Differences between corrosion products formed on copper exposed in Tokyo in summer and winter

We analyzed the copper corrosion products that formed during a month in summer and a month in winter at three sites in Tokyo using several analytical techniques. The X-ray diffraction patterns revealed that cuprite Cu₂O and posnjakite Cu₄SO₄(OH)₆·H₂O formed on copper exposed in summer. By contrast, only cuprite was found in winter exposed copper. The X-ray fluorescence results indicated that the amounts of sulfur and chlorine on the copper plates exposed in summer were much greater than those in winter. This could be explained by the change in particulate sulfate and sea salt concentrations. Depth profiling analysis by Auger electron spectroscopy revealed that the oxide layer formed in summer was thicker than that in winter. This difference in oxide layer thickness could have been due to the differences in temperature, relative humidity, and the amount of sulfur and chlorine on the copper plate.     

Influence of silicate ions on the formation of goethite from green rust in aqueous solution

We investigated the influence of silicate ions on the formation of goethite converted from hydroxysulphate green rust, which was synthesized by neutralizing mixted solution of Fe₂(SO₄)₃ and FeSO₄ with NaOH solution, by O₂ in an aqueous solution. The pH and oxidation-reduction potential of the suspension and the Fe and Si concentrations in supernatant solutions were analyzed. X-ray diffraction results for the solid particles formed during the conversion were consistent with the results of the solution analyses. The results indicated that silicate ions suppressed the conversion from green rust to α-FeOOH and distorted the linkages of FeO₆ octahedral units in the α-FeOOH structure.     

Influence of carbon content and microstructure on corrosion behaviour of low alloy steels in a Cl containing environment

Corrosion behaviour of low alloy steels (A and B) with different carbon content was studied by a salt fog test and an outdoor test. A commercial weathering steel 09CuPCrNi was used for comparison. The corrosion resistance of steels A and B with homogeneous microstructures was better than that of the commercial weathering steel 09CuPCrNi in the salt fog test. Steel A with an ultra-low-carbon content had far less weathering resistance than the other steels in the outdoor test. Selective corrosion of large pearlite produces stress in initial corrosion product films. Uniform corrosion product films with few cracks tend to form on homogeneous microstructures such as ferrite and bainite, and this is advantageous for the formation of a compact rust layer in the initial stage of atmospheric corrosion. However, uniform microstructures will result in over even interfaces between rust layers and bases, which will lead to frequent peeling of rust layers from bases because stress is induced by large temperature fluctuations and wet-dry alternations. Protection of the rust layer on a low alloy steel is dependent on the rust density and the bonding performance of the rust-base rather than the proportion of the rust phase in the initial stage of atmospheric corrosion. These results indicate that homogenous microstructures, proper amounts of carbon content and fine carbon-rich phases that are produced by appropriate processes are beneficial for the corrosion resistance of steels.     

Raman mapping of corrosion products formed onto spring steels during salt spray experiments. A correlation between the scale composition and the corrosion resistance

There is a growing trend in the automotive industry to reduce vehicles weight so as to increase fuel efficiency and therefore reduce CO₂ emissions. For many automotive components such as springs, weight reduction is sought through an increase in the mechanical properties (allowing smaller components size).For ultra high strength springs, a good corrosion resistance becomes essential to avoid surface damage that will be detrimental to the corrosion-fatigue resistance. Corrosion-fatigue failures indeed often initiate on surface defects caused by corrosion in service (corrosion pits). Therefore, while of moderate importance in conventional spring steels, the corrosion resistance of ultra high strength spring steels is of primary importance.Fine changes in steel chemical composition can have an important effect on corrosion resistance. To understand the individual action of each element on the corrosion resistance of spring steels, corrosion products formed on samples exposed to NaCl environments were characterized using Raman spectroscopy, in a purposely designed experimental tool that allows mapping of corrosion products on the steel surface (by nature and mass fraction).Different steel grades were thus characterized after accelerated corrosion tests, and a clear correlation was established between weight loss and the nature of the corrosion products.     

