Electrochemical, theoretical and XPS studies of 2-mercapto-1-methylimidazole adsorption on carbon steel in 1 M HClO4

The inhibition of the corrosion of carbon steel in 1 M HClO₄ by 2-mercapto-1-methylimidazole (MMI) has been investigated in relation to the concentration of the inhibitor as well as the temperature using weight loss and electrochemical measurements. The effect of the temperature on the corrosion behaviour with addition of different concentrations of MMI was studied in the temperature range 30-60 °C. Polarization curves reveal that MMI is a mixed type inhibitor. The inhibition efficiency of MMI is temperature independent but increases with the inhibitor concentration. Changes in impedance parameters (charge transfer resistance, R_t, and double-layer capacitance, C_dl) were indicative of adsorption of MMI on the metal surface, leading to the formation of a protective film. Adsorption of MMI on the carbon steel surface is found to obey the Langmuir adsorption isotherm. Some thermodynamic functions of dissolution and adsorption processes were also determined. The X-ray photoelectron spectroscopy (XPS) of the carbon steel indicated that MMI is chemically adsorbed on the steel surface. Moreover, the electronic properties such as highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO) energy levels and molecular orbital densities were calculated.     

The inhibitive effect of bipyrazolic derivatives on the corrosion of steel in hydrochloric acid solution

The effect of two pyrazole-type organic compounds, namely ethyl 5,5′-dimethyl-1′H-1,3′-bipyrazole-3 carboxylate (P1) and 3,5,5′-trimethyl-1′H-1,3′-bipyrazole (P2) on the corrosion behaviour of steel in 1 M hydrochloric acid (HCl) solution is investigated at 308 K by weight loss measurements, potentiodynamic polarisation and impedance spectroscopy (EIS) methods. The inhibition efficiencies obtained from cathodic Tafel plots, gravimetric and EIS methods are in good agreement. Results obtained show that the compound P2 is the best inhibitor and its efficiency reaches 84% at 10⁻³ M. Potentiodynamic polarisation studies show that pyrazolic derivatives are cathodic-type inhibitors and these compounds act on the cathodic reaction without changing the mechanism of the hydrogen evolution reaction. The inhibition efficiency of P2 is temperature-dependent in the range from 308 to 353 K and the associated activation energy has been determined. P2 adsorbs on the steel surface according to Langmuir adsorption model. The calculation of the total partial charge of inhibitor atoms is computed.     

Caffeine as non-toxic corrosion inhibitor for copper in aqueous solutions of potassium nitrate

Different electrochemical methods were employed in order to confirm the ability of caffeine (1,3,7-trimethylxanthine) to inhibit the corrosion processes of copper in aqueous potassium nitrate solutions in the absence and in the presence of chloride. Some experiments were repeated in potassium perchlorate in order to compare the influence of the medium. The interaction between the organic compound and the electrode surface occurs independently of the electrode potential. However, maximum interaction was observed at 0.0 V (Ag/AgCl) in aerated solutions, and at −0.25 V (Ag/AgCl) in deaerated solutions.The presence of the organic compound adsorbed on the electrode surface was confirmed by comparing the voltammograms of copper electrode in the absence and presence of 1.5 mmol L⁻¹ of dissolved caffeine. The same results were observed by comparing polarization curves in the absence and in the presence of caffeine.Anodic currents decrease noticeably in the presence of the organic compound. Chronoamperometric experiments were conclusive to prove the inhibitor capability of caffeine to decrease the corrosion dissolution processes of copper under anodic polarization.     

An electroactive co-polymer as corrosion inhibitor for steel in sulphuric acid medium

The corrosion behavior of mild steel in sulphuric acid solution containing various concentrations of a co-polymer formed between maleic anhydride and N-vinyl-2-pyrrolidone (VPMA) was investigated using weight-loss, polarization and electrochemical impedance techniques. The polymer acts as an effective corrosion inhibitor for steel in sulphuric acid medium. The inhibition process is attributed to the formation of an adsorbed film of co-polymer on the metal surface which protects the metal against corrosion. Scanning electron microscopy (SEM) studies of the metal surfaces confirmed the existence of an adsorbed film. The adsorption followed the Langmuir isotherm. The protection efficiency increased with increase in inhibitor concentration and decreased with increase in temperature and acid concentration. The thermodynamic functions of the adsorption and dissolution processes were evaluated.     

