The inhibition of benzimidazole derivatives on corrosion of iron in 1 M HCl solutions

The inhibitive action of some benzimidazole derivatives namely 2-aminobenzimidazole (AB), 2-(2-pyridyl)benzimidazole (PB), 2-aminomethylbenzimidazole (MB), 2-hydroxybenzimidazole (HB) and benzimidazole (B), against the corrosion of iron (99.9999%) in solutions of hydrochloric acid has been studied using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). At inhibitor concentration range (10⁻³-10⁻² M) in 1 M acid, the results showed that these compounds suppressed both cathodic and anodic processes of iron corrosion in 1 M HCl by adsorption on the iron surface according to Langmuir adsorption isotherm. The efficiency of these inhibitors increases in the order AB>PB>MB>HB>B. Both potentiodynamic and EIS measurements reveal that these compounds inhibit the iron corrosion in 1 M HCl and that the efficiency increases with increasing of the inhibitor concentration. Data obtained from EIS were analyzed to model the corrosion inhibition process through equivalent circuit. A correlation between the highest occupied molecular orbital E_HOMO and inhibition efficiencies was sought.     

Investigation of the inhibitive effect of ortho-substituted anilines on corrosion of iron in 1 M HCl solutions

The inhibitory activity of some o-substituted anilines on iron corrosion in hydrochloric acid (HCl) was studied in relation to inhibitor concentration using potentiodynamic and electrochemical impedance spectroscopy (EIS) measurements. O-substituted anilines were found to act as mixed type inhibitors. The results showed that o-substituted anilines suppressed both cathodic and anodic processes of iron corrosion in 1 M HCl by its adsorption on the iron surface according to Langmuir adsorption isotherm. Potentiodynamic and EIS measurements reveal that these compounds inhibit the iron corrosion in 1 M HCl and that the efficiency increases with increasing of the inhibitor concentration. Data obtained from EIS are analyzed to model the corrosion inhibition process through equivalent circuit.     

Molecular simulation, quantum chemical calculations and electrochemical studies for inhibition of mild steel by triazoles

The inhibition performance of three triazole derivatives on mild steel in 1 M HCl were tested by weight loss, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The adsorption behavior of these molecules at the Fe surface was studied by the molecular dynamics simulation method and the quantum chemical calculations. Results showed that these compounds inhibit the corrosion of mild steel in 1 M HCl solution significantly. Molecular simulation studies were applied to optimize the adsorption structures of triazole derivatives. The iron/inhibitor/solvent interfaces were simulated and the charges on the inhibitor molecules as well as their structural parameters were calculated in presence of solvent effects. Aminotriazole was the best inhibitor among the three triazole derivatives (triazole, aminotriazole and benzotriazole). The adsorption of the inhibitors on the mild steel surface in the acid solution was found to obey Langmuir's adsorption isotherm.     

In situ Raman spectroscopy and electrochemical techniques for studying corrosion and corrosion inhibition of iron in sodium chloride solutions

The corrosion of single crystal pure iron in 3.5% NaCl solutions and its inhibition by 3-amino-5-mercapto-1,2,4-triazole (AMTA) have been studied using in situ and ex situ Raman spectroscopy, cyclic voltammetry (CV), open-circuit potential (OCP), potentiodynamic polarization (PDP), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS) measurements. CV experiments indicated that the iron electrode in the chloride solution alone showed an anodic peak at ∼−650 mV after the 5th cycle shifted to ∼−610 mV after the 20th cycle; another cathodic peak appeared at ∼−990 mV. In the presence of 1.0 mM AMTA, these two peaks shifted to ∼550 and −1050 mV, respectively. OCP, PDP, CA and EIS revealed that the presence of AMTA and the increase of its concentration move the corrosion potential to more positive values and decrease both the corrosion current and corrosion rate. This effect also increases with increasing the immersion time of iron electrode to 24 h in the test electrolyte. In situ and ex situ Raman investigations confirmed that the addition of AMTA molecules to the chloride solution strongly inhibits the iron corrosion through their adsorption onto the surface blocking its active sites and preventing its corrosion.     

