Inhibitive properties of quaternary ammonium bromides of N-containing heterocycles on acid mild steel corrosion. Part I: Gravimetric and voltammetric results

Four quaternary ammonium bromides of different heterocyclic compounds were investigated as corrosion inhibitors of mild steel in 1 M HCl and 1 M H₂SO₄. Polarisation curves, polarisation resistance and gravimetric methods were used. The inhibitor efficiency was found to depend on both concentration and temperature. The inhibitors were of mixed type, influencing predominantly the anodic process. From the temperature dependences the apparent activation energy in 1 M HCl was determined in the presence of all studied compounds, found to be inferior to the activation energy in absence of inhibitor. The adsorption of the inhibitors was well described by the Frumkin or the Langmuir adsorption isotherms in both acidic media and the adsorption isotherm parameters were determined at room temperature. The influence of the molecular structure was discussed taking into account the different number of positive charges and the different heterocycles. The best inhibitive properties had 1-(carbamoylethyl)-4-methylpyridinium bromide.     

Effect of the molecular structure on the inhibitor properties of azoles on mild steel corrosion in 1 M hydrochloric acid

Five azoles were investigated as corrosion inhibitors of mild steel in 1 M HCl using gravimetric and polarisation techniques. The chosen azoles have similar chemical structure - their molecules have similar geometry and in an adsorption state almost the same area. The inhibiting properties were found to depend on both the concentration and the molecular structure of the compounds. The adsorption of benzimidazole and 1,3-benzothiazole is described by the Frumkin isotherm, while in the case of 1H-benzotiazole and indole the Langmuir isotherm can be applied. An attempt was made to correlate the inhibitive properties with the electronic structure of the molecules and it was found that the inhibitor properties are connected with the presence of aromatic structure which includes the heterocycle and depend on the number of the lone electron pairs. The HOMO and LUMO energies were calculated and it was found that their values can explain only some features of the observed phenomena.     

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.     

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.     

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.     

Sodium molybdate as a corrosion inhibitor for aluminium in H3PO4 solution

The inhibition effect of sodium molybdate (Na₂MoO₄) on the corrosion of aluminium in 1.0 M H₃PO₄ solution was studied by weight loss, potentiodynamic polarisation curves and electrochemical impedance spectroscopy (EIS) methods. The results show that Na₂MoO₄ is a good inhibitor, and the inhibition efficiency obtained by three methods is higher than 84% at 20 mM. The adsorption of Na₂MoO₄ obeys Freundlich isotherm at lower concentrations (1–7 mM), while Langmuir isotherm at higher concentrations (7–20 mM). Polarisation curves indicate that Na₂MoO₄ acts as an anodic inhibitor. EIS spectra exhibit three loops (two capacitive loops and one inductive loop).     

Corrosion and corrosion control of mild steel in concentrated H2SO4 solutions by a newly synthesized glycine derivative

A newly synthesized glycine derivative (GlyD1), 2-(4-(dimethylamino)benzylamino)acetic acid hydrochloride, was used to control mild steel corrosion in 4.0 M H₂SO₄ solutions at different temperatures (278–338 K). Tafel extrapolation, linear polarization resistance (LPR) and impedance methods were used to test corrosion inhibitor efficiency. 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. Results obtained were compared with an available glycine derivative (GlyD2) and glycine (Gly). Tafel polarization measurements revealed that the three tested inhibitors function as mixed-type compounds. The inhibition efficiency increased with increase in inhibitor concentration and decreased with temperature, suggesting the occurrence of physical adsorption. The adsorptive behaviour of the three inhibitors followed Temkin-type isotherm and the standard free energy changes of adsorption () were evaluated for the three tested inhibitors as a function of temperature. The inhibition performance of GlyD1 was much better than those of GlyD2 and Gly itself. Results obtained from the different corrosion evaluation techniques were in good agreement.     

Diphenolic Schiff bases as corrosion inhibitors for aluminium in 0.1 M HCl: Potentiodynamic polarisation and EQCM investigations

The effects of novel synthesised two Schiff bases on the corrosion of aluminium in 0.1 M HCl were investigated using potentiodynamic polarisation and electrochemical quartz crystal microbalance measurements. Results show that inhibition efficiencies increase with increase in inhibitor concentration. This reveals that the inhibition occurs through adsorption of the inhibitor molecules on the metal surface. Adsorption of these inhibitors follows Temkin adsorption isotherm. The correlation between the inhibitor performances and their molecular structures has been investigated using quantum chemical parameters obtained by MNDO (modified neglect of diatomic overlap) semi-empirical method. Calculated quantum chemical parameters indicate that Schiff bases adsorbed on aluminium surface by chemical mechanism.     

