Formation Of Anodic Oxide Films Research Articles

Electrokinetics-Driven Anodic Oxide Pore Formation: Linear and Weakly Nonlinear Analysis

Abstract Anodization of aluminium in an acidic medium facilitates the formation of well-ordered nanoporous anodic oxide films. The mechanism of pore formation is investigated as a morphological instability using a simplified model. The model accounts for the high field conduction law and field-assisted reactions (oxide formation/dissolution) only at the oxide-solution interface. The role of Butler–Volmer electrokinetics, electrolyte pH, anodic efficiency, and interface curvature on reaction kinetics are taken into account. Linear stability analysis suggests that the oxide film is unstable to well-defined wavelengths in specific ranges of parameters such as anodizing efficiency, applied voltage and electrolyte pH. Subsequently, a weakly nonlinear analysis is carried out to determine the nature of bifurcation beyond the stability threshold. Our findings indicate that the instability exhibits a subcritical nature, well in agreement with experimental observations.

Preparation of Ordered Nanohole Arrays by Two-Step Anodization of Austenitic Stainless Steel Substrates.

An anodic oxide film with a regular pore arrangement was formed by the two-step anodization of an austenitic stainless steel (JIS SUS304) substrate. In this study, we determined the anodization conditions under which the pore arrangement in the anodic oxide film became self-organized. After removing the anodic oxide film formed by the first anodization with a mixture containing CrO3 and HF, the residual substrate was anodized under the same conditions as those in the first anodization. As a result, we found that it was possible to form an anodic oxide film with pores arranged in a regular pattern from the surface to the bottom. This is the first report on the formation of anodic oxide films with ordered nanohole array structures by the two-step anodization of austenitic stainless steel. The interpore distance of the resulting nanohole array structures can be controlled by changing the anodization conditions. By measuring the capacitance of the anodic oxide film, we confirmed that its properties depended on the heat-treatment temperature and pore depth. In addition, no significant decrease in the capacity of anodic oxide films with ordered nanohole array structures was observed, even when the scan rate of the cyclic voltammogram measurement was increased. This is considered to be because the cylindrical pores facilitate ion diffusion to the bottom of the holes. Anodic oxide films obtained by the anodization of austenitic stainless steel substrates can be applied as electrodes for capacitors.

Performance and Properties of a Ti-Al Composite Anodic Oxide Film on AC-Etched Al Foil

AC-etched aluminum foils for an Al electrolytic capacitor were covered with a TiO2 film by a sol–gel coating and then anodized to 25 V in an ammonium adipate solution. The structure, properties, and performance of the anodic oxide films were examined by transmission electron microscopy (TEM), scanning electron microscopy (SEM), electrochemical impedance measurements (EIS), a general digital LCR meter, a TV characteristic tester, and multicycle pulse charging–discharging. It was found that the anodizing of aluminum coated with TiO2 films led to the formation of Al-Ti composite anodic oxide films, which consist of an outer Al-Ti composite oxide layer and an inner Al2O3 layer on the metal substrate. The capacitance (C25V) of the anodic oxide films formed on specimens with a TiO2 coating was about 10% larger than without a TiO2 coating. The specific resistance (Rox) of the Al-Ti composite film measured by EIS was lower than the blank one, accounting for a greater increase in the rise time (Tr) and a slight reduction in the withstand voltage (Vt). After hydration and a multicycle pulse charging–discharging destructive test, the Al-Ti composite anodic oxide film maintained the same good, comprehensive dielectric properties and performance as the blank one, thereby proving to be promising for acting as dielectric layers.

Electrochemical and surface characterization of anodized and fs-laser treated Ti6Al4V for osseo-repellent bone screws and dental implants

The surfaces of titanium grade 5 (Ti6Al4V) samples were altered on a micro and nano scale by femtosecond laser irradiation and subsequent electrochemical anodization. The produced micro-cones and nano-ripples covered by the additional oxide layer were characterised and their influence on osteoblast-like Saos-2 cell growth was studied. Surface topography and morphology were studied by Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM). From the wettability experiments, it was found that the contact angle vs. roughness follows the Wenzel equation and that the wettability increases after the anodization. The composition of the formed oxide layer was determined by X-ray photoelectron spectroscopy (XPS) and oxide incorporation of phosphate ions could be confirmed. Moreover, estimated electrochemical surface area (ECSA) of the femtosecond laser treated sample was 14 times larger compared to a polished sample. The anodic oxide film formation factors for different electrolytes were determined and were in the range of 1.3 nm V−1–2.0 nm V−1. Finally, the samples anodized with 0.1 M H2SO4 and 3 M H3PO4 showed decreased Saos-2 cell growth.

