On the corrosion inhibition of iron in hydrochloric acid solutions,Part I: Electrochemical DC and AC studies

The inhibitive action of 4-methyl pyrazole (4MP) against the corrosion of iron (99.9999%) in solutions of hydrochloric acid has been studied using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). At inhibitor concentration range (10^?3–10^?2 M) in 1.0 M acid, the results showed that 4MP suppressed mainly the anodic processes of iron corrosion in 1.0 M HCl by adsorption on the iron surface according to Temkin adsorption isotherm. Both potentiodynamic and EIS measurements reveal that 4MP inhibits the iron corrosion in 1.0 M HCl and that the efficiency increases with increasing inhibitor concentration. Data obtained from EIS were analyzed to model the corrosion inhibition process through an equivalent circuit.     

Electrochemical investigation of corrosion and corrosion inhibition of iron in hydrochloric acid solutions

The inhibition effect of 1-methyl pyrazole (MPA) on the acidic corrosion of iron in 1.0 M HCl was studied at different concentrations (10^?3–10^?2 M) by potentiodynamic polarization and electrochemical impedance spectroscopy, and EIS measurements. It is found from the polarization studies that methyl pyrazole (MPA) behaves mainly as anodic inhibitor in HCl. Values of polarization resistance (R_p) and double layer capacitance (C_dl) in the absence and presence of MPA in 1.0 M HCl are determined. The adsorption of MPA on iron surface from HCl is found to obey Temkin adsorption isotherm.     

Corrosion inhibition of copper in chloride media by 2-mercapto-4-(p-methoxyphenyl)-6-oxo-1,6-dihydropyrimidine-5-carbonitrile: Electrochemical and theoretical study

Electrochemical frequency modulation (EFM), electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization have been used to investigate the inhibition effect of a new pyrimidine heterocyclic derivative, namely 2-mercapto-4-(p-methoxyphenyl)-6-oxo-1,6-dihydropyrimidine-5-carbonitrile (MPD) on copper corrosion in 3.5% NaCl solutions at 25 ± 1 °C. The electrochemical investigations showed that MPD gives sufficient inhibition against copper corrosion in 3.5% NaCl solutions. Potentiodynamic polarization measurements have shown that the MPD inhibit both the cathodic and anodic processes and thus it classified as mixed-type inhibitor. EIS measurements indicate that the values of constant phase elements (CPEs) tend to decrease and both charge-transfer resistance and inhibition efficiency tend to increase by increasing the inhibitor concentration. Electrochemical kinetic parameters obtained using EFM methods were comparable with that calculated from traditional measurements (EIS and potentiodynamic polarization). Molecular simulation technique was used to investigate the adsorption configuration of MPD on copper surface. Number of electrons transferred from MPD to the copper surface was calculated by semi-empirical quantum chemical calculations.     

Polyvinyl alcohol–sulphanilic acid water soluble composite as corrosion inhibitor for mild steel in hydrochloric acid medium

The inhibitive action of synthesised polyvinyl alcohol–sulphanilic acid (PVASA) composite on the corrosion of commercial mild steel in 1 M HCl medium has been investigated by weight loss, potentiodynamic polarization, and electrochemical impedance spectroscopic (EIS) methods. Characterization of PVASA composite has been carried out using Fourier transform infrared spectroscopy (FTIR). Experimental results reveal that PVASA composite acts as an inhibitor in the acid environment. The inhibition efficiency increases with an increase in the concentration of the inhibitor. Maximum inhibition efficiency of PVASA composite was found to be 84% at 6000 ppm. Thermodynamic and kinetic parameters have been obtained from temperature studies. Electrochemical measurement reveals that PVASA composite acts as a mixed inhibitor and the adsorption follows Langmuir adsorption isotherm.     

Poly (vinyl alcohol – aniline) water soluble composite as corrosion inhibitor for mild steel in 1 M HCl

Poly (vinyl alcohol – aniline) PVAA composite was tested for its performance in protecting mild steel MS against corrosion in 1 M HCl. The inhibitive parameters were evaluated by means of weight loss, electrochemical polarization and impedance methods. Results indicated that the addition of PVAA to the acid reduces the corrosion of the metal. Inhibition efficiency increases with increase in inhibitor concentration. The results further revealed that PVAA at a concentration of 2000 ppm furnishes a maximum of 92% inhibition efficiency. Thermodynamic parameters such as free energy of adsorption, heat of adsorption, etc., had been evaluated from temperature studies. The adsorption of PVAA followed Langmuir and Temkin adsorption isotherms. Polarization curves revealed that PVAA is a mixed inhibitor.     

