Anodic oxides on InAlP formed in sodium tungstate electrolyte

Amorphous anodic oxide films on InAlP have been grown at high efficiency in sodium tungstate electrolyte. The films are shown to comprise an outer layer containing indium species, an intermediate layer containing indium and aluminium species and an inner layer containing indium, aluminium and phosphorus species_. The layering correlates with the influence on cation migration rates of the energies of In³⁺-O, Al³⁺-O and P⁵⁺-O bonds, which increase in this order. The film surface becomes increasingly rough with increase of the anodizing voltage as pores develop in the film, which appear to be associated with generation of oxygen gas.     

Corrosion performance of anodic films containing polyaniline and TiO2 nanoparticles on AA3105 aluminium alloy

The corrosion protection afforded to an AA3105 aluminium alloy supporting an anodic film with incorporated polyaniline and TiO₂ nanoparticles has been examined. The films were synthesised by simultaneous anodizing and electropolymerisation of aniline in the presence of nanoparticles. The morphology and composition of the films were probed by TEM, SEM, rf-GDOES and XPS. The resultant coatings comprised a thin porous anodic film of 2-3 µm thickness, with an outer hybrid polyaniline/TiO₂ layer of several tens nanometres thickness, with the dimensions of TiO₂ nanoparticles being below 10 nm. Electrochemical impedance spectroscopy analysis and salt spray testing revealed that TiO₂ containing films provide improved corrosion protection to the AA3105 aluminium alloy compared with the film without nanoparticles. The improved protection provided by the coatings containing TiO₂ nanoparticles is attributed to the TiO₂ particle-rich thin film layer formed on the outer part of the coating that acts as a blocking barrier layer for the anodic porous aluminium oxide film.     

Spark anodizing of β-Ti alloy for wear-resistant coating

Spark anodizing of a bcc solid solution Ti-15% V-3% Al-3% Cr-3% Sn alloy has been performed in an alkaline electrolyte containing aluminate and phosphate using dc-biased ac anodizing to form a wear-resistant coating on the alloy. The coating consists mainly of Al₂TiO₅, with rutile and γ-Al₂O₃ being present as minor oxide phases. Depth profiles of the coating, examined by glow discharge optical emission spectroscopy, have revealed that aluminium species, highly enriched in the coating, distribute uniformly in the coating, while phosphorus species, incorporated from the electrolyte, are located mainly in the inner part of the coating near the coating/alloy interface. The location of the phosphorus species should be associated with the porous nature of the coating, allowing access of the electrolyte directly to the inner parts of the coating. The porosity of the coating is reduced by anodizing to high voltages. The marked improvement of the wear resistance by the coating has been demonstrated from a pin-on-disc wear test.     

Development of anodic coatings on aluminium under sparking conditions in silicate electrolyte

Spark anodizing of aluminium at 5 A dm⁻² in sodium metasilicate/potassium hydroxide electrolytes is studied, with particular emphasis on the mechanism of coating growth, using transmission electron microscopy and surface analytical techniques, with coatings typically 10 μm, or more, thick. Two-layered coatings develop by deposition of an outer layer based on amorphous silica, associated with low levels of alkali-metal species, at the coating surface and growth of an inner, mainly alumina-based, layer, with an amorphous region next to the metal/coating interface. Formation of crystalline phases in the inner layer, mainly γ-Al₂O₃, with some α-Al₂O₃ and occasional δ-Al₂O, is assisted by local heating, and possibly also by ionic migration processes, arising from the rapid coating growth at sites of breakdown. Due to local access of electrolyte species in channels created by breakdown events, the silicon content in the inner coating regions varies widely, ranging from negligible levels to about 10 at.%. Silica deposition at the coating surface and formation of Al₂SiO₅ and Al₆Si₂O₁₃ phases is promoted by increased time of anodizing and concentration of metasilicate in the electrolyte. However, at sufficiently high concentration of metasilicate and pH, when more extreme voltage fluctuations accompany breakdown, the two-layered nature of coatings is replaced by a mixture of aluminium-rich and silicon-rich regions throughout the coating thickness.     