Changes in the Structure and Corrosion Protection Ability of Porous Anodic Oxide Films on Pure Al and Al Alloys by Pore Sealing Treatment

It is well known that corrosion protection of pure Al is enormously improved by the formation of porous anodic oxide films and by pore sealing treatment. However, the effects of anodizing and pore sealing on corrosion protection for Al alloys are unclear, because the alloying elements included in Al alloys affect the structure of anodic oxide films. In the present study, porous anodic oxide films are formed on pure Al, 1050-, 3003- and 5052-Al alloys, and pore sealing was carried out in boiling water. Changes in the structure and corrosion protection ability of porous anodic oxide films on pure Al and the Al alloys by pore sealing, were examined by scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). SEM observation showed that anodic oxide films formed on pure Al have a smooth surface after pore sealing, and that cracks are formed in anodic oxide films on 1050-, 3003- and 5052-aluminum alloys, after pore sealing. Corrosion protection after pore sealing increased with anodizing time on pure Al, but only slightly increased with anodizing time on the Al alloys.

Effect of the Passive Oxide Films Structure and Surface Temperature on the Rate of Anodic Dissolution of Chromium-Nickel and Titanium Alloys in Electrolytes for Their Electrochemical Machining. Part 2. Anodic Dissolution of Titanium Alloys in Nitrate and Chloride Solutions

An experimental study of the anodic dissolution of titanium and its alloys, including pulsed dissolution (up to 100 A/cm2) under control of hydrodynamic conditions and surface temperature in nitrate and chloride solutions, showed that the process is carried out through the electrochemical formation of anodic oxide films (AOF) which can be chemically dissolved. An AOF has a bilayered structure, i.e. two barrier films on the interface with a metal and a solution. Its model is PDM-III (Point Defect Model). At certain conditions, it is possible to achieve a steady state in which the film growth rate is compensated by the rate of its chemical dissolution (observed at pulsed conditions). In this case, over 100% current efficiency based on the ionization of titanium in the oxidation state is achieved. During the conducted experiments, when treated with the direct current, the rate of the electrochemical formation of an AOF exceeded the rate of its chemical dissolution, which led to a decrease in to current efficiency which did not exceed 75%. An increase of the dissolution rate takes place with an increase in the electrolyte flow rate. Upon reaching the thermokinetic instability (TKI) of the AOF (thermal explosion due to a feedback rate of the electrochemical reaction-surface tem-perature-rate of an electrochemical reaction), the interaction of electrolyte components with the surface free of the film takes place, and, as a result, an “anomalous” anodic dissolution is observed with the current efficiency greater than 100%. Regardless the nature of the electrolyte, TKI is achieved at a current density of 1 A/cm2. It is shown that in nitrate solutions with certain parameters of pulsed processing (duty factor 2, dc 50%), the dissolution rate, and, in the case of electrochemical machining, the feed rate of a cathode-tool, can be more than twice higher than the rate of machining with the direct current of the same density.

Formation of smooth anodic nanoporous iron oxide film for enhancing photocathodic protection on plain carbon steel

It is essential to fabricate smooth nanoporous iron oxide film with fewer defects on plain carbon steel (CS) to improve photocathodic protection of the film in corrosive media. For that, high temperature annealing heat treatment was chosen to manipulate the metallographic structure of CS in the muffle furnace at 900 °C with the duration of 30 min. Following that, the annealed CS was anodized in a mixture of aqueous ammonium fluoride solution and ethylene glycol to fabricate smooth nanoporous oxide film on CS. Finally, as-anodized oxide film was calcinated at 450 °C for 4 h in nitrogen atmosphere to form crystalline iron oxide film. Several electrochemical techniques were applied to analyze the photoelectron property and photocathodic protection performance of nanoporous iron oxide films. On the contrary, rough nanoporous iron oxide film with more striking defects was fabricated on untreated (no annealed) CS by using the same anodization and calcination processes. The results show that the metallographic structure of annealed CS behaved more uniform ferrite grains and fewer pearlite precipitate than untreated CS. Thereby, a smooth nanoporous iron oxide film with fewer defects formed on annealed CS. On the contrary, a rough nanoporous iron oxide film with more defects, such as dimples and cracks were fabricated on untreated CS. Both of iron oxide films were composed of hematite as the main phase and magnetite as the secondary phase. Therefore, the smooth iron oxide film displayed comparatively better conductivity and higher donor density under the condition of illumination than the rough film. On account of those, smooth film exhibits comparatively higher anodic and cathodic reaction activities and more excellent and stable photocathodic protection to the counter.

