Corrosion resistance of the Dhar iron pillar

The corrosion resistance of the 950-year old Dhar iron pillar has been addressed. The microstructure of a Dhar pillar iron sample exhibited characteristics typical of ancient Indian iron. Intergranular cracking indicated P segregation to the grain boundaries. The potentiodynamic polarization behaviour of the Dhar pillar iron and mild steel, evaluated in solutions of pH 1 and 7.6, indicate that the pillar iron is inferior to mild steel under complete immersion conditions. However, the excellent atmospheric corrosion resistance of the phosphoric Dhar pillar iron is due to the formation of a protective passive film on the surface. Rust analysis revealed the presence of crystalline magnetite (Fe_3−xO₄), α-Fe₂O₃ (hematite), goethite (α-FeOOH), lepidocrocite (γ-FeOOH), akaganeite (β-FeOOH) and phosphates, and amorphous δ-FeOOH phases. The rust cross-section revealed a layered structure at some locations.     

低碳钢在海水中的阴极电化学行为

采用电化学技术结合XRD分析, 研究了A3碳钢在海水中的阴极电化学行为, 探讨了锈层在阴极过程中的作用. 碳钢表面生成的锈层由内锈层和外锈层组成, 内锈层主要组成相为γ-FeOOH, α-FeOOH, β-FeOOH以及Fe₃O₄与γ-Fe₂O₃的混合物. 浸泡126 d时, 外锈层主要由γ-FeOOH组成; 浸泡364 d由γ-FeOOH, α-FeOOH, Fe₃O₄和 γ-Fe₂O₃组成. 不同锈层在阴极过程中所起的作用不同. 外锈层主要作用是阻碍溶解氧到达金属表面, 内锈层除此之外还可以参与还原反应, 加速阴极反应. 提出了一个评价锈层参与还原反应程度的参数α, 在浸泡不同时期锈层参与还原反应的比例不同, 浸泡前7 d, α值上升比较明显, 随后增加比较缓慢, 浸泡168 d后基本稳定. 探讨了内、外锈层组分的变化以及锈层各组分间的相互作用.     

Short-term atmospheric corrosion of mild steel at two weather and pollution monitored sites

Results are recorded of topographical details, weight loss and corrosion product analysis for short-term atmospheric exposure of mild steel, in relation to weather and pollutant factors. Various structured corrosion features, e.g. doughnut-like, were noted. The major corrosion product found was γ-Fe₂O₃,H₂O, with some α-Fe₂O₃,H₂O and α-FeOOH.Wet initial conditions of exposure and subsequent high levels of humidity, were found to have the dominant overriding effect in promoting corrosion losses. Smoke was shown to be capable of exerting a very strong influence upon the effective corrosivity of atmospheric sulphur dioxide.     

In-depth distribution of rusts on a plain carbon steel and weathering steels exposed to coastal-industrial atmosphere for 17 years

In-depth distribution of rusts on two weathering steels and a plain carbon steel exposed to atmosphere for 17 years under a bridge at a coastal + industrial region in Japan were studied. In the rust layer on all specimens, α-FeOOH, β-FeOOH, γ-FeOOH, Fe₃O₄ and so-called amorphous rust were found. Within rust layers, there were thick parts and thin parts, which were finely and complicatedly distributed on steels. Among these rust species, α-FeOOH was dominant on all specimens. α-FeOOH appeared almost homogeneously through the rust layer. Its concentration was higher on weathering steels than on plain carbon steel. β-FeOOH was found mainly at thick parts and was scarce at thin parts of rust layers. Concentration of α-FeOOH was higher and that of γ-FeOOH was lower on weathering steels than on plain carbon steel. Amorphous rust was located at the bottom of the rust layer irrespective of steel types. Concentration of magnetite was negatively correlated with concentration of β-FeOOH.     

Röntgenamorphe Phasen im Rost

X-ray amorphous phases in rust The sum of the crystalline phases found during a quantitative X-ray analysis of rust is always below 100%. An attempt was therefore made to identify amorphous phases in several characteristic Of different types Of rust; to this end a combination was used of quantitative phase analysis by X-rays and chemical extraction. Rust from industrial, forest and lake environments does not contain amorphous components. The crystalline deficit found during phase analysis is due to lattice distorsions in the crystalline Phase α-FeOOH, γ-FeOOH and Fe₃O₄; the distorsions are greatest in the α-phase and smallest in Fe₃O₄. Rust from water ducts and maritime environments sometimes contains X-ray amorphous components. It is possible, however, that these components are formed only by the treatment Of rust samples in the air and that rust of this type does not contain any amorphous phase in its original environment.     

