Copper(II) 8-hydroxyquinolinate 3D network film with corrosion inhibitor embedded for self-healing corrosion protection

This work presents a self-healing protective coating for copper. The complex coating is composed of copper(II) 8-hydroxyquinolinate (Cu(8HQ)₂) 3D network film storing corrosion inhibitor as base layer and epoxy as top layer covering on the base layer. The results of EIS and polarization curves reveal the self-healing effect of Cu(8HQ)₂ 3D network film with corrosion inhibitor embedded. After being scratched with a knife-edge, the complex coating rapidly releases inhibitor embedded in 3D network structure to suppress the corrosion process. The scratch on the coating is covered with inhibitor adsorption film and the anodic activity is restrained.     

Corrosion inhibition of copper in chloride media by 1,5-bis(4-dithiocarboxylate-1-dodecyl-5-hydroxy-3-methylpyrazolyl)pentane

The efficiency of 1,5-bis(4-dithiocarboxylate-1-dodecyl-5-hydroxy-3-methyl-pyrazolyl)pentane (BDTCPP) as copper corrosion inhibitor in 3.5% NaCl solutions was studied by electrochemical polarization methods (Tafel extrapolation and polarization resistance method), electrochemical impedance spectroscopy and immersion assays. Results obtained in this study reveal that BDTCPP is a good inhibitor and the potentiodynamic polarization studies clearly show that BDTCPP is a mixed-type inhibitor for copper in chloride solutions. It decreases the anodic reaction rate more strongly than the cathodic reaction rate and it renders the open circuit potential of copper more positive in 3.5% NaCl solutions. The UV analysis of the protective layer of BDTCPP after corrosion experiments shows that the inhibitor prevents copper corrosion by physisorption on the metal surface, followed by chemisorption of a protective Cu(II)-complex. This Cu(II) is generated by oxidation of the Cu(I) ion formed at the beginning of the corrosion process in the aerated solution of NaCl.     

Impedance and XPS study of benzotriazole films formed on copper, copper-zinc alloys and zinc in chloride solution

The formation of protective layers on copper, zinc and copper-zinc (Cu-10Zn and Cu-40Zn) alloys at open circuit potential in aerated, near neutral 0.5 M NaCl solution containing benzotriazole was studied using electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS). Benzotriazole (BTAH), generally known as an inhibitor of copper corrosion, also proved to be an efficient inhibitor for copper-zinc alloys and zinc metal. The surface layers formed on alloys in BTAH-inhibited solution comprised both polymer and oxide components, namely Cu(I)BTA and Zn(II)BTA polymers and Cu₂O and ZnO oxides, as proved by the in-depth profiling of the layers formed. A tentative structural model describing the improved corrosion resistance of Cu, Cu-xZn alloys and Zn in BTAH containing chloride solution is proposed.     

Some chemical aspects of the corrosion inhibition of copper by benztriazole

Measurements of the adsorption isotherm of benztriazole (BTA) on copper reveal that the inhibitor molecule is weakly held on the oxide covered surface until a critical solution concentration of BTA is reached above which good corrosion inhibition results. Consideration of the chemical equilibria between the oxides of copper and the dissociation of the BTA molecule in solution, show that this concentration corresponds closely to that at which the Cu(I)BTA complex is precipitated. The chemical nature of the complexes formed has been found by X-ray photo-electron spectroscopy to correspond closely to Cu(I)BTA for cuprous oxide-covered surfaces but is of a more complicated nature for cupric oxide-covered surfaces, although both seem to be equally effective in preventing the corrosion of copper. No tendency for the Cu(I) complex to oxidize to the Cu(II) state over short times was found. Polarization studies of the inhibition process suggest that the surface is largely covered by the complex; impedance measurements imply a double layer at the surface which forms sequentially with time.     

