Multianalytical in-situ investigations of the early stages of corrosion of copper, zinc and binary copper/zinc alloys

A new experimental infrared reflection absorption spectroscopy (IRRAS) set-up for in-situ investigation of corrosion phenomena occurring in the metal–atmosphere interface was developed. It was applied in combination with in-situ tapping-mode atomic force microscopy (TM-AFM) and phase detection imaging (PDI) to study the early stages of corrosion of pure copper and pure zinc as well as to determine the influence of increasing zinc contents in brass. Additionally, ex-situ secondary ion mass spectrometry (SIMS) investigations were carried out on the samples after exposure.The investigations were accomplished in synthetic air with 80% relative humidity (RH) and synthetic air with 80% RH and 250 ppb SO₂. The experiments showed that an increase of the zinc content in the brass alloy yields to an increase of the dimension of the corrosion features formed on the metal surface during weathering. Large features on top of smaller features were observed with TM-AFM on the surfaces exposed to SO₂-containing humidified air, which could be identified by IRRAS as metal sulphur compounds. Furthermore, an increased amount of physisorbed water on the metal surfaces was determined with IRRAS in dependence of the increasing zinc content in the brass samples.     

Corrosion product formation during NaCl induced atmospheric corrosion of magnesium alloy AZ91D

Magnesium alloy AZ91D was exposed in humid air at 95% relative humidity (RH) with a deposition of 70 μg/cm⁻² NaCl. The corrosion products formed and the surface electrolyte were analysed after different exposure times using ex situ and in situ FTIR spectroscopy, X-ray diffraction and Ion Chromatography. The results show that magnesium carbonates are the main solid corrosion products formed under these conditions. The corrosion products identified were the magnesium carbonates hydromagnesite (Mg₅ (CO₃)₄ (OH)₂4H₂O) and nesquehonite (MgCO₃ 3H₂O). The corrosion attack starts with the formation of magnesite at locations with higher NaCl contents. At 95% RH, a sequence of reactions was observed with the initial formation of magnesite, which transformed into nesquehonite after 2-3 days. Long exposures result in the formation of pits containing brucite (Mg(OH₂)) covered with hydromagnesite crusts. The hydromagnesite crusts restrict the transport of CO₂ and O₂ to the magnesium surface and thereby favour the formation of brucite. Analysis of the surface electrolyte showed that the NaCl applied on the surface at the beginning was essentially preserved during the initial corrosion process. Since the applied salt was not bound in sparingly soluble corrosion products a layer of NaCl electrolyte was present on the surface during the whole exposure. Thus, Na⁺ and Cl⁻ ions can participate in the corrosion process during the whole time and the availability of these species will not restrict the atmospheric corrosion of AZ91D under these conditions. It is suggested that the corrosion behaviour of AZ91D is rather controlled by factors related to the microstructure of the alloy and formation of solid carbonate containing corrosion products blocking active corrosion sites on the surface.     

Role of second phases in the stress corrosion cracking of a nickel-aluminium bronze in saline water

We investigated the role of second phases in the stress corrosion cracking of a complex copper-aluminium alloy CuAl₉Ni₃Fe₂. We conducted slow strain rate tensile tests in synthetic sea water. Cracking is mainly intergranular. The crack path is determined by the electrochemical interactions between the α matrix and the second phases. We observe the selective dissolution of the aluminium rich areas that are anodic with respect to the α matrix. Under cathodic polarisation, the detrimental effect on mechanical properties is enhanced. The number of cracks is reduced. Crack blunting by dissolution is impeded.     

Indoor atmospheric corrosion of copper and steel under heat trap conditions in Cuban tropical climate

Abstract

Corrosion behaviour of copper and steel under heat trap conditions in Cuban tropical climate is reported. Temperature and humidity reach higher values than those reported for traditional outdoor and indoor conditions. Annual calculated time of wetness is in the range corresponding to outdoor or ventilated sheds. This behaviour is not reported for other indoor conditions. Sulphur compounds deposition rate is higher than chloride deposition rate at all corrosion stations. Main corrosion products formed on steel and copper are goethite and brochantite respectively. No significant differences in the statistical influence of exposure time and time of wetness on atmospheric corrosion process of copper and steel under heat trap conditions are determined.     

