Experimental and theoretical studies of acridine orange as corrosion inhibitor for copper protection in acidic media

The corrosion process commonly limits the use of copper in practical applications. The use of corrosion inhibitors is one of the effective methods to reduce the corrosion rate of copper. In this research, the inhibition effect of acridine orange (3,6-bis(dimethylamine)acridine) (AcO) for the protection of copper in 0.5 ?M ?H₂SO₄ solution was studied. For this aim, the change of open circuit potential with exposure time (E_ocp-t), electrochemical impedance spectroscopy (EIS), linear polarization resistance (LPR), anodic and cathodic potentiodynamic polarization measurements (PP) and chronoamperometry (CA) techniques were used. Some quantum chemical parameters (E_HOMO, E_LUMO and dipole moment) were calculated and discussed. The AcO film formed over the copper surface was examined by SEM, EDX, AFM and contact angle measurements. The electrochemical data showed that AcO is an effective corrosion inhibitor even at low concentrations (ranging between 99.1% and %99.4 ?at concentrations from 0.01 ?mM to 1 ?mM). The corrosion rate of copper decreases in the presence of the inhibitor by reducing both anodic and cathodic rates, which is depended on its concentration. This compound behaves as mixed-type corrosion inhibitors with predominantly cathodic type. Its adsorption on the copper surface obeys Langmuir adsorption isotherm. The value of adsorption equilibrium constant (K_ads) and the standard free energy of adsorption were ΔG_ads 1.298 x 10³ ?M^?1 and -27.71 ?kJ/mol in the case of 0.5 ?M ?H₂SO₄ solution containing 1.0 ?mM AcO, which shows the adsorption is high and spontaneous. The adsorbed inhibitor film over the metal increase contact angle of the surface, which suggests the more hydrophobic properties of the surface are increasing coming from the orientation of hydrophobic sites to the electrolyte. The zero charge potential (E_pzc) studies showed that the surface charge of the metal is positive in the corrosive media containing the inhibitor. Quantum chemical calculations showed that the binding of inhibitor molecules to the metal surface takes place through N atoms of the inhibitor.     

Inhibiting effects of 2-mercapto-1-methylimidazole on copper corrosion in 0.5 M sulfuric acid

The inhibiting efficiency of 2-mercapto-1-methylimidazole (MMI) on copper corrosion in sulfuric acid was investigated at 30 °C. Its effectiveness was assessed through electrochemical impedance spectroscopy, potentiodynamic polarization and gravimetric measurements. The results of study reveal that the inhibition efficiency of MMI depends on its concentration and attains approximately 81% at 10^?4 M. The inhibitor was adsorbed on the copper surface according the Langmuir adsorption isotherm model. The value of standard free energy of adsorption was calculated from this isotherm.     

Utilization of biowaste as an eco-friendly biodegradable corrosion inhibitor for mild steel in 1 mol/L HCl solution

This report focuses on the application of a biodegradable biowaste [human hair-(HHR)], to produce a mild steel corrosion inhibitor. The performance of HHR extract in inhibiting metallic corrosion in 1 mol/L HCl was investigated. The analysis of the metal corrosion behavior using electrochemical and weight loss techniques revealed that HHR exhibits an efficient corrosion-mitigating effect via adsorption on the metal surface following a Langmuir isotherm. Tafel-plot results revealed the mixed-mode corrosion protection behavior of HHR. Surface analysis using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), atomic force microscopy (AFM), and Fourier transform infrared (FT-IR) spectroscopy provided evidence for the precipitation of a protective HHR film on the metal surface.     

Inhibitory action of aqueous Ruellia Tuberosa L leaves extract on the corrosion of copper in HCl solution

The inhibitive action of the aqueous extract of Ruellia tuberosa L (ART) on the corrosion of copper in 0.5 ​M HCl was investigated. The inhibition efficiency increased with the extract concentration, acid concentration, as well as increasing the temperature. The Polarization studies revealed that the ART act as a mixed-type inhibitor. Based on the analysis of electrochemical impedance spectroscopy, an equivalent circuit is suggested. The adsorption of the inhibitor ART on the copper surface obeyed the Langmuir adsorption isotherm. From the results of scanning electron microscopy, Fourier transform infrared spectroscopy, and energy-dispersive X-ray spectroscopy the adsorption of ART on the copper surface is confirmed.     