Computational and electrochemical investigation for corrosion inhibition of nickel in molar nitric acid by piperidines

The adsorption and corrosion inhibition behaviour of four selected piperidine derivatives, namely piperidine (pip), 2-methylpiperidine (2mp), 3-methylpiperidine (3mp), and 4-methylpiperidine (4mp) at nickel in 1.0 M HNO₃ solution were studied computationally by the molecular dynamics simulation and quantum chemical calculations and electrochemically by Tafel and impedance methods. The results indicate a strong dependence of the inhibition performance on the nature of the metal surface, in addition to the structural effects of piperidines. Inhibition is accomplished by adsorption of piperidines on the metal surface without detectable changes in the chemistry of corrosion. Adsorption is predominantly chemisorptive in the active region and by hydrogen bond formation in the passive region. The potential of zero charge (PZC) of the nickel electrode was determined in 1.0 M HNO₃ solutions in the absence and presence of 10⁻² M 2mp, and the electrostatic (physical) adsorption was discussed. The inhibition efficiency of these compounds increases in the order: 4mp > 3mp > 2mp > pip. Molecular simulation studies were applied to optimize the adsorption structures of piperidine derivatives. The nickel/inhibitor/solvent interfaces were simulated and the charges on the inhibitor molecules as well as their structural parameters were calculated in the presence of solvent effects. Quantum chemical calculations based on the ab initio method were performed to determine the relationship between the molecular structure of piperidines and their inhibition efficiency. Results obtained from Tafel and impedance methods are in good agreement and confirm theoretical studies.     

Advanced quantum chemical and electrochemical analysis of ravage drugs for corrosion inhibition of mild steel

The blocking of corrosive sites of soft (mild) steel has been studied using ravage drugs Pyrazinamide (Z), Isoniazid (H) and Rifampicin (R) in 0.5?M HCl medium. The degree of ability of these drugs to act as corrosion controlling agents was investigated by gravimetric measurements, potentiostatic polarization and electrochemical impedance spectroscopy. Their inhibition efficacy has, further been validated through theoretical and simulation studies. Though, all the drugs have shown good anticorrosive impact, but, rifampicin (R) has proven its greater efficacy as 97.06% at 1000?ppm and at 303?K. Polarization curves depict that the H and R drugs act through mixed mode of inhibition while Z drug is predominantly anodic in nature. The result of electrochemical impedance spectroscopy specifies that the corrosion reaction is resisted by charge transfer process. Morphology of un-corroded and corroded coupons was studied by scanning electron microscopy. The mechanism of adsorption is obeyed well through Langmuir isotherm and advocated a significant physiochemical type of interaction by the compounds on the metal surface. Thus, all the findings got via various experimental techniques along with that of obtained using Molecular Dynamics (MD) and Density Functional Theory (DFT) for the three compounds are in proper harmony.     

Undecyl substitution in imidazole and its action on corrosion inhibition of copper in aerated acidic chloride media

Inhibition of copper corrosion by imidazole (IM) and 1-n-undecyl-imidazole (UDIM) in 0.5 M HCl was investigated by weight-loss measurements, potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS). 1-n-undecyl-imidazole showed the better inhibitive effect compared with IM. Potentiodynamic polarization results revealed that both IM and UDIM acted as anodic inhibitors, in particular UDIM suppressed anodic current densities significantly. Molecular structure parameters of IM and UDIM were obtained by using an MM2 forcefield program and AM1 quantum chemical calculation. It was found that UDIM has higher levels of HOMO and LUMO energy and a larger electron density in its imidazoly ring. Presented as paper No.13-07 at 14th APCC conference, October 2006, Shanghai, China     

Electrochemical behavior of nickel in nitric acid and its corrosion inhibition using some thiosemicarbazone derivatives