Temperature effect on mild steel corrosion in acid media in presence of azoles

The inhibiting properties of four azoles (indole, benzimidazole, benzotriazole, benzothiazole) were investigated in case of mild steel corrosion in 1 M HCl. The effect of temperature was followed. Impedance spectroscopy, polarization resistance, gravimetric and polarization curves methods were applied. An adequate structural model of the interface in inhibitors presence is offered and the values of the corresponding parameters are calculated. The apparent activation energy of the process taking place in an inhibitor presence was determined on the ground of five temperature values in the range from 20 °C to 60 °C using the data obtained by two independent methods. Comparative investigations were carried out in 1 M H₂SO₄ aiming to elucidate the effect of the acid’s anion. The generalization of the data obtained provided to make conclusions concerning the mechanism of the inhibitors’ adsorption.     

Mono- and dicationic benzothiazolic quaternary ammonium bromides as mild steel corrosion inhibitors. Part II: Electrochemical impedance and polarisation resistance results

Seven quaternary ammonium bromides of different heterocyclic compounds were investigated as corrosion inhibitors of mild steel in 1 M HCl using electrochemical impedance and polarisation resistance techniques. Adequate structure models of the interface as well as some data on the kinetics of the partial processes are presented. Experimental data revealed frequency distribution of the capacitance, simulated as constant phase element. The values of the structure models and the time constants have been found by fitting the experimental curves. The values of the resistances were compared with those obtained from dc polarisation resistance measurements. The inhibitor efficiency of the studied compounds was determined.     

Corrosion inhibition efficiency and surface activity of benzothiazol-3-ium cationic Schiff base derivatives in hydrochloric acid

Two series of cationic Schiff base surfactants namely: 2-(benzylideneamino)-3-(2-oxo-2-alkoxyethyl)-1,3-benzothiazol-3-ium bromide and 2-[(4-methoxybenzylidene)amino]-3-(2-oxo-2-alkoxyethyl)-1,3-benzothiazol-3-ium bromide were prepared and confirmed using elemental analysis, FTIR, and ¹H NMR spectra. The surface activity of the synthesized Schiff bases showed their tendency towards adsorption at the interfaces. The prepared compounds were evaluated as corrosion inhibitors for carbon steel in 0.5 M HCl solution using gravimetric and polarization measurements. By fitting the gravimetric data, some thermodynamic and kinetic parameters were estimated. The adsorption of the inhibitors on the carbon steel surface obeyed Langmuir adsorption isotherm and had a physical mechanism. Polarization measurements showed that the synthesized inhibitors act as mixed inhibitors for carbon steel in the acidic media. The results of the corrosion inhibition using two different methods showed narrow differences in the obtained values between the two methods within 5%.     

Inhibitive properties, thermodynamic and quantum chemical studies of alloxazine on mild steel corrosion in H2SO4

Alloxazine (ALLOX) was tested as corrosion inhibitor for mild steel in 0.5 M H₂SO₄ solution using non-electrochemical technique (gravimetric and UV–Visible spectrophotometric measurements) at 303–333 K. ALLOX acts as inhibitor for mild steel in acidic medium. Inhibition efficiency increases with increase in concentration of ALLOX but decrease with rise in temperature. The adsorption of ALLOX was found to follow Temkin adsorption isotherm model. Both the activation and thermodynamic parameters governing the adsorption process were calculated and discussed. The adsorption follows a first-order kinetics. DFT study gave further insight into the mechanism of inhibition action of ALLOX.     

Electrochemical behaviour of carbon steel in acid chloride solution in the presence of dodecyl cysteine hydrochloride self-assembled on gold nanoparticles

In this work, the dodecyl cysteine hydrochloride surfactant was synthesized. The surface properties of this surfactant were studied using surface tension technique. The nanostructure of this surfactant with the prepared gold nanoparticles was investigated using TEM technique. The synthesized surfactant and its nanostructure with the prepared gold nanoparticles were examined as non-toxic corrosion inhibitors for carbon steel in 2 M HCl solution using potentiodynamic polarization and electrochemical impedance spectroscopy techniques. The results show that the percentage inhibition efficiency (η%) for each inhibitor increases with increasing concentration until critical micelle concentration (CMC) is reached. The maximum inhibition efficiency approached 76.6% in the presence of 175 ppm of dodecyl cysteine and 90.8% in the presence of the same concentration of dodecyl cysteine hydrochloride self-assembled on gold nanoparticles. Polarization data indicate that the selected additives act as mixed type inhibitors. The slopes of the cathodic and anodic Tafel lines (β_c and β_a) are approximately constant and independent of the inhibitor concentration. Analysis of the impedance spectra indicates that the charge transfer process mainly controls the corrosion process of carbon steel in 2 M HCl solution both in the absence and presence of the inhibitors. Adsorption of these inhibitors on carbon steel surface is found to obey the Langmuir adsorption isotherm. From the adsorption isotherms the values of adsorption equilibrium constants (K_ads) were calculated. The relatively high value of (K_ads) in case of dodecyl cysteine hydrochloride self-assembled on gold nanoparticles reveals a strong interaction between the inhibitor molecules and the metal surface.     

