Styrene butadiene co-polymer based conducting polymer composite as an effective corrosion protective coating

Electroactive conducting polymer composite coatings of polyaniline (PANI) are electrosynthesized on styrene–butadiene rubber (SBR) coated stainless steel electrode by potentiostatic method using aqueous H₂SO₄ as supporting electrolyte. The protective behaviour of these coatings in different corrosion media (3.5% NaCl and 0.5 M HCl) is investigated using Tafel polarization curves, open circuit potential measurements and electrochemical impedance spectroscopy. The results reveal that SBR/PANI composite coating is much better in corrosion protection than simple PANI coating. The corrosion potential of composite films shifts to more noble values indicating that SBR/PANI composite coating act as an effective corrosion protective layer.     

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.     

Evaluation of the corrosion resistance of Ni-Co-B coatings in simulated PEMFC environment

The corrosion resistance behavior of Ni-Co-B coated carbon steel, Al 6061 alloy and 304 stainless steel was evaluated in simulated proton exchange membrane fuel cell (PEMFC) environment. The phase structure of the NiCoB based alloy was determined by Rietveld analysis. The PEMFC environment was constituted of 0.5 M H₂SO₄ at 60 °C and the evaluation techniques employed included potentiodynamic polarization, linear polarization resistance, open circuit potential measurements and electrochemical impedance spectroscopy. The results showed that in all cases the corrosion resistance of the Ni-Co-B coating was higher than that of the uncoated alloys; about two orders of magnitude with respect to carbon steel and an order of magnitude compared to 304 stainless steel. Except for the uncoated 304 type stainless steel, the polarization curves for the coated specimens did not exhibit a passive region but only anodic dissolution. The corrosion potential value, E_corr, was always nobler for the coated samples than for the uncoated specimens. This was true for the stainless steel in the passive region, but in the active state for the carbon steel and Al 6061 alloy. The corrosion of the underlying alloy occurred due to filtering of the solution through coating defects like microcracks, pinholes, etc. During the filtering process the E_corr value of the coating decreased slowly until it reached a steady state value, close to the E_corr value of the underlying alloy.     

Electrochemical behaviour of a magnesium alloy containing rare earth elements

The corrosion of a magnesium alloy containing rare earth elements (WE43 type alloy) was studied in 0.05 and 0.5 M Na₂SO₄ or 0.1 and 1 M NaCl solutions using electrochemical techniques: linear polarization resistance, potentiodynamic polarization, impedance measurements. The electrolytes favoured anodic magnesium oxidation but the presence of rare earth elements improved the tendency of magnesium to passivation. The dissolution rates in chlorides were higher than in sulphates because chlorides, in contrast to sulphates, interfered with the formation and maintenance of a protective layer of corrosion products which decreased the severity of the attack. The effects of galvanic corrosion due to cathodic intermetallic precipitates at grain boundaries were particularly evident in chloride media at long testing times.     

Corrosion protection of stainless steel by a new and low-cost organic coating obtained from cashew nutshell liquid

In this work, the corrosion protection of 316L steel was promoted by an electro-synthesized polymer obtained from the technical cashew nutshell liquid (t-CNSL). Spectroscopic techniques confirmed the polymer formation. The polymer was dispersed in the ethyl acetate solvent and used to form coatings on 316L steel substrates. The coated samples were subjected to electrochemical tests in a saline environment. The coated electrode with poly(t-CNSL) polymer was exposed to the corrosive medium for 24 days, and superior corrosion protection was observed compared with the uncoated sample. The open circuit potential measurements showed that the coated sample possessed a more positive corrosion potential when compared with the uncoated substrate. The electrochemical impedance spectroscopy results indicated that the coated electrode's polarization resistance (R_p) recorded ~1.0 MΩ cm² after 24 days of exposure. A decrease in polarization resistance was observed with the exposure time due to the presence of micropores in the t-CNSL coating. The polarization curves exhibited that the coated electrode with poly(t-CNSL) has lower corrosion current density and less negative corrosion potential than the uncoated steel electrode. Therefore, t-CNSL favors the manufacture of thin poly(t-CNSL) coatings for corrosion protection purposes besides being a low-cost material.     

