Corrosion resistance of plasma-anodized AZ91D magnesium alloy by electrochemical methods

Anodic coatings formed on magnesium alloys by plasma anodization process are mainly used as protective coatings against corrosion. The effects of KOH concentration, anodization time and current density on properties of anodic layers formed on AZ91D magnesium alloy were investigated to obtain coatings with improved corrosion behaviour. The coatings were characterized by scanning electron microscopy (SEM), electron dispersion X-ray spectroscopy (EDX), X-ray diffraction (XRD) and micro-Raman spectroscopy. The film is porous and cracked, mainly composed of magnesium oxide (MgO), but contains all the elements present in the electrolyte and alloy. The corrosion behaviour of anodized Mg alloy was examined by using stationary and dynamic electrochemical techniques in corrosive water. The best corrosion resistance measured by electrochemical methods is obtained in the more concentrated electrolyte 3 M KOH + 0.5 M KF + 0.25 M Na₃PO₄·12 H₂O, with a long anodization time and a low current density. A double electrochemical effects of the anodized layer on the magnesium corrosion is observed: a large inhibition of the cathodic process and a stabilization of a large passivation plateau.     

Modification of titanium oxide layer by calcium and phosphorus

The aim of the study was to investigate the possibility of calcium and phosphorus ion implantation into an oxide film applied onto titanium during anodic passivation. The corrosion resistance of modified titanium in Tyrode's physiological solution has been identified. Anodic oxidation was carried out in two solutions. The first contained 20 g dm⁻³ NaH₂PO₂ in 4.3 M H₃PO₄ (K1), whereas the other, 20 g dm⁻³ Ca(H₂PO₂)₂ in 4.3 M H₃PO₄ (K2). Voltage of 100 and 150 V was applied. It has been found out that it is possible to incorporate Ca and P into the emerging passive layer. The application of the voltage of 150 V makes it very porous. It has been also demonstrated that titanium so modified presents higher resistance to corrosion in the investigated environment than titanium not modified in Tyrode's solution.     

Hydrogen entry into iron after potential jumps from cathodic to anodic polarization in 0.1 M NaOH without and with EDTA or sodium molybdate

Hydrogen can enter into iron or steel during anodic polarization when bare metal is exposed, e.g. during stress corrosion cracking, erosion or friction. The hydrogen permeation rate (HPR) through a 35-μm thick iron membrane was studied with the electrochemical technique in 0.1 M NaOH without and with EDTA or Na₂MoO₄ during cathodic and anodic polarization at 25 °C. Anodic polarization of the bare metal was performed by applying fast jumps of anodic potentials to the cathodically treated surface. The jumps resulted in transients of enhanced HPR which continued to rise despite the starting decay of anodic current. The enhanced HPR can be ascribed to acidification associated with anodic oxidation of iron. It is proposed that the continued rise of HPR during anodic current decay can be explained by the formation of low-protective layers which hinder diffusion of hydrated protons out of the metal surface and thereby increase their concentration at the surface. The enhancement of HPR was strongly decreased by EDTA, but increased by Na₂MoO₄ at noble potentials. It is suggested that these effects can be explained in terms of the thickness and type of low-protective layers.     

Corrosion resistant low temperature carburized SS 316 as bipolar plate material for PEMFC application

One of the current challenges for application of PEM fuel cell is to find corrosion resistant, electrically conductive, light weight, cost competitive bipolar plate material. Low temperature carburization (LTC) of stainless steels is a novel, patented process by Swagelok Company. This paper addresses the corrosion resistance characteristics of LTC SS 316 for polymer electrolyte membrane fuel cell (PEMFC) bipolar plate applications. Corrosion properties of this material were studied using potentiodynamic and potentiostatic tests in simulated (1 M H₂SO₄ + 2 ppm HF, 0.5 M H₂SO₄, pH: 4.0, and 5% HCl + 5% Na₂SO₄) PEMFC conditions. LTC SS 316 showed excellent corrosion resistance in these conditions compared to SS 316. The mechanism of anodic dissolution and general corrosion of LTC SS 316 was observed to be similar to SS 316 however the extent of LTC SS 316 corrosion was less. LTC SS 316 showed corrosion currents well below 16 μA cm⁻² in anodic and cathodic atmospheres under potentiostatic conditions. The potentiostatic current rapidly falls to ∼4.0 and ∼1.5 μA cm⁻² under anodic and cathodic conditions, respectively. LTC SS 316 was observed to form a thinner oxide layer as compared to SS 316 after 24 h of potentiostatic testing. Moreover LTC SS 316 lowered the interfacial contact resistance by approximately 24% as compared to SS 316 after corrosion testing. Hence this study clearly states the performance advantage of using LTC SS 316 as bipolar plate material as compared to conventional materials.     

