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.     

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     

阴极电压脉冲占空比对钛合金微弧氧化膜特性的影响

利用自制多功能微弧氧化电源,在保持双极性电压脉冲幅度不变的条件下,研究了阴极电压脉冲占空比（d_c）对钛合金微弧氧化膜特性的影响.结果表明：阴、阳极的峰值电流随处理时间的变化分为几个不同阶段,各阶段的开始和结束时间与d_c密切相关.氧化膜主要由金红石和锐钛矿相TiO₂组成,金红石相TiO₂的相对含量在d_c=50%附近随d_c的 关键词： 微弧氧化 钛合金 占空比     

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.     

Effect of palladium oxidation state on the kinetics and mechanism of the charge transfer reaction taking place at the Pd/YSZ interface

Electrode polarization and conductivity measurements were carried out at the Pd/YSZ interface and at conditions close to the Pd–PdO thermodynamic equilibrium. The steady-state current–overpotential characteristics were analyzed with a Butler–Volmer type of equation. Both, apparent exchange current density, I_o, and anodic/cathodic charge transfer coefficients (α_a/α_c), were calculated. Based on the experimental results, it was concluded that the charge transfer at the electrode is rate-determining in the case of PdO during anodic operation and Pd during cathodic operation, while in the other case mass transport of adsorbed oxygen species along the electrode/solid electrolyte interface is in competition with the charge transfer process.     

Effect of microarc oxidation coating on fatigue performance of Ti-Al-Zr alloy

Ceramic coatings of different thickness were fabricated on Ti6Al2Zr1Mo1V alloy by microarc oxidation (MAO), and the effect of the coating on fatigue life was evaluated by 810 Material Test System. The microstructure, phase and chemical composition of the coatings were determined by SEM, XRD and EDS techniques. The coating mainly consists of rutile and a small amount of anatase TiO₂. With oxidation time ranging from 10 to 30 min, the coating thickness increases from 13 to 25 μm, while the interface between coating and substrate becomes more zigzag, characterized by increasing overgrowth regions of coating into substrate. Under the same cyclic stress of 750 MPa, the fatigue life decreases from 2.08 × 10⁶ cycles for uncoated specimen to about 3 × 10⁴ cycles for microarc oxidized specimen. Under the cyclic stress, the thicker the coating, the more cracks initiate in the overgrowth regions of coating into substrate near the interface, which are considered as the notch sites of stress concentration to induce the crack initiation, also is the key factor to cause the facture.     

Effect of cation composition on the superconducting properties and on the microstructure of YBaCuO thin films

The surface morphology and superconducting properties of YBaCuO epitaxial films prepared through magnetron sputtering from targets of different cation composition were systematically studied. It was shown that small changes in the growth conditions and relatively small variations in the cation composition of the condensate noticeably affect the surface morphology of the films and their structural and superconducting properties, thus offering an efficient way of controlling the YBCO film parameters. It was found that the 90° off-axis configuration of the magnetron sputtering system permits realization of growth conditions in which the grown films do not contain CuO precipitates and exhibit good superconducting properties (T_c≥88 K, j_c(77 K)≥4×10⁶ A/cm²).     

Tunable structural color of anodic tantalum oxide films

Tantalum(Ta) oxide films with tunable structural color were fabricated easily using anodic oxidation.The structure,components,and surface valence states of the oxide films were investigated by using gazing incidence X-ray diffractometry,X-ray photoelectron microscopy,and surface analytical techniques.Their thickness and optical properties were studied by using spectroscopic ellipsometry and total reflectance spectrum.Color was accurately defined using L*a*b* scale.The thickness of compact Ta2O5 films was linearly dependent on anodizing voltage.The film color was tunable by adjusting the anodic voltage.The difference in color appearance resulted from the interference behavior between the interfaces of air-oxide and oxide-metal.     

