Structure and mechanical properties of ceramic coatings fabricated by plasma electrolytic oxidation on aluminized steel

Ceramic coatings were formed by plasma electrolytic oxidation (PEO) on aluminized steel. Characteristics of the average anodic voltages versus treatment time were observed during the PEO process. The micrographs, compositions and mechanical properties of ceramic coatings were investigated. The results show that the anodic voltage profile for processing of aluminized steel is similar to that for processing bulk Al alloy during early PEO stages and that the thickness of ceramic coating increases approximately linearly with the Al layer consumption. Once the Al layer is completely transformed, the FeAl intermetallic layer begins to participate in the PEO process. At this point, the anodic voltage of aluminized steel descends, and the thickness of ceramic coating grows more slowly. At the same time, some micro-cracks are observed at the Al₂O₃/FeAl interface. The final ceramic coating mainly consists of γ-Al₂O₃, mullite, and α-Al₂O₃ phases. PEO ceramic coatings have excellent elastic recovery and high load supporting performance. Nanohardness of ceramic coating reaches about 19.6 GPa.     

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.     

Characterization of oxide coatings formed on tantalum by plasma electrolytic oxidation in 12-tungstosilicic acid

Oxide coatings were formed on tantalum by plasma electrolytic oxidation (PEO) process in 12-tungstosilicic acid. The PEO process can be divided into three stages with respect to change of the voltage-time response. The contribution of electron current density in total current density during anodization results in the transformation of the slope of voltage-time curve. The surface morphology, chemical and phase composition of oxide coatings were investigated by AFM, SEM-EDX, XRD and Raman spectroscopy. Oxide coating morphology is strongly dependent of PEO time. The elemental components of PEO coatings are Ta, O, Si and W. The oxide coatings are partly crystallized and mainly composed of WO₃, Ta₂O₅ and SiO₂. Raman spectroscopy showed that the outer layer of oxide coatings formed during the PEO process is silicate tungsten bronze.     

Plasma electrolytic oxidation coating on AZ91 magnesium alloy modified by neodymium and its corrosion resistance

Ceramic coatings on the surfaces of Mg-9Al-1Zn (AZ91) magnesium alloy and Mg-9Al-1Zn-1Nd magnesium alloy (AZ91 magnesium alloy modified by neodymium, named as AZ91Nd in this paper) are synthesized in aluminate electrolyte by plasma electrolytic oxidation (PEO) process, respectively. X-ray diffraction and X-ray photoelectron spectroscopy analyses show the PEO coating on the Mg-9Al-1Zn-1Nd alloy comprises not only MgO and Al₂O₃, which are found in the coating on the AZ91 alloy, but also a trace amount of Nd₂O₃. Microstructure observations indicate the addition of Nd can decrease the sizes of β phases and form Al₂Nd intermetallics in the AZ91 alloy. The fine β phases can effectively restrain the formation of unclosed-holes and greatly decrease the sizes of pores in the coating during the PEO process. In addition, the Al₂Nd intermetallics can be completely covered due to the lateral growth of the PEO coatings formed on the α and β phases. As a result, the coating on the AZ91Nd alloy possesses a dense microstructure compared with that on the AZ91 alloy. The following corrosion tests indicate the corrosion resistance of the PEO coating on the AZ91Nd alloy is evidently higher than that of the PEO coating on the AZ91 alloy.     

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.     

Microstructure, bonding strength and thermal shock resistance of ceramic coatings on steels prepared by plasma electrolytic oxidation

Ceramic coatings were successfully prepared on steel by plasma electrolytic oxidation (PEO) in aluminate electrolyte and silicate electrolyte, respectively. The microstructure of the coatings including surface morphology, phase and element composition were studied by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. The bonding strength between the ceramic coating and the substrate was tested using different methods including tensile tests and shearing tests. The thermal shock resistance of the coatings was also evaluated. The results indicated that coatings obtained in both electrolytes were porous and coarse. The average diameters of the pores were below 10 μm. PEO coatings obtained in aluminate electrolyte were composed of Fe₃O₄ and FeAl₂O₄, while those obtained in silicate electrolyte were in a noncrystal state. PEO coatings obtained in aluminate electrolyte showed similar change trend of tensile strength and shearing strength with increasing treating time, namely, a relatively high values with middle time treating and low value with short and long time treating. The best coating was the samples treated with 30 min, whose tensile strength was 20.6 MPa and shearing strength was 16 MPa. The tensile strength and shearing strength of coatings obtained in silicate electrolyte were not strongly influenced by the treating time, the values of which were range in 14 ± 2 MPa and 11 ± 2 MPa, respectively. Coatings obtained in both electrolytes showed the best thermal shock resistance with middle time treating. Coatings obtained in silicate electrolyte show a little better thermal shock resistance than those obtained in aluminate electrolyte.     

