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.     

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.     

Proof by UV-visible modulated reflectance spectroscopy of the breakdown by carbonation of the passivating layer on iron in alkaline solution

Carbonation of concrete by atmospheric CO₂ may lead to breakdown of the passivating layer of the steel reinforcements, leading to catastrophic corrosion, if the pH of the electrolyte in the concrete pores decreases below 8. The nature of this carbonation process has been studied by means of potential-modulated reflectance (PMR) spectroscopy, following the changes in the PMR spectrum of air-passivated iron in 1M NaOH produced by sparging the electrolyte with a CO₂ + air mixture. Decreasing the pH from 8.02 to 7.69 produced the disappearance of the Fe₂O₃ PMR signal and nearly a doubling of the PMR maximum of FeOOH, pointing to a hydration of Fe₂O₃ to FeOOH preceding the breakdown of the passivating layer. A further decrease of only 0.07 pH units, down to pH 7.62, effected an increase of the corrosion rate of nearly two orders of magnitude and the disappearance of the PMR spectrum of the passivating layer, this being the first spectroscopic proof that depassivation by carbonation is due to a complete electrochemical dissolution of the passivating layer.     

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.     

A new hydrothermal blackening technology for Fe3O4 coatings of carbon steel

This paper proposes a new blackening technology for growing magnetite (Fe₃O₄) coating on surface of carbon steel. Dense black coating composed of Fe₃O₄ ultrafine particles could be successfully prepared by hydrothermal treatment of the carbon steel substrate in the N₂H₄·H₂O-FeSO₄-NaOH solution at 150 °C. Electrochemical analysis, including Tafel and electrochemical impedance spectroscopy, indicated that the anodic dissolution reaction was effectively limited and the corrosion resistance increased by the Fe₃O₄ coating. The key factors and growth mechanism for the hydrothermal formation of the Fe₃O₄ coating are also discussed.     

The mechanism of oxide whisker growth and hot corrosion of hot-dipped Al-Si coated 430 stainless steels in air-NaCl(g) atmosphere

The mechanisms of oxide whisker growth and hot corrosion of 430 stainless steel (430SS) and aluminide 430 stainless steel hot-dipped in a Al-10 wt.%Si molten bath (430HDAS) were studied at 750 and 850 °C in air mixed with 500 and 990 vppm NaCl_(g). The results showed that the loose Cr₂O₃ scale which formed on the 430SS could not prevent the corrosion of 430SS in a 500 vppm NaCl_(g) atmosphere, resulting in the formation of Fe₂O₃ scale. Fe₂O₃ whiskers grew at the grain boundary of the Fe₂O₃ scale. However, no Fe₂O₃ whiskers formed on the Fe₂O₃ scale while 430SS was exposed in a 900 vppm NaCl_(g) atmosphere. During the initial high-temperature corrosion of 430HDAS in a 500 vppm NaCl_(g) atmosphere, a dense Al₂O₃ scale formed on the surface of the specimens. Also, Al₂O₃ whiskers grew on the Al₂O₃ scale. As exposure time increased, cyclic chlorination/oxidation degraded the protective aluminide layer and caused the formation of Fe₂O₃ scale and Fe₂O₃ whiskers. The morphology of Fe₂O₃ whiskers formed at 750 °C is more slender than those formed at 850 °C. The formation and growth of both Fe₂O₃ and Al₂O₃ whiskers may be attributed to the chloridation of both the steel substrate and aluminide layer, accelerating the diffusion rate of metallic ions in the oxide scales.     

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.     

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.     

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.     

ESCA studies of Fe-Ti alloys

Fe-Ti alloys containing 5 to 47% Ti have been studied by ESCA. The alloys were exposed to 0.1 M NaCl for 24 h under open-circuit potential (OCP) during which passive films were formed. The passive film consisted of FeO and TiO₂ in the inner layer while Fe₂O₃, water, and hydroxyl groups were present in the outermost monolayers, irrespective of composition. The thickness of the passive layer was reduced from 4.4 nm to 1.0 nm with increasing Ti content. The amount of iron oxide in the passive layer also decreased with increasing Ti. Electrochemical techniques according to ASTM G59 and ASTM G5 were used for the determination of the relative corrosion rate of the alloys. Alloys with 5–28% Ti showed a relatively high corrosion rate but that with 47 wt.% Ti had a much lower corrosion rates.     

含碳Na-β(β")-Al2O3的导电性能

本文研究了含碳(1—10)wt％的Na-β(β″)-Al₂O₃,指出含碳6wt％以下仍是良好的快离子导体,而且由于混入了碳,离子电导率比纯的Na-β(β″)-Al₂O₃提高一到两个数量级。样品的体电阻,晶界电阻,双电层电容及其漏电阻等参量都随含碳量的不同而变化。文中详细地讨论了碳的影响。在-40℃到80℃温度范围测量了纯样品与含碳样品的电导温度特性,指出含碳的Na-β(β″)-Al₂O₃是做双电层电容器的良好材料。 关键词：     

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.     

