Corrosion of copper in aerated synthetic sea water solutions and its inhibition by 3-amino-1,2,4-triazole

Corrosion of copper in aerated synthetic sea water (3.5% NaCl) solutions and its inhibition by 3-amino-1,2,4-triazole (ATA) have been studied using electrochemical, gravimetric, and pH measurements, along with Raman spectroscopy. Electrochemical measurements indicated that the presence of ATA and the increase of its concentration suppress the corrosion process on the copper surface. This effect decreases cathodic, anodic, and corrosion (jcorr) currents and corrosion rates (Kcorr), while increasing polarization resistance (Rp), surface coverage (theta), and inhibition efficiency (IE%). Weight loss measurements indicated that the dissolution of copper and the accompanying change of pH decreased to a minimum even after 24 days immersion due to the presence of ATA and the increase of its concentration. Raman investigations revealed that the inhibition of copper corrosion is achieved by strong adsorption of ATA molecules onto the copper surface, preventing it from being corroded easily.     

Corrosion of copper in aerated acidic pickling solutions and its inhibition by 3-amino-1,2,4-triazole-5-thiol

Corrosion of copper in aerated acidic chloride pickling (0.5 M HCl) solutions and its inhibition by 3-amino-1,2,4-triazole-5-thiol (ATT) have been investigated using electrochemical techniques and weight-loss measurements, along with Raman spectroscopy. Electrochemical measurements for copper after varied immersion periods of 0, 24, and 48 h showed that the presence of ATT and the increase of its concentration significantly decrease cathodic, anodic, corrosion (j(Corr)) currents and corrosion rates (K(Corr)), as well as the dissolution currents at 300 mV vs Ag/AgCl, while increasing polarization resistance (Rp), degree of surface coverage (theta) and inhibition efficiency (IE%) to a great extent. Weight-loss measurements after different immersion periods of 6 to 48 h revealed that the dissolution of copper decreased to a minimum and the corresponding IE% increased with increasing ATT concentration. The detection of ATT molecules on the copper surface by Raman spectroscopy indicated that inhibition of copper corrosion is achieved by strong adsorption of ATT molecules onto the copper surface.     

3-氨基-1,2,4-三氮唑对铜的缓蚀性能和吸附行为

采用电化学和表面增强拉曼光谱(SERS)方法研究了新型环境友好型金属水处理剂3-氨基-1,2,4-三氮唑(ATA)对铜在3% NaCl溶液中的缓蚀性能和吸附行为. 结果表明, ATA对铜有较好的缓蚀作用, 其中ATA浓度为0.24 mmol·L-1时对铜的缓蚀效率最高, 为97.65%, 其吸附行为符合Langmuir吸附等温式, 吸附机理是典型的化学吸附援SERS表明, ATA分子通过很强的吸附于铜表面达到抑制其腐蚀的作用, 是ATA-与Cu+形成配合物来阻止氯离子化合物(CuCl-2)的生成.     

Inhibition of copper corrosion in 3.5% NaCl solutions by a new pyrimidine derivative: electrochemical and computer simulation techniques

A new pyrimidine heterocyclic derivative, namely 2-ethylthio-4-(p-methoxyphenyl)-6-oxo-1,6-dihydropyrimidine-5-carbonitrile (EPD) was prepared and its inhibition performance towards copper corrosion in 3.5% NaCl solutions was studied by potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and electrochemical frequency modulation (EFM) measurements. Experimental investigations showed that EPD reduces markedly the copper corrosion in 3.5% NaCl solutions. EFM can be used as a rapid and non destructive technique for corrosion rate measurements without prior knowledge of Tafel constants. Monte Carlo simulation technique incorporating molecular mechanics and molecular dynamics can be used to simulate the adsorption of pyrimidine derivative (EPD) on the Cu (111) surface in 3.5% NaCl.     

