A passivation mechanism of doped polyaniline on 410 stainless steel in deaerated H2SO4 solution

To investigate the role of polyaniline (PANI) in the corrosion protection of stainless steel (SS) in oxygen-deficient acidic solution, a separate doped PANI film electrode on a glass substrate was prepared and the test solution (1 M H₂SO₄) was purged with high-purity N₂ until dissolved oxygen level decreased more than two orders of magnitude. In this deaerated 1 M H₂SO₄ solution, the galvanic coupling interaction between the separate PANI film electrode and 410 SS was studied. Results reveal that the separate PANI film can passivate the 410 SS steadily for a long period of time. A variety of experimental methods including potentiodynamic measurement, potentiostatic (current-time) examination and X-ray photoelectron spectroscopy (XPS) are used to explore the mechanism by which the separate PANI film passivated the galvanic coupling SS in the deaerated sulfuric solution. These studies show that passivation is achieved because PANI film provides a large critical current at the early stage of coupling and a persistent passive current by its electrochemical dedoping/re-doping equilibrium activity with the acidic environment at the subsequent stage of coupling.     

Protection of type 430 stainless steel against pitting corrosion by ladder conductive polymer

Poly(o-phenylenediamine) (PoPD) was electropolymerized by cyclic voltammetry (CV) on 430 stainless steel from sulfuric acid solution containing o-phenylenediamine monomer. The formation of the polymer film is slower than that of polyaniline (PANI) film. Transparent and compact layers (∼1.0 μm) of PoPD deposited after 100 cycles, while thicker (∼3 μm), grainy and porous layers of PANI formed after 50 cycles. The PoPD layers protect the steel substrate from pitting in 3% NaCl but the layers of PANI fail, and pitting and crevice corrosion were observed on the steel surface. Both polymers keep the steel substrate in a passive state in sulfuric acid. After aging in acid solution the underlying oxides were investigated after peeling off the polymer layers; this showed an excellent passive film formed under PoPD. The passive steel was completely free from pitting after immersion in the chloride solution for 1 week.     

Effects of nanocrystallization on the corrosion behavior of 309 stainless steel

Nanocrystallized (NC) 309 stainless steel (309SS) coating has been fabricated on glass substrate by DC magnetron sputtering. The coating, with an average grain size less than 50 nm, had ferritic (bcc) structure rather than the austenitic (fcc) structure of the bulk steel. The electrochemical corrosion behavior of the NC coating and the bulk steel in solutions of 0.25 M Na₂SO₄ + 0.05 M H₂SO₄ and 0.5 M NaCl + 0.05 M H₂SO₄ was investigated by using potentiodynamic polarization, potentiostatic polarization and AC impedance techniques. The results showed that the corrosion behavior of the NC 309SS coating and 309SS bulk steel depended on the composition of the solutions. In the Na₂SO₄ solution there was only a little difference between the corrosion resistance of the passive films on the NC coating and the bulk steel. However, in the solution with chloride ions, the localized corrosion resistance of 309SS was greatly enhanced by nanocrystallization due to the formation of a compact and stable passive film on the NC coating. The electronic structure of the passive film formed on the NC coating and on the bulk steel was analyzed by means of capacitance measurements, and a corrosion mechanism is proposed.     

Study and optimization of a flexible electrochromic device based on polyaniline

The synthesis of polyaniline (PANI) thin films was made onto commercially available  cm polyethylene terephthalate (PET)/indium tin oxide (ITO) substrates. By depositing a gold frame previously to the electrochemical PANI synthesis, homogeneous electrochromic PANI layers were obtained. Complete flexible cells could then be built by using a transparent gel electrolyte and a simple PET/ITO counter-electrode. Branched poly(ethyleneimine) (BPEI)-H₃PO₄ and polymethylemethacrylate (PMMA)-PC-LiClO₄ were both tested as electrolytes, but only the latter led to a non-degrading system when the device undergoes several switching potential steps. This flexible, middle-scale and inexpensive device enabled to get a 18% transmission contrast at 780 nm within 3 min.     

