2-Mercaptobenzimidazole as a copper corrosion inhibitor: Part I. Long-term immersion, 3D-profilometry,and electrochemistry

The high corrosion inhibition effectiveness of 2-mercaptobenzimidazole (MBIH) in 3 wt.% aqueous NaCl solution is reported using long term immersion tests, 3D-profilometry, electrochemical impedance spectroscopy, and potentiodynamic curve measurements. The high corrosion inhibition performance was proven after 180 days of immersion. The impedance spectra were characterized by two time constants relating to charge transfer and finite layer thickness or semi-infinite diffusion of copper ions through the surface layer, therefore Cu corrosion in solution containing MBIH follows kinetic-controlled and diffusion-controlled processes. Moreover, it is shown that MBIH is a mixed-type inhibitor.     

2-Mercaptobenzimidazole as a copper corrosion inhibitor: Part II. Surface analysis using X-ray photoelectron spectroscopy

In Part I of this study, the high corrosion inhibition effectiveness of 2-mercaptobenzimidazole (MBIH) in 3 wt.% NaCl solution was unambiguously proven. In Part II, using angle-resolved X-ray photoelectron spectroscopy (XPS), the surface chemical structure and composition of adsorbed MBIH on Cu from the same solution was investigated. It was found that MBIH molecules are directed toward the Cu surface through their N and S atoms. The MBIH layer thickness is 1.9 ± 0.5 nm, as determined from a detailed analysis of the background in the XPS spectra. Tentative MBIH orientations on Cu were suggested based on the XPS measurements.     

Adsorption and corrosion inhibition of phytic acid calcium on the copper surface in 3 wt% NaCl solution

The adsorption and corrosion protection effect of phytic acid calcium (PAC) film on the copper surface in 3 wt% NaCl solution was investigated using potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and Raman spectroscopy. Polarization curves indicate that PAC is a mixed inhibitor, affecting both cathodic and anodic corrosion currents. The inhibition efficiency of PAC film reached 92.53% at an optimized condition. Adsorption of PAC molecules on the surface followed Langmuir adsorption isotherm and the standard Gibbs energy of −37.32 kJ mol⁻¹ indicated a chemisorptive way. Raman studies suggested that PAC molecule chemically anchored at the surface via PO groups.     

A new corrosion inhibitor for copper protection

Methyl 3-((2-mercaptophenyl)imino)butanoate (MMPB) was synthesized as inhibitor compound for copper protection. The molecule was designed with azole, thiol functional groups and carboxylate tail group. The inhibition efficiency was examined in acidic chloride media, by means of various electrochemical and spectroscopy techniques. Electrochemical study results showed that high efficiency of MMPB was mainly related with its capability of complex formation with Cu(I) at the surface. The thiol group also improves the adsorptive interaction with the surface, as the carboxylate groups provide extra intermolecular attraction.     

Sodium molybdate as a corrosion inhibitor for aluminium in H3PO4 solution

The inhibition effect of sodium molybdate (Na₂MoO₄) on the corrosion of aluminium in 1.0 M H₃PO₄ solution was studied by weight loss, potentiodynamic polarisation curves and electrochemical impedance spectroscopy (EIS) methods. The results show that Na₂MoO₄ is a good inhibitor, and the inhibition efficiency obtained by three methods is higher than 84% at 20 mM. The adsorption of Na₂MoO₄ obeys Freundlich isotherm at lower concentrations (1–7 mM), while Langmuir isotherm at higher concentrations (7–20 mM). Polarisation curves indicate that Na₂MoO₄ acts as an anodic inhibitor. EIS spectra exhibit three loops (two capacitive loops and one inductive loop).     

