Electrochemical synthesis of polythiophene on nickel coated mild steel and corrosion performance

Electrochemical polymerization of polythiophene (PTh) was investigated on nickel coated mild steel (MS) electrode, in LiClO₄ containing acetonitrile medium (ACN-LiClO₄). Nickel layer (1 μm thick) was deposited galvanostatically, from a proper bath solution. Then, the synthesis of PTh film was achieved in 0.1 M thiophene containing ACN-LiClO₄, by using cyclic voltammetry technique. The corrosion performances of nickel coated samples with and without polymer top coats were investigated in 3.5% NaCl solution, by using electrochemical impedance spectroscopy (EIS) and anodic polarization curves. The nickel coating behaved like a physical barrier and provided some protection to MS against corrosion. But its barrier property diminished significantly with time and failed to protect MS. It was shown that PTh top coat improved the barrier efficiency remarkably, and excellent protection efficiency was obtained against MS corrosion, for considerable exposure time in such aggressive environment.     

Electrodeposition of polyaniline, poly(2-iodoaniline), and poly(aniline-co-2-iodoaniline) on steel surfaces and corrosion protection of steel

Polyaniline (PANi), poly(2-iodoaniline) (PIANi), and poly(aniline-co-2-iodoaniline) (co-PIANi) were synthesized using cyclic voltammetry in acetonitrile solution containing tetrabuthylammonium perchlorate (TBAP) and perchloric acid (HClO₄) on 304-stainless steel electrodes. Adherent and black polymer films were obtained on the electrodes. The structure and properties of these polymer films were characterized by FTIR and UV-vis spectroscopy and electrochemical method. The corrosion performance of PANi, PIANi, and co-PIANi coated electrodes were investigated in 0.5 M hydrochloric acid (HCl) solutions by potentiodynamic polarization technique, open circuit potential-time curves and electrochemical impedance spectroscopy, EIS. It was found that the PANi film could provide much better protection than PIANi, and co-PIANi and PANi films have barrier property as well as acting as passivator. On the other hand PIANi and co-PIANi films are acting as barrier coatings which were related with the prevention of cathodic reaction taking place at metal\electrolyte interface. EIS measurement shows that every coating gives protection efficiency of greater than 75% after 48 h of immersion time in corrosive test solution.     

Synthesis, characterization, and corrosion protection properties of poly(N-(methacryloyloxymethyl) benzotriazole-co-methyl methacrylate) on mild steel

The copolymers from different feed ratios of N-(methacryloyloxymethyl) benzotriazole (MMBT) and methyl methacrylate (MMA) has been synthesised using free radical solution polymerization technique and characterized using FT-IR and ¹³C NMR spectroscopy. The thermal stability of the polymers was studied using theremogravimetrtic analysis (TGA). The corrosion behaviors of mild steel specimens dip coated with different composition of copolymers have been evaluated by potentiodynamic polarization and electrochemical impedance spectroscopic (EIS) method. These electrochemical properties were observed in 0.1 M HCl medium. The polarization and impedance measurements showed different corrosion protection efficiency with change in composition of the copolymers. It was found that the corrosion protection properties are owing to the barrier effect of the polymer layer covered on the mild steel surfaces. However, it was observed that the copolymer obtained from 1:1 mole ratio of MMBT and MMA exhibited better protection efficiency than other combinations.     

A novel electrodeposited Cu-Zn-Bi film with increased corrosion resistance in a 0.05 M K2SO4 solution

A single phase Cu-Zn-Bi film is fabricated on the steel wire by electrodeposition. Bi addition (∼1 wt.%) greatly increases the corrosion resistance of brass (Cu−36 wt.% Zn) film in a 0.05 M K₂SO₄ solution as shown by potentiodynamic polarization and electrochemical impendence spectroscopy (EIS) experiments. It is proposed that the main reason for the improvement in the corrosion resistance by the Bi addition is that it greatly increased the crack resistance, which thus prevents crack-induced galvanic corrosion occurring between the brass film and the steel substrate.     

