Electrochemical behaviour of passive films on molybdenum-containing austenitic stainless steels in aqueous solutions

Passivation and its breakdown reactions have been studied on Mo-containing stainless steel specimens using different electrochemical techniques. Mo-containing stainless steel specimens were polarized in both naturally aerated NaCl and Na₂SO₄ solutions of different concentrations at 25 ± 0.2 °C between −1000 and 1500 mV versus saturated calomel electrode (SCE). The results of potentiodynamic polarization showed that i_corr and i_c increases with increasing either Cl⁻ or SO₄²⁻ concentration indicating the decrease in passivity of the formed film. EIS measurements under open circuit conditions confirmed that the passivity of the film decrease with increase in either Cl⁻ or SO₄²⁻ concentration.     

Impedance investigation of passive 304 stainless steel in the pit pre-initiation state

The results of impedance measurements on stainless steel 304L by classical and dynamic electrochemical impedance spectroscopy (DEIS) have been presented. The investigation was focused on a transition of steel from passive state to the initial stage of pit formation. Based on the evolution of electrical parameters of the equivalent circuit it has been stated that the most probable mechanism of pit creation is the film-breaking model.     

Anodic growth of passive films on zirconium and hafnium

Galvanostatic potential-time curves on passive zirconium and hafnium electrodes are recorded and analysed in the light of the Cabrera—Mott equation and the high-field ion migration equation. For both metals, the kink-site density in the reacting metal surface (s) and the oxygen vacancy density in the passive film at the metal—oxide interface (N_o) appear to attain steady values which depend on the current density of metal oxidation (j) according to d log s/d log j ≈ 1/2 and d log N_o/d log j ≈ 3/4. Possible effects of space charge in the passive film are considered and found to be negligible under the conditions covered. Comparisons are made to the corresponding behaviour of some other passive metals and to the anodic dissolution of some active metals.     

Diffusivity of anion vacancies in WO3 passive films

The WO₃ films were grown in 0.1 M HClO₄ aqueous solution, at different formation potentials (E_f) in the range of 2.0-7.0 V versus sce, on W electrode. The anion diffusion coefficient (DO) of WO₃ films was calculated from EIS spectra, following the surface charge approach (at high-field limit approximation), the Point Defect Model and the Mott-Shottky analysis. Among the parameters necessary to evaluate DO, the half-jump distance (a) is very relevant, given that a small variation in a has a great impact in the calculation of DO. In this work, it is proposed the half-jump distance (a) should be evaluated from spectroscopic data (available in the literature). The value of a (∼1.9 Å) is taken from lattice constants of a-WO₃ (amorphous-WO₃), with different values of N (coordination number), and the lattice constants of m-WO₃ (monoclinic-WO₃). The calculated value of DO was ∼3 × 10⁻¹⁷ cm²/s.     

Influence of the dissolution of MnS inclusions under free corrosion and potentiostatic conditions on the composition of passive films and the electrochemical behaviour of stainless steels

The influence of the dissolution of MnS inclusions at the OCP value and 400 mV versus SCE on the chemical composition of passive films and the electrochemical behaviour of resulfurized austenitic stainless steel was studied in 1 M NaClO₄, pH 3, solution using SIMS, XPS, electrochemical impedance spectroscopy and the electrochemical microcell technique. The electrochemical dissolution (at 400 mV versus SCE) of inclusions occurred uniformly along the interface and this process was almost complete after 25 min immersion. A small amount of sulfur was detected on the matrix that exhibited a wide passive range. By contrast, the dissolution process under free corrosion was not uniform along the interface and numerous inclusions were partly dissolved. Grains close to the completely dissolved inclusions showed an active behaviour. This was connected with the adsorption of a large number of sulfur on the surface. In the two cases, the presence of sulfur species on the surface was also found to enhance the kinetics of cathodic reactions.     

