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.     

Corrosion inhibition of mild steel by plant extract in dilute HCl medium

The inhibition effect of Zenthoxylum alatum plant extract on the corrosion of mild steel in 5% and 15% aqueous hydrochloric acid solution has been investigated by weight loss and electrochemical impedance spectroscopy (EIS). The corrosion inhibition efficiency increases on increasing plant extract concentration till 2400 ppm. The effect of temperature on the corrosion behaviour of mild steel in 5% and 15% HCl with addition of plant extract was studied in the temperature range 50-80 °C. Surface analysis (SEM, XPS and FT-IR) was also carried out to establish the corrosion inhibitive property of this plant extract in HCl solution. Plant extract is able to reduce the corrosion of steel more effectively in 5% HCl than in 15% HCl. The adsorption of this plant extract on the mild steel surface obeys the Langmuir adsorption isotherm.     

Corrosion inhibition of aluminium in acidic and alkaline media by Sansevieria trifasciata extract

The inhibitive action of leaf extracts of Sansevieria trifasciata on aluminium corrosion in 2 M HCl and 2 M KOH solutions was studied using the gasometric technique. The results indicate that the extract functioned as a good inhibitor in both environments and inhibition efficiency increased with concentration. Synergistic effects increased the inhibition efficiency in the presence of halide additives. Temperature studies revealed a decrease in efficiency with rise in temperature and corrosion activation energies increased in the presence of the extract. A mechanism of physical adsorption is proposed for the inhibition behaviour. The adsorption characteristics of the inhibitor were approximated by Freundlich isotherm.     

Novel cationic gemini surfactants as corrosion inhibitors for carbon steel pipelines

In the present investigation novel cationic gemini surfactants namely: bis(p-(N,N,N-octyldimethylammonium bromide)benzylidene)benzene-1,4-diamine (I), bis(p-(N,N,N-decyldimethylammonium bromide)benzylidene)benzene-1,4-diamine (II), and bis(p-(N,N,N-dodecyldimethylammonium bromide)benzylidene)benzene-1,4-diamine (III) were synthesized, characterized, and tested as corrosion inhibitors for carbon steel in 1 M HCl solution. The corrosion inhibition efficiency was measured by using electrochemical impedance spectroscopy (EIS), potentiodynamic polarization, and weight loss methods. The obtained results showed that, the synthesized inhibitors are excellent inhibitors for carbon steel in 1 M HCl solution. The inhibition efficiency decreased in the temperature range 30-40 °C and then increased in the temperature range 40-60 °C. The prepared inhibitors act as mixed inhibitors. Thermodynamic and activation parameters were discussed. Adsorption of the synthesized inhibitors was found to follow the Langmuir’s adsorption isotherm. Mixed physical and chemical adsorption mechanism is proposed. The morphology of carbon steel samples was investigated by scanning electron microscopy (SEM).     

The effects of Phyllanthus amarus extract on corrosion and kinetics of corrosion process of aluminum in alkaline solution

The effect of the extract of Phyllanthus amarus leaves on the corrosion of aluminum in 2 M NaOH solution was studied using chemical technique. The extract acts as corrosion inhibitor, with 76% efficiency at the highest concentration in the alkaline environment and the inhibition efficiency increased with increasing concentration of the extract. The adsorption of the inhibitor on aluminum surface was in accordance with the Langmuir adsorption isotherm. A zero-order kinetics relationship with respect to aluminum was obtained with and without the extract from the kinetics treatment of the data.     

Inhibition effect of novel nonionic surfactants on the corrosion of carbon steel in acidic medium

The inhibition effect of novel nonionic surfactants on the corrosion of carbon steel (CS) in 1 M HCl was studied at different temperatures (20-60 °C) by weight loss, electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization methods. The CS surface morphology was investigated by SEM. The obtained results showed that the prepared nonionic surfactants are excellent inhibitor in 1 M HCl, and the inhibition efficiency (η) increases with the inhibitor concentration and temperature increasing. The adsorption of inhibitors on the CS surface obeys the Langmuir adsorption isotherm equation. Thermodynamic parameters have been obtained by adsorption theory. Polarization curves show that the synthesized inhibitors are mixed-type inhibitors in hydrochloric acid.     

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.     

Evaluation of the inhibitive effect of some plant extracts on the acid corrosion of mild steel

Corrosion inhibition of mild steel in 2 M HCl and 1 M H₂SO₄ by extracts of selected plants was investigated using a gasometric technique at temperatures of 30 and 60 °C. The studied plants materials include leaf extracts Occimum viridis (OV), Telferia occidentalis (TO), Azadirachta indica (AI) and Hibiscus sabdariffa (HS) as well as extracts from the seeds of Garcinia kola (GK). The results indicate that all the extracts inhibited the corrosion process in both acid media by virtue of adsorption and inhibition efficiency improved with concentration. Synergistic effects increased the inhibition efficiency in the presence of halide additives. Inhibition mechanisms were deduced from the temperature dependence of the inhibition efficiency as well as from assessment of kinetic and activation parameters that govern the processes. Comparative analysis of the inhibitor adsorption behaviour in 2 M HCl and 1 M H₂SO₄ as well as the effects of temperature and halide additives suggest that both protonated and molecular species could be responsible for the inhibiting action of the extracts.     