Anodizing—The pore makes the difference

AbstractThe presentation gives an insight into the fascinating world of anodizing as corrosion protection but also goes far beyond. Starting with an introduction to the formation of anodic oxide films and their characteristic features, the authors briefly outline the subject of pore nucleation and growth. The number, size, and shape of the pores essentially determine the properties and play a crucial role in the final application of the anodizing layers. The tailoring of pore design, considering the final application as well as the use of the porous oxide layers for subsequent functional modifications, is demonstrated by examples, exclusively developed in the working groups of the respective authors or in joint research projects, which were in part professionally accompanied and supported by the German Corrosion Society GfKORR e.V.

Corrosion behavior of copper, tin, and bronze CuSn14 in acid rain solution

AbstractThe corrosion behavior of copper, tin, and bronze CuSn14 is studied in simulated acid rain (pH 4.5) by electrochemical techniques, cyclic voltammetry and electrochemical impedance spectroscopy. The potentiodynamic formation of anodic oxide film on copper and tin is described in terms of high‐field model. Cyclic voltammetry shows that dissolution of bronze is higher than of pure copper metal in acid rain. Electrochemical impedance spectroscopy data reveal that oxide films formed on copper and tin have a higher resistance and suppressed diffusion process through the surface layer than the oxide film formed on bronze CuSn14 at the same conditions.

Influences of pulse frequency on formation and properties of composite anodic oxide films on Ti-10V-2Fe-3Al alloy

A thick composite anodic oxide film was fabricated in an environmentally friendly malic acid electrolyte containing PolyTetraFluoroEthylene (PTFE) nanoparticles on Ti-10V-2Fe-3Al alloys. The influence of pulse frequency on the morphology, microstructure and composition of composite anodic oxide films containing PTFE nanoparticles was investigated using Field Emission Scanning Electron Microscopy (FE-SEM) equipped with Energy Dispersive Spectroscopy (EDS), Atomic Force Microscopy (AFM) and Raman spectroscopy. The tribological properties in terms of the friction coefficient, wear loss and morphology of worn surfaces were measured by ball-on-disc tests. The electrochemical property was evaluated by potentiodynamic polarization. The results indicated that the titanium dioxide of composite anodic oxide films transformed from anatase to rutile with the change of pulse frequency, which could result from the electrochemical dynamic equilibrium. The combination of PTFE nanoparticles and malic acid electrolyte molecules can influence the energy fluctuation of electrochemical equilibrium and formation of composite anodic oxide films. Moreover, composite anodic oxide films fabricated under the condition of 1.0–2.0 Hz exhibited the best wear resistance and corrosion property. The schematic diagram of the film formation and PTFE nanoparticles spreading process under different frequencies was elucidated.

The Formation of Anodic Oxide Film by Anodizing Voltage and Time of 6061 Aluminum Alloy

The Formation of Anodic Oxide Film by Anodizing Voltage and Time of 6061 Aluminum Alloy

Improvement of corrosion properties of plasma in an aluminum alloy 6061-T6 by phytic acid anodization temperature

We report on the formation of anodic aluminum oxide (AAO) film using phytic acid (C6H18O24P6), a naturally obtainable and non-toxic organic acid electrolyte. When the temperature of the phytic acid electrolytes changes from 0 °C to 20 °C, the pore size increases, and the AAO film becomes less dense because the growth rate of the AAO film increases. In particular, when the temperature of the phytic acid electrolyte is above 15 °C, the AAO film changes dramatically. According to XRD analysis, the alpha-alumina intensity was relatively higher in the AAO film grown at low-temperatures (0, 5, 10 °C) than high-temperatures (15, 20 °C). It was possible to obtain a result that the properties were better. The microstructural change of the AAO film according to the temperature of the phytic acid electrolytes affected the breakdown voltage and the number of contamination particles that are generated, which are important properties for plasma corrosion protection coating materials. The AAO film grown in the low-temperature has the most suitable properties for use as a plasma corrosion protection coating material. Notably, the breakdown voltage of the AAO film is 0.45 kV at 14.9 μm thickness, with no observable crack on its surface after the plasma corrosion test. These findings provide significant evidence to support the application of phytic acid as an electrolyte to grow AAOfilms, and the AAOfilm grown in a phytic acid bath can be applied as a plasma corrosion protection coating material.