Cobalt-containing oxide layers on titanium, their composition, morphology, and catalytic activity in CO oxidation

In this study possibility to form the layered compositions CoO_x + SiO₂/TiO₂/Ti by plasma electrolytic oxidation (PEO) method was shown. Compositions have been obtained by both one-stage PEO method (Method I) with addition of Co(CH₃COO)₂ into silicate electrolyte and impregnation of preliminary obtained by the PEO method SiO₂/TiO₂/Ti systems in aqueous solutions containing cobalt salts with their following annealing (Method II). XRD, XPS and SEM/EDX were used to investigate the phase and element composition, microstructure of the coatings prepared by the two various methods. Catalytic activity of the cobalt-containing composites was investigated in the CO oxidation reaction. Under experimental conditions, the structures obtained by impregnation and annealing method were more active, than those obtained by one-stage PEO method. The surface structures of cobalt-containing coatings obtained by the PEO method and by impregnation and annealing differ in both quantitative and qualitative relation. The cobalt content on the surface of impregnating coatings is three times as much as that for those formed by one-stage PEO method. It is found that coatings obtained by the Method II have a more developed surface. The surface of CoO_x + SiO₂/TiO₂/Ti compositions obtained by the PEO method contains, presumably Co(OH)₂ and Co₃O₄. The surface of the similar compositions obtained by the Method II, possibly contains CoO, either Co₂O₃, or CoOOH. The combination of these factors, perhaps, also provides a higher activity of the compositions formed by the Method II.     

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.     

Corrosion and wear properties of PEO coatings formed on AM60B alloy in NaAlO2 electrolytes

Coatings with a thickness of 22-32 μm were formed on an AM60B magnesium alloy by plasma electrolytic oxidation (PEO) in electrolytes containing 12.0-24.0 g/l NaAlO₂ and other additives. SEM analyses of the coated samples showed that the coatings were compact with relatively low porosity. X-ray diffraction revealed that the coatings consisted of mainly MgAl₂O₄ and MgO phases. The relative amount of MgAl₂O₄ in the coating increased with increasing NaAlO₂ concentration. The relatively compact and thick coatings provide good corrosion protection for magnesium, as indicated by the results of potentiodynamic polarization tests. In addition, the PEO treatment also significantly improved the wear resistance of the alloy. Pin-on-disk wear tests showed that the PEO treatment reduced the wear volume loss by a factor of 10.     

Synthesis of ultrafine single crystals and nanostructured coatings of indium oxide from solution precursor

Indium oxide (In₂O₃) has been widely used in sensors, solar cells and microelectronics. There are several techniques available for making In₂O₃ such as vapor, electrochemical and atomic layer deposition, which are not only expensive but also time consuming processes. In this study, an inexpensive and straightforward synthesis approach is being presented to make micron/submicron size single crystals as well as nanostructured adherent coatings of In₂O₃ using Indium Chloride (InCl₃) powders and InCl₃ solution precursor. Both the powders and the solution precursor were calcined in a furnace to obtain the crystals; however, the liquid precursor was also treated by a DC plasma jet to obtain the nanostructured coatings. The phase transformations during thermal decomposition of InCl₃ powders and solution precursor were investigated via differential scanning calorimetry studies. The phase structure and crystallinity of the crystals and coatings were confirmed by X-ray diffraction. Microstructural characterization of the crystals and coatings was done by scanning electron microscopy, transmission electron microscopy and atomic force microscopy techniques. Size of the crystals was observed to be dependent on the heating schemes adapted during calcination. Solution precursor plasma sprayed In₂O₃ coatings showed porosity and ultrafine particulates with grain size ranging between 10 and 75 nm. Resistivity was determined to be ∼0.553 ± 0.337 kΩ cm. Optical transmittance of In₂O₃ coatings was ∼60-78% in the visible region and it was observed to decrease with increasing the number passes or the thickness of the coatings. Based on the optical transmission data, direct band gap of 3.57 eV was determined.     