The influence of pH value on the efficiency of imidazole based corrosion inhibitors of copper

The aim of this work is to establish the correlation between the solution pH and the inhibiting efficiency of two imidazole compounds (4-methyl-1-phenyl imidazole and 4-methyl-1-(p-tolyl) imidazole) in protection of copper from corrosion in chloride media.It was found that the inhibiting efficiency of both studied imidazoles enhances with the increase of the solution pH value, from about 20% in 0.5 M HCl to 92% in 0.5 M NaCl. This improvement was ascribed to stronger adsorption of neutral imidazole molecule, which can be expected at higher pH values, than that of the protonated imidazole cation, which may be expected in acid solutions.     

AC corrosion - Part 1: Effects on overpotentials of anodic and cathodic processes

AC-induced corrosion is a controversial subject and many aspects of it need to be clarified, first and foremost, the mechanism and relationship between AC density and corrosion rate. This paper (Part 1) presents and discusses the effects of AC interference on kinetics parameters; the effects on corrosion rate and corrosion mechanism will be discussed in Part 2. Polarisation curves were obtained in different solutions (soil-simulating solution, 35 g L⁻¹ NaCl, 1 M FeSO₄, 1 M CuSO₄ and 1 M ZnSO₄) on different metallic materials (carbon steel, galvanised steel, zinc and copper) in the presence of AC interference (30-1000 A/m²).     

Quinolin-5-ylmethylene-3-{[8-(trifluoromethyl)quinolin-4-yl]thio}propanohydrazide as an effective inhibitor of mild steel corrosion in HCl solution

Quinolin-5-ylmethylene-3-{[8-(trifluoromethyl)quinolin-4-yl]thio}propanohydrazide (QMQTPH) was synthesized, characterized and tested as a corrosion inhibitor for mild steel in 1 M and 2 M HCl solution using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). Polarization resistances calculated from the EIS measurements were in good agreement with those obtained from direct current (DC) polarization measurements. The mild steel samples were also analyzed by scanning electron microscopy (SEM). The results showed that QMQTPH is an excellent inhibitor for mild steel in acid medium. The inhibition was assumed to occur via adsorption of the inhibitor molecule on the metal surface. It acts as an anodic inhibitor. In the 30° to 60 °C temperature range, the QMQTPH adsorption follows Langmuir isotherm model. The protection efficiency increased with increasing inhibitor concentration in the range 10⁻⁵ − 10⁻³ M, but slightly decreased with increasing temperature.     

The inhibition effect of 2,4,6-tris (2-pyridyl)-1,3,5-triazine on corrosion of tin, indium and tin-indium alloys in hydrochloric acid solution

The influence of 2,4,6-tris (2-pyridyl)-1,3,5-triazine (TPTZ) on the corrosion of tin, indium and tin-indium alloys in 0.5 M HCl solution at different temperatures was studied. Potentiodynamic cathodic polarization and extrapolation of cathodic and anodic Tafel lines techniques were used to obtained experimental data. In the case of tin, the percent inhibition efficiency (IE%) increases as both concentration of TPTZ and temperature are increased. The value of activation energy (E_a) is smaller in the presence of TPTZ than that in uninhibited solution, and decreases with increasing the concentration. However, the effect of TPTZ on indium and the investigated alloys exhibited similar behavior; so, the maximum inhibition efficiency is observed at lowest concentration (10⁻⁶ M) of TPTZ. Then, the value of inhibition efficiency starts to decrease gradually with increasing TPTZ concentration than that of 10⁻⁶ M. But at higher concentration (10⁻³ M) the corrosion current density (I_corr) is still lower than that in uninhibited solution. SEM photographs support that the higher inhibition efficiency is observed at 10⁻⁶ M of TPTZ.The plots of ln K versus 1/T in the presence of the TPTZ in the case of tin, the inhibitor showed linear behavior. The standard enthalpy, ΔH°_ads., entropy, ΔS°_ads. and free energy changes of adsorption ΔG°_ads. were evaluated using Frumkin adsorption isotherm.     

Inhibitive effect of sodium eperuate on zinc corrosion in alkaline solutions

The effect of sodium eperuate prepared from Wallaba (Eperua falcata Aubl) extract on zinc corrosion was investigated in alkaline solutions with chloride ions (i.e., simulated concrete pore solutions) by using electrochemical techniques. Sodium eperuate inhibits the corrosion of zinc in 0.1 M NaCl solutions with pH 9.6. As its concentration increases to 1 g/L, the inhibition efficiency reaches approximately 92%. In alkaline solutions with pH 12.6, sodium eperuate has no adverse effect on passivity of zinc, and retards the chloride attack. These suggest that sodium eperuate is an effective inhibitor for the protection of zinc in alkaline environments.     

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.     