Etude Electrochimique Du Comportement Du Cuivre En Solution Alcaline Et De L'action Inhibitrice De La Cyclohexylamine

The behaviour of copper in a basic solution (pH 12) of Na₂SO₄ 0,1N has been investigated, in presence or not of cyclohexylamine, using polarization as well as double layer impedance measurements.The composition of the oxide film and the mechanism of reduction of CuO and Cu₂O are discussed. Some previous results concerning this mechanism are not confirmed. The expected formation of copper-cyclohexylamine complexes does not accelerate the corrosion process of copper: cyclohexylamine can be considered as a copper corrosion inhibitor, making the protective oxide film more stable by formation of a Cu(W NH₂)_x²⁺ complex.     

铜在含氯薄液膜和杂色曲霉作用下的腐蚀行为

目的 研究纯铜在含氯液膜和霉菌共同作用下的腐蚀行为与机理。方法 将海南文昌采集的一株野生杂色曲霉接种到质量分数分别为0.9%和3.5%的NaCl溶液中制成孢子悬浮液,将孢子悬浮液均匀喷洒到铜试样表面后进行恒温恒湿试验,试验不同周期后采用体视学显微镜、扫描电子显微镜观察铜试样的腐蚀形貌,采用X射线光电子能谱仪分析试验14 d的试样表面和氩离子刻蚀15 s后的成分。结果 纯铜在NaCl薄液膜下的腐蚀产物具有明显的双层结构,内层靠近基体的为致密的Cu2O钝化层,外层为疏松的Cu2(OH)2CO3和Cu2(OH)3Cl组成的Cu(II)碱式盐;无菌时,铜表面出现大量蓝绿色的Cu(II)碱式盐,杂色曲霉存在时,铜表面腐蚀产物主要为红棕色的Cu2O钝化膜,仅有少量Cu(II)碱式盐零星分布在Cu2O膜外层;0.9% NaCl薄液膜与霉菌共同作用时,试样表面腐蚀产物主要为Cu2O,当薄液膜中盐的质量分数升高到3.5%时,霉菌数量减少,Cu(II)碱式盐较0.9% NaCl薄液膜组增多。结论 纯铜的腐蚀产物由内层的Cu2O钝化层、外层的Cu2(OH)2CO3和Cu2(OH)3Cl组成双层结构。杂色曲霉通过呼吸作用影响液膜中的O2浓度进而影响铜的腐蚀产物组成,霉菌存在时腐蚀产物中Cu(II)碱式盐显著减少。含氯液膜与霉菌共同作用时,液膜中的NaCl浓度通过影响杂色曲霉的生长活性而影响腐蚀产物组成。     

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.     

Formation of oxides on copper in alkaline solution and their photoelectrochemical properties

The anodic formation of Cu(I) and Cu(II) oxides on polycrystalline copper in a deaerated alkaline solution is studied using the technique of the synchronous recording of transients of the photocurrent and polarization current. The oxide formation in a currentless mode is analyzed via the synchronous recording of photopotential and corrosion potential. It is found that copper is susceptible to corrosion oxidation due to traces of dissolved oxygen with the formation of a Cu(I) oxide. The preliminary formation of the underlayer of anodic Cu(I) oxide on copper hinders its further corrosion oxidation. It is confirmed that copper oxides Cu₂O and CuO, which appear on copper in both anodic and corrosion modes of formation, are p-type semiconductors. The initial stage of anodic oxidation of copper is characterized by the formation of an intermediate compound of Cu(I), possibly CuOH, which exhibits n-type conductivity. A film of Cu(I) oxide is thin and has a band gap of 2.2 eV for indirect optical transitions. Anodic polarization in the range of potentials of CuO formation leads to the formation of a thicker oxide film, which is a mixture of Cu(I) and Cu(II) oxides.     

