The effect of some triazole derivatives as inhibitors for the corrosion of mild steel in 5 % hydrochloric acid

Corrosion inhibition by triazole derivatives (n-MMT) on mild steel in 5 % hydrochloric acid (HCl) solutions has been investigated by weight loss and electrochemical methods. The results obtained revealed that these compounds performed excellently as corrosion inhibitors for mild steel in HCl solution. Potentiodynamic polarization studies showed that they suppressed both the anodic and cathodic processes and inhibited the corrosion of mild steel by blocking the active site of the metal. The effect of temperature on the corrosion behavior of mild steel in 5 % HCl with the addition of different concentrations of the inhibitors was studied in the temperature range from 303 to 333 K. The associated activation corrosion and free adsorption energies were determined. The adsorption of these compounds on the mild steel surface obeys the Langmuir adsorption isotherm. The effect of molecular structure on the inhibition efficiency has been investigated by quantum chemical calculations. The electronic properties of inhibitors were calculated and are discussed.     

Quantum chemical calculation for the inhibitory effect of compounds

The effects of the molecular structure on the corrosion inhibition efficiency are investigated by nine methods of calculations. The selected thio compounds were previously identified as corrosion inhibitors for mild steel in the 1.0 M HCl solution. The electronic properties such as highest occupied molecular orbital (EHOMO) energy, lowest unoccupied molecular orbital (ELUMO) energy, dipole moment (μ), and Fukui indices are calculated and discussed. Results show that the corrosion inhibition efficiency increase with the increase in both EHOMO and μ values, respectively, and decrease in ELUMO. QSAR approach is utilized in this study; a good relationship is found between the experimental corrosion inhibition efficiency (IE_exp, %) and the theoretical corrosion inhibition efficiency (IE_theor, %). The calculated inhibition efficiency is found closer to the experimental inhibition efficiency with a coefficient of correlation (R ²) of 0.875.     

Electrochemical and Theoretical Studies of 1-Alkyl-2-substituted Benzimidazoles as Corrosion Inhibitors for Carbon Steel Surface in HCl Medium

The inhibition efficiencies of newly synthesized four 1-alkyl-2-substituted benzimidazole compounds(a~d) have been studied for the corrosion of carbon steel in 1.0 M HCl by using potentiodynamic polarization measurement. The four inhibitors act as mixed-type inhibitors,which mainly inhibit cathodes. The inhibition efficiency of these compounds enhanced when the concentration of the inhibitors increased. A theoretical study of the corrosion inhibition efficiency of these compounds was carried out by using the B3 LYP level with the 6-31+G* basis set. Considering the solvent effect,the IEFPCM model was selected. Furthermore,the adsorption energies of the inhibitors with the iron(001) surface were studied by using molecular dynamic(MD) simulations. The theoretical results show that these inhibitors all exhibit several adsorption active-centers. Meanwhile,the MD simulations indicate that the adsorption occurs mostly through benzene ring and the lone pair electrons of the nitro atoms. These results demonstrated that the theoretical studies and MD simulations are reliable and promising methods for analyzing the inhibition efficiency of organic inhibitors.     

Performance of some thiophene derivatives as corrosion inhibitors for 304 stainless steel in aqueous solutions

The inhibitive effect of 2-cyano-3-hydroxy-4(Ar)-5-anilino thiophene derivatives on the corrosion of 304 stainless steel (SS) in 3 M HCl solution has been investigated by weight loss, galvanostatic polarization techniques, and potentiodynamic anodic polarization in 3.5 % NaCl. The results indicate that these compounds act as inhibitors retarding the anodic and cathodic corrosion reactions. The presence of inhibitors does not change the mechanism of either hydrogen evolution reaction or SS dissolution. The activation energy and some thermodynamic parameters are calculated and discussed. These compounds are mixed-type inhibitors in the acid solution, and their adsorption on the SS surface is found to obey the Temkin adsorption isotherm. The results suggest that the percentage inhibition of these thiophene derivatives increases with increasing inhibitor concentration and decreases with increasing temperature. The synergistic parameter (S) was calculated and found to have a value greater than unity, indicating that the enhanced inhibition efficiency caused by the addition of I^?, SCN^?, and Br^? is only due to a synergistic effect. The relationship between molecular structure and inhibition efficiency was elucidated by quantum-chemical calculations using semi-empirical self-consistent field (SCF) methods.     

