Mössbauer study of the corrosion behaviour of pure iron and weathering steel under a wet-dry cycle

Mossbauer spectroscopy (MBS) and X-ray diffraction (XRD) have been used to establish the composition of the rust layer formed on weathering steel and pure iron under several wet-dry cycles in a SO₂-polluted atmosphere. FeSO₃−3H₂O, FeSO₄−4H₂O, and poorly crystalline ferrihydrite were identified as the only corrosion products. The Mossbauer spectrum of FeSO₃−3H₂O is reported.     

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.     

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.     

Corrosion studies of iron and its alloys by means of57Fe Mössbauer spectroscopy

Some of the advantages and limitations of Mössbauer spectroscopy when used in corrosion research are shown by using three examples taken from the work of the authors on (i) the passive layer of iron, (ii) the corrosion of weathering steels by SO₂-polluted atmospheres and (iii) the performance of rust converters.     

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.     

Corrosion of weathering steel and iron under wet-dry cycling conditions: Influence of the rise of temperature during the dry period

The effect of a dry-hot period on the SO₂ corrosion of weatherig steel and pure iron under wet-dry cycling was investigated. Corrosion products were identified by Mössbauer spectroscopy and X-ray powder diffraction. The formation of an intermediate corrosion layer of spm α-FeOOH only on weathering steel was the most significant result.     

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.     

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^?).     

Comparative Mössbauer and sem study of the corrosion reaction of iron and weathering steel in SO2-polluted atmospheres

A kinetic CEMS study of the early corrosion stages of iron and weathering steel in low (LAC) and very low (VLAC) SO₂-polluted atmospheres has been carried out. The morphology and sulphur content of corrosion products were examined with SEM-EDAX.     

Indoor atmospheric corrosion of conventional weathering steels in the tropical atmosphere of Panama

One year indoor atmospheric corrosion examinations have been carried out on two conventional weathering steels for a year, at two test sites, Tocumen and Sherman Breakwater in Panama. They are environmentally classified by ISO 9223 as S₁P₀ τ ₄ and S₃P₀ τ ₅, respectively. In this humid-tropical marine climate corrosion rates are rather high, especially at Sherman Breakwater test site, mainly due to the high deposition of chloride, among other environmental conditions. Our results indicate that indoor corrosion is highly determined by the time of wetness and chloride ions. A-588 weathering steel corroded at a generally lower rate than COR-420 weathering steel. Rust characterization was performed by XRD, FTIR, and Mössbauer spectroscopy. Lepidocrocite, goethite, maghemite and akaganeite were found as corrosion products. Akaganeite is only detected when high chlorides deposition rates are obtained, and no washing effect occurs. This phase, together with maghemite, is obtained when there is greater aggressiveness in the environment.     

Re-examination of Dronino iron meteorite and its weathering products using Mössbauer spectroscopy with a high velocity resolution

Re-examination of Dronino iron meteorite and products of its weathering in the internal and external surface layers was carried out using Mössbauer spectroscopy with a high velocity resolution. New results showed the presence of α-Fe(Ni, Co), α ₂-Fe(Ni, Co) and γ-Fe(Ni, Co) phases with variations in Ni concentration in Dronino metallic iron alloy. The surface weathering products were supposed as magnetite and/or maghemite, goethite with different particles size and probably ferrihydrite in the internal layer and goethite with different particles size and probably ferrihydrite in the external layer.     

Analysis of atmospheric corrosion products of steel and coated steel by means of scattering Mössbauer spectrometry

Wearthering steels treated with and without zinc phosphate solution were exposed to atmosphere for 15 years and rust layers produced on the steels were analysed by scattering Mössbauer spectrometry (CEMS and XMS). γ-FeOOH, fine α-FeOOH, 5Fe₂O₃·9H₂O, γ-Fe₂O₃ and Fe₃O₄ were identified to be present in the rust formed on the steel without phosphate coating. Large particles of γ-Fe₂O₃ and Fe₃O₄ formed on the uncoated steel exposed to atmosphere in a position facing north on vertical plane. The layer structure of rust was affected by the position. The thin rust layer formed on the phosphate + carylite resin coated steel was considered to consist of γ-FeOOH, fine α-FeOOH, and fine γ-Fe₂O₃.     

Recent Research and Development in Solving Atmospheric Corrosion Problems of Steel Industries in Japan

A rust layer, so called protective rust layer, on a weathering low-alloy steel has strong protective ability for atmospheric corrosion of the steel. We have recently found through a large number of spectroscopic studies including Mössbauer spectroscopy that the protective rust layer forms after long-term phase transformation. The phase and structure of the rust definitely control the protective ability of the rust layer. From this recent knowledge, some new technologies have been developed. One is the surface-treatment technique that provides a possibility for obtaining the protective rust layer in a relatively short period even in the severe environments such as in marine and chloride (de-icing salts) containing environments. Others are based on selection of effective alloying elements for steel materials. These are particularly important for application in areas where protective rust layer formation may be hindered or prevented. In this paper, we mention recent progress in research and development on rusting protection by rust for atmospheric corrosion of steels in Japan.     

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 role of the spinel phases on the rust activity in corroded steels

Carbon, CS, and weathering steels, WS, were totally immersed in a NaCl containing solution. The influence of steel composition and the presence/absence of air flux into the solution on the physical properties of spinel and other iron phases were investigated. Large amounts of defective magnetite were formed only on CS, whereas little amounts of small grain-sized defective maghemite were detected only on WS. The chemical composition of the steels greatly affects the type of spinel phase being formed and their relative abundance. A non-aerated environment favored the formation of magnetite in CS. The protective ability of the rust was unfavored in the presence of large amounts of spinels.     

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.     

On the Rust Products Formed on Weathering and Carbon Steels Exposed to Chloride in Dry–Wet Cyclical Processes

The rust products formed on weathering and carbon steels exposed to dry–wet cyclical processes in different chloride-rich solutions are carefully examined by means of different techniques. Special emphasis is given to the methodology of analysis of the data using 300 K and 77 K Mössbauer spectrometry and X-ray diffraction. The rust that is loosely bound to the metal surface and that it is lost during the corrosion process, for both types of steel, was found to be composed of lepidocrocite, superparamagnetic goethite, hematite, and traces of akaganeite. On the other hand, the adherent rust, which is differentiated as scraped and hit according to the way it is obtained, from both steels was found to be composed of akaganeite, spinel phase, goethite exhibiting broad distribution of particle sizes and lepidocrocite. The relative abundances of rust components for both steels were very similar, suggesting similar corrosion processes. Mass loss measurements show that the corrosion rates increases with increasing the chloride concentration. The presence of large quantities of spinel phase and akaganeite are a consequence of a corrosion process under the influence of very high chloride concentrations. Our results are useful for assessing the behavior of weathering steels where the levels of chlorides are high or in contact with sea water.     

Aes study of the segregation behaviour of silicon in high-silicon steel during oxidation

The segregation behaviour of silicon during oxidation of a high-silicon steel has been investigated by AES. The results show that silicon seems to have two states of oxidation: one leading to the formation of SiO_x and iron oxides when the oxidation and the following heat treatments in vacuum are performed below 500°C and the other occurring at temperatures higher than 500°C, leading to the formation of SiO₂ and segregation of this species toward the surface without oxidation of iron.     

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.