Characterisation of corrosion products formed on copper exposed at indoor and outdoor sites with high H2S concentrations

Abstract

Corrosion products formed on copper exposed indoors and outdoors at sites with high hydrogen sulphide (H₂S) concentrations were characterised using several analytical techniques. The crystalline corrosion products that formed on the copper exposed indoors were chalcocite (Cu₂S) and cuprite (Cu₂O), while those that formed on the copper exposed outdoors were chalcocite, cuprite and basic copper sulphates. Surface analysis by X-ray photoelectron spectroscopy revealed differences between the copper exposed indoors and outdoors that are explained by the composition, localisation and oxidation of the corrosion products. The surface morphologies of the corrosion products also differed. Elemental depth profiling by glow discharge optical emission spectroscopy revealed that the corrosion products that formed indoors were mainly chalcocite with cuprite only at and near the surface. In contrast, the corrosion products that formed outdoors were a mixture of chalcocite and cuprite. These differences in corrosion products are attributed to the differences in relative humidity during exposure.     

Evolution of patinas on copper exposed in a suburban area

Copper plates were exposed under sheltered outdoor conditions for up to one year, starting in September 2001 in Musashino City, Tokyo, a suburban area. Following various periods of exposure, the patinas on the plates were characterized to investigate their evolution by using X-ray fluorescence analysis, X-ray diffraction, field emission scanning electron microscopy, and glow discharge optical emission spectroscopy. The difference in the roles of sulfur and chlorine in the early stages of copper patination were identified by analyzing the depth profiles of these two elements. Sulfur was found on top of the patina as cupric sulfates such as posnjakite (Cu₄SO₄(OH)₆ · H₂O) or brochantite (Cu₄SO₄(OH)₆). Brochantite appeared only after 12 months of exposure. In contrast, chlorine was found on the surface after only one month of exposure. It gradually penetrated the patina as the exposure period lengthened, forming copper chloride complexes. Chloride ions accumulated at the patina/copper interface, forming nantokite (CuCl), which promoted corrosion.     

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.     

Structure of corrosion film formed on copper exposed to controlled corrosive environment

This paper describes a transmission electron microscopy (TEM) investigation of copper coupons exposed to a corrosive mixed flowing gas environment (MFG). A focused ion beam (FIB) lift-out technique was used to extract electron transparent specimens for TEM investigation. A duplex corrosion film comprising cuprite (Cu₂O) and chalcocite (Cu₂S) developed on the copper substrate. The oxide demonstrated a dense morphology with evidence of chlorine in the oxide layer showing that chlorine plays an important role in the corrosion of copper transforming the protective Cu₂O layer to a non-protective layer. The outer layer of the Cu₂S demonstrated a porous morphology allowing easy penetration of water and gases.     

Copper patinas: an investigation by Auger electron spectroscopy

Auger electron spectroscopy in conjunction with Ar⁺ sputtering has been used to investigate four samples of copper that have been patinated by exposure to the atmosphere for periods ranging from 1 to 100 years. The elemental depth profiles were qualitatively similar for all samples. The patinas were covered with a thin layer of carbon containing species and consisted primarily of copper, sulfur, chlorine, and oxygen. The sulfur is present primarily near the surface of the patina and the chlorine is distributed throughout the patina. In two samples, 44 and 100 years old, significant amounts of chlorine were found in the portion of the patina nearest the bulk copper. A simple mass balance shows that the surface of the patina (beneath the carbon containing layer) is composed primarily of the mineral brochantite, Cu₄(SO₄)(OH)₆, as expected thermodynamically. A thermodynamic analysis also shows that atacamite, Cu₂Cl(OH)₃, the principal chlorine containing mineral found in the patinas, can be stable with respect to cuprite, Cu₂O, particularly in the immediate vicinity of unoxidized copper.     

Morphological study of 16-year patinas formed on copper in a wide range of atmospheric exposures

Much information is available on the atmospheric corrosion of copper and patina formation mechanisms in the short, mid and even long term. However, studies of the structure and morphology of patina layers are less abundant and mostly deal with patinas formed in the atmosphere over a small number of years. The present study concentrates on the structure and morphology of corrosion product films formed on copper after long-term atmospheric exposure (13-16 years) in five Spanish atmospheres of different types: rural, urban, industrial and marine (mild and severe). Characterisation has been performed by X-ray diffraction (XRD) and scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS). Long-term copper corrosion is higher in industrial and marine atmospheres and lower in rural and urban atmospheres. In all cases a decrease in the corrosion rate with exposure time is observed. The formation of antlerite [Cu₃SO₄(OH)₄] is seen in more acidic conditions and in specimen areas subject to a high time of wetness. The presence of nantokite (CuCl), which is not generally mentioned in field studies, has been detected under the cuprite layer very close to the base copper.     