2-Mercaptobenzoxazole as a copper corrosion inhibitor in chloride solution: Electrochemistry, 3D-profilometry,and XPS surface analysis

2-Mercaptobenzoxazole (MBOH) was studied as a corrosion inhibitor for Cu in 3 wt.% NaCl solution using EIS, a potentiodynamic curve, 3D-profilometry, and XPS measurements. It was shown that Cu corrosion in solution containing MBOH follows kinetic-controlled and diffusion-controlled processes and that MBOH is a mixed-type inhibitor. The diffusion coefficient of the Cu ions travelling through the solid surface layers was estimated to be on the order of 10⁻¹⁵–10⁻¹⁴ cm² s⁻¹. It was also demonstrated that the Cu(I)–MBOH complex is formed on the Cu surface and that the thickness of this surface layer is 1.4 ± 0.4 nm.     

Characterisation of anodic layers on Cu-10Sn bronze (RDE) in aerated NaCl solution

The anodic surfaces formed on Cu-10Sn (wt.%) alloy (α-bronze) are investigated in aerated 0.1 M aqueous chloride solution, using electrochemical reduction and characterisation methods such as scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). On the whole anodic domain, investigations performed on a bronze rotating disk electrode (RDE) reveal the systematic formation of a uniform oxidation layer. It is evidenced that the chemical composition of the layer varies with the applied anodic potential, but also that the latter always exhibits a poorly crystallised (probably nanocrystalline) hydrated and hydroxylated nature. Close to E_oc, the compounds are mainly (hydroxide) oxides of tin and copper, incorporating very low amounts of chlorides. At intermediate oxidation potentials corresponding to the active-passive transition, the first oxidation peak corresponds to the formation of hydrated tin oxyhydroxide chloride species which transforms in a more stable one - probably related to the Sn(II) → Sn(IV) oxidation. At higher anodic potential, on the current plateau, the layer contains hydrated tin (IV) oxyhydroxide and copper chloride (mainly CuCl). However, XRD and XPS results reveal that the barrier layer has a complex nature, including unidentified products and different spatially distributed charged surface zones. The corrosion mechanism involves an internal oxidation of the alloy linked to a preferential dissolution of copper, namely a decuprification. A decuprification factor f_Cu is defined and calculated. Both f_Cu and the layer thickness increase with the applied potential. We show unambiguously that the tin compounds remain in the corrosion layer, acting as stabilizing species. It is suggested that the tin species promote the formation of a network as for tin oxide xerogel, through which copper ions and anions migrate. Both the layer microstructure and the decuprification factor (f_Cu) are in agreement with those found in Type I patina of ancient bronzes.     

Synthesis and corrosion protection study of poly(o-ethylaniline) coatings on copper

Poly(o-ethylaniline) coatings were synthesized on copper (Cu) by electrochemical polymerization of o-ethylaniline in an aqueous salicylate solution by using cyclic voltammetry. The characterization of these coatings was carried out by cyclic voltammetry, UV-visible absorption spectroscopy, Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The results of these characterizations indicate that the aqueous salicylate solution is a suitable medium for the electrochemical polymerization of o-ethylaniline to generate strongly adherent and smooth poly(o-ethylaniline) coatings on Cu substrates. The performance of poly(o-ethylaniline) as protective coating against corrosion of Cu in aqueous 3% NaCl was assessed by the potentiodynamic polarization technique and electrochemical impedance spectroscopy (EIS). The results of these studies demonstrate that the poly(o-ethylaniline) coating has ability to protect the Cu against corrosion. The corrosion potential was about 0.078 V versus SCE more positive in aqueous 3% NaCl for the poly(o-ethylaniline) coated Cu (∼ 15 μm thick) than that of uncoated Cu and reduces the corrosion rate of Cu almost by a factor of 70.     

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.     