Sodium phthalamates as corrosion inhibitors for carbon steel in aqueous hydrochloric acid solution

Three compounds of N-alkyl-sodium phthalamates were synthesized and tested as corrosion inhibitors for carbon steel in 0.5 M aqueous hydrochloric acid. Tests showed that inhibitor efficiencies were related to aliphatic chain length and dependent on concentration. N-1-n-tetradecyl-sodium phthalamate displayed moderate efficiency against uniform corrosion, 42–86% at 25 °C and 25–60% at 40 °C. Tests indicated that compounds behave as mixed type inhibitors where molecular adsorption on steel followed Langmuir isotherm, whereas thermodynamic suggested that a physisorption process occurred. XPS analysis confirmed film formation on surface, where Fe⁺² complexes and Fe⁺² chelates with phthalamates prevented steel from further corrosion.     

Quantum chemical and experimental characterization of the effect of ziprasidone on the corrosion inhibition of steel in acid media

Ziprasidone is composed of the benzisothiozole-3-piperizine (BITP) and an indole moiety. The inhibition potential of ziprasidone for the corrosion of steel in 1.0 M HCl and 0.5 M H₂SO₄ was assessed by weight loss, polarisation, electrochemical impedance spectroscopy and quantum methods. The results showed that nearly 10 times lower concentration of ziprasidone showed the same efficiency that was rendered by BITP. This is related to the planarity of ziprasidone molecule, potential adsorption sites and the extensive distribution of LUMO orbitals on indole moiety which cause larger back donation. Ziprasidone follow Langmuir adsorption isotherm.     

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.     

The inhibitive effect of some bis-N,S-bidentate Schiff bases on corrosion behaviour of 304 stainless steel in hydrochloric acid solution

The inhibition effect of four new Schiff bases on the corrosion of 304 stainless steel in 1 M HCl has been studied by polarization, electrochemical impedance spectroscopy (EIS) and weight loss measurements. Polarization curves indicated that all studied Schiff bases act as mixed type (cathodic/anodic) inhibitors. The adsorption of the inhibitors was well described by the Langmuir adsorption isotherm and the adsorption isotherm parameters (K_ads, ΔG_ads) were determined at room temperature. Effect of temperature on the efficiency of the corrosion inhibition process was studied and the values of activation energy, pre-exponential factor (λ), enthalpy of activation and entropy of activation were calculated to elaborate the mechanism of corrosion inhibition. Differences in inhibition efficiency between four tested inhibitors are correlated with their chemical structures.     

Thermodynamic, electrochemical and quantum chemical investigation of some Schiff bases as corrosion inhibitors for mild steel in hydrochloric acid solutions

The corrosion inhibition of mild steel in 1.0 M HCl solution by four Schiff bases was investigated using weight loss and electrochemical measurements and quantum chemical calculations. All compounds showed >90% inhibition efficiency at their optimum concentrations. The activation energy (E_a) of corrosion and other thermodynamic parameters were calculated to elaborate the mechanism of corrosion inhibition. The adsorption of the inhibitors on the mild steel surface follows Langmuir isotherm model. Polarization studies indicated that all studied inhibitors are mixed type. The computed quantum chemical properties viz., electron affinity (EA) and molecular band gap (ΔE_MBG) show good correlation with experimental inhibition efficiencies.     

Inhibiting effects of some quinolines and organic phosphonium compounds on corrosion of mild steel in 3M HCl solution and their adsorption characteristics

Abstract

The inhibiting effects of quinoline, 8-hydroxyquinoline, benzo(f)quinoline, quinoline-2-thiol, triphenylbenzyl, and tetrabenzyl phosphonium chloride on the corrosion of mild steel (0.26 wt-%C) in deaerated 3M HCl solution have been studied using the determination of polarisation curves as well as linear polarisation measurements. Adsorption isotherms and thermodynamic parameters for the adsorption process of the inhibitors were also determined and are discussed. Except for benzo(f)quinoline, which acts as an accelerator of corrosion, the other quinolines act as corrosion inhibitors. The inhibition was found to be predominantly anodic with quinoline and 8-hydroxyquinoline, while quinoline-2-thiol is a mixed inhibitor. The increase in inhibition efficiency with temperature, the resulting Langmuir adsorption isotherm and the high negative values of the standard free energy of adsorption ΔG_a° denoted chemisorption. Triphenylbenzyl and tetrabenzyl phosphonium compounds were found to be inhibitors of the mixed type. High negative values of the standard free energy of adsorption and the resulting Temkin isotherm indicated chemisorption of the phosphonium compounds. The positive values of the standard enthalpy and entropy of adsorption indicated that adsorption of the inhibitors is associated with the desorption of H₂O molecules from the electrode surface. High values of the standard energy of activation E_a* of the inhibited corrosion process were interpreted in terms of deactivating coverage.     

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.