The First-Stage Kinetics of the Iron Anodic Ionization in Acidic Sulfate Solutions

The hypothesis that water molecules are involved in the anodic dissolution of iron in acidic sulfate solutions is confirmed experimentally. The oxidation of Fe⁰ iron to Fe⁺ is shown to proceed in stages: at the first stage, the interaction between the metal and water molecules results in the formation of surface charge-transfer complexes, which then decompose to form the adsorbed OH groups. The charge transfer in the complexes is estimated to be about 0.5.     

Determination of the corrosion products of iron in sea water with and without sulphides

A method was developed to characterize and quantify iron corrosion products in clean and sulphide polluted sea water. This method is based upon a selective dissolution with suitable reagents (methanol, glycine, bromine-methanol, hydrochloric acid etc.) of the various compounds and the subsequent chemical analysis of the various dissolved elements. The information thus obtained is integrated by a diffractometric X-ray analysis. The following corrosion products were found:

• Fe(OH)₂ = Fe₃O₄ ? FeO(OH) ? Fe₂O₃ + unidentified compound Cr (probably oxychloride) in sea water with pH = 8.1 having a 7 ppm D.O. content.

FeOC1 ? Fe(OH)₂ ? Fe₃O₄ ? FeO.OH in partially deoxygenated sea water (D.O. = 3 ppm) at pH 8.1; Fe_0.95S ? Fe(OH)₂ in sea water at pH = 7 with 10 ppm of sulphides; Fe_0.95S ? FeS ? Fe_3.6 · Fe_0.9(O · OH · C1) and FeOC1 ? iron oxisulphide ? Fe₃O₄ ? FeO(OH) ? Fe₂O₃ · H₂O in sea water at pH = 7 and 10 ppm initial sulphides left to oxidate. Since the method of chemical analysis thus developed supplies quantitative information in iron distribution among the various anions and on the various oxidation forms, it is deemed a useful tool for investigation of the corrosion kinetics and mechanism.     

Thermodynamic analysis of Na-S-Fe-H2O system for Bayer process

Thermodynamic diagrams of Na-S-Fe-H₂O system were constructed to analyze the behavior of sulfur and iron in the Bayer process. After digestion, iron mainly exists as Fe₃O₄ and Fe₂O₃ in red mud, and partial iron transfers into solution as Fe(OH)₃^-, HFeO₂^-, Fe(OH)₄^- and Fe(OH)₄^2-. The dominant species of sulfur is S^2-, followed by SO₄^2-, and then SO₃^2- and S₂O₃^2-. The thermodynamic analysis is consistent with the iron and sulfur species distribution in the solution obtained by experiments. When the temperature decreases, sulfur and iron can combine and precipitate. Controlling low potential and reducing temperature are beneficial to removing them from the solution. XRD patterns show that NaFeS₂·2H₂O, FeS and FeS₂ widely appear in red mud and precipitates of pyrite and high-sulfur bauxite digestion solution. Thermodynamic analysis can be utilized to guide the simultaneous removal of sulfur and iron in the Bayer process.     

Influence of lactate ions on the formation of rust

The formation of rust can be simulated by oxidation of aqueous suspensions of Fe(OH)₂ obtained by mixing solutions of NaOH and a Fe(II) salt. The aim of this study was to investigate the influence of organic species associated with microbially influenced corrosion. The lactate anion, often used as a carbon and electrons source for the development of microorganisms, was chosen as an example. Then, in the first part of the study, Fe(OH)₂ was precipitated using iron(II) lactate and NaOH. Its oxidation process involved two stages, as usually observed. The first stage led to a Fe(II-III) intermediate compound, the lactate green rust, . This compound has never been reported yet. Its existence demonstrates that the GR structure is able to incorporate a very wide range of anions, whatever the size and geometry. The second stage corresponded to the oxidation of . It led to ferrihydrite, the most poorly ordered form of iron(III) oxides and oxyhydroxides. In the second part of the study, the formation of rust in seawater was simulated by oxidation of Fe(OH)₂ in an aqueous media containing both Cl⁻ and anions. The first stage led to the sulphate green rust, , the second stage to lepidocrocite γ-FeOOH. Small amounts of iron(II) lactate were added to the reactants. Lactate ions did not modify the first stage but drastically perturbed the second stage, as ferrihydrite was obtained instead of γ-FeOOH.     