Polybithiophene and its bilayers with polyaniline coatings on stainless steel by electropolymerization in aqueous medium

For the first time, electrosynthesis of polybithiophene (PBTh) and its bilayers with polyaniline (PAni) coatings on stainless steel (SS) in aqueous oxalic acid solutions containing monomer and sodium dodecyl sulfate (SDS) was carried out by potentiodynamic synthesis technique. Smooth and adherent films were obtained on the steel surfaces. Homopolymers and bilayers were characterized by cyclic voltammetry, FTIR, UV–vis spectroscopies and SEM. Homopolymers were also characterized by means of conductivity and the number average molecular weight measurements. The effects of the scanning potential limits on electrosynthesis of PBTh and its bilayer coatings were investigated. The test for corrosion protection of the polymer coated and uncoated SS substrates were performed in highly aggressive 0.5 M NaCl and 0.5 M HCl solutions by linear potentiodynamic polarization and Tafel test technique, respectively. Corrosion test revealed that among the protective coatings obtained, PBTh as homopolymer and PAni/PBTh as bilayer exhibited the most effective anticorrosive properties. According to linear potendynamic polarization test, the dissolution current of these coatings at 1.6 V decreased to 99.8% and 99.6% in NaCl solution, respectively, when compared to that of uncoated SS surfaces.     

Electropolymerization of poly(N-ethyl aniline) on mild steel: Synthesis, characterization and corrosion protection

Poly(N-ethylaniline) (PNEA) coatings on the mild steel electrode were synthesized by electrochemical oxidation of N-ethylaniline using aqueous oxalic acid solutions as reaction medium. Electrodeposition was carried out by potentiodynamic, potentiostatic and galvanostatic synthesis techniques. Smooth, adhesive and thick PNEA coatings on mild steel could be electrosynthesized during sequential scanning of the potential region between −0.5 and 1.4 V versus SCE, with scan rate of 20 mV s⁻¹. The electrodeposited coatings were characterized by cyclic voltammetry, FT-IR and UV-vis techniques. Corrosion behavior of PNEA coated steels was investigated by linear anodic potentiodynamic polarization technique and Tafel test. Anodic potentiodynamic polarization results showed that electrodissolution current value of PNEA coated steel decreased about 90% compared to that of the uncoated steel in 0.5 M H₂SO₄ aqueous solution. Tafel plots showed also strong decrease of corrosion current for the PNEA coated electrode compared to the uncoated steel electrode in 3% NaCl as corrosive medium.     

Structure,mechanical and corrosion properties of DC reactive magnetron sputtered aluminum nitride (AlN) hard coatings on mild steel substrates

Aluminum nitride (AlN) coatings of about 2 μm thick were deposited on mild steel (MS) by means of direct current (DC) reactive magnetron sputtering. AlN coatings were prepared in an Ar + N₂ gas mixture and their crystal structure, microstructure, and topography were analyzed by X-ray diffractometry (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM), respectively. XRD revealed that the films are polycrystalline in nature and have a hexagonal wurtzite structure with a predominant peak observed along the (002) plane. SEM and AFM images showed the presence of continuously covered pebble like spherical grains on the surface. These coatings showed lower coefficient of friction and excellent wear resistance compared to the bare MS substrate. The potentiodynamic polarization studies showed lower corrosion current density and higher polarization resistance for the AlN/MS structure than the uncoated MS substrate.     

Electrochemical and time-of-flight secondary ion mass spectrometry analysis of ultra-thin metal oxide (Al2O3 and Ta2O5) coatings deposited by atomic layer deposition on stainless steel

