Corrosion Protection Of Copper Research Articles

Synergistic effect of molybdate or tungstate and water soluble thiol on the corrosion protection of copper

An approach to fabricate protective film on copper substrate utilizing molybdate or tungstate assisted by dithiol was proposed. The fabricated films exhibited double-layer structure. The top layer was an organic layer primarily composed of interconnected dithiol molecules through disulfide bonds originating from the oxidation of molybdate or tungstate. The Cu2S bottom-layer formed as a result of the cleavage of C-S bonds subsequent to the adsorption of dithiol molecules onto the copper matrix. The molybdate participated the film via MoOx and MoSx. Although no tungstate species were detected in the film, the oxidizing effect of tungstate facilitated a conversion of dithiol molecules into polymers, resulting in a significantly thicker surface layer. The corrosion protection efficiencies of the films reached 99.7 % and 99.8 %, respectively, attributed to the incorporation of molybdate or tungstate additives. Theoretical calculations provided valuable insights into the process of film formation and elucidated the relationship between film structure and anti-corrosion performance.

Synergistic effect of metal cation and 1-dimethylamino-2-propanol on copper corrosion protection in alkaline solution

BackgroundCopper (Cu) has versatile applications in microelectronic industry and its corrosion protection in the manufacturing process is an important reliability issue. MethodsIn this study, mixed type corrosion inhibitor is formulated by complexation of metal cation (Ni2+) and tertiary amine (1-dimethylamino-2-propanol), and its synergistic effect on the corrosion protection of Cu in alkaline solution is systematically investigated. Electrochemical, microstructural, and chemical state analyses of the Cu surfaces with and without the inhibitor protection are performed to realize the protection efficacy of the mixed type inhibitor against corrosion. Significant findingsThe results show that the polarization resistance of the Cu surface is increased with the introduction of mixed type inhibitor (Ni2+-1-dimethylamino-2-propanol), achieving a higher inhibition efficiency of 48 % compared to the cation-free inhibitor (1-dimethylamino-2-propanol) of 25 %. The higher inhibition efficiency is attributed to the stronger adsorption capability of mixed type inhibitor on the Cu surface as confirmed by the X-ray photoelectron spectroscopy analysis and quantum chemical calculations.

Coating of Carbon Nanotubes Using Chemical Method to Enhance the Corrosion Protection of Copper and Aluminum Metals in Seawater Medium

In this study, carbon nanotubes were prepared using a pure chemical method modified similar to the Hummers method with simple changes in the work steps. The carbon nanotubes were then coated and reduced on copper and aluminum metals using the electrodeposition method (EDP) for corrosion protection application in seawater medium (NaCl 3.5%) at four different temperatures: 20, 30, 40, and 50 °C, which were studied using three electrode potentiostats. All corrosion measurements, thermodynamics, and kinetics parameters were nominated from Tafel plots. The films deposited by the carbon nanotubes were examined by the SEM technique, and this technique showed the formation of carbon nanotubes.

Self-assembled monolayers of Ginkgo biloba exocarp extract for corrosion protection of copper

A self-assembled monolayer based on Ginkgo biloba exocarp extract (GBEE SAM) was prepared on a fresh copper surface, exhibiting effective inhibition behaviour for the substrate. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and contact angle tests were carried out to characterize the GBEE SAM, and the results indicate that the molecules of Ginkgo biloba exocarp extract are fortunately self-assembled on copper surface, building a hydrophobic SAM. Electrochemical measurements and scanning electron microscopy were performed to detect the inhibition efficiency of the SAM. It is suggested that the film manifests the anti-corrosion performance for the substrate with the highest inhibition efficiency of 97.86%. Besides, the value of ΔGads is −22.15 kJ/mol, which shows GBEE molecules could spontaneously adsorb on the copper surfaces with chemical and physical adsorption. Additionally, theoretical calculations were performed to assist further understanding of the adsorption and inhibition mechanism of GBEE SAM.