Spark anodizing behaviour of titanium and its alloys in alkaline aluminate electrolyte

Spark anodizing of titanium, Ti-6Al-4V and Ti-15V-3Al-3Cr-3Sn in alkaline aluminate electrolyte produces highly crystalline anodic films consisting mainly of Al₂TiO₅ with α- and γ-Al₂O₃ as minor oxide phases, irrespective of substrate composition. However, the apparent efficiency for film formation decreases in the following order: Ti-6Al-4V, titanium and Ti-15V-3Al-3Cr-3Sn. A large amount of aluminium species are incorporated from the electrolyte, probably by plasma-chemical reaction, and become distributed throughout the film thickness. This distribution indicates that the electrolyte penetrates near to the film/substrate interface through the discharge channels. Thus, the outwardly migrating aluminium ions under a high electric field can be present even in the inner part of the anodic films. Voids are developed at the film/substrate interface, particularly on the vanadium-containing alloys, reducing the adhesion of the anodic film to the substrate.     

Oxidation behaviour of PACVD TiBN coating at elevated temperatures

The elevated-temperature oxidation behaviour of a TiBN coating on a plasma-nitrided hot-work tool steel (DIN 1.2367) by means of plasma-assisted chemical vapour deposition (PACVD) was investigated under the condition where a coated die would be preheated prior to being mounted on the press for aluminium extrusion. The TiBN coating was found to possess good resistance to oxidation up to 400 °C. Rapid oxidation started to occur at 450 °C. Radio frequency glow discharge optical emission spectroscopy (rf-GDOES) indicated that the oxidised layer was thickened from 100 nm to 1.0 μm, as the soaking time at 500 °C was prolonged from 2 to 16 h, which was attributed to the high temperature that promoted the penetration of oxygen into the coating. rf-GDOES also showed that boron initially in the coating vanished from the oxidised layer when the temperature was 450 °C or higher. X-ray diffractometry confirmed that the oxidised layer was composed mainly of TiO₂. SEM revealed that the TiO₂ layer was pulverised, leaving many microcracks and cavities, as a result of the losses of boron oxide and nitrogen. The rapid oxidation at above 450 °C was attributed to the pulverised TiO₂ layer that was unable to hinder the diffusion of oxygen into the coating. It is therefore recommended to apply a protective gas during the preheating of the TiBN-coated die for aluminium extrusion. Alternatively, an advanced TiBN coating with enhanced resistance to oxidation must be developed, which will be conducive to its application for aluminium extrusion dies.     

Ba0.5Sr0.5TiO3铁电薄膜的微弧氧化成膜研究

以0.2 mol/L Ba(OH)2+0.2 mol/L Sr(OH)2溶液为电解液,采用微弧氧化法,在Ti板表面原位生长铁电薄膜,并对薄膜的物相构成、元素分布情况、截面结构及介电性能进行表征。结果表明:该工艺下制备的薄膜主要由四方相Ba0.5Sr0.5TiO3构成,薄膜致密层内,Ba,Sr,Ti和O元素分布都较均匀,但在微弧氧化孔洞附近存在含量波动;该薄膜在1 kHz下的介电常数较优,为411.3。最后对微弧氧化沉积铁电薄膜的成膜过程进行了分析,提出了微弧氧化过程中可能存在的化学反应。     

Surface Characteristics and Electrochemical Impedance Investigation of Spark-Anodized Ti-6Al-4V Alloy

In this study, the surface characteristic of oxide films on Ti-6Al-4V alloy formed by an anodic oxidation treatment in H₂SO₄/H₃PO₄ electrolyte at potentials higher than the breakdown voltage was evaluated. Morphology of the surface layers was studied by scanning electron microscope. The results indicated that the diameter of pores and porosity of oxide layer increase by increasing the anodizing voltage. The thickness measurement of the oxide layers showed a linear increase of thickness with increasing the anodizing voltage. The EDS analysis of oxide films formed in H₂SO₄/H₃PO₄ at potentials higher than breakdown voltage demonstrated precipitation of sulfur and phosphor elements from electrolyte into the oxide layer. X-ray diffraction was employed to exhibit the effect of anodizing voltage on the oxide layer structure. Roughness measurements of oxide layer showed that in spark anodizing, the Ra and Rz parameters would increase by increasing the anodizing voltage. The structure and Corrosion properties of oxide layers were studied using electrochemical impedance spectroscopy (EIS) techniques, in 0.9 wt.% NaCl solution. The obtained EIS spectra and their interpretation in terms of an equivalent circuit with the circuit elements indicated that the detailed impedance behavior is affected by three regions of the interface: the space charge region, the inner compact layer, and outer porous layer.     