Enhanced corrosion resistance of mild steel in normal sulfuric acid medium by 2,5-bis(n-thienyl)-1,3,4-thiadiazoles: Electrochemical, X-ray photoelectron spectroscopy and theoretical studies

The inhibitive action of some thiadiazole derivatives, namely 2,5-bis(2-thienyl)-1,3,4-thiadiazole (2-TTH) and 2,5-bis(3-thienyl)-1,3,4-thiadiazole (3-TTH) against the corrosion of mild steel in 0.5 M H₂SO₄ solution has been investigated using weight loss measurements, Tafel polarisation and electrochemical impedance spectroscopy (EIS) techniques. The experimental results obtained revealed that these compounds inhibited the steel corrosion in acid solution. The protection efficiency increased with increasing inhibitors concentration and the ability of the molecule to adsorb on the steel surface was dependent on the position of the sulphur atom on the thienyl substituent. Inhibition efficiency values obtained from various methods employed were in reasonable agreement. Potentiodynamic polarisation studies clearly showed that 2-TTH and 3-TTH acted as mixed inhibitors. Adsorption of these inhibitors on steel surface obeyed to Langmuir adsorption isotherm. X-ray photoelectron spectroscopy and the thermodynamic data of adsorption showed that inhibition of steel corrosion in normal sulphuric solution by n-TTH is due to the formation of a chemisorbed film on the steel surface. Molecular modelling was used to gain some insight, about structural and electronic effects in relation to the inhibiting efficiencies.     

Characterisation of the anodic layers formed on 2024 aluminium alloy, in tetraborate electrolyte containing molybdate ions

Anodic layer growth on 2024 aluminium alloy at 70 °C, under 40 V, during 60 min, in 50 g L⁻¹ di-sodium tetraborate solution containing di-sodium molybdate from 0.1 to 0.5 M (pH 10) is examined. Anodising behaviours strongly depend on additive concentration. Development of anodic films is favoured with weak molybdate additions (<0.3-0.4 M). The film thicknesses increase and the porosity of anodic layers decreases. Molybdenum (+VI), detected by X-ray photoelectron spectroscopy (XPS) analysis, is present in the anodic films and the Mo incorporation, studied by energy dispersive spectroscopy (EDS) analysis, increases with molybdate concentration. However, for high molybdate concentrations (>0.4 M), anodising behaviour becomes complex with the formation of a blue molybdenum oxide at the cathode. The growth of aluminium oxide is hindered. As the anodic layers are thinner, the Mo(+VI) incorporation significantly decreases. These two configurations implicate different corrosion performances in 5% sodium chloride solution at 35 °C. As the alkaline anodic layer formed with 0.3 M molybdate species is the thickest and the Mo incorporation is the more pronounced, its corrosion resistance is the highest. The effect of morphology and composition of anodic films on pitting corrosion is also discussed.     

Electrochemical synthesis of poly-6-amino-m-cresol (poly-AmC)

The electropolymerization of 6-amino-m-cresol (AmC) on a platinum electrode was studied in 0.1 M Na₂SO₄ solution containing 5 × 10⁻³ M 6-amino-m-cresol at different pHs using cyclic voltammetry technique. Voltammetric results showed that oxidation of 6-amino-m-cresol produced a passivating polymeric film on the platinum surface at all pHs studied. Synthesized polymer has bronze color on platinum. To investigate the structure of poly-6-amino-m-cresol (poly-AmC) films FTIR technique was employed. The spectroscopic results indicate that polymer chain consist of ring opened units rather than phenoxazine structure.     

Studies on corrosion protection of Al2024 T6 alloy by electropolymerized polyaniline coating

Aqueous electropolymerized polymer coatings on aluminum alloys can replace the carcinogenic chromate coating. In this work, the corrosion protection ability of electropolymerized polyaniline coating on Al2024 T6 alloy has been found out. The polyaniline coatings on aluminum were formed by galvanostatic and potentiostatic methods from a bath of 0.5 M oxalic acid containing 0.1 M aniline. The corrosion protection ability of the coating was found out by Tafel polarization and EIS in 1% NaCl solution. It has been found that polyaniline coated aluminum alloy has exhibited higher corrosion activity due to the presence of pores in the coating. However, the corrosion resistant property of polyaniline coated aluminum has been found to be improved to 90% by post-treatment in cerium containing solution at 60 °C.     

Mild steel protection with epoxy top coated polypyrrole and polyaniline in 3.5% NaCl

In this study, the corrosion behaviours of mild steel (MS) samples coated with single epoxy polyamine (MS/E), epoxy polyamine top-coated polypyrrole (MS/PPy/E) and polyaniline (MS/PANI/E) were investigated in 3.5% NaCl solution of pH 8. For this purpose, electrochemical impedance spectroscopy (EIS) and polarisation resistance measurements were utilized when the centres of the electrode surfaces were scratched. It was found that the PPy film reduced the corrosion protection efficiency of the epoxy coating when it was used as the primary film under the epoxy layer. The primary PANI coating was shown to improve significantly the protection efficiency of the epoxy coating against mild steel corrosion. This was related to its healing effect on surface passivation against attack by a corrosive environment along a defect.     