A Mössbauer spectroscopic study of rust formed during simulated atmospheric corrosion

Steel coupons were subjected to 100% relative humidity and were inoculated every day with 100 μl of 0.01 N solutions of NaCl, Na₂SO₄, LiCl or CsCl. The first solid rust constituent that formed contained significant amounts of both γ-FeOOH and ferrihydrite. In contrast, only γ-FeOOH was observed in the rust formed during atmospheric corrosion and during wet-dry cycling with distilled water in the laboratory. The ferrihydrite in time was converted to γ-FeOOH, α-FeOOH, and γ-Fe₂O₃. The fractions of ferrihydrite + γ-FeOOH in the rust formed as a function of time during atmospheric exposure and during rusting in the laboratory environment were the same in the two cases.     

Hydrogen permeation and corrosion behavior of high strength steel MCM 430 in cyclic wet-dry SO2 environment

Hydrogen permeation caused by corrosion under a cyclic wet (2 h)-dry (10 h) SO₂ condition was investigated for a high strength steel of MCM 430 by using an electrochemical technique in addition to the corrosion behavior obtained from weight loss measurement and the determination of corrosion products by using X-ray diffraction method. The hydrogen content converted from hydrogen permeation current density was observed in both wet and dry periods. The origin of proton was estimated to be from (1) the hydrolysis of ferrous ions, (2) the oxidation of ferrous ions and ferrous hydroxide, and (3) hydrolysis of SO₂ and formation of FeSO₄, but not from the dissociation of H₂O. With respect to the determination of the corrosion products consisting of inner (adherent) and outer (not adherent) layers, the outer layer is composed of α-FeOOH, amorphous phase and γ-FeOOH, where α-FeOOH increases with the increase in the wet-dry cycle, and amorphous phase shows the reverse trend. The corrosion product in the inner layer is mainly Fe₃O₄ with them. On the basis of the results obtained, the role of the dry or wet period, the effect of SO₂ and the corrosion process during the cyclic wet-dry periods were discussed.     

α-Fe2O3 nanoplates: PEG-600 assisted hydrothermal synthesis and formation mechanism

Quasi-hexagonal α-Fe₂O₃ nanoplates with lateral sizes of 40-60 nm and thickness of ca. 10 nm were fabricated by a facile poly(ethylene glycol 600) (PEG-600) assisted hydrothermal technique in combination with calcination method. The final α-Fe₂O₃ nanoplates inherited perfectly the morphology of the preliminarily hydrothermal products with phases of dominant α-Fe₂O₃ and minor α-FeOOH. The platelets could be tailored from nano- to meso- and to micro-scale via adjusting PEG-600 quantities. An adsorption-extension-attachment model was proposed to explain the formation and growth mechanism of the platelets. The as-obtained α-Fe₂O₃ nanoplates exhibited a specific Langmuir surface area of 59 m²/g and a maximum N₂ adsorption of 137.3 cm³/g at 1 atm. UV-vis measurement showed a strong absorption in a wide range from UV to visible light with a blue-shifting band gap of 2.33 eV due to the nanosize effect.     

Effects of DBU, morpholine, and DMA on corrosion of low carbon steel exposed to steam

Effects of morpholine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and dimethylamine (DMA) on oxidation kinetics and oxide phase formation/transformation of AISI 1018 steel at 120 °C were evaluated. Low carbon steel samples were exposed to steam in an autoclave containing amine added aqueous solution at pH of 9.5 for 1, 2, 4, 6, 8, and 12 h. Control samples exposed to plain steam and amines showed the highest and lowest weight loss respectively. Fourier Transform Infrared Spectrophotometry (FTIR) showed that DBU containing steam favored formation of magnetite (Fe₃O₄) while steam with DMA formed more α and γ-FeOOH. Transformation of magnetite to hematite (α-Fe₂O₃) was fastest for morpholine. Analysis of oxides morphology was done utilizing Scanning Electron Microscopy (SEM). Oxides formed in plain or DMA containing steam exhibited acicular particles of goethite/hematite (α-FeOOH/α-Fe₂O₃) compared to DBU containing steam that showed equiaxed particles of magnetite/maghemite (Fe₃O₄/γ-Fe₂O₃). Morpholine containing steam promoted agglomeration of thin sharp platelets into coarse flakes of hematite.     