The effect of Ni in the electrochemical properties of oxide layers grown on stainless steels

This study analyses the influence of Ni in the electrochemical behaviour of three different stainless steels in alkaline medium. The studied steels have increasing Ni content: AISI 430, AISI 304L and AISI 316. The obtained results are compared with those of a nickel base alloy (Ni > 42%, w/w) and a pure Ni electrode. Electrochemical impedance spectroscopy and cyclic voltammetry have been the main tools used to study the growth and evolution of the passive layers formed on those materials in alkaline medium. XPS and SEM have been employed for chemical and morphological characterization of the developed passive films.The presence of Ni promotes the formation of thinner and more protecting passive films. This fact noticed in the XPS analysis is reflected in the cyclic voltammograms by an important decrease of the magnetite formation peak current as well as that corresponding to Cr³⁺/Cr⁶⁺ oxidation. The low frequency limit of complex plane impedance plots also increases with the Ni content. In order to better characterise the resistivity of the electrochemically formed films, a more detailed impedance analysis in the high frequency range (1 kHz-10 MHz) has been performed. The analysis of the registered spectra indicates that Ni modifies the conductivity of the oxide layers, promoting the formation of more resistive oxide films.     

Corrosion behaviour of low-nickel austenitic stainless steels reinforcements: A comparative study in simulated pore solutions

The use of austenitic stainless steel reinforcements is one of the most reliable methods to assure the durability of reinforced concrete structures exposed to aggressive environments, but the initial cost of the material often limits its use in practice. Nickel is one of the alloying elements that raise most the cost of the stainless steels reinforcements. In this work the corrosion resistance of low-Ni 204Cu reinforcements is compared with that of more traditional austenitic stainless steels such as 304, 304L, 316, 316L and 316Ti. Polarization tests were carried out in simulated carbonated and non-carbonated pore solutions with different chloride concentrations. Results prove the very good corrosion behaviour of 204Cu stainless steel in carbonated media and in non-carbonated, chloride contaminated media. The corrosion resistance of low-Ni type 204Cu is only meaningfully lower than that of more traditional austenitic stainless steels in very highly aggressive solutions.     

Self-organisation of nanoscaled pores in anodic oxide overlayer on stainless steels

The nanoscaled morphology of the overlayer covering stainless steels after electropolishing in perchloric acid-based electrolyte was explored mainly by AFM and SEM. Two kinds of stainless steels were tested. For the austenitic one (AISI 304L), a quasi-periodic arrangement of pores in this overlayer has been observed. Depending on the experimental conditions, the distance between neighbouring pores ranged from 20 nm up to 230 nm. This inter-pore distance varied either with the applied voltage or with the current density for a constant voltage. From XPS spectra performed on the nanostructured surfaces, analysis of the energy shifts of Cr and Fe 2p levels showed that the anodic overlayer was enriched in Cr atoms compared to the 304L steel bulk composition. For the austeno-ferritic duplex stainless steel, the electropolished surface exhibited nanoscaled pores, which had grown and self-organised on both phases but with different characteristic dimensions.     

Surface enhanced Raman spectroelectrochemical studies of the corrosion films on iron and chromium in aqueous solution environments

“In situ” laser Raman spectra of the corrosion films on iron have been observed in aerated 5 M KOH and 0.15 M NaCl solutions via surface enhancement by the electrodeposition of a silver overlayer. Essentially the same spectra are observed in the two solutions as a function of applied potential in spite of a breakdown of passivity on iron in the chloride solution. Fe(OH)₂ and Fe₃O₄ are found in the prepassive potential region while FeOOH is present in the passive region. A film which is very difficult to reduce appears to be always present on the electrode surface even at hydrogen evolution potentials; this film is believed to be -FeOOH. Surface enhanced Raman spectra of the corrosion films on chromium have also been obtained in NaCl solution for the first time. The passive film has a composition that corresponds most closely to an amorphous form of Cr₂O₃, with some Cr(OH)₃ also present. The film is converted in the transpassive region to a higher oxide form, presumably CrO²⁻₄. Reversible reduction of this species to Cr₂O₃ is indicated.     

Composition and structure of the anodic films on titanium in aqueous solutions

Surface-enhanced Raman spectra of the amorphous film on titanium have been obtained for the first time. The anodic corrosion film at low potentials is identified to be highly disordered TiO₂ with some Ti₂O₃ also present. The presence of the anatase and rutile modifications of TiO₂ at high voltages ( 80V) is confirmed.     

pH sensing in aqueous solutions using a MnO2 thin film electrodeposited on a glassy carbon electrode

An electrolysis technique at a constant potential was used to develop a highly reproducible and fast elaboration method of adherent manganese dioxide thin films on a glassy carbon electrode from aqueous solutions containing sulfuric acid and manganese sulfate. The resulting films were found to have a nanostructured character presumably due rather to birnessite (δ-MnO₂) than to γ-MnO₂, as suggested by their Raman and XRD signatures. They lead to modified electrodes that present an obvious although complex pH dependent potentiometric response. This sensor indeed showed a single slope non-Nernstian linear behaviour over the 1.5–12 pH range for increasing pH direction (“trace”), whereas a Nernstian two slopes linear behaviour was observed for decreasing pH direction (“re-trace”). Preliminary EIS experiments carried out at a pH value of 1.8 seem to reveal a sensitivity mechanism based on proton insertion process at least at highly acidic pH values.     

