Kinetics of the electrolytic coloring process on anodized aluminum

The kinetics of tin electrodeposition during the electrolytic coloring of porous anodic oxide films on aluminum is studied as a function of the oxide properties, e.g., the thickness of the porous oxide layer, and the surface resistance offered by the barrier oxide layer. While the thickness of the porous oxide layer is controlled by the anodization time, the surface resistance is controlled by the anodization voltage, and the anodization bath temperature. Steady-state polarization measurements are employed to characterize the dependence of the coloring kinetics on the oxide properties. Measurements indicate that the kinetics of the electrolytic coloring process can be accelerated by: (i) reducing the surface resistance of the oxide film (primarily offered by the barrier oxide layer) by growing the oxide at a lower anodization voltage, and/or a higher bath temperature, or (ii) growing a thinner porous oxide layer by decreasing the anodization time. The electrochemical measurements are supported by gravimetric analysis of electrolytically colored alumina samples (using calibrated wavelength-dispersive X-ray fluorescence spectroscopy), and by optical spectrophotometry.     

铬酸浓度对铝阳极氧化多孔膜阻挡层形成过程的影响

对铝在不同浓度的铬酸中阳极氧化多孔膜阻挡层形成过程进行研究,随着铬酸浓度的增加,阻挡层形成电流密度增加,形成阻挡层所需的时间减少,阻挡层厚主变薄。这些现象可归结为阻挡层形成时应力集中的结果。     

In situ spectroscopic ellipsometric study of porous alumina film dissolution

Porous alumina films have been synthesised by anodisation of high purity aluminium in 0.4 M phosphoric acid at constant current density. The dissolution process of those coatings in 2 M phosphoric acid has been investigated by in situ spectroscopic ellipsometry (SE) combined with electrochemical measurements. A sharp drop of the open current potential is observed due to film removal. The dissolution time depends on total barrier layer thickness. Those results are confirmed by SE measurements. A three layer optical model has been used to interpret SE spectra. During the dissolution process, the porous top layer has a quasi-constant thickness, whereas porosity increases significantly. The dissolution proceeds within the pores. Only the thickness of pure alumina barrier layer (upper part) decreases during the dissolution process whereas the interface barrier layer (lower part) does not change.     

Embedded space charge in porous alumina films formed in phosphoric acid

The embedded charge in the barrier layers of porous alumina, formed potentiostatically in phosphoric acid was studied as a function of anodizing voltage (30-57 V) and bath temperature (18 and 21 °C). For that, the polarization measurements of as-grown and annealed alumina/Al samples were conducted in the same anodizing bath by anodic potential sweep at a scan rate of 2.6 V/min. The plane capacitor model was used for the assessment of the charge density in the barrier layers of as-grown porous alumina. For the barrier layers of films formed at 18 °C this value equals to 0.747 μC cm⁻² and does not depend on the anodizing voltage. Increase in electrolyte temperature rises the embedded charge density. Polarization measurements carried out in this paper clearly present that the barriers of phosphoric acid films grown at the anodizing voltages lower than 39 V contain a layer of virtual cathode while at higher voltages this layer disappers. The obtained results allow speaking about promising opportunities of potentiodynamic polarization measurements of alumina films in the same anodizing solution before and after annealing for the studies of charges embedded within the alumina barriers and for the regularities of ion transport.     

A modified Damascene electrodeposition process for bottom-up filling of recessed surface features

A modification of the conventional Damascene metallization process is described whereby selective removal of the thin wetting/seed layer from the sidewalls and free surfaces enables selective nucleation and bottom-up electrodeposition of metals and alloys in recessed surface features. The process is demonstrated by filling sub-micrometer trenches with electrodeposited Ni. A conventional PVD Cu seed layer is etched to remove Cu from the sidewalls and free surface while leaving a continuous Cu wetting layer intact on the trench bottom. The underlying non-wetting barrier layer provides a conductive path for electrodeposition from contacts on the perimeter of the work piece to the trench bottom. The robustness of the bottom-up Ni electrodeposition process is greatly increased by the addition of 2-mercaptobenzimidazole (MBI) to the plating bath. The additive hinders spurious nucleation of Ni on residual Cu patches that may remain on the free surface.     

磷酸浓度对铝阳极氧化多孔膜阻挡层形成过程的影响

引言 作者对磷酸溶液中高压直流电解条件下铝的阳极氧化地程进行了研究[1,2].     

Fabrication and characterization of alumina fiber by anodic oxidation and chemical dissolution processes

Alumina fiber was fabricated by an anodic oxidation process from pure aluminum or a chemical dissolution process from porous alumina. In the experiments, porous alumina layer was firstly formed on the surface of pure aluminum by anodic oxidation process in phosphoric acid electrolyte. The alumina fiber was obtained by either further anodic oxidation process or a chemical dissolution process from the porous alumina layer. The thickness of the porous alumina layer, the diameter and wall thickness of the pores in the porous alumina layer, and the length and diameter of the obtained alumina fiber were examined. The formation mechanism of the alumina fiber was discussed.     