FeGa3 and RuGa3: Semiconducting Intermetallic Compounds

The intermetallic compounds FeGa₃ and RuGa₃ were prepared from the elements using a Ga flux and their structures were refined from single-crystal X-ray data. Both compounds crystallize with the FeGa₃ structure type (tetragonal, space group P4₂/mnm, Z=4). Electrical resistivity measurements revealed a semiconducting behavior for FeGa₃ and RuGa₃, which is in contrast to the good metallic conductivity observed for the isotypic compound CoGa₃. The origin of the different electronic properties of these materials was investigated by first-principle calculations. It was found that in compounds adopting the FeGa₃ structure type the transition metal atoms and Ga atoms interact strongly. This opens a d-p hybridization bandgap with a size of about 0.31 eV in the density of states at the Fermi level for 17-electron compounds (i.e., FeGa₃ and RuGa₃). The electronic structure of CoGa₃ (an 18-electron compound) displays rigid band behavior with respect to FeGa₃. As a consequence, the Fermi level in CoGa₃ becomes located above the d-p hybridization gap which explains its metallic conductivity.     

Inhibition de la corrosion du cuivre en milieu HCl 0,5 M par les composes organiques de type triazole

Some triazole-type organic compounds were tested as corrosion inhibitors for copper in 0.5 M HCl solution at 20°C. Electrochemical (potentiodynamic polarization and polarization resistance measurements) and gravimetric methods were used for this study. The obtained results showed that 3-amino-1,2,4 triazole (ATA) and 3,5 diamino-1,2,4 triazole (DTA) effectively reduce the corrosion rate of copper. The inhibition efficiency (E%) of these compounds increases with their concentrations and attains maximum values at 10⁻³M and 10⁻⁴ for ATA and DTA, respectively. The variation of efficiency with logC shows that these inhibitors are adsorbed on the metallic surface according to the Frumkin adsorption isotherm model.     

Synthesis,X-ray structure and theoretical study of benzazole thioether and its zinc complex as corrosion inhibitors for steel in acidic medium

A ligand, 2-((benzo[d]thiazol-2-ylthio)methyl)-1H-benzo[d]imidazole, and its zinc complex have been synthesized. The structure of these compounds have been determined by spectroscopic techniques and single crystal X-ray diffraction. The corrosion inhibition study of these compounds for steel in 0.5 M H₂SO₄ medium has also been investigated using potentiodynamic polarization and EIS techniques. The quantum calculations were applied to investigate the relationship between the electronic properties and the corrosion inhibition efficiency of the two benzazoles derivatives. Surface analysis (XRF) indicated that the rust layer formed on the Cu-containing steels was enriched with Cu compounds. Polarization curves revealed that both inhibitors acted as a mixed-type inhibitor.     

Theoretical study of the inhibitive properties of a group of benzimidazoles

In this work, a group of benzimidazoles, namely benzimidazole (BIM), 2‐hexyl benzimidazole (2‐HBIM), and 2‐benzyl chloride benzimidazole (2‐ClBBIM), have been studied using density functional theory (DFT) at the level of B3LYP with the 6‐31G (d) and 6‐311G (d, p) base sets in order to elucidate the different inhibition efficiencies and reactive sites of these compounds as corrosion inhibitors. Based on the calculated results, the studied molecules interact with Fe‐atoms mainly in their stable pyridine‐N protonated forms. It is found that the inhibition efficiencies of the stable protonated molecules involved in this study have a certain relation with some parameters, such as the highest occupied molecular orbital energy (E_HOMO) and the global hardness (η). The results indicate that the C (7) atoms, as the reactive sites, receive electrons from Fe‐atoms, benzene ring denote electrons to vacant orbital of Fe‐atoms. Additionally, Fukui indices and the orbital analyses suggest that 2‐ClBBIM has the highest reaction activity among the three molecules, the efficiency order of three inhibitors is found to be 2‐ClBBIM > 2‐HBIM > BIM, which accords with experimental results. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Quantum chemical study of the inhibitive properties of 2-pyridyl-azoles