Photodegradation of dyes in aqueous solutions catalyzed by highly efficient nanocrystalline titania films

Thin nanocrystalline titanium dioxide films were deposited on glass rings by the sol-gel method in the presence of ethanol, acetic acid and the non-ionic surfactant Triton X-100. Nanocrystallites are formed due to surfactant self-organization that acts as a template. These films have high active surface area and are very efficient for the photodegradation of dyes in aqueous solutions. In addition, the catalyst can be easily recovered and can be repeatedly used without loss of efficiency. Three dyes were used: Basic Blue 41, Acid Orange 7, and Crystal Violet. Decoloration of solutions of Basic Blue is much faster than those of the other two dyes. A very low load of catalyst, i.e. 120 mg l⁻¹, is capable of bleaching dilute solutions in only a few hours by shining black light of 0.7 mW cm⁻². An inexpensive and simple reactor of cylindrical symmetry is described which employs a 4 W black-light tube as light source.     

Deterioration behavior of cellulose acetate films in acidic or basic aqueous solutions

The deterioration behavior of cellulose acetate (CA) films (degree of substitution = 2.5) was examined in hydrochloric acid (HCl) and sodium hydroxide (NaOH) solutions of various concentrations to determine acid and base catalytic effects in heterogeneous systems at room temperature. With concentrations of 0.5N HCl and 0.01N NaOH and higher, the physical properties of the films changed. The films, recovered after 1–10 days of immersion, were slightly opaque and rubbery from swelling in the solutions before drying. They became brittle and shrank when they dried. For HCl immersion, the weight change of a film depended on the HCl concentration and the immersion time. With 6.0N HCl, the film shape was broken, and a fine powder was deposited in the solution with a recovery of 53.8 wt %. The infrared spectrum of this deposit indicated that it was completely deacetylated cellulose. For NaOH immersion, although the weight change depended on the NaOH concentration, the weight loss reached 40–50% within the first 24 h, and it was constant with respect to the immersion time and base concentration in 0.5N NaOH or NaOH of a higher concentration. The infrared and gel permeation chromatography analyses showed that this deterioration mainly depended on the deacetylation of CA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3354–3361, 2004     

Effects of nitrogen on the passivation of nickel-free high nitrogen and manganese stainless steels in acidic chloride solutions

The role of nitrogen on the passivation of nickel-free high nitrogen and manganese stainless steels was investigated in 0.5 M H₂SO₄, 3.5% NaCl and 0.5 M H₂SO₄ + 0.5 M NaCl solutions using potentiodynamic polarization, electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy techniques. The passive film stability was enhanced in 0.5 M H₂SO₄ and the pitting resistance was improved in 3.5% NaCl solution by more nitrogen addition. The influence of nitrogen extended the whole anodic polarization region in 0.5 M H₂SO₄ + 0.5 M NaCl solution, as demonstrated by the enhanced dissolution resistance, promoted adsorption and passivation process, improved film protection and pitting resistance with increasing nitrogen content. Possible mechanisms relating to the role of nitrogen in different potential regions were discussed.     

Investigation of inhibiting properties of self-assembled films of 4-aminothiophenol on copper in 3.5% NaCl

A self-assembled monolayer (SAM) of 4-aminothiophenol (4-ATP) was formed on copper surface which was characterized using cyclic voltammetry, Fourier transform infrared spectroscopy, and Raman spectroscopic techniques. The surface morphology of the monolayer was examined by scanning electron microscopy. The anticorrosive property of the SAM was investigated using electrochemical impedance spectroscopy and polarization studies. The electrochemical measurements showed that the inhibition efficiency increased with the immersion time of copper in ethanolic solution of 4-ATP in 3.5% NaCl. The significant corrosion protection efficiency of SAM could be due to the compact and dense monolayer on metallic surfaces.     

