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.     

Corrosion and corrosion control of mild steel in concentrated H2SO4 solutions by a newly synthesized glycine derivative

A newly synthesized glycine derivative (GlyD1), 2-(4-(dimethylamino)benzylamino)acetic acid hydrochloride, was used to control mild steel corrosion in 4.0 M H₂SO₄ solutions at different temperatures (278–338 K). Tafel extrapolation, linear polarization resistance (LPR) and impedance methods were used to test corrosion inhibitor efficiency. An independent method of chemical analysis, namely ICP-AES (inductively coupled plasma atomic emission spectrometry) was also used to test validity of corrosion rate measured by Tafel extrapolation method. Results obtained were compared with an available glycine derivative (GlyD2) and glycine (Gly). Tafel polarization measurements revealed that the three tested inhibitors function as mixed-type compounds. The inhibition efficiency increased with increase in inhibitor concentration and decreased with temperature, suggesting the occurrence of physical adsorption. The adsorptive behaviour of the three inhibitors followed Temkin-type isotherm and the standard free energy changes of adsorption () were evaluated for the three tested inhibitors as a function of temperature. The inhibition performance of GlyD1 was much better than those of GlyD2 and Gly itself. Results obtained from the different corrosion evaluation techniques were in good agreement.     

A newly synthesized glycine derivative to control uniform and pitting corrosion processes of Al induced by SCN anions - Chemical, electrochemical and morphological studies

A newly synthesized glycine derivative (termed GlyD), 2-(4-(dimethylamino)benzylamino)acetic acid hydrochloride, was used to inhibit uniform and pitting corrosion processes of Al in 0.50 M KSCN solutions (pH 6.8) at 25 °C. For uniform corrosion inhibition study, Tafel extrapolation, linear polarization resistance and impedance methods were used, complemented with SEM examinations. An independent method of chemical analysis, namely ICP-AES (inductively coupled plasma atomic emission spectrometry) was also used to test validity of corrosion rate measured by Tafel extrapolation method. GlyD inhibited uniform corrosion, even at low concentrations, reaching a value of inhibition efficiency up to 97% at a concentration of 5 × 10⁻³ M. Results obtained from the different corrosion evaluation techniques were in good agreement. This new synthesized glycine derivative was also used to control pit nucleation and growth on the pitted Al surface based on cyclic polarization, potentiostatic and galvanostatic measurements. The pitting potential (E_pit) and the repassivation potential (E_rp) increased by the addition of GlyD. Thus GlyD suppressed pit nucleation and propagation. Nucleation of pit was found to take place after an incubation time (t_i). The rate of pit nucleation and growth decreased with increase in inhibitor concentration. Morphology of pitting was also studied as a function of the applied anodic potential and solution temperature. Cross-sectional view of pitted surface revealed the formation of large distorted hemispherical and narrow deep pits. GlyD was much better than Gly in controlling uniform and pitting corrosion processes of Al in these solutions.     

Copper corrosion inhibition in O2-saturated H2SO4 solutions

Corrosion inhibition of copper in O₂-saturated 0.50 M H₂SO₄ solutions by four selected amino acids, namely glycine (Gly), alanine (Ala), valine (Val), or tyrosine (Tyr), was studied using Tafel polarization, linear polarization, impedance, and electrochemical frequency modulation (EFM) at 30 °C. Protection efficiencies of almost 98% and 91% were obtained with 50 mM Tyr and Gly, respectively. On the other hand, Ala and Val reached only about 75%. Corrosion rates determined by the Tafel extrapolation method were in good agreement with those obtained by EFM and an independent chemical (i.e., non-electrochemical) method. The chemical method of confirmation of the corrosion rates involved determination of the dissolved Cu²⁺, using ICP-AES (inductively coupled plasma atomic emission spectrometry) method of chemical analysis. Nyquist plots exhibited a high frequency depressed semicircle followed by a straight line portion (Warburg diffusion tail) in the low-frequency region. The impedance data were interpreted according to two suitable equivalent circuits. The kinetics of dissolved O₂ reduction and hydrogen evolution reactions on copper surface were also studied in O₂-saturated 0.50 M H₂SO₄ solutions using polarization measurements combined with the rotating disc electrode (RDE). The Koutecky-Levich plot indicated that the dissolved O₂ reduction at the copper electrode was an apparent 4-electron process.     