氟化钾对AZ91D镁合金微弧氧化膜的生长及微观结构的影响

通过在NaOH和Na_2SiO_3组成的基础电解液中,分别不加及加入KF,对AZ91D镁合金进行微弧氧化处理,研究了KF的有无对镁合金微弧氧化膜的生长、微观结构及耐蚀性能的影响。结果表明:与不加KF相比,加入KF后,试样的起弧电压明显降低,击穿变得剧烈,试样表面火花较大,膜层的生长速率明显提高,膜层厚度显著增大,表面孔隙率稍有增大,但表面微孔数量减少。KF的加入有利于MgF_2、MgAl_2O_4的生成,与同样来自电解液的Si、O两元素相比,F~-更易被基体中的Mg所吸附,也容易通过已成膜层迁移到膜层的内部。电解液中含有KF时,膜层厚度显著增大,MgAl_2O_4物相含量增加,并生成新物相MgF_2,这些都有利于膜层耐蚀性的提高。     

Hydroxyapatite coating on titanium substrate by electrophoretic deposition method: Effects of titanium dioxide inner layer on adhesion strength and hydroxyapatite decomposition

Nanosized hydroxyapatite (HA) powders were prepared by a chemical precipitation method and electrophoretically deposited on Ti6Al4V substrates. The powders were calcined before the deposition process in order to obtain crack-free coating surfaces. As an inner layer between Ti6Al4V substrate and HA coating, nanosized titanium dioxide (TiO₂) powders were deposited, using different coating voltages, in order to connect substrate and HA tightly. Moreover, this layer is considered to be acting as a diffusion barrier, reducing the HA decomposition due to ion migration from the metal substrate into the HA. After the sintering stage, adhesion strengths of coatings were measured by shear testing, phase changes were studied by X-ray diffraction, and coating morphology was analyzed through scanning electron microscopy observations. Results showed that usage of the TiO₂ inner layer prevented HA decomposition. Furthermore, decreasing the voltage used in TiO₂ deposition resulted in crack-free surfaces and increased adhesion strength of the overall coating.     

Characterization of plasma electrolytic oxide formed on AZ91 Mg alloy in KMnO4 electrolyte

The aim of this work is to investigate microstructure, corrosion resistance characteristics and nanohardness of the oxide layer on AZ91 Mg alloy by applying different voltage with KMnO₄ contained solution. There are lots of closed pores that are filled with another oxide compound compared with the typical surface morphology with pore coated until 350 V of coating voltage. The thickness of oxide layer increases with increasing coating voltage. The oxide layer formed on AZ91 Mg alloy in electrolyte with potassium permanganate consists of MgO and Mn₂O₃. Corrosion potential of the oxide layer on AZ91 Mg alloy obtained at different plasma electrolytic oxidation(PEO) reaction stages increases with increasing coating voltage. The corrosion resistance of AZ91 Mg alloy depends on the existence of the manganese oxide in the oxide layer. The inner barrier layer composed of the MgO and Mn₂O₃ may serve as diffusion barrier to enhance the corrosion resistance and may partially explain the excellent anti-corrosion performance in corrosion test. Nanohardness values increase with increasing coating voltage. The increase in the nanohardness may be due to the effect of manganese oxide in the oxide layer on AZ91 Mg alloy coated from electrolyte containing KMnO₄.     

