Experimental and molecular dynamics studies on corrosion inhibition of mild steel by 2-amino-5-phenyl-1,3,4-thiadiazole

The corrosion inhibition of mild steel in 0.5 M H₂SO₄ and 1.0 M HCl by 2-amino-5-phenyl-1,3,4-thiadiazole (APT) has been studied using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) measurements. The results show that the inhibition efficiency increases with the increase of APT concentration in both acids, and the higher inhibition efficiency is obtained in 0.5 M H₂SO₄. The adsorption of APT molecules on the steel surface obeys Langmuir adsorption isotherm in both acids, and occurs spontaneously. The molecular dynamics method has also been used to simulate the adsorption of ATP molecule and solvent ions on the iron surface. The results show that with the adsorption of sulfate ions the Fe + anion + APT system has the higher negative interaction energy comparing to the case of the adsorption of chloride ions.     

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.     

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.     

Bis (benzimidazol-2-yl) disulphide: An efficient water soluble inhibitor for corrosion of mild steel in acid media

The inhibition effect of Bis (benzimidazol-2-yl) disulphide (BIMDS) on corrosion behavior of mild steel (MS) in 1.0 M HCl and 0.5 M H₂SO₄ was studied using different techniques. These studies have shown that studied compound is a good inhibitor for MS in 1.0 M HCl and 0.5 M H₂SO₄ solutions. Inhibitor showed better performance in 0.5 M H₂SO₄ solutions than 1.0 M HCl. Polarization measurements indicated that BIMDS is a mixed-type inhibitor in both acid media. Adsorption of inhibitor molecules on the mild steel surface showed Langmuir isotherm model in both acid media.     

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.     

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.     

Application of some ferrocene derivatives in the field of corrosion inhibition

Three ferrocene derivatives, namely 1,1′-diacetylferrocene (Diacetyl Fc), 1,1′-diformylferrocene (Diformyl Fc) and 2-benzimidazolythioacetylferrocene (BIM Fc) were synthesized and their inhibitive effects against mild steel corrosion in aerated 0.5 M H₂SO₄ and 1 M HCl solutions were evaluated. Corrosion measurements based on polarization resistance (R_p), potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) indicate that Diacetyl Fc, in most cases, accelerates mild steel corrosion in HCl while Diformyl Fc and BIM Fc act as weak inhibitors. In H₂SO₄ solution, ferrocene derivatives show good inhibition performance. The efficiency of the inhibitors follows the order: BIM Fc > Diformyl Fc ? Diacetyl Fc. Adsorption of both Diacetyl Fc and Diformyl Fc obey Langmuir adsorption isotherm with very low value of free energy of adsorption ΔG^° for the Diformyl Fc (physisorption) while adsorption of BIM Fc follows that of Frumkin with high negative value of ΔG^° (chemisorption). Both Diformyl Fc and BIM Fc act as mixed-type inhibitors with predominant effect on the anodic dissolution of iron. Analysis of the polarization curves and impedance spectra indicates that charge transfer process mainly controls mild steel corrosion in H₂SO₄ solution without and with ferrocene compounds. The mechanism of corrosion inhibition or acceleration by ferrocene derivatives was discussed in the light of the molecular structure of the additives.     

Synergistic effect of halide ions on improving corrosion inhibition behaviour of benzisothiozole-3-piperizine hydrochloride on mild steel in 0.5 M H2SO4 medium

The synergistic effect of iodide ions and benzisothiozole-3-piperizine hydrochloride (BITP) on corrosion inhibition of mild steel in 0.5 M H₂SO₄ solution has been studied by both chemical and electrochemical methods. The corrosion performance of BITP in 1.0 M HCl and 0.5 M H₂SO₄ media was examined and compared. The adsorption of BITP and its combination with iodide ions on mild steel surface followed Langmuir adsorption isotherm via chemisorption mechanism. The calculated values of synergism parameter (S_θ) were found to be greater than unity. This result clearly showed the existence of synergism between iodide ions and BITP molecules.     

