Corrosion behaviour of galvanized steel and electroplating steel in aqueous solution: AC impedance study and XPS

The efficiency of a new triazole derivative, namely, 2-{(2-hydroxyethyl)[(4-methyl-1H-1,2,3-benzotriazol-1-yl)methyl]amino}ethanol (TTA) has been studied for corrosion inhibition of galvanized steel and electroplating steel in aqueous solution. Corrosion inhibition was studied using electrochemical impedance spectroscopy (EIS). These studies have shown that TTA was a very good inhibitor. Data obtained from EIS show a frequency distribution and therefore a modelling element with frequency dispersion behaviour, a constant phase element (CPE) has been used. The corrosion behaviour of galvanized steel and electroplating steel in aqueous solution was also investigated in the presence of 4-methyl-1H-benzotriazole (TTA unsubstituted) by EIS. These studies have shown that the ability of the molecule to adsorb on the steel surface was dependent on the group in triazole ring substituent. X-ray photoelectron spectroscopy surface analysis with TTA shows that it chemisorbed on surface of galvanized steel and electroplating steel.     

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.     

Corrosion behaviour of AISI 304 stainless steel with Cu coatings in H2SO4

The work addresses the influence of cementation and electrodeposition of copper coatings on the corrosion resistance of AISI 304 stainless steel immersed in 30 wt.% H₂SO₄ at temperatures of 25 and 50 °C. Corrosion process was evaluated by gravimetric tests, DC measurements and electrochemical impedance spectroscopy (EIS). The specimen surfaces were analysed by scanning electron microscopy, X-ray photoelectron spectroscopy (XPS) and X-ray diffraction. The corrosion performance of AISI 304 stainless steel in sulphuric acid solution was greatly improved by copper coatings. The amount of copper deposited by the cementation process was sufficient to protect the stainless steel of corrosion. A greater amount of copper obtained by electrodeposition treatments does not supply further improvement in the corrosion behaviour. The improved corrosion resistance is related to copper dissolution at the initial stages of immersion tests and the presence of Cu²⁺ in the solution, which makes the medium more oxidizing, increasing the stability of the passive layer. In addition, the presence of copper at the surface reduces the overpotential of cathodic reaction, enabling the transition from an active region to the passive one.     

Establishment of equivalent circuits from electrochemical impedance spectroscopy study of corrosion inhibition of steel by pyrazine in sulphuric acidic solution

This paper describes the use of the electrochemical impedance spectroscopy technique (EIS) in order to study the corrosion inhibition process of steel in 0.5 M H₂SO₄ solution at the open circuit potential (OCP). Diethyl pyrazine-2,3-dicarboxylate (Prz) as a non-ionic surfactant (NS) inhibitor has been examined. The Nyquist diagrams consisted of a capacitive semicircle at high frequencies followed by a well-defined inductive loop at low frequency values. The impedance measurements were interpreted according to suitable equivalent circuits. The results obtained showed that the Prz is a good inhibitor. The inhibition efficiency increases with an increase in the surfactant concentration to attain 80% at the 5 × 10⁻³M. Prz is adsorbed on the steel surface according to a Langmuir isotherm adsorption model.     

The inhibitive effect of bipyrazolic derivatives on the corrosion of steel in hydrochloric acid solution

The effect of two pyrazole-type organic compounds, namely ethyl 5,5′-dimethyl-1′H-1,3′-bipyrazole-3 carboxylate (P1) and 3,5,5′-trimethyl-1′H-1,3′-bipyrazole (P2) on the corrosion behaviour of steel in 1 M hydrochloric acid (HCl) solution is investigated at 308 K by weight loss measurements, potentiodynamic polarisation and impedance spectroscopy (EIS) methods. The inhibition efficiencies obtained from cathodic Tafel plots, gravimetric and EIS methods are in good agreement. Results obtained show that the compound P2 is the best inhibitor and its efficiency reaches 84% at 10⁻³ M. Potentiodynamic polarisation studies show that pyrazolic derivatives are cathodic-type inhibitors and these compounds act on the cathodic reaction without changing the mechanism of the hydrogen evolution reaction. The inhibition efficiency of P2 is temperature-dependent in the range from 308 to 353 K and the associated activation energy has been determined. P2 adsorbs on the steel surface according to Langmuir adsorption model. The calculation of the total partial charge of inhibitor atoms is computed.     