Electrochemical synthesis of WO3/PANI composite for electrocatalytic reduction of iodate

Composite film of polyaniline (PANI) and tungsten oxide (WO₃) was electrodeposited by cyclic voltammetric technique from a solution of aniline and tungstic acid. The obtained WO₃/PANI film displayed a significant enhancement of electrocatalytic activity for iodate reduction and a better stability than that of pure WO₃ and PANI films. Result of amperometric experiment revealed a good linear relationship with concentration of IO₃⁻ from 20 to 500 μM, with a high sensitivity of 0.54 μA/μM and a detection limit of 2.7 μM for the determination of iodate. This composite film was also successfully applied in determination of iodate in commercial table salt.     

Potentiodynamic and potentiostatic deposition of polyaniline on stainless steel: Electrochemical and structural studies for a potential application to corrosion control

Polyaniline (PAn) films were electrodeposited on stainless steel 304 (SS) from 0.5 M H₂SO₄ solution containing 0.1 M aniline (An) by using potentiodynamic and potentiostatic techniques. In particular, PAn films were prepared as follows: (i) by cyclic potential sweep (CPS) deposition upon varying the upper potential limit (E_l) of the polymerization potential region between 0.8 and 1.1 V, while the lower potential limit was equal to −0.2 V; (ii) by potentiostatic deposition upon varying the applied potential (E_appl) between 0.8 and 1.1 V. The potential sweep rate (dE/dt) was also varied for the An polymerization during the CPS deposition. Variation of the E_l, dE/dt and E_appl affects the PAn growth leading to films of different electrochemical and structural properties. The electrochemical properties of the PAn were examined by using cyclic voltammetry. Scanning electron microscopy was used to reveal the structure and morphology of the PAn films. Monitoring the open circuit potential (E_OC) of the PAn-coated SS electrode in 0.5 M H₂SO₄ shows that the SS remains in the passive state. PAn films can also provide protection to SS in chloride-containing 0.5 M H₂SO₄ for the studied period of time, although pits were detected during prolonged immersion. The protection efficiency seems to be related with the parameters E_l, dE/dt and E_appl varied during polymerization. The mechanism of the SS protection provided by the PAn coatings is discussed in terms of the active role of PAn in corrosive environments.     

Changes on iron electrode surface during hydrogen permeation in borate buffer solution

Hydrogen interaction with oxide films grown on iron electrodes at open circuit potential (E_oc) and in the passive region (+0.30 V_ECS) was studied by chronopotentiometry, chronoamperometry and electrochemical impedance spectroscopy techniques. The results were obtained in deaerated 0.3 mol L⁻¹ H₃BO₃ + 0.075 mol L⁻¹ Na₂B₄O₇ (BB, pH 8.4) solution before, during and after hydrogen permeation. The iron oxide film modification was also investigated by means of in situ X-ray absorption near-edge spectroscopy (XANES) and scanning electrochemical microscopy (SECM) before and during hydrogen permeation. The main conclusion was that the passive film is reduced during the hydrogen diffusion. The hydrogen permeation stabilizes the iron surface at a potential close to the thermodynamic water stability line where hydrogen evolution can occur. The stationary condition required for the determination of the permeation parameters cannot be easily attained on iron surface during hydrogen permeation. Moreover, additional attention must be paid when obtaining the transport parameters using the classical permeation cell.     