Addition of Schiff Bases to Hybrid Silane Sol–Gel Coatings: An Efficient Strategy to Develop an Active System for Corrosion Protection of Copper

Addition of Schiff Bases to Hybrid Silane Sol–Gel Coatings: An Efficient Strategy to Develop an Active System for Corrosion Protection of Copper

Corrosion protection performance of a coating with 2-aminino-5-mercato-1,3,4-thiadizole-loaded hollow mesoporous silica on copper

Hollow mesoporous silica microspheres (HMSN) were selected as carriers for storing 2-aminino-5-mercato-1,3,4-thiadizole (ATM) in this experiment. The synthesised microspheres were uniformly dispersed, with a diameter of approximately 500 nm, as identified by scanning electron microscopy. HMSN, as excellent nanocarriers, were used to encapsulate ATM with a 19 wt% loading rate. Then, 18 wt% HMSN loaded with ATM was added to the coating. Electrochemical impedance spectroscopy and scanning Kelvin probes were used to investigate the self-healing ability of the coating with ATM encapsulated in hollow mesoporous silica microspheres. The copper corrosion caused by microdefects in the coating was delayed by controlling the slow release of ATM from the microspheres. The active corrosion resistance of the coatings was strengthened. By optimising the coating, the service life of the coating can be extended to achieve the long-term corrosion protection of copper.

Low temperature curing polyorganosilazane coatings for copper corrosion protection: effect of precursor concentration and relative humidity (R.H.)

Low temperature curing polyorganosilazane coatings for copper corrosion protection: effect of precursor concentration and relative humidity (R.H.)

Electrical compatibility of transmission fluids in electric vehicles

The in electrical vehicles, where the electric motor is inside the transmissielectrical compatibility of the automatic transmission fluids (ATFs) is very important on and in contact with the ATF. This work studies the influence of factors like temperature, time, and air exposition on the oxidation of three ATFs and their changes in electrical conductivity. The results showed that the higher content of additive the lower variations of electrical conductivity with the oxidation; the measurements of electrical conductivity are better than FT-IR ones for monitoring oil thermo-oxidative degradation at initial periods; the conventional ATFs could maintain good electrical compatibility in electrified drivelines, although their materials compatibility and copper corrosion protection of electrical components should be also tested.

Copper Corrosion Protection by 4-Hydrocoumarin Derivatives: Insight from Density Functional Theory, Ab Initio, and Monte Carlo Simulation Studies

The corrosion inhibition performance of 4-hydrocoumarin derivatives has been studied using weight loss, electrochemical impedance spectroscopy, potentiodynamic polarization, and electrochemical frequency modulation techniques. However, experimental studies have not explained why the methoxy (OCH3) group contributes more to the increase in corrosion inhibition than the methyl (CH3) and chlorine (Cl) functional groups. In this theoretical study, the electronic aspect of the target corrosion inhibitors will be studied in detail to help strengthen the explanation in the experimental research. Density functional theory, ab initio, and Monte Carlo simulations have been used to analyze the corrosion inhibition performance of 4 curcumin derivatives against copper. The quantum chemistry approach is carried out under gas and aqueous conditions in neutral and protonated inhibitors. The Monte Carlo simulation was used to observe the dynamics and the mechanism of inhibition of the target molecule on the copper surface. The quantum chemistry approach can mimic the geometrical parameters of molecular inhibitors. It can also explain electronically why the OCH3 functional group is superior to other substituents. The adsorption energy of the 4-hydroquinone derivative is linearly correlated with the reported experimental study. The level of corrosion inhibition efficiency is OCH3 > CH3 > H > Cl.

Hydrothermal synthesis of Zn-Mg-based layered double hydroxide coatings for the corrosion protection of copper in chloride and hydroxide media

Hydrothermal synthesis of Zn-Mg-based layered double hydroxide coatings for the corrosion protection of copper in chloride and hydroxide media

Corrosion Inhibition Properties of Thiazolidinedione Derivatives for Copper in 3.5 wt.% NaCl Medium

