Corrosion Inhibition Of Copper Research Articles

3-Alkylsulfonyl-5-amino-1,2,4-triazoles – new corrosion inhibitors of copper and copper-containing alloys

3-Alkylsulfonyl-5-amino-1,2,4-triazoles – new corrosion inhibitors of copper and copper-containing alloys

Synthesis of Ce, N co–doped carbon dots as green and effective corrosion inhibitor for copper in acid environment

Background: A new high-effectively corrosion inhibitor was used to replace the traditional corrosion inhibitor and reduce the environment pollution.Methods: Through hydrothermal synthesis, Ce and N co-doped carbon dots (Ce@N-CDs) were generated. Before the performance characterization, the microstructure and chemical composition of Ce@N-CDs were firstly investigated by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) techniques. The electrochemical test revealed that the IE of Ce-10% (200 mg/L) on copper was as high as 98%, presenting the best inhibition effect. According to the adsorption isotherm analysis, the Ce@N-CDs mainly adsorbed according to the Langmuir model, and the adsorption process was completed by combining physical and chemical adsorption.Significant findings: Through the morphology, energy dispersive spectrometer (EDS) and XPS analysis of copper surface after corrosion process, it was found that the Ce@N-CDs formed a dense adsorption/passivation film on the copper surface. The adsorption film mainly came from the pairing of unsaturated bonds between N-doped CDs (N-CDs) and copper surface. The passivation film mainly came from the oxide formed by the reaction between Ce and the surrounding environment. Their dense structure could effectively inhibit the infiltration and erosion of corrosive medium.

Interface adsorption of 5-amino-1,3,4-thiadiazole-2-thiol on chalcopyrite surface as flotation depressant in Cu/Mo separation

Flotation is an interfacial chemical reaction in essence. The selective adsorption of flotation reagents on mineral surfaces leads to the transition of hydrophilicity/hydrophobicity of mineral particles, and then to regulate the floatability differences between various minerals. 5-amino-1,3,4-thiadiazole-2-thiol (ATT) is a heterocyclic ring compound, which can chelate copper ions easily and usually used as a copper corrosion inhibitor. Based on those good chelating properties with copper ions, this paper attempted to apply ATT as a chalcopyrite depressant in the flotation separation of Cu/Mo ores. The adsorption mechanism of ATT on chalcopyrite surface was explored by means of UV–vis, FTIR, contact angle and XPS analysis, and it revealed the possibility of ATT using as a selective chalcopyrite depressant in the flotation separation of Cu/Mo ores by micro-flotation tests. Finally, the adsorption morphology of ATT depressant on chalcopyrite surface was unveiled by DFT method from a microscopic level. Through these FTIR and XPS analysis, combined with DFT simulation results, it was inferred that ATT was mainly chemically adsorbed on chalcopyrite surface by SCu and NCu bonds. These studies confirmed that ATT was very likely to be an excellent chalcopyrite depressant in Cu/Mo flotation separation.

Rosmarinus officinalis extract as eco-friendly corrosion inhibitor for copper in 1 M nitric acid solution: Experimental and theoretical studies

Rosmarinus officinalis extract (ROE) was studied chemically (mass loss, ML), electrochemically impedance spectrometry (EIS), and potentiodynamic polarization (PDP) as a corrosion inhibitor in 1 M nitric acid. According to ML, ROE is effective like a copper preservative in 1 M HNO3 acid solution at R.T by improving inhibitor concentration up to 77 % at 300 ppm and 25 °C. A study was conducted regarding the effect of temperature on copper adsorption, as well as the calculation of adsorption coefficients. Results indicated that physisorption increases with temperature, indicating a decrease in inhibition efficiency (%IE). Langmuir's adsorption model was consistent with the adsorption mechanism. Using the PDP method, the inhibitor accumulated on the copper surface in mixed forms. Moreover, EIS revealed that the value of double-layer capacitance dropped with an increased dose of ROE, while the charge transfer resistance improved. A different approach was taken to the examination of surfaces. Both theoretical studies and practical results were calculated and compared to demonstrate that the results were valid.