Ultra-thin (5–50 nm) layers of aluminium and tantalum oxides deposited by atomic layer deposition (ALD) on a stainless steel substrate (316L) for corrosion protection have been investigated by electrochemical methods (linear scan voltammetry, LSV, and electrochemical impedance spectroscopy, EIS) and time-of-flight secondary ion mass spectrometry, ToF-SIMS. The effects of the deposition temperature (250 °C and 160 °C) and coating thickness were addressed. ToF-SIMS elemental depth profiling shows a marked effect of the organic and water precursors used for deposition and of the substrate surface contamination on the level of C and OH trace contamination in the coating, and a beneficial effect of increasing the deposition temperature. The polarization data show a decrease of the current density by up to four orders of magnitude with increasing coating thickness from 5 to 50 nm. The 50 nm films block the pitting corrosion in 0.8 M NaCl. The uncoated surface fraction (quantified from the current density and allowing a ranking of the efficiency of the coating, also confirmed by the capacitance and resistance values extracted from the EIS data) was 0.03% with a 50 nm thick Al₂O₃ film deposited at 250 °C. The correlation between the porosity values of the coatings and the level of C and OH traces observed by ToF-SIMS points to a marked effect of the coating contaminants on the sealing performance of the coatings and on the corrosion resistance of the coated systems.     

The inhibition of corrosion and hydrogen embrittlement of AISI 410 stainless steel

A study was carried out on the inhibition of corrosion and hydrogen embrittlement of AISI 410 stainless steel by two organic inhibitors, namely benzotriazole and benzonitrile. Tensile testing, scanning electron microscopy, weight loss measurements and potentiodynamic polarization were the techniques used for this study. Tensile tests showed that 410 steel is highly susceptible to hydrogen stress cracking. Scanning electron microscopic observations of fracture surfaces showed a brittle quasi-cleavage type of failure when the steel was hydrogen charged from 0.5m H₂SO₄. Both inhibitors reduced hydrogen induced ductility loss though the fracture mode was unaltered. They showed increasing inhibition efficiencies for corrosion as well as cathodic hydrogen evolution as their concentration in H₂SO₄ increased from 3.9×10^–5 m to 8.4×10^–3 m. Benzonitrile was found to be a more efficient inhibitor than benzotriazole for AISI 410 stainless steel exposed to 0.5m H₂SO₄.     

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.     

Effects of cold work and sensitization treatment on the corrosion resistance of high nitrogen stainless steel in chloride solutions

The effects of cold work and sensitization treatment on the microstructure and corrosion resistance of a nickel-free high nitrogen stainless steel (HNSS) in 0.5 M H₂SO₄ + 0.5 M NaCl, 3.5% NaCl and 0.5 M NaOH + 0.5 M NaCl solutions have been investigated by microscopic observations, electrochemical tests and surface chemical analysis. Cold work introduced a high defect density into the matrix, resulting in a less protective passive film as well as reduced corrosion resistance for heavily cold worked HNSS in a 3.5% NaCl solution. No obvious degradation in corrosion resistance took place in a 0.5 M H₂SO₄ + 0.5 M NaCl solution, possibly due to the stability of the passive film in this solution. Sensitized HNSSs showed reduced corrosion resistance with increasing cold work level in both 3.5% NaCl and 0.5 M H₂SO₄ + 0.5 M NaCl solutions due to a reduction in the anti-corrosion elements in the matrix during the cold work-accelerated precipitation process. The cold work and sensitization treatment had no influence on the corrosion resistance of the HNSS in the 0.5 M NaOH + 0.5 M NaCl solution even though the property of the passive film changed. The effects of cold work and sensitization treatment on the characteristics of passive films formed in the three solutions are discussed.     

Anticorrosion efficiency of organic coatings depending on the pigment volume concentration of polyaniline phosphate

Polyaniline (PANI) was synthesized by reaction in an aqueous solution of ammonium peroxodisulfate and phosphoric acid. PANI was characterized by means of scanning electron microscopy and its physical–chemical properties were determined. Simultaneously with the synthesized PANI epoxy-ester coatings containing 3, 5, 10, 15, 20 and 24 vol.% of PANI as a corrosion inhibitor were formulated. The coatings were tested for their mechanical properties, film hardness and corrosion resistance. The testing of the anticorrosion efficiency of PANI as corrosion inhibitor was based on accelerated corrosion tests: in condensed water, NaCl mist, and condensing water and SO₂. The prepared PANI displayed inhibition effects in corrosion reactions progressing on a steel base under the organic coating. The synthesized PANI provides good anticorrosion efficiency in an epoxy-ester coating. The studied system does not contain any heavy metals harmful to the environment.     

