the variation of the optical emission spectra (OES). The spectrum of active species existed in the bubble layer. The bubble layer was initially broken down, followed by the breakdown of the dielectric barrier layer. Breakdown is the initial stage of discharge. A micro-discharge formation model, which assumes that the discharge ignition in the bubble layer developed at the oxide/electrolyte interface, was proposed. The active plasma species that appeared in different electrolytes during the PEO process were also studied. The appearance order of the excited active plasma species depended on the energy that the orbit transition of the species needed, but was not related to the anion concentration in the electrolyte. The anions in the electrolyte, except the OH⁻, also had little influence on the composition of the active plasma species during the PEO process. The active plasma species were mainly composed of metal atoms, metal cations, and gases produced by water decomposition. The electron temperature of the excited hydrogen was between 6 × 10³ and 3 × 10⁴ K. The high temperature provided the possibility of ceramic film melting and sintering. The source and transition of the active plasma species were also studied. They were found to undergo dissociation, ionization, and excitation processes.     

Plasma electrolytic oxidation of coupled light metals

Abstract

In order to assess the practicality of plasma electrolytic oxidation of parts consisting of more than one light metal, coupled metals, namely aluminium/AA 7075 aluminium alloy and AA 7075 aluminium alloy/ZE41 magnesium alloy, have been treated under alternating current conditions using constant total currents. Monitoring of the current flow to each component of the couples revealed differences in current densities on each metal, which varied with time. However, for the selected conditions, microdischarges were sustained on both metals and coatings were produced with thicknesses reasonably similar to those of coating on metals treated individually. Further, the transition to ‘soft’ sparking occurred at about the same time on both components of the couples.     

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.