Computational Foretelling and Experimental Implementation of the Performance of Polyacrylic Acid and Polyacrylamide Polymers as Eco-Friendly Corrosion Inhibitors for Copper in Nitric Acid.

Copper is primarily used in many industrial processes, but like many other metals, it suffers from corrosion damage. Polymers are not only one of the effective corrosion inhibitors but also are environmentally friendly agents in doing so. Hence, in this paper, the efficacy of two polyelectrolyte polymers, namely poly(acrylic acid) (PAA) and polyacrylamide (PAM), as corrosion inhibitors for copper in molar nitric acid medium was explored. Chemical, electrochemical, and microscopic tools were employed in this investigation. The weight-loss study revealed that the computed inhibition efficiencies (% IEs) of both PAA and PAM increased with their concentrations but diminished with increasing HNO3 concentration and temperature. The results revealed that, at similar concentrations, the values of % IEs of PAM are slightly higher than those recorded for PAA, where these values at 298 K reached 88% and 84% in the presence of a 250 mg/L of PAM and PAA, respectively. The prominent IE% values for the tested polymers are due to their strong adsorption on the Cu surface and follow the Langmuir adsorption isoform. Thermodynamic and kinetic parameters were also calculated and discussed. The kinetics of corrosion inhibition by PAA and PAM showed a negative first-order process. The results showed also that the used polymers played as mixed-kind inhibitors with anodic priority. The mechanisms of copper corrosion in nitric acid medium and its inhibition by the tested polymers were discussed. DFT calculations and molecular dynamic (MD) modelling were used to investigate the effect of PAA and PAM molecular configuration on their anti-corrosion behavior. The results indicated that the experimental and computational study are highly consistent.

2-(4-Morpholinothio)benzothiazole as a High-efficiency Corrosion Inhibitor for Copper in 0.5 M H2SO4 Solution

2-(4-Morpholinothio)benzothiazole as a High-efficiency Corrosion Inhibitor for Copper in 0.5 M H2SO4 Solution

A Study of the Synthesis and Characterization of New Acrylamide Derivatives for Use as Corrosion Inhibitors in Nitric Acid Solutions of Copper

The objective of this research was to explore the impact of corrosion inhibition of some synthetic acrylamide derivatives 2-cyano-N-(4-hydroxyphenyl)-3-(4-methoxyphenyl)acrylamide (ACR-2) and 2-cyano-N-(4-hydroxyphenyl)-3-phenylacrylamide (ACR-3) on copper in 1.0 M nitric acid solution using chemical and electrochemical methods, including mass loss as a chemical method and electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization (PP) as electrochemical methods. By Fourier-transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (1HNMR), and mass spectroscopy (MS) methods, the two compounds were verified and characterized. There is evidence that both compounds were effective corrosion inhibitors for copper in 1.0 M nitric acid (HNO3) solutions, as indicated by the PP curves, which show that these compounds may be considered mixed-type inhibitors. With the two compounds added, the value of the double-layer capacitance was reduced. In the case of 20 × 10−5 M, they reached maximum efficiencies of 84.5% and 86.1%, respectively. Having studied its behavior during adsorption on copper, it was concluded that it follows chemical adsorption and Langmuir isotherm. The theoretical computations and the experimental findings were compared using density functional theory (DFT) and Monte Carlo simulations (MC).

Experimental and theoretical research on the corrosion inhibition of 1-octyl-3-methylimidazolium L-prolinate for copper in 3.5% NaCl solution

An amino acid ionic liquid, namely 1-octyl-3-methylimidazolium L-prolinate ([OMIM]L-pro), was investigated as the corrosion inhibitor of copper in 3.5% NaCl solution through electrochemical techniques, surface analysis and molecular dynamics simulation. The results showed that [OMIM]L-pro was a mixed type inhibitor with a predominantly anodic action for copper in NaCl solution, its inhibition efficiency increased with the increase of concentration, but decreased with rising temperature, the highest inhibition efficiency was up to 97.5%. The adsorption of [OMIM]L-pro on the copper surface was found to follow the Langmuir isothermal equation, and the corrosion kinetic characteristics of copper in the test solution was discussed and analyzed. Moreover, L-prolinate anion was found to play a significant role in the corrosion inhibition performance of [OMIM]L-pro, but there was a synergistic effect between L-prolinate anion and imidazolium cation, which synergistically inhibited the corrosion of copper in NaCl solution. Molecular dynamics simulation data supported the experimental results.