Monolayer and bilayer conducting polymer coatings for corrosion protection of steel in 1 M H2SO4 solution

In this study, monolayer polypyrrole (PPY), polyaniline (PANI), and bilayer PPY/PANI, PANI/PPY coatings were deposited onto steel electrodes by electropolymerization in 0.1 M monomer and 0.3 M oxalic acid solution. Such corrosion parameters of these electrodes, as corrosion potentials, anodic Tafel constants and corrosion current densities were determined by means of current–potential curves as a function of time in 1 M H₂SO₄ solution. These findings were compared to the corrosion parameters of a bare steel electrode in the same acid solution. The monolayer and bilayer polymer coatings were characterized by the Fourier transform infrared (FTIR) spectroscopy and SEM. Bilayer coatings displayed better corrosion inhibition efficiencies than monolayer coatings. Furthermore, the PPY/PANI coatings offered superior corrosion protection than the PANI/PPY coatings.     

Corrosion behavior of titania films coated by liquid‐phase deposition on AISI304 stainless steel substrates

Fouling deposition and localized corrosion on the heat‐transfer surfaces of the stainless steel equipments often simultaneously exist, which can introduce additional thermal resistance to heat‐transfer and damage heat‐transfer surfaces. It is a good anticorrosion way to coat a barrier layer of certain materials on the metal surface. In this article, the TiO₂ coatings with nanoscale thicknesses were obtained by liquid‐phase deposition method on the substrates of AISI304 stainless steel (ASS). The coating thickness, surface roughness, surface morphology, crystal phase, and chemical element were characterized with the film thickness measuring instrument, roughmeter, atomic force microscopy, field emission scanning electron microscopy, X‐ray diffraction, and energy‐dispersive X‐ray spectroscopy analyzer, respectively. Corrosion behavior of the TiO₂ coatings was evaluated by potentiodynamic polarization, cyclic voltammograms scanning, and electrochemical impedance spectroscopy tests with the mixed corrosion solution composed of 3.5 wt. % NaCl and 0.05 M NaOH. It is shown that the TiO₂ coating is composed of the nanoparticles with smooth, crack‐free, dense, and uniform surface topography; the roughness of coating surface increases slightly compared with that of the polished ASS substrate. The anatase‐phase TiO₂ coatings are obtained when sintering temperature being varied from 573.15 to 923.15 K and exhibit better anticorrosion behavior compared with ASS surfaces. The corrosion current density decreases and the polarization resistance increases with the increase of the coating thickness. The corrosion resistance of the TiO₂ coatings deteriorates with the increase of the corrosion time. The capacitance and the resistance of the corrosion product layer between the interface of the ASS substrate and the TiO₂ coating are found after the corrosion time of 240 h. A corrosion model was introduced, and a possible new explanation on the anticorrosion mechanisms of the TiO₂ coating was also analyzed. The corrosion mechanism of the TiO₂ coating might comply with the multistage corrosion process. © 2011 American Institute of Chemical Engineers AIChE J, 58: 1907–1920, 2012     

Effect of electroless nickel interlayer on the electrochemical behavior of single layer CrN, TiN, TiAlN coatings and nanolayered TiAlN/CrN multilayer coatings prepared by reactive dc magnetron sputtering

The electrochemical behavior of single layer TiN, CrN, TiAlN and multilayer TiAlN/CrN coatings, deposited on steel substrates using a multi-target reactive direct current (dc) magnetron sputtering process, was studied in 3.5% NaCl solution. The total thickness of the coatings was about 1.5 μm. About 0.5 μm thick chromium interlayer was used to improve adhesion of the coatings. With an aim to improve the corrosion resistance, an additional interlayer of approximately 5 μm thick electroless nickel (EN) was deposited on the substrate. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) were used to study the corrosion behavior of the coatings. Scanning electron microscopy and energy dispersive X-ray analysis were used to characterize the corroded samples. The potentiodynamic polarization tests showed lower corrosion current density and higher polarization resistance (R_p) for the coatings with EN interlayer. For example, the corrosion current density of TiN coated steel was decreased by a factor of 10 by incorporating 5 μm thick EN interlayer. Similarly, multilayer coatings of TiAlN/CrN with EN interlayer showed about 30 times improved corrosion resistance as compared to the multilayers without EN interlayer. The porosity values were calculated from the potentiodynamic polarization data. The Nyquist and the Bode plots obtained from the EIS data were fitted by appropriate equivalent circuits. The pore resistance (R_pore), the charge transfer resistance (R_ct), the coating capacitance (Q_coat) and the double layer capacitance (Q_dl) of the coatings were obtained from the equivalent circuit. Multilayer coatings showed higher R_pore and R_ct values as compared to the single layer coatings. Similarly, the Q_coat and Q_dl values decreased from uncoated substrate to the multilayer coatings, indicating a decrease in the defect density by the addition of EN interlayer. These studies were confirmed by examining the corroded samples under scanning electron microscopy.     