Simulation atmosphärischer Korrosion durch dünne Elektrolytfilme

Simulation of atmospheric corrosion by thin films of electrolyte A method for investigation on atmospherical corrosion with the aid of thin electrolyte films is described, the special feature of this being the exact adjustability of the corrosion determining parameters. The investigations on the influence of pollutants showed that small additions of sodium chloride and sulphur dioxide into the water film cause two different types of corrosion of electrolytic copper: uniform growth of layer thickness and/or lateral surface growth of the corrosion products. In the initial phase the uniform growth of layer thickness on electrolytic copper depends on t² (t = time), later on proportional on t. The investigation of the corrosion in dependence on the thickness of electrolyte film showed new results regarding the transition of the bulk-electrolytical to thin film electrolyte corrosion (atmospheric corrosion). At electrolytic copper transition from uniform growth of layer thickness to lateral surface growth comes off, when reaching a film thickness of approx. 100 μm. The electrolyte was distilled water with an addition of 0,01%SO₂. The corrosion intensity of grey cast iron GG 25 under a film of pure water passes through a wide maximum of film thickness between 300 and 20 μm, with a weakly marked minimum on 100 μm, the corrosion intensity is decreasing at thinner films. It is herewith demonstrated that also under conditions excluding largely the convective oxygen transfer other corrosion types and -intensities show up when the films are only thin enough. The comparison of the effect of two vapour inhibitors, having been dissolved directly in the electrolyte films (dicyclohexyl-ammoniumnitrite and one usual in the trade of unknown composition) in different concentrations showed on grey cast iron GG 25 the superiority of the latter one.     

预制膜对铝合金微弧氧化陶瓷层生长过程的影响

在磷酸盐体系电解液中,利用微弧氧化技术,分别对有、无高温氧化预制膜的铝合金进行表面陶瓷化处理,研究了预制膜对陶瓷层生长的影响规律.结果表明:高温氧化预制膜有利于提高陶瓷层的生长速率,降低起弧电压;陶瓷层的生长先是以初期形成的陶瓷颗粒为核心呈线状扩展,然后多条线接合呈网状,最后蔓延成面;陶瓷层生长的初期以高温氧化预制膜熔化生成为主,到后期,则是以铝合金基体熔化生成为主,此时预制膜对陶瓷层生长过程的影响较小,但由预制膜生成的陶瓷对陶瓷层生长的影响较大.     

Characterization of phosphate films on aluminum surfaces

A thin layer of phosphate conversion coating was formed on pure aluminum in a commercial zinc-manganese phosphating bath. A number of surface analytical techniques were used to characterize the phosphate thin films formed after immersion times ranging from 30 s to 10 min. The coating contained mainly a crystalline structure with dispersed micrometer-scale cavities. The major constituents of the phosphate film were zinc, phosphorus, and oxygen; a small amount of manganese was also detected. Based on these results, a three-stage mechanism was proposed for the formation and the growth of phosphate conversion coatings on aluminum. Electrochemical impedance spectroscopy was used to evaluate the corrosion performance of phosphated and uncoated aluminum samples in 0.50 M Na₂SO₄ and 0.10 M H₂SO₄ solutions. Both types of samples exhibited a passive state in the neutral solution and general corrosion behavior in the acid solution.     

Transport numbers of metal and oxygen species in anodic tantala

The transport numbers of metal and oxygen species have been determined in amorphous anodic tantala films, using transmission electron microscopy to locate ion-implanted xenon marker layers within the films. The films were formed on sputtering-deposited tantalum at constant current density, in the range 0.01-10 mA cm⁻², in 0.06 wt% H₃PO₄ solution at either 20 or 85 °C. The films grow by migration of metal and oxygen species through the film thickness, with formation of new film material at the film/electrolyte and metal/film interfaces respectively. The cation transport number, t⁺, increases due to either increase in current density or decrease in temperature: for current densities in the selected range, t⁺ increases from 0.18 to 0.32 at 20 °C, and from 0.14 to 0.29 at 85 °C. Low concentrations of phosphorus species, incorporated into an outer layer of the film, migrate inward during film growth. The migration rates are slower than those of oxygen species, by a factor in the range 0.2-0.3.     

Species separation during coating growth on aluminium by spark anodizing

The mechanism of coating growth during sparking anodizing of aluminium is probed by use of an electrolyte containing both silicate and phosphate ions, with subsequent determination of the locations of silicon and phosphorus species through the coating thickness. Importantly, the main alumina-based layer of the coating contains incorporated silicon and phosphorus species of differing distributions. Phosphorus species are primarily found in a region next to the metal, representing roughly about 30% of the layer thickness. Silicon species are located mainly above this region to the layer surface. New coating material is added in discreet amounts associated with breakdown events, which provide short-circuit paths through the layer. The growth processes within the discharge region result in separation of the silicate- and phosphate-derived species, which may relate to their different mobilities, dependent upon factors such as charge, size and bonding with other species. Further, silicon-rich material is deposited at the surface of the alumina-based layer, which is often encountered in spark anodizing in silicate electrolyte.     

