Electrochemical frequency modulation and inductively coupled plasma atomic emission spectroscopy methods for monitoring corrosion rates and inhibition of low alloy steel corrosion in HCl solutions and a test for validity of the Tafel extrapolation method

The inhibition effect of glycine (Gly) towards the corrosion of low alloy steel ASTM A213 grade T22 boiler steel was studied in aerated stagnant 0.50 M HCl solutions in the temperature range 20-60 °C using potentiodynamic polarization (Tafel polarization and linear polarization) and impedance techniques, complemented with scanning electron microscope (SEM) and energy dispersive X-ray (EDX). Electrochemical frequency modulation (EFM), a non-destructive corrosion measurement technique that can directly give values of corrosion current without prior knowledge of Tafel constants, is also presented here. Experimental corrosion rates determined by the Tafel extrapolation method are compared with corrosion rates obtained by electrochemical, namely EFM technique, and chemical (i.e., non-electrochemical) method for steel in HCl. The chemical method of confirmation of the corrosion rates involved determination of the dissolved cation, using ICP-AES (inductively coupled plasma atomic emission spectrometry) method of analysis. Corrosion rates (in mm y⁻¹) obtained from the electrochemical (Tafel extrapolation and EFM) and the chemical method, ICP, are in a good agreement. Polarization studies have shown that Gly is a good “green”, mixed-type inhibitor with cathodic predominance. The inhibition process was attributed to the formation of an adsorbed film on the metal surface that protects the metal against corrosive agents. Scanning electron microscopy (SEM) and energy dispersion X-ray (EDX) examinations of the electrode surface confirmed the existence of such an adsorbed film. The inhibition efficiency increases with increase in Gly concentration, while it decreases with solution temperature. Temkin isotherm is successfully applied to describe the adsorption process. Thermodynamic functions for the adsorption process were determined.     

Polyacrylic acid as a corrosion inhibitor for aluminium in weakly alkaline solutions. Part I: Weight loss, polarization, impedance EFM and EDX studies

This part is devoted to study the influence of three selected polyacrylic acids (PAAs) with different molecular weights (PAA1 = 1800, PAA2 = 11,000 and PAA3 = 14,000 g mol⁻¹) on the corrosion inhibition of Al in weakly alkaline solutions (pH 8 and 10) at 30 °C. Measurements were conducted under different experimental conditions using chemical (weight loss) and electrochemical (potentiodynamic polarization and impedance) techniques, complemented with ex situ energy dispersive X-ray (EDX) examinations of the electrode surface. Electrochemical frequency modulation (EFM), a non-destructive corrosion measurement technique that can directly give values of corrosion current without prior knowledge of Tafel constants, is also presented here. The results demonstrated that these polymers inhibit the alkaline corrosion of Al. The inhibition effect of these polymers is due to their adsorption on Al surface. The isoelectric point (IEP) of aluminium oxide (pH 9) seems to be an important factor controlling corrosion inhibition and adsorption of the three polymers. The three polymers inhibit the corrosion reaction of aluminium excellently at pH 8, but less effectively at pH 10. Polarization measurements showed that the three polymers act as mixed-type inhibitors. The inhibition efficiencies of these polymers increase with increasing concentration, molecular weight and immersion time. Results obtained from the chemical and electrochemical measurements are in good agreements.     

Adsorption properties and inhibition of mild steel corrosion in sulphuric acid solution by ketoconazole: Experimental and theoretical investigation

Ketoconazole (KCZ) has been evaluated as a corrosion inhibitor for mild steel in aerated 0.1 M H₂SO₄ by gravimetric method. The effect of KCZ on the corrosion rate was determined at various temperatures and concentrations. The inhibition efficiency increases with increase in inhibitor concentration but decrease with rise in temperature. Adsorption followed the Langmuir isotherm with negative values of , suggesting a stable and a spontaneous inhibition process. Quantum chemical approach was further used to calculate some electronic properties of the molecule in order to ascertain any correlation between the inhibitive effect and molecular structure of ketoconazole.     