Phase Composition of Oxidised Layers Grown on Steel Exposed to Liquid Lead at 749 K

The corrosion resistance of AISI 316 LN stainless steel was studied in contact with stagnant, oxygen-saturated liquid lead at 749 K for times up to 1200 h. The reaction products were analysed by means of optical and scanning electron microscopy, electron probe microanalysis, X-ray diffraction analysis and Mössbauer spectroscopy. Thin layers of largely variable thickness formed on the surface, mainly consisting of Fe₃O₄, with small amounts of FeO in the inner regions, Fe₂O₃ and an Fe-Pb-O ternary product in the outermost regions. The alloying elements Cr and Ni diffused to a different extent into Fe₃O₄. A mechanism is proposed to explain formation and growth of the reaction products.

     

Experimental simulation of possible radiation-corrosive processes in container with spent nuclear fuel after groundwater ingress

Radiation corrosion in deaerated water/carbon steel systems has been studied. Kinetics of releasing corrosion products into the water and their sorption on the surface of steel tablets is affected by various factors (redox potential, absorbed dose, temperature, irradiation duration). Concentration of corrosion products in the solution was evaluated using various chemical methods. Total concentration of Fe²⁺/Fe³⁺ ions in liquid phase was determined by UV/VIS spectrometry. Solid phase was analysed using X-ray diffraction method. Corrosion processes were studied in deaerated distilled water and synthetic granitic water. Corrosion cells consisted of glass ampoules with inserted steel tablets, completely filled with deoxygenated water. Corrosion cells were carefully enclosed so that air diffusion into system during experiment was kept at minimum. ⁶⁰Co gamma sources with various dose rates were used for irradiation. The obtained results indicated that radiation noticeably contributed to the formation of corrosion products. Kinetics of radiation corrosion was strongly dependent on the parameters under study. The obtained experimental data should be taken into consideration when predicting effects of corrosion on containers with spent nuclear fuel using mathematical models.     

A CEMS Study of the Corrosion of Carbon Steel After Surface Laser Irradiation

The corrosion resistance of laser-irradiated carbon steel surfaces against SO₂-polluted atmospheres has been investigated by means of weight gain measurements and CEMS. The results show that the laser-irradiated samples present a higher corrosion resistance than the non-irradiated steel. The corrosion products are found to be superparamagnetic α-FeOOH and an amorphous Fe³⁺ oxyhydroxide. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synthesis of carbon-coated Fe3O4 nanorods as electrode material for supercapacitor

Carbon-coated Fe₃O₄ and pure Fe₃O₄ nanorods are synthesized via hydrothermal reaction and subsequent sintering procedure. The as-prepared products characterized by X-ray diffraction and scanning electron microscopy analysis indicate that carbon coating does not affect the structure and morphology of Fe₃O₄. Transmission electron microscope shows that Fe₃O₄ nanorods are homogeneously coated by carbon layer with a thickness of approximately 2 nm. The electrochemical properties measured by cyclic voltammetry, galvanostatic charge–discharge cycling and electrochemical impedance spectroscopy tests show that carbon-coated Fe₃O₄ (Fe₃O₄/C) nanorods present improved electrochemical performance due to the carbon layer. A specific capacitance of 275.9 F?g^?1 is achieved at a current density of 0.5 A g^?1 in 1 M Na₂SO₃ aqueous solution for the Fe₃O₄/C nanorods in comparison to that of 208.6 F?g^?1 for pure Fe₃O₄.     

Phase evolution of an aluminized steel by oxidation treatment

Effects of temperature and time on the microstructure and phase evolution for different thermal treatments were investigated with respect to the measurement of intermetallic layer thickness, phase identification and microhardness distribution in the aluminized zone of a steel substrate. The intermetallic phases present in the aluminized region after hot dip aluminizing is mainly Fe₂Al₅. The thickness of the intermetallic layers increases with increasing oxidation temperature and time. In the oxidation treatments of the aluminized steel in air, the initial Fe₂Al₅ phase remains at the temperature below 950 °C in 2-h, and the Fe₂Al₅ phase is completely transformed into low iron content Fe-Al intermetallics due to oxidation at 950 °C for 4 h. However, the Fe₂Al₅ phase remains in the outer layer of the aluminized samples diffusion-treated in vacuum regardless of diffusion time. The microhardness values of the Al₂O₃ and the intermetallic Fe₂Al₅, FeAl₂, FeAl and Fe₃Al phases are HV1150, HV1010, HV810, HV650 and HV320, respectively. The oxide layer formed on the steel substrate has an extremely fast adherence to the steel substrate and excellent properties of thermal shock resistance, high temperature oxidation resistance and anti-liquid aluminum corrosion.     

57Fe-DCEMS studies of thin corrosion layers

Summary The characterization of the corrosion products formed on an⁵⁷Fe film onto a low alloy steel disc after 4 h and 8 h exposure to an artificially SO₂-polluted atmosphere has been carried out by ICEMS/DCEMS. The corrosion products found are FeSO₃·3H₂O, FeSO₄·nH₂O, a third unidentified Fe²⁺ species, an amorphous Fe³⁺ oxyhydroxide and a second Fe³⁺ species which could correspond to superparamagnetic α-FeOOH or ferrihydrite. Although the DCEM spectra recorded at different electron energies do not show dramatic differences in the relative concentrations with depth, the results suggest that FeSO₃·3H₂O is preferentially located in the inner part of the corrosion layer whilst the outer part is richer in FeSO₄·nH₂O and Fe³⁺ species. Paper presented at the ICAME-95, Rimini, 10–16 September 1995     

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.     

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.