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 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.     

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.     

Raman spectroscopic studies of the corrosion of model iron electrodes in sodium chloride solution

We have explored the un‐enhanced Raman spectra of both single and twin electrodes in 3.5% NaCl solution (at ambient temperatures) over a range of applied potentials (between 20 and 200 mV) and times (between 0 and 5 h). Under these conditions, we observed the initial formation of ‘green rust’ (hydroxychlorides and/or hydroxycarbonates), followed by the formation of magnetite (Fe₃O₄) and then a mixture of the α‐ and γ‐FeOOH (goethite and lepidocrocite, respectively). These data are consistent with a model for corrosion during which the initially formed magnetite is either covered, or replaced, by layers of the FeOOH oxidation products. Fitting of the data as a function of time and potential shows that, although the product range is independent of potential, the relative kinetics of formation of magnetite and its subsequent conversion to the γ‐FeOOH were potential and time dependent. Analysis by mapping of the dry corroded surface showed a variety of species, including green rust, some Fe(OH)₃, as well as the γ‐FeOOH, and possibly some β‐FeOOH. But no surface magnetite was found, indicating that this material had been either covered up or converted to FeOOH. We noted several complications during this work, including the interference of resonance effects (on the Raman intensities) and the heterogeneity of the corrosion process (and hence distribution of species on the corroded surface). However, we believe that the use of un‐enhanced Raman methods has led to conclusions more likely to be relevant to ‘real’ corrosion processes. Copyright © 2007 John Wiley & Sons, Ltd.     

A Mössbauer spectroscopy study of the corrosion of nodular cast iron in mine waters

The corrosion of ductile cast iron in water containing different amounts of chloride ions was investigated under both static and dynamic conditions. Corrosion/time relationships were established for exposure times of up to 30 days. Post-corrosion investigations were performed, employing Mössbauer spectroscopy, optical microscopy and electrochemical techniques. It was found that the nature of the surface corrosion product formed under static conditions differed morphologically and chemically from that formed under dynamic conditions. The latter was a hard layer consisting of a mixture of - and -FeOOH (situated on an underlying cementite layer), whereas the static tests resulted in a soft, spongy corrosion product, identified as -FeOOH.     

Conversion electron and X-ray Mössbauer studies of boronized low-carbon steel under corrosion and oxidation conditions

Iron-boride layers on low-carbon steel were produced by thermochemical diffusion process. The surface interaction products: Fe₂B, FeB, FeB_x (x>1) and a solid solution of iron in boron were identified by surface Mössbauer spectroscopy (CEMS and XMS). Samples of original and boronized steel were subjected to corrosion process by immersion in HCl (0.1 N) solution for 150 h. While the steel sample was strongly corroded, none corrosion product was found on the boronized sample surface. However, significant changes in relative percentages of the various iron boride phases were detected. Also, samples of original and boronized steel were subjected to oxidation process by heat-treatment in air at 300°C for 8 h and 500°C for 4 h. At 300°C, while bulk Fe₃O₄ and -Fe₂O₃ were formed on the steel surface, none iron oxide was detected on the boronized surface. At 500° C, while only pure bulk -Fe₂O₃ was detected on the steel surface, a particle size distribution of-Fe₂O₃, with particle size of about 100 Å, was probably formed on the boronized surface, as evidenced by CEMS.     

Green Rusts and Their Relationship to Iron Corrosion; a Key Role in Microbially Influenced Corrosion

