Characterization of Iron Oxides Commonly Formed as Corrosion Products on Steel
TL;DR: In this paper, the relative fraction of each iron oxide can be accurately determined from the Mossbauer subspectral area and recoil-free fraction for each phase, at temperatures of 300K, 77K and 4K.
Abstract: 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 Mossbauer 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 Mossbauer subspectral area and recoil-free fraction of each phase. The different Mossbauer 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.
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TL;DR: In this article, a very low laser powers were applied to distinguish between the different iron oxides occurring in soils, and a wuestite band at about 595 cm −1 could be established enabling a non-ambiguous identification of this mineral by its Raman spectrum.
Abstract: SUMMARY Raman spectroscopy uses the inelastic scattering of electromagnetic radiation by molecules. Monochromatic light of a laser interacts with phonons, the vibrational modes in the crystal lattice. The energy of the scattered light is shifted by the scattering. The shifts in energy yield the Raman spectrum that is specific for each mineral because the phonons are specific for each mineral. In this study, Raman spectroscopy of synthetic and natural iron (oxy)hydroxides and iron oxides was performed to test its potential in environmental magnetic studies and soil science. The main aim was to distinguish between the different iron oxides occurring in soils. Most of them can be identified by magnetic methods, but there are some minerals that are not easy to differentiate from each other. In these cases, the magnetic methods can be complemented by Raman spectroscopy. A major challenge is the fast transformation of many iron minerals if laser power is applied, especially if the material is poorly crystallized as often is the case in environmental material. In this study, very low laser powers were applied. Nevertheless, the investigated iron minerals could be distinguished from each other. Thus, a magnetic method to discern lepidocrocite and ferrihydrite in soil samples could be corroborated. It is also shown that Raman spectroscopy is an easy method to distinguish magnetite and maghemite. Due to the low laser powers applied, a wuestite band at about 595 cm −1 could be established enabling a non-ambiguous identification of this mineral by its Raman spectrum. Furthermore, the potential of the method to investigate magnetic material produced by soil bacteria is demonstrated.
667 citations
Cites methods from "Characterization of Iron Oxides Com..."
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...The method has been used for the analysis of corrosion products (Oh et al. 1998; Thibeau et al. 1978) or oxide scales formed in production processes (Bhattacharya et al. 2006), the characterization of pigments in archaeological material (Clark & Curri 1998; Damiani et al. 2003) and historical…...
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TL;DR: In this article, three iron oxide polymorphs, hematite, maghemite, and magnetite, were produced on KBr substrates using a conventional electron beam deposition technique coupled with thermal annealing.
Abstract: Thin films of three iron oxide polymorphs, hematite, maghemite, and magnetite, were produced on KBr substrates using a conventional electron beam deposition technique coupled with thermal annealing. This method allowed for iron oxide thin films free from chemical precursor contaminants. The films were characterized using Fourier-transform infrared spectroscopy (FTIR), Raman microspectroscopy, and ellipsometry. These spectroscopic techniques allowed for a clear assignment of the phase of the iron oxide polymorph films produced along with an examination of the degree of crystallinity possessed by the films. The films produced were uniform in phase and exhibited decreasing crystallinity as the thickness increased from 40 to 250 nm.
653 citations
TL;DR: In this paper, structural and magnetic properties, methods of synthesis, and applications of seven iron(III) oxide polymorphs, including rare beta, epsilon, amorphous, and high pressure forms, are reviewed.
Abstract: Structural and magnetic properties, methods of synthesis, and applications of seven iron(III) oxide polymorphs, including rare beta, epsilon, amorphous, and high-pressure forms, are reviewed. Thermal transformations resulting in the formation of iron oxides are classified according to different parameters, and their mechanisms are discussed. 57Fe Mossbauer spectroscopy is presented as a powerful tool for the identification, distinction, and characterization of individual polymorphs. The advantages of Mossbauer spectroscopy are demonstrated with two examples related to the study of the thermally induced solid-state reactions of Fe2(SO4)3.
571 citations
TL;DR: In this paper, the micro-Raman spectra of hematite, magnetite and other iron oxides were compared with literature data and compared with a Stokes-Anti-Stokes procedure was used to control the local temperature during the measurement and also for calibration of the wavenumbers.
Abstract: Films and powders of iron oxide (Fe2O3) prepared by two different sol–gel syntheses, starting from Fe(NO3)3·9H2O or FeCl3·6H2O, were investigated by Raman microscopy. Different phases with different morphology were produced according to the preparation. The spectra obtained in the micro-Raman configuration were compared with the ambiguous data in the literature given by conventional Raman techniques. The principal difficulty in the correct interpretation of the Raman spectrum of the iron oxides is the co-existence of different phases. Contradictory results are also explained by laser–induced thermal effects which easily change the wavenumbers and lineshapes of the phonons. A Stokes–Anti-Stokes procedure was utilized to control the local temperature during the measurement and also for calibration of the wavenumbers. The micro-Raman spectra of hematite, magnetite and other iron oxides are presented and compared with literature data. Copyright © 1999 John Wiley & Sons, Ltd.
