Application of polyaniline to galvanic anodic protection on stainless steel in H2SO4 solutions

A stand-alone polyaniline (PANI) film electrode was made and then applied to protect 1Cr13 stainless steel (a type of stainless steel typically used in China, 0–15% C, 13% Cr) from corrosion in highly acidic solution, up to 5 M H₂SO₄. The stand-alone PANI electrode and 1Cr13 were coupled to study their galvanic interactions. PANI is a cathode while 1Cr13 is an anodic. The results indicate that PANI with a certain area can quickly passivate the stainless steel and effectively maintain the steady passive state for a long period of time. This specific method of PANI preventing 1Cr13 from corrosion is called galvanic anodic protection (GAP). Moreover, the efficiency, mechanism, and security of GAP were discussed. The results demonstrate that the stand-alone PANI electrode may have a potential application to galvanic anodic protection on stainless steel in highly corrosive H₂SO₄ solutions.     

Corrosion and passivation mechanism of chromium diboride coatings on stainless steel

The corrosion resistance of fully crystalline CrB₂ coatings magnetron sputtered onto AISI 316L stainless steel was tested in acidic solutions. CrB₂ coatings showed excellent corrosion protection, but suffered a breakdown when an anodic potential of greater than about +1 V (SHE) was applied to the surface in a 1 M HCl electrolyte. The coating failure at high potentials is attributed to transpassive dissolution of the coating at volume defects, enabling the electrolyte to reach the underlying 316L substrate, resulting in its rapid corrosion and subsequent fracturing of the coating. Electrochemical data and potential-pH (Pourbaix) diagrams, constructed from thermodynamic data, indicate that the corrosion resistance of CrB₂ is due to the formation of a Cr(III) oxide passive film in the absence of activation corrosion.     

Photogenerated cathode protection properties of nano-sized TiO2/WO3 coating

Nano-sized TiO₂/WO₃ bilayer coatings were prepared on type 304 stainless steel substrate by sol-gel method. The performance of photo-electrochemical and photogenerated cathode protection of the coating was investigated by the electrochemical method. The results show that the bilayer coating with four TiO₂ layers and three WO₃ layers exhibits the highest photo-electrochemical efficiency and the best corrosion resistance property. Type 304 stainless steel with the coating can maintain cathode protection for 6 h in the dark after irradiation by UV illumination for 1 h. In addition, the mechanism of the photogenerated cathode protection for the bilayer coating was also explored.     

Poly(N-methylaniline) coatings on stainless steel by electropolymerization

Poly(N-methylaniline) (PNMA) coatings have been electropolymerized on 304 stainless steel alloy by potentiodynamic, galvanostatic and potentiostatic synthesis techniques from aqueous solutions of 0.1 M N-methylaniline (NMA) and 0.3 M oxalic acid. Characterization of PNMA coatings was carried out by cyclic voltammetry, UV-Vis and FTIR spectroscopy techniques. Corrosion behavior of PNMA coated stainless steel electrodes was investigated using linear anodic potentiodynamic polarization, Tafel test, chronoamperometry and electrochemical impedance spectroscopy (EIS) techniques in 0.5 M aqueous HCl solutions. Corrosion test results showed that PNMA coatings possessed protection to uncoated stainless steel against corrosion.     

The effect of epoxy coating containing emeraldine base and hydrofluoric acid doped polyaniline on the corrosion protection of AZ91D magnesium alloy

Corrosion protection of epoxy coatings containing emeraldine base polyaniline (PANI) or hydrofluoric acid doped PANI on AZ91D magnesium alloy were studied by EIS and Pull-Off Adhesion Test. The results indicated that the addition of emeraldine base PANI or hydrofluoric acid doped PANI could improve the corrosion resistance of epoxy coating. The epoxy coating containing hydrofluoric acid doped PANI had the best performance of the corrosion protection among three systems under investigation. The corrosion product film was analyzed by XPS indicating that PANI changed the chemical structure of the corrosion film. The protective mechanism imparted by PANI was discussed.     

Molten salt synthesis of perovskite conversion coatings: A novel approach for corrosion protection of stainless steels in molten carbonate fuel cells

A novel conversion coating process has been developed to meet the stability requirements of stainless steel hardware in the demanding MCFC fuel cell environments. The process applies a perovskite-based coating by exploiting spontaneous oxidizing reactions of the metallic surface with La₂O₃ in eutectic alkali carbonate mixtures. By using well controlled synthesis procedures, conversion coating layers covering the entire metallic surface with a uniform and compact structure could be obtained. The as-formed coatings with a surface morphology of agglomerated crystallite particles consisted of a thin (<5 μm) LaFeO₃ perovskite layer grown over a thicker (>5 μm) LiFeO₂-rich layer. Test coupons of 316L stainless steel with the perovskite conversion coating were analyzed for corrosion protection and interfacial resistivity properties. It was found that the conversion coating is highly conductive while showing excellent long-term corrosion stability in simulated MCFC environments. These results suggested that perovskite coatings formed by molten salt conversion reactions could be particularly attractive to confer optimal protection and electrical continuity to MCFC current collectors.     