Four molecules that have been proven to act as corrosion inhibitors of mild steel in acidic media are studied. The inhibitive efficiency of these molecules is explained by means of electronic structure calculations of the protonated species that seem to represent better the actual situation of the experimental conditions. By assuming that the interaction between the inhibitor and the metallic surface occurs through donation and back-donation, it is shown, with a simple charge transfer model, that the interaction energy is favored when hardness increases, in agreement with the experimentally observed inhibition efficiencies. A local analysis with Hirshfeld condensed Fukui functions, and local Fukui functions, provides further support to the donation and back-donation mechanism.     

Anti-corrosive property of bioinspired environmental benign imidazole and isoxazoline heterocyclics: A cumulative studies of experimental and DFT methods

In the present study, four imidazoline (IDZ) and four isoxazolines (ISO) heterocyclics differing in the nature of methoxy (-OCH₃) and aromatic (phenyl and naphthyl) moieties are synthesized, characterized and evaluated as corrosion inhibitors for mild steel in acidic solution of 1 M HCl. Results showed that imidazoline based heterocyclic compounds are better corrosion inhibitors than isoxazoline based heterocyclics and both classes of compounds showed inhibition efficiency of more than 85% at 20 mgL⁻¹ concentration. Results further showed that inhibitors containing methoxy, phenyl, and naphthyl moieties showed higher protection efficiency as compared to the inhibitors without these moieties. PDP Study revealed that investigated IDZs and ISOs acted as mixed type inhibitors and their adsorption on the metallic surface followed the Langmuir adsorption isotherm model. All the experimental results were corroborated by density function theory (DFT) based quantum chemical calculations. Numerous DFT based indices calculated for neutral as well as protonated forms of the IDZs and ISOs in order to get better insight about metal-IDZs/ISOs interactions. Outcomes of the DFT analysis showed that protonated (cationic) form of the all the inhibitors are more strongly adsorbed on the metallic surface as compared to their neutral form.     

Cucumber (Cucumis sativus L.) Leaf Extract as a Green Corrosion Inhibitor for Carbon Steel in Acidic Solution: Electrochemical,Functional and Molecular Analysis

An extract of cucumber leaves (ECSL) was prepared as a green corrosion inhibitor for carbon steel. Its carbon steel corrosion inhibition performance against 0.5 mol L⁻¹ H₂SO₄ was investigated using electrochemical methods and scanning electron microscopy (SEM). Its composition was analyzed by gas chromatography and mass spectroscopy (GC−MS). Quantum chemical calculations and molecular dynamics simulations (MDS) were conducted to elucidate the adsorption mechanism of the inhibitor molecules on the carbon steel surface. The results indicated that the inhibition efficiency increases with its increasing concentration. The extract acted as a mixed type corrosion inhibitor, and its inhibition properties were ascribed to the geometric coverage effect induced by its adsorption on the metal surface in accordance with Langmuir’s law. The active components in the extract were identified as mainly organic compounds with functional groups such as aromatic moieties and heteroatoms. The inhibition activities of ECSL are delivered through the ability of the active components to adsorb on the metal surface through their functional groups to form a protective layer which hinders the contact of aggressive substances with carbon steel and thus suppresses its corrosion. This research provides an important reference for the design of green corrosion inhibitors based on plant waste materials.     