Influence of nanocrystallization on passive behavior of Ni-based superalloy in acidic solutions

The electrochemical corrosion behaviors of Ni-based superalloy nanocrystalline coating (NC) fabricated by a magnetron sputtering technique have been investigated in comparison with cast alloy in 0.25 M Na₂SO₄ + 0.05 M H₂SO₄ and 0.5 M NaCl + 0.05 M H₂SO₄ solution, respectively. Compared with cast alloy, the NC coating had a little higher passive current density in Na₂SO₄ acidic solution, while it had superior resistance to pitting corrosion in NaCl acidic solution. The semiconductive type of passive film of the NC coating was p-type in both acidic solutions, while, that of cast alloy changed from p-type in Na₂SO₄ acidic solution to n-type in NaCl acidic solution. XPS results indicated that Cr₂O₃ was the main component for the passive films of the NC coating as well as those of the cast alloy. No chloride ion was found in the passive film of NC coating while it was in the passive film of cast alloy. The chloride ions adsorbing on the surface of cast alloy incorporated into the passive film, which induced the formation of n-type oxide film. The nanocrystallization of Ni-base superalloy obviously weakened the adsorption of chloride ions on surface, which decreased the susceptibility of pitting corrosion in acidic solution.     

Participation of the dissolved O2 in the passive layer formation on Zn surface in neutral media

The composition of the passive layers formed on Zn electrode in naturally aerated and de-aerated 0.1 M KClO₄ solution were studied using X-ray photoelectron spectroscopic measurements (XPS). A correlation between the presence of dissolved O₂ and the formation of an interior passive layer was carried out. Librated Cl⁻ from the perchlorate reduction reaction was detected in its solutions during Zn electrode polarization. The librated Cl⁻ concentration reached its maximum value at −1.4 V. Moreover, in the studied potential range the perchlorate reduction rate increases in absence of dissolved oxygen. Chrono-amperometry and electrochemical impedance spectroscopy (EIS) were performed for the stationary and the rotating disc Zn electrodes in naturally aerated and de-aerated 0.1 M KClO₄ solution. EIS technique showed a change in the electrode impedance with the experimental conditions as a result of changing the reactions occurring in the electrode vicinity. The obtained data were fitted to three different equivalent circuits depending on the electrode potential. The protective nature of the passive layers formed in different experimental conditions was found to decrease with rotating the electrode and de-aerating the solution.     

Electrochemical nitrite nanosensor developed with amine- and sulphate-functionalised polystyrene latex beads self-assembled on polyaniline

Aniline doped with polyvinyl sulphonate (PV-SO₃⁻) was electropolymerised on screen printed carbon (SPCE) and glassy carbon (GCE) electrodes. Then nano-structured polystyrene (PS_NP) latex beads functionalised with amine (PS_NP-NH₂) and sulphate (PS_NP-OSO₃⁻) were self-assembled on the modified SPCE and GCE. The resultant polyaniline nanocomposites (PANI|PS_NP-NH₂ or PANI|PS_NP-OSO₃⁻) were characterised by cyclic voltammetry (CV), UV-vis spectroscopy and scanning electron microscopy (SEM). Brown-Anson analysis of the multi-scan rate CV responses of the various PANI films gave surface concentrations of the order of 10⁻⁸ mol cm⁻². UV-vis spectra of the PANI films dissolved in dimethyl sulphoxide showed typical strong absorbance maxima at 480 and 740 nm associated with benzenoid π-π* transition and quinoid excitons of polyaniline, respectively. The SEM images of the PANI nanocomposite films showed cauliflower-like structures that are <100 nm in diameter. When applied as electrochemical nitrite sensor, sensitivity values of 60, 40 and 30 μA/mM were obtained for electrode systems containing PANI|PS_NP-NH₂, PANI and PANI|PS_NP-SO₃⁻, respectively. The corresponding limits of detection of the sensors were 7.4, 9.2 and 38.2 μM NO₂⁻.     