A study of the inhibition of iron corrosion in HCl solutions by some amino acids

The performance of three selected amino acids, namely alanine (Ala), cysteine (Cys) and S-methyl cysteine (S-MCys) as safe corrosion inhibitors for iron in aerated stagnant 1.0 M HCl solutions was evaluated by Tafel polarization and impedance measurements. Results indicate that Ala acts mainly as a cathodic inhibitor, while Cys and S-MCys function as mixed-type inhibitors. Cys, which contains a mercapto group in its molecular structure, was the most effective among the inhibitors tested, while Ala was less effective than S-MCys. The low inhibition efficiency recorded for S-MCys compared with that of Cys was attributed to steric effects caused by the substituent methyl on the mercapto group. Electrochemical frequency modulation (EFM) technique and inductively coupled plasma atomic emission spectrometry (ICP-AES), were also applied to make accurate determination of corrosion rates. Validation of the Tafel extrapolation method for measuring corrosion rates was tested. Rates of corrosion rates (in μm y⁻¹) obtained from Tafel extrapolation method are in good agreement with those measured using EFM and ICP methods. Some theoretical studies, including molecular dynamics (MD) and density functional theory (DFT), were also employed to establish the correlation between the structure (molecular and electronic) of the three tested inhibitors and the inhibition efficiency. Adsorption via hydrogen bonding was discussed here based on some theoretical studies. Experimental and theoretical results were in good agreement.     

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.     

Monitoring corrosion and corrosion control of iron in HCl by non-ionic surfactants of the TRITON-X series – Part II. Temperature effect, activation energies and thermodynamics of adsorption

The inhibition characteristics of non-ionic surfactants of the TRITON-X series, namely TRITON-X-100 (TX-100), TRITON-X-165 (TX-165) and TRITON-X-305 (TX-305), on the corrosion of iron was studied in 1.0 M HCl solutions as a function of inhibitor concentration (0.005–0.075 g L⁻¹) and solution temperature (278–338 K). Measurements were conducted based on Tafel extrapolation method. 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. Experimental corrosion rates determined by the Tafel extrapolation method were compared with corrosion rates obtained by the EFM technique and an independent method of chemical analysis. The chemical method of confirmation of the corrosion rates involved determination of the dissolved cation, using ICP-AES (inductively coupled plasma atomic emission spectrometry). The aim was to confirm validation of corrosion rates measured by the Tafel extrapolation method. Results obtained showed that, in all cases, the inhibition efficiency increased with increase in temperature, suggesting that chemical adsorption occurs. The adsorptive behaviour of the three surfactants followed Temkin-type isotherm. The standard free energies of adsorption decreased with temperature, reflecting better inhibition performance. These findings confirm chemisorption of the tested inhibitors. Thermodynamic activation functions of the dissolution process were also calculated as a function of each inhibitor concentration. All the results obtained from the methods employed are in reasonable agreement.     

A measurement system based on electrochemical frequency modulation technique for monitoring the early corrosion of mild steel in seawater

The electrochemical frequency modulation (EFM) technique, featuring of obtaining the Tafel constants directly, small polarization and short measuring time, offers a novel way for electrochemical corrosion monitoring. According to current research, the EFM approach should be mostly limited to those corrosion systems with fairly high corrosion rate, such as mild steel or iron in acidic environment. In this paper, a system for EFM measurement was set up with a potentiostat, a laptop, a NI DAQ card and applications developed with LabVIEW 7.0. It was then applied to the mild steel/seawater system. The early corrosion rate for mild steel in Zhoushan seawater was determined in laboratory with EFM technique and another two general electrochemical techniques as well-analysis of the polarization curve in the vicinity of the corrosion potential and electrochemical impedance spectroscopy. The EFM measurements were performed with 0.02 and 0.05 Hz potential perturbation frequencies, and the EFM data were analyzed with activation-controlled equation. It was shown that the corrosion rates determined with EFM technique were higher than the real values, especially at longer exposed times when diffusion-controlled effect became obvious. But they were still at the same order of magnitude as those obtained with polarization curve analysis or weight loss method.     

Monitoring corrosion and corrosion control of iron in HCl by non-ionic surfactants of the TRITON-X series - Part I. Tafel polarisation, ICP-AES and EFM studies

The corrosion inhibition characteristics of non-ionic surfactants of the TRITON-X series, known as TRITON-X-100 (TX-100), TRITON-X-165 (TX-165) and TRITON-X-305 (TX-305), on iron in 1.0 M HCl solution were studied. Measurements were conducted in 1.0 M HCl solutions without and with various concentrations of the three selected surfactants using chemical (ICP-AES method of analysis of dissolved cations) and electrochemical (Tafel polarisation and EFM) techniques at 25 °C. These measurements were complemented with SEM and EDX examinations of the electrode surface. Polarisation data showed that the non-ionic surfactants used in this study acted as mixed-type inhibitors with cathodic predominance. The protection efficiency increased with increase in surfactant concentration. Maximum protection efficiency of the surfactant was observed at concentrations around its CMC. From their molecular structure, these surfactants may adsorb on the metal surface through two lone pairs of electrons on the oxygen atoms of the hydrophilic head group.     