The adsorption and corrosion inhibition behavior of three selected thiosemicarbazone derivatives, namely 3-pyridinecarboxaldehyde thiosemicarbazone (META), isonicotinaldehyde thiosemicarbazone (PARA) and 2-pyridinecarboxaldehyde thiosemicarbazone (ORTHO) at the nickel surface were studied electrochemically by Tafel and impedance methods and computationally by carrying out Monte Carlo searches of configurational space on nickel/thiosemicarbazone derivative system. Electrochemical measurements showed that the inhibition efficiency of these compounds increased with increase in their concentration. The recorded inhibition efficiencies of the three tested thiosemicarbazone increase in the order: META > PARA > ORTHO. Polarization studies showed that these compounds act as mixed-type inhibitors for nickel corrosion in 1.0 M HNO₃ solutions. Results obtained from Tafel and impedance methods are in good agreement. Thiosemicarbazone derivatives have been simulated as adsorbate on Ni (1 1 1) substrate and the adsorption energy, binding energy and the low energy adsorption sites have been identified on nickel surface.     

Study of the inhibition of the corrosion of iron steel in neutral solution by electrochemical techniques and theoritical calculations

The effect of triazole organic molecules (triazole thiol and amino triazole) containing heteroatoms such as nitrogen or sulfur on the corrosion behavior of iron was investigated. Electrochemical studies of the iron samples were performed in an aerated solution of NaCl (3%) by means of electrochemical impedance spectroscopy (EIS) as well as polarisation curves. These results are completed with theoretical calculations, which allow determining the possible anchoring site suitable for bonding.     

Evaluation of electrochemical frequency modulation as a new technique for monitoring corrosion and corrosion inhibition of carbon steel in perchloric acid using hydrazine carbodithioic acid derivatives

Electrochemical frequency modulation, EFM is a new technique for corrosion rate measurements. With the EFM technique, the corrosion rate and corrosion kinetic parameters can be obtained instantaneously without prior knowledge of Tafel slopes, which makes this method an ideal technique for application as a corrosion monitoring tool. Results obtained with the EFM technique were shown to be in agreement with chemical (weight loss) and electrochemical methods (Tafel extrapolation and electrochemical impedance spectroscopy, EIS) for corrosion rate measurements. New synthesized hydrazine carbodithioic acid derivatives namely, N′-furan-2-yl-methylene-hydrazine carbodithioic acid (A), N′-(4-dimethylamino-benzylidene)-hydrazine carbodithioic acid (B) and N′-(3-nitro-benzylidene)-hydrazine carbodithioic acid (C) were examined as corrosion inhibitors for carbon steel in 1 M perchloric acid solution. The results obtained from both chemical and electrochemical measurements show that these compounds suppressed both anodic and cathodic processes of carbon steel corrosion in 1 M HClO₄ by adsorption on the electrode surface. The adsorption mode follows the Langmuir adsorption isotherm. The efficiency of the inhibitors increases in the order C > B > A.     

Electrochemical frequency modulation as a new technique for monitoring corrosion inhibition of iron in acid media by new thiourea derivative

The electrochemical frequency modulation EFM technique provides a new tool for electrochemical corrosion monitoring. EFM is a non-destructive technique as electrochemical impedance spectroscopy (EIS). EFM technique was used in comparison with the traditional dc and ac techniques. Results obtained by EFM technique were shown to be in agreement with other electrochemical techniques. With EFM technique, a corrosion rate can be obtained instantaneously in very short time which makes this technique ideal in online corrosion monitoring. New synthesized thiourea derivative named 1,3-diarylidenethiourea (DAT) was examined as a new corrosion inhibitor for iron in 1 M hydrochloric acid solution.     

