On the growth sequence of highly ordered nanoporous anodic aluminium oxide

Anodic aluminium oxide films were fabricated by well known two-step anodizing process in oxalic acid electrolyte. The ordering characteristics (ordered pore domains, average pore diameter size and through-pore arrangement) of anodic aluminium oxide films, obtained in different growth sequences, were identified by microscopic analysis such as ex situ contact-mode atomic force microcopy and scanning electron microscopy. Flattened areas in which some pits are seen mostly cover the electropolished surface of aluminium. Single anodizing of aluminium produces a broad distribution of nanopore size, whereas induces a highly ordered hemispherical pattern, which plays the ordered nucleation sites for the second anodizing step. Moreover, a quasi-linear growth behavior exists for the ordered domain growth versus the duration of first step anodizing. The through-pore arrangement of ideally grown membranes is not influenced by increasing the duration of second step anodizing.     

The duplex nature of anodic barrier films formed on aluminium in aqueous borate and borate-glycol solutions

Direct transmission electron microscopy of ultramicrotomed sections of aluminium and its anodic films formed in borate-containing environments, and subsequent electron-beam-induced crystallization, has been employed to gain further insight into the development of contaminated Al₂O₃ during anodizing. For film formation in ammonium pentaborate solution, it is suggested that borate species incorporated into the Al₂O₃ film material are immobile during anodizing. Conversely, the borate species incorporated into the film material during anodizing in the ammonium pentaborate-ethylene glycol electrolyte are apparently mobile in the field. Thus, on a direct interpretation basis, the apparent aluminium transport number can be assessed from the extents of the differently textured regions apparent after electron-beam-induced crystallization in which the borate species are immobile.     

泡沫铝合金阳极氧化工艺研究

以草酸为电解液,对泡沫铝合金材料进行阳极氧化处理,制备多孔有序阳极氧化铝阵列模板,采用SEM扫描电镜对其形貌进行分析.研究了电流密度、电解液浓度、电解温度等条件对氧化铝膜结构的影响,并对一步法和两步法制得的多孔氧化铝膜进行了比较,结果表明,氧化膜上的微孔分布均匀,孔径大小基本相同;两步阳极氧化法制备的多孔氧化铝模板的有序性优于一步氧化法.     

Microstructure of porous anodic oxide films on aluminium

Microstructure of porous anodized films of aluminium prepared in sulphuric acid solution are different from those prepared in an oxalic or phosphoric acid solution. Transmission electron microscopy reveals a multilayer or higher order structure in the former films. Infrared spectra and specific surface area were also studied for these films and new functional properties of the films suitable for new materials were found. In contrast to the fibrous colloidal structure in the cells and barrier layer in the conventional films anodized in a sulphuric acid solution at d.c. 15 V, a network structure is formed in the cells and barrier layer in the hard films prepared at higher voltage of d.c. 25 V. The microstructure changes according to the anodizing conditions. A new model for these sulphuric acid films is presented, i.e. the cell walls are constructed from five layers and the fracture of the films occurs at the centre of the cell walls. Centre barrier layer (4 to 6 nm in thickness) composed of aluminium oxide of high crystallinity was found in a barrier layer at the bottom of the pore, and the thickness is independent on the applied voltage of the anodizing. Increase in thickness of the barrier layer due to applied voltage is governed by that of the outer barrier layer.     

AZ31镁合金环境友好阳极氧化处理研究

通过正交试验得到AZ31镁合金无铬、无强氧化物的阳极氧化处理配方及工艺,运用扫描电子显微镜、X射线衍射分析及电化学测试系统对阳极氧化膜的组织结构与耐蚀性进行了表征。结果表明,该环境友好阳极氧化工艺可在AZ31镁合金表面形成具有一定耐蚀性的阳极氧化膜;所得阳极氧化膜表面质量好,是一种多孔的陶瓷膜,膜的物相主要是晶态的MgO、ZnO、Mg以及非晶态的MgAl2O4、Mg18Al23等;阳极氧化处理试样的自腐蚀电流密度减小,而腐蚀电位有所提高,说明镁合金表面形成的阳极氧化膜提高了镁合金表面的耐腐蚀性能。     

