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.     

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.     

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.     

Inhibitive effect of diethylcarbamazine on the corrosion of mild steel in hydrochloric acid

Potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), weight loss measurements and atomic force microscopy techniques were used to investigate the inhibitory effect of diethylcarbamazine (DECM) on corrosion of mild steel in HCl solution. The inhibitor showed >90% inhibition efficiency at 5.01 × 10⁻⁴ M. Results obtained revealed that inhibition occurs through adsorption of inhibitor molecules on metal surface without modifying the mechanism of corrosion process. Potentiodynamic polarization studies suggested that it is a mixed type inhibitor, predominantly controls cathodic reaction. Activation parameters (E_a, ΔH and ΔS) and thermodynamic parameters (, and ) were calculated to investigate mechanism of inhibition.     

Inhibition of mild steel corrosion in acid solution by Pheniramine drug: Experimental and theoretical study

Inhibition of mild steel corrosion in 1 M HCl solution by Pheniramine drug was studied using weight loss, electrochemical impedance spectroscopy, linear polarization resistance, and potentiodynamic polarization measurements. The values of activation energy (E_a) and different thermodynamic parameters such as adsorption equilibrium constant (K_ads), free energy of adsorption , adsorption enthalpy and adsorption entropy were calculated and discussed. The adsorption process of studied drug on mild steel surface obeys the Langmuir adsorption isotherm. Potentiodynamic polarization measurements showed that Pheniramine is mixed-type inhibitor. Further, theoretical calculations were carried out and relations between computed parameters and experimental inhibition efficiency were discussed.     

Inhibition of iron corrosion in acid solutions by Cefatrexyl: Behaviour near and at the corrosion potential

The corrosion inhibition of iron in HCl, HClO₄, H₂SO₄ and H₃PO₄ solutions (1M for each) by cefatrexyl has been studied by polarization resistance (R_p) and electrochemical impedance spectroscopy (EIS) at the corrosion potential. The results obtained at 30 °C revealed that cefatrexyl acts as a weak inhibitor in HCl solution while it shows excellent inhibition performance in the remaining acids. Adsorption of cefatrexyl in HCl solution obeys Langmuir’s isotherm with a very low value of the free energy of adsorption (physisorption) while its adsorption in the other acids follows Temkin’s isotherm with very high negative values of (chemisorption). Data obtained from EIS measurements were analyzed to model the corrosion inhibition process through appropriate equivalent circuit models. The calculated values of the apparent activation energy (E_a) and the pre-exponential factor (λ) indicate that cefatrexyl blocks nearly the whole active centers of iron surface in H₃PO₄ solution even at elevated temperatures. The inhibition mechanism of cefatrexyl was discussed.     

Effect of 4-(N,N-diethylamino)benzaldehyde thiosemicarbazone on the corrosion of aged 18 Ni 250 grade maraging steel in phosphoric acid solution

4-(N,N-diethylamino)benzaldehyde thiosemicarbazone (DEABT) was studied for its corrosion inhibition property on the corrosion of aged 18 Ni 250 grade maraging steel in 0.67 M phosphoric acid at 30–50 °C by potentiodynamic polarization, EIS and weight loss techniques. Inhibition efficiency of DEABT was found to increase with the increase in DEABT concentration and decrease with the increase in temperature. The activation energy E_a and other thermodynamic parameters (Δ, Δ, Δ) have been evaluated and discussed. The adsorption of DEABT on aged maraging steel surface obeys the Langmuir adsorption isotherm model and the inhibitor showed mixed type inhibition behavior.     

Influence of 1,2-diaminoethane on the mechanism of aluminium corrosion in sulphuric acid solutions

The influence of 1,2-diaminoethane (DAE) on aluminium corrosion in H₂SO₄ solutions (pH 3) was investigated. In pure H₂SO₄, rapid uniform corrosion is followed by inhibition due to the formation of stable Al-sulphate binuclear bidentate metal bound surface complexes via a ligand exchange mechanism with two neighbouring sites. Metastable pitting is also observed. DAE acts as a strong corrosion inhibitor for both uniform and localised corrosion, due to the formation of Al-DAE monodentate hydrogen-bond surface complexes either by direct adsorption of the protonated molecule on Al-OH sites or via a ligand exchange mechanism with the proton of an site.     

