Corrosion inhibitors for copper

The author presents, in a summarizing review, the results of experimental work aimed at finding new corrosion inhibitors for copper. Particular emphasis is placed on relations between inhibitor structure and inhibiting efficiency and on possible reaction between the inbibitor and the particular acid species resulting in an inactivation of the latter. The acids investigated include nitric, phosphoric, hydrochloric, acetic, lactic and malic acids; other media studied were sodium hydroxide, ammonium chloride and potassium perchlorate.     

Corrosion characteristics of copper microparticles and copper nanoparticles in distilled water

The corrosion characteristics of copper microparticles and copper nanoparticles in distilled water were investigated in this paper. The Cu²⁺ transformations of copper microparticles and copper nanoparticles in distilled water were tested by using absorbance measurement, the structures of their corrosion products were determined by using XRD and TEM techniques. The results of absorbance measurement show that the corrosion characteristics of copper nanoparticles in distilled water are quite different from that of copper microparticles. The Cu²⁺ transformations ratio of copper microparticles increases slowly with the increasing of immersion time and levels off eventually, but the Cu²⁺ transformations ratio of copper nanoparticles increases sharply with the increasing of immersion time and gets to peak rapidly, and then decreases as the immersion time increases and levels off finally. The results of XRD present that they have different corrosion products, the corrosion products of copper microparticles in distilled water are Cu and CuO, but the nanoparticles are Cu, CuO, Cu(OH,Cl)₂ · 2H₂O and Cu₂(CO₃)(OH)₂. All these differences owe to the size effect of copper particles.     

Corrosion behaviour of aluminium in copper containing environment

Corrosion behaviour of pure aluminium galvanically connected to metallic copper or in the presence of Cu²⁺ ions was investigated by electrochemical measurements in Na₂SO₄ and Na₂SO₄ + NaCl test solutions. It has been found that in aerated Cl⁻ ion containing solutions pitting corrosion of aluminium emerged immediately, while in the absence of oxygen this process was less violent. Effect of passivating pre-treatment of aluminium surface on corrosion behaviour Cu-Al bimetallic system is also demonstrated.     

Corrosion characteristics of copper in magnetized sea water

The corrosion characteristics of copper in magnetic action system were investigated by mass loss method, electrochemical test, scanning electron microscopy （SEM） and energy analysis. It is found that the corrosion process of copper is influenced by magnetic field. The flow corrosion rate of copper decreases at the initial segment, then drives to gentle stage at the final segment. From electrochemical test, the corrosion rate of copper in the magnetized sea water is minimal compared with that in 3.5% NaCl solution and sea water. Electlochemical impedance spectroscopy （EIS） plots of copper in 3.5% NaCl, sea water and magnetized sea water are similar. However, EIS plot of copper in magnetized sea water shifts rightwards due to the effect of magnetic field on sea water. The corrosion process of copper in magnetized sea water is pitting corrosion. The surfaces of samples are finer in magnetized sea water relative to those in 3.5% NaCl solution and sea water. The corrosion products of copper include large amount of Cu element, O element and Cl element. Cu2O and CuCl2 are the primary products. This suggests that electromagnetic treatment has remarkable effect on the corrosion of copper.     

Corrosion electrochemical mechanism ofchemical mechanical polishing of copper in K3Fe（CN）6 solution

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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.     

Corrosion domain analysis of copper corrosion in aqueous media

Abstract

The technology that is being developed in Sweden for the disposal of high level nuclear waste calls for storage of the waste in copper canisters, which are encapsulated in a bentonite buffer contained in drill holes in the floors of drifts (tunnels) in a granitic rock repository. A controversial issue has arisen during the development of this technology: that copper, when in contact with pure water under anoxic conditions corrodes and hence is not immune as previously believed. This issue is resolved in the present paper by deriving corrosion domain diagrams as a means of presenting the thermodynamics of the system in the clearest form possible, when assessing the immunity and activation of copper.     

紫铜海水管焊接部位在海水中的腐蚀特征

采用金相显微镜、X射线衍射仪、扫描电镜结合能谱测试技术研究了紫铜海水管焊接接头部位在海水中的腐蚀特征。结果表明:采用黄铜焊条的接头部位为α β双相黄铜,在海水中发生了严重的不均匀脱锌腐蚀,脱锌后合金表面的颜色由黄变为紫红;腐蚀产物主要由ZnCl2和ZnSO4等锌盐和锌的氧化物ZnO2和ZnO组成,此外还含有少量的铜绿Cu3(SO4)(OH)4;采用白铜焊条的接头部位为Cu-Ni-Zn三元单相固溶体(α相),在海水中浸泡前后结构未发生变化,表面较致密、无明显孔洞和点蚀,与黄铜焊缝相比,具有优异的耐海水腐蚀性能。     

纯铜离子渗镀钛层的耐蚀性

采用加弧辉光离子渗镀技术, 实现了在纯铜表面形成均匀的渗镀钛层. 用电化学测试技术对渗镀层在0.5moL/LH2SO4溶液中的耐蚀性进行了对比试验研究. 结果表明渗镀钛层的耐蚀性能大大提高, 与钛板相当, 并对渗镀层钛浓度的分布、渗镀层显微硬度、渗镀层相的结构进行了测定.     

