The simultaneous presence of green rust 2 and sulfate reducing bacteria in the corrosion of steel sheet piles in a harbour area

Mössbauer spectroscopy and X-ray diffraction analysis allow to detect the presence of green rust 2, the ferrous-ferric sulfated compound of composition, 4Fe(OH)₂,2FeOOH,FeSO₄,nH₂O, mixed with magnetite at the surface of steel sheets corroded in a harbour area where the presence of sulfate reducing bacteria are also detected.     

Spectroscopic studies of the corrosion of model iron electrodes in carbonate and phosphate buffer solutions

We have extended our unenhanced (non-SERS) Raman spectroscopic investigations to include a study of the corrosion of an iron electrode in carbonate and phosphate buffer solutions. The measurements have been supported by electrochemical investigations (via cyclic voltammetry), enabling oxidation and reduction reactions to be systematically followed at variable applied potentials. In a carbonate buffer (pH = 9.4) the surface oxidation led to the formation of a ‘green rust’ (a hydrated hydroxy-carbonate), followed by the α- and β-forms of FeOOH and an underlying magnetite layer formed on the cathodic (reduction) cycle. In a phosphate buffer (pH = 7.7) the surface was passivated by hydrated phosphates of iron [identified as FePO₄ · xH₂O and Fe₃(PO₄)₂·8H₂O]. The formation of oxides (Fe₂O₃ and Fe₃O₄) were inferred from voltammetry, but spectral identification was more difficult because of broad, ill-defined spectra. Despite the challenges of using unenhanced Raman spectroscopy, we believe that the effort was worthwhile, the reactions identified being more likely to be relevant to real electrochemical environments. Copyright © 2008 John Wiley & Sons, Ltd.     

Influence of Cu and Ni on the morphology and composition of the rust layer of steels exposed to industrial environment

Four samples of steels with alloying elements were exposed to an industrial environment during 1,955 days, aiming to elucidate the effect of the alloying elements Cu and Ni on the resistance of weathering steels to corrosion processes. The samples were characterized with optical microscopy, scanning electron microscopy (SEM), powder X-ray diffraction (XRD), saturation magnetization measurements and with energy dispersive (EDS), infrared, Mössbauer and Raman spectroscopies. All the steels originated orange and dark corrosion layers; their thicknesses were determined from the SEM images. EDS data of such rust layers showed that the alloying element content decreases from the steel core towards the outer part of the rust layer. Moreover, in the dark rust layer some light-gray regions were identified in the W and Cu-alloy steel, where relatively higher Cr and Cu contents were found. XRD patterns, infrared, Raman and Mössbauer spectra (298, 110 and 4 K) indicated that the corrosion products are qualitatively the same, containing lepidocrocite (γFeOOH; hereinafter, it may be referred to as simply L), goethite (αFeOOH; G), feroxyhite (δ′FeOOH; F), hematite (αFe₂O₃; H) and magnetite (Fe₃O₄; M) in all samples; this composition does not depend upon the steel type, but their relative concentrations is related to the alloying element. Mössbauer data reveal the presence of (super)paramagnetic iron oxides in the corrosion products. Saturation magnetization measurements suggest that feroxyhite may be an occurring ferrimagnetic phase in the rust layer.     

Raman identification of corrosion products on automotive galvanized steel sheets

Iron oxides (haematite, maghemite, magnetite), (oxy)hydroxides (lepidocrocite), carbonates, as well as zinc carbonate and oxide, have been identified on corroded galvanized steel samples after corrosion accelerating tests in the laboratory and compared with those observed on samples taken from vehicles that have been in circulation for five years in severe weather conditions. Spectra recorded on the corroded parts are compared with synthesized compounds. (Hydroxy)carbonates are clearly evidenced on galvanized and phosphated steel sheets. Corrosion layers beneath the paint could be detected. White regions always correspond to a ZnO‐rich phase but maghemite (γ‐Fe₂O₃) and sometimes akaganite (β‐FeOOHCl) are observed at the centre (maroon) of very corroded spots. Maghemite is observed in strongly corroded regions. Goethite (α‐) and lepidocrocite (γ‐FeOOH) (and akaganite) are observed at the surface of less corroded regions of phosphate‐free galvanized steel and are absent for phosphate‐coated steel. Green rust is observed only on galvanized samples corroded in the laboratory. Copyright © 2008 John Wiley & Sons, Ltd.     