Growth of etch pits formed during sonoelectrochemical etching of aluminum

Anodes of aluminum electrolytic capacitor, which requires large surface area for a high capacitance, are prepared with electrochemical etching. Ultrasound contributes to the increase of etch pit density by prohibiting anodic oxide film formation and induces uniform tunnel length distribution by enhancing the transport of corrosion product, AlCl₃, present inside etch tunnels. Compared to low 28 kHz, smaller and higher density of cavitation bubbles at 68 kHz frequency induces higher pit and tunnel density and increases the survival rate of tunnels to 55.8% in the process of tunnel growth from 3 to 12 μm. It results in the increase of capacitance by 110% at anodization voltage of 100 V.     

Synthesis and electrochemical evaluation of polypyrrole coatings electrodeposited onto AA-2024 alloy

Polypyrrole coating was successfully deposited on anodized 2024 unclad aluminum alloy showing that the presence of the anodic film is the key factor to ensure better adhesion to the polymer coating. Corrosion resistance of the conductive polymer layers grown for three and five cycles were evaluated in a 3 wt.% NaCl solution using polarization curves and impedance spectroscopy. It was found that the thermally treated polymer coating with higher thickness (five cycles) exhibited the best corrosion performance. This best coating shifts the corrosion potential towards nobler values, about 650 mV, and the exchange current density decreases two orders of magnitude regarding the anodic layer. The partial reduction of the structure of the polymer promoted by the thermal treatment plays a key role in the corrosion resistance of the coating allowing to the thermally treated polymer layer to act as a physical barrier against corrosion.     

Fabrication of novel porous Pd particles and their electroactivity towards ethanol oxidation in alkaline media

Novel porous Pd particles (nanoPd-PEG, nanoPd-PEG-EDTA, nanoPd-HCHO-EDTA, nanoPd-EG, nanoPd-HCHO and nanoPd-EG-EDTA) were synthesized by a hydrothermal method using different reduction agents in the absence and presence of EDTA and investigated as electrocatalysts for ethanol oxidation in alkaline solutions. Results showed that PdCl₂ was hydrothermally reduced to nano-scale palladium particles and a three-dimensional texture was formed for Pd particles. Presence of EDTA was favorable for the formation of Pd nanoparticles with small sizes of ca. 70 nm. Ethanol oxidation on the present Pd catalysts took place at a more negative anodic potential in 1 M NaOH solution. Among the electrocatalysts investigated, the electrocatalytic activity of the nanoPd-HCHO-EDTA was the greatest, which was characterized by the largest anodic peak current density of 151 mA cm⁻² and lowest onset oxidation potential of −0.788 V (vs. SCE) for the positive scan. Very low charge transfer resistances on the nanoPd-HCHO-EDTA in 1 M NaOH containing various concentrations of ethanol were obtained according to the analysis for electrochemical impedance spectra (EIS). The prepared porous Pd catalysts were promising alternatives to Pt electrodes applied in alkaline direct alcohol fuel cells.     

Importance of water content in formation of porous anodic niobium oxide films in hot phosphate-glycerol electrolyte

Niobium has been anodized at a constant current density to 10 V with a current decay in 0.8 mol dm⁻³ K₂HPO₄-glycerol electrolyte containing 0.08-0.65 mass% water at 433 K to develop porous anodic oxide films. The film growth rate is markedly increased when the water content is reduced to 0.08 mass%; a 28 μm-thick porous film is developed in this electrolyte by anodizing for 3.6 ks, while the thickness is 4.6 and 2.6 μm in the electrolytes containing 0.16 and 0.65 mass% water respectively. For all the electrolytes, the film thickness changes approximately linearly with the charge passed during anodizing, indicating that chemical dissolution of the developing oxide is negligible. SIMS depth profiling analysis was carried for anodic films formed in electrolyte containing ∼0.4 mass% water with and without enrichment of H₂¹⁸O. Findings disclose that water in the electrolyte is a predominant source of oxygen in the anodic oxide films. The anodic films formed in the electrolyte containing 0.65 mass% water are practically free from phosphorus species. Reduction in water content increased the incorporation of phosphorus species.     