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.     

Effect of fillers on magnesium–poly(ethylene oxide) solid polymer electrolyte

A solid polymer electrolyte (SPE) film consisting of poly(ethylene oxide) (PEO) with magnesium chloride as electrolytic salt and B₂O₃ as the filler has been prepared by solution casting technique. The polymeric film was flexible and self-standing with proper mechanical strength and studied for application in a solid-state rechargeable magnesium battery. The interactions between the filler and PEO chains are studied by differential scanning calorimeter and Fourier transform infrared techniques. Composition of SPE is optimized, and maximum conductivity is obtained at 2 wt% B₂O₃. Filler seems to increase the number of free magnesium cations by decoordinating the bond between magnesium cations and ether oxygen of PEO. Cyclic voltammetry results show the reversible capability of magnesium electrode. Solid-state magnesium cell employing magnesium anode, SPE, and manganese oxide was assembled, and its open circuit voltage is found to be 1.9 V.     

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.     

Cells studies on PEO/PEG/NaClO<Subscript>3</Subscript> thin-film electrolyte system based on composite V<Subscript>2</Subscript>O<Subscript>5</Subscript> electrode

The thin-film solid polymer electrolyte based on polyethylene oxide (PEO) with sodium chlorite (NaClO₃) has been prepared by a solution-cast technique. The electrolyte was characterized by X-ray diffraction (XRD), infrared (IR), cyclic voltammetry, alternating current conductivity, and Wagner’s polarization studies. The complexation of NaClO₃ with PEO was confirmed through the XRD and IR studies. The transference number measurement has shown that the ion transport is predominant over electrons in the polymer electrolytes (t _ions ≈ 0.94). The conductivity enhancement was observed in the case of the PEO/NaClO₃ system with the addition of plasticizers (low-molecular-weight polyethylene glycol, organic solvents propylene carbonate and dimethyl formamide. Cyclic voltammetry analysis showed the stability and redox character of the electrolyte and electrode. Finally, polymer electrolyte systems were examined by electrochemical cell studies using V₂O₅ and composite V₂O₅ cathode at temperature of 35 °C. Overall, the plasticized electrolyte shows a better electrochemical performance, and a higher discharge capacity was observed in composite V₂O₅-based cells over V₂O₅-based cells.     

Nano-composite solid polymer electrolytes for solid state ionic devices

Recent research efforts to improve the ambient temperature conductivity in polyethylene oxide (PEO) based solid polymer electrolytes have been directed towards the incorporation of ultra-fine nano-sized particles of ceramic fillers such as Al₂O₃, γ-LiAlO₂, SiO₂ and TiO₂ into the polymer electrolyte. In these PEO based nano-composite polymer electrolytes, conductivity enhancements of up to two orders of magnitude have been achieved. Thermal, electrical conductivity and dielectric relaxation measurements performed on several nano-composite polymer electrolyte systems have shown that the degree of enhancement depends primarily on the grain size. In this paper, results of three nano-composite polymer electrolyte systems, PEO:LiTFSI:Al₂O₃, PEO:LiTf:Al₂O₃ and PEO:LiTf: SiO₂ are discussed as representative examples. It is suggested that the conductivity enhancement is due to the creation of additional sites and favourable conduction pathways for ionic transport through Lewis acidbase type interactions between the filler surface groups (H/OH) and the ionic species. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Channai, India, Nov. 28–30, 2003.     

Coating formation by plasma electrolytic oxidation on ZC71/SiC/12p-T6 magnesium metal matrix composite

Plasma electrolytic oxidation (PEO) of a ZC71/SiC/12p-T6 magnesium metal matrix composite (MMC) is investigated in relation to coating growth and corrosion behaviour. PEO treatment was undertaken at 350 mA cm⁻² (rms) and 50 Hz with a square waveform in stirred 0.05 M Na₂SiO₃.5H₂O/0.1 M KOH electrolyte. The findings revealed thick, dense oxide coatings, with an average hardness of 3.4 GPa, formed at an average rate of ∼1 μm min⁻¹ for treatment times up to 100 min and ∼0.2 μm min⁻¹ for later times. The coatings are composed mainly of MgO and Mg₂SiO₄, with an increased silicon content in the outer regions, constituting <10% of the coating thickness. SiC particles are incorporated into the coating, with formation of a silicon-rich layer at the particle/coating interface due to exposure to high temperatures during coating formation. The distribution of the particles in the coating indicated growth of new oxide at the metal/coating interface. The corrosion rate of the MMC in 3.5% NaCl is reduced by approximately two orders of magnitude by the PEO treatment.     