Testing validity of the Tafel extrapolation method for monitoring corrosion of cold rolled steel in HCl solutions - Experimental and theoretical studies

The protection influence of glycine (Gly) and a one of its derivatives, namely 2-(bis(2-aminoethyl)amino) acetic acid, designated here as GlyD; where GlyD stands for “glycine derivative”, against cold rolled steel (CRS) corrosion was studied in aerated stagnant 1.0 M HCl solutions at 25 °C. Measurements were conducted under various experimental conditions using Tafel polarization, linear polarization and impedance techniques. These studies have shown that Gly and GlyD are very good “green”, mixed-type inhibitors. GlyD is more effective than Gly itself in inhibiting the acid corrosion of CRS. Electrochemical frequency modulation (EFM) and inductively coupled plasma-atomic emission spectroscopy (ICP-AES) method of analysis are also presented here for monitoring corrosion. Corrosion rates obtained from both EFM and ICP-AES methods are comparable with those recorded using Tafel extrapolation method, confirming validation of corrosion rates measured by the latter. Adsorption via H-bond is discussed here, based on the presence of oxide film on the electrode surface as well as the number of NH linkages in the inhibitor molecule. Quantum chemical method was also employed to explore the relationship between the inhibitor molecular properties and its protection efficiency. The density function theory (DFT) is used to study the structural properties of Gly and GlyD in aqueous phase in an attempt to understand their inhibition mechanism. The protection efficiencies of these compounds showed a certain relationship to highest occupied molecular orbital (HOMO) energy, Mulliken atomic charges and Fukui indices.     

DFT and electrochemical studies of tris(benzimidazole-2-ylmethyl)amine as an efficient corrosion inhibitor for carbon steel surface

The corrosion inhibition properties of tris(benzimidazole-2-ylmethyl)amine (TBMA) were analyzed by DFT and electrochemical techniques such as polarization curves and electrochemical impedance spectroscopy (EIS). DFT results clearly show that TBMA posses corrosion inhibition properties by having a delocalization region (N₁C₂N₃) in the benzimidazole ring that gives up their π electron density through its HOMO orbital to the metal LUMO to form a adsorption layer over the metallic surface; this has been proved by interacting the TBMA and its protonated structures with the surface of Fe₁₃ cluster, showing that the protonated moiety adsorbs strongly on the iron surface than that of the neutral structure. Electrochemical impedance data demonstrate that the interface between the electrode and the TBMA solution decreases the charge capacitance and simultaneously increases the function of the charge/discharge of the interface, facilitating the formation of adsorption layer over the iron surface.     

The effect of microstructure and non-metallic inclusions on corrosion behavior of low carbon steel in chloride containing solutions

The effect of microstructure and inclusions on corrosion of API-5L Х60-Х100 low carbon steel is examined in acetate buffer solutions (pH 6) containing chloride. Microstructure was varied by preliminary heat treatment resulting in following series: ferrite–pearlite, ferrite–bainite, ferrite–martensite, and demonstrated the minor effect on the active dissolution kinetics, as well as oxide and sulfide inclusions. The current in the passive region and breakdown potential appeared to be sensitive to both types of inclusions and steel microstructure. Voltammetric parameters are listed which correlate with corrosion rate under open circuit and can be used to predict both short- and long-term corrosion behavior.     

Inhibitive and adsorption behaviour of carboxymethyl cellulose on mild steel corrosion in sulphuric acid solution

Chemical methods were used to assess the inhibitive and adsorption behaviour of carboxymethyl cellulose (CMC) for mild steel in H₂SO₄ solution at 30-60 °C. Results obtained show that CMC act as inhibitor for mild steel in H₂SO₄. The inhibition efficiency was found to increase with increase in CMC concentration but decreased with rise in temperature, which is suggestive of physical adsorption mechanism. The adsorption of the CMC onto the mild steel surface was found to follow Langmuir and Dubinin-Radushkevich adsorption isotherm models. The inhibition mechanism was further corroborated by the values of activation parameters obtained from the experimental data.     