Corrosion properties of electrodeposited cobalt in sulfate solutions containing chloride ions

The corrosion properties of electrodeposited pure cobalt were investigated in deaerated 0.5 M Na₂SO₄ solutions at pH 5, 7, 10 and 13 by using polarization techniques. The effect of chloride concentration (0.01 and 0.1 M NaCl) was also studied. The results showed that increasing pH shifted the anodic polarization curves to more negative potentials. At pH 5 and 7, cobalt exhibited active dissolution without any distinctive transition to passivation. However, at pH 10, the metal surface was partially passivated and anodic current increased sharply at approximately −0.2 V_SCE and the corroded surface revealed several well-defined pits. On the other hand, at pH 13, a clear passivation region was observed within the potential range of −0.5 to 0.6 V_SCE. With increasing chloride concentrations of 0, 0.01, and 0.1 M at pH 10, both the anodic current and the number of pits on the cobalt surface were gradually increased. X-ray photoelectron spectroscopic investigations showed that the cobalt surface was covered mostly with cobalt hydroxide after anodic polarization at pH 10 in 0.1 M NaCl.     

Effect of ethylenediamine tetraacetic acid disodium on the corrosion of cold rolled steel in the presence of benzotriazole in hydrochloric acid

The inhibition behavior of cold rolled steel in 0.1 M hydrochloric acid (HCl) by ethylenediamine tetraacetic acid disodium (EDTA) in the absence and presence of benzotriazole (BTA) was investigated with Tafel polarization curve and electrochemical impedance spectroscopy (EIS). The polarization curve results show that the single EDTA acts as an anodic type inhibitor while the combination of EDTA and BTA acts as mixed type inhibitor and mainly inhibits anodic reaction. All impedance spectra in EIS tests exhibit one capacitive loop which indicates that the corrosion reaction is controlled by charge transfer process. Inhibition efficiencies obtained from Tafel polarization, charge transfer resistance (R_t) are consistent. The corrosion of cold rolled steel in 0.1 M HCl is obviously reduced by EDTA in combination with lower concentrations of BTA. Fourier transform infrared spectroscopy (FTIR) and atomic force microscopy (AFM) were used to characterize the corrosion surface of cold rolled steel. Probable mechanisms are present to explain the experimental results.     

Effects of 1,4-naphthoquinone on aluminum corrosion in 0.50 M sodium chloride solutions

Effects of 1,4-naphthoquinone (NQ) have been investigated as a corrosion inhibitor for aluminum in aerated and de-aerated solutions of 0.50 M NaCl using potentiodynamic polarization, chronoamperometry (CA), open-circuit potential (OCP), electrochemical impedance spectroscopic (EIS), scanning electron microscopic (SEM), cyclic voltammetric, and quartz crystal analyzer (QCA) techniques. These measurements revealed that the presence of NQ shifted the corrosion and pitting potentials to more noble values and decreased the anodic currents in the passive region in both aerated and de-aerated chloride solutions, and the surface and polarization resistances are increased as the concentration of NQ is increased. The most effective concentration of NQ for corrosion inhibition was found to be 1.0 × 10⁻³ M in both aerated and de-aerated chloride solutions. The QCA data indicate that adsorption of NQ molecules plays an important role in protecting the pits on the aluminum surface. The SEM images show that the presence of NQ decreased the severity of the pitting corrosion of aluminum to a great extent at −675 mV versus Ag/AgCl.     

Platinum-modified titanium anodes for the electrolytic destruction of nitric acid

Three sets of electrodes, namely Pt electroplated Ti (PET) and diffusion annealed PET (DAPET) of plating thickness 3, 5, 7 and 10 μm and thermochemically glazed mixed oxide coated titanium anode (MOCTA-G) were evaluated for their performance, with a view to optimizing the current density conditions for maximum efficiency during the electrolytic destruction of nitric acid. In the acid killing by electro-reduction process, concentration of nitric acid in the high level waste (HLW) from the spent nuclear fuel reprocessing plant was brought down from about 4 to 0.5 M in order to reduce the amount of HLW by subsequent evaporation and to minimise the corrosion in waste tanks during storage of the concentrated waste solution. The electrochemical reduction of 4 and 8 M nitric acid to near neutral conditions was carried out with the above-said anodes and Ti cathode at various cathodic current densities ranging from 10 to 80 mA cm⁻². At current densities below 15 mA cm⁻² MOCTA-G electrode worked satisfactorily, whereas PET and DAPET electrodes could withstand and function well at much higher cathodic current densities (up to 80 mA cm⁻²). The life assessment of a 3 μm thick PET electrode at a cathodic current density of 60 mA cm⁻² in 8 M HNO₃ for a period of 110 h showed no failure. Phase identification of the plated electrodes was done by XRD measurements and their surface morphology was investigated by SEM.     