The Combined Action of Organic Inhibitors on Copper and Aluminium Metals and Aluminium Alloy Containing Copper

The approach used in the present work involves investigating the corrosion protection properties of mixed inhibitors for copper and aluminium substrates in chloride-containing solutions, which serve as a benchmark for studies of the alloy AA2024, with Cu and Al being the main culprits for localized corrosion. A synergistic mixture of inhibitors could find potential applications in novel blending combinations, such as in cooling water as an inhibitor in closed systems or incorporated in various protective coatings as additives, nano-containers, etc. If possible, the protective inhibitor film should show irreversibility of inhibition which can be defined as the ability to, once formed, retains its protective properties when the concentration of the corrosion inhibitor decreases. This irreversibility of the protective properties is essential for long-term protection.Inhibitory action of organic molecules, 2-mercaptobenzimidazole (MBI) and octylphosphonic acid (OPA) and their binary combinations on aluminium, copper and aluminium alloy 2024-T3 was investigated in chloride environments by conventional electrochemical methods and surface-analytical techniques [1,2]. In addition, the influence of pre-treatment of the metal surface and the choice of solvent for liquid-phase deposition on adsorption of MBI and OPA was studied on individual metals, Al and Cu [3]. Although OPA is not an inhibitor for Cu, it can synergistically boost corrosion inhibition of copper when added to MBI. In contrast, a synergistic effect between MBI and OPA as corrosion inhibitors was not observed for AA2024-T3. The mechanism was proposed where the thickness and structure of the surface layer are dependent on the pH. For the sample exposed to MBI at pH 5.5, where the Cu2O is stable, a thin Cu(I)MBI film is formed.In contrast, when exposed to the mixture of MBI and OPA at a pH of 4, the amount of produced Cu+ ions is boosted, and a much thicker Cu(I)MBI film forms by dissolution-precipitation mechanism. This layer exhibits high inhibitory effectiveness on copper substrate. At even lower pH, the thick compact Cu(I)MBI film does not form due to intensive dissolution of the Cu2O underlayer, resulting in a voluminous product. The postulated mechanism is confirmed by electrochemical data and composition of the layer by X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectroscopy and focused-ion beam scanning electron microscopy with chemical analysis.Immersion of AA2024 in an OPA-containing solution caused significant localized corrosion, while no local electrochemical activity on AA2024 was detected in an MBI-containing solution, indicating that the MBI inhibitor was very effective against pitting corrosion. Figure shows FIB/SEM (cross-section) analysis of local corrosion induced by Al2CuMg phase after 24 h immersion of AA2024 in 3 wt.% NaCl containing 1 mM MBI. The chemical analysis employed at the cross-section (yellow rectangles) of the Al2CuMg revealed that the MBI layer reduces the dissolution rate of dealloying of this phase and the rate of oxygen reduction on the copper remnant sites.This study shows that the behaviour of each combination of inhibitor and metal substrate is unique and cannot be translated to the more complex system such as alloy. Therefore, a profound understanding of the inhibition mechanism of individual metals is a prerequisite for further investigation of the corrosion inhibition of aluminium alloys. Acknowledgements: The financial support of the project by the Slovenian Research Agency is acknowledged (grants No. P1-0134, P2-0393 and BI-US/22-24-140) is acknowledged. Barbara Kapun, BSc, is acknowledged for FIB-SEM-EDS analysis.