Outdoor atmospheric corrosion of copper in Saudi Arabia

Abstract

Copper specimens have been exposed to the action of marine, marine industrial, urban and rural atmospheres of Saudi Arabia. Environmental factors such as average temperature, average relative humidity and deposition rates of atmospheric pollutants (i.e. Cl^- and SO₂) was investigated. By applying the standard ISO 9223, the aggressiveness of the atmospheres corresponding to the different test stations has been determined. Calculations of corrosion rates were made via loss of weight after one, two and three years of exposure and characterisation of the corrosion products formed on samples have been analysed using X-ray diffraction. Three main sequences have been identified on outdoor copper, representing different reaction routes in chloride dominated environments. Many kinds of patina were found on copper specimens such as cuprite (Cu₂ O), atacamite (Cu₂ Cl(OH)₃), paratacamite (Cu₂ (OH)₃Cl), copper amine nitrite hydroxide, gerhardite, copper hydroxide nitrate and copper amine nitrate.     

Effects of blending on surface characteristics of copper corrosion products in drinking water distribution systems

Copper scales formed over 6-months during exposure to ground, surface and saline waters were characterized by EDS, XRD and XPS. Scale color and hardness were light red-brown-black/hard for high alkalinity and blue-green/soft for high SO₄ or Cl waters. Cl was present in surface or saline copper scales. The Cu/Cu₂O ratio decreased with time indicating an e transfer copper corrosion mechanism. Cu₂O, CuO, and Cu(OH)₂ dominated the top 0.5-1 A° scale indicating continuous corrosion. Cu₂O oxidation to CuO increased with alkalinity, and depended on time and pH. Total copper release was predicted using a Cu(OH)₂ model.     

A study of copper runoff in an urban atmosphere

Initiated by the concern in several countries regarding the release of copper from, e.g., roofs, facings and other outdoor constructions, the present study aims to compare runoff rates with corrosion rates during exposure of copper in an urban atmosphere. The copper runoff rate turns out to be relatively stable during the 2 year period studied, with an average rate per year of around 135 μg Cu cm⁻². This stable runoff rate is associated with the formation and dissolution properties of cuprite (Cu₂O), which is the dominating copper patina phase throughout the 2 year period. The copper corrosion rate, on the other hand, is highly time-dependent. It exhibits an initially high value and decreases with exposure time. As a consequence, the ratio between copper runoff and copper mass loss is very low in the beginning, around 7% after 1 month, and increases with time to reach around 22% after 2 years. With prolonged exposure this ratio eventually reaches 100%, corresponding to a copper patina thickness that does not change any further with time.     

The valence state of copper in anodic films formed on Al-1at.% Cu alloy

During anodising of Al-Cu alloys, copper species are incorporated into the anodic alumina film, where they migrate outward faster than Al³⁺ ions. In the present study of an Al-1at.% Cu alloy, the valence state of the incorporated copper species was investigated by X-ray photoelectron spectroscopy, revealing the presence of Cu²⁺ ions within the amorphous alumina film. However, extended X-ray irradiation led to reduction of units of CuO to Cu₂O, probably due mainly to interactions with electrons from the X-ray window of the instrument and photoelectrons from the specimen. The XPS analysis employed films formed on thin sputtering-deposited alloy/electropolished aluminium specimens. Such an approach enables sufficient concentrations of copper species to be developed in the anodic film for their ready detection.     

X-ray diffraction phase analysis of crystalline copper corrosion products after treatment in different chloride solutions

The corrosion products Cu₂(OH)₃Cl, Cu₂O, and CuCl₂ were identified on the surface of copper plates after their four days treating in three different sodium chloride, sodium/magnesium, and sodium/calcium chloride solutions using X-ray diffraction powder analysis. However, the quantitative proportions of individual corrosion products differ and depend on the type of chloride solution used. Treating of copper plates only in the sodium chloride solution produced the mixture of corrosion products where Cu₂O is prevailing over the Cu₂(OH)₃Cl and CuCl₂ was not identified. The sample developed after treating of the cooper surface in the sodium/magnesium chloride solution contains Cu₂(OH)₃Cl and CuCl₂ prevailing over the Cu₂O, while the sample developed after treatment of copper in sodium/calcium chloride solution contains Cu₂(OH)₃Cl prevailing over CuCl₂ and Cu₂O was not identified.     