Electrical properties of polyaniline films formed in acid with and without Cs+ ions in the electrolyte

The effect of Cs⁺ ions added to the electrolyte for polyaniline films electrosynthesized in 0.1 m aniline/0.5m H₂SO₄ was investigated. Some properties of PANI films, such as the capacitance, the ohmic resistance and the charge-transfer resistance were obtained using electrochemical impedance spectroscopy. It was found that Cs⁺ ions used during PANI synthesis change its morphology, with a consequent increase in capacitance and conductivity, and a decrease in charge-transfer resistance.     

Corrosion protection of carbon steel by thin films of poly(3-alkyl thiophenes) in 0.5 M H2SO4

Poly(3-octyl thiophene) (P3OT) and poly(3-hexylthiophene) (P3HT) dissolved in toluene were deposited onto 1018 carbon steel and corroded in 0.5 M H₂SO₄. P3OT and P3HT films were chemically deposited by drop casting onto 1018-type carbon steel with two surface finishing, i.e. abraded with 600-emery paper and with alumina (Al₂O₃) particles of 1.0 μm in diameter (mirror finish). Their corrosion resistance was estimated by using potentiodynamic polarization curves, linear polarization resistance (LPR), and electrochemical impedance spectroscopy, EIS, techniques. In all cases, polymeric films protected the substrate against corrosion, but the protection was improved if the surface was polished with Al₂O₃ particles of 1.0 μm in diameter. The polymer which gave the best protection was P3HT because the amount of defects was much lower than that for the P3OT films. The polymers did not act only as a barrier layer against aggressive environment, but they improved the passive film properties by decreasing the critical current necessary to passivate the substrate, increasing the pitting potential and broadening the passive interval.     

Conducting polymer based hybrid nano-composites for enhanced corrosion protective coatings

Hybrid composite coatings containing zinc oxide (ZnO) and polyaniline (PANI) as nano-additives dispersions were prepared with poly(vinyl acetate) (PVAc) as the major matrix. The steel plates dip-coated with these formulations were tested for corrosion protection by immersion in saline water over long periods. The Tafel plots for the determination of open circuit potential (OCP) and corrosion current (I_corr) were recorded. The coatings containing both ZnO and PANI showed improved corrosion resistance as compared to the single component coating. The I_corr values of PVAc–ZnO–PANI are found to be two-order magnitude lower than that of PVAc and PVAc–ZnO coatings. The results are explained on the basis of enhancement in barrier properties due to nano-particulate additives in PVAc–ZnO–PANI film together with the redox behaviour of PANI and protective oxide layer formation near the substrate.     

Impedance spectroscopy study of anodic growth of thick zirconium oxide films in H2SO4, Na2SO4 and NaOH solutions

Anodic zirconium oxide films were grown potentiodynamically at a constant sweep rate up to the breakdown potential on rod electrodes made of 99.8% metallic zirconium. Different media of different pH were tested, namely 0.5 M H₂SO₄ (pH 0.3), 0.1 M Na₂SO₄ (pH 9) and 0.1 M NaOH (pH 13). By electrochemical impedance spectroscopy and scanning electron microscopy the oxide film thickness was monitored during the voltage scan. The behaviour was found to be different in the presence and absence of sulphate anions. In the presence of SO₄²⁻, the films were dense but breakdown occurred at 300–340 nm. In NaOH, two relaxations appeared above 50 V and were ascribed to a bi-layered coating structure and the maximum layer thickness was 720 nm before breakdown.