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Macrocyclic compounds as green corrosion inhibitors for aluminium: electrochemical, surface and quantum chemical studies
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In the present work, two macrocyclic compounds namely 5,6,11,12-tetramethyl-1,2,4,7,8,10-hexaazacyclododeca-4,6,10,12-tetraene-3,9-dithione (TMCD) and 5,6,11,12-tetraphenyl-1,2,4,7,8,10-hexaazacyclododeca-4,6,10,12-tetraene-3,9-dithione (TMPD) have been synthesized and for the first time reported as inhibitors against the corrosion of aluminium in 1 M hydrochloric acid. The synthesized compounds were characterized using 1 H NMR and 13 C NMR. The corrosion inhibition behaviour of TMCD and TMPD was studied using gravimetric measurements, electrochemical impedance spectroscopy and potentiodynamic polarization studies. The surface analysis was carried out using AFM and SEM. Theoretical studies on the adsorption behaviour of inhibitor were carried out using the Density Functional Theory method. A detailed study of the effect of temperature and the influence of immersion time is presented using weight loss technique. Potentiodynamic polarization study proves that the corrosion inhibition efficiencies of TMCD and TMPD at 400 mg L-1 concentration are 97.30% and 89.71% respectively. Both the inhibitors behaved as mixed type but exhibit cathodic predominance. The results of EIS-Nyquist plots show inductive behavior at low frequency characteristic of the electrochemical behaviour of aluminium. The increase in polarization resistance with concentration suggests the adsorption and corrosion inhibition behaviour for both TMCD and TMPD. The AFM studies reveal a considerable decrease in surface roughness in the presence of inhibitors compared to blank sample and the SEM images show a highly smooth surface of the metal sample in the presence of inhibitors. The Fukui functions, global softness and Mulliken charges reveal that the sites for electrophilic attack are the hetero atoms. The frontier molecular orbital energies, the molecular orbital energy gap and the other quantum Int. J. Corros. Scale Inhib., 2018, 7, no. 3, 443-459 444 chemical parameters corroborated the experimental observations and suggested a better performance of TMCD compared to TMPD molecule.
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... The distribution of atomic charges within a molecule can significantly influence its interaction with other species, especially when considering chemisorption involving coordination bonds and physical interactions like van der Waals forces [176][177][178][179][180][181]. Chemisorption involves the formation of chemical bonds between the adsorbate (an inhibitor molecule) and the adsorbent surface (iron). ...
Corrosion control is of paramount importance in the realm of metals, and the quest for effective inhibitors is ongoing. This study delves into the potential corrosion inhibitory effect of N-phenyl-N′-[5-phenyl-1,2,4-thiadiazol-3-yl]thiourea (NPPTT) on mild steel when exposed to a corrosive 1 M HCl solution. Employing a dual approach, we combine experimental weight loss techniques with Density Functional Theory (DFT) calculations to comprehensively analyze inhibition efficiency and the underlying molecular interactions in the corrosion inhibition process. Our investigation begins with the confirmation of the inhibitor's structural properties through experimental synthesis and characterization techniques. Subsequently, we assess the corrosion inhibition capability by immersing mild steel samples in the aggressive HCl solution, both with and without the inhibitor. Our findings reveal a significant reduction in the corrosion rate, signifying the potential of NPPTT as an effective corrosion inhibitor. At an inhibitor concentration of 0.5 mM and an immersion time of 5 hours at 303 K, the inhibition efficiency reaches 93.9%. To unravel the mechanistic insights at the molecular level, DFT calculations are employed. Quantum chemical parameters are computed, shedding light on how NPPTT molecules interact with the mild steel surface through a combination of electrostatic interactions, coordination bonds, and other molecular linkages. These theoretical findings corroborate the experimental results, enhancing our comprehension of the inhibitor's action. Notably, our adsorption isotherm studies align with the Langmuir adsorption model, further confirming the inhibitor's adherence to the metal surface. In summary, this combined theoretical and experimental investigation explores the corrosion inhibitory potential of NPPTT for mild steel in a corrosive, acidic environment. Our holistic approach not only validates the inhibitor's Int. J. Corros. Scale Inhib., 2024, 13, no. 1, 38-78 39 efficiency but also advances our understanding of its molecular interactions, offering valuable insights for corrosion prevention strategies and the development of effective corrosion mitigation approaches in industrial settings.