Characteristics and machining applications of Ti(Y)N coatings

The Ti(Y)N coatings were successfully deposited onto 18-8 stainless steel substrates by the hollow cathode discharge ion-plating method. The influence of the rare-earth element yttrium on the TiN coating properties was studied. The results show that the adhesion of the coating to the substrate were evidently enhanced by adding a small amount (0.2 wt.%) of the rare-earth element yttrium, showing a critical load of about 390 g which is much higher than that (230 g) of the TiN coating/substrate. Investigation on the corrosion resistance of the Ti(Y)N coating and the TiN coating was performed in 0.5 N Na₂SO₄ + 0.1 N H₂SO₄ + 0.1 N NaCl corrosion media by means of an electrochemical potentiodynamic polarization. The Ti(Y)N coating exhibited much better corrosion resistance than the TiN coating, whose passivity maintaining current is about one order in magnitude smaller than that of the TiN coating.The Ti(Y)N coatings deposited on some HSS-based tools were presented and compared with the TiN coating. The service lifetime of Ti(Y)N coated tools is approximately 36% higher (on the pinion shape cutters) and about 50% higher (on punch side pin) compared to that of TiN coated. The Ti(Y)N coatings showed such excellent performance. It is attributed to that the transition area of Ti(Y)N/substrate consisted of three sublayers which revealed a gradual change of phase structure and composition, so that the adhesion of the coating/substrate was evidently enhanced. Moreover, Ti(Y)N coating showed a preferred orientation with (111) plane which is favorable to improve wear resistance and corrosion resistance of the coating.     

Hot corrosion of YSZ/Al2O3 dispersed NiCrAlY plasma-sprayed coatings in Na2SO4-10 wt.% NaCl melt

This study examines the effect of ytrria stabilized zirconia (YSZ) dispersion on hot corrosion behaviour of NiCrAlY bond coat. Hot corrosion studies were conducted on NiCrAlY and NiCrAlY containing 25, 50 and 75 wt.% YSZ coatings obtained through the air plasma spray technique, in Na₂SO₄ + 10 wt.% NaCl environment at 800 °C. The results show that YSZ dispersion lowers the overall hot corrosion tendency of the NiCrAlY, though it enhances the inherent hot corrosion tendency of its metallic constituent (NiCrAlY). Furthermore, there exists a threshold oxide level beyond which it adversely affects the hot corrosion of the coating.     

Electro-Synthesis of Nano-Colloidal PANI/ND Composite for Enhancement of Corrosion-Protection Effect of PANI Coatings

The polyaniline/nanodiamond (PANI/ND) nanocomposite coating was prepared on mild steel via electrochemical polymerization using cyclic voltammetry technique. The ultrasonic irradiation was used for effectively dispersing ND particles in electropolymerization solution. The prepared nanocomposite films were found to be nano-colloidal, and very adherent with low porosity. The corrosion performance of the coatings was investigated in 0.5 M H₂SO₄ solution by electrochemical impedance spectroscopy and polarization methods. The obtained results showed that the presence of ND particles significantly enhanced the corrosion protection performance of the PANI films in 0.5 M H₂SO₄ corrosive medium. X-ray diffraction and FT-IR techniques confirmed the intercalation of the nanoparticles in PANI matrix.     

Poly(3‐octylthiophene) thermally treated as coating for corrosion protection of SS304 in sulfuric acid media

Poly(3‐octylthiophene) (P3OT) was synthesized by direct oxidation of the 3‐octylthiophene monomer using ferric chloride (FeCl₃) as an oxidant. Using the drop‐casting technique, P3OT coatings were deposited onto 304 type stainless steel electrodes. For the purpose of determining the effect of thermal annealing on the corrosion protection of stainless steel with P3OT coatings, the coated electrodes were thermally annealed for 30 h at two different temperatures, 55 and 100 °C. The corrosion behavior of P3OT coated stainless steel was investigated in 0.5 M sulfuric acid (H₂SO₄) at room temperature using potentiodynamic polarization curves (PPC), linear polarization resistance (LPR), and electrochemical impedance spectroscopy (EIS). The results indicated that the thermally treated P3OT coatings improved the corrosion resistance of the stainless steel in 0.5 M H₂SO₄. The best corrosion protection was obtained by the P3OT coating annealed at 100 °C. In order to study the temperature effect on the morphology of the coatings before and after the corrosive environment and compare it with corrosion protection, atomic force microscopy (AFM) and scanning electronic microscopy (SEM) were used.     