Ceratonia siliqua extract as a green corrosion inhibitor for copper and brass in nitric acid solutions

ABSTRACT

The influence of extract of ceratonia siliqua extract on the corrosion of copper and brass in aqueous 1 M nitric acid was examined by weight loss, potentiodynamic polarization, electrochemical impedance spectroscopy and electrochemical frequency modulation techniques. The surface morphology was analyzed using scanning electron microscope and energy dispersive X-ray techniques. Potentiodynamic polarization curves indicated that the plant extract behaves as cathodic inhibitor. The results indicate that the extract solution of the plant could serve as an effective inhibitor for the corrosion of copper and brass in nitric acid media. As temperature increases, percentage of inhibition decreases. The degree of surface coverage of the adsorbed inhibitor was determined by weight-loss technique, and it was found that the results obeyed the Langmuir adsorption isotherm.     

Experimental and theoretical studies of carbon steel corrosion protection in phosphoric acid solution by expired lansoprazole and rabeprazole drugs

The effects of expired lansoprazole and rabeprazole on the corrosion protection of carbon steel in phosphoric acid (3.0 ?M) solution were examined by Tafel polarization and electrochemical impedance spectroscopy (EIS). Lansoprazole and rabeprazole concentrations (0.5, 1.0, 5.0 and 10 ?mM) in acid solution were raised, which improved corrosion prevention. Both lansoprazole and rabeprazole as the mixed inhibitors retarded the anodic and cathodic processes, as indicated by polarization data. With the increasing temperature in the range of 25–55 ?°C, the inhibition efficiency drops from 92.9% to 69.3% for lansoprazole and from 94.8% to 74.2% for rabeprazole. The major decrease in the inhibition efficiency with ascending temperature proved the physisorption of the drugs. The activation energies for carbon steel corrosion in H₃PO₄solution were enhanced from 41.6 ?kJ ?mol^?1 to 81.9 ?kJ.mol^?1and 85.9 ?kJ ?mol^?1 for lansoprazole and rabeprazole, respectively. The influence of temperature on the corrosion process of carbon steel in the acid medium was used to derive the thermodynamic quantities of corrosion. The adsorption of both lansoprazole and rabeprazole on carbon steel followed the Langmuir adsorption isotherm. The polarization data yielded outcomes that were consistent with the results arising from impedance measurements. The theoretical study of both lansoprazole and rabeprazole was done by a density functional theory (DFT) approach to realize the effects of molecular structure on their inhibitive action. Both lansoprazole and rabeprazole contain a higher E_HOMO, a lower E_LUMO and a lower energy gap than some inhibitors earlier reported as good corrosion inhibitors in the literature.     

Inhibition of copper corrosion by arylazotriazoles in nitric acid solution

Summary A study has been made to investigate the effect of some azoheterocyclic dyes of the type 3-arylazo 1,2,4-triazole (AT) on the corrosion of copper exposed to 0.5M nitric acid solution at different temperatures and at differentAT concentrations. Using potentiodynamic polarization andTafel electrochemical methods, it can be shown thatAT compounds are good inhibitors of copper corrosion in HNO₃ solution. The kinetic and thermodynamic parameters of the inhibited system were determined. The high inhibition efficiency of these compounds may be due to the adsorption of the additive itself and/or the adsorption of the formed Cu(II)-AT complexes at the polarized electrode interface. Cathodic polarization measurements showed thatAT dyes are predominantly cationic inhibitors.