Employing electrochemical frequency modulation for studying corrosion and corrosion inhibition of copper in sodium chloride solutions

The inhibition effect of 2-carboxymethylthio-4-(p-methoxyphenyl)-6-oxo-1,6-dihy-dropyrimidine-5-carbonitrile (CPD) towards the corrosion of copper was studied in aerated stagnant 3.5% NaCl at 25 °C using ac techniques include electrochemical frequency modulation and electrochemical impedance spectroscopy as well as potentiodynamic polarization measurements. Corrosion rates determined using electrochemical frequency modulation (EFM) which measures the non-linear behaviour of a corroding system are compared with corrosion rates obtained from traditional electrochemical techniques and show good agreement. Data obtained from EIS were analyzed to model the corrosion inhibition process through equivalent circuit. Polarization measurements showed that CPD acts as mixed-type inhibitor. The inhibition efficiency increases with an increase in the concentration of CPD. The adsorption of the inhibitor on the copper surface in the sodium chloride solution was found to obey Langmuir’s adsorption isotherm. A mixed inhibition mechanism is proposed for the inhibitive effects of CPD as revealed by potentiodynamic polarization technique.     

Electrochemical kinetics of the hydrogen reaction on platinum in concentrated HCl(aq)

The hydrogen reaction in concentrated HCl(aq) solutions is a key reaction for the CuCl(aq)/HCl(aq) electrolytic cell. Here, electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV) were used to obtain new data for the hydrogen reaction on platinum submerged in highly concentrated acidic solutions at 25 °C and 0.1 MPa. LSV and EIS data were collected for Pt in 0.5 mol/L H₂SO₄(aq), 1 mol/L HCl(aq) and 7.71 mol/L HCl(aq) solutions. It was found that exchange current density (j₀) values varied between 1 and 2 mA/cm². An equivalent circuit model was used to obtain comparable j₀ and limiting current density values from EIS data relative to values obtained with LSV data. It was found that as the concentration of acid increased, a noticeable decrease in the performance was observed.     

Mass transfer effect on corrosion inhibition process of copper–nickel alloy in hydrochloric acid by Benzotriazole

The corrosion inhibition of copper–nickel alloy by Benzotriazole (BTA) in 1.5 M HCl has been investigated by weight loss and polarization techniques at different temperatures. Maximum value of inhibitor efficiency was 99.8% for BTA at 35 °C and 0.1 M inhibitor concentration, while the lower value was 86.8% at 55 °C and 0.02 M inhibitor concentration. The non-linear region of the polarization curve near the corrosion potential can be discussed depending on data of over potential as a function of current densities. These data can be analyzed by suggestion of a mathematical model to take into account the effect of mass transfer on activation process.     

Corrosion inhibition of carbon steel immersed in a 1 M HCl solution using benzothiazole derivatives

Corrosion inhibition effect of 2-mercaptobenzothiazole (MBT) and 2-aminobenzothiazole (ABT) compounds on ST-37 carbon steel in 1 M hydrochloric acid solution was investigated by electrochemical impedance spectroscopy (EIS), and it was observed that both of these compounds have corrosion inhibition effect on carbon steel. Evaluation of electrochemical behavior in test solutions showed that by increasing the immersion time from 15 to 300 min, corrosion resistance of samples is increased and at the same immersion time MBT has a better corrosion inhibition in comparison to ABT. AFM technique was performed for MBT and ABT. The results of calculations showed superior inhibition efficiency of MBT in comparison to ABT. This can cause easier protonation and consequently adsorption on the metal surface occurs.     

