EIS monitoring study of atmospheric corrosion under variable relative humidity

Electrochemical impedance spectroscopy (EIS) technique was used to investigate atmospheric corrosion in laboratory simulated environments with variable relative humidity (RH) and fixed Cl⁻ content. The results show the suitability of EIS for analyzing electrochemical corrosion behaviour at 5-100% RH. At 5-30% RH, EIS spectra reflected the character of the electrode, whereas at 40-100% RH, the model of EIS spectra was established with the help of surface analysis. From 70% RH, the film resistance (R_r) reflects the degree of corrosion and the charge transfer resistance (R_t) provides quantitative representation of the corrosion rate, which were verified by weight loss tests.     

The influence of relative humidity and temperature on the acetic acid vapour-induced atmospheric corrosion of lead

The acetic-acid induced atmospheric corrosion of lead was studied at 22.0 °C and 30-95% RH and at 4 °C and 95% RH. The samples were exposed to synthetic air with careful control of relative humidity, temperature, acetic acid concentration (170 ppb) and flow conditions. Reference exposures were carried out in clean humid air. Samples were analysed by gravimetry, ion chromatography, quantitative carbonate analysis, ESEM and XRD. Traces of acetic acid vapour strongly accelerate the atmospheric corrosion of lead. The corrosion rate is only weakly dependent on relative humidity in the range 95-50% RH. The accumulated amount of acetate is independent of RH in the range 95-40%. Lead corrosion in humid air in the presence of acetic acid vapour exhibits a negative correlation with temperature. The crystalline corrosion products formed on lead in the presence of acetic acid vapour were lead acetate oxide hydrate (Pb(CH₃COO)₂ · 2PbO · H₂O) and massicot (β-PbO) together with plumbonacrite (Pb₁₀O(CO₃)₆(OH)₆) or hydrocerussite (Pb₃(CO₃)₂(OH)₂). The transformation of lead acetate oxide hydrate into hydrocerussite and vice versa was also studied. The mechanism of corrosion is addressed, and the implications of this study for combating the corrosion of lead organ pipes in historical organs are discussed.     

Atmospheric corrosion in Mauritius

Abstract

Carbon steel is commonly used in Mauritius, and information related to its atmospheric corrosion behaviour in the Mauritian atmosphere is not readily available. Hence, the present study was performed to obtain relevant data and to develop a model for predicting the atmospheric corrosion degradation of carbon steel in Mauritius. Carbon steel samples were exposed outdoors at several sites, according to BS EN ISO 8565. They were removed after specific time periods, and their mass loss was determined. At the same time, the sites’ environmental parameters were monitored. From the mass loss measurements and the environmental parameters considered, it was found that the corrosivity of the Mauritian atmosphere falls in category C3 to C4, according to ISO 9223. A model was developed using the SPSS software, and it was found that the atmospheric corrosion in Mauritius depends mainly on the time of exposure and the carbon content of carbon steel.     

An XPS study of copper corrosion originated by formic acid vapour at 40% and 80% relative humidity

Copper corrosion products originated by the action of formic acid vapours at 40% and 80% relative humidity for a period of 21 days were analysed. Three formic vapour concentration levels (10, 100 and 300 ppm) were generated in laboratory tests at 30°C. The corrosion product layers were characterised using X‐ray photoelectron spectroscopy (XPS) in conjunction with Ar⁺‐ion sputtering. The components identified in the patina layers were cuprite (Cu₂O), copper hydroxide (Cu(OH)₂) and copper formate (Cu(HCOO)₂). Copper formate was formed by a complex mechanism including copper hydroxide and formic acid.     