Quantitative determination of corrosion products and adsorbed water on copper in humid air containing SO2 by IR-RAS measurements

The time dependency of the amounts of corrosion products and co-existing adsorbed water on copper in humid air containing SO₂ was estimated from a series of in situ time-resolved IR-RAS spectra on the basis of the relations between the band intensities and the mass changes of the corrosion products, which were determined by simultaneous measurement of IR-RAS and QCM. The amounts of both corrosion products increased slowly at the initial stage and later increased rapidly. Although the relative humidity was kept constant, the amount of adsorbed water increased nearly the same behavior as that of corrosion products in the stage of relatively small amounts of corrosion products and later increased rapidly when the amounts of corrosion products increased. In humid air without SO₂, sulfite gradually decomposed and some of it changed into sulfate.     

Studies on the initial stages of zinc atmospheric corrosion in the presence of chloride

A four-year exposure program was carried out in Taiwan in which 23 test sites with different climatic and pollution conditions were chosen and evaluated according to ISO standards 9223-9226. Examination of the results indicated that most of the tests sites were very corrosive to zinc specimens and there was a severe white rust problem for freshly galvanized items stored in high humidity outdoors environments. In addition, the initial stages of zinc atmospheric corrosion in the presence of chloride were studied quantitatively in a non-aqueous electrolyte (methanol) using ex situ electrochemical impedance spectroscopy (EIS) to determine polarization resistance (R_p). The samples were exposed to the synthetic atmospheres with careful controlled relative humidity, temperature, and contaminating salts. It was observed that a change of R_p was accompanied by a change in the corrosion product on the zinc surface, and that the R_p increased with relative humidity (RH) during pre-exposure. Furthermore, the corrosion products of zinc were analyzed qualitatively by grazing-angle X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. Zinc hydroxycarbonate (Zn₅(CO₃)₂(OH)₆) and zinc oxide (ZnO) in this surface layer were found to provide protection against chloride contaminants.     

The atmospheric corrosion of copper by hydrogen sulphide in underground conditions

The atmospheric corrosion of copper by hydrogen sulphide has been followed during field tests using different sulphide concentrations, for 77 days, and during exposure to a well-defined synthetic atmosphere in a test chamber. The main components formed at the surface of the samples are copper oxides and sulphide. We show that exposure tests performed for short times in synthetic atmospheres cannot be extrapolated to long time exposure in real conditions, since three successive phases of film growth are observed. The mechanism of film growth is discussed, assuming that cationic diffusion through the cuprous oxides and sulphide is the rate-determining step.     

A microscopic study of the effects of particle size and composition of atmospheric aerosols on the corrosion of mild steel

A novel approach to measure the corrosion effects of aerosols as a function of their aerodynamic size and chemical composition was used to study the effects of atmospheric aerosols on mild steel at a rural coastal site. The technique uses collocated micro-orifice uniform deposition impactor samplers to deposit ambient atmospheric particles on exposure steel coupons and collect aerosol samples for ionic analyses. Rusts were found on the coupons with aerosols but none on the blank coupons even the blanks were incubated at the same conditions. FTIR analysis shows that the composition of rusts changes gradually with the aerosol particle size.     

A mechanistic study of initial atmospheric corrosion kinetics using electrical resistance sensors

This paper describes a novel experimental approach to the study of atmospheric corrosion of iron and zinc, utilising electrical resistance sensors that are sensitive to corrosion losses of the order of one atomic monolayer. Using such devices, a mechanistic study of the initial stages in the atmospheric corrosion of iron and zinc was performed in a rectangular flow cell using controlled relative humidity (RH), temperature and gas flow rate. Additionally, the effects of SO₂ contamination in the gas phase and prior NaCl contamination of the metal surface were studied. It was found that the initial corrosion kinetics of iron and zinc are, not unexpectedly, dominated by the development of surface corrosion product films, but that the growth kinetics vary with metal, humidity, etc. Specifically, in the presence of gas-phase SO₂, activation energies and kinetic and chemical rate orders were consistent with control of the atmospheric corrosion process by solution-phase oxidation of sulphite–sulphate ion. For iron, this implies that the well-known sulphate-nest theory is inoperative at least during the early stages of atmospheric corrosion. In contrast, for chloride–contaminated zinc, the data were consistent with a rate-controlled diffusion of a species, probably water vapour or oxygen, through a thickening corrosion product film. Finally, the kinetic and chemical rate orders for corrosion of chloride–contaminated iron precluded a diffusion-controlled mechanism, but were consistent with a rate-controlling process involving some regeneration of chloride: e.g. as in metal–ion hydrolysis in a pit or similar localised corrosion events.     