Einfluß der Bestrahlung mit hochenergetischen Sauerstoffionen auf die kritische Stromdichte supraleitender Nb3Sn-Schichten

Nb₃Sn diffusion layers were irradiated with 24 MeV oxygen ions at fluences from 3.2×10¹³ up to 1.6×10¹⁵ cm^?2. The enhancement of the superconducting critical current density Δj _c has been measured as a function of fluence and of the external magnetic fieldH _a(j _c⊥H _a). The thermal annealing treatment of the defects concerning thej _c and induced by irradiation, has been investigated in the temperature region from 200 to 800 °C. The results are compared with the measurements of irradiation of Nb₃Sn with protons and deuterons. The measured data are discussed in connection with size of defects, cluster distance, fluxline distance and pinning-force.     

Studies on electrodeposition of Fe-W alloys for fuel cell applications

Electrodeposition of Fe-W alloy has been carried out from acidic triammonium citrate (TAC) complex bath solution. The deposit is characterised by XRD, SEM, EDAX, XPS and polarization techniques. The alloys are amorphous and become partially crystalline on heat treatment. The composition (Fe/W) of elements in the coating and their oxidation states vary from the surface to the bulk of the material. The coatings exhibit as novel electrode material with low over voltage and good corrosion resistance for anodic oxidation of methanol in H₂SO₄ medium. The anodic peak current, a measure of oxidation reaction rate is considerably high on Fe-W alloy when compared to pure Fe and also the relative surface area of Fe by alloying it with W found to increase by 1200-fold.     

Effect of structural water on the critical characteristics of highly textured YBa2Cu3O6.9

The effect of low-temperature treatment (200°C) in a humid argon atmosphere and subsequent annealing (930°C) on the critical parameters of a highly textured YBa₂Cu₃O_6.9 has been studied. During annealing at T = 200°C, the absorbed water is incorporated into the structure of the compound, which is accompanied by the deterioration of its superconducting properties. However, after the recovery annealing at T = 930°C and subsequent oxidation, the superconducting characteristics (j _c , B _1c , and F _p ) are improved. This is explained by the formation of 124-type planar defects, which are effective pinning centers, especially in high fields applied perpendicular to the c axis (⊥ c). The optimum conditions of double annealing substantially increasing the critical current density (j _c ≥ 10⁴ A/cm²) in an external magnetic field up to 10 T and also the first critical fields have been found. In fields up to ～3 T, the critical current density j _c is isotropic despite the conservation of high texture in the samples.     

Preparation and in vitro characterization of aerosol-deposited hydroxyapatite coatings with different surface roughnesses

Hydroxyapatite (HA) coatings with different surface roughnesses were deposited on a Ti substrate via aerosol deposition (AD). The effect of the surface roughness on the cellular response to the coating was investigated. The surface roughness was controlled by manipulating the particle size distribution of the raw powder used for deposition and by varying the coating thickness. The coatings obtained from the 1100 °C-heated powder exhibited relatively smooth surfaces, whereas those fabricated using the 1050 °C-heated powder had network-structured rough surfaces with large surface areas and were superior in terms of their adhesion strengths and in vitro cell responses. The surface roughness (R_a) values of the coatings fabricated using the 1050 °C-heated powder increased from approximately 0.65 to 1.03 μm as the coating thickness increased to 10 μm. The coatings with a rough surface had good adhesion to the Ti substrate, exhibiting high adhesion strengths ranging from 37.6 to 29.5 MPa, depending on the coating thickness. The optimum biological performance was observed for the 5 μm-thick HA coating with an intermediate surface roughness value of 0.82 μm.     

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%.     

Diamond-like carbon coatings for the protection of metallic artefacts: effect on the aesthetic appearance