Synergistic effect of polyaspartic acid and iodide ion on corrosion inhibition of mild steel in H2SO4

The inhibition effect of polyaspartic acid (PASP) and its synergistic effect with KI on mild steel corrosion in 0.5 M H₂SO₄ solution are studied by weight loss and electrochemical methods. The inhibition efficiency increases with the concentration of PASP and increases further with the presence of 1 mM KI. Result of the zero charge potential measurement shows that iodide ion promotes the film formation of PASP greatly. The mild steel surfaces after immersion test were analyzed using scanning electron microscopy and X-ray photoelectron spectroscopy. An adsorption model is proposed to elucidate the synergistic mechanism of synergistic effect.     

Inhibiting effects of butyl triphenyl phosphonium bromide on corrosion of mild steel in 0.5 M sulphuric acid solution and its adsorption characteristics

Butyl triphenyl phosphonium bromide (BuTPPB) has been evaluated as a corrosion inhibitor for mild steel in 0.5 M H₂SO₄ solutions using galvanostatic polarisation and potentiostatic polarisation measurements. The study was also complemented by infra red (IR) spectroscopy, scanning electron microscopy (SEM) and quantum chemical calculations. Galvanostatic polarisation measurements showed that the presence of BuTPPB in aerated 0.5 M H₂SO₄ solutions decreases corrosion currents to a great extent and the corrosion rate decreases with increasing inhibitor concentration at a constant temperature. At 298K, inhibition efficiency was found to be 94.5% for 10⁻⁷ M BuTPPB which increased to about 99% for the BuTPPB concentration of 10⁻² M. The effect of temperature on the corrosion behaviour of mild steel was studied at five different temperatures ranging from 298 to 338K. The polarisation curves clearly indicate that BuTPPB acts as a mixed type inhibitor. Adsorption of BuTPPB on the mild steel surface follows the Langmuir isotherm.Potentiostatic polarisation measurements showed that passivation was observed only for lower BuTPPB concentrations (10⁻⁵ and 10⁻⁷ mol l⁻¹) for the mild steel in 0.5 M H₂SO₄. IR and SEM investigations also confirmed the adsorption of BuTPPB on the mild steel surface in 0.5 M H₂SO₄ solutions. The molecular parameters obtained using PM3 semi-empirical method, were correlated with the experimentally measured inhibitor efficiencies.     

Substitutional adsorption isotherms and corrosion inhibitive properties of some oxadiazol-triazole derivative in acidic solution

A newly synthesized oxadiazol-triazole derivative (TOMP), was investigated as corrosion inhibitor of mild steel in 0.5 M H₂SO₄ solution using weight loss measurements, polarization and electrochemical impedance spectroscopy (EIS) methods. Results obtained revealed that TOMP is effective corrosion inhibitor for mild steel in sulphuric acid and its efficiency attains more than 97.6% at 298 K. The number of water molecules (X) replaced by a molecule of organic adsorbate was determined from the substitutional adsorption isotherms applied to the data obtained from the weight loss experiments performed on mild steel specimen in acidic solution in the 298-333 K range.     

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.     

Effect of 2,2′ benzothiazolyl disulfide on the corrosion of mild steel in acid media

2,2′ benzothiazolyl disulfide (BTDS) has been synthesised and their inhibiting action on mild steel corrosion in 1 M HCl and 0.5 M H₂SO₄ at 308 K has been investigated using weight loss, EIS, polarization and SEM study. BTDS showed better efficiency in 0.5 M H₂SO₄ compared to 1 M HCl. Polarization studies revealed that BTDS is a mixed type inhibitor in both acids predominantly cathodic in 1 M HCl where as predominantly anodic in 0.5 M H₂SO₄. Thermodynamic parameters i.e. free energy of adsorption, enthalpy, entropy and activation energy were calculated, the values of these parameters showed good interaction.     