饱和NaCl溶液浸泡下混凝土试块中有机阻锈剂对钢筋腐蚀行为的影响

利用电化学阻抗谱(EIS)、半电池腐蚀电位(Ecorr)和宏观电池腐蚀电流密度(Icorr)测量技术,在饱和NaCl溶液浸泡的硬化混凝土试块中,研究了4种醇胺基阻锈剂对钢筋电极腐蚀电化学行为的影响和长期阻锈性能.在浸泡初始的100d内,与空白样相比,添加阻锈剂后钢筋电极腐蚀电位升高,阻抗膜值增大,腐蚀电流密度值降低,表明电极表面处于钝态,阻锈剂表现出良好的阻锈性能.随浸泡时间延长,电极腐蚀电位和阻抗膜值下降,腐蚀电流密度增大.浸泡后期,除添加醇胺基CI-4样外,电极电位和腐蚀电流密度与空白样相比无明显差别,表明电极由钝态转变为活性腐蚀状态.但添加CI-4样品,钢筋电极始终保持在钝化状态,阻锈性能最好.基于阻锈剂与Cl-间的竞争吸附,分析探讨了可能的阻锈机理.     

Effects of exposure time on the anodic dissolution of Monel-400 in aerated stagnant sodium chloride solutions

The anodic dissolution of Monel-400 (63.0% Ni, 28–34% Cu) alloy after its immersion in freely aerated stagnant 3.5% NaCl solutions for 0, 24, and 72 h has been investigated. The study was carried out using a variety of electrochemical techniques and gravimetric measurements after varied exposure periods (5–160 days). The work was complemented by scanning electron microscopy and energy dispersive X-ray analyzer (SEM/EDX) investigations. The electrochemical measurements showed that Monel suffers both general and pitting corrosion. The severity of uniform corrosion decreased, while pitting one increased with increasing the immersion time to 24 h and further to 72 h before measurements. Gravimetric data indicated that the weight loss increased, while the corrosion rate decreased for Monel with time. SEM images and EDX profile analyses confirmed that the corrosion of Monel after 160 days immersion in NaCl solutions occurs due to the selective dissolution of nickel.     

Inhibition of copper corrosion by self-assembled monolayers of triazole derivative in chloride-containing solution

The self-assembled monolayers (SAMs) derived from 3-undecane-4-amino-5-mercapto-1,2,4-triazole (UAMT) on copper surface have been characterized by contact angle test, X-ray photoelectron spectroscopy, and electrochemical techniques. It is found that the UAMT molecules can spontaneously adsorb to copper surface to form compact and oriented monolayers, which can prevent the corrosion of copper in chloride-containing solution effectively. The electrochemical measurements prove that the adsorption of UAMT molecules on copper surface typically processes with a two-step adsorption consisting of a fast initial adsorption and a slowly following reorganization in 10^?4-M UAMT solution, and the adsorption of UAMT obeys the Langmuir model in the initial adsorption process. Furthermore, the effects of the immersion time, ultrasonic irradiation, and UAMT concentration on the anticorrosion property of SAMs are studied, and the adsorption isotherm of UAMT on copper is followed.     

Enhanced copper surface protection in aqueous solutions containing short-chain alkanoic acid potassium salts

The ability of dissolved potassium monocarboxylate salts to produce surface passivation and to inhibit aqueous corrosion of copper was studied. The electrochemical measurements indicate that the inhibiting efficiency of these compounds, with a general formula Cn-1H2n-1COOK or CnK (n=3...12), is dependent on the hydrocarbon chain length. The inhibiting efficiency was higher for a longer hydrocarbon chain of n-alkanoic acid. The degree of copper protection was found to increase with an increase in n-alkanoic acid potassium salt concentration; the optimum concentration of potassium dodecanoate (C12K) in sulfate solutions was found to be 0.07 M. The protective layers formed at the copper surface subsequent to exposure in various n-alkanoic acid potassium salt solutions were characterized by contact angle measurements, electrochemical impedance spectroscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared reflection spectroscopy. Pronounced copper protection was attributed to the growth of a protective film on the copper surface, containing both copper oxides and copper carboxylate compounds. It is suggested that the organic molecules enhance copper protection by covering copper oxides with a thin and dense organic layer, which prevents water molecules or aggressive anions from interacting with the copper surface.     