Corrosion inhibition of steel in 0.5 M H2SO4 by [(2-pyridin-4-ylethyl)thio]acetic acid

The influence of [(2-pyridin-4-ylethyl)thio]acetic acid (P1) and pyridine (P2) on the corrosion inhibition of steel in sulphuric acid solution is studied using weight loss, potentiodynamic polarisation and linear polarisation resistance (R_p) and electrochemical impedance spectroscopy (EIS) measurements. Results obtained show that P1 is the best inhibitor and its inhibition efficiency (E%) increases with the increase of concentration. The highest E% of 82% is observed at 5 × 10⁻³ M. Potentiodynamic polarisation studies clearly reveal that P1 acts as a mixed inhibitor. The inhibitor studied reduces the corrosion rates. E% values obtained from various methods used are in good agreement. Adsorption of P1 on steel surface obeys to Langmuir adsorption isotherm. Effect of temperature indicates that E% decreases with temperature between 298 and 353 K.     

Investigation of the inhibitive effect of triphenyltin 2-thiophene carboxylate on corrosion of steel in 2 M H3PO4 solutions

A new organic compound was synthesised and tested as corrosion inhibitor of steel in phosphoric acid medium using gravimetric, electrochemical polarisation and electrochemical impedance spectroscopy (EIS) measurements. Results obtained show that the inhibitor studied is a good cathodic inhibitor. EIS results show that the change in the impedance parameters (R_T and C_dl) with concentration of triphenyltin 2-thiophene carboxylate (TTC) is indicative of the adsorption of molecules leading to the formation of a protective layer on the surface of steel. The effect of the temperature on the steel corrosion in 2 M H₃PO₄ and with addition of various concentrations of TTC in the range of temperature 298-348 K was studied. The associated apparent activation corrosion energy has been determined.     

Pyridine–pyrazole compound as inhibitor for steel in 1 M HCl

The influence of 3,5-dimethyl-1H-pyrazole (P1), pyridine (P2) and 2-(3-methyl-1H-pyrazol-5-yl) pyridine (P3) on the corrosion inhibition of steel in molar hydrochloric acid solution is studied using weight-loss, potentiodynamic and EIS measurements. Results obtained shows that P3 is the best inhibitor and its inhibition efficiency increases with the increase of concentration to attain 89% since 10⁻³ M. Potentiodynamic polarisation studies clearly reveal that it acts essentially as a cathodic inhibitor. The inhibitor studied reduces the corrosion rates. E (%) values obtained from various methods used are in good agreement. Adsorption of P3 on steel surface has an S-shaped adsorption isotherm.     

Raman and IR spectroscopy study of corrosion products on the surface of the hot‐dip galvanized steel with alkaline mud adhesion

The corrosion products formed on hot‐dip galvanized steel sheets for the automobile application with adhesion of alkaline mud containing different Cl⁻ ion contents are investigated by means of Raman and infrared (IR) spectroscopy. Results show that the Cl⁻ ion content in alkaline mud has great influence on the corrosion behavior of the galvanized steel. The Cl⁻ ions are responsible for the formation of the Zn₅Cl₂(OH)₈· H₂O layer on the surface of the steel at the early stage of corrosion. The rest of the Cl⁻ ions then penetrate and interrupt corrosion product layer resulting in pitting corrosion. Subsequently, the red corrosion product of α‐FeOOH (shaped as needle‐like structure) is formed, which then transforms into black rust of Fe₃O₄ (having a shape of slim needle). It is interesting to find out that pitting depth is inversely proportional to the Cl⁻ ion content. However, corrosion rate decreases with the increase of the Cl⁻ ions in mud. Copyright © 2009 John Wiley & Sons, Ltd.     

Holographic interferometry as electrochemical emission spectroscopy of carbon steel in seawater with low concentration of RA-41 corrosion inhibitor

In the present investigation, holographic interferometry was utilized for the first time to determine the rate change of the number of the fringe evolutions during the corrosion test of carbon steel in blank seawater and with seawater with different concentrations of a corrosion inhibitor. In other words, the anodic dissolution behaviors (corrosion) of the carbon steel were determined simultaneously by holographic interferometry, an electromagnetic method, and by the electrochemical impedance (EI) spectroscopy, an electronic method. So, the abrupt rate change of the number of the fringe evolutions during corrosion test (EI) spectroscopy, of the carbon steel is called electrochemical emission spectroscopy. The corrosion process of the steel samples was carried out in blank seawater and seawater with different concentrations, 5–20 ppm, of RA-41 corrosion inhibitor using the EI spectroscopy method, at room temperature. The electrochemical emission spectra of the carbon steel in different solutions represent a detailed picture of the rate change of the anodic dissolution of the steel throughout the corrosion processes. Furthermore, the optical interferometry data of the carbon steel were compared to the data, which were obtained from the EI spectroscopy. Consequently, holographic interferometric is found very useful for monitoring the anodic dissolution behaviors of metals, in which the number of the fringe evolutions of the steel samples can be determined in situ.     