Corrosion potential oscillation of stainless steel in concentrated sulphuric acid: I. Electrochemical aspects

The spontaneous oscillation of corrosion potential between the active and passive states of UNS S30403 stainless steel has been studied in 93.5 wt.% sulphuric acid at 60 °C. Detailed electrochemical analysis of the kinetics of the oscillating potential has suggested the presence of a nickel salt which is stable over a limited potential range. The nickel salt is subject to dissolution at potentials more positive than −0.25 V (MSE), while at lower potentials—less than −0.35 V (MSE)—a stable salt film is formed. A critical coverage of the salt on the surface is the prerequisite for the mixed potential to be shifted into the passive range by an increase in the exchange current density for the sulphuric acid cathodic reaction. However, when the coverage exceeds a critical value, such as can be produced by a potentiostatic hold, the salt effectively blocks the formation of a passive film.     

Investigation of the effect of CrO and MoO on carbon steel corrosion using AFM and electrochemical techniques

The effect of chromate ( ) and molybdate ( ) ions on the corrosion of carbon steel in 0.5 M NaCl solution has been studied using electrochemical measurements and atomic force microscopy (AFM) technique. Potentiodynamic polarization data suggest that both and have inhibition effect on carbon steel corrosion, and the inhibition efficiency increases with increase in concentrations of and ; at the same concentration, the inhibition efficiency of is higher than that of . The increase in concentrations of and anions causes a shift of the breakdown potential (E_b) in the positive direction, indicating the inhibitive effect of the added anions on the pitting attack. At the same concentrations, the breakdown potential of is higher than that of . Electrochemical impedance spectroscopy (EIS) tests reveal that the charge transfer resistance and passive film resistance increase with increase in concentrations of or ; at the same concentrations, as for the charge transfer resistance and passive film resistance were bigger than those of . AFM imaging technique shows that local corrosion was inhibited obviously after the addtion of or , and passive film of was much more compact than that of . AFM force–distance curves indicate that the passive film of is much stiffer than that of .     

Improvement of the corrosion resistance of a low carbon steel using a two step plasma treatment

The aim of this work was the improvement of the corrosion resistance and mechanical properties of a low alloyed carbon steel using a duplex plasma treatment. The first step of the plasma treatment consisted in a nitriding treatment with a N₂/H₂ gas mixture. The second step consisted in a carbon treatment using a CH₄/H₂ gas mixture, the entire treatment occurring in the same inductively coupled plasma reactor without exposition to the atmosphere. Topological and chemical analysis indicated that the superficial layer induced by the plasma treatment was homogeneous, hard, enriched in nitrogen, carbon and oxygen. The surface layers gave good passivation properties to the 30CrMo12 steel. The electrochemical properties of the treated samples were studied by electrochemical impedance spectroscopy and voltammetry in an aerated 0.5 mol/l NaCl solution. For the optimal conditions of treatment, the rate of protection of the duplex steel was more than 99.6% and remained constant for long immersion times.     

Electrochemical and analytical study of corrosion inhibition on carbon steel in HCl medium by 1,12-bis(1,2,4-triazolyl)dodecane

1,12-bis(1,2,4-triazolyl)dodecane (dTC12) is an excellent corrosion inhibitor for carbon steel in deaerated 1 M HCl solution. In this work electrochemical and analytical techniques were used to study the inhibition of corrosion on carbon steel in acidic medium. The carbon steel corrosion inhibition of dTC12 was attributed to the synergistic effect between chloride anion and quaternary ammonium ion. The protective efficiency of the film was higher than 90%, indicating that corrosion of carbon steel in 1 M HCl is reduced by dTC12.The effect of dissolved oxygen on the inhibition efficiency was also investigated. The results show that the inhibition efficiency increases in early stage and decreases for a long immersion time.     

Contribution of electrochemical dissolution during pickling of low carbon steel in acidic solutions

An electrochemical cell coupled with ICP-OES chemical analysis was used to explore the role of chemical and electrochemical reactions in pickling of low carbon steel in acidic media. Impedance spectroscopy was used to highlight scale properties. Dissolution of hematite is shown to be mainly of chemical nature, whereas the dissolution of magnetite and wüstite is both chemical and electrochemical. Initially, chemical dissolution of the scale dominated. The electrochemical reactions included oxidation of magnetite and wüstite and reduction of ferric ions formed by chemical dissolution. After the electrolyte reached the steel substrate, electrochemical dissolution of the iron was the main reaction.     