Growth of porous anodic films on FVS0812 aluminium alloy

The formation of porous anodic films on FVS0812 aluminium alloy has been examined by transmission electron microscopy in order to elucidate the processes of film growth. A complex morphology of film material is revealed containing relatively tortuous, branched and terminated porosity and relatively large cavities. The morphology is associated with the differing anodic oxidation behaviour of the aluminium matrix and silicide dispersion regions of the alloy and the differing chemical stabilities of the resultant film regions. The anodic oxidation of the silicide proceeds more slowly than that of the aluminium matrix, with the production of film material of much finer morphology. The reduced rate of oxidation of the silicide is attributed to the effects of alloying element species in the anodic film material and pore solution. The rate of oxidation of the silicide is sufficient for most of the particles to be oxidized completely during anodizing. However, the resultant film material subsequently dissolves in the pore solution leaving relatively large cavities in the film. The differing oxidation rates of the alloy components, coupled with locally differing film properties, leads to a relatively rough alloy/film interface.© 1998 Kluwer Academic Publishers     

Purity and morphology of aluminium films

A continuous wire feed source of aluminium of 99.999% purity in conjunction with a composite ceramic boat has been used to deposit aluminium films of high purity in vacuum. The impurity content was analysed by proton-induced X-ray analysis with a Van de Graaff accelerator, supplemented by X-ray fluorescence, optical emission and Auger electron spectroscopy. The low impurity content achieved ( 50 atomic ppm) is attributed to the small quantity of molten aluminium maintained in the boat at one time.

The morphology of the Al films was studied by reflection electron diffraction, X-ray diffraction and scanning electron microscopy. Thick Al films grew with {111} and {311} texture orientations. The grain size variation with thickness generally followed the known variation with the deposition rate.     

Synthesis and characterization of molybdenum disulphide formed from ammonium tetrathiomolybdate

An investigation has been carried out into the possibility of in situ formation of MoS2 within porous anodic films on aluminium, to improve subsequent tribological behaviour, by re-anodizing in thiomolybdate electrolyte. Acidification of thiomolybdate was employed to simulate the conditions for formation of the sulphide at the anodic film/electrolyte interface, followed by appropriate vacuum heat treatments to study possible temperature effects on the sulphide due to either friction or Joule heating during anodizing. The products of both acidification and heat treatment, characterized by X-ray powder diffraction and scanning electron microscopy, were compared with those formed by direct thermal decomposition of ammonium tetrathiomolybdate crystals. The precipitate formed by acidification was mainly amorphous molybdenum trisulphide (MoS3), which on heat treatment at 450 and 850°C yielded 3R-MoS2. 3R-MoS2 also formed by the thermal decomposition of thiomolybdate crystals. Thermogravimetric and differential thermal analyses showed that the decomposition of MoS3 to MoS2 occurred in the range 220–370°C and revealed the sequence of reaction steps. The findings suggest that mainly amorphous MoS3 is formed as a consequence of changes in the pH of the film/electrolyte interface during re-anodizing but the product is relatively easily transformed to crystalline MoS2 on moderate heating which may occur during wear processes.     

Influence of anodization on the fatigue strength of 7050-T7451 aluminium alloy

In recent years, with higher demand for improved quality and corrosion resistance, recovered substrates have been extensively used. Consequently residual stresses originated from these coatings reduce the fatigue strength of a component. Due to this negative influence occasioned by corrosion resistance protective coatings, an effective process like shot peening must be considered to improve the fatigue strength. The shot peening treatment pushes the crack sources beneath the surface in most of medium and high cycle cases due to the compressive residual stress field (CRSF) induced. The aim of this study was to evaluate the influence on the fatigue life of anodic films grown on 7050-T7451 aluminium alloy by sulphuric acid anodizing, chromic acid anodizing and hard anodizing. The influence on the rotating and reverse bending fatigue strength of anodic films grown on the aluminium alloy is to degrade the stress life fatigue performance of the base material. A consistent gain in fatigue life in relation to the base material was obtained through the shot peening process in coated specimens, associated to a residual stress field compressive near the surface, useful to avoid fatigue crack nucleation and delay or even stop crack propagation.     

电流密度对AZ91D镁合金阳极氧化膜表面形貌及粘接性能的影响

采用恒电流方式在AZ91D镁合金表面制备多孔阳极氧化膜。通过电压-时间曲线研究了电流密度对氧化行为的影响。采用SEM、单板拉剪试验研究了电流密度对氧化膜表面形貌及拉伸强度的影响。结果表明,电流密度不影响击穿电压及临界电压的大小。随着电流密度增加,电压达到击穿电压及临界电压的时间缩短,氧化膜孔隙率及拉伸强度均先增加后减小,当电流密度为10 mA/cm~2时拉伸强度最大,可达到22.40 MPa。     

Prozess zur Anodisierung von Aluminiumbändern mit hoher elektrischer Durchschlagsspannung

Process for anodizing of aluminum stripes with high electrical breakdown voltage The Aim of the research was to develop an anodizing process for generating a high breakdown voltage on aluminum stripes in the shortest processing time possible. In order to vary process parameters in a wide range, a flexible discontinuous anodizing laboratory device was designed in cooperation with Steinert Elektromagnetbau GmbH Köln. By means of the liquid contact method, conditions equal to non‐solid contact anodizing of aluminum stripes in continuous laboratory devices were simulated. The research was focused on the development of the current pulse shape. The results show that the highest possible breakdown voltages can be achieved in a short processing time using suitable electrical parameters (current pulse shape) and the appropriate post‐treatment. The films generated by the new technology (current pulse shape referred to as “TUCAL”) reveal a higher pore density than conventional layers. This results in a higher ductility (less tendency for cracking).     