The effects of Cl ion concentration and relative humidity on atmospheric corrosion behaviour of PCB-Cu under adsorbed thin electrolyte layer

The effects of Cl⁻ ion concentration and relative humidity on atmospheric corrosion behaviour of PCB-Cu under adsorbed thin electrolyte layer were investigated by cathodic polarization curves and electrochemical impedance spectroscopy. Results indicated that the cathodic process of PCB-Cu corrosion was dominated by the reduction of oxygen and corrosion products. The cathodic current density increased with increasing relative humidity and Cl⁻ ion concentration. The corrosion rate was initially dominated by oxygen reduction, but at the later stage of corrosion, the anodic process began to affect the corrosion rate due to the accumulation of corrosion products.     

Monitoring corrosion rates and localised corrosion in low conductivity water

Monitoring of low corrosion rates and localised corrosion in a media with low conductivity is a challenge. In municipal district heating, quality control may be improved by implementing on-line corrosion monitoring if a suitable technique can be identified to measure both uniform and localised corrosion. Electrochemical techniques (LPR, EIS, crevice corrosion current) as well as direct measurement techniques (high-sensitive electrical resistance, weight loss) have been applied in operating plants. Changes in the corrosion processes are best monitored in non-aggressive, low conductivity media with sensitive electrical resistance technique and crevice corrosion current measurements.     

Atmospheric corrosion of carbon steel in Colombia

The corrosion behaviour of carbon steel at six test sites in Colombia and its relationship with exposure time and environmental characteristics of each site were investigated. The corrosion products were characterized by XRD, SEM and EDS. It was found that in Barranquilla, the most aggressive site, corrosion depends mainly on chlorides. Furthermore, in the more aggressive environments there was a greater tendency to formation of protective corrosion products. Lepidocrocite and goethite were found as major constituents of rust. A structure not reported in the literature was found, corresponding to strings of several hundred micrometers long and consisting of lepidocrocite plates.     

Atmospheric corrosion of zinc induced by runoff

Atmospheric corrosion and runoff of zinc were investigated during two years in humid tropical climate on hot dip galvanized steel and zinc samples. The high zinc mass loss (14.70 g m⁻²) is induced by the intensive zinc release (12.40 g m⁻²). No corrosion phase containing chloride was detected on the zinc surface, while a variety of sulfates not dissolved by rains reveals the sensitivity of zinc to SO₂ pollutant. However, two chloride-containing corrosion products were detected on the galvanized steel. Exponential equation is proposed that fits well the experimental data for zinc mass loss induced by runoff process as a function of the time of wetness. The formula gives possibility to predict the mass loss even before a steady state in the corrosion process has been reached. This equation can converge to a Benarie lineal function (C = At_w), when the coefficient b = 1 for the corrosion which is accelerated with the partial removal of the corrosion layer during the runoff phenomena.     

Atmospheric corrosion of splat cooled aluminum alloy foils

One aspect of pollution frequently ignored in studies is that of its influence on today’s industry. For additional information on pollution and control, see pages 41–47 in this issue.     

Atmospheric corrosion of nickel in various outdoor environments

As part of a field exposure program in the north-west of France on atmospheric corrosion of metal and alloys, this study presents the results of the behaviour of nickel panels exposed in industrial, urban and rural atmospheres. Mass measurements were investigated during the exposure and adherent corrosion layers were followed by means of several methods of analysis: Fourier transform infrared reflection-absorption spectroscopy, X-ray diffraction and scanning electron microscopy with X-ray microanalysis. In order to determine all the chemical species formed in the corrosion layers, corrosion products released from the surface by rainfall were also studied by collecting the streaming water from the nickel surfaces. Anionic and cationic quantities in the streaming water were determined respectively with ionic chromatography and polarography. The nickel attack appears as a pitting corrosion process accompanied by the formation of soluble corrosion products in dry exposure periods, these being regularly dissolved by rainfall events. Pits are associated with the formation of nickel salts, mainly sulphates and chlorides with small amounts of nitrate, and surrounded by carbonate species. The corrosion rate increases from rural to industrial areas.     