Identification of corrosion products resulting from accelerated oxidation process

Abstract

Scanning electron microscopy analysis, X-ray powder diffraction and room temperature ⁵⁷Fe Mössbauer spectroscopy were used to identify the corrosion products of uncoated and coated low alloy steels (LAS) and low carbon steels (LCS) resulting from an accelerated steam oxidation test for 180 h at 660°C. From the Mössbauer spectral analysis, it was shown that in all cases, a series of iron compounds such as α-Fe₂O₃, Fe₃O₄, γ-Fe₂O₃, δ-FeOOH, α-FeOOH, Fe(OH)₂ and Fe(OH)₃ were formed, while XRD measurements revealed only the α-Fe₂O₃ and/or Fe₃O₄/γ-Fe₂O₃ phases. In the LAS uncoated sample, an amorphous phase with magnetic features is found. In the spectra of the borided samples and of the uncoated LCS, an additional doublet was observed, which reveals the presence of a superparamagnetic phase. From the relative areas of the subspectra, it is concluded that the boron aluminised sample underwent the lowest degradation. The mechanism proposed for corrosion products formation is based on the dissociation process.     

Iron oxide hollow spheres: Microwave–hydrothermal ionic liquid preparation,formation mechanism,crystal phase and morphology control and properties

This paper reports on the microwave–hydrothermal ionic liquid method for the synthesis of a variety of iron oxide nanostructures such as α-FeOOH hollow spheres, β-FeOOH architectures and α-Fe₂O₃ nanoparticles. The formation mechanism for α-FeOOH hollow spheres is discussed. The effects of the reaction parameters on the morphology and crystal phase of the final product are studied. The relationship between the morphology and crystal phase of the product is discussed. A general thermal transformation strategy is designed to prepare α-Fe₂O₃ hollow spheres using α-FeOOH hollow spheres as the precursor and template. By thermal treatment of the as-prepared α-FeOOH hollow spheres, α-Fe₂O₃ hollow spheres showing good photocatalytic activity are obtained. And by autocatalysis of the adsorbed available Fe(II) on the α-FeOOH surfaces, Fe₃O₄ hollow spheres are also obtained.     

Microstructural changes in particles detected during the transformation from β-FeOOH to α-Fe2O3 in dense aqueous suspensions

The hydrothermal transformation from β-FeOOH to α-Fe₂O₃ in dense aqueous suspensions, obtained by partial neutralization of concentrated FeCl₃ solution with concentrated NaOH solution, was investigated. Mössbauer spectroscopy was used for the phase analysis of samples, as well as the complementary techniques XRD and FT-IR. The size and morphology of the particles were inspected with FE-SEM. At the beginning of the crystallization process very fine β-FeOOH particles were formed, which transformed to α-Fe₂O₃ (end-product) with a prolonged time of heating. A small amount or traces of α-FeOOH as an intermediate phase were detected by FT-IR and FE-SEM. Gradual formation of α-Fe₂O₃ double spheres with ring was monitored. Double spheres with ring were formed by the aggregation mechanism. The orientation effect of α-Fe₂O₃ subunits in double spheres with ring was observed. α-Fe₂O₃ double spheres with ring also showed two narrow particle size distributions.     

Field sludge characterization obtained from inner of pipelines

Physicochemical characterization of sludge obtained from refined hydrocarbons transmission pipeline was carried out through Mössbauer spectroscopy and X-ray diffraction. The Mössbauer and X-ray patterns indicate the presence of corrosion products composed of different iron oxide and sulfide phases. Hematite (α-Fe₂O₃), magnetite (Fe₃O₄), maghemite (γ-Fe₂O₃), magnetic and superparamagnetic goethite (α-FeOOH), pyrrhotite (Fe_1−xS), akaganeite (β-FeOOH), and lepidocrocite (γ-FeOOH) were identified as corrosion products in samples obtained from pipeline transporting Magna and Premium gasoline. For diesel transmission pipeline, hematite, magnetite, and magnetic goethite were identified. Corrosion products follow a simple reaction mechanism of steel dissolution in aerated aqueous media at a near-neutral pH. Chemical composition of the corrosion products depends on H₂O and sulfur inherent in fluids (traces). These results can be useful for decision-making with regard to pipeline corrosion control.     

Characteristics of iron corrosion scales established under blending of ground, surface, and saline waters and their impacts on iron release in the pipe distribution system

Interior scales on PVC, lined ductile iron (LDI), unlined cast iron (UCI) and galvanized steel (G) were analyzed by XRD, RMS, and XPS after contact with varying water quality for 1 year. FeCO₃, α-FeOOH, β-FeOOH, γ-Fe₂O₃, Fe₃O₄ were identified as primary UCI corrosion products. No FeCO₃ was found on G. The order of Fe release was UCI > G ? LDI > PVC. For UCI, Fe release decreased as % Fe₃O₄ increased and as % Fe₂O₃ decreased in scale. Soluble Fe and FeCO₃ transformation indicated FeCO₃ solid was controlling Fe release. FeCO₃ model and pilot data showed Fe increased as alkalinity and pH decreased.     