Cupressus arizonica fruit essential oil: A novel green inhibitor for acid corrosion of carbon steel

Natural-based corrosion inhibitors have gained great research interest thanks to their low cost and higher performance. The Cupressus arizonica fruit essential oil (CAFEO) has a higher extraction yield than leaves; however, it has less antibacterial and antifungal activities. The three main components in the CAFEO were α-pinene (51.07%), myrcene (17.92%), and limonene (9.66%). Essential oils with a higher percentage of α-pinene were found to have outstanding corrosion inhibition properties. Therefore, herein, the CAFEO was investigated as a green corrosion inhibitor for carbon steel (CS) in 1.0 mol/L HCl using electrochemical, i.e., potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS), and scanning electron microscope (SEM) techniques. The experimental results revealed that CAFEO successfully inhibited the carbon steel corrosion in 1.0 mol/L HCl solution. Results from PDP indicated that the inhibitor had a mixed-type effect with a predominance cathodic character. EIS data showed that the charge transfer resistance of the CS electrode increased from 20.9 Ω cm² in blank solution to 294.5 Ω cm² in HCl solution inhibited with 0.5 g/L of CAFEO at 298 K, leading to a significant decrease in the double layer capacitance values and an inhibition efficiency (η%) of 93%. The high temperatures showed a negative effect on the corrosion inhibition efficiency of the tested inhibitor. At 323 K, the η% of CAFEO decreased to 77%. Besides, SEM images showed that the inhibitor formed a protective barrier against acid attack, preventing carbon steel from corrosion. Theoretical calculations by Density Functional Theory (DFT) were performed to investigate the reactivity of the three main components of CAFEO.     

Corrosion behavior of CoCrMoW cast alloy in lactic acid environment for surgical applications

The corrosion behavior of CoCrMoW alloy in lactic acid environment during 168 h of immersion at 37 °C has been studied and assessed by means of electrochemical techniques (open circuit potential (OCP), potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS)). Further, the oxide film thickness formed after immersion and the quantity of ions released have been evaluated by X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma optical spectroscopy (ICP-OES). A good correlation between the results, related to the oxide film thickness, obtained from these experimental techniques was achieved. The research has also shown that the tendency of growing of oxide film becomes slower as the time of immersion is longer. The higher corrosion resistance of CoCrMoW alloy in lactic acid environment is due to the formation of the oxide film highly enriched in Cr(III) on the alloy surface. With a small corrosion rate, e.g. 45 nm year⁻¹, this alloy is characterized as “Perfect Stable” according to ISO 8044/2000. Overall, the present study provides additional evidences with respect to the benefic influence of tungsten on passivity, explained by a higher resistance to pitting corrosion of the CoCrMoW alloy in lactic acid with sodium chloride.     

Corrosion inhibition of carbon steel in hydrochloric acid 0.5 M by hexa methylene diamine tetramethyl-phosphonic acid

The efficiency of hexa methylene diamine tetra methyl-phosphonic acid (HMDTMP), as corrosion inhibitor for carbon steel in 0.5 M HCl, has been determined by gravimetric and electrochemical measurements. Polarization curves indicate that the compound is a mixed inhibitor, affecting both cathodic and anodic corrosion currents. Adsorption of HMDTMP derivatives on the carbon steel surface is in agreement with the Langmuir adsorption isotherm model, and the calculated Gibbs free energy value confirms the chemical nature of the adsorption. EIS results show that the charge in the impedance parameters (R_t and C_dl) with concentrations of HMDTMP is indicative. The adsorption of this molecule leads to the formation of a protective layer on carbon steel surface. The electrochemical results have also been supplemented by surface morphological studies.     

Spirulina platensis – A novel green inhibitor for acid corrosion of mild steel

The inhibition of the corrosion of mild steel in 1 M HCl and 1 M H₂SO₄ by Spirulina platensis has been studied at different temperatures viz., 303 K, 313 K and 323 K by weight loss method, potentiodynamic polarization method, electrochemical impedance spectroscopy measurements and SEM analysis. The inhibition efficiency increased with increasing concentration of the inhibitor in both HCl and H₂SO₄ media. The results of weight loss studies correlated well with those of impedance and polarization studies. From the results of weight loss studies at various temperatures, the mode of adsorption is confirmed to be physisorption. Further the adsorption has been found to follow Temkin isotherm. From this isotherm, the free energy of adsorption (ΔG) and entropy (ΔS) are calculated. The study reveals the corrosion inhibition potential of S. platensis in both the acid media, thus bringing to light another facet of this microalga as it has so far been used only to produce antioxidant principles, finding extensive use in medicine especially as neutraceutical.     