Experimental and theoretical calculations on corrosion inhibition of steel in 1 M H2SO4 by crown type polyethers

The corrosion inhibitive efficiencies of two crown type polyethers, namely dibenzo-bis-imino crown ether (C-1) and dibenzo-diaza crown ether (C-2), which are macrocyclic Schiff base and its reduced form (macrocyclic amine), respectively, for the steel in 1 M H₂SO₄ have been investigated by Tafel extrapolation and linear polarization methods. Corrosion and adsorption isotherm parameters were determined from current-potential curves. The studies show that C-1 and C-2 inhibit the corrosion of the steel in H₂SO₄ solution. Semiempirical AM1 method was used for theoretical calculations. The obtained results of these calculations for the compounds were found to be consistent with the experimental findings.     

2,2′-Dithiobis(3-cyano-4,6-dimethylpyridine): A new class of acid corrosion inhibitors for mild steel

The title compound (PyS)₂ has been synthesized and its inhibiting action on the corrosion of mild steel in 1-5 M H₂SO₄ solutions at 35-50 °C has been investigated by polarization resistance (R_p), polarization curves and electrochemical impedance spectroscopy (EIS). (PyS)₂ showed excellent performance and its efficiency did not affect either by increasing the acid concentration or rise of temperature. Polarization curves indicated that (PyS)₂ behaves mainly as anodic inhibitor in 1 M H₂SO₄ solutions and as a mixed-type inhibitor in 3 and 5 M H₂SO₄ solutions at different temperatures. Adsorption of (PyS)₂ on the steel surface followed Temkin’s adsorption isotherm with a very high negative value of the free energy of adsorption . The activation parameters of the corrosion process were calculated. EIS showed that the charge transfer controls the corrosion process in the uninhibited and inhibited solutions.     

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.     

Effect of hexamethylpararosaniline chloride (crystal violet) on mild steel corrosion in acidic media

The corrosion inhibition of mild steel in 0.5 M H₂SO₄ and 1 M HCl by hexamethylpararosaniline chloride (HMPC) was investigated using the gravimetric technique in the temperature range 303–333 K. The results indicate that HPMC inhibited the corrosion reaction in both acid media at all temperatures and inhibition efficiency increased with HMPC concentration. The inhibiting action is attributed to general adsorption of protonated and molecular HPMC species on the corroding metal surface. Adsorption followed a modified Langmuir isotherm and the Temkin isotherm, with very high negative values of the free energy of adsorption (). An increase in temperature reduced the inhibition efficiency of HPMC in 0.5 M H₂SO₄ but increased efficiency in 1 M HCl. Activation parameters such as activation energy (E_a), activation enthalpy (ΔH^∗) and activation entropy (ΔS^∗) as well as the adsorption heat (Q_ads) were evaluated from the effect of temperature on corrosion and inhibition processes.     

Experimental and theoretical investigation of organic compounds as inhibitors for mild steel corrosion in sulfuric acid medium

Three synthesized organic compounds were tested as corrosion inhibitors for mild steel in sulfuric acid medium by potentiostatic polarization, FTIR spectroscopy and SEM techniques. Quantum chemical parameters were also calculated to characterize adsorption mechanism. Acceptable correlations were obtained between inhibition efficiency and the calculated quantum chemical parameters. It was found that the investigated compounds exhibit a good inhibition effect especially at 8-10 ppm range concentration, which makes them commercially important. The adsorption of inhibitors on the surface obeys Langmuir adsorption isotherm. The values of activation energy and the thermodynamic parameters, such as K_ads, , and were calculated.     

The inhibition action of ammonium salts of O,O′-dialkyldithiophosphoric acid on carbon dioxide corrosion of mild steel

Ammonium salts of O,O′-dialkyldithiophosphoric acids (RО)₂ Р(S) S⁻ HN⁺, were synthesized and tested as inhibitors for carbon dioxide corrosion of mild steel using weight loss, polarization curves, electrochemical impedance spectroscopy and scanning electron microscopy methods. High inhibition efficiency has been found for all compounds (η = 70–99%) at very low concentrations (0.25–5) mg l⁻¹. Polarization curves show that the title compounds can be considered as inhibitors of the mixed type. The absorption of inhibitor molecules on the mild steel surface obeys the Langmuir isotherm. Inhibition efficiency for some ammonium salts increases with temperature. The activation energy and some thermodynamic parameters were computed.     