Some aspects of the mechanism of high-temperature oxidation of nickel in SO2

A number of investigations on the mechanism of reaction of nickel with SO₂ has been summarized. The calculation results of the equilibrium gas composition in homogeneous SO₂+O₂ mixtures are described over wide ranges of temperatures (500–1100°C) and initial gas compositions. The Ni–O–S phase diagram at 540°C has been compared with data on the stability of interaction products under conditions close to equilibrium. The catalytic activity of NiO has been verified to accelerate the attainment of thermodynamic equilibrium in the SO₂–O₂–SO₃ system. The most effective catalytic activity of NiO occurred at 650–800°C. A monolayer (6 Å) of NiSO₄ was detected on the scale surface by ESCA. This surface phase is assumed to be formed either as an activated complex on the NiO catalyst or as the locally stable NiSO₄ phase. Both assumptions lead to a possible recognition of the sulfate intermediate mechanism.     

Das anodische und kathodische Verhalten des Eisens in sulfathaltigen Elektrolyten. Chaire d'Electrochimie,Faculté des Sciences,Strasbourg, France

The anodic and cathodic behaviour of iron in sulphate containing electrolytes The formation of Fe₂(SO₄)₃ on passive iron at p_H = 1 appears probable from a thermodynamical point of view. At high SO₄^2? concentrations the equilibrium system contains but low concentrations of Fe³⁺, and no Fe²⁺ ions, a fact showing the relatively elevated stability of the Fe₂(SO₄)₃ layer on passive iron. In slightly acid solution (p_H = 4) the passivity of the iron is determined by iron oxide layers. The formation of FeSO₄ from metallic iron and sulphate ions is restricted to the transpassive zone (p_H 4 to 7), in alkaline solutions even to the active zone. In the p_H region 2 to 14 the passive layer on iron has about the same composition in the systems Fe|H₂O + SO₄^2? and Fe|H₂O.     

Phase transformations during tempering of quenched Fe−N alloys

Conclusions It was found that tempering processes are similar in quenched steel and nitrided iron — in the first stage of tempering (20–180°) the martensite with nitrogen transforms, with formation of metastable F₁₆N₂ and temper martensite; in the second stage (180–300°) the retained austenite decomposes and the Fe₁₆N₂ Fe₄N transformation occurs; in the third stage (300–550°) the number of lattice defects decreases and the Fe₄N particles coalesce. After quenching and tempering at 500–600° the alloy consists of a ferrite—nitride mixture of the type of temper sorbite in carbon steel.Kiev Polytechnical Institute. Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 3, pp. 28–30, March, 1974.     

Coprecipitation thermodynamics of iron(II-III) hydroxysulphate green rust from Fe(II) and Fe(III) salts

Iron(II-III) hydroxysulphate GR(SO₄²⁻) was prepared by precipitating a mixture of Fe(II) and Fe(III) sulphate solutions with NaOH, accompanied in most cases by iron(II) hydroxide, spinel iron oxide(s) or goethite. Its [Fe(II)]/[Fe(III)] ratio determined by transmission Mössbauer spectroscopy was 2±0.2, whatever the initial [Fe(II)]/[Fe(III)] ratio in solution. Proportion of Fe(OH)₂ increased when the initial [Fe(II)]/[Fe(III)] ratio increased, whereas proportion of α-FeOOH or spinel oxide(s) increased when this ratio decreased. GR(SO₄²⁻) is metastable vs. Fe₃O₄ except in a limited domain around neutral pH. Precipitation from solutions containing both Fe(II) and Fe(III) dissolved species seems to favour GRs formation with respect to stable systems involving iron (oxyhydr)oxides.     

Anodic Behavior of White Iron Phases in Oxalic Media

Potential–pH diagrams of the iron–oxalic acid and ferric carbide–oxalic acid systems taking into account the equilibrium iron or ferric carbide and ferrous (II) oxalate are plotted. Kinetic investigations of the anodic dissolution of white iron, containing ferritic (99.975% Fe) and cementite (Fe₃C) phases, oxalic acid environment evidence that the alloy is passivated due to the formation of a FeC₂O₄ polylayer.     