Berberine as a natural source inhibitor for mild steel in 1 M H2SO4

Berberine was abstracted from coptis chinensis and its inhibition efficiency on corrosion of mild steel in 1 M H₂SO₄ was investigated through weight loss experiment, electrochemical techniques and scanning electronic microscope (SEM) with energy disperse spectrometer (EDS). The weight loss results showed that berberine is an excellent corrosion inhibitor for mild steel immersed in 1 M H₂SO₄. Potentiodynamic curves suggested that berberine suppressed both cathodic and anodic processes for its concentrations higher than 1.0 × 10⁻⁴ M and mainly cathodic reaction was suppressed for lower concentrations. The Nyquist diagrams of impedance for mild steel in 1 M H₂SO₄ containing berberine with different concentrations showed one capacitive loop, and the polarization resistance increased with the inhibitor concentration rising. A good fit to Flory-Huggins isotherm was obtained between surface coverage degree and inhibitor concentration. The surface morphology and EDS analysis for mild steel specimens in sulfuric acid in the absence and presence of the inhibitor also proved the results obtained by the weight loss and electrochemical experiments. The correlation of inhibition effect and molecular structure of berberine was then discussed by quantum chemistry study.     

Growth process of atomically flat anodic films on titanium under potentiostatical electrochemical treatment in H2SO4 solution

The as-deposited titanium film on silicon wafer was electrochemically treated in potential sweep and potential step modes in 0.1 M H₂SO₄ solution at 30 °C. Under the anodization conditions of potential sweep and properly modulated cyclic voltammetry (CV), nanoscale grains, step-terrace structure and atomic images were clearly observed on the surface of anodic oxide film on titanium. Under potential step conditions, if the anodization time was short (1 s), no grains could be found on the anodic oxide film surface, even though the potential was high up to 9000 mV. Moreover, whatever potential sweep or potential step mode was performed, sufficient time (low sweep rate means a prolonged anodization time) was needed for the formation of nanoscale grains, atomically flat surface and step-terrace structure on the anodized titanium film.     

Corrosion behavior of boride layers evaluated by the EIS technique

The corrosion behavior of boride layers at the AISI 304 steel surface is evaluated in the present study. Electrochemical impedance spectroscopy (EIS) technique was used for the evaluation of the polarization resistance at the steel surface, with the aid of AUTOLAB potentiostat. Samples were treated with boron paste thickness of 4 and 5 mm, in the range of temperatures 1123 ≤ T ≤ 1273 K and exposed time of 4 and 6 h. The electrochemical technique employed 10 mV AC with a frequency scan range from 8 kHz to 3 mHz in deaerated 0.1 M NaCl solution. Nyquist diagrams show that the highest values of corrosion resistance are present in the samples borided at the temperature of 1273 K, with treatment time of 4 h and 4 mm of boron paste thickness. The values of corrosion resistance on borided steels are compared with the porosity exhibited in the layers.     

Corrosion resistant surface for vanadium nitride and hafnium nitride layers as function of grain size

In this research it was studied vanadium nitride (VN) and hafnium nitride (HfN) film, which were deposited onto silicon (Si (100)) and AISI 4140 steel substrates via r.f. magnetron sputtering technique in Ar/N₂ atmosphere with purity at 99.99% for both V and Hf metallic targets. Both films were approximately 1.2±0.1 µm thick. The crystallography structures that were evaluated via X-ray diffraction analysis (XRD) showed preferential orientations in the Bragg planes VN (200) and HfN (111). The chemical compositions for both films were characterized by EDX. Atomic Force Microscopy (AFM) was used to study the morphology; the results reveal grain sizes of 78±2 nm for VN and 58±2 nm for HfN and roughness values of 4.2±0.1 nm for VN and 1.5±0.1 nm for HfN films. The electrochemical performance in VN and HfN films deposited onto steel 4140 were studied by Tafel polarization curves and impedance spectroscopy methods (EIS) under contact with sodium chloride at 3.5 wt% solution, therefore, it was found that the corrosion rate decreased about 95% in VN and 99% for HfN films in relation to uncoated 4140 steel, thus demonstrating, the protecting effect of VN and HfN films under a corrosive environment as function of morphological characteristics (grain size).     

