Evolution of micro-arc oxidation behaviors of the hot-dipping aluminum coatings on Q235 steel substrate

Micro-arc oxidation (MAO) is not applicable to prepare ceramic coatings on the surface of steel directly. In this work, hybrid method of MAO and hot-dipping aluminum (HDA) were employed to fabricate composite ceramic coatings on the surface of Q235 steel. The evolution of MAO coatings, such as growth rate, thickness of the total coatings, ingrown and outgrown coatings, cross section and surface morphologies and phase composition of the ceramic coatings were studied. The results indicate that both the current density and the processing time can affect the total thickness, the growth rate and the ratio of ingrown and outgrown thickness of the ceramic coatings. The total thickness, outgrown thickness and growth rate have maximum values with the processing time prolonged. The time when the maximum value appears decreases and the ingrown dominant turns to outgrown dominant little by little with the current density increasing. The composite coatings obtained by this hybrid method consists of three layers from inside to outside, i.e. Fe-Al alloy layer next to the substrate, aluminum layer between the Fe-Al layer and the ceramic coatings which is as the top exterior layer. Metallurgical bonding was observed between every of the two layers. There are many micro-pores and micro-cracks, which act as discharge channels and result of quick and non-uniform cooling of melted sections in the MAO 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. Compared with the others, the β-Al₂O₃ content is the least. The MAO process can be divided into three periods, namely the common anodic oxidation stage, the stable MAO stage and the ceramic coatings destroyed stage. The exterior loose part of the ceramic coatings was destroyed badly in the last period which should be avoided during the MAO process.     

Deposition of duplex Al2O3/aluminum coatings on steel using a combined technique of arc spraying and plasma electrolytic oxidation

Plasma electrolytic oxidation (PEO) is a cost-effective technique that can be used to prepare ceramic coatings on metals such as Ti, Al, Mg, Nb, etc., and their alloys, but this promising technique cannot be used to modify the surface properties of steels, which are the most widely used materials in engineering. In order to prepare metallurgically bonded ceramic coatings on steels, a combined technique of arc spraying and plasma electrolytic oxidation (PEO) was adopted. In this work, metallurgically bonded ceramic coatings on steels were obtained using this method. We firstly prepared aluminum coatings on steels by arc spraying, and then obtained the metallurgically bonded ceramic coatings on aluminum coatings by PEO. The characteristics of duplex coatings were analyzed by X-ray diffractometer (XRD) and scanning electron microscopy (SEM). The corrosion and wear resistance of the ceramic coatings were also studied. The results show that, duplex Al₂O₃/aluminum coatings have been deposited on steel substrate after the combined treatment. The ceramic coatings are mainly composed of α-Al₂O₃, γ-Al₂O₃, θ-Al₂O₃ and some amorphous phase. The duplex coatings show favorable corrosion and wear resistance properties. The investigations indicate that the combination of arc spraying and plasma electrolytic oxidation proves a promising technique for surface modification of steels for protective purposes.     

电流密度对铝合金微弧氧化膜物理化学特性的影响

利用微弧氧化(MAO)技术，在LYl2铝合金上沉积了显微硬度达42.14GPa的超硬陶瓷膜.采用x射线衍射仪和显微硬度计研究了阳极电流密度j_a和阴极、阳极电流密度比j_c/j_a对MAO膜相构成和力学特性的影响.此外，利用扫描电子显微镜和恒电位仪分别对膜的微结构和抗点腐蚀特性进行了分析.结果表明，高j_a制备的膜主要含α-Al₂O₃相，低j_a制备的膜主要含γ-Al₂O₃相.显微硬度测试表明，这类膜有较高的硬度，但以j_a=15A/dm²和j_c/j_a=0.7制备的陶瓷膜硬度最高.抗点腐蚀测试表明，j_c/j_a对陶瓷膜的微结构有很强的影响. 关键词： 微弧氧化 显微硬度 电流密度 抗点腐蚀     

电解等离子体法制备Al2O3陶瓷层及其特性研究

利用电弧喷铝并重熔后进行电解等离子体处理(EPP)的方法在Q235钢基体上制备出呈冶金结 合的Al₂O₃陶瓷层.利用XRD，SEM和EDS等手段对陶瓷层的成分和显 微组织进行了分析， 测定了陶瓷层的耐蚀性能和耐磨性能.实验结果表明，陶瓷层主要由α-Al₂O3，γ-Al₂O₃，θ-Al₂O₃以及一 些非晶相组成，组织致密，耐蚀性能和耐磨性能良好. 关键词： 电解等离子体处理 陶瓷层 复合技术 生长机理     