Mössbauer spectroscopy (MS) has often been used to characterise double-layered hydroxysalts usually named green rusts (GR) and to follow their Fe(II)/Fe(III) ratio during the oxidation process of Fe(OH)₂ in the presence of aggressive anions such as Cl^–, SO ₄ ^2– , CO ₃ ^2– ,.... They are intermediate compounds between the initial metal Fe(0) via the Fe(II) and the final Fe(III) (oxyhydr)oxides constituting the usual rusts. E–pH Pourbaix diagrams of iron for predicting the aqueous corrosion conditions of iron-based materials are determined by monitoring the electrode potential E _h and pH vs. time. The crystal structure of GRs, in any case constituted of layers of [Fe^II _(1–x)Fe^III _x (OH)₂] ^x+ that alternate with interlayers [(x/n)A ^n–(mx/n)H₂O] ^x– made of A ^n– anions and water molecules, are presented. Several examples of the role of GRs are discussed, from chloride pitting of concrete reinforcing bars to bacterial corrosion of cast iron in water pipes or steel sheet piles in harbours. The efficiency of corrosion inhibitors like phosphate and their relationship to the oxidation of GRs are presented from basic MS studies. But most importantly, the evidence by MS of the dissimilatory reduction of a common ferric oxyhydroxide, -FeOOH lepidocrocite, into a GR by the action of a bacterium, Shewanella putrefaciens, opens the path through which microbially influenced corrosion (MIC) operates. A cycling of aerobic and anaerobic conditions is necessary where GRs but also magnetite play likely the key role.     

Study on corrosion properties of pipelines in simulated produced water saturated with supercritical CO2

This work aims at systematically investigating the corrosion properties of three pipeline steels in static simulated produced water (SPW) saturated with supercritical carbon dioxide using weight-loss tests. SEM, XRD and XPS were employed to study the chemical composition and structure of the corroded surface. The results showed that the corrosion rates of the tested steels significantly decreased with increasing the exposure temperature and time in static SPW saturated with SC-CO₂. The surface film on the corroded surface, which markedly influenced the CO₂ corrosion behavior of the samples, was mainly composed of (Fe, Ca)CO₃ and α-FeOOH. Inhomogeneous element distribution of carbon, oxygen, calcium and iron in the surface film was observed. (Fe, Ca)CO₃ formed at a lower temperature was more stable than that formed at elevated temperatures.     

Mössbauer and XRD analysis of corrosion products on weathering steel treated by wet-dry cycles using various solutions

Weathering steels (COR-TEN) were corroded by wet-dry cycles using a splay of various solutions in a laboratory. Corrosion products on weathering steel were characterized by X-ray diffractometry and Mössbauer spectrometry at room and low temperatures. Fine α-FeOOH, γ-FeOOH and γ-Fe ₂ O ₃ are fundamentally formed in various atmospheric conditions. β-FeOOH is additionally formed under the existence of chloride ions, but not formed when sulfate ions are coexisting. Spraying a NaF solution prevents the progress of corrosion.     

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.     

Fe–Mn–Al–C Alloys: a Study of Their Corrosion Behaviour in SO2 Environments

The corrosion reaction of four Fe–Mn–Al alloys exposed to a cycling, dry–humid, SO₂ (0.001% by volume) polluted atmosphere was studied. ICEMS, XPS, AES-SAM and transmission Mössbauer spectroscopy at different temperatures were employed to characterize the corrosion products. The analytical results indicate that (i) ferrihydrite is the main component of the rust; (ii) there is an abundant presence of Mn²⁺ and SO₃ ^2–/SO₄ ^2– on the top of the corrosion layer, the concentration of SO₄ ^2– increasing with the number of cycles; and (iii) the magnetic hyperfine pattern exhibited by the series of low-temperature spectra of the rust is quite different from that observed in the rust formed under similar corrosive environments on iron and weathering steel. This latter finding is correlated with a slow rate of transformation of the Fe³⁺ species formed at the early stages of corrosion into -FeOOH, the usual final product of this type of corrosion processes. The sulphate anions, abundant inside the electrolyte during the wet periods, could be incorporated to the ferrihydrite structure being responsible for the Mössbauer spectral pattern recorded from the corrosion products at low temperatures.     

