Formation of Fe(III)-containing mackinawite from hydroxysulphate green rust by sulphate reducing bacteria

The interactions between Fe(II–III) hydroxysulphate GR() and sulphate reducing bacteria (SRB) were studied. The considered SRB, Desulfovibrio desulfuricans subsp. aestuarii ATCC 29578, were added with GR() to culture media. Different conditions were envisioned, corresponding to various concentrations of bacteria, various sources of sulphate (dissolved  + GR() or GR() alone) and various atmospheres (N₂:H₂ or N₂:CO₂:H₂). In the first part of the study, CO₂ was deliberately omitted so as to avoid the formation of carbonated compounds, and GR() was the only source of sulphate. Cell concentration increases from 4 × 10⁷ to 7 × 10⁸ cells/mL in 2 weeks. The evolution with time of the iron compounds, monitored by Raman spectroscopy and X-ray diffraction, showed the progressive formation of a FeS compound, the Fe(III)-containing mackinawite. This result is consistent with the association GR()/SRB/FeS observed in rust layers formed on steel in seawater. In the presence of CO₂ and additional dissolved sulphate species, a rapid growth of the bacteria could be observed, leading to the total transformation of GR() into mackinawite, found in three physico-chemical states (nanocrystalline, crystalline stoichiometric FeS and Fe(III)-containing), and siderite FeCO₃.     

Formation of the Fe(II)-Fe(III) hydroxysulphate green rust during marine corrosion of steel

Rust layers formed on steel sheet piles immersed 1 m above the mud line for 25 years were analysed by Raman spectroscopy, scanning electron microscopy and elemental X-ray mappings (Fe, S, O). They consist of three main strata, the inner one mainly composed of magnetite, the intermediate one of iron(III) oxyhydroxides and the outer one of hydroxysulphate green rust GR(SO₄²⁻). Simulations of GRs formation in solutions having large [Cl⁻]/[SO₄²⁻] ratios revealed that the hydroxysulphate GR(SO₄²⁻) was obtained instead of the hydroxychloride GR(Cl⁻), as demonstrated by X-ray diffraction and transmission Mössbauer spectroscopy analyses. Measurements of the [S], [Fe] and [Cl] concentrations allowed us to establish that GR(SO₄²⁻) formed along with a drastic impoverishment of the solution in sulphate ions; the [Cl⁻]/[SO₄²⁻] ratio increased from 12 to 240. The GR, acting like a “sulphate pump”, may favour the colonisation of the rust layers by sulphate reducing bacteria.     

Coprecipitation thermodynamics of iron(II-III) hydroxysulphate green rust from Fe(II) and Fe(III) salts

Iron(II-III) hydroxysulphate GR(SO₄²⁻) was prepared by precipitating a mixture of Fe(II) and Fe(III) sulphate solutions with NaOH, accompanied in most cases by iron(II) hydroxide, spinel iron oxide(s) or goethite. Its [Fe(II)]/[Fe(III)] ratio determined by transmission Mössbauer spectroscopy was 2±0.2, whatever the initial [Fe(II)]/[Fe(III)] ratio in solution. Proportion of Fe(OH)₂ increased when the initial [Fe(II)]/[Fe(III)] ratio increased, whereas proportion of α-FeOOH or spinel oxide(s) increased when this ratio decreased. GR(SO₄²⁻) is metastable vs. Fe₃O₄ except in a limited domain around neutral pH. Precipitation from solutions containing both Fe(II) and Fe(III) dissolved species seems to favour GRs formation with respect to stable systems involving iron (oxyhydr)oxides.     