... In order to better optimize PTM as a corrosion inhibitor, further researches and studies are required to reveal the exact reasons why inhibiting efficiency reduces with increasing temperatures. Such knowledge could be used in designing measures that would increase the efficacy and stability of "PMT" inhibition especially in high temperatures [175][176][177][178][179]. Exploring other parameters including dosage, time exposure, and potential interactions between PMT and other additives would provide deeper insights into its corrosion inhibition mechanism. ...
Metals are frequently exposed to corrosion by a wide variety of sources in various manufacturing environments. Effective inhibitors are urgently necessary to put an end to this situation. The investigation that follows requests to evaluate the potential of 5-(4-pyridyl)-3-mercapto-1,2,4-triazole (PMT) to prevent mild steel from corroding in an acid environment. PMTs inhibitory mechanisms were identified by weight loss experiments, Density Functional Theory (DFT) calculations and Langmuir adsorption isotherm analysis. The study found that when mild steel was dipped into 1 M HCl under optimal inhibitor conditions and at a concentration of 0.5 mM, the inhibition efficiency reached 97.1% at 303 K. Experiments of weight loss and density functional theory (DFT) are utilized to explore inhibitory mechanisms, and are also offered indicates about PMT's adsorption behavior on metal surfaces. The Langmuir adsorption isotherm suggestions a first indication about the compound's effectiveness, but it may also assist as a starting point for future developments in research on corrosion inhibition. These results provide some important knowledge to us about the fundamental mechanism of corrosion protection, and have important applications to industries trying to protect metals from corroding threatened in aggressive environments.
... As the exploration of heterocyclic compounds for corrosion inhibition in acidic solutions continues to evolve, a crucial facet of research involves a comparative analysis of these compounds. This section delves into the effectiveness of various heterocyclic compounds, considering key factors such as inhibition efficiency, cost-effectiveness, and environmental considerations [169][170][171]. ...
Corrosion poses a persistent challenge in acidic environments, necessitating the exploration of effective corrosion inhibitors. This mini-review focuses on the utilization of heterocyclic compounds as corrosion inhibitors in acidic solutions. Beginning with an overview of corrosion mechanisms in acidic environments, we delve into the diverse array of heterocyclic compounds investigated for their corrosion inhibition properties. Emphasis is placed on elucidating the mechanisms through which these compounds mitigate corrosion, ranging from surface adsorption to film formation. Recent advancements in the field are highlighted, showcasing novel compounds and formulations exhibiting promising results. A comparative analysis evaluates the effectiveness of various heterocyclic compounds, considering factors such as inhibition efficiency, cost, and environmental considerations. Despite notable successes, challenges and limitations are discussed, paving the way for future research directions. In conclusion, this mini-review underscores the significant strides made in harnessing heterocyclic compounds as corrosion inhibitors, offering a glimpse into their potential impact on addressing corrosion challenges in acidic environments.
... Возможность применения макроциклических соединений в качестве ингибиторов коррозии (ИК) металлов за последние десятилетия также многократно подтверждалась [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27]. Благодаря объемному размеру молекулы ФЦ их комплексы с катионами металла могут эффективно препятствовать доступу агрессивных ионов и кислорода к поверхности металла. ...
... Thus, the presence of π systems and O as heteroatoms in Tween 80 micelles as shown in Figure 5 can lead to the remarkable inhibition efficiency of Tween 80. These heteroatoms play a significant role in the contact with the aluminum surface via the adsorption mechanism, resulting in an increase in the degree of surface coverage (θ) [29][30][31][32]. ...