Evaluation of crude methanolic mangrove leaves extract for antibiofilm efficacy against biofilm-forming bacteria on a cooling tower wastewater system

The present study demonstrated microbial corrosion protection of MS 1010 on cooling tower water using plant-based inhibitors derived from methanolic extraction of dry mangrove leaves (R.mangle and A.marina), and its assessment of antibacterial activity against corrosive bacteria (B.megaterium) was investigated. FT-IR and GC–MS analyzed the inhibitors component and corrosion behavior of MS 1010 on cooling water, with and without inhibitors were analyzed by EIS and Tafel studies. GC–MS spectra confirmed the presence of Myo-Inositol, 4-C-methyl and chromene as major constituents presented on the R.mangle whereas Lupeol, trifluoroacetate and beta-amyrin compounds were found on the A.marina. In the cooling water, these two inhibitors demonstrated outstanding antibacterial activity and controlled biofilm growth. As plant-based inhibitors were used in cooling water systems, EIS data showed a significant increase in R_ct value when compared to the control system. Tafel plot indicates inhibitors have mixed inhibitory effects and for the systems with and without inhibitors, the i_corr value was 1.5649A and 2.0875A, respectively. At the optimal dose of 25 ppm, the inhibitory efficiency of MERM and MEAM was 81% and 80%, respectively. The overall discussion reveals that inhibitor substances can be absorbed on the metal surface and then act as a dual role in inhibiting corrosive bacterial growth and barrier to the corrosion process in the cooling water system.     

Corrosion Inhibition Using Harmal Leaf Extract as an Eco-Friendly Corrosion Inhibitor

Extract of natural plants is one of the most important metallic corrosion inhibitors. They are readily available, nontoxic, environmentally friendly, biodegradable, highly efficient, and renewable. The present project focuses on the corrosion inhibition effects of Peganum Harmala leaf extract. The equivalent circuit with two time constants with film and charge transfer components gave the best fitting of impedance data. Extraction of active species by sonication proved to be an effective new method to extract the inhibitors. High percent inhibition efficacy IE% of 98% for 283.4 ppm solutions was attained using impedance spectroscopy EIS measurements. The values of charge transfer R_ct increases while the double layer capacitance C_dl values decrease with increasing Harmal extract concentration. This indicates the formation of protective film. The polarization curves show that the Harmal extract acts as a cathodic-type inhibitor. It is found that the adsorption of Harmal molecules onto the steel surface followed Langmuir isotherm. Fourier-transform infrared spectroscopy FTIR was used to determine the electron-rich functional groups in Harmal extract, which contribute to corrosion inhibition effect. Scanning electron microscopy SEM measurement of a steel surface clearly proves the anticorrosion effect of Harmal leaves.     

Synthesis of a new class of corrosion inhibitors derived from natural fatty acid: 13‐Docosenoic acid amide derivatives for oil and gas industry

As corrosion inhibitors, a series of new amide derivatives of 13‐docosenoic acid was synthesized in yields of above 90% by reacting 13-docosenoic acid with primary and secondary aliphatic and aromatic amines. The inhibition efficiencies (%IEs) of these compounds at various concentrations for the suppression of corrosion of mild steel in 1.00 M HCl exposed for 96 h (4 days) at temperatures in the range 298–333 K were measured via gravimetric corrosion measurements. At 100 ppm, all compounds yielded satisfactory corrosion %IE in 1.00 M HCl; compounds 2 and 7 exhibited remarkable %IE of 70.0 and 74.7%, respectively. The results of gravimetric measurements further revealed that compound 7 performed excellently at 60 °C, with %IE = 96.8 at 500 ppm. Quantum chemical density functional theory (DFT) calculations helped predict that compound 7 should have more aromatic character, enabling it to serve as a donor-center for the empty d-orbital of the metal atoms, leading to higher corrosion IE. The adsorption of the inhibitor molecules on the surface of mild steel followed the Langmuir adsorption model, and the free energy of adsorption (ΔG_ads) value indicated that the inhibitors are adsorbed through a combined physisorption and chemisorption mechanism to provide effective surface coverage.     