On the inhibition of mild steel corrosion by 4-amino-5-phenyl-4H-1, 2, 4-trizole-3-thiol

The corrosion inhibition of mild steel in a 2.5 M H₂SO₄ solution by 4-amino-5-phenyl-4H-1, 2, 4-trizole-3-thiol (APTT) was studied at different temperatures, utilising open circuit potential, potentiodynamic and impedance measurements. The results indicate that APTT performed as an excellent mixed-type inhibitor for mild steel corrosion in a 2.5 M H₂SO₄ solution and that the inhibition efficiencies increased with the inhibitor concentration but decreased proportionally with temperature. The kinetic and thermodynamic parameters for adsorption of APTT on the mild steel surface were calculated. A chemisorption mechanism of APTT molecules on the mild steel surface was proposed based on the thermodynamic adsorption parameters.     

The effect of H2S concentration on the corrosion behavior of carbon steel at 90 °C

The electrochemical behavior of SAE-1020 carbon steel in 0.25 M Na₂SO₄ solution containing different concentrations of H₂S at 90 °C was investigated using the methods of weight loss, electrochemical measurements, scanning electron microscopy (SEM) and X-ray diffraction (XRD). The results showed that the corrosion rate of carbon steel increased significantly with the increase of H₂S concentration. H₂S accelerated the corrosion rate of SAE-1020 carbon steel by a promoted hydrogen evolution reaction. Severe corrosion cavities were observed on the carbon steel surface in the solutions containing H₂S due to cementites stripped off from the grain boundary. The loose corrosion products formed on the steel surfaces were composed of mackinawite.     

Experimental and theoretical studies of thiazoles as corrosion inhibitors for mild steel in sulphuric acid solution

The inhibition effects of 2-amino-5-mercapto-1,3,4-thiadiazole (2A5MT) and 2-mercaptothiazoline (2MT) on mild steel corrosion in 1.0 M H₂SO₄ were studied with potentiodynamic polarization, linear polarization resistance and electrochemical impedance spectroscopy techniques. It was shown that both 2A5MT and 2MT act as good corrosion inhibitors for mild steel protection. The high inhibition efficiencies were attributed to the simple blocking effect by adsorption of inhibitor molecules on the steel surface. The effects of the presence of extra NH₂ group and N atom in 2A5MT on the ability to act as corrosion inhibitors were investigated by theoretical calculations.     

Caffeic acid as a green corrosion inhibitor for mild steel

The inhibitor effect of the naturally occurring biological molecule caffeic acid on the corrosion of mild steel in 0.1 M H₂SO₄ was investigated by weight loss, potentiodynamic polarization, electrochemical impedance and Raman spectroscopy. The different techniques confirmed the adsorption of caffeic acid onto the mild steel surface and consequently the inhibition of the corrosion process. Caffeic acid acts by decreasing the available cathodic reaction area and modifying the activation energy of the anodic reaction. A mechanism is proposed to explain the inhibitory action of the corrosion inhibitor.     

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.     

Design and synthesis of a novel class of inhibitors for mild steel corrosion in acidic and carbon dioxide-saturated saline media

p-(9-(2-Methylisoxazolidin-5-yl)nonyloxy)benzaldehyde I, prepared using a cycloaddition protocol, was elaborated into its cinnamaldehyde derivative II which upon quarternization with propargyl chloride afforded III bearing an interesting blend of structural traits suitable for imparting inhibition of mild steel corrosion. Novel compounds I–III showed efficient inhibition against mild steel corrosion in CO₂–0.5 M NaCl (40 °C, 1 atm; 120 °C, 10 bar), 1, 4, 7.7 M HCl, and 0.5 M H₂SO₄ at 60 °C as determined by gravimetry and electrochemical methods. The presence of carbonaceous surface and nitrogen, as revealed by XPS study, indicated the formation of a film covering the metal surface, which imparted corrosion inhibition.     

Sulphuric acid corrosion of ultrafine-grained mild steel processed by equal-channel angular pressing

A bulk ultrafine-grained (UFG) mild steel with a ferrite grain size of approximately 200 nm and a dispersed distribution of iron carbide particles was fabricated by equal-channel angular pressing (ECAP) at 400 °C. The corrosion behaviour of the ECAP-processed mild steel and pure iron was investigated in a 0.5 mol/L H₂SO₄ solution. They exhibited a higher corrosion rate and better anodic passivity properties due to the presence of more crystalline defects. As a result of the refinement of the iron carbide particles, the forming ability of a continuous dense passive film was improved.