The atmospheric corrosion of iron as studied by Mössbauer spectroscopy

The composition of the rust on the surface of steel panels was determined after atmospheric exposure times of 2 weeks, 2 months and 6 months. The initial product is γ-FeOOH which converts in time to a mixture of α-FeOOH and γ-Fe₂O₃. Steel exposed for times of the order of 25 years is covered with corrosion product consisting largely of γ-Fe₂O₃. The similarity between the composition of the corrosion products and precipitates formed from FeSO₄ solution under mildly acidic conditions at 90°C suggests that the dominant anion in these atmospheric corrosion experiments is sulfate.     

Composition and protective ability of rust layer formed on weathering steel exposed to various environments

The compositional change of rust (corrosion products) layer formed on weathering steel exposed to atmosphere with different amount of air-borne sea salt particles in Japan have been investigated by the X-ray diffraction method. The mass ratio (α/γ) of crystalline α-FeOOH to γ-FeOOH, in the rust layer formed on the weathering steel exposed in an industrial environment, increases with an increase in exposure duration. The α/γ is closely related to the corrosion rate in environments when the amount of air-borne salt is less than 0.2 mg NaCl/dm²/day (2.31 × 10⁻⁷ g NaCl/m²/s). However this is not the case in seaside environments with a higher amount of air-borne salts. The mass ratio (α/γ^∗) of crystalline α-FeOOH to the total mass of γ-FeOOH, β-FeOOH and Fe₃O₄, in the rust layer formed on the weathering steel is related to the corrosion rate even in seaside environments certainly more than 0.2 mg/dm²/day (2.31 × 10⁻⁷ g/m²/s) of air-borne salt particles. When the α/γ^∗ is more than 1, a higher corrosion rate more than 0.01 mm/year (3.17 × 10⁻¹³ m/s) is not observed. The α/γ^∗ is a protective ability index of rust formed on weathering steel.     

An electrochemical study of phase-transitions in rust layers

Isolated rust layers have been investigated by electrochemical methods to find out whether their reduction and re-oxidation can affect the atmospheric corrosion of iron. At potentials below 0 mV, first a thin Fe²⁺-containing surface layer is formed on top of the γ-FeOOH. This reduced surface layer can dissolve into the cell electrolyte at acid pH, or at lower potentials the Fe²⁺-ions can react with γ-FeOOH to Fe₃O₄. The formation of magnetite could be followed by in-situ magnetic measurements. The reduced surface layer can easily be oxidized back to γ-FeOOH, magnetite can partly be oxidized to γ-Fe₂O₃.     

Mechanisms of the dechlorination of iron archaeological artefacts extracted from seawater

Treatments based on the immersion of iron artefacts in NaOH or KOH solutions with or without cathodic polarisation of the metal core, used for conservation purposes, were applied to Gallo-Roman iron ingots excavated from the Mediterranean Sea. The transformation of the initial layer of β-Fe₂(OH)₃Cl was followed with time. The resulting phases were characterised by a complete set of multi-scale complementary techniques. It could be demonstrated that the main process involved successively the transformation of β-Fe₂(OH)₃Cl into Fe(OH)₂ and the oxidation of Fe(OH)₂ into α-/δ-FeOOH and magnetite. Cathodic polarisation accelerated, via migration processes, the removal of chloride ions.     

The mechanism of formation of iron oxide and oxyhydroxides in aqueous solutions at room temperature

For a better understanding of the atmospheric rusting of iron and steels, the present work is aimed to explore the mechanism of formation of green rusts, Fe₃O₄, α-FeOOH, β-FeOOH, γ-FeOOH, δ-FeOOH and amorphous ferric oxyhydroxide in aqueous solution at room temperature. The formation processes on which end products are determined are strongly affected by the oxidation rate, pH and the structure and composition of initial and intermediate species of iron. The systematic diagram of formation processes of iron oxide and oxyhydroxides has been presented, in which both dissolved and solid species of iron are included.     

Cu、Mn的协同作用对低合金钢在模拟海洋大气环境中腐蚀的影响

    用增重法、扫描电镜、X射线衍射、电子探针和X射线光电子能谱等手段研究了在模拟海洋大气干湿交替环境下16Mn钢和Cu-Mn耐候钢的腐蚀行为及Cu、Mn共添加对低合金钢腐蚀行为的影响.结果表明：Cu-Mn耐候钢的腐蚀速率低于16Mn钢,其锈层更致密;两种钢的铁锈均由Fe₃O₄,α-FeOOH,β-FeOOH,γ-FeOOH和大量无定形相组成;添加Cu使Fe₃O₄含量增加,添加Mn使γ-FeOOH含量减少;Cu在Cu-Mn耐候钢锈层中以CuFeO₂存在;Mn在两种钢锈蚀初期以MnO存在,后期为Mn₃O₄.Cu、Mn的协同作用使Cu-Mn耐候钢抗大气腐蚀性能优于16Mn钢.