Mechanisms of long-term anaerobic corrosion of iron archaeological artefacts in seawater

An iron ingot immersed during 2000 years at 12 m depth in the sea has been examined with the help of a combination of microscale techniques. This methodology allowed us to show that the main phase precipitated during the immersion is an iron hydroxychloride (β-Fe₂(OH)₃Cl) that is characteristic of corrosion in anoxic and chlorinated medium. Moreover locally on the external part of the corrosion products sulphur containing phases have been identified as mackinawite (FeS) in nanocrystalline or slightly oxidised state. The presence of this phase could be explained by the activity of sulphate-reducing bacteria. The presence of β-Fe₂(OH)₃Cl could be interpreted via a thermodynamic modelling taking into account the environmental conditions.     

Characterizing the effect of carbon steel exposure in sulfide containing solutions to microbially induced corrosion

This article compares the electrochemical effects induced by inorganic sulfide and sulfate reducing bacteria on the corrosion of carbon steel – a subject of concern for pipelines. Biological microcosms, containing varying concentrations of bioorganic content, were studied to investigate changes to the morphology of biofilms and corrosion product deposits. Raman analysis indicated mackinawite (FeS_1−x) was the dominant iron sulfide phase grown both abiotically and biotically. A fascinating feature of biological media, void of an organic electron donor, was the formation of putative nanowires that may be grown to acquire energy from carbon steel by promoting the measured cathodic reaction.     

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.     

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.     

Weatherability of 09CuPCrNi steel in a tropical marine environment

The stability of weathering steel (09CuPCrNi) exposed at tropical marine environments for varied periods was investigated. The synergistic effect of exposure environment and alloy elements on weatherability was also studied. The classical weight loss method was used to evaluate weatherability, while the iron rust layers formed on weathering steel under different conditions were analyzed by using Infrared spectroscopy (IR), electron probe of mass analysis (EPMA) and electrochemical techniques. The results show that under low chloride deposition, the enrichment of Cr plays an important role on improving weatherability; conversely chloride ion is primary factor to whittle weatherability in high chloride deposition.     

A proposal to evaluate the amount of corroded iron converted into adherent rust in steels exposed to corrosion

To calculate the amount of iron corroded from the steels that form part of the adherent rust, α, we propose a procedure that considers mass measurements and the use of spectroscopic techniques to estimate the relative iron phase abundances. We derived an equation to calculate α and evaluate it for carbon steels (CS) and weathering steels (WS) exposed to accelerated outdoor corrosion tests. The values of α are estimated at 0.93 and 0.76 for CS and WS after 2 years of exposure, respectively. The relative iron phase abundances pointed out to a non-protective and active type of rust.     

Influence of silicon species on the transformation of green rust I(Cl) in aqueous solution by oxidation

X-ray diffraction (XRD) and solution analysis were used for characterizing the influence of different silicon species on oxidation of green rust (GRI(Cl⁻)) suspension. While addition of silicon to metallic iron enhanced the formation of β-FeOOH, GRI(Cl⁻) in aqueous solution oxidized into lepidocrocite and oxidation was delayed in presence of silica and silicate species as noticed from potential, pH, and dissolved oxygen (DO) measurements. Transmission electron micrographs showed that the particle size of lepidocrocite was reduced due to silicate addition. The influence of silicate was attributed to its adsorption on GRI(Cl⁻) and lepidocrocite particles as confirmed from ICP-AES analysis of supernatant solution.     

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.     

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 outer rust layers on corrosion of carbon steel and weathering steel during wet–dry cycles

The influence of the rust layers of carbon steel and weathering steel on the corrosion were investigated. It was found that corrosion of carbon steel slows down when its outer rust layer is removed. This phenomenon might be attributed to the shortening of the wetting time in wet–dry cycles when the outer rust layers are removed. What is more, growth time of the corrosion products is shortened as well, which results in the formation of the fine corrosion products. However, the behavior of corrosion of weathering steel is not obviously influenced by the outer rust layer and the wetting time.     