Effect of postreatment on the corrosion behaviour of tartaric-sulphuric anodic films

Unclad and clad AA2024 T3 specimens were anodised in a chromium-free tartaric-sulphuric acid bath (TSA) and subsequently postreated by different processes including impregnation in a cold, concentrated chromate solution, Cr-free hot-water sealing, and dichromate hot-water sealing. The purpose of this work is to evaluate the effectiveness of the classical postreatments used in the aircraft industry on the TSA-anodic films and their corrosion resistance behaviour. TSA-anodic films were characterised by scanning electron microscopy (SEM) and their thicknesses were measured by SEM and the eddy current method. Electrochemical impedance spectroscopy (EIS) was used to characterise the barrier and porous layers, and jointly with potentiodynamic polarisation allowed the evaluation of corrosion resistance parameters with immersion time in NaCl solution for anodised and postreated specimens. In all cases the postreatments increased the resistance of the barrier layer against degradation. However, the NaCl electrolyte easily penetrated TSA-anodised porous layers when they were not postreated, while penetration was slightly more difficult in cold-postreated specimens. The effective pore plugging was observed in the sealed TSA specimens resulting in an improved corrosion resistance. On the other hand, unsealed clad AA2024 specimens showed a self-sealing process of the TSA-anodic layer, which was slower for the cold chromate solution-postreated specimens.     

柠檬酸钠体系中Ni・Fe合金的电沉积行为

采用循环伏安曲线、电化学阻抗谱、计时电流曲线等方法对柠檬酸钠体系中Ni-Fe合金的电沉积行为进行了研究。结果表明:柠檬酸钠体系中Ni-Fe合金电沉积是一个受扩散控制的不可逆过程。随着电位的增大,电沉积依次经历了电化学活化阶段、电结晶成核阶段、动力学-扩散混合控制阶段和扩散控制阶段。阴极附近未被及时消耗的FeOH+会覆盖在电极表面,阻碍金属离子扩散到电极表面放电,使电化学阻抗谱低频端存在阻挡层扩散阻抗特征。随着电位的增大,Ni-Fe合金的成核速率逐渐加快。Ni-Fe合金的成核机制在低电位下表现为连续成核,在高电位下表现为瞬时成核。     

Effect of concentration of Cu(II) on throwing power in electrodeposition on porous reticular cathode

The effect of concentration of Cu(II) on the throwing power has been studied in the electrodeposition of Cu on the porous reticular cathode with electrolytes of CuSO₄ and H₂SO₄. Hull cell tests as well as the electrodeposition on the porous reticular cathode have been carried out to illustrate the variation of throwing power with concentration of Cu(II). It was observed that the cathodic polarizability was increased with decrease in concentration of Cu(II). In the Hull cell tests, the morphology and the thickness of Cu layer were influenced remarkably by concentration of Cu(II). It was also found that both the throwing power and the limiting current density should be taken into account so as to obtain the uniform and regular deposits of Cu in the electrodeposition on the porous reticular cathode.     

Porous Alumina Films with Width-Controllable Alumina Stripes

Porous alumina films had been fabricated by anodizing from aluminum films after an electropolishing procedure. Alumina stripes without pores can be distinguished on the surface of the porous alumina films. The width of the alumina stripes increases proportionally with the anodizing voltage. And the pores tend to be initiated close to the alumina stripes. These phenomena can be ascribed to the electric field distribution in the alumina barrier layer caused by the geometric structure of the aluminum surface.     

Cobalt and Nickel Nanopillars on Aluminium Substrates by Direct Current Electrodeposition Process

A fast and cost-effective technique is applied for fabricating cobalt and nickel nanopillars on aluminium substrates. By applying an electrochemical process, the aluminium oxide barrier layer is removed from the pore bottom tips of nanoporous anodic alumina templates. So, cobalt and nickel nanopillars are fabricated into these templates by DC electrodeposition. The resulting nanostructure remains on the aluminium substrate. In this way, this method could be used to fabricate a wide range of nanostructures which could be integrated in new nanodevices.     

Electrochemical impedance spectroscopic study of barrier layer thinning in nanostructured aluminium

The electrochemical behaviour of electropolished and anodised aluminium was studied by electrochemical impedance spectroscopy (EIS). Freshly electropolished aluminium behaves as a pure capacitor exhibiting Warburg impedance at low frequencies. Storage of the electropolished aluminium, even in an air-tight bottle, results in the reconstruction of a uniform compact barrier layer. The impedance response of a stored electropolished aluminium as well as anodised aluminium after oxide removal, done by chemical etching, exhibits only a capacitive loop in the complex plane. The effect of the oxide layer thickness on the impedance data was investigated for layers formed during anodising at a cell potential of 15 or 23 V. Impedance measurements carried out over a wide range of frequencies gave useful information on the efficiency of the thinning of the barrier layer at the bottom of porous aluminium oxide layers. The rate of thinning of the barrier layer was estimated for samples anodised at different voltage.     