Weight loss, polarization, electrochemical impedance spectroscopy, SEM and EDX studies of the corrosion inhibition of copper in aerated NaCl solutions

This work reports results of weight loss, potentiodynamic polarization and impedance measurements on the corrosion inhibition of copper in aerated non-stirred 3% NaCl solutions in the temperature range 15–65 °C using sodium oleate (SO) as an anionic surfactant inhibitor. These studies have shown that SO is a very good ”green”, mixed-type inhibitor. The inhibition process was attributed to the formation of an adsorbed film on the metal surface that protects the metal against corrosive agents. Scanning electron microscopy (SEM) and energy dispersion X-ray (EDX) observations of the electrode surface confirmed the existence of such an adsorbed film. The inhibition efficiency increases with increasing surfactant concentration and time of immersion, while it decreases with solution temperature. Maximum inhibition efficiency of the surfactant is observed at concentrations around its critical micellar concentration (CMC). The potential of zero charge (pzc) of copper was studied by ac impedance, and the mechanism of adsorption is discussed. The sigmoidal shape of the adsorption isotherm confirms the applicability of Frumkin’s equation to describe the adsorption process. Thermodynamic functions for the adsorption process were determined.     

利用量子化学特征的模糊人工神经网络预测咪唑啉衍生物缓蚀效率

针对咪唑啉衍生物的量子化学特征参数与缓蚀效率存在复杂非线性关系，在利用多因素方差分析判断其相关性的基础上建立以最高占据轨道能量、最低未占据轨道能量、分子偶极矩、单点能、硬度、软度、亲核进攻指数、亲电进攻指数、电子转移参数以及咪唑环上非氢原子静电荷之和等量子化学特征参数为输入，以缓蚀效率为输出的模糊人工神经网络。结果表明，咪唑啉衍生物的量子化学特征参数及其缓蚀效率之间具有非常显著的相关性，据此所创建的Takagi-Sugeno型模糊人工神经网络预测模型采用10-30-1网络结构，通过Momentum优化算法对其进行反复训练直至其均方误差小于容许收敛误差限0.005，训练、测试阶段模型输出值与期望值近似呈线性关系，决定系数为0.9999，关联度较高，验证阶段该模型亦表现出良好的可靠性。因此利用量子化学特征的模糊人工神经网络预测模型能够准确预测不同咪唑啉系列衍生物的缓蚀效率。     

Studying phosphate corrosion inhibition at the cut edge of coil coated galvanized steel using the SVET and EIS

The work deals with the effect of sodium phosphate on the corrosion at the cut edge of electrogalvanized steel, studied by potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and the scanning vibrating electrode technique (SVET). Mapping of the ionic currents revealed that in non-inhibiting solution, the cathode shifts away from the anode as zinc corrosion products precipitate along concentric whitish lines that result from the location of the peak cathodic current. Sodium phosphate inhibits corrosion at the cut edge by precipitation of gel-like zinc phosphate clusters with barrier properties. Breakdown and repassivation of this layer can occur under certain conditions.     

Corrosion inhibition and adsorption behavior of new Schiff base surfactant on steel in acidic environment: Experimental and theoretical studies

Synthesis, adsorption and corrosion inhibiting effect of new Schiff base surfactant named 4-hydroxy-3-(3-phenyl-allylideneamino)-benzene sulphonic acid2-[2-(2-{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethoxy]-ethyl ether (abbreviated as PAAB) on mild steel in 1.0 M HCl were investigated using weight loss, and potentiodynamic polarization techniques. The results revealed that this compound inhibited the corrosion reaction in HCl environment. The results indicated that this inhibitor was adsorbed on the metal/solution interface. Theoretical study of the adsorption behavior of this compound was carried out in the framework of the semiempirical (SE) and molecular dynamics (MD).     

An electrochemical and mechanical approach to the corrosion resistance of cathodic electrocoatings under combined cyclic and DC polarization conditions

A modified AC/DC/AC test has been introduced. It consists of a combination of EIS test, cathodic polarizations, wet and dry cycles. This test method was applied to cathodically electrocoated mild steel substrates baked at different conditions. This study aims at characterizing protective behavior of under-, normal- and over-baked electrocoatings under cyclic corrosion conditions. It was found that the resistive failure is the dominant failure mechanism of all the coatings in this test. It was also found that a low crosslink density coating withstands the mechanical stresses due to dry–wet cycles better than a higher crosslink density one.     