The Influence of Ni Content on the Stability of Copper—Nickel Alloys in Alkaline Sulphate Solutions

The electrochemical behaviour of copper–nickel alloys with different Ni content (5–65%) in sulphate solutions of pH 12 was investigated. The effects of temperature, immersion time, and concentration of sulphate ions were also studied. Different electrochemical methods such as open-circuit potential measurements, polarization techniques and electrochemical impedance spectroscopy (EIS) were used. Potentiodynamic measurements reveal that the increase in nickel content increases the corrosion rate of the alloy in sulphate solution linearly. Nevertheless, an increase in the nickel content along with increase in immersion time improves the stability of the Cu–Ni alloys due to the formation of a stable passive film. An equivalent circuit model for the electrode/electrolyte interface under different conditions was proposed. The experimental impedance data were fitted to theoretical data according to the proposed model. The relevance of the model to the corrosion/passivation phenomena occurring at the electrode/solution interface was discussed.     

The electrochemical reduction of oxygen on zinc corrosion films in alkaline solutions

Kinetics of the O₂ reduction has been characterized on Zn corrosion films by Pt/Zn rotating ring-disc electrode (RRDE) and EIS methods. On zinc-oxide films a two-step reduction was identified in various buffer solutions of pH 10.5, while a small quantity of H₂O₂ intermediate could be detected. On the basis of results obtained from Pt/Zn and Pt/Pt RRDE experiments in solutions containing H₂O₂, it was further confirmed that the HO₂⁻ was reduced to OH⁻ through the zinc-oxide corrosion layer. Capacitance data of the zinc-oxide/electrolyte interface calculated from steady-state impedance diagrams measured at various cathodic potentials indicate the presence of a space charge layer of the semi-metallic ZnO. The solid-state reaction mechanism of HO₂⁻ disproportion with participation of Zn_i⁺ interstitials, oxygen ion vacancies of the non-stoichiometric Zn-oxide, and chemisorbed HO₂⁻ is discussed.     

Investigation of oxide film formation on 316L stainless steel in high-temperature aqueous environments

Oxide films were grown on the surface of 316L stainless steel subjected to high temperatures and a high-pressure aqueous environment (250 °C and 7 MPa). The morphology, chemical compositions and corrosion properties of oxide films were investigated by scanning electron microscopy (SEM), auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization techniques. The results indicated that oxide films formed at 250 °C were more corrosion resistant and thicker than were oxide films formed in air at room temperature (25 °C). These distinctions are correlated with the structure and chemical compositions of oxide films. It was found that both films contained a double-layer structure comprised of mixed iron–nickel oxides and chromium oxides. Iron was present as FeO, Fe₂O₃ and FeOOH; Cr was present as Cr₂O₃, Cr(OH)₃ and CrO₃; and Ni existed as Ni(OH)₂ within the oxide films formed at 250 °C.     

Chemical composition and electronic structure of the passive layer formed on stainless steels in a glucose-oxidase solution

This article deals with the interaction between the passive layer formed on UNS S30403 and S31254 stainless steels and an enzymatic solution containing glucose oxidase (GOx) and its substrate d-glucose. This enzymatic solution is often used to reproduce in laboratory the ennoblement occuring in non-sterile aerated aqueous environments because of the biofilm settlement on the surface of the metallic material. GOx catalyses the oxidation of d-glucose to gluconic acid by reducing oxygen to hydrogen peroxide and produces an organic acid. Thanks to photocurrent measurements, XPS analysis and Mott-Schottky diagrams, it is here shown that such an environment generates modifications in the chemical composition and electronic structure of the passive layer: it induces a relative enrichment of the n-type semi-conducting phase containing chromium (chromine Cr₂O₃) and an increase of the donors density in the space charge region.     

Performance of polyaniline pigmented vinyl acrylic coating on steel in aqueous solutions

Using electrochemical impedance spectroscopy method, the performance of vinyl acrylic coating containing polyaniline on steel in 0.1 N HCl, 3% NaCl and cement extract (pH 13.0) has been evaluated. The resistance of the paint coating in all the media has been found to decrease initially from 10⁸ to 10⁶ Ω cm². On subsequent exposure to the aqueous media, the resistance of the coating has been found to increase steadily. Further, the open circuit potential values have been found to shift in active direction initially and then move in noble direction with longer immersion period due to the passivating effect of polyaniline pigment.