Wear and corrosion properties of a low carbon steel processed by means of SMAT followed by lower temperature chromizing treatment

A duplex lower temperature chromizing treatment at 600 °C for 120 min followed by 860 °C for 90 min was performed on a low carbon steel plate with a nanostructured surface layer, induced by surface mechanical attrition treatment (SMAT) [Z.B. Wang, J. Lu, K. Lu, Acta Mater. 53 (2005) 2081]. Microhardness, wear and corrosion resistances of the chromized SMAT sample were measured, in comparison with those of the chromized coarse-grained counterpart and the as-annealed coarse-grained sample. Experimental results showed that these properties were improved markedly. The much enhanced properties of the chromized SMAT sample relative to the chromized coarse-grained counterpart might originate from its superior microstructures, i.e., a much thicker chromized surface layer with smaller grains and more homogenous phase-distribution, due to the employed processes of the SMAT and the duplex lower temperature chromizing treatment.     

Corrosion monitoring of mild steel in sulphuric acid solutions in presence of some thiazole derivatives – Molecular dynamics, chemical and electrochemical studies

The physical behavior of three selected thiazole derivatives, namely 2-Amino-4-(p-tolyl)thiazole (APT), 2-Methoxy-1,3-thiazole (MTT) and Thiazole-4-carboxaldehyde (TCA) at iron (1 1 0) surface dissolved in aqueous solution were studied via molecular dynamics (MD) simulations. From the calculated binding energies, APT showed preferred adsorption on the steel surface among the three tested thiazole derivatives. The inhibition performance of the three thiazoles on the corrosion of mild steel in 0.5 M H₂SO₄ solutions was investigated at 25 °C. Measurements were conducted under various experimental conditions using weight loss, Tafel polarization and electrochemical impedance spectroscopy. Electrochemical frequency modulation (EFM) technique was also employed here to make accurate determination of the corrosion rates and test validation of the Tafel extrapolation method for measuring corrosion rates. Polarization curves showed that the three thiazole derivatives were of mixed-type inhibitors for mild steel corrosion in 0.5 M H₂SO₄ solution. EFM results were in agreement with other traditional chemical and electrochemical techniques used in corrosion rate measurements. Chemical and electrochemical measurements are consistent with computational study that APT is the most effective inhibitor among the tested thiazoles.     

Enhanced corrosion resistance of carbon steel in normal sulfuric acid medium by some macrocyclic polyether compounds containing a 1,3,4-thiadiazole moiety: AC impedance and computational studies

We report here the use of macrocyclic polyether compounds containing a 1,3,4-thiadiazole moiety (n-MCTH) in the corrosion inhibition of C38 carbon steel in 0.5 M H₂SO₄ acid medium.

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The aim of this work is devoted to study the inhibition characteristics of these compounds for acid corrosion of C38 steel using electrochemical impedance spectroscopy (EIS). Data obtained from EIS show a frequency distribution and therefore a modeling element with frequency dispersion behaviour, a constant phase element (CPE) has been used. The experimental results obtained revealed that these compounds inhibited the steel corrosion in acid solution and the protection efficiency increased with increasing inhibitors concentration. The difference in their inhibitive action can be explained on the basis of the number of oxygen atoms present in the polyether ring which contribute to the chemisorption strength through the donor acceptor bond between the non bonding electron pair and the vacant orbital of metal surface. Adsorption of n-MCTH was found to follow the Langmuir’s adsorption isotherm. The thermodynamic functions of adsorption process were calculated and the interpretation of the results is given. These results are complemented with quantum chemical study in order to provide an explanation of the differences between the probed inhibitors. Correlation between the inhibition efficiency and the structure of these compounds are presented.     