Pyridine–pyrazole compound as inhibitor for steel in 1 M HCl

The influence of 3,5-dimethyl-1H-pyrazole (P1), pyridine (P2) and 2-(3-methyl-1H-pyrazol-5-yl) pyridine (P3) on the corrosion inhibition of steel in molar hydrochloric acid solution is studied using weight-loss, potentiodynamic and EIS measurements. Results obtained shows that P3 is the best inhibitor and its inhibition efficiency increases with the increase of concentration to attain 89% since 10⁻³ M. Potentiodynamic polarisation studies clearly reveal that it acts essentially as a cathodic inhibitor. The inhibitor studied reduces the corrosion rates. E (%) values obtained from various methods used are in good agreement. Adsorption of P3 on steel surface has an S-shaped adsorption isotherm.     

Effects of 2-amino-5-(ethylthio)-1,3,4-thiadiazole on copper corrosion as a corrosion inhibitor in 3% NaCl solutions

Effects of 2-amino-5-(ethylthio)-1,3,4-thiadiazole (ATD) on copper corrosion as a corrosion inhibitor in de-aerated, aerated and oxygenated 3% NaCl solutions have been studied using potentiodynamic polarization, potentiostatic current-time, electrochemical impedance spectroscopic (EIS), weight loss and pH measurements along with scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) investigations. Potentiodynamic polarization measurements indicated that the presence of ATD in these solutions greatly decreases cathodic, anodic and corrosion currents. Potentiostatic current-time measurements and SEM/EDX investigations also showed that the ATD molecules are strongly adsorbed on the copper surface preventing it from being corroded easily. EIS measurements revealed that the charge transfer resistance increases due to the presence of ATD, and this effect increases with oxygen content in the solution. Weight loss measurements gave an inhibition efficiency of about 83% with 1.0 mM ATD present, increasing to about 94% at the ATD concentration of 5.0 mM. Results together are internally consistent with each other, showing that ATD is a good mixed-type inhibitor for copper corrosion with its inhibition efficiency increasing in the order of oxygenated > aerated > de-aerated 3% NaCl solutions.     

The effect of some Schiff bases on the corrosion of aluminum in hydrochloric acid solution

The inhibition effect of Schiff bases benzylidene-(2-methoxy-phenyl)-amine (A), (2-methoxy-phenyl)-(4-methyl-benzylidene)-amine (B), (4-chloro-benzylidene)-(2-methoxy-phenyl)-amine (C) and (4-nitro-bezylidene)-(2-methoxy-phenyl)-amine (D) on the corrosion of aluminum in 1 M HCl has been studied by polarization, electrochemical impedance spectroscopy (EIS) and weight loss measurements. It has been found that all the studied Schiff bases are excellent inhibitors. Maximum inhibition was obtained for 0.01 M Schiff base A. Results show that the inhibition efficiency increases with decreasing in temperature and increasing in concentration of Schiff base. Polarization curves reveal that the used inhibitors are mixed type inhibitors. The surface adsorption of the Schiff bases leads to a decrease of double layer capacitance as well as an increase of polarization resistance. The inhibitor performance depends strongly on the type of function groups substituted on benzene ring. The adsorption of used compounds on the aluminum surface obeys a Langmuir isotherm and has a physical mechanism. Thermodynamic parameters for both dissolution and adsorption processes were determined. The quantum chemical study of the corrosion inhibition efficiency of the Schiff bases on Al in molar HCl was carried out.     

2-Mercaptobenzothiazole doped chitosan/11-alkanethiolate acid composite coating: Dual function for copper protection

Chitosan (CS) hydrogel loaded with the well-known corrosion inhibitor 2-mercaptobenzothiazole (MBT) has been introduced into a composite coating to improve copper protection. This composite coating, which has both anticorrosion and antibacterial properties, was fabricated onto the surface of copper by combining a simple self-assembled monolayer technique with a sol-gel method. The anti-corrosion ability of the coating in 3.5 wt.% NaCl solution was investigated by electrochemical methods including potentiodynamic polarization and electrochemical impedance spectroscopy. The protection efficiency of the coating is 97.70%, calculated on the basis of the corrosion current density. The stability and integrity of the composite coating were evaluated by field emission scanning electron microscopy (FESEM) and energy dispersive spectrometry (EDS). The FESEM and EDS results suggest that the composite coating endows the copper substrate with antibacterial properties, as untreated bare copper underwent microbiologically influenced corrosion in the presence of sulphate reducing bacteria (SRB). This antibacterial feature was further confirmed by the SRB culture method. In a 3.5% NaCl solution and highly corrosive SRB culture media, the as-prepared CS based composite coating gave corrosion protection by exhibiting better barrier effects against the attack of aggressive environments.     