Chemical characterization and anticorrosion properties of corrosion products formed on pure copper in synthetic rainwater of Rio de Janeiro and São Paulo

This work aims to characterize corrosion products formed on copper samples exposed to synthetic rainwater of Rio de Janeiro and São Paulo. XRD and XPS were employed to determine their composition, while electrochemical techniques were used to evaluate their protective properties. XRD and XPS indicated the thickening of the corrosion layer with time. Electrochemical results showed that the protectiveness of the corrosion layer depends on the solution composition. Based on our findings a corrosion mechanism for copper in simulated rainwater is proposed where the role of NH₄⁺ ions in the cuprite layer partial regeneration is taken into account.     

Characterization of corrosion products on chalcographic copper plates after 200 years' exposure to indoor atmospheres

This work studies the characterization of corrosion products formed on six eighteenth century chalcographic copper plates preserved in the National Chalcography Collection in the San Fernando Royal Academy of Fine Arts in Madrid. The experimental methods used were X-ray diffraction analysis (XRDA), Infrared spectroscopy (IRS), Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). The main compounds found were malachite CuCO₃ · Cu(OH)₂, atacamite CuCl₂· 3Cu(OH)₂, nantokite CuCl, tenorite CuO, and cuprite Cu₂O. Cuprite is the main compound found on the smooth areas of chalcographic plates, forming tarnish films. The thickness of the tarnish films is approximately 10–15 Å.     

Cathodic reduction of the duplex oxide films formed on copper in air with high relative humidity at 60 °C

The cathodic reduction of duplex air-formed oxide film on copper was performed at a constant current density of i_c = −50 μA cm⁻² in deaerated 0.1 M KCl solution to investigate the sequence of cathodic reduction of each oxide layer and its mechanism. The single-phase thick CuO film on copper was also cathodically reduced at i_c = −50 μA cm⁻² or −2.5 mA cm⁻². The surface characterizations of the air-formed oxide film and single-phase CuO film before cathodic reduction and after partial or complete cathodic reduction were performed by XPS and X-ray diffraction, respectively.The two plateau regions appeared in the potential vs. time curve during cathodic reduction of the duplex air-formed oxide film on copper, while one plateau region was observed in the potential-time curve during cathodic reduction of the single-phase CuO film on copper. The potential in the first plateau region for the air-formed film coincided with that in the plateau region for the CuO film. The results of XPS and X-ray diffraction suggested that in the first plateau region, the outer CuO layer is directly reduced to metallic Cu, while in the second plateau region, the inner Cu₂O layer is reduced to metallic Cu.     

Surface characterization and corrosion behavior of a novel gold-imitation copper alloy with high tarnish resistance in salt spray environment

A novel gold-imitation copper alloy (CuZnAlNiSnBRe) was designed and its corrosion behavior in salt spray environment was investigated. The new alloy has better tarnish resistance and corrosion resistance than the current coinage alloy used in China (H7211). A multi-layer film formed on the surface of the new alloy after a period of exposure to salt spray was responsible for the good resistance of the alloy. The corrosion products were a mixture of CuO, Cu₂O, ZnO, Al₂O₃ and Al(OH)₃, with the transition from Cu₂O to CuO occurring during the corrosion process.     

A study of the initial oxidation of copper in 0.1 MPa oxygen and the effect of purity by metallographic methods

To clarify the initial oxidation mechanism of copper, the oxidation was carried out at 400 °C in 0.1 MPa oxygen using 99.9999% (6 N) and 99.5% (2 N) pure specimens. Oxidation of 6 N copper after 60 s showed that the number density of the oxide nuclei varied with the face of copper crystals, while the nucleation occurred preferentially at the grain boundaries. A metallographic examination indicated that the products of initial oxidation consist of both CuO and Cu₂O. CuO is firstly formed as a thin uniform film on the copper surface, and then Cu₂O nucleates and grows beneath the CuO film. This result is different from the conclusion reached in the literature that CuO does not appear until the laterally growing Cu₂O nuclei have covered the whole surface using other methods. In contrast to 6 N copper, nucleation of Cu₂O was much delayed for 2 N copper, though a thin CuO film was similarly formed on 2 N copper surface. Impurities in 2 N copper should be responsible for slow nucleation of Cu₂O and slow growth of nuclei.     