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Hemmung der Korrosion von Kupfer in salpetersaurer Lösung durch Arylazotriazole

Zusammenfassung Der Effekt einiger azoheterocyclischer Farbstoffe des Typs 3-Arylazo-1,2,4-triazol (AT) auf die Korrosion von Kupfer in 0.5M Salpetersäure bei verschiedenen Temperaturen und unterschiedlichenAT-Konzentrationen wurde untersucht. Potentiodynamische Polarisation und elektrochemische Methoden nachTafel zeigen, daß Verbindungen vom TypAT gute Korrosionsinhibitoren für Kupfer gegenüber HNO₃ sind. Die kinetischen und thermodynamischen Parameter des inhibierten Systems wurden bestimmt. Die hohe inhibitorische Wirksamkeit der untersuchten Verbindungen kann auf die Adsorption des Additivs selbst oder auf jene des Cu(II)-AT-Komplexes an der polarisierten Elektrodenoberfläche zurückzuführen sein. Kathodenpolarisationsmessungen zeigen, daßAT-Farbstoffe vorwiegend kationische Inhibitoren sind.

     

Extract sarampa wood (Xylocarpus Moluccensis) as an eco-friendly corrosion inhibitor for mild steel in HCl 1M

Plant extracts are currently being used as eco-friendly corrosion inhibitors. In this study, the inhibitive performance of Xylocarpus Moluccensis extract (XME) was used as an eco-friendly corrosion inhibitor for the first time. The extract was studied using electrochemical measurement on mild steel in 1M HCl. Results from FIR and phytochemical confirmed that Xylocarpus Moluccensis extract contains compound hydroxyl group, phenolic, and flavonoid content which can be used as a corrosion inhibitor. The inhibition efficiency was determined using Tafel polarization and electrochemical impedance spectroscopy and showed 68% efficiency in 500 ppm. Langmuir adsorption isotherm was used to determine the adsorption mechanism of XME. Surface characterization (AFM) was also used to study the surface morphology of protective film inhibitors.     

The influence of aniline and its derivatives on the corrosion behaviour of copper in acid solution

The inhibiting action of aniline and its derivatives on the corrosion of copper in hydrochloric acid has been investigated, with emphasis on the role of substituents. With this purpose five different anilines were selected: aniline, p-chloro aniline, p-nitro aniline, p-methoxy and p-methyl aniline. The electrochemical and gravimetric results, obtained in the absence and presence of different concentrations of inhibitors, revealed that aniline reduces the corrosion of copper, with a critical concentration of 10^–2 M. Furthermore, the interaction energy calculated as G_ads gave a value of 4.2 kcal mol^–1 indicating physisorption of the organic compound at the copper surface. The results have also shown that substituents, either electron donors (–CH₃, –OCH₃) or, electron acceptors (–NO₂, –Cl) in para position, decrease the inhibition action of aniline. A theoretical study using molecular mechanic and ab initio Hartree Fock methods, to model the adsorption of aniline on copper (100) showed results in good agreement with the experimental data. Aniline adsorbs parallel to the copper surface, showing no preference for a specific adsorption site. On the other hand, from ab initio Hartree Fock calculations, an adsorption energy between 2 kcal/mol and 5 kcal/mol is obtained, which is close to the experimental value, confirming that the adsorption of aniline on the metal substrate is rather weak. In view of these results, the orientation of the aniline molecule with respect to the copper surface is considered to be the dominant effect.     

Fluconazole as an inhibitor for aluminium corrosion in 0.1 M HCl

The interfacial behavior of fluconazole (FLC) between aluminium and hydrochloric acid has been investigated by using weight loss technique at 30–50 °C. The results showed that fluconazole is an excellent corrosion inhibitor for aluminium in acidic medium. Inhibition efficiency increased with increase in the concentrations of fluconazole but decreased with rise in temperature. The adsorption of the inhibitor on the aluminium surface is found to accord with Temkin adsorption isotherm. Some thermodynamic and activation parameters have been calculated and analysed. The mechanism of physical adsorption is proposed from the values of E_a and obtained. The correlation of inhibition effect and molecular structure of fluconazole was then discussed by quantum chemistry study to further provide insight into the mechanism of the inhibitory action.     