Electric Resistance Measurements of Anodic Oxide Films on Titanium and Zirconium

Valve metals such as titanium and zirconium can be subjected to anodization to form a thick compact oxide film in fluoride-free electrolytes at room temperature, and the thickness and structure of the film can be controlled by anodization conditions. Although various studies on the formation, characterization and application of anodic titanium oxide film as well as zirconium oxide film have been carried out so far, the electrical resistivity of the anodic oxide films is quite limited. In the present work, we measured electric resistance of the anodic oxide films formed on titanium and zirconium under various anodization conditions, aiming at investigating effects of anodization on electrical resistivity of anodic oxide films.

ELECTROCHEMICAL SYNTHESIS OF POROUS CRYSTALLINE TANTAL OXIDE

Self-organization of nanoscale structures during electrochemical processing is most pronounced during the formation of porous anodic metal oxides (aluminum, titanium, tungsten, niobium, tantalum). These oxides contain arrays oriented perpendicular to the pore substrate. A distinctive feature of these films is a high degree of orderliness in the arrangement of pores and the possibility of controlled variation of the pore diameter in a wide range (from 10 to 150 nm). In this work, the features of the electrochemical formation of nanoporous oxide coatings on tantalum in acid-fluoride and organic electrolytes are investigated. Tantalum foil with a thickness of 0.1 mm and a purity of 99.99 % was used as a working electrode. For the formation of tantalum oxides, 1 M H2SO4 solutions with the addition of HF (0.1 M; 0.25 M; 0.5 M; 1 M) and an organic electrolyte were used: EG + 5.5 М H2O + 0.05 М H3PO4 + 0.8 М NH4F, EG + 5.5 М H2O + 0.05 М H3PO4 + 0.8 М NaF. Polarization studies were carried out on a P-45X potentiostat. in potentiodynamic mode. The reference electrode is saturated silver chloride. The magnitudes of the potentials are given relative to the normal hydrogen electrode. The morphology of the obtained coatings was studied using scanning electron microscopy using a JSM-7001F microscope. It is shown that the use of fluoride ion activator and electrolytes of different nature allows at the initial stage of anodizing to provide conditions for the formation of a crystalline anodic oxide film with different surface morphology. By varying the anodizing regime on tantalum, it is possible to synthesize porous films of amorphous or crystalline types. To obtain a crystalline porous oxide of tantalum with a developed surface, it is advisable to use an organic aprotic electrolyte composition: EG + 5.5 М H2O + 0.05 М H3PO4 + 0.8 М NH4F.

Effects of anodization parameters on the corrosion resistance of 6061 Al alloy using the Taguchi method

Anodizing 6061 aluminum alloy (AA6061) in a H2SO4 electrolyte solution is a crucial process in the formation of anodic aluminum oxide (AAO) film for enhancing the material’s corrosion resistance. In this work, the effects of electrolyte concentration, current density, and anodization time parameters on the evolution of corrosion resistance in AA6061 alloy were investigated using the Taguchi method. Each anodization parameter had three levels using an experimental set of L9 orthogonal arrays. Variation in the bias voltage was recorded during the AAO process, and an energy-dispersive spectrometer was used to analyze the variations in the composition of the oxidized films. Variations in surface morphology and cross-sections of the AAO were examined using a scanning electron microscope. Finally, the potentiostatic polarization method was used to judge the relative corrosion resistance of the oxidized films. The oxidized film with the best corrosion resistance (Icorr = 8.516 × 10−11 A/cm2) was obtained by anodizing at a current density of 1 A/dm2 in 1 M sulfuric acid for 20 min.

Flow Instability Mechanism for Formation of Self-Ordered Porous Anodic Oxide Films

Experimental studies have suggested that oxide flow plays an important role in the growth of porous anodic oxide films on reactive metals. Here a mathematical model for anodic oxide formation is presented that includes viscous flow of oxide, along with high-field ionic conduction and interfacial oxygen transfer and metal dissolution reactions. Flow is driven by near-surface compressive stress, as has been detected by measurements of residual stress distributions in anodic alumina. Linear stability analysis of the model shows that pattern formation at the solution interface is possible near the critical value of a parameter expressing competition between stabilizing electrochemical oxide formation and destabilizing flow. According to the critical parameter value, pattern formation requires that the Faradaic efficiency for oxygen transfer at the solution interface must be close to the transport number for electrical migration of oxygen ions across the film. This relationship between efficiency and transport number is indeed suggested by experimental data. A scaling ratio of pore separation to voltage, as characteristically found in anodic films, is predicted by the wavelength at the critical point.