Characterization of atmospheric corrosion in Al/Ag lap joints

Lap joints fabricated using Al2024T3/commercially pure Ag sheet couples with nylon fasteners were exposed to standard field tests in a tropical marine atmosphere for a total period of six months. Atmospheric conditions were recorded using a weather monitoring station. Simultaneously, samples were also exposed in a salt spray chamber according to ASTM B117 and GM 9540P standards. Corrosion data was obtained for monthly intervals for both field and laboratory samples. Weight loss, pitting characteristics and the nature of the corrosion products were evaluated. Corrosion mechanisms based on the observed atmospheric corrosion phenomena are proposed.     

Effect of cations on corrosion of zinc and carbon steel covered with chloride deposits under atmospheric conditions

The effect of sodium, calcium, and magnesium chlorides deposited on zinc and carbon steel surfaces was studied under atmospheric conditions. The cations strongly affected the corrosion rate of zinc, whereas they had a significantly lower impact on the corrosion of carbon steel. The corrosivity of cations of chloride salts for zinc increased in order of Mg²⁺ < Ca²⁺ < Na⁺. The higher corrosion resistance of zinc treated with calcium and magnesium chlorides was connected to prevention of formation of hydrozincite during zinc exposure in wet air. It was observed that zinc weight loss and the carbonate to simonkolleite ratio in corrosion products were correlating. The principal protective effect of bivalent cations can be seen in the decrease of pH of the surface electrolyte, which was caused by hydrolysis of such cations and subsequent formation of simonkolleite that blocked the cathodic sites.     

Comparative investigation into the corrosion of different bronze alloys suitable for outdoor sculptures

Several bronze alloys, suitable for production of outdoor sculptures, were developed in the frame of the European project “Eurocare-Bronzart”. The elemental composition of the alloys was searched to fulfil specific criteria such as: reduction of lead content, good resistance toward corrosion and aesthetic characteristics conformable to artistic purposes. After metallurgical characterization, the resistance toward corrosion was evaluated in artificial environments. Ageing experiments were performed in a salt spray cabinet and in a climatic chamber in the presence of a controlled concentration of SO₂. The Thin Layer Activation (TLA) method was applied to calculate the thickness loss of activated specimens exposed to artificial corrosive atmospheres. After artificial ageing experiments the surface of the materials was investigated by SEM-EDS techniques.The bronze alloys containing different percentage of nickel showed the best properties of resistance toward corrosion.     

The atmospheric corrosion of quaternary bronzes: The leaching action of acid rain

The effect of leaching rain on the corrosion behaviour of bronze UNSC83600 was investigated as to the influence of alloying elements (Cu, Sn, Zn, Pb) through dropping tests simulating a severe runoff condition with a solution reproducing natural acid rain. Corrosion was followed with time monitoring both samples and leaching solutions (up to 30 days) by SEM, EDS, Raman spectroscopy, XRD, AAS. The bronze patina behaves as a porous layer enriched in stable tin compounds allowing uniform dissolution of Cu, Zn and partly of Pb. Laboratory results are in good agreement with field studies of outdoor bronzes in unsheltered condition.     

Characterisation of initial atmospheric corrosion carbon steels by field exposure and laboratory simulation

The early stages of the evolution of atmospheric corrosion of carbon steels exposed in both a laboratory simulated and a natural atmosphere environment in Shenyang have been observed by in situ scanning electron microscopy. In the case of laboratory cyclic wet-dry tests, even though the chloride content level is very low, filiform corrosion is initiated in the early stage. The filiform corrosion grows in random directions, forming a network of ridges. White nodules nucleate and grow on the ridges during continued corrosion and eventually connect with each other to form the initial corrosion scale. Pits were also found on the surface beneath corrosion products. In the case of a natural atmospheric environment, both filiform corrosion and other localized corrosion, such as pitting and inter-granular attack take place in the initial stage. It is obvious that there is variety of localized corrosion in the initial stage of atmospheric corrosion.     