Phase Analysis of Corrosion Products from Nuclear Power Plants

The variability of the properties and the composition of the corrosion products of the stainless CrNi and mild steels in dependence on the conditions (temperature, acidity, etc.) is of such a range that, in practice, it is impossible to determine the properties of the corrosion products for an actual case from the theoretical data only. Since the decontamination processes for the materials of the water-cooled reactor (VVER-440) secondary circuits are in a process of development, it is necessary to draw the needed information by the measurement and analysis of the real specimens [1]. The corrosion layer was separated by scraping the rust off the surface and the powder samples were studied by transmission Mössbauer spectroscopy. It should be noted that the gamma spectroscopic measurements give no evidence of the presence of low-energy gamma radiation emitted from the samples. The scrapped specimen powder was homogenised (using the 50 m sieve) and fixed into the special holder. The ⁵⁷Co in Rh matrix was used as the radioactive Mössbauer source. Measured spectra were fitted using program NORMOS SITE. According to the results obtained from Mössbauer spectra, it is possible to establish that the main component of secondary circuit's corrosion products is magnetite Fe₃O₄. Next components are hematite -Fe₂O₃ and hydroxide akagenite -FeOOH, which is characterised by a significant paramagnetic doublet in the middle of the spectra. The sextets corresponding to base materials (martensite and austenite steels) were identified in all measured spectra.     

Corrosion products on steel 20 in aerated hydrazine solutions: Mössbauer study

Composition of corrosion layers on steel 20 in aerated solutions with hydrazine concentrations less than 11 ppm was studied at 50, 60, and 80°C in dynamic conditions by transmission Mössbauer spectroscopy and X-ray diffraction as supplementary technique. Corrosion rates were determined by gravimetric method. A comparison with corrosion in water at 80°C was made. The observed layers have not any protective character. For 0.1 m/s linear velocity, they are composed by nonstoichiometric magnetite, (Fe_3?x O₄,x=0.02–0.04) with lepidocrocite (γ-FeOOH) as secondary phase at 50°C. Haematite (α-Fe₂O₃) is observed at 60 and 80°C with a 19 nm particle size. It becomes smaller for higher velocity (0.7 m/s).     

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.     

Corrosion processes and their inhibition as studied by Mössbauer conversion and other electron spectroscopies

To study corrosion processes of iron and steel and measures of their inhibition, a detailed knowledge of the phase composition and of phase transformations in very thin layers close to the attacked surface of the material is necessary. The information depths of integral (ICEMS) and depth selective (DCEMS) conversion electron Mössbauer spectroscopy are well suited for such investigations, but some effort is necessary if technical samples, i.e. nonenriched in⁵⁷Fe, are to be studied. In many cases of practical importance, full information on the corroded surfaces cannot be got from Mössbauer spectra only, and a combination with Auger and photoelectron spectroscopies, in-including scanning and sputter options, is found to be most informative. This is demonstrated by three examples. The high corrosion resistance of stainless steel X1 CrNiSi 18 15 against boiling HNO₃ is found to be due to a SiO₂ layer formed on the surface and growing with duration of exposure. Nearly no iron oxides are formed, although the composition of the alloy close to the metal surface is slightly influenced. Transformer sheet steel (Fe?3%Si), commercially available after a thermal pretreatment, is covered by an insulating layer containing iron oxides and a large amount of Fe₂SiO₄. By the method combination it was found that a very thick layer below the metallic surface is also modified by the pretreatment. There, one finds pure α-iron containing clusters of SiO₂ which have been formed by internal oxidation. The passivation of iron and steel (DIN 1623) in sulphate solution and in a phosphate buffer was studied in detail. Phase composition and thickness of the passive layer, as thin as a few nm only, were analyzed in dependence on the applied anodic potential and the duration of the passivating procedure. From the experiments, a model of the passive layer was derived, which is a modification of a p-i-n junction proposed elsewhere. The real passivation is ascribed to a layer, only a few monolayers thick, which has a highly disordered structure and provides the transition from cubic to orthorhombic structure. Some thermodynamical considerations show that immediately on an iron substrate, an oxide layer should always contain a high concentration of Fe²⁺ forming an equilibrium oxide. The absence of Fe²⁺ in Mössbauer spectra is interpreted by the assumption that this layer may be extremely thin, i.e. a few monolayers only.     