Effects of electrolyte pH and temperature on dielectric properties of anodic oxide films formed on niobium

The effects of electrolyte pH and temperature on the structure and properties of anodic oxide films formed on niobium in phosphoric acid solution with the addition of NH₄OH for pH adjustment have been investigated. The film thickness formed at the same voltage slightly increased with increasing pH and significantly increased with increasing electrolyte temperature. The capacitance of the film was independent of electrolyte pH in an acid region, while it notably increased with increasing pH in an alkaline region. The relative permittivity of the film changed 43.7-80.5 when the electrolyte pH was increased from 1.6 to 10. The incorporation depth and content of phosphorus in the film were markedly suppressed at pH 10, and nitrogen was found to penetrate into a depth of 70%. Furthermore, the apparent transport number of Nb⁵⁺ ion decreased from 0.26 to 0.02 by a pH increase from 1.6 to 10. The notable changes in structure and dielectric properties of the anodic niobia film formed in the alkaline region would primarily be caused by the different incorporation behavior of electrolyte species such as phosphorous and nitrogen.     

镁合金环保型阳极氧化工艺研究

通过环保型阳极氧化工艺在MB2镁合金表面获得了表面质量良好的银灰色氧化膜层,用金相显微硬度计、扫描电镜和X射线衍射等表面分析手段,研究了氧化膜层的显微硬度、截面形貌和相结构,并采用动电位扫描的电化学方法考察了氧化膜的耐腐蚀性能.结果表明：氧化膜层的主要成分为MgO、MgAl2O4、Al2O3;膜层具有多孔结构,孔径较为均匀,分为内外两层,外层为疏松层,内层为与基体结合牢固的致密层;阳极氧化电流密度和电解液中铝盐浓度是影响阳极氧化膜层性能的主要因素;所得膜层的显微硬度值高达558.4 HV,同时其耐蚀性能也远优于传统含铬DOW17工艺所成的防护膜,且所用电解液无铬无磷更为环保经济.     

Crystallization of anodic titania on titanium and its alloys

Crystallization of amorphous anodic films grown at constant current density on sputtering-deposited titanium, and Ti-Si and Ti-Al alloys, in ammonium pentaborate electrolyte, has been examined directly by transmission electron microscopy. In the case of titanium, anatase develops at relatively low voltage in the inner film region, formed by inward migration of oxygen species. In contrast, the outer film region, formed at the film/electrolyte interface, is composed of amorphous oxide only. Oxide crystals are particularly found near the plane, separating the two regions, which is located at a depth of 35-38% of the film thickness. Oxide zones, of size ∼ 1 nm, with a relatively ordered structure, developed at the metal/film interface, are considered to lead to transformation of the inner region structure. The incorporation into the film of either aluminium or silicon species suppresses the formation of crystalline oxide to much increased voltages. However, eventually nanocrystals form at ∼40% of the film thickness, probably originating from pre-cursor nuclei in the air-formed on the as-deposited alloy.     

Influence of laser treatment on the electrical properties of plasma-enhanced-atomic-layer-deposited TiO2 thin films

TiO₂ dielectric films with 38 nm thickness were grown on Si (100) substrates at 200°C by plasma-enhancedatomic-layer deposition. Laser-irradiated TiO₂ films maintained an amorphous phase similar to as-grown films and showed an increase in permittivity and leakage current density with increasing laser powers and the number of laser shots at constant laser power. Laser-irradiation of TiO₂ films at room temperature produced oxygen vacancies at the film surface and new Ti³⁻ valences. The electrons and space charges produced through the defect chemistry increased the leakage current density and permittivity in laser-irradiated TiO₂ films, respectively. The dielectric and electrical properties of the laser-irradiated TiO₂ films were completely recovered to correspond with those of as-grown films by post-annealing at 300°C for 5 min in O₂ ambient.