Corrosion and layer formation of passive copper in alkaline solutions

Copper forms passivating layers in alkaline solutions. Depending on the electrode potential a Cu₂O or a Cu₂O/CuO, Cu(OH)₂ layer is present. The structure and composition of the film has been examined by different methods like X-ray Photoelectron Spectroscopy (XPS), Ion Scattering Spectroscopy (ISS) and in situ Photoacoustic Spectroscopy (PAS). The thickness and growth of the passive layer has been determined by its electrochemical reduction i. e. the charges of potentiodynamic reduction peaks or the evaluation of the corresponding galvanostatic steps. The results support a high field mechanism for the oxide formation with an inverse logarithmic rate law and a linear increase of the oxide thickness with the electrode potential. The capacity of a Cu₂O-layer refers to the characteristics of a thin semiconducting film. Studies with a rotating Pt split ring Cu disc electrode permit the subdivision of the current density into a part of layer formation and corrosion. The efficiency for the corrosion part is very small during the beginning of oxide formation and achieves ν = 90% after some few minutes. In the potential range of Cu₂O formation only ν = 50% is achieved.     

铁锰二元合金耐液锌腐蚀机理

研究了四种不同Mn含量的铁锰二元合金在450℃液锌中的腐蚀行为,探讨了Mn对铁锌反应的影响规律。结果表明,铁锰二元合金在液锌中的腐蚀属于溶解性腐蚀。随着锰含量的增加,腐蚀速率有较大变化。含锰量为10wt%的合金,其腐蚀速率为5.79×10-3g.cm-2.h-1,含锰量为15wt%的合金,其腐蚀速率为3.64×10-2.gcm-2.h-1。锰含量为10wt%时,腐蚀产物由致密的δ相层和块状的ζ相层组成,致密的较厚的δ相层的存在,降低了铁锌反应速率,合金表现出较好的耐液锌腐蚀能力,而锰含量为15wt%时,腐蚀产物由大量疏松的颗粒状ζ相分布在液锌相中组成,疏松的组织恶化了合金的耐液锌腐蚀能力。     

Corrosion inhibition of copper by purine or adenine in sulphate solutions

The influence of the concentration of purine (PU) or adenine (AD) on the spontaneous dissolution of copper in 0.5 M Na₂SO₄ solutions (pH 6.8 and 1.0) was studied. The investigations involved weight loss measurements, quartz crystal microbalance (QCM) techniques and scanning electron microscopy (SEM). The inhibition efficiency increases with an increase in the concentration of PU or AD. An adherent layer of inhibitors are postulated to account for the protective effect. The adsorption of both inhibitors was found to occur on the surface of copper according to the Langmuir isotherm. The values of standard free energies of adsorption suggest the chemical adsorption of PU and AD on copper surface.     

铜合金及其复合材料在氯化钠盐雾中的腐蚀行为

通过氯化钠盐雾腐蚀实验,结合X射线衍射(XRD)和电子探针(EPMA)分析,研究了铜合金及其复合材料在氯化钠盐雾中的腐蚀行为.结果表明:在实验初期材料的腐蚀速度随时间的延长而降低,约96 h以后腐蚀速度基本不再变化;BZn15-17与纯镍复合材料的耐蚀性最好;实验初期和后期的腐蚀产物组成基本相同,2种白铜合金的主要腐蚀产物都是CuCl2@2H2O,黄铜合金的主要腐蚀产物为CuCl,其次为CuCl2@2H2O和(CuZn)2(OH)3Cl;腐蚀形貌变化较大.     

Corrosion behaviour of copper under chloride-containing thin electrolyte layer

The corrosion behaviour of copper under chloride-containing thin electrolyte layers (TEL) was investigated using electrochemical impedance spectroscopy (EIS), cathodic polarization, linear polarization, SEM/EDS and XRD. The results indicate that the copper corrosion rate increases as TEL thickness decreases during the initial stages. After 192 h of immersion, the corrosion rate of copper under TEL in this order: 300 > 402 > 199 > bulk solution > 101 μm. The corrosion behaviour is uniform under TEL, and pitting is the primary corrosion type in the bulk solution. A corrosion model of the behaviour of copper under chloride-containing TEL is proposed.     