Electrochemical properties and corrosion inhibition of AA6061 in tropical seawater

The corrosion inhibition of aluminum and its alloys is the subject of tremendous technological importance due to the increased industrial applications of these materials. This study reports the results of potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) on the corrosion inhibition of AA6061 aluminum alloys in seawater using sodium benzoate as an inhibitor. The electrochemical measurements for aluminum alloys in seawater after varied immersion period showed that the presence of sodium benzoate significantly decreases the corrosion currents densities (i_corr), corrosion rates and double layer capacitance (C_dl), as simultaneously increase the values of polarization resistance (R_p). Charge transfer process and development of thin film on the specimen have been proven by morphology study using SEM.     

Corrosion inhibition of carbon steel immersed in a 1 M HCl solution using benzothiazole derivatives

Corrosion inhibition effect of 2-mercaptobenzothiazole (MBT) and 2-aminobenzothiazole (ABT) compounds on ST-37 carbon steel in 1 M hydrochloric acid solution was investigated by electrochemical impedance spectroscopy (EIS), and it was observed that both of these compounds have corrosion inhibition effect on carbon steel. Evaluation of electrochemical behavior in test solutions showed that by increasing the immersion time from 15 to 300 min, corrosion resistance of samples is increased and at the same immersion time MBT has a better corrosion inhibition in comparison to ABT. AFM technique was performed for MBT and ABT. The results of calculations showed superior inhibition efficiency of MBT in comparison to ABT. This can cause easier protonation and consequently adsorption on the metal surface occurs.     

硫酸溶液中1,1’-硫代羰基二咪唑在碳钢上的吸附及缓蚀影响和碘离子的增强效应

The inhibition effect of 1,1’-thiocarbonyldiimidazole (TCDI) on the corrosion behaviors of mild steel (MS) in 0.5 mol·L -1 H2SO4 solution was studied with the help of potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and linear polarization resistance (LPR) techniques. The effect of immersion time on the inhibition effect of TCDI was also investigated over 72 h. For the long-term tests, hydrogen evolution with immersion time (VH2-t) was measured in addition to the three techniques already mentioned. The thermodynamic parameters, such as adsorption equilibrium constant (Kads) and adsorption free energy (⊿Gads) values, were calculated and discussed. To clarify inhibition mechanism, the synergistic effect of iodide ion was also investigated. The potential of zero charge (PZC) of the MS was studied by electrochemical impedance spectroscopy method, and a mechanism of adsorption process was proposed. It was demonstrated that inhibition efficiency increased with the increase in TCDI concentration and synergistically increased in the presence of KI. The inhibition efficiency was discussed in terms of adsorption of inhibitor molecules on the metal surface and protective filmformation.     

Corrosion inhibition of copper in chloride media by 2-mercapto-4-(p-methoxyphenyl)-6-oxo-1,6-dihydropyrimidine-5-carbonitrile: Electrochemical and theoretical study

Electrochemical frequency modulation (EFM), electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization have been used to investigate the inhibition effect of a new pyrimidine heterocyclic derivative, namely 2-mercapto-4-(p-methoxyphenyl)-6-oxo-1,6-dihydropyrimidine-5-carbonitrile (MPD) on copper corrosion in 3.5% NaCl solutions at 25 ± 1 °C. The electrochemical investigations showed that MPD gives sufficient inhibition against copper corrosion in 3.5% NaCl solutions. Potentiodynamic polarization measurements have shown that the MPD inhibit both the cathodic and anodic processes and thus it classified as mixed-type inhibitor. EIS measurements indicate that the values of constant phase elements (CPEs) tend to decrease and both charge-transfer resistance and inhibition efficiency tend to increase by increasing the inhibitor concentration. Electrochemical kinetic parameters obtained using EFM methods were comparable with that calculated from traditional measurements (EIS and potentiodynamic polarization). Molecular simulation technique was used to investigate the adsorption configuration of MPD on copper surface. Number of electrons transferred from MPD to the copper surface was calculated by semi-empirical quantum chemical calculations.     

What determines the inhibition effectiveness of ATA, BTAH, and BTAOH corrosion inhibitors on copper?