Plasma-enhanced chemical vapour deposition (PECVD) is an environmentally friendly process used to deposit a variety of nano-structured coatings for the protection or the surface modification of metallic artefacts like the SiO₂-like films that have been successfully tested on ancient silver, bronze and iron artefacts as barriers against aggressive agents. This paper deals with the preliminary results of a wider investigation aimed to the development of eco-sustainable coatings for the protection of Cu and Ag-based artefacts of archaeological and historic interest. Diamond-like carbon (DLC) coatings have been deposited by PECVD in different experimental conditions, in a capacitively coupled asymmetric plasma reactor, placing the substrates either on electrically powered electrode (cathodic mode) or grounded electrode (anodic mode) with and without hydrogen addition in the gas mixture. The final goal is to develop a coating with good protective effectiveness against aggressive atmospheres and contemporarily with negligible effects on the aesthetic appearance of the artefacts. The evaluation of possible colour changes of the surface patinas, due to coating process, was performed by optical microscopy and colorimetric measurements. Furthermore, to evaluate the reversibility of the thin DLC layer, an etching treatment in oxygen plasma has been successfully carried out and optimized. The chemical-physical characterization of the deposited DLC coatings was performed by means of the combined use of micro-Raman and XPS spectroscopies. The results show that the DLC films obtained in the anodic mode, may be proposed as a viable alternative to polymeric coatings for the protection of metallic ancient objects.     

General expansions for nuclear surface and curvature energy coefficients in series of volume terms and surface moments

General expansions for the surface,a _s , and curvature,a _c , energy coefficients in series of volume terms (incompressibility and higher order derivatives of the volume energy per particle) and surface moments (surface thickness, skewness, kurtosis,...) are discussed. It is also shown that the ratio (a _c ?a _s ² ) is better represented by such expansions thana _s ora _c alone.     

Kinetic studies of the electrochemical nitrogen reduction and incorporation into yttria stabilized zirconia

The kinetics of the electrochemical reduction of molecular nitrogen at gold micro electrodes on yttria stabilized zirconia (YSZ) solid oxide electrolyte is studied by steady state polarization measurements. From the η / lg i plot for both cathodic and anodic polarization the apparent transfer coefficients α_a and α_c are evaluated. The sum of α_a + α_c exceeds unity and thus a multistep electron transfer process is suggested. The concept of the stoichiometric number is applied to the electrode reaction N₂ + 6e⁻ = 2N³⁻ supposing that the overall process involves at least two intermediate species. On the basis of the evaluation of the experimental results the reaction N₂⁻ + e⁻ ⇌ N₂²⁻ is suggested as the rate determining reaction step for the cathodic nitrogen reduction and nitride formation.     

The influence of nonpolar organics adsorption on the electrochemical behaviour of powdered activated carbon electrodes in aqueous electrolytes

Adsorption and electrochemical studies were carried out on three activated carbon samples first oxidized, then heat-treated under vacuum (at 180, 500 and 900 °C). The investigations were performed with aqueous electrolyte (Na₂HPO₄ and H₃PO₄) solutions containing selected nonpolar organics (benzene and n-hexane). Adsorption measurements were carried out on solution with a wide range of organics concentration (up to saturation point). Cyclovoltammetric curves of powdered electrodes prepared from the activated carbon samples were recorded for the organics in saturated solutions. The electric double layer capacities of the anodic and cathodic parts were estimated, and the surface anodic and cathodic charge was calculated both in absence and presence of organics in the electrochemical systems. The relative surface charge (in relation to systems without organics) was found to decrease with a reduction in the concentration of surface oxygen-containing groups. Other physicochemical parameters characterizing the degree of surface oxidation (total oxygen concentration, primary water adsorption centres) were also taken into consideration. The correlation between adsorption capacity towards the nonpolar organic compounds (obtained from adsorption isotherms) and change of surface charge was analyzed.     

Effect of an external magnetic field and a trapped magnetic flux on the current-voltage characteristics of a granular high-temperature superconductor YBa2Cu3O7−δ

A comparative study of the current-voltage characteristics of the high-temperature ceramic superconductor YBa₂Cu₃O_～6.95 at T = 77.3 K is performed over wide ranges of external magnetic fields H _ext and “treatment” fields H _treat. It is found that the field dependences of the parameters a and j _c involved in the exponential equation E = a(j ? j _c)^v describing the current-voltage characteristics depend substantially on the method used for applying the magnetic field, whereas the exponent v ～ 2 depends on neither the method of application nor on the magnetic field strength. The field dependence of the trapped magnetic field H _trap is determined.     

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.     

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.