Experimental and computational chemical studies on the corrosion inhibition of new pyrimidinone derivatives for copper in nitric acid

Inhibition of copper corrosion by some pyrimidinone derivatives, namely; (E)-N-(3-((1,3-dimethyl-2,4,6-trioxohexahydropyrimidin-5-yl)diazenyl)-2,5-diethoxyphenyl)benzamide (MA-975) and(E)-6-(4-((4-chlorophenyl)diazenyl)-3-methyl-5-oxo-4,5-dihydro-1H-pyrazol-1-yl)-1,3 dimethylpyrimidine-2,4(1H,3H)-dione (MA-978C) in 1.0 M nitric acid (HNO3) was studied using weight loss (WL), electrochemical impedance spectroscopy (EIS), and potentiodynamic polarization (PP) measurements. The efficiency of inhibition increases as the concentration of inhibitor increases, and it also increases as the temperature increases. With the addition of the examined inhibitors, significant corrosion protection was obtained, and (MA-975) showed a very promising % IE (89.59%) at 21 × 10−6 M using the (WL) method. The polarization data revealed that these compounds act as mixed-type compounds and are adsorbed on the copper surface following Langmuir adsorption isotherm forming a protective thin film protecting the metal in the corrosive media. Scanning electron microscopy (SEM) and Energy Dispersive X-ray were used to examine the surface morphology of copper samples. Quantum calculations and Monte Carlo simulation techniques were applied with informative yields and the results matched the experimental findings.

Corrosion inhibition of copper in sulfuric acid by Leonurus japonicus Houtt. extract as a green corrosion inhibitor: Combination of experimental and theoretical research

BackgroundBased on the consideration of green and safety in industrial production, the demand and desire for green corrosion inhibitors are increasingly strong. MethodsIn this study, we selected Leonurus japonicus Houtt. leaves extract (LLE) extracted by water. Electrochemistry experiments and morphology characterization showed excellent anti-corrosion performance of LLE for copper in 0.5 mol∙L1 H2SO4. The chemical bond information measured by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) indicated that LLE adsorbed on Cu/H2SO4 interface by chemical bonding. Through quantum chemical calculation and molecular dynamics simulation analysis, the adsorption reaction mechanism was profoundly studied. Significant findsElectrochemical test data showed that the inhibition efficiency of 400mg/L LLE arrived at 90% at 298 K, 308K and 318 K. After processing the data, it is concluded that LLE protective film belonged to Langmuir adsorption. By calculating thermodynamic and kinetic parameters of corrosion, it is found that the activation complex is formed by the binding of Cu+ and LLE in the adsorption layer.

Copper corrosion inhibition in nitric acid solution by 2-(1,3-dihydrobenzimidazol-2-ylidene) -3-oxo-3-(pyridin-3-yl) propanenitrile: Gravimetric, Quantum chemical and QSPR studies

The metal corrosion threat in the metallurgical industry is becoming increasingly important. So in this work, the inhibition properties of 2-(1,3-dihydrobenzimidazol-2-ylidene)-3-oxo-3-(pyridin-3-yl) propanenitrile for copper corrosion in 1 M nitric acid medium were evaluated by mass loss technique, density functional theory (DFT) and quantitative structure-property relationship (QSPR) model. The results show that this compound was excellent anticorrosive properties with a maximum inhibition efficiency of 89.39 % for a concentration of 0.2 mM at 323 K. The inhibition efficiency increases with increasing temperature and inhibitor concentration. Adsorption isotherms reported that the molecule adsorbs on copper surface according to Langmuir isotherm. Thermodynamic adsorption and activation parameters were determined and analyzed. They revealed spontaneous adsorption and a strong interaction between the molecule and copper surface. DFT calculations at the B3LYP level with 6-31G(d,p) and 6-311G(d,p) basis set permitted to explain the electronic exchanges between molecule and copper, thus justifying the experimentally obtained inhibition efficiency values. A local reactivity study of molecules indicated that N (29) and C (7) atoms are the likely sites for nucleophilic and electrophilic attacks, respectively. In addition, QSPR model was used to correlate experimental inhibition efficiency with the descriptor parameters of the studied molecule, and it is found that the calculated inhibition efficiencies are close to experimental inhibition efficiencies. Finally, this study showed a good correlation between theoretical and experimental data.