不同土壤湿度下硫酸盐还原菌对锌腐蚀的影响

利用微生物分析、交流阻抗测试技术等方法 ,研究了在不同湿度的同一类型土壤中硫酸盐还原菌对纯锌腐蚀的影响。结果表明 :土壤湿度对菌类生长的影响是显著的 ,硫酸盐还原菌量随着湿度的提高有递增现象 ;在不同的湿度下 ,接菌土壤中纯锌腐蚀速率和点蚀深度都明显大于灭菌土壤 ;随着含水量的增大 ,纯锌腐蚀速率也增大 ,当土壤含水量增大到 10 %～ 15 %时 ,腐蚀速率达到最大 ,然后腐蚀速率随着湿度增大而趋于减小 ;纯锌在接菌及灭菌土壤中的阻抗图谱均表现为单容抗半圆 ,在接菌土壤中阻抗值及阻抗半圆均比在灭菌土壤中小很多 ,说明硫酸盐还原菌增大了纯锌在土壤中的腐蚀速率。     

Monitoring Atmospheric corrosion with electrochemical methods in laboratory environment

An atmospheric corrosion monitor (ACM) has been developed for monitoring atmospheric corrosion of Zn-coated iron and tin and SnPb coated copper in salt spray and hot steam atmosphere using the electrochemical technique of polarization resistance R_p. ACM for Sn and SnPb coatings is made using the printed circuits technology. The measurement of atmospheric corrosion using the R_p principle and the impulse galvanostatic method, is a novelty in the atmospheric corrosion studies. The method is fast, sensitive, non-destructive and suitable for all the anodic and cathodic coatings used on metals.     

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.     

Atmospheric corrosion of field-exposed magnesium alloy AZ91D

The magnesium alloy AZ91D was exposed in three different types of atmospheric environment, viz. urban, rural and marine exposure sites. Corrosion rates, corrosion products formed, and the influence of the microstructure on the corrosion behaviour of the alloy were investigated. The corrosion rate of AZ91D exposed in the marine environment was 4.2 μm/year, and in the rural and urban environments 2.2 and 1.8 μm/year, respectively. The main corrosion product found was magnesium carbonate hydromagnesite (Mg₅(CO₃)₄(OH)₂·4H₂O), which was formed at all three exposure sites. The corrosion attack started in the -phase in larger grains at the boundary between the -phase and the eutectic -/β-phase. Microgalvanic elements were formed with the eutectic -/β-Mg phase as cathodic site and the -Mg grains as anodes. The Al–Mn particles played a minor roll in the initiation process, even though these particles are the most noble in the microstructure and thus the driving force for a corrosion attack around these particles could be expected to be high. A close resemblance was observed between the corrosion mechanisms operating under the field-exposure conditions described here and the mechanisms operating under the previously reported laboratory conditions.     

Atmospheric corrosion of zinc Part 2: Marine atmospheres

Abstract

This paper summarises the results obtained in the MICAT (Mapa Ibero-Americano de Corrosão Atmosférica (Latin American Map of Atmospheric Corrosion)) atmospheric corrosion project (an Iberoamerican project on atmospheric corrosion, involving 14 countries and 75 atmospheric test sites) for zinc specimens exposed in the Latin American region for 1–4 years at 23 pure marine and 19 mixed marine (i.e. SO₂ polluted) sites. The atmospheres at these sites were characterised climatologically and in terms of their pollution levels so that their corrosivity could be expressed in accordance with ISO standards. Morphological and chemical characterisation of the zinc corrosion product layers (ZCPLs) was performed using scanning electron microscopy coupled with energy dispersive spectrometry (SEM–EDS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and soluble salt evaluation techniques. The results obtained show that the corrosion rate of zinc is a function of both the chloride pollution level and the time of wetness. Some synergetic effects of Cl^- and SO₂ were demonstrated, although some special types of behaviour were also observed.     