Influence of adipic acid on anodic film formation and corrosion resistance of 2024 aluminum alloy

The influence of adipic acid on the formation and corrosion resistance of anodic oxide film fabricated on 2024 aluminum alloy was investigated. The morphology was investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), respectively. The corrosion resistance was evaluated by electrochemical impedance spectroscopy (EIS). The results showed that the adipic acid was absorbed at the electrolyte/anodic layer interface during anodizing. The corrosion rate of anodic film decreased and the film thickness increased. The film was uniform and compact especially at the film/substrate interface. After sealing procedure, anodic film formed with the addition of adipic acid exhibited improved dielectric property and corrosion resistance in aggressive environment.

Characterization of anodic oxide film growth on Ti6Al4V in NaTESi electrolyte with associated adhesive bonding behaviour

The formation of anodic oxide films on the Ti6Al4V alloy in the NaTESi electrolyte has been studied in the present paper. An anodic film with a shallow pore-like texture was formed after anodizing to 10V. Porous anodic films with increased porosity were generated after anodizing from 20 to 40V, and the pores were developed mainly within the α phase. Significant amounts of sodium species were incorporated in the films, and the amount increased with increasing anodizing voltage. The current efficiency for the anodic film growth increased from 10 to 30V, but decreased from 30 to 40V due to the occurrence of more oxygen evolution. The film thicknesses determined by RBS were 15nm, 65nm, 115nm and 250nm at 10, 20, 30 and 40V respectively. The film thickness generated at 10V showed good agreement with the thickness of 11nm revealed by transmission electron microscopy. The Raman spectra indicated that the degree of crystallinity of the anodic film increased at higher voltages. The dielectric permittivity of the film was estimated as ∼118 according to the results from transmission electron microscopy and electrochemical impedance spectroscopy. Single-lap shear bonding tests were employed to compare the strength of adhesively joined titanium alloy anodized to different voltages. The results revealed appreciable increase in bond strength with increasing anodic film thickness.

(Invited) Inhomogeneity of Barrier Layer Inducing Irregularity of Porous Anodic Oxide Film on Aluminum

Porous anodic oxide films formed on various metals, especially anodic alumina, have attracted huge attention as a starting material in the fabrication of nano-devices because of the high controllability of porous structures in nanometer scale such as pore size, pore interval, as well as pore depth by changing electrolysis condition in addition to their high regularity of pore arrangement. In recent years, mechanism of self-ordering of anodic alumina films has been intensely studied. We proposed anodizing under high electric field strength as a key factor for self-ordering of pore arrangement (1). However, only a few reports are found on the mechanism of irregularity or defects formation of porous anodic oxide films. For example, an regular deposition of metals into all anodic pores are often difficult because of irregularity of the barrier layer. In the case of anodic films formed on aluminum in chromic acid solution, for example, sever pore blanching appears especially at the higher voltage. Anodic alumina films formed in phosphoric acid and Ematal bath also indicates numerous pore branching and caved pores in the cell wall (2, 3) where anodizing conditions such as high formation voltage and relatively low dissolution ability of electrolytes to anodic oxides are used. These irregularities were caused by defects/holes induced by electric breakdown between pore bottom and protrusion at triple points of cell boundary. Impurity elements in metals and alloys also bring defects and irregularity into porous structures. Furthermore, anodic films formed at some specific condition, especially on titanium, yielded tubular structure having interspaces at cell boundaries. All of these irregularities should be created only at the barrier layer grown under the anodic field by specific reactions other than stable anodic oxide growth. This inhomogeneity of barrier layer such as unevenness of the thickness and voids that induce irregularity in porous oxide seems to be playing an important role at an application for industry both in a positive and negative way. In this paper, we report the specific futures of irregularity appeared in porous anodic oxides films formed on aluminum and evaluated to get unified formation mechanism of such imperfections to be induced in the oxides grown on various substrates. [1] S. Ono, M. Saito, M. Ishiguro and H. Asoh, J.Electrochem. Soc., 151, B473 (2004). [2] S. Ono, H.Ichinose and N. Masuko, J.Electrochem.Soc., 138, 3705 (1991) [3] S. Ono and N. Masuko, J. Jpn Inst. Light Metal, 43, 453 (1993).

Growth of anodic oxide films on iron-triad metal monosilicides in sulfuric acid electrolyte

The mechanism and kinetics of electrochemical formation of anodic oxide films on iron-triad metal monosilicides in the 0.5 M H2SO4 solution in the potential range of 0.5 to 1.5 V (NHE) were studied by the methods of polarization and impedance measurements. It was concluded that the oxide films on the surface of studied silicides consisted predominantly of SiO2 and exhibited high barrier properties. The oxide film thickness and specific resistance in relation to the electrode potential were calculated from the impedance data. The constants of oxide film growth were determined.