Corrosion inhibition of copper and aluminium by 2-mercaptobenzimidazole and octylphosphonic acid—Surface pre-treatment and method of film preparation

The optimal surface pre-treatment conditions for improved adsorption of 2-mercaptobenzimidazole (MBI) and octylphosphonic acid (OPA) on copper and aluminium substrates are presented. For this purpose, mechanical and chemical pre-treatments were employed, which included grinding/polishing and etching/desmutting, respectively. In addition, organic films for both pre-treated samples were prepared by liquid-phase deposition from ethanol or an aqueous solution containing MBI and OPA inhibitors. The mechanism of formation and degradation of the films on Cu and Al samples in 3 wt.% NaCl were investigated by electrochemical methods, whereas morphology and bonding of inhibitors were studied by scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. It was shown that the surface pre-treatment did not significantly influence the chemistries of Cu and Al. However, the method of film formation, including the use of two different solvents, was crucial. The inhibitor films on Cu and Al were not formed in an ethanol solution but only deposited from aqueous solutions. A significant reduction in corrosion current density revealed that MBI is an effective inhibitor for Cu, while this characteristic is absent for Al. On the other hand, OPA behaves the other way around.

Synthesis of tolyl guanidine as copper corrosion inhibitor with a complementary study on electrochemical and in silico evaluation

A rapid and new synthetic route for N,N′-di-o-tolyl guanidine (DTG) synthesis from cheap materials is reported. The performance of DTG as an excellent inhibitor for delaying copper (Cu) corrosion with an efficiency higher than 98% at 20 × 10−6 M in an acidic solution was investigated via electrochemical measurements. These measurements included PDP, EFM, and EIS spectroscopy. The experimental data indicated that DTG has an efficient inhibiting effect on the corrosion of Cu in acidic media.The DTG was adsorbed on to the Cu surface via chemical adsorption and followed the Langmuir route. The PDP measurements revealed that DTG acted as a mixed inhibitor. Furthermore, EIS data showed that the DTG adsorbed through the metal/electrolyte interface. This resulted in forming a DTG protective layer on the Cu surface, thereby impeding the dissolution of Cu in the acidic solution. The corrosive solution containing the DTG inhibitor after immersion of the Cu specimen for 48 h, which promoted the formation of a complex between the Cu cation and DTG, was investigated via ultraviolet/visible spectroscopy. In addition, the formation of a DTG protective layer on the Cu surface was confirmed via scanning electron microscopy and atomic force microscopy analysis of the Cu surface morphology. Moreover, the active centers for interaction with the Cu surface in an acidic solution were investigated via in silico evaluation of DTG.

Investigation of Solupred as a pharmaceutical drug as a corrosion inhibitor for copper corrosion in 1.0 M sulfamic acid solution

Investigation of Solupred as a pharmaceutical drug as a corrosion inhibitor for copper corrosion in 1.0 M sulfamic acid solution

Electrophoretic deposition of graphene coating as a corrosion inhibitor for copper in NaCl solution

Graphene coating on pure copper substrate was successfully prepared by electrophoretic deposition (EPD) technology. The effects of deposition parameters on the coating structure and its corrosion resistance in 3.5 wt% NaCl solution were investigated. The results show that the open circuit potential (OCP) of the coating sample (−0.107 V) is about 0.1 V higher than that of the substrate (−0.199 V), and the corrosion current density (Icorr) decreases by an order of magnitude. Moreover, too long deposition time or too high deposition voltage will cause defects in the deposited coating, resulting in the weakening of corrosion resistance. The optimum deposition condition is 30 V for 40 min.

Study of synergy of monoethanolamine and urea on copper corrosion inhibition in alkaline solution