Investigation of alkylamine self-assembled films on iron electrodes by SEM, FT-IR, EIS and molecular simulations

Alkylamine were used to form self-assembled films for the inhibition of the corrosion of iron in 0.5 M H₂SO₄ solution. The films were characterized by electrochemical impedance spectroscopy (EIS) and surface analysis techniques including SEM and FT-IR. EIS results indicate that the inhibition ability of these alkylamine self-assembled films depends on the immersion time and the alky chain length of the adsorbate. Both longer immersion time of the electrode in the solution and longer alky chain will result in stronger inhibition ability of the films. However, when the immersion time was increased over some critical point, the inhibition ability was almost invariable. Also when the chain length reached a certain degree such as 14 carbon atoms, the inhibition ability decreased on the contrary. The ability of the corrosion inhibition of the tetradecylamine and dodecylthiol mixed films improved remarkably comparing with the tetradecylamine or dodecylthiol single films. In addition, molecular simulation was used to discuss the adsorption mechanism and good agreement with electrochemical results was obtained.     

Experimental and atomistic simulation studies of corrosion inhibition of copper by a new benzotriazole derivative in acid medium

The efficiency of N-(2-thiazolyl)-1H-benzotriazole-1-carbothioamide (TBC) as a non-toxic corrosion inhibitor for copper in 0.5 M HCl has been tested by weight loss and electrochemical techniques. Electrochemical techniques show that TBC is a mixed-type inhibitor and its inhibition mechanism on copper surface is adsorption assisted by H-bond formation. Impedance measurements show a wide peak presumably given by more than one time constant in the presence of TBC. Also, impedance results show that the values of CPEs (constant phase elements) tend to decrease and both polarization resistance and inhibition efficiency tend to increase with increasing of TBC concentration due to an increase in the electric double layer. Monte Carlo simulations incorporating molecular mechanics and molecular dynamics show that the TBC adsorb on the copper surface firmly through the thiazolyl and carbothioamide groups, the adsorption energy as well as hydrogen bond length have been calculated for both TBC and benzotriazole (BTA) for comparison. Quantum chemical calculations reveal that TBC has higher HOMO, lower LUMO, lower energy gap and lower dipole moment (μ) than BTA, which proves that TBC is better copper corrosion inhibitor compared with BTA in 0.5 M HCl.     

肉桂醛及其复配体系在盐酸中对铁缓蚀作用的研究

主要通过失重法即测量金属试样浸入腐蚀介质一定时间后的质量变化来测定腐蚀速率,从而研究肉桂醛及其复配体系在盐酸介质中对铁的缓蚀性能,并讨论了用量、温度、时间、肉桂醛浓度对铁缓蚀性的影响,结果表明,肉桂醛、邻苯二胺与1,10-菲罗啉三者以1.2:1:1的质量比复配时,对铁丝的缓蚀效果最佳,缓蚀率为94.5%.     

Corrosion inhibition of carbon steel in hydrochloric acid by cationic arylthiophenes as new eco-friendly inhibitors: Experimental and quantum chemical study

This study describes the adsorption behavior of three arylthiophene derivatives namely: 2-(4-amidino-3-fluorophenyl)-5-[4-methoxy phenyl] thiophene dihydrochloride salt (MA-1217), 2-(4-amidinophenyl)-5-[4-chlorophenyl] thiophene dihydrochloride salt (MA-1316) and 2-(4-amidino-3-fluorophenyl)-5-[4-chlorophenyl]thiophene dihydrochloride salt (MA-1312) at C-steel in 1.0 mol·L^-1 HCl interface using experimental and theoretical studies. Electrochemical and mass loss measurements showed that the inhibition efficiency (IE) of the arylthiophene derivatives increases with increasing concentrations and exhibited maximum efficiency 89% at 21×10^-6 mol·L^-1 (MA-1217) by mass loss method. The investigated arylthiophene derivatives obey the Langmuir adsorption isotherm. From polarization studies the arylthiophene derivatives act as mixed-type inhibitors. Surface analysis were carried out and discussed. The mode of orientation and adsorption of inhibitor molecules on C-steel surface was studied using molecular dynamics (MD) simulations. Quantum chemical parameters as well as the radial distribution function indices and binding energies confirm the experimental results.