Characterisation of titanium oxide film grown in 0.9% NaCl at different sweep rates

The nature of the anodic oxide film that forms on titanium on titanium in 0.9% NaCl has been investigated using a wide range of techniques. A linear relationship was found between the critical current density required for passivation of titanium in 0.9% NaCl and the sweep rate. Anodic oxide films formed on titanium in 0.9% NaCl appear to consist of two layers, an inner compact layer, the growth of which continues to follow a high field growth law, and a porous less protective outer porous layer. XPS and XRD indicated that passive films on titanium consist mainly of TiO₂. However, hydroxides and lower oxides are also present, especially in rapidly grown films. XRD data indicated that in 0.9% NaCl the anodic oxide film is formed through the preferential removal atoms in the plane of (0 0 2) in the course of electrochemical reaction. A model based analysis XPS spectra was proposed to explain the growth rate dependence of the degree of protection offered by anodic oxide films on titanium. XPS clearly demonstrated the present of Ti(III) and Ti(II) cations in the passive film. This is strong evidence that cation migration more likely dominates over anion migration in the growth mechanism of anodic oxide film. XPS data also revealed that the concentrations of Ti(III) and Ti(II) species within the oxide films increased as the oxide/metal interface was approached.     

Electrochemical behaviour of titanium in H2SO4-MnSO4 electrolytes

The corrosion of titanium in H₂SO₄ electrolytes (0.001-1.0 M) at temperatures from ambient to 98 °C has been investigated using steady-state polarization measurements. Four distinct regions of behaviour were identified, namely active corrosion, the active-passive transition, passive region and the dielectric breakdown region. The active corrosion and active-passive transition were characterized by anodic peak current (i_m) and voltage (E_m), which in turn were found to vary with the experimental conditions, i.e., d(log?(im))/dpH=−0.8±0.1 and dE_m/dpH which was −71 mV at 98 °C, −58 mV at 80 °C and −28 mV at 60 °C. The activation energy for titanium corrosion, determined from temperature studies, was found to be 67.7 kJ mol⁻¹ in 0.1 M H₂SO₄ and 56.7 kJ mol⁻¹ in 1.0 M H₂SO₄. The dielectric breakdown voltage (E_d) of the passive TiO₂ film was found to vary depending on how much TiO₂ was present. The inclusion of Mn²⁺ into the H₂SO₄ electrolyte, as is done during the commercial electrodeposition of manganese dioxide, resulted in a decrease in titanium corrosion current, possibly due to Mn²⁺ adsorption limiting electrolyte access to the substrate.     

Electrochemical properties of boron-carbon-nitride films formed by magnetron sputtering

The electrochemical behavior of B_1.0C_2.4N_1.0 thin film was investigated in acidic, neutral and alkaline solutions. The anodic polarization curve of the film in 1 M NaOH showed the anodic dissolution of the film. The curve of the film in 1 M HCl showed no anodic dissolution. The cathodic polarization curve in 1 M NaCl showed shift to a negative potential side, but the anodic polarization curve was the same as that of Pt. The anodic dissolution in 1 M NaOH depended on potentials, that is, no anodic dissolution was recognized in a potential range of −0.2 to 0.1 V but the dissolution rate increased with increasing potential in a range of 0.1-0.6 V. The anodic current density of the film is directly proportional to the dissolution rate at potentials higher than 0.1 V. The dissolution rate of the film was increased with increasing solution pH.     

Study on the corrosion behavior of reinforcing steel in simulated concrete pore solutions using in situ Raman spectroscopy assisted by electrochemical techniques

In situ Raman spectroscopy, electrochemical impedance spectroscopy (EIS) and polarization curves were used to study the corrosion behavior of reinforcing steel in simulated concrete pore (SCP) solutions (saturated Ca(OH)₂ solutions). Results indicated that the reinforcing steel remained passive in chloride-free SCP solutions. However, the anodic polarization curve of the steel did not exhibit a stable passive region in the SCP solution with 0.5 M NaCl, the corrosion current density exceeded 0.1 μA cm⁻², the steel surface was unstable with chloride attack and localized corrosion appeared on it with FeCO₃ and Fe₂O₃ as the main corrosion products.     