Corrosion of niobium in sulphuric and hydrochloric acid solutions at 75 and 95 °C

New Pourbaix diagrams were calculated at 25, 75 and 95 °C for the Nb-H₂O system. The species and were considered. Potentiodynamic polarization and mass loss experiments (14 days) were conducted in concentrated H₂SO₄ (20, 40 and 80 wt%) and HCl (20 and 38 wt%) solutions at 75 and 95 °C. Nb forms a metastable pentoxide (Nb₂O₅) in H₂SO₄ and HCl solutions which dissolves as . Corrosion rates decrease between the 40% and the 80% H₂SO₄ solutions. SEM micrographs show generalized pitting in the 20% and 40% H₂SO₄ solutions. Mass loss corrosion rates did not exceed 306 μm/yr. Corrosion rates estimated by Tafel extrapolation were within two orders of magnitude of those measured by mass loss and it is shown that this finding is consistent with the thickening of the oxide.     

Three pyrazine derivatives as corrosion inhibitors for steel in 1.0 M H2SO4 solution

The inhibition effect of three pyrazine derivatives of 2-methylpyrazine (MP), 2-aminopyrazine (AP) and 2-amino-5-bromopyrazine (ABP) on the corrosion of cold rolled steel (CRS) in 1.0 M H₂SO₄ solution was studied by weight loss, potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) methods. The results show that all pyrazine compounds are good inhibitors, and inhibition efficiency follows the order: ABP > AP > MP. The adsorption of each inhibitor on CRS surface obeys Langmuir adsorption isotherm. For all these pyrazine derivatives, they act as mixed-type inhibitors. The probable inhibitive mechanism is proposed from the viewpoint of adsorption theory.     

Phosphate ions used as green inhibitor against copper corrosion in tap water

Three dosages of ions are evaluated as corrosion inhibitors of copper in artificial tap water by measuring the corrosion potential, polarization resistance, electrochemical impedance and reflectance spectra. The water is moderately hard, highly carbonated and chloride-rich. The results show that the surface film is composed by Cu₂O. When the inhibiting agent is added, the film becomes thicker, denser and more compact. This behaviour is attributed to CuO incorporating into the passive layer. The optimal dosage of inhibitor is 10 mg l⁻¹ P when the polarization resistance increases three times. The inhibitor retards the pit initiation, without hindering pit growth.     

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.     

Hydrophobic-tailed bicycloisoxazolidines: A comparative study of the newly synthesized compounds on the inhibition of mild steel corrosion in hydrochloric and sulfuric acid media

The cycloaddition reactions of the cyclic nitrones 1-pyrroline 1-oxide and 3,4,5,6-tetrahydropyridine 1-oxide with alkenes, 11-phenoxy-1-undecene and 11-p-methoxyphenoxy-1-undecene, afforded cycloaddition products (bicyclic isoxazolidines) in excellent yields. One of the cycloadducts on reaction with propargyl chloride and ring opening with zinc in acetic acid afforded quaternary ammonium salt and aminoalcohol, respectively. All the new inhibitor molecules in the presence of 400 ppm at 60 °C achieved inhibition efficiencies, determined by gravimetric method, in the range 99-99.6% and 85-99% for mild steel in 1 M HCl and 0.5 M H₂SO₄, respectively. Comparable results were obtained by the electrochemical methods using Tafel plots and electrochemical impedance spectroscopy for the synthesized compounds. The isoxazolidine derivatives were also found to be good inhibitors of mold steel corrosion in synthetic brine. Negative values of in the acidic media ensured the spontaneity of the adsorption process. While the corrosion inhibition by these molecules was predominantly under cathodic control in 1 M HCl, the inhibition in 0.5 M H₂SO₄ was found to be under anodic control. The isoxazolidines and their derivatives were found to be among a rare class of molecules, which provide suitable inhibition mechanism for the corrosion inhibition in HCl as well as in H₂SO₄ media.     

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.