Tracing correlations of corrosion products and microclimate data on outdoor bronze monuments by Principal Component Analysis

Although the corrosion of outdoor bronzes has been extensively studied for the last decades, there is no quantitative correlation of corrosion products to microclimatic factors. The present work aims to demonstrate how Principal Component Analysis (PCA) can serve this purpose. Thirty corrosion product samples were collected from the bronze monument of Theodoros Kolokotronis (Nafplio, Greece) and analysed using X-Ray Diffractometry (XRD). The quantitative XRD data together with data on surface orientation and exposure to rain or wind were treated by PCA and three distinct groups were found. Each group includes samples of similar composition and microclimate characteristics showing that PCA may give useful information on corrosion mechanisms.     

The effect of synthetic zinc corrosion products on corrosion of electrogalvanized steel. II. Zinc reactivity and galvanic coupling zinc/steel in presence of zinc corrosion products

The reactivity of zinc under synthetic zinc patinas and the galvanic coupling in steel/patina/Zn are studied. Zn₅(OH)₆(CO₃)₂ and Na₂Zn₃(CO₃)₄⋅3H₂O inhibit zinc anodic dissolution in NaCl, while Zn₅(OH)₈Cl₂ H₂O and Zn₄(OH)₆SO₄ nH₂O do not. The galvanic current in steel/patina/NaCl/Zn is smaller as compared to steel/NaCl/Zn. The inhibiting effect decreases with time for Na₂Zn₃(CO₃)₄⋅3H₂O or Zn₄(OH)₆SO₄ nH₂O due to the transformation into Zn(OH)₂. In NaHCO₃, the polarity between zinc and steel can reverse. The effect of confinement on the cathodic current is stronger than the initial effect of patina which is explained by the instability of the patinas under rapid pH-increase.     

Role of climatic conditions on corrosion characteristics of structural steels

Corrosion behaviour of low alloy (LASS) and plain carbon (PCSS) structural steels exposed in different types of climatic conditions and nature of rust formed on their surfaces have been studied after 2 years of exposures. The test sites were chosen to represent four types of environments who strongly influence the corrosion of metals and alloys. They include (a) humid-saline, (b) humid-saline-urban (c) humid-industrial and (d) plain dry-urban environments. Mass loss, Raman spectroscopy, scanning electron microscopy and electrochemical impedance spectroscopic studies have been performed to study the corrosion behaviour and characterise the nature of rusts formed on these steels. Mass loss measurement technique has been used to determine the loss of thickness of steels during their atmospheric and salt spray exposures. Results indicate that the corrosion rate of steels is strongly influenced by the climatic conditions prevailing at the exposure sites. The presence of SO₂ and salinity in the environments change the structure and protective properties of rust formed on the steels’ surface. Electrochemical impedance and cyclic polarisation studies of the steels in simulated environments have been performed to understand the mechanism of corrosion in different climatic conditions.     

Atomic-scale structure and morphology of ferric oxyhydroxides formed by corrosion of iron in various aqueous media

Fine particles of corrosion products consisting of one kind of ferric oxyhydroxide, either γ-FeOOH (lepidocrocite) or α-FeOOH (goethite), were directly prepared by dipping pure iron into aqueous solutions containing sodium chloride, sodium sulfate, or their mixed salts with sodium bicarbonate. Quantitative X-ray structural analysis using an in-house X-ray diffraction apparatus has been used for characterizing the atomic-scale structure of these ferric oxyhydroxide particles. The morphology of the γ-FeOOH and α-FeOOH particles was observed by transmission electron microscopy (TEM), and their bonding structures were analyzed using Fourier transform infrared spectroscopy (FT-IR). The realistic atomic-scale structures in the γ-FeOOH and α-FeOOH particles were estimated by fitting the interference functions with the help of the reverse Monte Carlo (RMC) simulation technique. The results showed that the linkages of fundamental FeO₆ octahedral units in the particles were deviated from the ideal crystal structure. The structural deviation is believed to be due to the incorporation of foreign anions during the formation of these particles in the aqueous solutions. The resultant atomic-scale structures in the γ-FeOOH and α-FeOOH particles were correlated with their morphology and bonding structure.     