On the corrosion inhibition of low carbon steel in concentrated sulphuric acid solutions. Part I: Chemical and electrochemical (AC and DC) studies

The influence of the concentration of adenine (AD), as a safe inhibitor, on the corrosion of low carbon steel (LCS) in aerated 4.0 M H₂SO₄ solutions was studied. The investigations involved weight loss, potentiodynamic polarization, impedance and electrochemical frequency modulation (EFM) methods. Variations of open-circuit potential (OCP) as a function of time till steady-state potentials were also studied. Measurements were conducted under the influence of various experimental conditions complemented with ex situ EDX examinations of the electrode surface. By using EFM measurements, corrosion current density was determined without prior knowledge of Tafel slopes. Results obtained revealed that together with iodide ion, AD is an effective corrosion inhibitor for LCS corrosion in H₂SO₄ solutions. Synergism between iodide ion and AD was proposed. Potentiodynamic polarization studies showed that AD alone and the mixture of AD and iodide ions act as mixed-type inhibitors for the corrosion of LCS in 4.0 M H₂SO₄ solution. The inhibition mechanism involves the electrostatic adsorption of protonated AD molecules on the LCS surface charged with a negative layer of chemisorbed I⁻ ions. An adherent layer of inhibitor is postulated to account for the protective effect. EDX examinations of the electrode surface confirmed the existence of such adherent layer on the electrode surface. The inhibition efficiency increases with increase in the concentration of AD and immersion time. The potential of zero charge (PZC) of the LCS electrode was determined in 4.0 M H₂SO₄ solutions in the absence and presence of 0.001 M KI, and the mechanism of adsorption was discussed. The results obtained from chemical and electrochemical measurements were in good agreement.     

Synthesis and evaluation of Tris-hydroxymethyl-(2-hydroxybenzylidenamino)-methane as a corrosion inhibitor for cold rolled steel in hydrochloric acid

Tris-hydroxymethyl-(2-hydroxybenzylidenamino)-methane (THHM) was synthesized. The effect of THHM on the corrosion of cold rolled steel (CRS) in 0.1 M hydrochloric acid was then investigated by Tafel polarization curve and electrochemical impedance spectroscopy (EIS). Polarization curve results clearly reveal the fact that THHM is a good cathodic type inhibitor. EIS results confirm its corrosion inhibition ability. The inhibition efficiency increases with increasing THHM concentration but decreases with immersion time. Atomic force microscopy (AFM) reveals that a protective film forms on the surface of the inhibited sample. The adsorption of this inhibitor is found to follow the Langmuir adsorption isotherm. THHM adsorbs on the sample probably by chemisorption.     

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.     

Inhibition effect of methyl violet on the corrosion of cold rolled steel in 1.0 M HCl solution

The inhibition effect of methyl violet (MV) on the corrosion of cold rolled steel (CRS) in 1.0 M HCl solution at 20-50 °C was studied by weight loss, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM) methods. The results show that MV is an excellent inhibitor even with very low concentration, and the adsorption of MV on CRS surface obeys Langmuir adsorption isotherm. Potentiodynamic polarization curves reveal that MV behaves as a mixed-type inhibitor. EIS spectra exhibit one capacitive loop and confirm the inhibitive ability. The inhibition action of MV is also evidenced by SEM.     

Cefotaxime sodium: A new and efficient corrosion inhibitor for mild steel in hydrochloric acid solution

The corrosion inhibition of mild steel in 1 M HCl solution by cefotaxime sodium has been studied by Tafel polarization, electrochemical impedance spectroscopy (EIS) and weight loss measurement. The inhibitor showed 95.8% inhibition efficiency at optimum concentration 300 ppm. Results obtained revealed that inhibition occurs through adsorption of the cefotaxime on metal surface without modifying the mechanism of corrosion process. Potentiodynamic polarization studies suggest that it is a mixed type of inhibitor. Electrochemical impedance spectroscopy techniques were also used to investigate the mechanism of corrosion inhibition.     