The influence of Zn-dopant on the precipitation of α-FeOOH in highly alkaline media

The influence of Zn-dopant on the precipitation of α-FeOOH in highly alkaline media was monitored by X-ray diffraction (XRD), ⁵⁷Fe Mössbauer and Fourier transform infrared (FT-IR) spectroscopies and field emission scanning electron microscopy (FE SEM). Acicular and monodisperse α-FeOOH particles were precipitated at a very high pH by adding a tetramethylammonium hydroxide solution to an aqueous solution of FeCl₃. The XRD analysis of the samples precipitated in the presence of Zn²⁺ ions showed the formation of solid solutions of α-(Fe, Zn)OOH up to a concentration ratio r = [Zn]/([Zn] + [Fe]) = 0.0909. ZnFe₂O₄ was additionally formed in the precipitate for r = 0.1111, whereas the three phases α-FeOOH, α-Fe₂O₃ and ZnFe₂O₄ were formed for r = 0.1304. In the corresponding FT-IR spectra, the FeOH and FeO stretching bands were sensitive to the Zn²⁺ substitution, whereas the FeOH bending bands of α-FeOOH at 892 and 796 cm⁻¹ were almost insensitive. The Mössbauer spectra showed a high sensitivity to the formation of α-(Fe, Zn)OOH solid solutions which were monitored on the basis of a decrease in B_hf values in dependence on Zn-doping. A strictly linear decrease in B_hf for α-FeOOH doped with Zn²⁺ ions was measured up to r = 0.0291, whereas for r = 0.0476 and higher there was a deviation from linearity. The presence of α-(Fe, Zn)OOH, α-Fe₂O₃ and ZnFe₂O₄ phases in the samples was determined quantitatively by Mössbauer spectroscopy. Likewise, Mössbauer spectroscopy did not show any formation of the solid solutions of α-Fe₂O₃ with Zn²⁺ ions. FE SEM showed a strong effect of Zn-doping on the elongation of acicular α-FeOOH particles (500–700 nm in length) up to r = 0.1111. For r = 0.1304 the sizes of ZnFe₂O₄ particles were around 30–50 nm, and those of α-Fe₂O₃ particles were around 500 nm, whereas a relatively small number of very elongated α-(Fe, Zn)OOH particles was observed. A possible mechanism of the formation of α-(Fe, Zn)OOH, α-Fe₂O₃ and ZnFe₂O₄ particles was suggested.     

Prediction of pathways for the dissolution of iron

Previous mechanisms for the anodic dissolution of iron have been reviewed, and experimental evidence to distinguish between them is given. Of the various values found in the literature for the anodic Tafel slope, the values of 30 and 40 mV at (30°C) seem to be the most accurate. These two values have been taken as criteria for the possible mechanisms. New reaction pathways have been suggested which also involve the formation of Fe(OH)₂, FeOH⁺, and Fe₂OH⁺ as intermediates, and both the Tafel slope and the reaction order with respect to OH^? for these pathways have been deduced from steady state kinetics. The data thus obtained show that many of the proposed rate-determining steps give rise to the same results derived for previous mechanisms, thus indicating that such previous mechanisms are not the only possible ones. Difficulties associated with the work on iron, and with the present state of steady state kinetics are also outlined.     

The dissolution of iron under cathodic polarization

It has been shown that the dissolution rate for iron at cathodic potential is higher than expected on the grounds of the Wagner-Traud mixed potential theory. This observation cannot be explained by a parallel chemical process as suggested by Kolotyrkin et al. The dissolution appeared to be unaffected by potential, pH, cations (Li⁺, Na⁺, K⁺), anions (SO^2?₄, Cl^?, ClO^?₄) and solvent (water-dioxan mixtures). However, the dissolution rate was decreased by an order of magnitude when the electrode was connected to a strong magnet, suggesting that the mechanical degradation of the surface under the influence of the cathodically evolved hydrogen is the main cause of the measured effects.     

The Inhibitive Effect of Traces of SO2 on the Oxidation of Iron

The oxidation of Fe was investigated at 500–700°C in the presence of O₂ with 0–1000 ppm SO₂. The exposures were carried out in a thermobalance and lasted for 24 h. The oxidized samples were investigated by grazing-angle XRD, SEM/EDX, GDOES and XPS. The rate of oxidation of pure iron is slowed down by traces of O₂ in O₂ below 600°C while SO₂ has no effect on oxidation rate at higher temperatures. Exposure to SO₂<600°C resulted in the formation of small amounts of sulfate at the gas/oxide interface. In addition, sulfur, probably sulfide, accumulated at the metal/oxide interface. The influence of SO₂ on oxidation rate is attributed to surface sulfate. The sulfur distribution in the scale is rationalized in terms of the thermodynamic stability of compounds in the Fe–O–S system. Exposure to SO₂ caused the formation of hematite whiskers.     