Analysis of the composition of the passive film on iron under pitting conditions in 0.05 M NaOH/NaCl using Raman microscopy in situ with anodic polarisation and MCR‐ALS

The composition of the surface film formed on pure iron was investigated in a solution of 0.05 M NaOH and 0.05 M NaCl. Raman spectra of the film were recorded in situ during anodic polarisation over the passive region after addition of the NaCl to the electrolyte, under conditions of preresonance enhancement using excitation at 636.4 nm. Multivariate curve resolution with alternating least squares analysis was applied to the spectra to measure the relative amounts of different iron oxide and oxyhydroxides in the film at different potentials. The water content was also determined in this way from Raman spectra recorded using excitation at 514.5 nm. It was found that the composition of the film and the amount of incorporated water were influenced by the applied anodic potential. The results show that stable pitting can occur when the composition changes from the primary constituents β‐FeOOH and Green Complex (a hydrated, amorphous magnetite) with smaller amounts of γ‐Fe₂O₃ and γ‐FeOOH, to δ‐FeOOH and Green Complex, simultaneously with a reduction in water content. These changes result in conditions that favour the rate of localised breakdown of the film by Cl⁻ ions over the rate of repassivation by water in the passive film. Copyright © 2011 John Wiley & Sons, Ltd.     

Products obtained by microbially-induced corrosion of steel in a marine environment: Role of green rust two

An unusual low-water corrosion of steel sheet piles has been systematically investigated in a channel harbour (Boulogne sur Mer, France). An analysis of the environment reveals that all sampling of dark rust taken at different heights above marine sediments and kept in anaerobic conditions present unusual concentrations of sulfate-reducing bacteria. The rust products have been characterized by Mössbauer spectroscopy and X-ray diffraction, comprising the ferrous—ferric sulfated compounds of formula 4Fe(OH)₂ · 2FeOOH · FeSO₄ ·nH₂O, called green rust 2, mixed sometimes with magnetite and a small amount of ferrous sulfide.     

Raman and IR spectroscopy study of corrosion products on the surface of the hot‐dip galvanized steel with alkaline mud adhesion

The corrosion products formed on hot‐dip galvanized steel sheets for the automobile application with adhesion of alkaline mud containing different Cl⁻ ion contents are investigated by means of Raman and infrared (IR) spectroscopy. Results show that the Cl⁻ ion content in alkaline mud has great influence on the corrosion behavior of the galvanized steel. The Cl⁻ ions are responsible for the formation of the Zn₅Cl₂(OH)₈· H₂O layer on the surface of the steel at the early stage of corrosion. The rest of the Cl⁻ ions then penetrate and interrupt corrosion product layer resulting in pitting corrosion. Subsequently, the red corrosion product of α‐FeOOH (shaped as needle‐like structure) is formed, which then transforms into black rust of Fe₃O₄ (having a shape of slim needle). It is interesting to find out that pitting depth is inversely proportional to the Cl⁻ ion content. However, corrosion rate decreases with the increase of the Cl⁻ ions in mud. Copyright © 2009 John Wiley & Sons, Ltd.     

Kinetics and structural studies of the atmospheric corrosion of carbon steels in Panama

The corrosion of a carbon steel was studied in different atmospheres at sites in the Republic of Panama. The weight loss (corrosion penetration) suffered by the carbon steel is related to time by a bilogarithmic law. Mössbauer spectroscopy indicated the rust was composed of non-stoichiometric magnetite (Fe_3-xO₄), maghemite (γ-Fe₂O₃), goethite (α-FeOOH) of intermediate particle size, lepidocrocite (γ-FeOOH) and superparamagnetic particles. Magnetite formation is related to the alternating dry--wet cycles. Goethite is related to corrosion penetration by a saturation type of behavior, following a Langmuir type of relationship. Goethite in rust protects steel against further atmospheric corrosion.     

The substitution of Fe2+ ions by Ni2+ ions in the green rust 2 compound studied by Mössbauer effect

Green rust 2 is usually obtained by oxidizing an initial mixture of FeSO₄ and NaOH solutions and a complete oxidation leads mainly towards γ oxyhydroxide known as lepidorocite. By adding some NiSO₄ one can stop at the first stage and Mössbauer spectra reveral only ferric doublets. This implies that the initial formula 4Fe(OH)₂, 2FeOOH, FeSO₄ of green rust 2 must be replaced byxNi(OH)₂, (6?x)FeOOH, NiSO₄, wherex scans from 2 to 4. It also means that all initial ferrous ions become oxidized into the ferric state leaving the Ni₂₊ ions unchanged. Therefore the end product of oxidation is the nickel containing green rust 2 at the place of the usual lepidocrocite.     