The structure and properties of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Al coatings deposited by microarc oxidation on graphite substrates

Protective α-Al₂O₃ coatings on the surface of a graphite article have been obtained by method of electric-arc metallization with aluminum and microarc oxidation (anodic spark process). Investigation of the obtained coating by scanning electron microscopy (SEM), X-ray diffraction (XRD), and proton elastic recoil detection analysis (ERDA) showed good quality of the Al and α-Al₂O₃ coatings on graphite. The proposed technology can be used for obtaining protective coatings in low-accessible sites of graphite articles.     

Improvement of the corrosion behavior of low carbon steel by laser surface alloying

In the present study, an integrated layer of iron aluminides of FeAl and Fe₃Al was formed on the surface of a low carbon steel sheet by a two-step process. The first step was hot dipping of the steel in a molten aluminum pool and secondly laser surface processing using a pulsed Nd:YAG laser. The corrosion resistance of the coated specimens was evaluated by activation polarization and Tafel methods. The results show that laser processing of the aluminized steel leads to a considerable increase in its corrosion resistance compared to both uncoated and merely aluminized materials.     

Effects of ultrasound on the evolution of plasma electrolytic oxidation process on 6061Al alloy

The plasma electrolytic oxidation (PEO) process of 6061Al alloy was carried out under the conditions with and without the assistance of ultrasound, respectively. The effects of ultrasound on the evolution of voltage, micro-discharge, morphology and composition of PEO coatings were investigated. The results show that ultrasound can greatly decrease the dielectric breakdown voltage of the coatings, increase the number of micro-discharges while decrease their average size, promote the evolution of micro-discharges, decrease the number and the average size of residual discharge pores in the coatings after 30 min of the process, promote the homogeneous distribution of elements and the formation of α-Al₂O₃ and 3Al₂O₃⋅2SiO₂ in the coatings.     

Growth characteristics of micro-plasma oxidation ceramic coatings on Ti alloy by inductively coupled plasma-atomic emission spectrometer technique

The aim of this work was to study the growth characteristics of micro-plasma oxidation ceramic coatings on Ti-6Al-4V alloy. Compound ceramic coatings were prepared on Ti-6Al-4V alloy by pulsed micro-plasma oxidation (MPO) in NaAlO₂ solution. The phase composition and surface morphology of the coating were investigated by X-ray diffractometry and scanning electron microscopy. The solution of Ti from the substrate and the content of Al in the electrolyte were studied by inductively coupled plasma-atomic emission spectrometer (ICP-AES) technique. Ti from the substrate dissolved and came into the coating and the electrolyte during MPO process. The content of Ti in the electrolyte under the pulsed bi-polar mode was more than that of the pulsed single-polar mode. The phase composition and structure of the coating was attributable to the space steric hindrance of Al congregated on the electrode surface due to the effect of the electric field and the electrolyte characters. For the pulsed single-polar mode, the coating was mainly composed of a large amount of α-Al₂O₃ and a small amount of γ-Al₂O₃. And the coating was mainly structured by Al from the electrolyte. However, the coating was composed of a large amount of Al₂TiO₅ and a little α-Al₂O₃ and rutile TiO₂ for the pulsed bi-polar mode. And the coating was structured both by Ti from the substrate and Al from the electrolyte.     

Influence of treating frequency on microstructure and properties of Al2O3 coating on 304 stainless steel by cathodic plasma electrolytic deposition

Alumina ceramic coatings were fabricated on 304 stainless steel by cathodic plasma electrolytic deposition (CPED). Influence of treating frequency of the power supply on the microstructure and properties of the coatings were studied. The results indicated that coatings obtained at various frequencies on 304 stainless steels were all composed of α-Al₂O₃ and γ-Al₂O₃, and α-Al₂O₃ was the dominant phase. The contents of α-Al₂O₃ decreased gradually in a very small rate with increasing the frequency and γ-Al₂O₃ gradually increased. The surface of alumina ceramic coating was porous. With increasing the frequency, the coating surface gradually became less rough and more compact, resulting in low surface roughness. The bonding strength of Al₂O₃ coating was higher than 22 MPa and was not strongly affected by treating frequency. With increasing the frequency, the alumina coated steels showed better and gradually increasing corrosion resistance than the uncoated one in 3.5% NaCl solution. The coating steel with desirable corrosion resistance was obtained at 800 Hz whose corrosion current potential and corrosion density were −0.237 V and 7.367 × 10⁻⁸ A/cm², respectively.     