β-cyclodextrin modified xanthan gum as an eco-friendly corrosion inhibitor for L80 steel in 1 M HCl

The development of eco-friendly corrosion inhibitors is a subject of several investigations, especially natural polymers. Aimed at suppressing the corrosion of L80 steel in 1 mol/L hydrochloric acid (HCl), a novel natural polymer inhibitor was developed based on xanthan gum (XG) and β-Cyclodextrin (β-CD) in this work. The corrosion inhibition effect of β-cyclodextrin modified xanthan gum (β-CD-XG) on L80 steel was evaluated by electrochemical methods, and surface analysis technology. Adsorption isotherm studies, Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS) were used to explore the corrosion inhibition mechanism of β-CD-XG on L80 steel. The results suggested that β-CD-XG was classified as a mixed-type inhibitor, and mainly suppressed the anode metal dissolution by a tight adsorption film. The formation of the film was attributed to the chemisorption of –OH, –COO-, –CH₂–O–, and –CH₂–O–CH₂– groups on the surface of L80 steel, which conformed to the Langmuir adsorption model. The experimental results illustrated that the maximum corrosion inhibition efficiency of 94.74% was acquired at 200 mg/L β-CD-XG at 293 K.

Graphic abstract

     

A theoretical study on the inhibition efficiencies of some quinoxalines as corrosion inhibitors of copper in nitric acid

Quantum chemical calculations based on DFT method were performed on three quinoxalines compounds namely ethyl 2-(4-(2-ethoxy-2-oxoethyl)-2-p-tolylquinoxalin-1(4H)-yl)acetate (Q1), 1-[4-acetyl-2-(4-chlorophenyl)quinoxalin-1(4H)-yl]acetone (Q2) and 2-(4-methylphenyl)-1,4-dihydroquinoxaline (Q3), used as corrosion inhibitors for copper in nitric acid media to determine the relationship between the molecular structure of quinoxalines and inhibition efficiency. Quantum chemical parameters such as the highest occupied molecular orbital energy (E_HOMO), the lowest unoccupied molecular orbital energy (E_LUMO), energy gap (ΔE), dipole moment (μ), electronegativity (χ), electron affinity (A), global hardness (η), softness (σ), ionization potential (I), the fraction of electrons transferred (ΔN), and the total energy (TE), were calculated. The theoretically obtained results were found to be consistent with the experimental data reported.     

Benzalkonium chloride/titanium dioxide as an effective corrosion inhibitor for carbon steel in a sulfuric acid solution

In this study, the corrosion performance of carbon steel samples in 0.5 M sulfuric acid by the addition of novel inhibitors, 200 ppm of (25% and 50%) titanium dioxide nanoparticles in benzalkonium chloride, was thoroughly investigated. Gravimetric measurements, cyclic and linear potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and hydrogen collection by water displacement evaluated inhibition performance. Analogously, TiO₂/ILB (50%), TiO₂/ILB (75%), and ILB inhibitors enhanced corrosion protection with over 80% inhibition efficiency in electrochemical tests. In addition, weight loss and hydrogen collection measurements reached comparable results. According to potentiodynamic polarization curves, inhibitors exhibited dual behavior, but cathodic protection was more predominant. Scanning electron microscopy (SEM) was employed to examine the surface morphology before and after immersion using corrosion tests. The correlation between electronic properties and inhibition efficiencies of tilted inhibitors was determined by simple linear regression. Electronic properties were calculated for neutral and protonated forms using a polarizable continuum model by the DFT method at the B3LYP/6-311+G (d, p) level of theory. The active adsorbed sites of HM1-HM3 on the metal surface were determined by analyzing their corresponding electrostatic surface potentials (ESP). Furthermore, molecular dynamics simulations were performed to illustrate the most conceivable adsorption configuration between the inhibitors and metal surfaces.     