Growth kinetics of passivating oxide film of Inconel alloy 600 in 0.1 M Na2SO4 solution at 25-300 °C using the abrading electrode technique and ac impedance spectroscopy

The growth kinetics of passivating oxide film of Inconel alloy 600 has been investigated in aqueous 0.1 M Na₂SO₄ solution at temperatures 25-300 °C and at pressures 0.1-8 MPa by analyses of potentiostatic current transients and ac impedance spectra. From the analysis of current transients, it was realized that the oxide film grown on the specimen has only one-layer structure below 60 °C, but it is composed of two layers with different structures, i.e. an inner layer and an outer layer, above 100 °C. In addition, ac impedance spectra exhibited one capacitive loop below 60 °C, but they exhibited two capacitive loops above 100 °C. This substantiates that the structure of the oxide film changed from one-layer structure below 60 °C to two-layer structure above 100 °C. Moreover, from the analysis of ac impedance spectra, it was found that the value of the apparent specific resistivity of the inner layer decreased with rising solution temperature, but that value of the apparent relative permittivity increased.     

Electrosynthesis and protection role of polyaniline–polvinylalcohol composite on stainless steel

Polyaniline–polyvinyl alcohol (PANI–PVA) composite has been electrodeposited on stainless steel surface from aqueous sulfuric acid solution of aniline monomer in presence of soluble PVA at different concentrations. The PVA increased the rate of electropolymerization where 4 g/L PVA formed a composite of 37 wt% PANI and 63 wt% PVA composition. The composite layer exhibited more adhesion to the steel surface in comparison with PANI layer but with less thermal stability. It has higher protection role for the stainless steel (SS) against general and pitting corrosion. It enhanced the passivation of the SS surface by increasing the thickness of oxide film and improving the composition.     

Electrochemical synthesis and anticorrosive properties of Nafion-poly(aniline-co-o-aminophenol) coatings on stainless steel

The objective of this work was to compare the electrochemical behavior and possible anticorrosive properties of composite with Nafion^®, poly(aniline-co-o-aminophenol) (P(An-co-OAP)) and polyaniline (PAn) films with those of corresponding simple films. The electrochemical synthesis of polymer films was carried out on stainless steel AISI 304 (SS) surfaces by using the cyclic potential sweep (CPS) deposition. Scanning electron microscopy (SEM) was used for the characterization of the structure and morphology of deposited films. Evaluation of anticorrosive properties of films in 0.5 M H₂SO₄ without and with chlorides was achieved by monitoring the open circuit potential (E_OC) of coated SS electrodes as well as by tracing the anodic current-potential polarization curves. These studies have shown that the SS remains in its passive state in the presence of polymer coatings. Composite with Nafion^®, P(An-co-OAP) and PAn films, keep their redox activity in chloride-containing acid solutions providing almost a complete protection of the SS substrate against pitting corrosion. These films prevent chloride exchange with solution because of the cation permselectivity of the Nafion^® membrane. The charge compensation during redox reactions occurs mainly by protons since sulfonate groups of Nafion^® act as dopants in composite films. The redox behavior of the Nafion^®-P(An-co-OAP) film is improved as compared with that of the Nafion^®-PAn film in both Cl⁻-free and Cl⁻-containing solutions. This behavior may be ascribed to the functional group -OH that facilitates charge compensation through proton during redox 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.     

Synthesis and characterization of poly(aniline) and poly(o-anisidine) films in sulphamic acid solution and their anticorrosion properties

Poly(o-anisidine) (POA) and polyaniline (PANI) coatings were synthesized on platinum (Pt) surface and stainless steel (SS) in monomer containing 0.50 M sulphamic acid (SA) solution by means of cyclic voltammetry (CV) technique. Meanwhile, poly(o-anisidine) film was also deposited with a different scan rate on SS electrode. The behaviour of PANI and POA films obtained on stainless steel examined by CV was different from the one obtained for PANI and POA on Pt electrode. The corrosion performances of PANI and POA coatings in 3.5% NaCl solution were investigated with anodic polarization technique and electrochemical impedance spectroscopy (EIS). EIS measurements verified the effect of monomers and that of scan rate on corrosion inhibition of coatings on SS electrode. The results showed that POA film synthesized at low scan rate exhibited an effective anticorrosive property on SS electrode. POA synthesized at low scan rate and PANI coatings provided a remarkable anodic protection to SS substrate for longer exposure time than the one observed for POA coating produced at high scan rate as well as that of bare SS electrode.     