Structural characterization and properties of lanthanum film as chromate replacement for tinplate

Sulfide-stain resistance of La-passivated, unpassivated and Cr-passivated tinplate was measured using a cysteine tarnish test. Corrosion behavior of these tinplates was investigated using electrochemical impedance spectroscopy (EIS) measurement. The morphology, composition and thickness of lanthanum film were studied by atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and X-ray fluorescence spectrometry (XRF), respectively. La-passivation treatment remarkably enhances sulfide-stain resistance of tinplate, and sulfide-stain resistance of La-passivated tinplate is slightly higher than that of Cr-passivated tinplate. La-passivation treatment also significantly improves corrosion protection property of tinplate. In contact with 3.5% NaCl solution, corrosion resistance of La-passivated tinplate is close to that of Cr-passivated tinplate, and in contact with 0.1 M citric-citrate buffer solution, corrosion resistance of La-passivated tinplate is higher than that of Cr-passivated tinplate. Lanthanum film is composed of spherical particles about 50-1000 nm in diameter, while most part of tinplate's surface is covered with the small particles about 50-200 nm. The film mainly consists of lanthanum and oxygen, which mainly exist as La₂O₃ and its hydrates such as La(OH)₃ and LaOOH. The amount of lanthanum in the film is about 0.0409 g/m².     

Characterization and corrosion studies of titania-coated NiTi prepared by sol-gel technique and steam crystallization

Nickel titanium (NiTi) was dip-coated with titania via the sol-gel route using titanium butoxide (Ti(OC₄H₉)₄) as precursor. The as-coated titania film was crystallized to form anatase by treatment in steam at 105 °C. The crystallized film was relatively thick (about 750 nm) and even. Atomic force microscopy (AFM) revealed that the film was dense with a surface roughness of about 3 nm, and was composed of particles of about 100 nm. X-ray diffractometry (XRD) showed that these particles were composed of nanocrystallites of a few nanometers. Nanoindentation tests of the titania film indicated that the film was tough, possibly due to the nano-size of the crystallites. The mean hardness H and elastic modulus E of the coating were about 1.5 and 70 GPa, respectively. Direct pull-off test recorded a mean coating-substrate bonding strength larger than 17 MPa. Electrochemical impedance spectroscopic (EIS) study and cyclic polarization tests showed that the corrosion resistance of the coated NiTi samples in Hanks’ solution was increased by about two orders of magnitude compared with the substrate. Taken together, the present study showed that steam crystallization is a feasible low-temperature treatment method for sol-gel derived titania coating on NiTi in biomedical applications.     

Effect of deformation on the electrochemical behavior of hot-dip galvanized steel sheets

The main purpose of employing pre-coated steel sheets is to minimize corrosion of steel. However, coatings can be severely affected by forming processes. In the forming processes, due to the different modes of deformation, the strain levels are different and so can affect the properties of the coatings to a varying degree. Special attention has to be paid to the influence of deformation conditions on the performance of the coating, as regards protection against corrosion. The adhesion of the coating must remain good, and the surface should not be damaged during forming. Therefore, it is necessary to study the behavior of its corrosion resistance against the deformation.In this work, effect of strain path on the corrosion behavior of hot-dip galvanized steel sheets has been studied. Corrosion behavior of hot-dip galvanized steel sheets at various strain levels has been evaluated under four different strain paths namely, biaxial, plane strain, uniaxial (drawing) and tensile modes. The sheets were deformed by a limiting dome height test (LDH) set-up. A correlation between the degree of deformation and the loss in extent of corrosion protection offered by the coating has been established by carrying out electrochemical studies such as potentiodynamic polarization and impedance spectroscopy (EIS) in 3.5% NaCl solution. The present study shows that increase in deformation increases the extent of delamination of the coating for all the modes of deformation. The severity of deformation on delamination, however, has been found to vary in the order of, tensile < uniaxial < plane < biaxial.     