Non-uniform distribution of rust layer around steel bar in concrete

The thickness of rusted layers at steel/concrete interface from a chloride-exposed reinforced concrete specimen was observed by digital microscopy. The non-uniform corrosion front is presented by a Gaussian function, the parameters in the model, including the non-uniformity coefficient, the spread coefficient, and the uniformity coefficient, are studied to describe the non-uniform distribute characters of rust layer. Comparing with the models proposed by other researchers, the Gaussian model can describe the non-uniform rust layer better. The location of corrosion peak along the perimeter of rebar and the condition for corrosion spreading across the entire circumference of rebar are discussed.     

Multianalytical approach to study the dissolution process of weathering steel: The role of urban pollution

Weathering steel, in spite of its resistance against the atmospheric corrosion can be damaged due to the affection of environmental stressors. In fact, the presence of soluble salts formed after greenhouse acid gases impact, can accelerate the corrosion process. In this work three weathering steel sculptures exposed to urban atmosphere were studied. Portable Raman assisted by reflectance infrared spectroscopy, micro X-ray fluorescence and ion chromatography were used to diagnose the decaying process suffered by these structures. The role of calcium sulfate formed in situ upon the reaction of SO₂ with calcite particles deposited on the surface of the sculptures was studied.     

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.     

Atmospheric corrosion of Ni-advanced weathering steels in marine atmospheres of moderate salinity

One conventional and three Ni-advanced weathering steels have been exposed for one year in two marine atmospheres of moderate aggressivity (30 and 75 mg Cl⁻/m² d). The rusts generated have been analysed by polarised light optical microscopy, SEM, XRD, Raman spectroscopy and Mössbauer spectroscopy.The presence of high nickel (1–3% weight) contents in the steel composition leads to higher corrosion resistance in moderate marine atmospheres. The presence of nickel in the weathering steel also raises the proportion of nanophasic (superparamagnetic) goethite in the inner rust layer.     

The atmospheric corrosion kinetics of low carbon steel in a tropical marine environment

The atmospheric corrosion kinetics of low carbon steel exposed for up to 36 months in marine and industrial sites was studied by weight loss measurements. The results show that the mechanism and kinetics of the atmospheric corrosion process presents transition behaviour in marine environments with high chloride ion content and high relative humidity, whereas no transition appears in industrial environment. The average corrosion velocity in marine site reaches a maximum during the period of transition and then fluctuates in a certain range; however, the instantaneous corrosion velocity follows different exponential functions before and after the period of transition.     

On the penetration of corrosion products from reinforcing steel into concrete due to chloride-induced corrosion

Reinforced concretes were corroded to varying degrees by exposing to cyclic NaCl spray and 40 °C drying. The amount of corrosion products and induced damage were measured using image analysis. We found that corrosion products can accumulate at steel-concrete interface as well as penetrate cement paste and deposit within hydration products, relicts of reacted slag, and air voids. As corrosion increases, the products tend to accumulate at the steel-concrete interface, while the amount penetrating cement paste remains relatively constant. Only a small amount of corrosion is needed to induce visible cover cracking. Implications on modelling time to cover cracking are discussed.     

Effect of surface condition on the initial corrosion of galvanized reinforcing steel embedded in concrete

The present work was aimed at determining the effect of coating surface condition on the initial corrosion of hot-dip galvanized reinforcing steel bar (HDG rebar) in ordinary Portland cement (OPC) concrete. During zinc corrosion in OPC concrete, calcium hydroxyzincate (CHZ) formed on untreated HDG steel provided sufficient protection against corrosion. Therefore, it is concluded that treating HDG rebar with dilute chromic acid is unnecessary as a method of passivating zinc. A layer of zinc oxide and zinc carbonate formed, through weathering, on HDG bars increased the initial corrosion rate and passivation time compared with the non-weathered rebar exposed to concrete. HDG steel with an alloyed coating, i.e. containing only of Fe-Zn intermetallic phases, required a longer time to passivate than those with a pure zinc surface layer. The lower zinc content of the surface limited the rate of CHZ formation; hence, delayed passivation. Regardless of the surface condition, the coating depth loss after two days of embedment in ordinary Portland cement concrete was insignificant.