The Effect of Magnetic Field on Corrosion Inhibitor of Copper in 0.5 M HCl Solution

Corrosion of metals within magnetic field (MF) had been actively studied for better understanding of the corrosion mechanism when the magnetic sources are presented. However, findings regarding the effect of MF on metals are inconclusive, and there is a lack of studies of MF interaction with various corrosion control techniques, such as corrosion inhibitor. In this paper, the effect of MF on the corrosion of copper in 0.5 M hydrochloric acid (HCl) solution, with or without corrosion inhibitor were studied. Benzotriazole (BTA), a common copper inhibitor, was chosen as the inhibitor for this study. To determine the effect of MF, a MF of 13 mT, generated using a pair of permanent neodymium magnet, was applied during weight loss and electrochemical tests. The results showed that corrosion inhibition efficiency of BTA decreased when it is under an applied MF. A decrease from 47% to 60% in inhibition efficiency had been observed for all samples in an applied MF. By using Tafel extrapolation technique on the polarization curves, it revealed that MF had increased the corrosion current of copper in HCl, causing a decrease in the inhibition efficiency.     

Assembly of succinic acid and isoxazolidine motifs in a single entity to mitigate CO2 corrosion of mild steel in saline media

Inhibition of CO₂ corrosion of mild steel in 0.5 M NaCl under atmospheric pressure at 40 °C as well as high pressure (10 bar) at 120 °C by 2-[2-methyl-4(or 5)-alkylisoxazolidin-5(or 4)-yl)methyl]succinic acids, a new class of molecules having inhibitive motifs of succinic acid, isoxazolidine and hydrophobic alkyl chain assembled in a single entity, has been examined by gravimetric and electrochemical methods. Inhibitor molecule containing CH₃(CH₂)₈ outperformed its counterpart with a shorter hydrophobe CH₃(CH₂)₄ and two other commercial imidazoline-based inhibitors. The effectiveness of these new inhibitors was also evaluated by electrochemical impedance spectroscopy. The inhibition efficiency by EIS was found to be 75%, 91% and 98% in the presence of 1, 5 and 20 ppm, respectively, at 40 °C. The potentiodynamic polarization studies indicated that the new inhibitors act as anodic inhibitors. The adsorption of the synthesized inhibitors follows Temkin adsorption isotherm model with favorable high values of –ΔG°_ads and −ΔH°_ads pointing the inhibitors adsorbed on the metal surface by chemisorption process. The XPS study confirmed the adsorption of the inhibitors on the metal surface.     

An experimental and theoretical investigation on adsorption properties of some diphenolic Schiff bases as corrosion inhibitors at acidic solution/mild steel interface

The effect of novel synthesized three Schiff bases, namely, 1,3-bis[2-(2-hydroxy benzylidenamino) phenoxy] propane (P1), 1,3-bis[2-(5-chloro-2-hydroxybenzylidenamino) phenoxy] propane (P2), and 1,3-bis[2-(5-bromo-2-hydroxybenzylidenamino) phenoxy] propane (P3), on the corrosion of mild steel in 0.1 M HCl was investigated using potentiodynamic polarization and electrochemical impedance spectroscopy methods. Polarization measurements suggest that P1 acts as mixed type inhibitor while P2 and P3 behave as mainly cathodic inhibitors for acidic corrosion of steel. All electrochemical measurements show that inhibition efficiencies increase with increase in inhibitor concentration. This reveals that inhibitive actions of inhibitors were mainly due to adsorption on steel surface. Adsorption of these inhibitors follows Temkin adsorption isotherm. The correlation between the adsorption ability of inhibitors and their molecular structures has been investigated using quantum chemical parameters obtained by MNDO semi-empirical method. Calculated quantum chemical parameters indicate that Schiff bases adsorbed on steel surface by chemical mechanism.     