Khillah extract as inhibitor for acid corrosion of SX 316 steel

The inhibitive effect of the extract of khillah (Ammi visnaga) seeds, on the corrosion of SX 316 steel in HCl solution was determined using weight loss measurements as well as potentiostatic technique. It was found that the presence of the extract reduces markedly the corrosion rate of steel in the acid solution. The inhibition efficiency increases as the extract concentration is increased. The inhibitive effect of khillah extract was discussed on the basis of adsorption of its components on the metal surface. Negative values were calculated for the energy of adsorption indicating the spontaneity of the adsorption process. The formation of insoluble complexes as a result of interaction between iron cations and khellin, which present in the extract, was also discussed.     

Inhibiting effects of some oxadiazole derivatives on the corrosion of mild steel in perchloric acid solution

The efficiency of 3,5-bis(n-pyridyl)-1,3,4-oxadiazole (n-POX, n = 1, 2, 3), as corrosion inhibitors for mild steel in 1 M perchloric acid (HClO₄) have been determined by weight loss measurements and electrochemical studies. The results show that these inhibitors revealed a good corrosion inhibition even at very low concentrations. Comparison of results among those obtained by the studied oxadiazoles shows that 3-POX was the best inhibitor. Polarisation curves indicate that n-pyridyl substituted-1,3,4-oxadiazoles are mixed type inhibitors in 1 M HClO₄. The adsorption of these inhibitors follows a Langmuir isotherm model. The electronic properties of n-POX, obtained using the AM1 semi-empirical quantum chemical approach, were correlated with their experimental efficiencies using the linear resistance model (LR).     

The inhibited effect of some tetrazolic compounds towards the corrosion of brass in nitric acid solution

The effect of the addition of some tetrazolic type organic compounds: 1-phenyl-5-mercapto-1,2,3,4-tetrazole (PMT), 1,2,3,4-tetrazole (TTZ), 5-amino-1,2,3,4-tetrazole (AT) and 1-phenyl-1,2,3,4-tetrazole (PT) on the corrosion of brass in nitric acid is studied by weight loss, polarisation and electrochemical impedance spectroscopy (EIS) measurements. The explored methods gave almost similar results. Results obtained reveal that PMT is the best inhibitor and the inhibition efficiency (E%) follows the sequence: PMT > PT > AT > TTZ. Polarization measurements also indicated that tetrazoles acted as mixed-type inhibitors without changing the mechanism of the hydrogen evolution reaction. Partial π-charge on atoms has been calculated. Correlation between the highest occupied molecular orbital energy E_HOMO and inhibition efficiencies was sought. The adsorption of PMT on the brass surface followed the Langmuir isotherm. Effect of temperature is also studied in the (25-50 °C) range.     

Tween-40 as corrosion inhibitor for cold rolled steel in sulphuric acid: Weight loss study, electrochemical characterization, and AFM

The inhibition action of a non-ionic surfactant of tween-40 on the corrosion of cold rolled steel (CRS) in 0.5-7.0 M sulphuric acid (H₂SO₄) was studied by weight loss and potentiodynamic polarization methods. Atomic force microscope (AFM) provided the surface conditions. The inhibition efficiency increases with the tween-40 concentration, while decreases with the sulphuric acid concentration. The adsorption of inhibitor on the cold rolled steel surface obeys the Langmuir adsorption isotherm equation. Effect of immersion time was studied and discussed. The effect of temperature on the corrosion behavior of cold rolled steel was also studied at four temperatures ranging from 30 to 60 °C, the thermodynamic parameters such as adsorption heat, adsorption free energy and adsorption entropy were calculated. A kinetic study of cold rolled steel in uninhibited and inhibited acid was also discussed. The kinetic parameters such as apparent activation energy, pre-exponential factor, rate constant, and reaction constant were calculated for the reactions of corrosion. The inhibition effect is satisfactorily explained by both thermodynamic and kinetic parameters. Polarization curves show that tween-40 is a cathodic-type inhibitor in sulphuric acid. The results obtained from weight loss and potentiodynamic polarization are in good agreement, and the tween-40 inhibition action could also be evidenced by surface AFM images.     

Enhanced corrosion resistance of mild steel in molar hydrochloric acid solution by 1,4-bis(2-pyridyl)-5H-pyridazino[4,5-b]indole: Electrochemical, theoretical and XPS studies

The inhibition effect of the new pyridazine derivative, namely 1,4-bis(2-pyridyl)-5H-pyridazino[4,5-b]indole (PPI) against mild steel corrosion in 1 M HCl solutions was evaluated using weigh loss and electrochemical techniques (potentiodynamic polarisation curves and impedance spectroscopy). The experimental results suggest that PPI is a good corrosion inhibitor and the inhibition efficiency increased with the increase of PPI concentration, while the adsorption followed the Langmuir isotherm. X-ray photoelectron spectroscopy (XPS) and theoretical calculation of electronic density were carried out to establish the mechanism of corrosion inhibition of mild steel with PPI in 1 M HCl medium. The inhibition action of this compound was, assumed to occur via adsorption on the steel surface through the active centres contained of the molecule. The corrosion inhibition is due to the formation of a chemisorbed film on the steel surface.     