The dissolution of iron under cathodic polarization

It has been shown that the dissolution rate for iron at cathodic potential is higher than expected on the grounds of the Wagner-Traud mixed potential theory. This observation cannot be explained by a parallel chemical process as suggested by Kolotyrkin et al. The dissolution appeared to be unaffected by potential, pH, cations (Li⁺, Na⁺, K⁺), anions (SO^2-₄, Cl^?, ClO^-₄) and solvent (water-dioxan mixtures). However, the dissolution rate was decreased by an order of magnitude when the electrode was connected to a strong magnet, suggesting that the mechanical degradation of the surface under the influence of the cathodically evolved hydrogen is the main cause of the measured effects.     

Magnetic properties of (Fe)1−x–(Al2O3)x and (Fe50Ni50)1−x–(Al2O3)x nanocomposite magnetic media synthesized using gel like Al2O3 matrix

Composites with ferromagnetic nanoparticles, Fe and Fe₅₀Ni₅₀, dispersed in Al₂O₃ have been synthesized by a solution phase technique. The structure and magnetic properties of these composites with varying fractions of Al₂O₃ have been investigated. Both Fe and Fe₅₀Ni₅₀ nanoparticles are amorphous in the as-prepared state and become crystalline on heat treating with near equilibrium lattice parameters of 0.287 nm and 0.358 nm respectively. The interparticle distance increases with increasing Al₂O₃ from 0 wt.% to 20 wt.%. The size of Fe nanoparticles is 40 nm while the Fe₅₀Ni₅₀ nanoparticles are 20 nm in size. The Fe and Fe₅₀Ni₅₀ nanoparticles dispersed composites are found to be ferromagnetic at room temperature both in the as-prepared and heat treated conditions with clear coercive fields of 5.5–35 × 10³ A m⁻¹. The saturation magnetization increases by orders of magnitude on heat treatment, for e.g. from <1.0 emu g⁻¹ to 143.4 emu g⁻¹ for Fe–15 wt.% Al₂O₃ and 95.6 emu g⁻¹ for Fe₅₀Ni₅₀–15 wt.% Al₂O₃. The Fe-composites exhibit a Curie transition at 1000 K while the Fe₅₀Ni₅₀ composites exhibit a transition at 880 K, both temperatures close to bulk values.     

Sulfidation—oxidation behavior of alloy 800H in SO2-O2 and H2-H2S-CO-CO2 atmospheres

The high-temperature-corrosion behavior of alloy 800H has been studied in an oxidizing (SO₂–O₂, =0.23 atm, =1.9×10^–29 atm) and a reducing (H₂–H₂S–CO–CO₂–N₂, =1.5×10^–18 atm =4.3×10^–8 atm, a_c=0.03) sulfidizing environment, at 750°C and 850°C, respectively. When corroded in SO₂–O₂, the protective chromia scale which developed on the alloy in the early stages cracked and spalled in quite a short time period. This led to the growth of iron and nickel sulfides beneath the chromia layer, causing more chromia spallation. When correded in H₂–H₂S–CO–CO₂–N₂, the alloy exhibited breakaway corrosion in about 35hr, at which stage liquid nodules formed on the sample surface. The nodules were studied in detail and were found to consist of three layers. The growth mechanism of such nodules is proposed.     

Influence of temperature and the role of chromium on the kinetics of sulfidation of 310 stainless steel