An investigation on the mechanisms of ant nest corrosion of copper tube in formic acid environment

Copper tubes used in air-conditioners and refrigerators often fail due to ant nest corrosion (ANC) in formic acid environment. In this paper, corrosion behavior and corrosion mechanisms of copper tubes in formic acid (HCOOH) were analyzed by vapor corrosion tests, optical microscopy (OM), scanning electron microscope (SEM), energy-dispersive X-ray spectrometry (EDS). The effects of the surface condition on ANC of copper tube were also investigated. Results showed that ANC of copper tube was a spontaneous process. The surface integrity of copper tube surface oxide layer is not the decisive factor of ANC. ANC originated from the dissolution of the surface oxide layer in HCOOH, which exposed fresh copper matrix. ANC is a special electrochemical corrosion, where the copper matrix acts as an anode and the undissolved surface oxide layer acts as a cathode due to the potential difference. The accumulation of corrosion products consisting of Cu(HCOO)₂ and Cu₂O can produce a wedge effect and generate many microcracks until to penetrate the copper tube wall. These findings would provide a deep understanding of the corrosion behavior of copper and copper alloys.     

Corrosion protective poly(o-toluidine) coatings on copper

This study examines the use of poly(o-toulidine) (POT) coatings for corrosion protection of copper (Cu) in an aqueous solution of 3% NaCl. The POT coatings were synthesized on Cu substrates under cyclic voltammetric conditions from an aqueous solution of sodium oxalate. The resulting, POT coatings were uniform, shiny and strongly adherent to the Cu substrates. These coatings were characterized by cyclic voltammetry (CV), UV-visible absorption spectroscopy, Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). The ability of POT to serve as a corrosion protective coating for Cu was examined by potentiodynamic polarization measurements and CV. The results of this study clearly reveal that the POT acts as corrosion protective coating on Cu and reduces the corrosion rate of Cu almost by a factor of 40.     

Study of inhibition mechanism and efficiency of indole-5-carboxylic acid on corrosion of copper in aerated 0·5M H2 SO4

Abstract

Inhibition of the corrosion of copper in aerated 0·5M sulphuric acid solutions containing various concentrations of indole-5-carboxylic acid was studied in the temperature range 25–55°C using potentiodynamic curves (Tafel lines), weight loss, analytical methods, and determination of double layer capacitance. The corrosion rates reveal good corrosion inhibition, up to 95% in the concentration range of 1 × 10^-4–4 × 10^-3M. Tafel anodic slopes in inhibited acid solutions are considerably higher than those in uninhibited acid solutions. This points to a change in the corrosion mechanism of copper in the presence of indole-5-carboxylic acid. Under these conditions, copper could electro-oxidise primarily to Cu⁺ rather than to Cu²⁺, forming slightly soluble [Cu–(indole-5-carboxylic)_n ]⁺_(ads) complexes. Corrosion rates determined by the weight loss method in both the absence and presence of inhibitor are much higher (on average by a factor of about 6) than those obtained with the potentiodynamic method. This points to a limitation of the Tafel line extrapolation method in corrosion rate determination. The double layer capacitance–potential curves indicate considerable adsorption of the inhibitor over a wide potential range (-600 to +200 mV with regard to E_corr ).     

A correlation between electrochemical behaviour, composition and semiconducting properties of naturally grown oxide films on copper

Copper(I) oxide films formed under open-circuit potential in neutral aqueous solutions have been characterized, using coulometry, photocurrent spectroscopy and X-ray photo-electron spectroscopy (XPS). The reduction potential of the oxide layer was found to depend on the presence in the electrolyte of chloride ions, Cu(II) or Cu(I) ionic species or of a corrosion inhibitor. XPS analyses were performed on these oxide layers, and showed in some cases an evolution of the oxidation state of copper from + 2 to + 1 state throughout the film. Different conducting properties of the cuprous oxides could be demonstrated through photo-electrochemical measurements, and the formation of a duplex Cu₂O layer with two semiconducting components of different stoichiometries was discussed.     