1,3-Bis(3-hyroxymethyl-5-methyl-1-pyrazole) propane as corrosion inhibitor for steel in 0.5 M H2SO4 solution

The effect of addition of 1,3-bis(3-hyroxymethyl-5-methyl-1-pyrazole) propane (M = 264 g). HMPP on steel corrosion in 0.5 M sulphuric acid is studied by weight-loss, electrochemical polarisation and electrochemical impedance spectroscopy (EIS) measurements at various temperatures. The results obtained showed that HMPP acts as a good corrosion inhibitor. The inhibition efficiency increases with the bipyrazole compound to attain 88%. It acts as a mixed-type inhibitor. Trends in the increase of charge-transfer resistance and decrease of capacitance values also show the adsorption of the molecule on the metal surface. The bipyrazole adsorbs on the steel surface according to the Langmuir isotherm adsorption model. Effect of temperature indicates that inhibition efficiency decreases with temperature between 25 and 85 °C.     

Synergistic effect between 4-(2-pyridylazo) resorcin and chloride ion on the corrosion of cold rolled steel in 0.5 M sulfuric acid

The corrosion inhibition of 1-(2-pyridylazo)-2-naphthol (PAR) on the corrosion of cold rolled steel in 0.5 M sulfuric acid (H₂SO₄) was studied using weight loss method and potentiodynamic polarization method. Results obtained revealed that together with chloride ion, PAR is an effective corrosion inhibitor for steel corrosion in sulfuric acid. It was found that for steel corrosion inhibition in the presence of single PAR in sulfuric acid the Temkin adsorption isotherm may be used to explain the adsorption phenomenon. For the mixture of PAR and NaCl used as corrosion inhibitor, however, the Langmuir adsorption isotherm can be used to satisfactorily elucidate the adsorption of mixture of PAR and NaCl. Potentiodynamic polarization studies showed that single PAR mainly acts as a cathodic inhibitor for the corrosion of steel in 0.5 M sulfuric acid. The mixture of PAR and chloride ion, however, acts as a mixed type inhibitor that mainly inhibits cathodic reaction of the steel corrosion in sulfuric acid. By means of electrochemical polarization tests, a desorption potential at ca. −370 mV was observed for the adsorption of mixture of PAR and chloride ion, when potential reaches this value, adsorbed inhibitor molecule heavily departs from the steel surface. For the mixture of PAR and chloride ion, thermodynamic parameters such as adsorption heat, adsorption entropy and adsorption free energy were obtained from experimental data of the temperature studies of the inhibition process at four temperatures ranging from 30 to 45 °C, the kinetic data such as apparent activation energies and pre-exponential factors at different concentrations of the inhibitor were calculated, and the effect of the apparent activation energies and pre-exponential factors on the corrosion rates of cold rolled steel was discussed. The most suitable range of inhibitor concentration was discussed. The inhibitive action was satisfactorily explained by using both thermodynamic and kinetic models. Synergism between chloride ion and PAR was proposed. The results obtained from weight loss and potentiodynamic polarization were in good agreement.     

Synergistic effect between 4-(2-pyridylazo) resorcin and chloride ion on the corrosion of cold rolled steel in 1.0 M phosphoric acid

The synergistic inhibition between 4-(2-pyridylazo) resorcin (PAR) and chloride ion on the corrosion of cold rolled steel in 1.0 M phosphoric acid was studied using weight loss and potentiodynamic polarization method. Results obtained revealed that single PAR is not an effective inhibitor for steel corrosion in phosphoric acid, but in the presence of chloride ion, PAR may act as a good inhibitor due to the synergism. It is found that the adsorption of PAR accords with the Langmuir adsorption isotherm in the absence and presence of chloride ion. Potentiodynamic polarization studies show that PAR is an anodic inhibitor for steel in 1.0 M phosphoric acid, and with addition of chloride ion PAR acts as a mixed type inhibitor. The experimental temperature ranges from 30 to 45 °C. The kinetic data such as apparent activation energies and pre-exponential factors at different concentrations of the inhibitor were calculated, and the effect of the apparent activation energies and pre-exponential factors on the corrosion rates of cold rolled steel was discussed. The inhibitive action was satisfactorily explained by using kinetic models.     