Copper is the third-most-produced metal globally due to its exceptional mechanical and thermal properties, among others. However, it suffers serious dissolution issues when exposed to corrosive mediums. Herein, two thiazolidinedione derivatives, namely, (Z)-5-(4-methylbenzylidene)thiazolidine-2,4-dione (MTZD) and (Z)-3-allyl-5-(4-methylbenzylidene)thiazolidine-2,4-dione (ATZD), were synthesized and applied for corrosion protection of copper in 3.5 wt.% NaCl medium. The corrosion inhibition performance of tested compounds was evaluated at different experimental conditions using electrochemical impedance spectroscopy (EIS), potentiodynamic polarization curves (PPC) and atomic force microscopy (AFM). EIS results revealed that the addition of studied inhibitors limited the dissolution of copper in NaCl solution, leading to a high polarization resistance compared with the blank solution. In addition, PPC suggested that tested compounds had a mixed-type effect, decreasing anodic and cathodic corrosion reactions. Moreover, surface characterization by AFM indicated a significant decrease in surface roughness of copper after the addition of inhibitors. Outcomes from the present study suggest that ATZD (IE% = 96%) outperforms MTZD (IE% = 90%) slightly, due to the presence of additional –C3H5 unit (–CH2–CH = CH2) in the molecular scaffold of MTZD.

Ultrasonically Assisted Macrocyclic Ring Compound Coatings for Corrosion Protection of Copper in 3.5% NaCl Solution

Macrocyclic ring compounds are potential corrosion inhibitors due to their high planarity, rigidity, and presence of many heteroatoms such as nitrogen, oxygen, phosphorus, and sulfur. However, their application as corrosion inhibitors has been faced with the challenge of insolubility in most organic and aqueous solvents. To overcome this challenge and to harness the untapped hydrophobic property of these compounds, this research, via ultrasonication method, dispersed a macrocyclic ring compound known as free-based phthalocyanine (Pc) to fabricate a corrosion-resistant coating on the Cu surface. The Cu samples were coated through a 24 h immersion by self-assembly method in different systems of sonicated and nonsonicated solutions of the compound in dimethyl sulfoxide (DMSO). The effect of sonication and immersion duration on the coating morphology, compactness, and consequent corrosion inhibition was analyzed. Electrochemical and surface imaging techniques revealed higher corrosion protection in 3.5% NaCl for the Pc-coated Cu samples after sonication compared to the nonsonicated systems.

Roles of Chloride Ions in the Formation of Corrosion Protective Films on Copper

Unambiguous evidence is presented that the chloride ions play a dual role in the formation of a micrometre thick film of polymerized [Cu-Cl-MBI] n . This occurs when the copper is exposed to 3 wt.% NaCl solution containing 1 mM of mixture of inhibitors 2-mercaptobenzimidazole, MBI, and octylphosphonic acid, OPA, in the molar ratio MBI:OPA of 9:1. The chloride ions act simultaneously as a promoter of polymerized [Cu–MBI] n /[Cu–Cl–MBI] n film formation and a reactant that is incorporated in the film, as confirmed by time-of-flight secondary ion mass spectrometry. Also, formation of a Cu2O film under the Cu-inhibitor film was proven by focused ion beam microscopy, with chemical analysis being employed at the cross-section of the thick polymerized film. The Cu(I) oxide underlayer, together with the porous straw-like morphology of the [Cu–Cl–MBI] n overlayer, is believed to be responsible for the excellent corrosion protection of copper, even in a chloride environment without the reservoir of MBI+OPA. We also report a new insight into the mechanism of degradation of the Cu–MBI/Cu–Cl–MBI film that results in the formation of (MBI)2 dimers. The inhibitor layer, formed in NaCl solution and containing the synergistic combination of MBI and OPA, showed outstanding resistance to degradation.

Titanium-containing organic–inorganic hybrid coatings for the corrosion protection of copper in sodium chloride medium

In the present work, two titanium precursors, titanium tetraisopropanolate (TTIP) and tetrabutyl titanate (TBOT), have been used to prepare titanium-based hybrid coatings by sol–gel method, with glycidyl ether oxypropyl trimethoxysilane (GPTMS) as the coupling reagent. The prepared hybrid coating materials are characterized by Fourier transform infrared (FT-IR) spectroscopy, powder X-ray diffraction analysis (PXRD), and thermogravimetric (TG) analysis. The morphology of the coating has been studied by scanning electron microscope (SEM). The corrosion protection of the hybrid coatings in 3.5 wt% sodium chloride medium are studied by the electrochemical impedance spectroscopy (EIS) and polarization method, and the results show that the hybrid coatings show corrosion protection of Cu substrates in aqueous 3.5% NaCl medium with a maximum corrosion inhibition efficiency of 88.9% achieved.