Effect of three 2-allyl-p-mentha-6,8-dien-2-ols on inhibition of mild steel corrosion in 1 M HCl

2-Allyl-p-mentha-6,8-dien-2-ols P1−P3 synthesized from carvone P are tested as corrosion inhibitors of steel in 1 M HCl using weight loss measurements, potentiodynamic polarisation and impedance spectroscopy (EIS) methods. The addition of 2-allyl-p-mentha-6,8-dien-2-ols reduced the corrosion rate. Potentiodynamic polarisation studies clearly reveal that the presence of inhibitors does not change the mechanism of hydrogen evolution and that they act essentially as cathodic inhibitors. 2-Allyl-p-mentha-6,8-dien-2-ols tested adsorb on the steel surface according to Langmuir isotherm. From the adsorption isotherm some thermodynamic data for the adsorption process are calculated and discussed. EIS measurements show the increase of the charge-transfer resistance with the inhibitor concentration. The highest inhibition efficiency (92%) is obtained for P1 at 3 g/L. The corrosion rate decreases with the rise of temperature. The corresponding activation energies are determined.     

Monitoring corrosion and corrosion control of low alloy ASTM A213 grade T22 boiler steel in HCl solutions

Rates of corrosion of low alloy ASTM A213 grade T22 boiler steel were monitored in aerated stagnant 0.50 M HCl solutions at different temperatures (283–303 K) using Tafel extrapolation method and the non-destructive electrochemical frequency modulation (EFM) technique, complemented with XPS examinations. Serine (Ser) was introduced as a corrosion-safe inhibitor. Corrosion rates (in μm y^?1) obtained from these two methods was in good agreement. Tafel plots showed that Ser acted mainly as a cathodic-type inhibitor. The inhibition process was attributed to the formation of an adsorbed film on the metal surface that protects the metal against corrosive agents. XPS examinations of the electrode surface confirmed the existence of such adsorbed film. The inhibition efficiency increased with increase in Ser concentration, while it decreased with temperature, suggesting physical adsorption. Activation energies have been calculated in the absence and presence of various concentrations of Ser by measuring the temperature dependence of the corrosion rate obtained from the two methods employed. It was found that the activation energy in the presence of Ser is higher than that in bare HCl solution. The adsorptive behaviour of Ser followed Temkin-type isotherm. The standard free energy of adsorption was estimated to be ?25 kJ mol^?1 at 303 K. These results confirmed the occurrence of physical adsorption.     

The irreversible characteristic analysis of thiourea on copper electrodes in aqueous 0.5 mol/L sulphuric acid

The reaction behaviors of various concentrations thiourea (TU) on copper electrode in 0.5 mol/L H₂SO₄ solution were investigated by electrochemical impedance spectroscopy (EIS) and single crystallogram. The loop at low frequency shifts negatively with the concentration of TU increasing to 0.25 mol/L in the research. It reveals the adsorption of TU converts the acidic corrosion of copper electrode to the final irreversible complexation of copper and TU. Furthermore, the dependence of irreversiblility on Cu(I)–TU complex surface coverage (θ) was discussed by an EIS mathematical model. The three-dimensional supermolecular network structure of [Cu₂(NH₂CSNH₂)₆]SO₄ · H₂O enhances the stability of the complex, and leads to the final irreversibility of whole reaction.     

Inhibition effect of hexadecyl pyridinium bromide on the corrosion behavior of some austenitic stainless steels in H2SO4 solutions

The inhibition effect of hexadecyl pyridinium bromide (HDPB) as a cationic surfactant on the corrosion behavior of some Egyptian austenitic stainless steel SS 304L, SS 316H and SS 304H in 0.5 M H₂SO₄ solutions was investigated by using potentiodynamic polarization technique and electrochemical impedance spectroscopy (EIS). The results indicate that HDPB is a good inhibitor for the samples under investigation in 0.5 M H₂SO₄ solutions. In addition, the inhibition efficiency η% increases with the inhibitor concentration while decreases with the increasing temperature referring to physical adsorption. The adsorption of the inhibitor obeys a Temkin adsorption isotherm. Polarization curves show that HDPB is a mixed inhibitor in H₂SO₄ solutions. The results obtained from polarization and impedance measurements are in good agreement. Activation-free energies, enthalpies, and entropies for the inhibition process of HDPB were determined.