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.     

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.     

1,3-Bis(3-hyroxymethyl-5-methyl-1-pyrazole) propane as corrosion inhibitor for steel in 0.5 M H2SO4 solution

The effect of addition of 1,3-bis(3-hyroxymethyl-5-methyl-1-pyrazole) propane (M = 264 g). HMPP on steel corrosion in 0.5 M sulphuric acid is studied by weight-loss, electrochemical polarisation and electrochemical impedance spectroscopy (EIS) measurements at various temperatures. The results obtained showed that HMPP acts as a good corrosion inhibitor. The inhibition efficiency increases with the bipyrazole compound to attain 88%. It acts as a mixed-type inhibitor. Trends in the increase of charge-transfer resistance and decrease of capacitance values also show the adsorption of the molecule on the metal surface. The bipyrazole adsorbs on the steel surface according to the Langmuir isotherm adsorption model. Effect of temperature indicates that inhibition efficiency decreases with temperature between 25 and 85 °C.     

Synergistic effect between 4-(2-pyridylazo) resorcin and chloride ion on the corrosion of cold rolled steel in 0.5 M sulfuric acid

The corrosion inhibition of 1-(2-pyridylazo)-2-naphthol (PAR) on the corrosion of cold rolled steel in 0.5 M sulfuric acid (H₂SO₄) was studied using weight loss method and potentiodynamic polarization method. Results obtained revealed that together with chloride ion, PAR is an effective corrosion inhibitor for steel corrosion in sulfuric acid. It was found that for steel corrosion inhibition in the presence of single PAR in sulfuric acid the Temkin adsorption isotherm may be used to explain the adsorption phenomenon. For the mixture of PAR and NaCl used as corrosion inhibitor, however, the Langmuir adsorption isotherm can be used to satisfactorily elucidate the adsorption of mixture of PAR and NaCl. Potentiodynamic polarization studies showed that single PAR mainly acts as a cathodic inhibitor for the corrosion of steel in 0.5 M sulfuric acid. The mixture of PAR and chloride ion, however, acts as a mixed type inhibitor that mainly inhibits cathodic reaction of the steel corrosion in sulfuric acid. By means of electrochemical polarization tests, a desorption potential at ca. −370 mV was observed for the adsorption of mixture of PAR and chloride ion, when potential reaches this value, adsorbed inhibitor molecule heavily departs from the steel surface. For the mixture of PAR and chloride ion, thermodynamic parameters such as adsorption heat, adsorption entropy and adsorption free energy were obtained from experimental data of the temperature studies of the inhibition process at four temperatures ranging from 30 to 45 °C, the kinetic data such as apparent activation energies and pre-exponential factors at different concentrations of the inhibitor were calculated, and the effect of the apparent activation energies and pre-exponential factors on the corrosion rates of cold rolled steel was discussed. The most suitable range of inhibitor concentration was discussed. The inhibitive action was satisfactorily explained by using both thermodynamic and kinetic models. Synergism between chloride ion and PAR was proposed. The results obtained from weight loss and potentiodynamic polarization were in good agreement.     

Surface analysis of inhibitor films formed by imidazolines and amides on mild steel in an acidic environment

Imidazolines and amidic precursors were synthesized with good yields through an optimized process. These compounds were evaluated as corrosion inhibitors in an aqueous solution of 1.0 M HCl by gravimetric and polarization techniques. AISI 1018 carbon steel displayed a corrosion rate dependent on the molecular structure and concentration of inhibitor in the testing environment. Adsorption of inhibitors was found to follow the Langmuir's isotherm, this concept together with Gibbs’ free energy provided the basis to arrange corrosion inhibitors according to efficiency and stability. The surface analysis by AFM displayed that the damage on the metallic surface was considerably reduced in the presence of certain inhibitors. XPS determined the presence of a layer of inhibitor on the metal surface with protective properties.     