Effect of the alkyl chain length on micelle formation for bis(N-alkyl-N,N-dimethylethylammonium)ether dibromides

Dimeric alkylammonium salts – gemini surfactants – due to their unusual very low critical micelle concentration and minimal inhibitory concentration are subject to intensive research as surface active and antimicrobial compounds. Thanks to the presence of two positively charged nitrogen atoms and a large molecular surface, gemini surfactants are also very efficient corrosion inhibitors. To strengthen the electrostatic adsorption of ammonium cations on a metal surface, which is a key parameter in the inhibition of corrosion, heteroatoms (O, S, N, or P) and π-electron systems can be introduced into the gemini surfactant structure to increase chemical adsorption. In this study, we investigated the relationship between the alkyl chain length and critical micelle concentration for gemini surfactants containing an oxygen atom in the spacer, that is, bis(N-alkyl-N,N-dimethylethylammonium)ether dibromides, for potential use as corrosion inhibitors.     

Corrosion Inhibition Efficiency of Polytriethanolamine Surfactants for Pipe-Lines Carbon Steel in 1M HCl

Fifteen organic compounds were prepared from triethanolamine and its derivative. The triethanolamine was polymerized by condensation to get P₄, P₆, and P₈ at different molecular weight. The P8 was ethoxylated at different ethylene oxide units (en) (40, 100, and 120) to obtain three compounds (E(en)P₈). Every degree of ethoxylate was esterified with 1, 4, and 8 moles of oleic acid to get on 9 ethoxylated polytriethanolamine esters (E(en)P₈Om). The effect of adding these organic compounds on the electrochemical behavior of carbon steel in 1 M HCl was investigated by using the weight loss technique. The reported results in this study show that the addition of these surfactants inhibits the corrosion of carbon steel. The inhibition efficiency (I%) for each inhibitor increases with increasing the concentration. The maximum inhibition efficiency (95%) was obtained by (E(40)P₈O₁) at 600 ppm. The inhibitive efficiency was discussed on the light of chemical structure of the used inhibitors.     

Synthesis and Stability of Lanthanum Superhydrides

Recent theoretical calculations predict that megabar pressure stabilizes very hydrogen‐rich simple compounds having new clathrate‐like structures and remarkable electronic properties including room‐temperature superconductivity. X‐ray diffraction and optical studies demonstrate that superhydrides of lanthanum can be synthesized with La atoms in an fcc lattice at 170 GPa upon heating to about 1000 K. The results match the predicted cubic metallic phase of LaH₁₀ having cages of thirty‐two hydrogen atoms surrounding each La atom. Upon decompression, the fcc‐based structure undergoes a rhombohedral distortion of the La sublattice. The superhydride phases consist of an atomic hydrogen sublattice with H?H distances of about 1.1 Å, which are close to predictions for solid atomic metallic hydrogen at these pressures. With stability below 200 GPa, the superhydride is thus the closest analogue to solid atomic metallic hydrogen yet to be synthesized and characterized.     

Electrochemical and Quantum Chemical Studies of Azoles as Corrosion Inhibitors for Mild Steel in Hydrochloric Acid

The inhibition effect of three azole compounds, 2-aminobenzimidazole(ABM), 2-aminothiazole(AT) and 2-aminobenzothiazole(ABT), on the corrosion of mild steel in a 1 mol/L HCl solution was investigated by means of potentiodynamic polarization measurement, electrochemical impedance spectroscopy(EIS) and scanning electron mi-croscopy(SEM). The correlation between inhibition efficiency and molecular structure of inhibitor was theoretically studied via quantum chemical calculations. The results show that the inhibition efficiency(η) of the inhibitors follows the order of η_ABT >η_AT >η_ABM. Moreover, ABM, AT and ABT belong to mixed-type inhibitors. The adsorption of the inhibitors on the steel surface follows the Langmuir adsorption isotherm, with both physisorption and chemisorption.