Validated numerical modeling of galvanic corrosion of zinc and aluminum coatings

A time-dependent finite element model was developed to simulate the corrosion of zinc and aluminum coatings, galvanically coupled to a mild steel substrate in deaerated 0.01 M H₂SO₄ electrolyte. The simulations of galvanic corrosion for each of the coatings were compared to experimental measurements of open circuit potential, and changes in coating geometry measured via surface profilometry. Good agreement between the model predictions and corrosion tests were observed initially for both coatings. However, in the case of the zinc coating, divergence was observed between the simulation and the corrosion test after approximately 40 min, due to a decrease in the reactivity of the zinc surface.     

A comparative study on the corrosion behaviour of 304 austenitic stainless steel in sulfamic and sulfuric acid solutions

Potentiodynamic polarization and EIS have been employed to compare the corrosion behaviour of 304 stainless steel in NH₂SO₃H and H₂SO₄ solutions. Corrosion tests were carried out as a function of the acid’s concentration (0.1-0.5 M) and solution temperature (20-60 ^oC). The corrosion rate is higher in H₂SO₄ than in H₂NSO₃H in all concentrations and temperatures. Values of the activation energy (E_a) revealed that the corrosion process is faster in H₂SO₄ than in NH₂SO₃H solution. EIS data showed that the display of Nyquist plots, and hence the mechanism of corrosion, depends not only on the acid concentration but also on the solution temperature. In 0.1 M concentration, the equivalent circuits R_e(R_ctQ_dl) and R_e(R_ctQ_dl)(RQ)_ads describe the corrosion systems in H₂NSO₃H and H₂SO₄ solutions respectively. At concentrations ?0.2 M, the equivalent circuit R_e(R_ctQ_dl)Q_diff is applicable. Adsorption of the counter ion of the acid on the steel surface and the stability of the surface complex may explain the observed corrosion rates.     

Corrosion protection of magnesium alloy AZ31 sheets by spin coating process with poly(ether imide) [PEI]

In the present study, the potential of poly(ether imide) as corrosion protective coating for magnesium alloys was evaluated using the spin coating technique. The influence of different parameters on the coating properties was evaluated and the corrosion behaviour of the coatings was investigated using electrochemical impedance spectroscopy. The best corrosion protection was obtained preparing the coatings under N₂ atmosphere, using 15 wt.% solution in N′N′-dimethylacetamide (DMAc) which resulted in a coating of approximately 2 μm thickness, with an initial impedance of 10⁹ Ω cm² and of 10⁵ Ω cm² after 240 h of exposure to a 3.5% NaCl solution.     

Synergistic effect of halide ions on improving corrosion inhibition behaviour of benzisothiozole-3-piperizine hydrochloride on mild steel in 0.5 M H2SO4 medium

The synergistic effect of iodide ions and benzisothiozole-3-piperizine hydrochloride (BITP) on corrosion inhibition of mild steel in 0.5 M H₂SO₄ solution has been studied by both chemical and electrochemical methods. The corrosion performance of BITP in 1.0 M HCl and 0.5 M H₂SO₄ media was examined and compared. The adsorption of BITP and its combination with iodide ions on mild steel surface followed Langmuir adsorption isotherm via chemisorption mechanism. The calculated values of synergism parameter (S_θ) were found to be greater than unity. This result clearly showed the existence of synergism between iodide ions and BITP molecules.     

An ultrathin polymer coating of carboxylate self-assembled monolayer adsorbed on passivated iron to prevent iron corrosion in 0.1 M Na2SO4

For preparing an ultrathin two-dimensional polymer coating adsorbed on passivated iron, a 16-hydroxyhexadecanoate ion HO(CH₂)₁₅CO₂⁻ self-assembled monolayer (SAM) was modified with 1,2-bis(triethoxysilyl)ethane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ and octadecyltriethoxysilane C₁₈H₃₇Si(OC₂H₅)₃. Protection of passivated iron against passive film breakdown and corrosion of iron was investigated by monitoring of the open-circuit potential and repeated polarization measurements in an aerated 0.1 M Na₂SO₄ solution during immersion for many hours. The time required for passive film breakdown of the polymer-coated electrode was markedly higher in this solution than that of the passivated one, indicating protection of the passive film from breakdown by coverage with the polymer coating. The protective efficiencies of the passive film covered with the coating were extremely high, more than 99.9% in 0.1 M Na₂SO₄ before the passive film was broken down, showing prominent cooperative suppression of iron corrosion in the solution by coverage with the passive film and polymer coating. The polymer-coated surface was characterized by contact angle measurement and electron-probe microanalysis (EPMA). Prevention of passive film breakdown and iron corrosion for the polymer-coated electrode healed in 0.1 M NaNO₃ was also examined in 0.1 M Na₂SO₄.     