The sulfidation of 310 stainless steel was studied over the temperature range from 910 to 1285° K. By adjusting the ratio of hydrogen to hydrogen sulfide, variations in sulfur potential were obtained. The effect of temperature on sulfidation was determined at three different sulfur potentials: 39 N·m^–2, 1.4×10^–2 N·m^–2, and 1.5×10^–4 N·m^–2. All sulfide scales contained one or two surface layers in addition to a subscale. The second outer layer (OL-II), furthest from the alloy, contained primarily Fe-Ni-S. The first outer layer0 (OL-I), nearest the subscale, contained Fe-Cr-S. The subscale consisted of sulfide inclusions in the metal matrix. Two different phases were observed in OL-II depending on the temperature and sulfur potential. Below 1065°K OL-II is composed of a mixture of monosulfides of iron and nickel (Fe Ni)_1–xS and pentlandite (Fe_4.5Ni_4.5S₈) with the pentlandite phase exsolved as lamellae upon cooling. At temperatures higher than 1065°K only the pentlandite phase was formed, which melted above 1145°K at sulfur potentials greater than 10^–2 N·m^–2, yielding metal-rich iron-nickel-sulfur. Above 1145°K, and at sulfur potentials less than 10^–2 N·m^–2, OL-II ceased to exist (this temperature is termed transition temperature). Below the transition temperature, where OL-II exists, OL-I could be represented by the general composition (Fe, Cr)_1–xS. This phase on cooling transformed into an array of structures differing in FeCr ratio. These substructures, however, were not observed in quenched samples. Above the transition temperature OL-I changed to a chromium-rich sulfide composition and was associated with a sudden decrease in reaction rate. Subscale formation was found to be due to the dissociation of OL-I at the scale-metal interface, and the extent of subscale growth was found to depend on the temperature and the sulfur potential, as well as the composition of OL-I. At a given temperature and sulfur potential the weight-gain data obeyed the parabolic rate law after an initial transient period. The parabolic rate constants obtained at the sulfur potential of 39 N·m^–2 did not show a break when the logarithm of the rate constant was plotted as a function of the inverse of absolute temperature. Sulfidation carried out at a sulfur potential below 2 × 10^–2 N·m^–2, however, did show a break at 1145°K. This break was found to be associated with the changes which had occurred in the FeCr ratio of OL-I. Below the transition temperature the activation energy was found to be approximately 125 kJ · mole^–1. Above the transition temperature the rate of sulfidation decreased with temperature but depended on the FeCr ratio in the ironchromium-sulfide layers of the OL-I. A reaction mechanism consistent with the experimental results has been proposed in which the diffusion of cations through OL-I is the rate-controlling step. Below the transition temperature the diffusion of Fe and Ni through OL-I contributes to the scale formation, whereas above the transition temperature the diffusion of Cr through OL-I controls the scale formation. Existing literature on the Fe-Ni-S system is compared with the present results.     

“Anionic effect” in copper plating from sulfate aqueous-ethanolic electrolyte containing cyclic polyester

It is shown that, in contrast to aqueous electrolytes, where the electrode process is promoted by the electroreduction of activated surface complexes of Cu²⁺ with SO ₄ ^2– anions, in aqueous-ethanolic electrolytes, it is promoted by sulfate complexes of copper(II) formed in the solution bulk and needing dissociation prior to the discharge. In the presence of cyclic polyester, the discharging complex species have to permeate through the barrier layer at the cathode surface. The layer consists of ethanol molecules and electroneutral associates of sulfate ions with Cu²⁺ cations containing crown-ester molecules in the coordination sphere. As a result, the electrode reaction is considerably inhibited with an increase in the concentration of SO ₄ ^2– anions (anionic effect), and tribotechnical characteristics of copper coatings are significantly improved.Translated from Zashchita Metallov, Vol. 41, No. 2, 2005, pp. 162–167.Original Russian Text Copyright © 2005 by Kuznetsov, Skibina, Geshel, Loskutnikova, Kuznetsova.     

The corrosion behavior of Fe-Al alloys in H2/H2S/H2O atmospheres at 700–900°C

The corrosion behavior of five Fe-Al binary alloys containing up to 40 at. % Al was studied over the temperature range of 700–900°C in a H₂/H₂S/H₂O mixture with varying sulfur partial pressures of 10^–7–10^–5 atm. and oxygen partial pressures of 10^–24–10^–2° atm. The corrosion kinetics followed the parabolic rate law in all cases, regardless of temperature and alloy composition. The parabolic rate constants decreased with increasing Al content. The scales formed on Fe-5 and –10 at.% Al were duplex, consisting of an outer layer of iron sulfide (FeS or Fe_1–xS) and an inner complex scale of FeAl₂S₄ and FeS. Alloys having intermediate Al contents (Fe-18 and –28 at.% Al) formed scales that consisted of mostly iron sulfide and Al₂O₃ as well as minor a amount of FeAl₂S₄. The amount of Al₂O₃ increased with increasing Al content. The Fe 40 at.% Al formed only Al₂O₃ at 700°C, while most Al₂O₃ and some FeS were detected at T800°C. The formation of Al₂O₃ was responsible for the reduction of the corrosion rates.     

Mechanism of the initial stages of iron passivation in acidic sulfate solutions

Anodic and cathodic potentiostatic current transients of freshly formed iron (99.95%) electrodes in 0.5 M aqueous acidic (pH 1.7–3.2) sulfate solutions are examined. The initial stages of iron passivation are confirmed to be determined by the following several processes each prevailing in a definite period: the formation of surface charge-transfer complexes (H₂O) _δ+ ^ads (first 3–5 ms) and their transformation into adsorbed OH⁻ groups (subsequent 10–50 ms) with the concurrent adsorption of hydrogen atoms H_ads by iron.