A comparative study of the corrosion inhibition of mild steel in sulphuric acid by 4,4-dimethyloxazolidine-2-thione

The corrosion protection of mild steel in a 2.5 M H₂SO₄ solution by 4,4-dimethyloxazolidine-2-thione (DMT) was studied at different temperatures by measuring changes in open circuit potential (OCP), potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS). Corrosion current densities calculated from EIS data were comparable to those obtained from polarisation measurements. Results showed that DMT inhibited mild steel corrosion in a 2.5 M H₂SO₄ solution and indicated that the inhibition efficiencies increased with the concentration of inhibitor, but decreased proportionally with temperature. Polarisation curves showed that DMT is a mixed-type inhibitor. Changes in impedance parameters suggested the adsorption of DMT on the mild steel surface, leading to the formation of protective films. The DMT adsorption on the mild steel surface followed the Langmuir adsorption isotherm. The kinetic and thermodynamic parameters for dissolution and adsorption were investigated. Comprehensive adsorption (physisorption and chemisorption) of the inhibitor molecules on the mild steel surface was suggested based on the thermodynamic adsorption parameters.     

The effect of neutral red on the corrosion inhibition of cold rolled steel in 1.0 M hydrochloric acid

The corrosion inhibition of neutral red on the corrosion of cold rolled steel in 1.0 M hydrochloric acid (HCl) was studied using weight loss method and potentiodynamic polarization method. Results obtained revealed that neutral red is an effective inhibitor. It was found that the adsorption of neutral red could prevent steel from weight loss and the adsorption accorded with the Langmuir adsorption isotherm. Potentiodynamic polarization studies showed that neutral red mainly acted as a mixed-type inhibitor for steel in 1.0 M hydrochloric acid. 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 most suitable range of inhibitor concentration was discussed. The kinetic data such as apparent activation energies and pre-exponential factors at different concentrations of the inhibitor were calculated, the effect of the apparent activation energies and pre-exponential factors on the corrosion rates of cold rolled steel was discussed. The inhibitive action was satisfactorily explained by using both thermodynamic and kinetic models. Synergism between chloride ion and neutral red was proposed. The results obtained from weight loss and potentiodynamic polarization were in good agreement.     

Electrochemical studies on the effect of pyrazolo‐containing compounds on the corrosion of carbon steel in 1 M sulphuric acid

The effect of some synthesized pyrazolo containing compounds on the corrosion of carbon steel in 1 M H₂SO₄ was investigated. The investigation involved electrochemical polarization methods (potentiodynamic, Tafel extrapolation and the determination of the polarization resistance). A significant decrease in the corrosion rate of carbon steel was observed in the presence of the investigated compounds. The results show that these compounds act as mixed type inhibitors, but the cathode is more preferentially polarized. The relative inhibition efficiency of these compounds depends on both the nature and concentrations of the investigated compounds. Compounds are found to adsorb on the carbon steel surface according to the Langmuir adsorption isotherm.     

Novel benzimidazole derivatives as corrosion inhibitors of mild steel in the acidic media. Part I: Gravimetric,electrochemical, SEM and XPS studies

Three novel benzimidazole derivatives, 2-aminomethyl benzimidazole (ABI), bis (2-benzimidazolylmethyl) amine (BBIA) and tri (2-benzimidazolylmethyl) amine (TBIA), have been studied as inhibitors for mild steel in 1.0 M HCl. The three compounds prevent mild steel from corrosion by adsorption on the steel surface and forming insoluble complex with ferrous species. Inhibition efficiency increases with the increase in the number of benzimidazole segments in the molecules (TBIA > BBIA > ABI). Protection efficiency of the inhibitors depends on concentration of inhibitor, temperature and concentration of hydrochloric acid.     

Lignin terpolymer for corrosion inhibition of mild steel in 10% hydrochloric acid medium

Lignin terpolymer has been obtained by grafting copolymerization of both dimethyl diallyl ammonium chloride (DMDAAC) and acrylamide (AM) onto lignin. The corrosion inhibition properties of the terpolymer were tested. The results showed that the highest corrosion inhibition percentage was over 95% in 10% HCl acid medium at 25 °C and 80 °C. The lignin terpolymer inhibitor adsorption followed Temkin isotherm at 25 °C and 80 °C, and the adsorption capability was in reverse proportion to the temperature according to −ΔG_ads. The effects of corrosion inhibition are the comprehensive synergistic effect through the graft reaction among lignin, AM and DMDAAC.