471 citations
TL;DR: A general model is developed that considers spinel defects and absorbed/adsorbed species as dominant controls on structural changes with particle size in hematite nanoparticles, including solid-state phase transitions, and supports the existence of intermediate phases during dehydration of goethite.
Abstract: Using Fourier Transform InfraRed (FTIR) spectroscopy, Raman spectroscopy, X-ray diffraction (XRD), and Transmission Electron Microscopy (TEM), we characterize the structure and/or morphology of hematite (α-Fe2O3) particles with sizes of 7, 18, 39 and 120 nm. It is found that these nanoparticles possess maghemite (γ-Fe2O3)-like defects in the near surface regions, to which a vibrational mode at 690 cm−1, active both in FTIR and Raman spectra, is assigned. The fraction of the maghemite-like defects and the net lattice disorder are inversely related to the particle size. However, the effect is opposite for nanoparticles grown by sintering of smaller hematite precursors under conditions when the formation of a uniform hematite-like structure throughout the aggregate is restricted by kinetic issues. This means that not only particle size but also the growth kinetics determines the structure of the nanoparticles. The observed structural changes are interpreted as size-induced α-Fe2O3
↔
γ-Fe2O3 phase transitions. We develop a general model that considers spinel defects and absorbed/adsorbed species (in our case, hydroxyls) as dominant controls on structural changes with particle size in hematite nanoparticles, including solid-state phase transitions. These changes are represented by trajectories in a phase diagram built in three phase coordinates—concentrations of spinel defects, absorbed impurities, and adsorbed species. The critical size for the onset of the α
→
γ phase transition depends on the particle environment, and for the dry particles used in this study is about 40 nm. The model supports the existence of intermediate phases (protohematite and hydrohematite) during dehydration of goethite. We also demonstrate that the hematite structure is significantly less defective when the nanoparticles are immersed in water or KBr matrix, which is explained by the effects of the electrochemical double layer and increased rigidity of the particle environment. Finally, we revise the problem of applicability of IR spectroscopy to the lattice vibrations of hematite nanoparticles, demonstrating that structural comparison of different samples is much more reliable if it is based on the Eu band at about 460 cm−1 and the spinel band at 690 cm−1, instead of the A2u/Eu band at about 550 cm−1 used in previous work. The new methodology is applied to analysis of the reported IR spectra of Martian hematite.
387 citations
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TL;DR: In this paper, the inner stable and protective rust layer which covered the surface of weathering steel mainly consists of nano-particles of α-FeOOH containing a considerable amount of Cr.
430 citations
TL;DR: In this article, the Raman spectra of FeO, Fe3O4, α-Fe2O3, α -FeOOH, and γ-FeOH, the common products of iron oxidation have been measured.
Abstract: Raman spectra of FeO, Fe3O4, α-Fe2O3, α-FeOOH, and γ-FeOOH, the common products of iron oxidation, have been measured. The spectra of FeO and Fe3O4 appear to be identical. Armco iron oxidized in air at 250°C was examined by Raman spectroscopy after varying periods of exposure and the surface film was found to contain Fe3O4 and α-Fe2O3.
286 citations
TL;DR: In this article, the second-order Doppler shift of α-Fe2O3 with selected Fe2+ or Fe3+ compounds was used to calculate the Mossbauer fraction f for various ferrous and/or ferric-containing oxides and oxyhydroxides, silicates and carbonates.
Abstract: The Mossbauer fractions f for various ferrous- and/or ferric-containing oxides and oxyhydroxides, silicates and carbonates were evaluated from the experimental temperature dependence of their center shifts, using the Debye approximation for the second-order Doppler shift. It is concluded that ferrous ions exhibit a lower fraction as compared to ferric ions. Using standard mixtures of α-Fe2O3 with selected Fe2+ or Fe3+ compounds, it is found that the calculated Fe3+
f values are somewhat overestimated with respect to those of Fe2+. Possible explanations for this shortcoming are discussed and it is suggested that a different temperature dependence of the intrinsic isomer shift is the most likely reason. This suggestion is corroborated by analyses of hematite and hedenbergite data which are available for temperatures up to 900 K and 800 K respectively.
217 citations
TL;DR: In this paper, the Evans model of atmospheric corrosion was used to replace Fe 3 O 4 by Fe(OH) 2 as the reduced state in the reduced states of Fe(O 4 ) and α-FeOOH.
186 citations
TL;DR: In this paper, it was found that the ratio of magnetite to hematite in the surface oxide film appears to increase with increasing water vapor pressure, ascending temperature, and extending oxidation time.
Abstract: Laser Raman spectroscopy (LRS) has been applied for the detection and characterization of thin corrosion films formed on iron in air at a temperature range from 100 to 150 C. In situ ellipsometric measurements have also been conducted for quantitative estimations of the film growth kinetics. It is found that (1) the oxidation of iron in dry air leads to the formation of a surface oxide film composed primarily of magnetite and (2) the water vapor in air accelerates the formation of hematite. The ratio of magnetite to hematite in the surface oxide film appears to increase with (1) increasing water vapor pressure, (2) ascending temperature, and (3) extending oxidation time.
144 citations