(Invited) Surface Analytical Study of Adsorption Mechanisms of 2-Mercaptobenzothiazole and 2-Mercaptobenzimidazole Corrosion Inhibitors on Cu

The corrosion of metals and alloys is an important issue in industrial applications with an annual global cost estimated to be about 3% of the global GDP (2013). In order to mitigate corrosion, inhibitors are widely used and developed including on copper, a metal which is widely used for its high thermal and electrical conductivity but not totally immune against corrosion.In this work, 2-mercaptobenzothiazole (2-MBT) and 2-mercaptobenzimidazole (2-MBI) [1-2], two structurally related molecules already known for their inhibitory action against corrosion of copper, were studied. The objective was to understand the interaction mechanisms of these two corrosion inhibitors with copper in a well-controlled environment and their influence on the reactivity of copper.To this end, 2-MBT and 2-MBI were dosed at room temperature on a model copper surface, Cu(111), by ultra-low pressure (~10-9 mbar) gas evaporation in ultra-high vacuum conditions. The surfaces were characterized by X-ray Photoelectron Spectroscopy (XPS) and Scanning Tunneling Microscopy (STM) at various growth stages of the inhibitor layer. Thermal stability of the adsorbed molecular layers was also investigated.Growth of molecular layers for 2-MBT and 2-MBI was evidenced on Cu(111) in metallic state with the formation of a monolayer at 5–10 L (1 L = 1×10-6 Torr·s) and multilayers at higher exposure. An excess of sulfur was observed by XPS, with a S 2p component at the same binding energy as atomic S bonded to Cu, indicating a partial decomposition of the molecules at the initial stages of adsorption. STM characterization at low exposure (3–4 L) revealed locally ordered triangular structures for 2-MBT on Cu(111), which can be attributed to atomic S and S of the molecule bonded to Cu, and flat-lying molecules in the multilayer. While adsorption of 2-MBI leads to the formation of an ordered monolayer with different organizations including a (√7×√7)R19.1° structure, which may be attributed to the adsorption of atomic S. Molecules in the monolayer and multilayer are also lying flat. The thickness of the molecular layers was calculated from XPS attenuation to be of the order of several nanometers.The pre-adsorbed molecular layers were observed to markedly decrease the reactivity of copper towards oxygen. Annealing of the molecular layers to above 100°C leads to a partial decomposition and desorption of the inhibitors, and the formation of (√7×√7)R19.1° structure.This study brings new insight into the corrosion inhibition mechanisms of 2-MBT and 2-MBI on copper, which contributes to the knowledge-based development of more efficient corrosion inhibitors for the corrosion protection of copper and its alloys. This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (ERC Advanced Grant CIMNAS no. 741123). [1] M. Petrovic Mihajlovic, M. Antonijevic, International journal of electrochemical science 10 (2015) 1027-1053.[2] M. Finšgar, D. K. Merl, Corrosion Science 83 (2014) 64-175.

A new trend in corrosion protection of copper in acidic medium by using Jujube shell extract as an effective green and environmentally safe corrosion inhibitor: Experimental, quantum chemistry approach and Monte Carlo simulation study

An effective and eco-friendly Jujube shell (JS) extract was studied as a corrosion inhibitor for copper in 1 M hydrochloric acid. This work was investigated by potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and weight loss coupled with atomic absorption spectroscopy techniques. Atomic force microscopy (AFM), Scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry (EDS) revealed the surface morphology in the presence and absence of inhibitor on the metal surface. The experimental results reveal that the JS extract act as a cathodic-type with an inhibition efficiency (IE%) up to 91% for 2 g L−1 at 298 K. In addition, this extract shows good inhibitory activity at a wide range of temperatures. The thermodynamic parameters were determined and discussed. Meanwhile, Monte Carlo simulation and Quantum chemical calculations by application of density functional theory (DFT) were carried out to help better understand the inhibition mechanism of this extract on the copper surface. The results indicated the feasibility of using the Jujube shell (JS) extract as a corrosion inhibitor in acid environment.

In Situ X-ray Diffraction and Spectro-Microscopic Study of ALD Protected Copper Films.