Chitosan as an eco-friendly inhibitor for copper corrosion in acidic medium: protocol and characterization

Natural biopolymer chitosan organic compound (COC) has been used as a copper corrosion inhibitor in molar hydrochloric medium. This study was conducted by weight loss, polarization curves and electrochemical impedance spectroscopy measurements. Scanning electron microscopy, energy dispersive X-ray spectrometry and atomic force microscopy studies were used to characterize the surface of uninhibited and inhibited copper specimens. The study of the temperature effect was carried out to reveal the chemical nature of adsorption. The inhibition efficiency tends to increase by increasing inhibitor concentration to reach a maximum of 87% at 10^?1 mg L^?1. The values of inhibitor efficiency estimated by different electrochemical and gravimetric methods indicate the performance of copper in HCl medium containing COC. Adsorption of COC was found to follow the Langmuir adsorption isotherm. In order to get a better understanding of the relationship between the inhibition efficiency and molecular structure of COC, quantum chemical and molecular dynamics simulation approaches were performed to get a better understanding of the relationship between the inhibition efficiency and molecular structure of chitosan.     

4-phenyl-decahydro-1H-1,5-benzodiazepin-2-one as novel and effective corrosion inhibitor for carbon steel in 1 M HCl solution: A combined experimental and empirical studies

The heterocyclic system, namely 4-phenyl-decahydro-1H-1,5-benzodiazepin-2-one (POBZ) was inspected as a corrosion inhibitor of carbon steel (CS) in a 1 M HCl medium through electrochemical impedance spectroscopy (EIS), potentiodynamic polarization measurements (PDP), and scanning electron microscopy (SEM). The experimental data indicate that the inhibiting action augments with augmenting POBZ amount and reduces with augmenting temperature. The inhibiting action efficiency of 90.98% is obtained with 0.001 M at 303 K. The potentiodynamic polarization (PDP) results mentioned that the POBZ is of mixed type. The adsorption of POBZ on the CS followed Langmuir isotherm. SEM exams affirmed that the steel surface is smooth in presence of POBZ. In light of the calculations of density functional theory (DFT) and molecular dynamics simulation, the mechanism of POBZ inhibitory activity was addressed.     

Electrochemical and computational studies of an expired vilazodone Drug as environmentally safe corrosion inhibitor for aluminum in chloride medium

Through using chemical and electrochemical methods, the theoretical and experimental investigation of the expired vilazodone drug's ability to prevent corrosion on aluminium (Al) in a corrosive medium of HCl (1 M) has been examined. Weighing tests (WL), electrochemical (impedance spectroscopy (EIS), potentiodynamic polarization (PDP)), atomic force microscopy (AFM), scanning electron microscope (SEM), and Fourier transform infrared spectroscopy (FTIR) tests at 25 °C have all been used to investigate Vilazodone's capability to prevent corrosion of Al in 1 M HCl in the concentration in the range of 25–150 ppm. The corrosion inhibition effect of the investigate Vilazodone's against Al in acid environment was investigated weight loss and electrochemical methods. The highest % inhibition efficiency (%IE) was 95% resulted from weight loss technique at the highest concentration for inhibitor. According to the PDP data, this examined vilazodone function as a mixed-type inhibitor, impacting both the anodic and cathodic reactions. The inhibitors covered the active points of the metal surface, according to electrochemical impedance spectroscopy (EIS), to prevent corrosion. It was discovered that the inhibitor adsorption on the Al surface obeyed the Langmuir adsorption isothermal model. AFM, SEM, and FTIR surface examinations proved the inhibitor had a significant protective effect against Al dissolution in 1 M HCl. The outcomes from chemical and electrochemical methods are relatively consistent. Vilazodone acted as an effective corrosion inhibitor, according to all of the experimental data.     

Phenyl semicarbazide derivatives as corrosion inhibitors for aluminium in hydrochloric acid solution

Summary Measurements of the corrosion rate of aluminium in 2N HCl at 27°C with and without addition of phenyl semicarbazide derivatives (10^–3–10^–5 mol/l) were performed. The adsorption of these compounds was elucidated. Results show that phenyl semicarbazide derivatives are adsorbed on the aluminium surface according to the Frumkin isotherm. From the adsorption isotherm some thermodynamic data for the adsorption process (G° _ads . andf) are calculated and discussed.