Surface characterization and corrosion behavior of 70/30 Cu-Ni alloy in pristine and sulfide-containing simulated seawater

The corrosion behavior of the 70/30 Cu-Ni alloy in stagnant, aerated pristine and sulfide-containing simulated seawater as a function of exposure time was investigated with polarization curve measurement and electrochemical impedance spectroscopy (EIS). It was demonstrated that the compact protective oxide film formed on the 70/30 Cu-Ni alloy resulted in the decrease of corrosion rate in aerated pristine seawater; while the corrosion rate of 70/30 Cu-Ni alloy in aerated sulfide-containing seawater increased dramatically due to the catalysis of the sulfide ions or sulfide scale for both the cathodic and anodic reactions. The impedance spectra and the corresponding equivalent circuits confirmed that a duplex layer of a surface film was formed on the 70/30 Cu-Ni alloy in aerated pristine seawater after a period of time and that the inner layer was responsible for the good resistance of the alloy; while only a porous and non-protective corrosion product layer formed on the 70/30 Cu-Ni alloy in aerated sulfide-containing seawater, which made small values of charge transfer resistance (R_ct) to last for a abnormally long time by interfering with the growth of the protective oxide film. The composition of the surface film on the alloy in pristine and sulfide-containing seawater for different exposure times were investigated thoroughly by XPS. It was found that the duplex corrosion product layer formed on the alloy in pristine seawater was composed of an inner Cu₂O and an outer CuO layer. The porous and non-protective corrosion product layer formed on the alloy in aerated sulfide-containing seawater was a mixture of CuCl, Cu₂S, NiS, Cu₂O and NiO with trace amounts of CuO and Ni(OH)₂ and that the most significant component was Cu₂S. In addition, SEM was used to analyze the topography of the 70/30 Cu-Ni alloy in both solutions after different exposure times.     

Combinatorial corrosion study of the passivation of aluminium copper alloys

An Al_96.1–Cu_3.9 to Al_51.4–Cu_48.6 material library was obtained by thermal co-deposition and characterized by EDX and XRD. The crystallographic data reveals the presence of Al₂Cu and pure aluminium depending on the film composition and following the stoichiometry. Utilizing a scanning droplet cell setup, the zero current potential for anodization, the oxide formation factor and the dielectric constant of the oxide formed are presented with high resolution along the composition gradient.While the dielectric constant of the oxide formed remains nearly unaffected by the increasing copper content of the base material along the composition gradient, the zero current potential shows well defined steps between 6.9 and 8.5 at.% as well as between 20.9 and 26.7 at.% copper indicating an increased thickness of the native oxide present on the film. Additionally, starting around 25 at.% copper, oxygen evolution gradually superimposes the oxide growth and in turn significantly reduces the current efficiency for anodization. The formation of the intermetallic phase Al₂Cu was linked to both phenomena as it promotes the growth of native oxides and current leakage by oxygen evolution.     

The Effect of Impurities on the Formation of the Inner Porous Layer in the Cu2O Scale During Copper Oxidation

The effect of impurities on the formation of the inner porous layer in the Cu₂O scale during copper oxidation was examined using 99.99 (4N), 99.9999% (6N) and floating-zone-refined (FZR, >99.9999) copper specimens at 800° C. Oxidation for 240 min shows that an inner porous layer was formed in the Cu₂O scale near the Cu₂O/Cu interface for 4N copper, but not for 6N and FZR copper. The results support that the inner porous layer in the oxide scale is related to impurities from the metal base.     

The characterization of patina components by X-ray diffraction and evolved gas analysis

Fourteen patinated copper specimens, seven each from the Statue of Liberty, New York Habor and from roofs at AT&T Bell Laboratories in Murray Hill, NJ, ranged in atmospheric exposure from 1 to 100 years. X-ray diffraction showed the presence of cuprite, Cu₂O, and brochantite, Cu₄(SO₄)(OH)₆, in all specimens and antlerite, Cu₃(SO₄)(OH)₄ (up to 0.7 times brochantite), atacamite, Cu₂Cl(OH)₃ (up to 1.6 times brochantite), and/or posnjakite, Cu₄(SO₄)(OH)₆ · 2H₂O (up to 5.2 times brochantite) in some. Posnjakite has been previously reported as a patina component only once during short term exposures in Eurasia. It appears to be an early corrosion product which subsequently converts to brochantite. Mass spectrographic examination of gases emitted from heated patinas provides further information on patina composition, in particular on the presence of both carbonate and oxalate in widely varying ratios.