Template electrosynthesis of aligned Cu2O nanowires: Part I. Fabrication and characterization

Large arrays of aligned copper oxide nanowires were produced by electrodeposition, using anodic alumina membranes as template. We have studied the effect of two fundamental parameters involved in fabrication process: potential perturbation and bath composition. Performing electrodeposition from a copper acetate/sodium acetate bath (pH 6.5), we found that chemical composition of nanowires varied in dependence on the shape of the applied potential perturbation: pure copper oxide nanowires were produced by pulsed potential, whilst continuous electrodeposition resulted in a co-deposition of Cu and Cu₂O. In a copper lactate bath, buffered at pH 10, the shape of perturbation did not influence the chemical composition of nanowires, consisting of pure copper oxide. Besides, bath composition influenced the crystallographic structure of nanowires: in the acetate bath polycrystalline nanowires, having a maximum length of about 2.5 μm, were obtained whilst in the lactate electrolyte Cu₂O nanowires with a preferential orientation along the (2 0 0) plane were deposited. In every case, nanowire diameters were uniform with an average value of about 200 nm. Growth rate of nanowires was influenced by the shape of potential pulse.     

Highly porous α-Al2O3 ceramics obtained by sintering atomic layer deposited inverse opals

A process for generating highly porous α-Al₂O₃ ceramics has been developed. In this paper, a combination of self-assembly and atomic layer deposition is demonstrated as a means to fabricate inverse alumina opals, which have their structures transformed via sintering. The resulting highly porous structure is stable even after a 4 h dwell time at 1400 °C, in contrast to structures generated by conventional powder metallurgy, sol-gel or colloidal powder suspension infiltration methods. TEM analysis reveals that the structure consists of single grain domains of up to 3 µm, each containing a randomly interconnected network of alumina ligaments that share a common crystalline orientation, suggesting a different mechanism of grain boundary migration during sintering. These highly porous α-alumina ceramics are considered to be ideal for filtration or catalysis applications.     

Initial Growth of Single-Crystalline Nanowires: From 3D Nucleation to 2D Growth

The initial growth stage of the single-crystalline Sb and Co nanowires with preferential orientation was studied, which were synthesized in porous anodic alumina membranes by the pulsed electrodeposition technique. It was revealed that the initial growth of the nanowires is a three-dimensional nucleation process, and then gradually transforms to two-dimensional growth via progressive nucleation mechanism, which resulting in a structure transition from polycrystalline to single crystalline. The competition among the nuclei inside the nanoscaled-confined channel and the growth kinetics is responsible for the structure transition of the initial grown nanowires.     

Seedless copper electroplating on Ta from a “single” electrolytic bath

An alternative approach for copper electroplating on Ta surface from a “single” injected bath is being described in this work. Copper electrodeposition over a thin TaN/Ta barrier was performed in a two-step process: (1) activation conducted by electrochemically reduction of Ta oxide from the TaN/Ta barrier at a negative potential of −2 V for a short period (“removal” step) and (2) copper electroplating performed in the invariable electrochemical bath by injecting a solution containing Cu-ions. Supplementary Cu plating is continued by shifting the applied potential to −1.2 V in the same electrolytic bath. It was also established that addition of low content (up to 10 ppm) dimercaptothiadiazole (DMcT) improves Cu nucleation and growth on Ta surface and allows a conformal features fillings. Copper layer deposited is characterized with an excellent adhesion to the Ta surface.     

一步电沉积制备高活性高稳定镍铁合金析氧电催化剂

以镍网为基底,通过一步电沉积方法成功制备出用于碱性水电解的多孔镍铁合金析氧反应(Oxygen Evolution Reaction,OER)电极.镍铁的沉积伴随强烈的析氢,此条件下构筑出的多级孔结构成为电极用于OER反应时液相中传质与气泡释放的适宜传递通道.在析氧反应中,电流密度为10 mA·cm-2时的过电位仅为21...     

动态水热法制备Silicalite-1分子筛膜包覆多孔缺陷Al2O3微球

采用晶种涂覆-预晶化-晶化成膜的动态水热法成功在具有多孔缺陷的氧化铝微球上合成Silicalite-1分子筛膜。以乙醇作为润湿试剂在氧化铝表面涂覆一层晶种,将涂覆过晶种的载体加入到分子筛合成液中预晶化,一层分子筛完全覆盖载体并与载体结合牢固。预晶化后的载体在动态水热条件下处理3天,得到致密分子筛膜包覆的Al₂O₃微球。运用X射线衍射（XRD）和扫描电镜（SEM）对所得材料进行表征。结果表明,包覆的分子筛膜具有典型的MFI结构,晶粒交互生长,厚度约为3μm。考察了TPAOH用量和水量对分子筛膜微观结构的影响,结果发现TPAOH用量主要影响Silicalite-1分子筛膜的形貌,当TPAOH用量为0.17时,合成的Silicalite-1分子筛膜连续致密,而水量对分子筛膜微观结构的影响较小。这种晶种涂覆-预晶化-晶化成膜的方法有助于在多孔缺陷的Al₂O₃微球上制备高质量的分子筛膜。