In many applications of copper in industry and research, copper migration and degradation of metallic copper to its oxides is a common problem. There are numerous ways to overcome this degradation with varying success. Atomic layer deposition (ALD) based encapsulation and passivation of the metallic copper recently emerged as a serious route to success owing to the conformality and density of the ALD films. So far, the majority of the studies have been focused on corrosion protection of copper in a variety of chemical environments, mostly at ambient temperature. An investigation of the stability of the ALD film stacks and copper's interaction with them at elevated temperatures has been lacking. Here, we study the mitigation of copper oxidation and migration in 50 nm thick Al2O3/TiO2 and Al2O3/SiO2 bilayer ALD stacks. First, the corrosion dynamics were investigated via in situ X-ray diffraction (XRD) at 350 °C under atmospheric conditions, and second, the interaction of copper with the passivation layers have been examined post factum using detailed spectro-microscopic investigations. According to the XRD results, both ALD films exhibited excellent oxidation protection. In contrast, bare Cu immediately started to oxidize at 350 °C and transformed entirely to its known oxide phases in 4 h. Spectro-microscopic studies revealed that there are structural and chemical changes on the top surface and within the film stacks. The TiO2 layer was crystallized during annealing, while the SiO2 layer stayed in the amorphous phase, which was analyzed by grazing incidence XRD and transmission electron microscopy. According to scanning electron microscopy and X-ray photoelectron spectroscopy analysis, copper was detected on the surface with a higher amount in Al2O3/TiO2 than Al2O3/SiO2, 5.2 at.% and 0.7 at.%, respectively. Based on the surface and cross-sectional analysis, copper migration was observed on both layers, albeit more substantially in Al2O3/TiO2. In the case of Al2O3/SiO2, the bulk of the copper was captured at the interface of the two oxides.

Corrosion protection of copper and copper alloys in different corrosive medium using environmentally friendly corrosion inhibitors

AbstractThe corrosion mechanism of copper and copper alloy is reviewed. A number of scientific papers have been investigated to determine the corrosion mechanism and protection techniques of copper and copper alloy corrosion. Results have shown that copper can be corroded in an acidic or an alkaline environment, and oxide formation is the corrosion initiation process. The use of corrosion inhibitors is one of several ways of controlling metal corrosion. There are inorganic (toxic) and organic (green) corrosion inhibitors invented so far. Nowadays, environmental issue is a concern of several scientists in the world. From the results of recent scientific papers, green corrosion inhibitors can be used for copper corrosion protection and they are both economical and environmentally safe. Furthermore, future researches are needed to determine more efficient, environmentally friendly corrosion inhibitors for copper and copper alloys.

Sol-gel based hybrid silane coatings for enhanced corrosion protection of copper in aqueous sodium chloride

In this study, various concentrations of p-aminothiophenol doped 3-glycidoxypropyltrimethoxysilane based sol-gel matrices (PATP-GPTMS) are prepared through hydrolysis and condensation reactions. The prepared PATP-GPTMS sol-gel is applied on the polished copper (Cu) surface (PATP-GPTMS/Cu) by self-assembly technique. The surface profile of resultant coatings are characterized by important analytical tools such as Fourier transform infra-red (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and stylus profilometer. The surface morphologies of coatings are acquired by scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDX) and atomic force microscopy (AFM) techniques. The FT-IR and XPS results revealed the linking of PATP and thiol monolayer on Cu surface in 0.1 M PATP-GPTMS/Cu coating. Further, the corrosion protection ability of PATP-GPTMS/Cu coatings in 3.5% sodium chloride (NaCl) medium are studied by common electrochemical tools. The electrochemical impedance spectroscopy (EIS) results showed that PATP-GPTMS/Cu coating exhibit improved corrosion resistance than the undoped GPTMS/Cu coating. The maximum corrosion inhibition efficiency of 96.39% is achieved on 12 h self-assembly technique based sol-gel coating of 0.1 M PATP-GPTMS/Cu by polarization method. All the results exposed that, the PATP-GPTMS/Cu coating enhanced the corrosion protection of Cu in aqueous 3.5% NaCl medium.

Copper corrosion protection in neutral media by dicarboxylic acid salts

Copper corrosion protection in neutral media by dicarboxylic acid salts