Potent inhibition of copper corrosion in neutral chloride media by novel non-toxic thiadiazole derivatives

Inhibiting effect of two novel non-toxic thiadiazole derivatives on copper were investigated in 3.5% NaCl solution using weight loss and electrochemical measurements. Presence of inhibitors and increase of concentration greatly decrease corrosion rate, parameters determined from polarization curves and EIS plots show that inhibitors decrease both cathodic and anodic current densities, suppressing charge transfer process by adsorption on copper surface. Thermodynamic calculation indicates chemisorption obeys Langmuir isotherm. Surface layers were characterized by SEM coupled with EDX. Raman micro-spectroscopy reveals that inhibitor molecules suppress copper corrosion via formation of thiadiazole–Cu complex. Relationships between inhibition efficiency and molecular orbital were also evaluated.     

Novel application of a hormone biosynthetic inhibitor for the corrosion resistance enhancement of copper in synthetic seawater

Effects of a hormone biosynthetic inhibitor on corrosion resistance of copper in synthetic seawater under various conditions were evaluated via quantum chemistry calculations, weight loss, electrochemical techniques, SEM, EDS, and FTIR. Comparable results show that uniconazole acts as a mixed-type inhibitor, suppressing charge transfer process by adsorption on copper surface. Thermodynamic calculation indicates that chemisorption is in accordance with Langmuir isotherm and adsorption amount increases with immersion time. The corrosion resistance with inhibitor under alkaline conditions is better than that under acidic or neutral conditions. Good inhibition performances at different temperatures and during a long time immersion are observed.     

Characterization of the copper/electrolyte interface on two copper conductors under high voltage

The effect of a high applied voltage up to 30 V between two copper conductors is investigated in a 0.05 mol L⁻¹ sodium chloride solution. It appears that the potential is mainly applied to the anode/electrolyte interface and that, after a fast decay, the overall current density reaches a constant value, which is independent of the applied potential. This “passive” behaviour is attributed to the formation of a copper(I) chloride layer at the surface of the anode that limits the dissolution rate of copper in the electrolyte. It is shown that electromigration of chloride ions trough the CuCl layer controls the overall anodic reaction.     

Nitrotetrazolium blue chloride as a novel corrosion inhibitor of steel in sulfuric acid solution

The inhibition effect of nitrotetrazolium blue chloride (NTBC) on the corrosion of cold rolled steel (CRS) in 0.5 M H₂SO₄ was investigated by weight loss, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) methods. The results show that NTBC is a good inhibitor, and the adsorption of NTBC on CRS surface obeys Langmuir adsorption isotherm. Polarization curves show that NTBC acts as a mixed-type inhibitor. EIS spectra consist of large capacitive loop at high frequencies followed by a small inductive one at low frequency values, and charge transfer resistance increases with the inhibitor concentration.     

Electrochemical corrosion of unalloyed copper in chloride media--a critical review

The literature dealing with the electrochemical corrosion characteristics of unalloyed copper in aqueous chloride media is examined. The enormous quantity of polarisation and mixed/corrosion potential data that has been made available in the literature over the last 50 years has been compiled and discussed in a comprehensive review. For a wide range of electrode geometries, the importance of the chloride ion and the mass transport of anodic corrosion products on the corrosion behaviour of copper are made clear for both freshly polished and ‘filmed’ surfaces.     

A study on new benzotriazole derivatives as inhibitors on copper corrosion in ground water

The corrosion inhibition properties of newly synthesized 1-(2-pyrrole carbonyl)-benzotriazole (PCBT) and 1-(2-thienyl carbonyl)-benzotriazole (TCBT) in combination with the non-ionic surfactant Triton X-100 (TX-100) on metallic copper were studied in ground water environment and the results were compared with benzotriazole (BTA). Various electrochemical studies such as open circuit potential (OCP), potentiodynamic polarization, ac impedance and cyclic voltammetric (CV) were made. Surface analytical techniques like FT-IR and XRD were also performed. The results indicated that PCBT is a better corrosion inhibitor for copper and the formulation consisting of PCBT and TX-100 offered improved inhibition efficiency (IE) in a synergistic manner.     