Inhibition effect of nonionic surfactant on the corrosion of cold rolled steel in hydrochloric acid

The inhibition effect of Tween-20 as a nonionic surfactant on the corrosion of cold rolled steel (CRS) in 1.0-8.0 M HCl has been studied at different temperatures (20-50 °C) by weight loss and potentiodynamic polarization methods. Atomic force microscope (AFM) provided the CRS surface conditions. The results show that Tween-20 is a good inhibitor in 1.0 M HCl, and the inhibition efficiency (IE) increases with the inhibitor concentration, while decreases with increasing the hydrochloric acid concentration and temperature. Effect of immersion time was also studied and discussed. The adsorption of inhibitor on the CRS surface obeys the Langmuir adsorption isotherm equation. Both thermodynamic and kinetic parameters have been obtained by adsorption theory and kinetic equations. The inhibition effect is satisfactorily explained by the parameters. Polarization curves show that Tween-20 is a mixed-type inhibitor in hydrochloric acid. The results obtained from weight loss and polarization are in good agreement, and Tween-20 inhibition action could also be evidenced by surface AFM images.     

An evaluation of the electrochemical frequency modulation (EFM) technique

The EFM technique has been used to calculate anodic and cathodic Tafel slopes as well as corrosion current densities for the systems Cu/NaCl, Al 5083/NaCl, stainless steel/NaCl and mild steel in H₂SO₄ and NaCl. These values have been compared with those obtained from the analysis of polarization curves determined in the vicinity of the corrosion potential. In addition, polarization resistance values calculated based on the analysis of EFM data have been compared with values obtained from analysis of impedance data collected for the same systems. In most cases the corrosion rates determined with the EFM technique were much higher than the values determined with the other two techniques. This result is mainly due to the fact that for systems with low corrosion rates the modulation frequencies that are used in the EFM technique are in the capacitive region of the impedance spectra. Good agreement of corrosion rates obtained with the EFM and the polarization techniques was only observed for the mild steel/H₂SO₄ system that has very high corrosion rates. Analysis of EFM data assuming charge transfer or diffusion control produced different Tafel slopes and corrosion rates, but the same polarization resistance (R_p) values. When the EFM technique was applied to a resistor, the calculated R_p value equaled the value of the resistance which is further proof that the EFM technique measures the impedance of a corroding system in a narrow frequency band. The difference to the traditional EIS technique is that the amplitude of the ac signal can be different at different frequencies.     

Blue tetrazolium as a novel corrosion inhibitor for cold rolled steel in hydrochloric acid solution

The inhibition effect of blue tetrazolium (BT) on the corrosion of cold rolled steel (CRS) in 1.0 M HCl solution at 20 °C was investigated by weight loss, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM) methods. The results show that BT is a very good inhibitor, and the adsorption of BT on CRS surface obeys Langmuir adsorption isotherm. Polarization curves reveal that BT acts as a mixed-type inhibitor. EIS spectra exhibit one capacitive loop and confirm the inhibitive ability. The inhibition action of BT is also evidenced by SEM images.     

Investigating accuracy of the Tafel extrapolation method in HCl solutions

This paper discusses the validity and accuracy of the Tafel extrapolation method for determining corrosion rates of carbon steel in 1, 2 and 3 M HCl solutions open to air. Corrosion rates obtained from polarization experiments were compared with that of weight loss method. For analysing data obtained from polarization experiments electrochemical impedance spectroscopy (EIS) measurements were performed before polarization experiments. The results showed that formation of a corrosion product film and increasing the polarization resistance (R_p) of this film with time cause the corrosion rates obtained from Tafel extrapolation tend to be higher than corrosion rates obtained from weight loss test.     

Inhibition effect of 6-benzylaminopurine on the corrosion of cold rolled steel in H2SO4 solution

The inhibition effect of 6-benzylaminopurine (BAP) on the corrosion of cold rolled steel (CRS) in 1.0-7.0 M H₂SO₄ at 25-50 °C was studied by weight loss and potentiodynamic polarization methods. Fourier transform infrared spectroscopy (FTIR) and atomic force microscope (AFM) were used to characterize the CRS surface. The results showed that BAP was a good inhibitor in 1.0 M H₂SO₄, and the adsorption of BAP obeyed the Temkin adsorption isotherm. Polarization curves showed that BAP acted as a mixed-type inhibitor in sulfuric acid. Depending on the results, the inhibitive mechanism was proposed.     

The effects of pharmaceutically active compound doxycycline on the corrosion of mild steel in hydrochloric acid solution

Corrosion inhibition of mild steel in hydrochloric acid solution by doxycycline has been studied by weight loss measurements, polarization resistance, Tafel polarization and electrochemical impedance spectroscopy. The inhibitor showed more than 95% inhibition efficiency at optimum concentration 9.02 × 10⁻⁴ M. Potentiodynamic polarization suggests that it is a mixed type of inhibitor. Electrochemical impedance spectroscopy was used to investigate the mechanism of corrosion inhibition. Thermodynamic parameters were calculated to investigate mechanism of inhibition. The compound follows Langmuir adsorption isotherm. AFM studies of mild steel surface with and without inhibitor were performed and calculated roughness also supported the inhibition data.