Behaviour of bismuth during simulated processing of model aluminium capacitor foils

The production of high specification, aluminium-based, electrolytic capacitors requires optimization of material composition and heat and surface treatments in order to maximize the area available for formation of the dielectric, anodic film. Commercial foils contain low additions of copper and lead in order to achieve this goal. The present study examines the effects of heat and surface treatments on aluminium foil containing either 50 or 1000 ppm bismuth, as a replacement for lead, by a combination of Rutherford backscattering spectroscopy and scanning electron microscopy. Heat treatment at 823 K results in segregation of bismuth to the surface regions of the foils, with enrichments in the range 4–8 × 10¹⁴ Bi atoms cm^–2, localized mainly just beneath the thermal oxide, for the selected treatment conditions. The enrichment reduces following alkaline etching, to the range 1–4 × 10¹⁴ Bi atoms cm^–2. This level of enrichment is maintained during subsequent anodizing, with the enrichment partitioned between the metal and the outermost layers of the anodic films. The enrichment of the metal is about 4 × 10¹³ Bi atoms cm^–2. Electropolishing in perchloric acid solution eliminates the enrichment developed during the heat treatment, probably due to activation during the polishing process. The enrichment remains very low or negligible during subsequent anodizing. The general behaviours of bismuth and lead are similar in aluminium foils subject to the selected heat and surface treatments. However, additional studies are needed of tunnel etching to determine the feasibility of substitution of lead by bismuth in commercial foils.     

Formation of relatively pure alumina films by anodic polarization

Barrier-type film formation on aluminium in aqueous sodium and potassium hydroxide electrolytes of pH 11 was monitored using transmission electron microscopy of ultramicrotomed sections of the film attached to the substrate. Film growth to relatively low voltages in sodium hydroxide at a constant current density of 50 A m⁻² and associated high current efficiency develops typical barrier-type films of relatively pure alumina, as assessed by Rutherford backscattering spectroscopy, unlike the case with other forming electrolytes in which characteristic anions are generally incorporated in the outer regions of the films. For film growth in potassium hydroxide at a constant current density of 300 A m⁻² to high voltages, which is associated with an overall relatively low current efficiency of formation, an irregular film morphology develops, reminiscent of the appearance of barrier-type films that have suffered dielectric breakdown. In the present situation, where films were formed to voltages less than the breakdown voltage, it is thought that local current concentration, assisted by local heating, contributes to the morphology revealed; “conducting channels” within the film section provide the means for such non-uniform film growth, but precise reasons for their development are not yet clear.     

A comparison of TiN films produced by reactive d.c. sputtering and ion-assisted deposition

The properties of TiN films produced by reactive d.c. sputtering have been compared with those formed by deposition during irradiation by 10 keV nitrogen ions. Films were deposited on aluminium, nickel, molybdenum, silicon and titanium substrates which were chosen because they have a range of mechanical properties. The composition of the films has been studied by Rutherford backscattering, nuclear reaction analysis and transmission electron microscopy and data concerning their hardness and adhesion are also presented. It was found that the films produced by ion-assisted deposition (IAD) were nearly stoichiometric TiN with a predominant (100) orientation while the reactively sputtered films were less crystalline and contained a significant amount of oxygen and carbon throughout the film. There was also considerable improvement in the adhesion of the IAD films but their hardness was only marginally improved.     

纳米孔氮化镓材料的制备和研究

介绍了一种在氮化镓外延片表面制备得到孔径为纳米量级的多孔结构的工艺.用电化学方法制备出孔径为纳米量级的多孔阳极氧化铝模板作为掩模,经过电感耦合等离子体(ICP)刻蚀制备得到纳米孔氮化镓材料.孔的大小和孔间距可以通过改变阳极氧化条件来控制,改变刻蚀时间可以控制孔深.刻蚀所用气体为氯气和惰性气体的混合物.扫描电镜照片显示,掩模图形能够很好地转移到GaN材料上.刻蚀后的材料经光荧光谱(PL Spectra)谱和Raman散射谱测试,显示出良好的光学特性,并在一定程度上释放了应力.     