Three corrosion inhibitors for copper-3-amino-1,2,4-triazole (ATA), benzotriazole (BTAH), and 1-hydroxybenzotriazole (BTAOH)-were investigated by corrosion experiments and atomistic computer simulations. The trend of corrosion inhibition effectiveness of the three inhibitors on copper in near-neutral chloride solution is determined experimentally as BTAH ? ATA ? BTAOH. A careful analysis of the results of computer simulations based on density functional theory allowed to pinpoint the superior inhibiting action of BTAH and ATA as a result of their ability to form strong N-Cu chemical bonds in deprotonated form. While these bonds are not as strong as the Cl-Cu bonds, the presence of solvent favors the adsorption of inhibitor molecules onto the surface due to stronger solvation of the Cl(-) anions. Moreover, benzotriazole displays the largest affinity among the three inhibitors to form intermolecular aggregates, such as [BTA-Cu](n) polymeric complex. This is another factor contributing to the stability of the protective inhibitor film on the surface, thus making benzotriazole an outstanding corrosion inhibitor for copper. These findings cannot be anticipated on the basis of inhibitors' molecular electronic properties alone, thus emphasizing the importance of a rigorous modeling of the interactions between the components of the corrosion system in corrosion inhibition studies.     

Corrosion inhibition of mild steel by highly stable polydentate schiff base derived from 1,3- propanediamine in aqueous acidic solution

Recently, the hydrolysis of Schiff bases under experimental conditions gives suspicion for their corrosion inhibition performance. The current study employs a stable Schiff base namely, 2,2′-{propane-1,3-diylbis[azanylylidene (E) methanylylidene]}bis(6-methoxyphenol) (LPD) as corrosion inhibitor for mild steel (MS) in 1 M HCl solution. The presence of the characteristic peak of the imine group in UV-visible spectra was taken as an indicator for LPD stability in acidic media. The inhibition action was examined using electrochemical techniques including potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) besides gravimetric measurement. The inhibition efficiency reached 95.93 % for 0.75 mM LPD after 24 h of immersion at 25 °C. This high efficiency is owing to the presence of the characteristic imine group and other heteroatoms and π- electrons of the aromatic benzene rings. The mechanism of inhibition depends on adsorption phenomena on mild steel surface which obeys Langmuir isotherm model. The calculated values of adsorption equilibrium constant (K_ads), adsorption free energy ΔG_ads, adsorption enthalpy ΔH_ads and adsorption entropy ΔS_ads indicated spontaneous exothermic adsorption process of both physical and chemical nature. By rising temperature, the inhibition efficiency of LPD was decreased. The calculated activation energy was increased as the concentration of LPD increased. LPD was considered as a mixed-type inhibitor as indicated from PDP measurements. The obtained surface morphology and composition analysis using SEM/EDS, AFM and FTIR techniques ensures the high efficiency of LPD as corrosion inhibitor.     

Corrosion protection of carbon steel in acidic media by expired bupropion drug; experimental and theoretical study

The effects of expired bupropion on the corrosion protection of carbon steel in hydrochloric acid (1.0 M) and sulfuric acid (0.5 M) solutions were examined by Fourier transform infrared (FTIR) spectroscopy, Tafel polarization and electrochemical impedance spectroscopy (EIS). Bupropion concentrations in both acid solutions were raised, which improved corrosion prevention. Bupropion was a mixed inhibitor because it retarded the anodic and cathodic processes, as indicated by polarization data. The inhibition efficiency decreased with the increasing temperature from 25 to 55 °C. In the presence of bupropion, the activation energies of corrosion in both acid solutions increased. The thermodynamic quantities were deduced from the influence of temperature on the corrosion process of carbon steel in both acid media. Bupropion adsorption on carbon steel followed the Langmuir adsorption isotherm. The polarization data yielded outcomes consistent with the results arising from impedance measurements. FTIR spectroscopy showed the active sites of bupropion molecule during adsorption on the alloy surface. The theoretical study and molecular dynamics simulation of bupropion was done by a density functional theory (DFT) approach to realize the effects of molecular structure on the inhibitive action of bupropion.     