Superconductor-insulator transition in disordered boson-superlattices

We calculate the transport properties of a disordered Bose condensate. A superlattice made from two-dimensional planes of bosons in the condensate phase is considered. The disorder is due to charged impurities. We consider a homogeneous distribution of impurities and also impurities randomly distributed in planes. The dispersion relation of the collective excitations (plasmons) for the clean boson superlattice is calculated. The disorder induced phase transiton from a superfluid phase to an insulator phase is discussed and the static conductivity ( _c ) at the transition point is expressed in terms of the microscopic parameters of the model. For strongly coupled planes we find that _c is of ordere ²/h. The relation of our theoretical results to experiments with high-temperature superconductors is discussed.     

A study of electrochemically-induced corrosion of low carbon steel in a medium modelling acid rain

Complementary electrochemical, spectrophotometric and electron microsopic investigations were made in addition to the conversion electron Mössbauer spectroscopic (CEMS) measurements to learn more about the mechanism of corrosion of low carbon steel samples in aqueous sulfate and sulfite containing sulfate solutions (pH 3.5, 6.5 and 8.5). Passivation of iron in pure sulfate solution was studied in detail in earlier papers. In the present work, we used a solution containing both sulfate and sulfite anions to obtain more information about the effect of acid rain on low carbon steel samples. The compositions and thicknesses of the passive films formed due to the electrochemical treatments were determined from the CEM spectra. -FeOOH was found in each case on the surface of the samples; nevertheless, at pH 3.5 the sextet belonging to Fe₃C appears in the CEM spectra, and also FeSO₄ · H₂O was detected in low concentration after the shortest polarization time (90 min). The results of the applied methods proved that the sulfite ions induce pitting corrosion at pH 3.5 and 6.5, while the measurements referred to suppressed pitting at pH 8.5.     

Investigation of the Thermal Stability of Laser Nitrided Iron and Stainless Steel by Annealing Treatments

Laser nitriding has revealed to be a very promising and effective treatment to improve the technical properties, like surface hardness and corrosion-wear resistance, of iron and steels. The high nitrogen concentration, the fastness and precision of the treatment and the easy experimental setup make this technique very suitable for applications on industrial scale. Samples of pure iron and austenitic stainless steel have been irradiated with ns laser pulses in the UV radiation range and analyzed by means of Conversion Electron Mössbauer Spectroscopy (CEMS), Resonant Nuclear Reaction Analysis (RNRA), Grazing Incidence X-Ray Diffraction (GXRD) and Microhardness. Mössbauer Spectroscopy, in particular, is capable of detecting the phase composition of the nitrided layer and therefore represents an essential tool for these kind of analysis. The thermal stability of the treated samples have been investigated by subsequent annealings at increasing temperatures in vacuum and in air. For iron samples the annealing treatment at 250°C shows a rather drastic phase transformation from phase (fcc) into (Fe₄N) while a strong depletion of N has been observed for 400°C or higher, regardless of the ambient pressure (atmospheric or vacuum). On the other hand, the stainless steel shows a very good thermal stability up to 500°C, but higher temperatures induce a gradual decrease in the nitrogen concentration which seems to be a common feature for both pure iron and stainless steel. Furthermore, annealing in air leads to the formation of a thin oxide layer on the surface of the iron sample which is easily characterized by Mössbauer spectroscopy.     

Corrosion reaction of iron exposed to the open atmosphere in the Antarctic

Within a cooperative program for the elaboration of a Latin American Map of Atmospheric Corrosion, weathering steel and mild steel samples were exposed to the Antarctic atmosphere and the corrosion products analyzed by ICEMS, XPS and XRD. Superparamagnetic -FeOOH was the main corrosion product after 24 h of exposure. Cl^– ions are found on the surface of the corroded samples by XPS.     

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.