Corrosion of copper and silver plates by volcanic gases

Corrosion products that had been formed on copper and silver plates exposed in Miyake Island, where suffered a volcanic eruption in 2000, were analyzed by X-ray techniques to get better understanding of copper and silver corrosion in harsh environment. The exposure experiment was carried out from September 2004 to April 2005. Many kinds of patina were found on copper such as cuprite (Cu₂O), posnjakite (Cu₄SO₄(OH)₆ · H₂O), brochantite (Cu₄SO₄(OH)₆), antlerite (Cu₃SO₄(OH)₄), and geerite (Cu₈S₅). For silver, silver chloride (AgCl) and silver sulfide (Ag₂S) were formed. Although the volcanic activity had greatly subsided, the atmospheric corrosion of copper and silver plates exposed on Miyake Island was mainly affected by volcanic gases, wet-dry cycles in the environment, and sea-salt aerosols.     

Corrosion behaviour of copper containing low alloy steels in sulphuric acid

The influence of the addition of Cu on the corrosion resistance of low alloy steel in sulphuric acid was investigated using AC and DC electrochemical methods and a weight loss test, which took place in 10 wt% H₂SO₄ solution at room temperature. The electrochemical measurements indicated that the corrosion rate is suppressed by the addition of Cu due to a higher hydrogen overpotential and prevention of the active dissolution. Surface analyses (XPS, EPMA and SEM) of the corroded surfaces conducted after the immersion test indicated that the rust layer formed on the Cu containing steels was enriched with Cu compounds.     

Corrosion mechanism of model zinc-magnesium alloys in atmospheric conditions

Recently, superior corrosion properties of zinc coatings alloyed with magnesium have been reported. Corrosion behaviour of model zinc-magnesium alloys was studied to understand better the protective mechanism of magnesium in zinc. Alloys containing from 1 to 32 wt.% magnesium, pure zinc, and pure magnesium were contaminated with sodium chloride and exposed to humid air for 28 days. Composition of corrosion products was analyzed using infrared spectroscopy (FTIR), ion chromatography (IC), and Auger electron spectroscopy (AES). The exposure tests were completed with scanning Kelvin probe (SKP) and electrochemical measurements. Weight loss of ZnMg alloys with 1-16 wt.% magnesium was lower than that of pure zinc. Up to 10-fold drop in weight loss was found for materials with 4-8 wt.% Mg in the structure. The improved corrosion stability of ZnMg alloys was connected to the presence of an Mg-based film adjacent to the metal surface. It ensured stable passivity in chloride environment and limited the efficiency of oxygen reduction.     

Corrosion of copper in seawater and its aerosols in a tropical island

A complete characterization of copper corrosion behavior has been carried out under permanent immersion, water line, splash zone and at the atmosphere (near and far from the sea) at the tropical Cuban archipelago. No significant differences have been determined for corrosion of copper under complete immersion for test sites representative of Cuban archipelago. The maximum corrosion rate was observed on the line of water, related to the partial removing of the corrosion products layer due to water movement (waves) and a higher availability of oxygen. Patina composition was characterized using XRD, IR, EDS and SEM techniques. Paratacamite (Cu₂(OH)₃Cl) was the main component of the patina formed under complete immersion, on the line of water and in the splash zone. In poorly polluted atmospheric marine environments also atacamite (another structural modification of Cu₂(OH)₃Cl) was found. When environmental SO₂ reaches a competitive level with the chloride aerosol the patina formed is a complex mixture of basic cupric chlorides (paratacamite and atacamite) and basic cupric sulfates, antlerite (Cu₃(SO₄)(OH)₄) and brochantite (Cu₄(SO₄)(OH)₆). Brochantite and basic cupric chlorides are detected at inland rural sites. The patina morphology reveals details about the local environment in which it is formed and shed light on its more or less protective role for the metal. The relatively large corrosion rate under complete immersion and on the line of water is related to the formation of a patina with poor adherence to the metal surface and to a porous layer of cuprite formed by relatively large octahedral crystals.     

Corrosion of ultra-fine grained copper fabricated by equal-channel angular pressing

Corrosion of ultra-fine grain (UFG) copper fabricated by equal-channel angular pressing (ECAP) has been investigated in comparison with that in recrystallized coarse grain (CG) copper. Corrosion current was estimated by a Tafel extrapolation method to examine the kinetics of corrosion in a modified Livingstone etchant, which is sensitive to dislocations and grain boundaries. UFG copper exhibited a lower corrosion current in comparison with that in its recrystallized coarse grain (CG) counterpart despite the fact that the dislocation density and total fraction of grain boundaries are much greater in UFG copper than in CG copper. Corrosion damage on the surface of UFG copper is macroscopically rather uniform whereas obvious attack at grain boundaries and selective corrosion of some grain interiors were observed in CG copper.