Atmospheric corrosion of zinc Part 1: Rural and urban atmospheres

Abstract

This paper summarises the results obtianed in the MICAT (Mapa Ibero-Americano de Corrosão Atmosférica (Latin American Map of Atmospheric Corrosion)) atmospheric corrosion project (an Iberoamerican project on atmospheric corrosion, involving 14 countries and 75 atmospheric test sites) for zinc specimens exposed for 1–4 years in 21 rural and urban atmospheres of the Latin American region. During the study, all of these atmospheres were characterised according to international standards. Complementary morphological and chemical studies were carried out using scanning electron microscopy coupled with energy dispersive spectrometry (SEM–EDS), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) techniques, in order to correlate atmospheric characteristics and the properties of zinc corrosion product layers (ZCPLs). Soluble salts retained in these ZCPLs were also determined. The study has provided clear evidence about the wide range of zinc corrosion rates occurring in rural atmospheres and suggests an interpretation of this behaviour.     

Atmospheric corrosion behaviour of 30CrMnSiA high-strength steel in rural,industrial and marine atmosphere environments

The atmospheric corrosion behaviour of 30CrMnSiA high-strength steel exposed in rural, industrial and marine atmosphere environments in China for 60 months was investigated in virtue of the weight loss, X-ray diffractometer (XRD), scanning electron microscope (SEM) and grey relational analysis. The results showed that 30CrMnSiA high-strength steel exhibited the highest corrosion susceptibility and the lowest corrosion susceptibility in marine atmosphere environment and rural atmosphere environment, respectively. Lepidocrocite and goethite were found as the major constituents of the rust layer in three types of atmosphere environments, and akaganeite was also detected in marine atmosphere environment. The rust layer exhibited the tendency of flaking away from the substrate and becoming dense in marine atmosphere environment and rural atmosphere environment, respectively. Grey relational analysis demonstrated that, among a variety of environmental factors, the airborne sea-salt was the primary factor influencing the atmospheric corrosion of 30CrMnSiA high-strength steel.     

Comparison of corrosion rates obtained from laboratory and field data

Generally, corrosion rates for sheet pile walls observed in nature and those obtained in the laboratory are different. In order to compare natural and laboratory corrosion rates, corrosion tests were carried out with an electrochemical corrosion cell. Various mild steel samples which were taken out from different sheet pile structures were examined with synthetic brackish water and synthetic seawater as immersion media. It was ensured that the electrical conductivity and the pH‐values were identical to those of the natural waters from which the sheet pile samples came from. The experimental results indicate that underwater corrosion rates in nature are only about one tenth to one eighth of the laboratory values. The corrosion rates in nature depend on the media and the corrosion zone. Furthermore, in laboratory test procedures, the initial corrosion is always tested whereas in nature a “protecting” layer of rust is formed, that lowers corrosion. Therefore, comparison of the values of the experiments with those from nature should be defined in accordance to age and zone of hydraulic steel structures. As a consequence, a corrosion coefficient with consideration of the age of structures was formed. The introduction of the coefficients's dependence on the lifetime of the construction allows improved corrosion rate predictions when the chemical composition of the immersion media is detected.     

Quantitative study of exfoliation corrosion: Exfoliation of slices in humidity technique

A new technique, exfoliation of slices in humidity (ESH), was developed for the determination of exfoliation corrosion (EFC) susceptibility and quantification of EFC kinetics. Two AA7178 plates taken from the wingskin of a retired KC135 airplane were used as test samples. Slices of the plate were pretreated by potentiostatic polarization in chloride solution to develop localized corrosion sites. Subsequent exposure to high humidity after pretreatment of properly oriented and unconstrained samples resulted in the development of EFC at the edges of the slices. The EFC kinetics were determined by measuring the width of the central unattacked region of the samples. The ESH results were representative of the different EFC behavior of the two plates during outdoor exposure. These results show the capability of the ESH test to discriminate between plates of varying susceptibility and to determine EFC rates quantitatively. The different susceptibility of the two plates to EFC was attributed to differences in microstructure and grain boundary chemistry.