Corrosion performance of high pressure die-cast Al-6Si-3Ni and Al-6Si-3Ni-2Cu alloys in aqueous NaCl solution

The corrosion performance of high pressure die-cast Al-6Si-3Ni (SN63) and Al-6Si-3Ni-2Cu (SNC632) alloys in 3.5% (mass fraction) NaCl solution was investigated. X-ray diffraction (XRD) and microstructural studies revealed the presence of single phase Si and binary Al₃Ni/Al₃Ni₂ phases along the grain boundary. Besides, the single Cu phase was also identified at the grain boundaries of the SNC632 alloy. Electrochemical corrosion results revealed that, the SNC632 alloy exhibited nobler shift in corrosion potential (?_corr), lower corrosion current density (J_corr) and higher corrosion resistance compared to the SN63 alloy. Equivalent circuit curve fitting analysis of electrochemical impedance spectroscopy (EIS) results revealed the existence of two interfaces between the electrolyte and substrate. The surface layer and charge transfer resistance (R_ct) of the SNC632 alloy was higher than that of the SN63 alloy. Immersion corrosion test results also confirmed the lower corrosion rate of the SNC632 alloy and substantiated the electrochemical corrosion results. Cu addition improved the corrosion resistance, which was mainly attributed to the absence of secondary Cu containing intermetallic phases in the SNC632 alloy and Cu presented as single phase.     

Corrosion inhibition of copper by heterocyclic compounds

The corrosion inhibition of copper in aerated 0.5 M H₂SO₄ solution in presence of two classes of heterocyclic compounds, namely phenylazo-pyrazolones (PAP) or hydroxy quinoline and bromobenzyl-carboxy-1,2,3 triazole (BCT) derivatives was studied. The corrosion parameters were obtained at different inhibitor concentrations and the temperature effect was also investigated. The corrosion rate of copper was determined; using Tafel method and the polarization resistance (R_p) technique. The electrolyte solution was analysed using cyclic voltammetry and UV-visible spectroscopy. The results were compared with that of some prepared Cu-complexes in order to explain the inhibition mechanism. Moreover, the thermodynamic activation parameters of the Cu-corrosion reaction were calculated and discussed in relation to the stability of the protective layer. The inhibition effect was attributed to the adsorption of the dye molecules, the precipitation of Cu-chelates and/or formation of π-complexes at the electrode surface.     

A study on the 65‐35 brass corrosion inhibitor

The influence of new inhibitor namely 1,3‐bis‐diethylamino‐propan‐2‐ol (DEAP) on the dezincification corrosion of 65‐35 brass in simulated atmospheric water was studied by potentiostatic current transient measurement, solution analysis and surface evaluation techniques. Potentiostatic current transient results showed that the investigated inhibitor can effectively inhibit the chemical dissolution of brass in simulated atmospheric water. Solution analysis revealed that the weigh loss of brass electrode remarkably decreased in the presence of DEAP, changing from 7.375 × 10^?3 mg (blank) to 9.567 × 10^?4 mg (10^?2 M). The scanning electron microscope (SEM) and electron probe microanalyzer (EPMA) measurements showed that DEAP may better adsorb to zinc component than to copper component, inhibiting the dezincification of brass in solution by a mixed complex film of Zn(II)‐DEAP and Cu(I)‐DEAP. The nature of the inhibited film was analyzed by an X‐ray photoelectron spectroscope (XPS) analyzer.     

A novel process for copper protection in the simulated industrial cooling water based on click synthesis and self‐assembling method

The triazole inhibitor of 1‐(p‐tolylthio)‐1H‐1,2,3‐triazole‐4‐carboxylic acid (TTC) was synthesized via the Cu(I)‐catalyzed azide‐alkyne 1,3‐dipolar cycloaddition reaction. The self‐assembling method was performed to fabricate the self‐assembled film of TTC on the copper surface. The electrochemical measurement results indicate that the TTC film can efficiently protect the copper from corrosion in high concentrated industrial cooling water. The protection efficiency of TTC film for copper is 92.2%. Surface characterizations imply that the copper with TTC film after corrosion is covered with multiple protective layers. It probably contains Cu(I) and Cu(II) complexes mixed with nitrogenous compound, Cl^? and SO₄^2?. The result of quantum chemical calculation shows that the superior performance of TTC film is related to the adsorption of TTC molecules on copper surface horizontally. This kind of adsorption is mainly achieved via the adsorption centers of triazole ring and O atoms in TTC molecule.