Raman study of a deuterated iron hydroxycarbonate to assess long‐term corrosion mechanisms in anoxic soils

In several contexts such as cultural heritage, oil and gas or nuclear waste disposal, the long‐term corrosion mechanisms of iron in anoxic soils are studied. For this purpose, corrosion layers formed on ferrous archaeological artefacts from the site of Glinet (16th century, Normandy, France) were characterised. The main phases identified are siderite (FeCO₃), chukanovite (iron hydroxycarbonate: Fe₂(OH)₂CO₃ and magnetite (Fe₃O₄). In order to provide reliable Raman references for further studies on carbonated systems, the iron hydroxycarbonate (chukanovite) was synthesised on iron discs. The corrosion mechanisms were investigated by re‐corroding the archaeological samples in a deuterated solution. Raman characterisation on cross sections inside the layer revealed the presence of deuterated chukanovite, allowing the deuterium tracing of the spreading of the corrosion. A set of chukanovite samples was synthesised with various D/H ratios. Using these reference data, the proportion of deuterated chukanovite in re‐corroded artefacts was evaluated, and the corrosion rate was estimated as less than 1.6 µm/year. Copyright © 2010 John Wiley & Sons, Ltd.     

Deterioration of iron archaeological artefacts: micro‐Raman investigation on Cl‐containing corrosion products

Deterioration after excavation of archaeological iron artefacts buried in soil is often associated with the presence of chlorinated phases in corrosion products, leading to serious problems for conservation of metallic objects of cultural heritage. Therefore, in order to better understand the corrosion process related to the presence of chlorine, some high‐resolution techniques of material characterisation are implemented. The analyses are realised on cross sections of corroded iron objects excavated from archaeological sites dated from the 12th to the 16th century A.D. Cl‐containing phases appear even when the Cl level in the water is low. In addition to the common oxy‐hydroxide‐containing chloride, akaganeite (β–FeOOH) often mentioned in the literature, a ferrous hydroxychloride β–Fe₂(OH)₃Cl was also found in the corrosion layers. Moreover, part of the study is based on the preparation and desalinisation of pure akaganeite powder in order to characterise the influence of the chloride content on its crystalline structure as characterised by Raman spectroscopy. Copyright © 2007 John Wiley & Sons, Ltd.     

Characterization of corrosion products formed on the surface of carbon steel by Raman spectroscopy

Corrosion of carbon steel in seashore salty soils containing 10, 20, and 34 wt% (saturated) water was investigated. The corrosion rate was measured and corrosion products were analyzed using Raman spectroscopy. It was found that carbon steel in the soil with 10 wt% water content had the largest corrosion rate and the corrosion was dominated by localized corrosion. The corrosion rate drops dramatically and turns to be general corrosion with increase of water content. The corrosion products in the soil with 20 and 34 wt% water content are mainly composed of α‐FeOOH, while in the soil with 10 wt% water content, the products show a delaminated structure of two layers with the inner layer mainly consisting of α‐FeOOH and the outer layer composed of Fe₂O₃ and Fe₃O₄. Copyright © 2008 John Wiley & Sons, Ltd.     

The growth of the passive film on iron in 0.05 M NaOH studied in situ by Raman micro‐spectroscopy and electrochemical polarisation. Part I: near‐resonance enhancement of the Raman spectra of iron oxide and oxyhydroxide compounds

Raman spectroscopy, in principle, is an excellent technique for the study of molecular species developed on metal surfaces during electrochemical investigations. However, the use of the more common laser wavelengths such as the 514.5‐nm line results in spectra of less than optimal intensity, particularly for iron oxide compounds. In the present work, near‐resonance enhancement of the Raman spectra was investigated for the iron oxide and iron oxyhydroxide compounds previously reported to be present in the passive film on iron, using a tuneable dye laser producing excitation wavelengths between 560 and 637 nm. These compounds were hematite (α‐Fe₂O₃), maghemite (γ‐Fe₂O₃), magnetite (Fe₃O₄), goethite (α‐FeOOH), akaganeite (β‐FeOOH), lepidocrocite (γ‐FeOOH) and feroxyhyte (δ‐FeOOH). Optimum enhancement, when compared to that with the 514.5‐nm line, was obtained for all the iron oxide and oxyhydroxide standard samples in the low wavenumber region (<1000 cm⁻¹) using an excitation wavelength of 636.4 nm. Particularly significant enhancement was obtained for lepidocrocite, hematite and goethite. Copyright © 2010 John Wiley & Sons, Ltd.     