Understanding barium sulfate precipitation onto stainless steel

This paper investigates the influence of barium sulfate scaling and scaling inhibitors on the electrochemical behaviour of stainless steel. The results of a synchrotron radiation grazing incidence X-ray diffraction (SR-GIXRD) and electrochemical impedance spectroscopy (EIS) study on stainless steel shows that different scaling inhibitors interact uniquely with the substrate when barium sulfate is precipitated on the electrode surface. The main effect of the substrate in the presence of inhibitor is a tendency to form smaller barium sulfate particles. The SR-GIXRD patterns obtained in the presence of the two inhibitors were different to each other and to the control, with the carboxylate showing greater amounts of barite solids precipitated together with iron(III) and (II) sulfate, while the phosphonate showed low amounts of barite solid were precipitated. The presence of iron sulfates on the electrode surface as detected by SR-GIXRD, in the case of NTA, suggests that scaling inhibitors are not always benign, and can promote the dissolution of iron species from the substrate.     

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.     

Holographic interferometry as electrochemical emission spectroscopy of a carbon steel in 5–20 ppm TROS C-70 inhibited seawater

In the present investigation, holographic interferometry was utilized for the first time to determine the rate change of the number of the fringe evolutions during the corrosion test of a carbon steel in blank seawater and seawater with different concentrations of a corrosion inhibitor. In other words, the anodic dissolution behaviors (corrosion) of the carbon steel were determined simultaneously by holographic interferometry, as an electromagnetic method, and by the electrochemical impedance (EI) spectroscopy, as an electronic method. So, the abrupt rate change of the number of the fringe evolutions during corrosion tests, EI spectroscopy, of the carbon steel is called electrochemical emission spectroscopy. The corrosion process of the steel samples was carried out in blank seawater and seawater with different concentrations, 5–20 ppm, of TROS C-70 corrosion inhibitor using the EI spectroscopy method, at room temperature. The electrochemical-emission spectra of the carbon steel in different solutions represent a detailed picture of the rate change of the anodic dissolution of the steel throughout the corrosion processes. Furthermore, the optical interferometry data of the carbon steel were compared to the data, which was obtained from the EI. spectroscopy. Consequently, holographic interferometry is found very useful for monitoring the anodic dissolution behaviors of metals, in which the number of the fringe evolutions of the steel samples can be determined in situ.     

Electrochemical, theoretical and XPS studies of 2-mercapto-1-methylimidazole adsorption on carbon steel in 1 M HClO4

The inhibition of the corrosion of carbon steel in 1 M HClO₄ by 2-mercapto-1-methylimidazole (MMI) has been investigated in relation to the concentration of the inhibitor as well as the temperature using weight loss and electrochemical measurements. The effect of the temperature on the corrosion behaviour with addition of different concentrations of MMI was studied in the temperature range 30-60 °C. Polarization curves reveal that MMI is a mixed type inhibitor. The inhibition efficiency of MMI is temperature independent but increases with the inhibitor concentration. Changes in impedance parameters (charge transfer resistance, R_t, and double-layer capacitance, C_dl) were indicative of adsorption of MMI on the metal surface, leading to the formation of a protective film. Adsorption of MMI on the carbon steel surface is found to obey the Langmuir adsorption isotherm. Some thermodynamic functions of dissolution and adsorption processes were also determined. The X-ray photoelectron spectroscopy (XPS) of the carbon steel indicated that MMI is chemically adsorbed on the steel surface. Moreover, the electronic properties such as highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO) energy levels and molecular orbital densities were calculated.     

Enhanced corrosion resistance of mild steel in molar hydrochloric acid solution by 1,4-bis(2-pyridyl)-5H-pyridazino[4,5-b]indole: Electrochemical, theoretical and XPS studies

The inhibition effect of the new pyridazine derivative, namely 1,4-bis(2-pyridyl)-5H-pyridazino[4,5-b]indole (PPI) against mild steel corrosion in 1 M HCl solutions was evaluated using weigh loss and electrochemical techniques (potentiodynamic polarisation curves and impedance spectroscopy). The experimental results suggest that PPI is a good corrosion inhibitor and the inhibition efficiency increased with the increase of PPI concentration, while the adsorption followed the Langmuir isotherm. X-ray photoelectron spectroscopy (XPS) and theoretical calculation of electronic density were carried out to establish the mechanism of corrosion inhibition of mild steel with PPI in 1 M HCl medium. The inhibition action of this compound was, assumed to occur via adsorption on the steel surface through the active centres contained of the molecule. The corrosion inhibition is due to the formation of a chemisorbed film on the steel surface.