Preparation and properties of ceramic coating on Q235 carbon steel by plasma electrolytic oxidation

Ceramic coating was achieved on Q235 carbon steel by PEO (plasma electrolytic oxidation, PEO) without any pretreatment in sodium aluminate system. The discharge process as well as the accompanied surface morphology evolution was analyzed. The phase and elemental composition of the coatings were also investigated. The corrosion, mechanical and tribological properties of the ceramic coating were primarily studied. It is found that the coating surface was porous and the thickness of the coating was about 120 μm. The coating mainly consisted of FeAl₂O₄, Fe₃O₄ and a little γ-A1₂O₃. The corrosion current of the coated sample was 3.082 × 10⁻⁷ A/cm², which was decreased by two orders of magnitude compared with the uncoated one. The micro hardness of the ceramic coating was 1210 Hv, which was about three times as that of the uncoated sample. The friction coefficient of coated sample was also well improved. Investigations revealed that PEO provided a promising technique for preparation of protective ceramic coatings on steels.     

Ultra-hard ceramic coatings fabricated through microarc oxidation on aluminium alloy

Ultra-hard ceramic coatings with microhardness of 2535 Hv have been synthesized on the Al alloy substrate by microarc oxidation (MAO) technique. The effects of anodic current density (j_a) and the ratio of cathodic to anodic current density (j_c/j_a) on the mechanical and corrosion resistance properties of MAO coatings have been studied by microhardness and pitting corrosion tests, respectively. In addition, the phase composition and microstructure of the coatings were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The results show that the coatings prepared at high anodic current density consist mainly of α-Al₂O₃, while those fabricated at low anodic current density are almost composed of γ-Al₂O₃. Microhardness test shows that the coatings have high microhardness, and the highest one is found in the coating formed at j_a = 15 A/dm² and j_c/j_a = 0.7. Pitting corrosion test shows that the structure of coatings is strongly influenced by the varying j_c/j_a.     

Phase evolution of an aluminized steel by oxidation treatment

Effects of temperature and time on the microstructure and phase evolution for different thermal treatments were investigated with respect to the measurement of intermetallic layer thickness, phase identification and microhardness distribution in the aluminized zone of a steel substrate. The intermetallic phases present in the aluminized region after hot dip aluminizing is mainly Fe₂Al₅. The thickness of the intermetallic layers increases with increasing oxidation temperature and time. In the oxidation treatments of the aluminized steel in air, the initial Fe₂Al₅ phase remains at the temperature below 950 °C in 2-h, and the Fe₂Al₅ phase is completely transformed into low iron content Fe-Al intermetallics due to oxidation at 950 °C for 4 h. However, the Fe₂Al₅ phase remains in the outer layer of the aluminized samples diffusion-treated in vacuum regardless of diffusion time. The microhardness values of the Al₂O₃ and the intermetallic Fe₂Al₅, FeAl₂, FeAl and Fe₃Al phases are HV1150, HV1010, HV810, HV650 and HV320, respectively. The oxide layer formed on the steel substrate has an extremely fast adherence to the steel substrate and excellent properties of thermal shock resistance, high temperature oxidation resistance and anti-liquid aluminum corrosion.     

Effect of α-Al2O3 on the properties of cold sprayed Al/α-Al2O3 composite coatings on AZ91D magnesium alloy

Composite coatings using pure Al powder blended with α-Al₂O₃ as feedstock were deposited on AZ91D magnesium alloy substrates by cold spray (CS). The content of α-Al₂O₃ in the feedstock was 25 wt.% and 50 wt.%, respectively. The effects of α-Al₂O₃ on the porosity, microhardness, adhesion and tensile strength of the coatings were studied. Electrochemical tests were carried out in neutral 3.5 wt.% NaCl solution to evaluate the effect of α-Al₂O₃ on the corrosion behavior of the coatings. The results showed that the composite coatings possessed lower porosity, higher adhesion strength and tensile strength than cold sprayed pure Al coating. The corrosion current densities of the composite coatings were similar to that of the pure Al coating and much higher than that of bare AZ91D magnesium alloy.     