Degradation of galvanised iron roofing material in Tanzania by atmospheric corrosion

Abstract

Galvanised iron is popular in many applications, particular as a roofing material. However, just like other materials, especially metallic ones, it is prone to degradation by corrosion. In this particular study, the degradation of galvanised roof sheets was investigated at a coastal, urban and rural site in Tanzania, Africa. Samples were exposed to various outdoor environments over a period of 3 years. In addition, some accelerated laboratory investigations were conducted in different simulated air pollution environments in an artificial corrosion chamber constructed for this purpose to supplement the outdoor exposure tests. It was found that the combination of the tropical climate and increasing air pollution due to industrial development in the capital Dar-es-Salaam resulted in substantial atmospheric corrosion of the roof sheets, which eventually leads to failure and the necessity for replacement. The rural site had the lowest degree of atmospheric corrosion as expected. A combination of different corrosion products was identified as a result of the atmospheric corrosion by Raman and EDX analyses. The information gained from this investigation could be utilised to construct more durable structures requiring less frequent replacement and maintenance in future.     

Effect of direct current electric field on atmospheric corrosion behavior of copper under thin electrolyte layer

A thin layer electrochemical cell was successfully developed to study the atmospheric corrosion behavior of copper film in printed circuit board (PCB-Cu) under thin electrolyte layer (TEL) and direct current electric field (DCEF) by electrochemical impedance and electrochemical noise analysis. The electrochemical measurements and SEM morphologies after corrosion test indicate that DCEF decreases the corrosion of PCB-Cu under TEL. The corrosion rate and probability of pitting corrosion of PCB-Cu under DCEF decrease due to the electric migration of aggressive Cl⁻ ion out of working electrode surface.     

应用电化学方法原位研究薄液膜下青铜的大气腐蚀行为(英文)

采用阴极极化曲线、开路电位和电化学阻抗谱,监测青铜在不同薄液膜厚度下的大气腐蚀行为。阴极极化曲线结果表明,阴极极限电流密度随着液膜的减薄而增大。电化学阻抗谱结果表明,在腐蚀初期,腐蚀速率随着液膜的减薄而增加,这主要是由于腐蚀速率是由阴极过程控制的;随着时间的延长,腐蚀程度随着液膜厚度的变化从强到弱的趋势为:150μm,310μm,100μm,本体溶液,57μm。开路电位和电化学阻抗谱实验较好地再现了原位电化学腐蚀信息,且电化学结果与物理表征具有良好的一致性。     

Atmospheric corrosion of copper and the colour, structure and composition of natural patinas on copper

This paper describes the results of atmospheric corrosion testing and of an examination of patina samples from Brisbane, Denmark, Sweden, France, USA and Austria. The aim was threefold: (1) to determine the structure of natural patinas and to relate their structure to their appearance in service and to the atmospheric corrosion of copper; (2) to understand why a brown rust coloured layer forms on the surface of some copper patinas; (3) to understand why some patinas are still black in colour despite being of significant age. During the atmospheric corrosion of copper, a two-layer patina forms on the copper surface. Cuprite is the initial corrosion product and cuprite is always the patina layer in contact with the copper. The growth laws describing patina formation indicate that the decreasing corrosion rate with increasing exposure time is due to the protective nature of the cuprite layer. The green patinas were typically characterised by an outer layer of brochantite, which forms as individual crystals on the surface of the cuprite layer, probably by a precipitation reaction from an aqueous surface layer on the cuprite layer. Natural patinas come in a variety of colours. The colour is controlled by the amount of the patina and its chemical composition. Thin patinas containing predominantly cuprite were black. If the patina was sufficiently thick, and the [Fe]/[Cu] ratio was low, then the patina was green, whereas if the [Fe]/[Cu] ratio was approximately 10 at%, then the patina is rust brown in colour. The iron was in solid solution in the brochantite, which might be designated as a (copper/iron) hydroxysulphate. In the brown patinas examined, the iron was distributed predominately in the outermost part of the patina.     

Advances in understanding atmospheric corrosion of iron. I. Rust characterisation of ancient ferrous artefacts exposed to indoor atmospheric corrosion

Metallic substrates and rust layers of several hundred year old (y.o.) ferrous artefacts were characterised. Composition, structure and porosity of the rust were analysed by different methods: OM, SEM, EDS, EPMA, XRD, μXRD, SAXS, BET and mercury porosimetry.Several important parameters to describe an old rust layer were determined and measured. These parameters will be used for the modelling of long-term indoor atmospheric corrosion.