Corrosive behavior of chromium carbide-based films formed on steel using a filtered cathodic vacuum arc system

The formation of chromium carbide-based hard-coatings on steels using a 90°-bend filtered cathodic vacuum arc (FCVA) has extensive industrial applications; such coatings are free of macroparticles and exhibit excellent characteristics. In this investigation, a working pressure of C₂H₂/Ar was adopted to synthesize amorphous chromium carbide film (a-C:Cr) and crystalline chromium carbide film (cryst-Cr₃C₂) from a Cr target (99.95%) at 500 °C under a substrate voltage of −50 V. The corrosion behavior of a-C:Cr coated on steel (a-C:Cr/steel) and cryst-Cr₃C₂ coated on steel (cryst-Cr₃C₂/steel) were compared in terms of open-circuit potentials (OCP) and polarization resistance (R_p) in an aerated 3.5 wt% NaCl aqueous solution, as determined by electrochemical impedance spectroscopy (EIS). The XRD results indicated that the transformation of a-C:Cr to cryst-Cr₃C₂ is distinct as the working pressure declines from 1.2 × 10⁻² to 2.9 × 10⁻³ Torr. The OCP of a-C:Cr/steel and cryst-Cr₃C₂/steel resemble each other and both assembly are nobler than uncoated steel. The R_p of the coatings exceeds that of the uncoated steel. The SEM observation and the EIS results demonstrate that the cryst-Cr₃C₂/steel more effectively isolates the defects than dose a-C:Cr/steel.     

Preparation of superhydrophobic films on titanium as effective corrosion barriers

Stable superhydrophobic films were prepared on the electrochemical oxidized titania/titanium substrate by a simple immersion technique into a methanol solution of hydrolyzed 1H,1H,2H,2H-perfluorooctyltriethoxysilane [CF₃(CF₂)₅(CH₂)₂Si(OCH₂CH₃)₃, PTES] for 1 h at room temperature followed by a short annealing at 140 °C in air for 1 h. The surface morphologies and chemical composition of the film were characterized by means of water contact angle (CA), field emission scanning electron microscopy (FESEM), atomic force microscope (AFM) and X-ray photoelectron spectroscopy (XPS). The water contact angle on the surface of this film was measured to be as high as 160°. SEM images showed that the resulting surfaces exhibited special hierarchical structure. The special hierarchical structure along with the low surface energy leads to the high surface superhydrophobicity. The corrosion resistance ability and durance property of the superhydrophobic film in 3.5 wt.% NaCl solution was evaluated by the electrochemical impedance spectroscopy (EIS). The anticorrosion properties of the superhydrophobic film are compared to those of unmodified pure titanium and titania/titanium substrates. The results showed that the superhydrophobic film provides an effective corrosion resistant coating for the titanium metal even with immersion periods up to 90 d in the 3.5 wt.% NaCl solution, pointing to promising future applications.     

Development of electroless Ni-Zn-P/nano-TiO2 composite coatings and their properties

Ni-Zn-P-TiO₂ composite coatings were successfully obtained on low carbon steel by electroless plating technique. Deposits were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive analysis (EDS) studies. The hardness and microstructure of as plated and heat treated Ni-Zn-P and Ni-Zn-P-TiO₂ composite coatings were analyzed. The change in microstructure and higher hardness was noticed for heat treated composite. The corrosion resistance behavior of as plated and heat treated Ni-Zn-P and Ni-Zn-P-TiO₂ coatings was investigated by anodic polarization, Tafel plots and electrochemical impedance spectroscopic (EIS) studies in 3.5 wt% NaCl solution. The composite coating exhibited enhanced corrosion resistance property over Ni-Zn-P coating.     

Experimental and theoretical study for corrosion inhibition of mild steel in hydrochloric acid solution by some new hydrazine carbodithioic acid derivatives

The corrosion inhibition of mild steel in 0.5 M hydrochloric acid solutions by some new hydrazine carbodithioic acid derivatives namely N′-furan-2-yl-methylene-hydrazine carbodithioic acid (A), N′-(4-dimethylamino-benzylidene)-hydrazine carbodithioic acid (B) and N′-(3-nitro-benzylidene)-hydrazine carbodithioic (C) was studied using chemical (weight loss) and electrochemical (potentiodynamic and electrochemical impedance spectroscopy, EIS) measurements. These measurements show that the inhibition efficiency obtained by these compounds increased by increasing their concentration. The inhibition efficiency follow the order C > B > A. Polarization studies show that these compounds act as mixed type inhibitors in 0.5 M HCl solutions. These inhibitors function through adsorption following Langmuir isotherm. The electronic properties of these inhibitors, obtained using PM3 semi-empirical self-consistence field method, have been correlated with their experimental efficiencies using non-linear regression method.