Electrochemical and thermodynamic investigation of diniconazole and triadimefon as corrosion inhibitors for copper in synthetic seawater

This paper presents the investigation of diniconzole and triadimefon as chemical corrosion inhibitors for freshly polished copper in synthetic seawater (3.5% NaCl solution). Determination of weight loss, polarization curves, electrochemical impedance spectroscopy (EIS), and SEM, were performed to analyze the inhibiting performance of these compounds. Polarization curves show that they act as mixed-type inhibitors. EIS indicates that an adsorption film of the inhibitors is formed on copper surface. The highest values of inhibition efficiency are respectively, 99.2% and 97.3% at 100 mg/L concentration. Thermodynamic calculation suggests that chemisorptions between the compounds and copper are accordance with Langmuir adsorption isotherm.     

Phosphate ions used as green inhibitor against copper corrosion in tap water

Three dosages of ions are evaluated as corrosion inhibitors of copper in artificial tap water by measuring the corrosion potential, polarization resistance, electrochemical impedance and reflectance spectra. The water is moderately hard, highly carbonated and chloride-rich. The results show that the surface film is composed by Cu₂O. When the inhibiting agent is added, the film becomes thicker, denser and more compact. This behaviour is attributed to CuO incorporating into the passive layer. The optimal dosage of inhibitor is 10 mg l⁻¹ P when the polarization resistance increases three times. The inhibitor retards the pit initiation, without hindering pit growth.     

Super-hydrophobic metal-complex film fabricated electrochemically on copper as a barrier to corrosive medium

Metal-complex film with super-hydrophobic property is fabricated on copper (Cu) surface with one-step electrochemical method in laurylamine/ethanol solution. “Dissolution–coordination–precipitation” model is proposed to illuminate formation mechanism of Cu(II)-laurylamine complex film. The super-hydrophobic film can act as a barrier to corrosion of underlying copper with inhibition efficiency close to 100%, and it maintains stability within a wide potential range. The origin of such corrosion protection property is explained from view point that hierarchical micro-structure of the super-hydrophobic film can maintain a stable air/liquid interface which inhibits erosion of corrosive medium.     

Corrosion and corrosion inhibition of Cu-20%Fe alloy in sodium chloride solution

The electrochemical behavior of copper (Cu), iron (Fe) and Cu-20%Fe alloy was investigated in 1.0 M sodium chloride solution of pH 2. The effect of thiourea (TU) addition on the corrosion rate of the Cu-20%Fe electrode was also studied. Open-circuit potential measurements (OCP), polarization and electrochemical impedance spectroscopy (EIS) were used. The results showed that the corrosion rates of the three electrodes follow the sequence: Cu < Cu-20%Fe < Fe. Potentiostatic polarization of the Cu-20%Fe electrode in the range −0.70 V to −0.45 V (SCE), showed that iron dissolves selectively from the Cu-20%Fe electrode surface and the rate of the selective dissolution reaction depends on the applied potential. At anodic potential of −0.45 V, thiourea molecules adsorb at the alloy surface according to the Langmuir adsorption isotherm. Increasing thiourea concentration (up to 5 mM), decreases the selective dissolution reaction and the inhibition efficiency η reach 91%. At [TU] > 5 mM, the dissolution rate of the Cu-20%Fe electrode increases due to formation of soluble thiourea complexes. At cathodic (−0.6 V), the inhibition efficiency of thiourea decreases markedly owing to a decrease of the rate of the selective dissolution reaction and/or desorption of thiourea molecules. The results indicated that thiourea acts mainly as inhibitor of the selective dissolution reaction of the Cu-20%Fe electrode in chloride solution.     