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%.     

Improvement on HVOF sprayed Diamalloy coatings by laser irradiation

We investigated the structure change, surface properties (roughness, porosity, and hardness), tribological, and electrochemical performances of HVOF sprayed Ni-20Cr-10W-9Mo-4Cu-1C-1B-1Fe (Diamalloy-4006) coatings before and after laser irradiation. The results showed that the friction and wear resistance of the coatings were improved significantly with an optimized laser irradiation process. The improvement can be attributed to the improved roughness and hardness, as well as the formation of oxides Cu _x O and Cr₂O₃ tribofilms. With the laser irradiation treatment, the local corrosion of the coating had a decrease and the selective corrosion resistance of the Diamalloy-4006 coating was improved as a result of the decreasing the size and number of the pores, especially compact interface achieved by laser irradiation.     

Plasma-electrolytic formation, composition and catalytic activity of manganese oxide containing structures on titanium

In the present work, we report the data about formation of TiO₂-rutile or TiO₂ and Mn₂O₃, Mn₃O₄ containing oxide structures on titanium in aqueous electrolytes by means of plasma-electrolytic deposition. The layers formed are characterized by X-ray diffraction, electron probe microanalysis and scanning electron microscopy methods. The PEO coatings on titanium formed in sodium tetraborate solution contain the TiO₂ stabile rutile modification that is important when utilizing such a structure as a catalyst carrier. Manganese acetate adding into the electrolyte leads to formation of layers that contain Mn₂O₃, Mn₃O₄ and TiO₂-rutile in outer region. The manganese content in the surface layer depends on the formation conditions as well as on manganese acetate concentration in the electrolyte. Catalytic activity of the layers in CO → CO₂ reaction is studied in the static and flow conditions. The manganese-containing layers obtained possess the catalytic activity in CO → CO₂ oxidation reaction at the temperature range of 250-350 °C. The catalytic activity depends on the concentration and surface distribution of manganese as well as on the layers morphology.     

Growth characteristics of plasma electrolytic oxidation ceramic coatings on Ti-6Al-4V alloy

The aim of this work is to discuss the growth characteristics of the ceramic coatings on Ti alloy by plasma electrolytic oxidation (PEO) technique. Ceramic coatings were prepared on Ti alloy by plasma electrolytic oxidation in different electrolyte solutions under different pulse modes. The composition and the structure of the coatings were investigated by X-ray diffraction and scanning electron microscopy (SEM), respectively. The amount of the dissolved titanium into the electrolytes during PEO process was measured by inductively coupled plasma-atomic emission spectrometer (ICP-AES). The structure and the composition of the coatings were related to the mode of the spark discharge during PEO process. (a) Under the pulsed single-polar mode: In Na₃PO₄ solution, the spark discharge was mainly due to the breakdown of the oxide film, and the coatings prepared were porous and mainly structured by the Ti from the substrate. In K₄ZrF₆-H₃PO₄ and NaAlO₂-Na₃PO₄ solutions, the main mode of the spark discharge was the breakdown of the oxide film at the initial stage, and then changed into the breakdown of the vapor envelope, and the coatings were rough and thick, and mainly structured by the elements from the electrolyte. (b) Under the pulsed bi-polar mode in NaAlO₂-Na₃PO₄ solution, the spark discharge may be mainly due to the breakdown of the oxide film, the coatings prepared were dense in inner layer and loose in outer layer, and structured by the elements from both the substrate and the electrolyte. Besides, the ICP-AES analyses showed that the amount of the dissolved titanium in the electrolyte during PEO process was more under the breakdown of the oxide film than under the breakdown of the vapor envelope, which was consistent with the changes of the structure of the coatings. Cathode pulse in the pulsed bi-polar mode increased the amount of the dissolved titanium in the electrolyte, compared with the pulsed single-polar one.