Atmospheric corrosion in the Gulf of México

The corrosion products on steels exposed at two sites in Campeche, México and one site at Kure Beach, USA, have been investigated to determine the extent to which different marine conditions and exposure times control the oxide formation. The corroded coupons were analyzed by Mössbauer, Raman and infrared spectroscopy as well as X‐ray diffraction, in order to completely identify the oxides and map their location in the corrosion coating. The coating compositions were determined by Mössbauer spectroscopy using a new parameter, the relative recoilless fraction (F-value) which gives the atomic fraction of iron in each oxide phase from the Mössbauer sub‐spectral areas. For short exposure times, less than three months, an amorphous oxyhydroxide was detected after which a predominance of lepidocrocite (γ-FeOOH), and akaganeite (β-FeOOH) were observed in the corrosion coatings with the fraction of the later phase increasing at sites with higher atmospheric chloride concentrations. The analysis also showed that small clusters of magnetite (Fe₃O₄), and maghemite (γ(Fe₂O₃), were seen in the micro-Raman spectra but were not always identified by Mössbauer spectroscopy. For longer exposure times, goethite (α-FeOOH), was also identified but little or no β-FeOOH was observed. It was determined by the Raman analysis that the corrosion products generally consisted of inner and outer layers. The protective layer, which acted as a barrier to slow further corrosion, consisted of the α-FeOOH and nano-sized γ-Fe₂O₃ phases and corresponded to the inner layer close to the steel substrate. The outer layer was formed from high γ-FeOOH and low α-FeOOH concentrations.     

Portable Raman study on the conservation state of four CorTen steel‐based sculptures by Eduardo Chillida impacted by urban atmospheres

Weathering steel, and particularly CorTen steel, is a very used material for modern artworks exhibited outdoors. One of the characteristic that makes this material so attractive to artists is the property to develop a protective rust layer composed by iron oxides which preserves its metallic core from atmospheric corrosion. This study was conducted to evaluate the conservation state of four CorTen sculptures by Eduardo Chillida, located in different places of Bilbao city (north of Spain) and affected by different factors (environmental among others) by using Raman spectroscopy. Measurements were performed in situ with a handheld Raman spectrometer mounted on a tripod with x–y–z axes motorization at the micron level. The most common oxyhydroxides detected were lepidocrocite (γ‐FeO(OH)), goethite (α‐FeO(OH)), hematite ( ‐Fe₂O₃) and magnetite (Fe₃O₄), being goethite the most stable phase. All the iron oxyhydroxides were identified in all of the studied sculptures but their relative amounts were different for each sculpture. The consequences of the marine aerosols exposure in the steel surface were also studied, detecting limonite (FeO(OH)·nH₂O) and akaganeite (β‐FeO(OH)). The results confirmed that the evolution of the rust layer present on the analyzed weathering steels is different, depending both on the exposure and the particular type of the steel. Copyright © 2012 John Wiley & Sons, Ltd.     

Characterization of initial atmospheric corrosion of conventional weathering steels and a mild steel in a tropical atmosphere

The phases and compositions of the corrosion products of a mild steel (A-36) and two weathering steels (A-588 and COR 420) formed after 3 months exposure to the tropical marine atmosphere of Panama were examined using FTIR and Mössbauer spectroscopy. The results show that amorphous or crystallized iron oxyhydroxides goethite α-FeOOH and lepidocrocite γ-FeOOH are early corrosion products. Maghemite γ-Fe₂O₃ and magnetite Fe₃O₄ have also been identified and found to be prominent components for steels exposed to the most aggressive conditions. The formation of akaganeite β-FeOOH was observed when chlorides were occluded within the rust. FTIR showed the presence of hematite α-Fe₂O₃ in one sample.     