• Cu corrosion in TMAH-containing solution is investigated. • MEA and urea are used as corrosion inhibitors to retard the Cu corrosion. • The synergy of MEA and urea on Cu corrosion inhibition is concentration ratio dependent. • Cu corrosion becomes more serious at low concentration ratio of MEA to urea. • Cu corrosion is effectively retarded at high concentration ratio of MEA to urea. Tetramethylammonium hydroxide (TMAH) is an important constituent used in the post cleaning process of chemical mechanical planarization and lithography; however, its corrosive property causes damage to the Cu metallization. Addition of corrosion inhibitor in the cleaning solution is a promising method to protect Cu. In this study, two corrosion inhibitors, monoethanolamine (MEA) and urea, are used to investigate their synergy on the Cu corrosion protection. Electrochemical and four-point probe methods are adopted to analyze the corrosion behaviors of Cu. Microstructural characterizations of Cu are performed using scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. X-ray photoelectron spectroscopy is used to realize the adsorption behaviors of inhibitors on the Cu surface. The results of corrosion current ( I corr ) and charge transfer resistance ( R ct ) indicate that addition of MEA and urea at an identical concentration does not produce a typical synergistic effect on the Cu corrosion protection due to mutual interference of two inhibitors. An increase of the MEA concentration overcomes the mutual interference, giving rise to a reduction of I corr and an increase of R ct . The effective retardation of the Cu corrosion is attributed to the sufficiency of inhibitors which can construct a dense protection layer on the Cu surface.

Corrosion inhibition performance of 2-ethyl phenyl-2, 5-dithiohydrazodicarbonamide on Fe (110)/Cu (111) in acidic/alkaline solutions: Synthesis, experimental, theoretical, and molecular dynamic studies

Herein, 2-ethyl phenyl-2,5-dithiohydrazodicarbonamide (2EPDCA) was synthesised and tested as a corrosion inhibitor for mild steel (MS) and copper (Cu) in 1 M HCl and 3.5% NaCl, respectively. Fourier transform infrared spectroscopy (FT-IR) and (NMR) nuclear magnetic resonance (1H, 13C) were used to identify the chemical structure. Both experimental and computational approaches have been conducted to evaluate inhibitor efficiency on both metal systems. The electrochemical results showed that the 2EPDCA inhibition efficiency for MS systems was 95% at 1 × 10−2 M, while in copper systems it was 97.5% at 1 × 10−2 M. The Langmuir adsorption isotherm was fitted using adsorption surface coverage data, and for inhibitor in both systems, the kind of adsorption was mixed (physisorption and chemisorption). Through scanning electron microscopy (SEM), EDX, and atomic force microscopy (AFM) tests, we have confirmed the presence of the inhibitor molecules on the metal surface in both systems. Quantum chemistry simulations indicate that the superior corrosion inhibition efficacy of 2EPDCA on copper compared to mild steel surfaces is attributable to the former's greater electron donating propensity on copper. The adsorption of 2EPDCA molecules on Fe (110) and Cu (111) surfaces was further verified by molecular dynamic simulations, with the former having a greater adsorption energy. The results indicate that the corrosion inhibitor was effective even in harsh conditions, and it can be thought of as a novel corrosion inhibitor for mild steel and copper that provides good protection.

Synthesis, Characterization and Evaluation of Some Pyranopyrazole Derivatives as Multifunction Additives for Medium Lubricating Oils

The current work involves synthesis of 6-amino-4-(4-hydroxyl-3-methoxyphenyl)-3-methyl-1-phenyl-1,4- dihydropyrano[2,3-c]pyrazole-5-carbonitrile (2) by condensation of 2-(4-hydroxyl-3-methoxybenzylidine) malononitrile (1) with 3-methyl-1-phenyl-2-pyrazolin-5-one. The product 2 was then reacted with various aldehydes to form a series of Schiff base derivatives 3a-h. The reaction of the chosen Schiff base derivatives (3a and 3b) with mercaptoacetic acid gave thiazolidinone derivatives (4a and 4b). The structures of prepared compounds were confirmed using FT-IR, 1H NMR, and 13C NMR spectroscopies. They were evaluated as good copper corrosion inhibitors, anti-rust, and antioxidants. This was done by mixing them with the base medium lubricating oil (type 60 stock) provided by the Iraqi Midland Refineries Company/Al-Daura according to the American Society of Testing and Materials ASTM-D130, ASTM-D665, and Institute of Petroleum's testing method, oxidation stability test (IP-280), respectively.

Novel 1, 2, 4-Triazole Derivatives as Corrosion Inhibitors for Copper in HNO3 Solution

Novel 1, 2, 4-Triazole Derivatives as Corrosion Inhibitors for Copper in HNO3 Solution