Investigation of Ceramic-Like Coatings Formed on Aluminum Composites by Microarc Oxidation

Ceramic-like coatings with a thickness of up to 40 μm are formed on aluminum composites without additives and with copper additives (1 and 4.5%) in a silicate-alkaline electrolyte by microarc oxidation. The composites are prepared by powder metallurgy (cold pressing and sintering in forevacuum). An increase in the copper concentration in the composites to 4.5% leads to the retardation of anode voltage growth on the initial stage of oxidation corresponding to the formation of a barrier layer. The coatings are studied by scanning electron microscopy, X-ray microanalysis, X-ray photoelectron spectroscopy, and X-ray diffraction. The morphology of their surface corresponds to the morphology of the surface of coatings on compact aluminum alloys. According to X-ray photoelectron spectroscopy, a thin 1-μm layer forms on the surface. It consists predominantly of electrolyte components. X-ray diffraction analysis shows that the coatings mainly consist of γ-Al₂O₃ oxide as well as the η-Al₂O₃ phase, the peaks of which are broadened. This broadening is characteristic of the amorphous component and may be due to the presence of nanocrystalline regions in the coating structure. In the coatings on the composite Al + 4.5% Cu, mullite Al₂SiO₅ and copper oxide CuO are also found. The excess aluminum content may be associated with residual unoxidized aluminum inclusions in the structure of the coatings.     

Effects of duty ratio at low frequency on growth mechanism of micro-plasma oxidation ceramic coatings on Ti alloy

The aim of this work is to study the effects of duty ratio on the growth mechanism of the ceramic coatings on Ti-6Al-4V alloy prepared by pulsed single-polar MPO at 50 Hz in NaAlO₂ solution. The phase composition of the coatings was studied by X-ray diffraction, and the morphology and the element distribution in the coating were examined through scanning electron microscopy and energy dispersive spectroscopy. The thickness of the coatings was measured by eddy current coating thickness gauge. The corrosion resistance of the coated samples was examined by linear sweep voltammetry technique in 3.5% NaCl solution. The changes of the duty ratio (D) of the anode process led to the changes of the mode of the spark discharge during the pulsed single-polar MPO process, which further influenced the structure and the morphology of the ceramic coatings. The coatings prepared at D = 10% were composed of a large amount of Al₂TiO₅ and a little γ-Al₂O₃ while the coatings prepared at D = 45% were mainly composed of α-Al₂O₃ and γ-Al₂O₃. The coating thickness and the roughness were both increased with the increasing D due to the formation of Al₂O₃. The formation of Al₂TiO₅ resulted from the spark discharge due to the breakdown of the oxide film, while the formation of Al₂O₃ resulted from the spark discharge due to the breakdown of the vapor envelope. The ceramic coatings improved the corrosion resistance of Ti-6Al-4V alloy. And the surface morphology and the coating thickness determined the corrosion resistance of the coated samples prepared at D = 45% was better than that of the coated samples prepared at D = 10%.     

In situ formation of low friction ceramic coatings on carbon steel by plasma electrolytic oxidation in two types of electrolytes

In situ formation of ceramic coatings on Q235 carbon steel was achieved by plasma electrolytic oxidation (PEO) in carbonate electrolyte and silicate electrolyte, respectively. The surface and cross-section morphology, phase and elemental composition of PEO coatings were examined by means of scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDS). The bond strength of the coating was determined using a direct pull-off test. The hardness as well as tribological properties of the ceramic coating was primarily studied. The results indicated that the coating obtained in carbonate electrolyte was Fe₃O₄, while the coating achieved from silicate electrolyte was proved to be amorphous. Both kinds of coatings showed coarse and porous surface. The Fe₃O₄ coatings obtained in carbonate electrolyte showed a high bonding strength to the substrate up to 20 ± 2 MPa and the value was 15 ± 2 MPa for the amorphous coatings obtained in carbonate electrolyte. The micro hardness of the amorphous coating and the Fe₃O₄ coating was 1001 Hv and 1413 Hv, respectively, which was more than two and three times as that of the Q235 alloy substrate (415 Hv). The friction coefficient exhibited by amorphous coating and Fe₃O₄ coating was 0.13 and 0.11, respectively, both lower than the uncoated Q235 substrate which ranged from 0.17 to 0.35.     