Indoor atmospheric corrosion in Cuba. A report about indoor localized corrosion

Indoor weight loss of steel, chloride, sulphur compounds and dust deposition rate were determined in six storehouses having different characteristics. Relative humidity and temperature were determined in three storehouses. A model for indoor corrosion of steel depending on time of exposure and deposition of dust, sulphur compounds and chlorides is proposed. Dust deposition plays an important role indoors. The position of the sample has also a significant influence on corrosion. Indoor corrosion aggressivity in Cuban storehouses ranges in classification IC3 and IC4 according to the new ISO proposal of indoor aggressivity.A report about the presence of localized corrosion indoors (filiform like) using a special designed sample is made.     

The role of rusts in corrosion and corrosion protection of iron and steel

The processes of atmospheric corrosion of iron and steel and the properties of corrosion products (rusts) are modeled based on a quantitative evaluation of the chemical reactions pertaining to corrosion to elucidate the conditions with which corrosion-protective rust films form. Based on the model, it is suggested that in the initial stage of corrosion, in the rusts, the pH of the aquatic system is maintained at 9.31 owing to an equilibrium with iron(II) hydroxide and the rate of air-oxidation at this pH is very fast, and that dense, self-repairing rust films form, protecting the underlying iron and steel. However, after corrosion stops, the rust film deteriorates due to the dissolution and shrinkage by aging, and the deteriorated rust film separates the anode and cathode reaction products (Fe²⁺ and OH⁻ ions) to cause crevice corrosion. The air-oxidation of iron(II) in anode channels without the presence of OH⁻ ions results in strongly acidic solutions (pH 1.41), causing acid-corrosion. It is proposed that good catalysts (e.g. copper(II) and phosphate ions) accelerate the air-oxidation at low pH, delaying the crevice- and acid-corrosion stages. Further, it is argued that iron compounds with negative charges due to the non-stoichiometric proportions of the lattice oxide ions and metal ions (solid oxoanions of iron) exhibit stable cation-selective permeability even with a drop in pH. Rust films including such compounds would stop the passage of aggressive anions and act to protect iron and steel.     

Assessment of protective function of steel rust layers by N2 adsorption

The specific surface area (SA) of the rusts formed by exposing various kinds of steels in different situations was determined by N₂ adsorption. The SA values of the rusts increased with the increase of corrosion rate, implying that the rust layers with large SA exhibit a high resistance to corrosion. The suppression of rusting by compact rust layers was interpreted by the blockage of pores in rust layers by the adsorption and capillary condensation of water. The SA values clearly reflect the corrosion levels estimated by the external observation. It was convinced that the SA measurement is a universal quantitative technique to appraisal the protective function of rust layers.     

Structure and properties of Ti(IV)-doped zinc hydroxychloride rusts formed at various temperatures

To simulate the atmospheric corrosion of steels galvanized with Ti–Zn alloys under different atmospheric temperatures, Ti(IV)-doped zinc hydroxychloride (Zn₅(OH)₈Cl₂·H₂O: ZHC) was prepared at various aging temperatures of 6–120 °C. Adding the Ti(IV) inhibited the crystallization and particle growth of ZHC, showing a minimum at 50 °C. Higher aging temperature promoted the formation of TiO₂ nano-particles. Elevating the aging temperature suppressed the adsorption of H₂O and CO₂ on Ti(IV)-doped ZHC. These results suggest that the alloying Ti in galvanized steel forms compact zinc rust layer at various atmospheric temperatures in marine environment, which would lead to the enhancement of corrosion resistance.     

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.     

Characterization of AISI 4340 corrosion products using Raman spectroscopy

Most of the currently available corrosion product characterization techniques require extensive samples preparation methods and cannot be employed under aqueous conditions. Raman spectroscopy possesses the advantage of characterization of the corrosion products under practical operation conditions, including aqueous, without any sample preparation procedures. The present study examines the corrosion characteristics of AISI-4340 steel at aqueous and atmospheric environments using Raman spectroscopy. FeO, Fe₂O₃, and Fe₃O₄ were observed as the main corrosion products. The measured oxides thicknesses ratio were compared to the theoretic value obtained from Tammann equation.     