Experimental and computational studies of naphthyridine derivatives as corrosion inhibitor for N80 steel in 15% hydrochloric acid

The inhibition effect of three naphthyridine derivatives namely 2-amino-4-(4-methoxyphenyl)-1,8-naphthyridine-3-carbonitrile (ANC-1), 2-amino-4-(4-methylphenyl)-1,8-naphthyridine-3-carbonitrile (ANC-2) and 2-amino-4-(3-nitrophenyl)-1,8-naphthyridine-3-carbonitrile (ANC-3) as corrosion inhibitors for N80 steel in 15% HCl by using gravimetric, electrochemical techniques (EIS and potentiodynamic polarization), SEM, EDX and quantum chemical calculation. The order of inhibition efficiency is ANC-1>ANC-2>ANC-3. Potentiodynamic polarization reveals that these inhibitors are mixed type with predominant cathodic control. Studied inhibitors obey the Langmuir adsorption isotherm. The quantum calculation is in good agreement with experimental results.     

Inhibitive action of indole-5-carboxylic acid towards corrosion of mild steel in deaerated 0.5 M sulfuric acid solutions

Inhibition of mild steel corrosion in deaerated 0.5 M sulfuric acid solutions containing various concentrations of indole-5-carboxylic acid is studied in the temperature range from 25 to 55 °C using weight-loss, potentiodynamic and spectrophotometric tests. The adsorptive behaviour of inhibitor is also investigated using electrochemical impedance spectroscopy measurements. The indole-5-carboxylic acid is found to shift the corrosion potentials towards more noble values. This shift indicates that the addition of inhibitor mainly affects the anodic process, raising the anodic overpotential more than that of the cathodic, i.e. the indole-5-carboxylic acid behaves as mixed-type inhibitor. Because the cathodic Tafel slopes for hydrogen reduction (b_c) are affected, the inhibitor probably affects the hydrogen reduction mechanism. The activation energy values (E_a) indicate that the indole-5-carboxylic acid increases the activation energy of the corrosion reaction. The adsorption behaviour of indole-5-carboxylic acid follows Langmuir's isotherm. Both the low values of and its decrease with temperature suggest physical adsorption. Double layer capacitance-potential curves indicate considerable adsorption of the inhibitor in the potential range (−400 to −800 mV/_SCE).     

Inhibition of copper corrosion by bis-(1,1′-benzotriazoly)-α,ω-diamide compounds in aerated sulfuric acid solution

Three kinds of novel corrosion inhibitors, bis-(1,1′-benzotriazoly)-α,ω-succinyldiamide (BSU), bis-(1,1′-benzotriazoly)-α,ω-adipoyldiamide (BAD), and bis-(1,1′-benzotriazoly)-α,ω-azelayldiamide (BAZ) were synthesized and certified by IR and ¹H NMR. Their corrosion inhibition effects for copper in 0.5 M H₂SO₄ were evaluated by weight-loss method. It shows that among the three compounds, only BSU behaves better compared with BTA. The inhibition efficiency (IE) increased with increasing BSU concentration to 85.2% at the 5 × 10⁻⁴ M level. Polarization studies showed that BSU suppressed both anodic and cathodic corrosion reactions. The minimum energy conformation of these compounds was obtained by MM2 force field program. The two benzotriazoly moieties in BSU molecule are more parallel than in other compounds. This is benefit to increase the inhibition effects of BSU.     

Investigation of the inhibiting action of O-, S- and N-dithiocarbamato(1,4,8,11-tetraazacyclotetradecane)cobalt(III) complexes on the corrosion of iron in HClO4 acid

The inhibiting properties of four macrocyclic cobalt(III) complexes of the general formula [Co^III(Rdtc)cyclam](ClO₄)₂, where cyclam and Rdtc⁻ refer to 1,4,8,11-tetraazacyclotetradecane and morpholine-, thiomorpholine-, piperazine-, N-methylpiperazine-dithiocarbamates, respectively, has been studied on the corrosion of iron in aerated 0.1 M HClO₄ solutions by potentiodynamic polarization (dc) technique and electrochemical impedance spectroscopy (ac). Inhibitor efficiency for the corrosion of iron is found to be better for cobalt complexes then for related amino-ligands. The impedance increases with inhibitor concentration. Polarization curves indicate that the inhibitors are predominantly mixed-type. Better protection by the complex inhibitors was obtained with longer immersion time. The best fit for inhibitors adsorption is obtained using the Langmuir isotherm model. Molecular modeling calculations were used to correlate structural properties of the complex species and their inhibition efficiency.