2-Amino-5-(4-pyridinyl)-1,3,4-thiadiazole monolayers on copper surface: Observation of the relationship between its corrosion inhibition and adsorption structure

Corrosion inhibition behavior of 2-amino-5-(4-pyridinyl)-1,3,4-thiadiazole (4-APTD) monolayers on copper surface were investigated by electrochemical impedance spectroscopy (EIS), electrochemical polarization measurement and surface-enhanced Raman scattering (SERS) experiment. The EIS mechanism of the copper surface with 4-APTD monolayers fitted to the mode of R(Q(R(QR))). The electrochemical polarization measurements indicated high inhibition efficiency of about 90.4%. SERS results suggested that 4-APTD molecules anchored at copper surface in a tilted orientation directly via N³ and N¹² atoms. The transition adsorption states of 4-APTD on the copper surface were observed as the potential applied from 0 to −1.6 V vs. SCE.     

Electrochemical quartz crystal microbalance and electrochemical impedance spectroscopy study of copper corrosion inhibition by imidazoles

The aim of this work is to obtain deeper insight into the mechanism of the protective action of three imidazole-based corrosion inhibitors. Investigations were performed on copper in 3% NaCl, by electrochemical impedance spectroscopy and electrochemical quartz crystal microbalance measurements. The kinetic changes in the corrosion processes were monitored over time. In spite of similar molecular structure, differences in the inhibiting mechanism of three imidazole compounds were observed. The two inhibitors with a tolyl substituent decreased the copper corrosion rate due to the formation of a thin adsorbate layer; however, slow formation of a thick layer was observed for 4-methyl-1-phenyl imidazole. From electrochemical impedance spectroscopy studies, it was observed that all three inhibitors protected the copper efficiently, and in some cases, the degree of the protection increased with time.     

Inhibition of copper corrosion in sodium chloride solution by the self-assembled monolayer of sodium diethyldithiocarbamate

Sodium diethyldithiocarbamate (DDTC) self-assembled monolayer (SAM) on copper surface has been investigated by SERS and EDS and the results show that DDTC SAM is chemisorbed on copper surface by its S atoms with tilted orientation. Corrosion inhibition ability of DDTC SAM was measured in 3% NaCl solution using electrochemical methods. The impedance results indicate that the maximum inhibition efficiency of DDTC SAM can reach 99%. Quantum chemical calculations show that DDTC has relatively small ΔE between HOMO and LUMO and large negative charge in its two sulfur atoms, which facilitates the formation of a DDTC SAM on copper surface.     

Self-assembled monolayer of 2-(octadecylthio)benzothiazole for corrosion protection of copper

Self-assembled monolayer (SAM) of 2-(octadecylthio)benzothiazole (2-OTBT) was formed on a fresh copper surface obtained by nitric acid etching. Optimum conditions for formation of SAM have been established. XPS, AFM and FTIR studies have been used to characterize the SAM. Corrosion protection ability of the SAM has been evaluated in aqueous NaCl solution using electrochemical impedance, EQCN, potentiodynamic polarization and weight-loss studies. 2-OTBT SAM is found to have excellent corrosion protection efficiency in the aq. NaCl solution. The mechanism of corrosion inhibition of copper by 2-OTBT SAM is discussed.     

Superhydrophobic fluoropolymer-modified copper surface via surface graft polymerisation for corrosion protection

With the objective of developing materials with repellent surfaces by combining both low surface energy and rough structure, superhydrophobic fluoropolymer films were prepared via surface graft polymerisation from copper substrates. A vinyl-terminated trimethoxysilane was firstly immobilised on the etched-copper surface to introduce active carbon–carbon double bonds. Subsequent graft polymerisation of 2,2,3,4,4,4-hexafluorobutyl acrylate (HFBA), in the presence of a polymerisation initiator 4,4′-azobis-(4-cyanpentanoic acid), yielded the fluoropolymer films on the copper substrates. The resultant P(HFBA)-grafted surfaces not only exhibited desired superhydrophobic property with water contact angle above 150°, but substantially improved the corrosion resistance of copper substrates.