Time of wetness in tropical climate: Considerations on the estimation of TOW according to ISO 9223 standard

This work was focused on the discrepancies between the TOW determined according ISO 9223 standard and data obtained for indoor and outdoor conditions in humid tropical climate. It was observed that for temperatures higher than 25 °C the determination of TOW changed. Some proposals are made based on the results obtained in the present research conducted in Cuba and Mexico in order to improve the estimation of TOW. Such proposals take into account the linear relationship between time of exposure and TOW, the effect of rain, the role of air contaminants, temperature and the differences between outdoor and indoor exposure conditions.     

Morphology and phase composition of corrosion products formed at the zinc-iron interface of a galvanized steel

The corrosion products formed on the inner wall of pipes made of galvanized low carbon steel, exposed for ∼2 years to water flowing in a large household heating system, were analysed using X-ray diffraction, Mössbauer and Raman spectroscopic techniques, as well as metallographic techniques. Products grew in the form of large-sized tubercles that gradually developed causing base metal losses up to perforation of the steel pipe. Considerable differences in the phase composition were found between the products formed in contact with the steel and those constituting the outer part of tubercles. The former were mainly made of FeCO₃ (siderite), with small amounts of Zn₅(CO₃)₂(OH)₆ (hydrozincite), ZnCO₃ (smithsonite), (Fe,Zn)CO₃ mixed carbonate and CaCO₃ (calcite), the latter mainly by Fe(III) oxyhydroxide goethite. Both parts of the tubercles also contained small amounts of other ferric oxyhydroxides, γ-FeOOH (lepidocrocite) and β-FeOOH (akaganeite), and very small amounts of hematite. The procedures used proved effective for an adequate identification of both the iron-containing and iron-free compounds in the corrosion products as well as for suggesting a corrosion mechanism.     

Long-term corrosion resistance of metallic reinforcements in concrete—a study of corrosion mechanisms based on archaeological artefacts

This paper presents an analytical study on ferrous reinforcements embedded in binders found in ancient buildings aged from the Gallo-Roman period to the beginning of the 20th c. AD. The study of this kind of archaeological analogues is necessary to improve knowledge on the long-term corrosion behaviour of low carbon steels that could be used in concrete to build the substructure of nuclear wastes storage or reversible disposal facilities. The corrosion system can be described as a multi-layer pattern made of metal, a dense corrosion product layer, a transformed medium and a binder. The morphological, and physico-chemical properties like composition, structure and porosities of each part were studied with different analytical methods like optical and electronical microscopies, Energy Dispersive Spectrometry coupled with Scanning Electron Microscopy, Electron Probe MicroAnalysis, Mercury porosimetry, micro-Raman spectroscopy and micro-Diffraction under Synchrotron Radiation. Moreover, average corrosion rates were evaluated. These rates are relatively low compared to the same parameters measured on low alloyed contemporary steels and are comparable with corrosion rates noted for passivated systems.     

Influence of silicon on local structure and morphology of γ-FeOOH and α-FeOOH particles

The extended X-ray absorption fine structure (EXAFS) method was used for investigating the local structures of lepidocrocite and goethite with and without silicon. The structure and morphology of these particles were investigated using X-ray diffraction and transmission electron microscopy, respectively. The bonding structure was examined by Fourier transform infrared spectroscopy (FT-IR). When silicon species was added, the structure and morphology changed while the linkage of FeO₆ octahedral units was distorted. The FT-IR spectra revealed the formation of the Fe-O-Si bond in particles containing silicate ions, and the characteristic bond affects the local structure and morphology of the particles.     

The effect of oxygen partial pressure on the filiform corrosion of organic coated iron

An in-situ time-lapse optical microscopy study, using a novel dual-compartment cell is used to gain mechanistic understanding of filiform corrosion (FFC) affecting an organic-coated iron surface. The apparatus allows independent control of environments surrounding the filament head and tail regions. When oxygen-containing environments surround the filament head, an anterior cathodic arc is formed, constraining the filament head electrolyte. When oxygen is removed from the vicinity of the head, FFC propagation rates remain unchanged, although the constraining arc is not present. Maximum propagation is observed when oxygen is available for transport through the filament tail to the rear of the head.