Investigation of the corrosion protection of SiOx-like oxide films deposited by plasma-enhanced chemical vapor deposition onto carbon steel

The paper reports on the corrosion behavior of carbon steel coated with thin SiO_x-like oxide films. The SiO_x-like coatings were deposited by plasma-enhanced chemical vapor deposition (PECVD) and their thickness was varied between 20 and 200 nm. The coated carbon steel interfaces were investigated for their corrosion protection efficiency when immersed in an aqueous saline solution of 3% NaCl. FTIR measurements and electrochemical impedance spectroscopy (EIS) experiments revealed that thin SiO_x-like coating layers (20 nm thick) do not prevent the carbon steel from corrosion, while thicker silica layers (d ≥ 100 nm) protect efficiently carbon steel interfaces in highly saline media with a protection efficiency of about 96% for a 200 nm thick coating.     

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.     

Passivity of OC404 steel modified electrochemically with CeO2-Ce2O3 layers in sulfuric acid media

The effect of cerium oxides film, formed electrochemically on OC404 stainless steel (SS), upon the corrosion behavior of steel in 0.1N H₂SO₄ was investigated. The modification of the steel surface by deposition of cerium oxides films was found to improve the steel corrosion resistance. A linear dependence between the stationary corrosion potential of the cerium oxides/SS system and the cerium concentration in the oxide film was established. The shift of the corrosion potential in the positive direction was found to depend on the proceeding of a depolarizing cathode reaction of CeO₂ reduction (instead of the hydrogen depolarizing reaction) occurring on the cathodic zones, formed by this oxide. On the basis of XPS analyses of the samples, subjected to real corrosion under the conditions of self-dissolution, a pronounced drop of the surface concentration of CeO₂ was established. This is a proof of the occurrence of an effective cathode process of CeO₂ reduction to Ce₂O₃, which was then dissolved in H₂SO₄. Data were obtained (XPS) on the composition and structure of the surface film (SEM) after electrodeposition of cerium oxides and after corrosion in the sulfuric acid medium under consideration for time intervals ranging from 50 up to 1000 h. The ICP-AES studies acquired data on the quantity of dissolved elements, forming the passive layer. After exposure to the corrosive medium, the deposited layer showed enrichment in oxides of chromium and aluminium. The passive film on stainless steel, modified in this way, proved to be more stable to the effect of aggressive sulfuric acid medium, compared to the case of natural passive film.     

In situ electrochemical preparation of multi-walled carbon nanotubes/polyaniline composite on the stainless steel

Polyaniline–carbon nanotubes (PANI–CNTs) composites have been deposited via in situ electropolymerization on stainless steel (SS) surface. The presence of the oxidized multi-walled carbon nanotubes (mCNTs) in the composite was confirmed by thermal gravimetric analysis (TGA) and scanning electron microscope. Introducing 28 and 70 mg L⁻¹ mCNT in the electrolyte increased the growth rate of PANI from 38 to 67 and 83 mC/cycle, respectively. The mCNT decreases the porosity of the PANI, forming networks which held the polymer. Influences of the composite layer on the passivation and corrosion of the stainless steel were studied and compared with pure PANI layer. It was confirmed that a higher resistant passive film was formed on the steel under the composite layer compared to that formed under the pure PANI.     

High anticorrosion chromate-free passive films made by Titanate and waterborne polyurethane on galvanized steel sheet

In this study, environmental friendly hybrid passive films on galvanized steel sheet were prepared from waterborne polyurethane and Titanate. The experimental results show that the optimized composition in passive solution was 30 g/L TiOSO₄, 5 g/L (NH₂)₂CS, 10 g/L NH₄F and 150 g/L WPU. The samples were dipped into passive solution for 10 s, dried at 120 °C for 15 s. Though the film's thickness is just 0.5 μm, the white rust resistance is excellent.