Synthesis of TiO2 scaffold by a 2 step bi-layer process using a molten salt synthesis technique

TiO₂ scaffolds of anisotropic rutile particles were grown from rutile seeds by using molten salt synthesis techniques. The rutile seeds were either in the form of a separate layer applied on a substrate or a sintered bulk pellet. Mixtures of amorphous titanium hydroxide and salt applied as coatings on the rutile seeds were heat treated. Depending on the morphology of the seed layer, heat treatment temperature, time and salt medium, rutile was grown with different morphologies and microstructures. For NaCl-KCl eutectic salt mixture and heat treatment at 700 °C for 5 h, nano-whiskers of 20-50 nm diameter and 0.5-1 μm length were obtained. For the NaCl salt sample treated at 850 ºC for 20 h, rutile platelets of 2-5 μm thick, 2-10 μm wide and 5-25 μm in length were produced. X-ray diffraction and Raman scattering were used to identify and characterize the rutile phase of the nanowhiskers.     

Structural features of self-organized nanopore arrays formed by anodization of aluminum in oxalic acid at relatively high temperatures

Anodic aluminum oxide (AAO) membranes with a highly ordered nanopore arrangement typically serve as ideal templates for the formation of various nanostructured materials. A typical procedure of the template preparation is based on a two-step self-organized anodization of aluminum carried out at the temperature of about 1-3 °C. In the current study, AAO templates were fabricated in 0.3 M oxalic acid under the anodizing potential range of 30-65 V at a relatively high electrolyte temperature ranging from 20 to 30 °C. Due to a high rate of porous oxide growth, about 5-10-fold higher than in low-temperature anodizing, the process of the template fabrication can be shorten significantly. Similarly to the low-temperature anodization, the best hexagonal pore arrangement is observed for samples anodized at 40 V. With a prolonged duration of the first anodizing step the order degree of triangular nanoporous lattice, observed after the second anodization, improves considerably. The effects of the anodizing potential and the process duration on the structural features of porous anodic alumina such as: pore diameter (D_p), interpore distance (D_c), porosity (P), pore density (n) and anodizing ratio (B_U) were investigated in details at various temperatures. The obtained results were compared with theoretical predictions and data reported in the literature.     

Influence of chloride ion concentration on the electrochemical corrosion behaviour of plasma electrolytic oxidation coated AM50 magnesium alloy

The electrochemical degradation of a silicate- and a phosphate-based plasma electrolytic oxidation (PEO) coated AM50 magnesium alloy obtained using a pulsed DC power supply was investigated using potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS) in NaCl solutions of different chloride ion concentrations viz., 0.01 M, 0.1 M, 0.5 M and 1 M. The surface of the PEO coated specimens after 50 h of immersion/EIS testing was examined by optical microscopy and scanning electron microscopy. The results showed that the corrosion deterioration of PEO coated magnesium alloy in NaCl solutions was significantly influenced by chloride ion concentration. The silicate-based coating was found to offer a superior corrosion resistance to the magnesium substrate than the phosphate-based coatings in lower chloride ion concentration NaCl solutions (0.01 M and 0.1 M NaCl). On the other hand both these PEO coatings were found to be highly susceptible to localized damage, and could not provide an effective corrosion protection to Mg alloy substrate in solutions containing higher chloride concentrations (0.5 M and 1 M). The extent of localized damage was observed to be more with increase in chloride concentration in both the cases.     

Mechanism of formation and growth of sunflower-shaped imperfections in anodic oxide films on niobium

Anodizing of niobium has been investigated to develop niobium solid electrolytic capacitors. Chemically polished niobium specimens were anodized in a diluted phosphoric acid solution, initially galvanostatically at i_a = 4 A m⁻² up to E_a = 100 V, and then potentiostatically at E_a = 100 V for t_pa = 43.2 ks. During the galvanostatic anodizing, the anode potential increased almost linearly with time, while, during potentiostatic anodizing, the anodic current decreased up to t_pa = 3.6 ks, and then increased slowly before decreasing again after t_pa = 30.0 ks. Images of FE-SEM and in situ AFM showed that nuclei of imperfections were formed at the ridge of cell structures before t_pa = 3.6 ks. After formation, the imperfection nuclei grew, showing cracking and rolling-up of the anodic oxide film, and crystalline oxide was formed at the center of imperfections after t_pa = 3.6 ks. The growth of imperfections caused increases in the anodic current between t_pa = 3.6 and 30.0 ks. Long-term anodizing caused a coalescence of the imperfections, leading to decreases in the anodic current after t_pa = 30.0 ks. As the imperfections grew, the dielectric dispersion of the anodic oxide films became serious, showing a bias voltage dependence of the parallel equivalent capacitance, C_p, and a dielectric dissipation factor, tan δ. The mechanism of formation and growth of the imperfections, and the correlation between the structure and dielectric properties of anodic oxide films is discussed.