The influence of nonionic surfactant micelles such as Tween 80, polyethylene glycol 400, and coco glucoside on the inhibition of aluminum corrosion in hydrobromic acid solutions was investigated via weight reduction, thermometric, and electrical conductivity techniques. In the absence of inhibitors, the rise in temperature and acid levels has led to a tremendous acceleration in the aluminum corrosion in HBr solutions. Intriguingly, coco glucoside, PEG 400, and Tween 80 have shown a remarkable inhibitory action on the corrosion of aluminum in the corrosive solutions at different temperatures. The findings demonstrated that the inhibition efficacy of inhibitors and the extent of surface coverage of the micelles on aluminum rise with higher concentration of the inhibitor and decline with rising temperature. Notably, Tween 80 was a more effective inhibitor than PEG 400, and coco glucoside at all temperatures. This effect may be explained by the force and type of their micelles' adsorption on the aluminum surface, which occurs when hydrophilic regions of coherent layers of micelles donate their electrons to the metal surface. Also, the thermodynamic factors (ΔH°, ΔS°, and Ea) for the corrosion and adsorption processes were assessed and addressed. The experimental data were best fit by models of Langmuir, Temkin, and Flory-Huggins adsorption isotherms fit each other well.
... Thus, the presence of π systems and O as heteroatoms in Tween 80 micelles as shown in Figure 5 can lead to the remarkable inhibition efficiency of Tween 80. These heteroatoms play a significant role in the contact with the aluminum surface via the adsorption mechanism, resulting in an increase in the degree of surface coverage (θ) [29][30][31][32]. ...
The influence of nonionic surfactant micelles such as Tween 80, polyethylene glycol 400, and coco glucoside on the inhibition of aluminum corrosion in hydrobromic acid solutions was investigated via weight reduction, thermometric, and electrical conductivity techniques. In the absence of inhibitors, the rise in temperature and acid levels has led to a tremendous acceleration in the aluminum corrosion in HBr solutions. Intriguingly, coco glucoside, PEG 400, and Tween 80 have shown a remarkable inhibitory action on the corrosion of aluminum in the corrosive solutions at different temperatures. The findings demonstrated that the inhibition efficacy of inhibitors and the extent of surface coverage of the micelles on aluminum rise with higher concentration of the inhibitor and decline with rising temperature. Notably, Tween 80 was a more effective inhibitor than PEG 400, and coco glucoside at all temperatures. This effect may be explained by the force and type of their micelles’ adsorption on the aluminum surface, which occurs when hydrophilic regions of coherent layers of micelles donate their electrons to the metal surface. Also, the thermodynamic factors (ΔH0, ΔS0, and Ea) for the corrosion and adsorption processes were assessed and addressed. The experimental data were best fit by models of Langmuir, Temkin, and Flory–Huggins adsorption isotherms fit each other well.
... where Q denotes the magnitude of CPE, ω is the angular frequency and [29]. Also, the decrease of C dl values with the addition of the examined compounds is due to the adsorption of the molecules of the compound, replacing water at the mild steel-solution interface and leading to a decrease in the local dielectric constant and/or an increase of the thickness of the electrical double layer [30]. ...
The inhibitive action of some quaternary N-heterocyclic compounds namely 1-methyl-4[4′(-X)-styryl] pyridinium iodides (X: -H, -Cl and -OH)on the corrosion of Al–Cu alloy in 0.5 M HCl solutions was evaluated by potentiodynamic polarization, electrochemical impedance spectroscopy and weight loss measurements. All the studied compounds showed good inhibitive characteristics against the corrosion of Al–Cu alloy in the tested solutions and their performance increases with inhibitor concentration. Polarization data indicated that the studied compounds are cathodic inhibitors without changing the mechanism of hydrogen evolution reaction.The adsorption of all inhibitors on Al–Cu alloy obeys Langmiur adsorption isotherm. The effect of temperature (30–70 °C) on the inhibition efficiency at certain concentration of the studied compounds was investigated. The data revealed that the studied compounds have good pickling inhibitor's quality as they perform well even at relatively high temperature. The corrosion activation parameters (Ea, ΔH*, ΔS* and ΔG*) were estimated and discussed. It was found that Ea values for Al–Cu alloy corrosion in the inhibited solutions were higher than that for the uninhibited solution, indicating good inhibitor characteristics with physical adsorption mechanism. The effect of acid, s anion on the performance of the studied inhibitors was studied and discussed.
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