电偶腐蚀对接触电极间压紧力的影响

电偶腐蚀会导致受载结构中内力的变化,从而改变结构性能。研究电偶腐蚀对结构内力的影响规律,利于提高相关结构的设计水平。设计接触端面为圆平面的圆柱形电极,采用恒位移加载方式使两个接触面相互压紧,同时将电极浸泡在质量分数3.5%的NaCl溶液中进行腐蚀,测试给出了压紧力随腐蚀时间的变化曲线。与实验状态相对应,用电极表层腐蚀区的径向和轴向尺寸以及等效弹性常数表征电偶腐蚀效应,根据实验观察近似取定腐蚀区尺寸,建立微观尺度的材料性能模拟模型和宏观尺度的结构力学模拟模型,计算给出了腐蚀区的材料性能参数和腐蚀一定时间后电极之间的压紧力,计算结果与实验结果大致吻合。该项研究同时为数值模拟电偶腐蚀对结构力学行为的影响提供了新的方法。     

Synthesis and characterisation of the Fe(II–III) hydroxy-formate green rust

A new methodology was envisioned in order to prepare green rust compounds build on organic anions that could intervene in microbiologically influenced corrosion processes of iron and steel. The formate ion was chosen as an example. The formation of rust was simulated by the oxidation of aqueous suspensions of Fe(OH)₂ precipitated from Fe(II) lactate and sodium hydroxide, in the presence of sodium formate to promote the formation of the corresponding green rust. The evolution of the precipitate with time was followed by transmission Mössbauer spectroscopy at 15 K. It was observed that the initial hydroxide was transformed into a new GR compound. Its spectrum is composed of three quadrupole doublets, D ₁ (δ?=?1.28 mm s^?1, Δ?=?2.75 mm s^?1) and D ₂ (δ?=?1.28 mm s^?1, Δ?=?2.48 mm s^?1) that correspond to Fe(II) and D ₃ (δ?=?0.49 mm s^?1, Δ?=?0.37 mm s^?1) that corresponds to Fe(III). The relative area of D ₃, close to the proportion of Fe(III) in the GR, was found at 28.5?±?1.5% (～2/7). Raman spectroscopy confirmed that the intermediate compound was a Fe(II–III) hydroxy-formate, GR(HCOO^?).     

Characterization of Iron Oxides Commonly Formed as Corrosion Products on Steel

For fundamental studies of the atmospheric corrosion of steel, it is useful to identify the iron oxide phases present in rust layers. The nine iron oxide phases, iron hydroxide (Fe(OH)₂), iron trihydroxide (Fe(OH)₃), goethite (α-FeOOH), akaganeite (β-FeOOH), lepidocrocite (γ-FeOOH), feroxyhite (δ-FeOOH), hematite (α-Fe₂O₃), maghemite (γ-Fe₂O₃) and magnetite (Fe₃O₄) are among those which have been reported to be present in the corrosion coatings on steel. Each iron oxide phase is uniquely characterized by different hyperfine parameters from M?ssbauer analysis, at temperatures of 300K, 77K and 4K. Many of these oxide phases can also be identified by use of Raman spectroscopy. The relative fraction of each iron oxide can be accurately determined from the M?ssbauer subspectral area and recoil-free fraction of each phase. The different M?ssbauer geometries also provide some depth dependent phase identification for corrosion layers present on the steel substrate. Micro-Raman spectroscopy can be used to uniquely identify each iron oxide phase to a high spatial resolution of about 1 μm. This revised version was published online in August 2006 with corrections to the Cover Date.     

Kinetics of formation of green rust 2 in the steady acidic sulphated medium

The kinetics of formation of green rust 2, 4Fe(OH)₂.2FeOOH.FeSO₄.nH₂O, called “GR2, was followed by Mössbauer spectroscopy in the controlled aeration of a mixture of 0.4 M FeSO₄ and 0.4 M NaOH. Mössbauer spectra run at 78 K of the reaction products taken at different time intervals display an average of seven doublets. The initial products of reaction consists of a badly crystallized ferrous hydroxide, FE(OH)₂., called “FH”, which disappears first at about 1/3 of the total time of formation of GR2, and sulphated ferrous hydroxide, 4Fe(OH)₂.FeSO₄.nH₂O, called “SFH”. The kinetics of oxidation of SFH into GR2 can be described by a linear growth reaction and the transformation is considered to be in situ.