包铝层和氧化时间对2E12铝合金硫酸阳极氧化及膜层性能的影响

对保留表面包铝和去除包铝的2E12-T3铝合金采用硫酸阳极氧化处理工艺,研究了包铝层和氧化时间对铝合金阳极氧化行为及膜层耐蚀性的影响。采用扫描电子显微镜观察氧化膜的表面以及截面形貌,应用动电位扫描极化曲线和电化学阻抗谱对膜层的电化学性能进行分析。结果表明:两种铝合金表面均能形成具有防护性能的阳极氧化膜,膜层随氧化时间延长而增厚。富铜的第二相颗粒会使得不带包铝的2E12铝合金氧化膜具有更多孔洞缺陷,甚至出现微裂纹。保留包铝的2E12铝合金表面氧化膜更厚,孔洞缺陷少,耐蚀性更好。阳极氧化30min和45min的2E12铝合金阳极氧化膜具有较低的腐蚀电流和较高的多孔层阻抗,耐蚀性好。     

Mechanical and Abrasive Wear Properties of Anodic Oxide Layers Formed on Aluminium

Aluminium oxide coatings were formed on aluminium substrates in oxalic acid-sulphuric acid bath.Abrasion tests of the obtained anodic layers were carried out on a pin-on-disc machine in accordance with the ISO/DP 825 specifications.The Vickers microhardness,D(HV0.2),and the abrasion weight loss,Wa(mg) were measured.Influence of oxalic acid concentration(Cox),bath temperature(T) and anodic current density(J) on D and Wa has been examined,and the sulphuric acid concentration(Csul) was maintained at 160 g·L-1....     

Behaviour of hydrogen impurity in aluminium alloys during anodizing

The present study examines the behaviour of hydrogen impurity in an Al-6.5 at.% W alloy during anodizing, using elastic recoil detection and nuclear reaction analyses. Increased concentrations of hydrogen are found near the alloy/anodic film interface, amounting to ∼2×10¹⁵ H atoms cm⁻² for the particular alloy, containing 0.1-0.3 at.% hydrogen in the bulk regions, and conditions of anodizing. The enrichment arises from hydrogen in the alloy (i) diffusing to the interface, which acts as a trap, or (ii) accumulating at the interface, due to the growth of the anodic film, or a combination of both processes. Diffusion is consistent with the known mobility of hydrogen in aluminium near ambient temperature. Further, accumulation, and subsequent oxidation, of hydrogen are expected based on the general behaviour of alloying elements in anodized aluminium. The anodic films contained ∼0.1-0.3 at.% hydrogen, originating from either the electrolyte or the alloy.     

The efficiency of nanotube formation on titanium anodized under voltage and current control in fluoride/glycerol electrolyte

The formation of nanotubes on titanium is compared for anodizing under controlled voltage and controlled current in a fluoride/glycerol electrolyte. Rutherford backscattering spectroscopy and nuclear reaction analysis are employed to determine the film compositions. Film morphologies are examined by electron microscopy. The findings reveal films of approximate composition TiO(2).0.15TiF(4) that probably also contain derivatives of glycerol. Controlled voltage conditions resulted in more uniform final nanotube dimensions, for a particular charge density, and the highest efficiency of film growth, with the charge of the titanium in the film representing ～48% of the charge passed during anodizing. Under current control, the efficiency decreased from ～40% to ～23% with increase of the current density from 0.1 to 0.5?mA?cm(-2). Further, the thickness of the barrier layer was sometimes enhanced under current control, possibly due to a non-uniform current distribution and consequently elevated local temperature.     

Composition and density of non-thickness-limited anodic films on aluminium and tantalum

The unusual occurrence of anodic films of unlimited thickness has been recently reported for anodizing of tantalum in certain dehydrated, high-temperature electrolytes with organic solvents. The precise nature of these films is still uncertain. In the present work, non-thickness-limited (NTL) anodic films were formed at 0.1 mA cm⁻² on aluminium and tantalum in glycerol/phosphate electrolyte at 453 K and then examined by Rutherford backscattering spectroscopy (RBS). The results disclosed films composed of alumina and tantala, free of phosphorus species at the resolution of the measurements. Most notably, the densities of the NTL alumina and tantala were about 2.4 and 3.6 g cm⁻³, respectively. These values are less than those of compact anodic films of the type usually grown at high efficiency in aqueous electrolytes by respective factors of about 1.3 and 2.2. This difference in density is attributed primarily to the morphology and structure of NTL film materials, which incorporate significant porosity.