Corrosion protection with polyaniline and polypyrrole as anticorrosive additives for epoxy paint

Accelerated immersion tests have been carried out in the laboratory to investigate the performance of polyaniline emeraldine salt and polypyrrole composite with carbon black as additives of an epoxy paint coating. The steel panels coated with paint modified with polyaniline emeraldine salt presented the best protection after 720 h of exposure in 3.5% NaCl solution. The results indicated that this conducting polymer might works as both corrosion inhibitor and adhesion promoter. The protective mechanism imparted by conducting polymers is also discussed.     

Corrosion of aluminium in copper-aluminium couples under a marine environment: Influence of polyaniline deposited onto copper

In this study, we examined how aluminium corrosion in Al-Cu/PANI galvanic couples in a marine environment is influenced by deposition of polyaniline (PANI) on copper. Polarization curves and immersion assays in 0.1 M NaCl were performed. The morphologies of etched Al and corrosion products were observed by SEM, and the Al ions in solution were quantified by atomic absorption spectroscopy. A reduction in aluminium damage due to galvanic corrosion was observed as a result of decreased effective area for the oxygen reduction reaction on Cu/PANI electrode. Furthermore, an electrochemical reduction of PANI from leucoemeraldine to emeraldine base is proposed.     

Inhibiting effects of butyl triphenyl phosphonium bromide on corrosion of mild steel in 0.5 M sulphuric acid solution and its adsorption characteristics

Butyl triphenyl phosphonium bromide (BuTPPB) has been evaluated as a corrosion inhibitor for mild steel in 0.5 M H₂SO₄ solutions using galvanostatic polarisation and potentiostatic polarisation measurements. The study was also complemented by infra red (IR) spectroscopy, scanning electron microscopy (SEM) and quantum chemical calculations. Galvanostatic polarisation measurements showed that the presence of BuTPPB in aerated 0.5 M H₂SO₄ solutions decreases corrosion currents to a great extent and the corrosion rate decreases with increasing inhibitor concentration at a constant temperature. At 298K, inhibition efficiency was found to be 94.5% for 10⁻⁷ M BuTPPB which increased to about 99% for the BuTPPB concentration of 10⁻² M. The effect of temperature on the corrosion behaviour of mild steel was studied at five different temperatures ranging from 298 to 338K. The polarisation curves clearly indicate that BuTPPB acts as a mixed type inhibitor. Adsorption of BuTPPB on the mild steel surface follows the Langmuir isotherm.Potentiostatic polarisation measurements showed that passivation was observed only for lower BuTPPB concentrations (10⁻⁵ and 10⁻⁷ mol l⁻¹) for the mild steel in 0.5 M H₂SO₄. IR and SEM investigations also confirmed the adsorption of BuTPPB on the mild steel surface in 0.5 M H₂SO₄ solutions. The molecular parameters obtained using PM3 semi-empirical method, were correlated with the experimentally measured inhibitor efficiencies.     

Corrosion behavior of TiN coated type 316 stainless steel in simulated PEMFC environments

The corrosion behavior of TiN coated type 316 stainless steel (SS) was investigated in simulated proton exchange membrane fuel cell environments, i.e. 0.01 M HCl + 0.01 M Na₂SO₄ solutions bubbled with pure oxygen and hydrogen gases, respectively, by using electrochemical measurement techniques. 316SS substrate can passivate spontaneously in simulated cathode environment, while it is in active state at the corrosion potential in simulated anode environment. TiN coatings have much better corrosion resistance and passivity under both simulated conditions. No significant degradation takes place in TiN coatings under the typical load conditions of fuel cell for 4 h. The loss of small part of coatings occurs during the immersion tests of TiN coatings in the oxygen environment for 1000 h and in the hydrogen environment for 240 h, respectively, but the exposed substrate areas are passivated in both environments. The results reveal that TiN coating can offer 316SS higher corrosion resistance and electric conductivity, and that further effort to improve the coating quality and to evaluate the long-term stability of 316SS/TiN coating systems under simulated conditions are deserved. In addition, the characteristics of corrosion process for TiN coatings on passivatable substrate were discussed in detail.     

The structure and high temperature corrosion performance of medium-thickness aluminide coatings on nickel-based superalloy GTD-111

Simple and Si-modified aluminide coatings having medium-thickness (40-60 μm) have been applied on the superalloy GTD-111 by a slurry technique. Hot corrosion and cyclic oxidation performance of the uncoated and the coated superalloy were investigated by exposing samples to a molten film of Na₂SO₄-40 %wt NaVO₃-10%wt NaCl at 780 °C and 1 h cyclic oxidation at 1100 °C in air, respectively. The presence of silicon in the aluminide structure increased the oxidation resistance by a factor of 1.7 times. In addition, a SiO₂-containing scale, which formed on the Si-containing coating surface, was stable during of the hot corrosion testing.