The resistance to wear and corrosion of laser-cladding Al2O3 ceramic coating on Mg alloy

The paper presents a study on the preparation of Al₂O₃ ceramic coating on AZ91HP Mg alloy by laser remelting plasma-sprayed coating. It was found that after laser remelting, the coating exhibited obvious layer-like characteristics due to influence of temperature distribution, thermophysical parameters and layer thickness. According to the microstructural difference, the coating can be divided into the melted zone with the α-Al₂O₃ column-like crystal, the sintered zone with flock-like structure, the residual plasma-sprayed zone with loosened structure. Because of the dense column-like crystal, the hardness, wear and corrosion resistance of the laser remelted coating are much higher than those of the plasma-sprayed coating and as-received Mg alloy.     

Microstructure and corrosion resistance behavior of ceramic coatings on biomedical NiTi alloy prepared by micro-arc oxidation

In this paper, ceramic coatings were prepared on biomedical NiTi alloys by micro-arc oxidation (MAO) in constant voltage mode. The current density-time response was recorded during the MAO process. The microstructure, element distribution and phase composition of the coatings prepared at different MAO treatment times were investigated by scanning electron microscopy (SEM), energy dispersive X-ray spectrometer (EDS), thin-film X-ray diffraction (TF-XRD) and X-ray photoelectron spectroscopy (XPS). The corrosion behavior of the coatings in 0.9% NaCl solution was evaluated by the potentiodynamic polarization test. It is found that the coatings become more compact with increasing the MAO treatment time, and the growth rate of coating decreases. The results of TF-XRD, EDS and XPS indicate that the coatings are composed of a large amount of γ-Al₂O₃ and a little α-Al₂O₃, TiO₂ and Ni₂O₃. The Ni content of the coatings is about 3 at.%, which is greatly lower than that of NiTi substrate. The bonding strength of coating-substrate is higher than 40 MPa for all the samples in this study. The corrosion resistance of the coatings is about two orders of magnitude higher than that of the uncoated NiTi alloy.     

Microstructure and mechanical properties of alumina coatings prepared by double glow plasma technique

Low-temperature growth (600 °C) of α-Al₂O₃ coatings on the stainless steel substrate by double glow plasma technique was achieved. The compositions and microstructures of the coatings prepared at different oxygen flow rates were characterized, respectively, by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectrometry. A phenomenological mechanism for the formation of the Al₂O₃ ceramic coatings during the oxidation process was proposed on the basis of the experimental results. It was obvious that the oxygen flow rates had a great effect on the surface structure of the prepared Al₂O₃ coatings. The dense and smooth Al₂O₃ coatings were prepared at the oxygen flow rate of 15 sccm. In addition, the correlations between the mechanical properties of Al₂O₃ coating and oxygen flow rates were also discussed. The coating prepared at 15 sccm oxygen flow rate exhibited the best mechanical properties with a maximum hardness of 31 GPa and elastic modulus of 321 GPa. The corresponding critical load of scratch adherence for this sample was 47 N.     

Structure of Al2O3 thin layers synthesized on the silicon surface by atomic layer deposition

The distribution of the phase and chemical composition at an Al₂O₃/Si interface is studied by depth-resolved ultrasoft x-ray emission spectroscopy. The interface is formed by atomic layer deposition of Al₂O₃ films of various thicknesses (from several to several nanometers to several hundreds of nanometers) on the Si(100) surface (c-Si) or on a 50-nm-thick SiO₂ buffer layer on Si. L _2,3 bands of Al and Si are used for analysis. It is found that the properties of coatings and Al₂O₃/Si interfaces substantially depend on the thickness of the Al₂O₃ layer, which is explained by the complicated character of the process kinetics. At a small thickness of coatings (up to 10–30 nm), the Al₂O₃ layer contains inclusions of oxidized Si atoms, whose concentration increases as the interface is approached. As the thickness increases, a layer containing inclusions of metallic Al clusters forms. A thin interlayer of Si atoms occurring in an unconventional chemical state is found. When the SiO₂ buffer layer is used (Al₂O₃/SiO₂/Si), the structure of the interface and the coating becomes more perfect. The Al₂O₃ layer does not contain inclusions of metallic aluminum, does not vary with the sample thickness, and has a distinguished boundary with silicon.