Corrosion prevention of mild steel in acidic medium by 2-Pyrrolidin-1-yl-1,3-thiazole-5-carboxylic acid: Theoretical and experimental approach

The inhibition efficiency of 2-Pyrrolidin-1-yl-1,3-thiazole-5-carboxylic acid (PTCA) against mild steel (MS) corrosion was investigated in acidic solution by using quantum chemical calculations based on Density Functional Theory (DFT) method and electrochemical measurements. The electrochemical impedance spectroscopy (EIS), potentiodynamic, potential zero charge (pzc) analysis and electrochemical noise (EN) measurements at various concentrations (from 0.1 to 10 mM) and immersion times were utilized in experimental part. The surface analysis was achieved scanning electron microscope (SEM) and contact angle measurements in the absence and presence of 10 mM PTCA. According to DFT results, PTCA exhibited 3.737 eV band gap and 8.130 Debye dipole moment which were a signal of potentially convenient corrosion inhibitor properties. PTCA has a remarkable corrosion inhibition capability to mild steel, which inhibited both anodic and cathodic corrosion rates, relying on it's physically adsorption on the metal solution interface and protection ability was increased with increasing PTCA concentration. The obtained adsorption equilibrium constant was 11.11 × 10³ M^-1 and calculated standard free energy of adsorption was ?33.03 kJ mol^?1. The determined activation energy values were 55.58 kJ mol^?1 and 96.86 kJ mol^?1 in 0.5 M HCl in the absence and presence of 10 mM PTCA, respectively. PTCA demonstrated a strong inhibition efficiency of 98.3%, after 168 h immersion, according to the EIS results. As a consequently, we recommend that PTCA is a convenient inhibitor in 0.1 M HCl for mild steel protection against corrosion.     

A study of copper corrosion inhibition by self-assembled films of 3-mercapto-1<Emphasis Type="Italic">H</Emphasis>-1,2,4-triazole

Self-assembled monolayers of 3-mercapto-1H-1,2,4-triazole (MTA) was formed over a copper surface at various immersion periods. Fourier transform infrared spectroscopy and cyclic voltammetry were used to characterize the films. Atomic force microscopy and scanning electron microscopy were employed for the characterization of surface morphology. The wettability of the film was examined using contact angle measurements. The corrosion protection ability of the films was assessed in a chloride solution using electrochemical impedance spectroscopy and polarization measurements. The results of the study clearly ascertained the protection ability of self-assembled films of the MTA over copper. The theoretical studies also vouched for the experimental results.     

Employing electrochemical frequency modulation for studying corrosion and corrosion inhibition of copper in sodium chloride solutions

The inhibition effect of 2-carboxymethylthio-4-(p-methoxyphenyl)-6-oxo-1,6-dihy-dropyrimidine-5-carbonitrile (CPD) towards the corrosion of copper was studied in aerated stagnant 3.5% NaCl at 25 °C using ac techniques include electrochemical frequency modulation and electrochemical impedance spectroscopy as well as potentiodynamic polarization measurements. Corrosion rates determined using electrochemical frequency modulation (EFM) which measures the non-linear behaviour of a corroding system are compared with corrosion rates obtained from traditional electrochemical techniques and show good agreement. Data obtained from EIS were analyzed to model the corrosion inhibition process through equivalent circuit. Polarization measurements showed that CPD acts as mixed-type inhibitor. The inhibition efficiency increases with an increase in the concentration of CPD. The adsorption of the inhibitor on the copper surface in the sodium chloride solution was found to obey Langmuir’s adsorption isotherm. A mixed inhibition mechanism is proposed for the inhibitive effects of CPD as revealed by potentiodynamic polarization technique.     

AMT在青铜电极表面上吸附的SERS研究

对AMT在青铜上的吸附行为进行激光拉曼电化学研究，通过改变青铜电极的电极电位对在有无Cl－存在条件下各主要拉曼振动峰进行观察.结果表明, AMT垂直吸附在青铜表面，有Cl－存在下， Cl－与AMT分子共吸附在青铜表面上.外加阳极极化电流、加入Cl－将增加AMT在青铜表面上的吸附.     

铁表面自组装缓蚀功能膜的电化学阻抗谱研究

在铁表面自组装十四烷基胺膜.研究该膜在0.5 mol/LH2SO4溶液中对铁的缓蚀性能.电化学阻抗谱测试表明,随着组装时间的延长,缓蚀性能也随之增强,最大缓蚀效率为68.7%.而以十二烷基硫醇和十四烷基胺修饰的混合膜则更为致密、稳定,对铁的缓蚀能力也明显优于仅以十二烷基硫醇或十四烷基胺修饰的单一膜,其缓蚀效率可提高至78.2%.