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Phenylsemicarbazide als Korrosionsinhibitoren für Aluminium in salzsauren Lösungen

Zusammenfassung Es wurden Messungen der Korrosionsgeschwindigkeit von Aluminium in 2N HCl bei 27°C mit und ohne Zusatz von Phenylsemicarbaziden (10^–3–10^–5 mol/l) durchgeführt. Es wurde die Adsorption dieser Verbindungen untersucht, wobei sich zeigte, daß die Adsorption der Phenylsemicarbazidderivate der Frumkin-Isotherme gehorcht. Aus der Isotherme wurden einige thermodynamische Parameter des Adsorptionsprozesses (G° _ads. ,f) berechnet.

     

Medicago sativa as a green corrosion inhibitor for 1018 carbon steel in 0.5 M H2SO4 solution

A study on the use of the methanol extract of Medicago sativa as a green corrosion inhibitor for 1018 carbon steel in 0.5?M of sulfuric acid has been carried out by using potentiodynamic polarization curves, electrochemical impedance spectroscopy and gravimetric tests. Testing temperatures were 25°C, 40°C and 60°C. Results showed that M. sativa is a good corrosion inhibitor, with its efficiency increasing with its concentration and with time, but decreasing with the temperature. M. sativa forms a passive film on top of the steel with a passive current density and pitting potential values lower than that for uninhibited solution, and remained on the steel for 8–12?h. This film formed by iron ions and heteroatoms present in OH^? and amine groups from the extract are adsorbed on the steel and form a protective film on to the steel.     

Influence of 5-chloro and 5-methyl benzotriazole on the corrosion of copper in acid solution: an experimental and a theoretical approach

The inhibition of copper corrosion in aerated 0.1 mol l⁻¹ hydrochloric acid solutions was studied using electrochemical polarization in the presence of different concentrations of benzotriazole and its two derivatives, 5-chloro and 5-methyl benzotriazole. The inhibition efficiencies obtained from cathodic Tafel plots increased markedly with increase in the additive concentration. Benzotriazole and 5-methyl-benzotriazole were found to be cathodic type corrosion inhibitors for concentrations higher than 10⁻⁴ mol l⁻¹ . However, the 5-chloro-benzotriazole was found to be a mixed inhibitor for concentrations up to 10⁻³ mol l⁻¹, above this concentration the inhibitor behaves as an anodic type inhibitor. The inhibitors are physisorbed on the copper surface following a Langmuir’s isotherm. The inhibition efficiencies depended on the inhibitor concentration and follows the order 5-chloro-benzotriazole > 5-methyl-benzotriazole > 1-H-benzotriazole. From the theoretical calculations, the change in the inhibition mechanism observed for 5-chloro-benzotriazole at concentrations higher than 10⁻³ mol l⁻¹ is associated with the electronic acceptor characteristic of chloro, which increases the benzotriazole acidity allowing the formation of CuBTA.     

Gravimetric,electrochemical, and morphological studies of an isoxazole derivative as corrosion inhibitor for mild steel in 1M HCl

In present study, an isoxazole derivative, namely, (Z)-4-(4-hydroxy-3-methoxybenzylidene)-3-methylisoxazol-5(4H)-one referred here as (IOD) has been studied as an environment-friendly corrosion inhibitor for mild steel (MS) in acidic medium (1 M HCl). The present work was investigated by gravimetric, electrochemical impedance spectroscopy (EIS), potentiodynamic polarization (PDP), fourier-transform infrared (FT-IR) spectroscopy techniques. Atomic force microscopy (AFM), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDS) confirmed the surface morphologies of the MS surface with and without IOD in the acid medium. The inhibition efficiency (I.E.) of IOD was increased by rising its concentration attaining maximum value (96.6%) at 300 ppm at 30 °C and decreases with increasing temperature from 30 °C to 60 °C. The adsorption of studied inhibitor followed Langmuir adsorption isotherm model. The PDP study revealed that the IOD acts as a mixed-type inhibitor with predominating anodic effect. The EIS study confirmed that increasing IOD concentration enhances the charge transfer resistance (R_ct) and then reduces the double layer capacitance (C_dl) owing to the development of a protective layer on the MS surface.