Benzimidazole and its derivatives as corrosion inhibitors for mild steel in 1M HCl solution

In this paper, the inhibition ability of benzimidazole and its derivatives against the corrosion of mild steel in 1M HCl solution was studied. The change of impedance parameters observed by variation of inhibitors concentration within the range of 50-250 ppm was an indication of their adsorption. The thermodynamic adsorption parameters proposed that these inhibitors retard both cathodic and anodic processes through physical adsorption and blocking the active corrosion sites. The adsorption of these compounds obeyed the Langmuir’s adsorption isotherm. The inhibition efficiency was increased with inhibitor concentration in the order of 2-mercaptobenzimidazole > 2-methylbenzimidazole > benzimidazole, which is in accordance with the variation of apparent activation energy of corrosion.     

Adsorption and inhibitive properties of some new Mannich bases of Isatin derivatives on corrosion of mild steel in acidic media

Adsorption of four derivatives of piperidinylmethylindoline-2-one on mild steel surface in 1 M HCl solution and its corrosion inhibition properties has been studied by a series of techniques, such as polarization, electrochemical impedance spectroscopy (EIS), weight loss and quantum chemical calculation methods. The values of activation energy (E_a) for mild steel corrosion and various thermodynamic parameters were calculated and discussed. Potentiodynamic polarization measurements showed that all inhibitors are mixed type. The degree of surface coverage was determined by using weight loss measurements and it was found that adsorption process of studied inhibitors on mild steel surface obeys Langmuir adsorption isotherm.     

Polyphosphate derivatives of guanidine and urea copolymer: Inhibiting corrosion effect of Armco iron in acid solution and antibacterial activity

A new corrosion inhibitor, namely, polyphosphate derivative of guanidine and urea copolymer (PGUC) has been synthesised and its inhibiting action on the corrosion of Armco iron in molar hydrochloric acid (1 M HCl) has been investigated at 30 °C using electrochemical impedance spectroscopy method (EIS). Data obtained from EIS measurements were analysed to model the corrosion inhibition process through appropriate equivalent circuit model. The experimental results revealed that PGUC is an efficient inhibitor and the inhibition efficiency increases with increase in inhibitor concentration, reaching value up to 91% at a concentration of 11.5 g/l. Adsorption of PGUC on the Armco iron surface in 1 M HCl solution follows Temkin’s isotherm. The low negative value of the standard free energy of adsorption, , indicates the physical nature of adsorption (physisorption) of PGUC. The inhibition mechanism of PGUC was discussed. This inhibitor can be used as biocides in aqueous environments. The results showed also that the PGUC has a broad inhibitory spectrum against both Gram positive and Gram negative bacteria. The MIC measured for Staphylococcus aureus was of ca 6-fold lower than the efficient inhibitory corrosion concentration of PGUC (11.5 g/l). However, the MICs measured for Escherichia coli and Pseudomonas aeruginosa were of ca 2.7-fold and of ca 10.9 higher than this concentration.     

Galvanic corrosion between the constituent phases in duplex stainless steel

The exclusive single-phase with the exact chemical composition of the constituent phase in 2205 duplex stainless steel (DSS) could be prepared using selective dissolution method. The respective electrochemical behavior of each constituent phase could then be measured. The experimental results showed that the two distinct peaks in the active-to-passive transition region of the polarization curve determined in 2 M H₂SO₄ + 0.5 M HCl mixed solution were actually corresponded to the respective anodic peaks of the single austenite and ferrite phases. A polarity reversion was found between austenite and ferrite phases in mixed H₂SO₄ + HCl solution and HNO₃ solution. Galvanic current measurements also revealed that austenite was anode in HNO₃ solution, but became cathode when exposed in 2 M H₂SO₄ + 0.5 M HCl mixed solution.     

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.     

Corrosion control of mild steel using 3,5-bis(4-methoxyphenyl)-4-amino-1,2,4-triazole in normal hydrochloric acid medium

The inhibition performance of the 3,5-bis(4-methoxyphenyl)-4-amino-1,2,4-triazole (4-MAT) on mild steel in normal hydrochloric acid medium (1 M HCl) at 30 °C was tested by weight loss, potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS) techniques. This organic compound inhibits the acidic corrosion even at very low concentration, reaching a value of inhibition efficiency up to 98% at a concentration of 3 × 10⁻⁴ M. The results obtained from the different corrosion evaluation techniques are in good agreement. Polarisation curves indicate that 4-MAT is a mixed inhibitor, affecting both cathodic and anodic corrosion currents. Data, obtained from EIS measurements, were analyzed to model the corrosion inhibition process through appropriate equivalent circuit model, a constant phase element (CPE) has been used. The adsorption of 4-MAT on the steel surface, in 1 M HCl solution, obeys to Langmuir’s isotherm with a very high negative value of the free energy of adsorption ΔG°_ads (chemisorption). X-ray photoelectron spectroscopy (XPS) was carried out to establish the mechanism of corrosion inhibition of mild steel in 1 M HCl medium in the presence of 3,5-bis(4-methoxyphenyl)-4-amino-1,2,4-triazole (4-MAT).