Corrosion behavior of steel under wet and dry cycles containing Cr ion

The corrosion behavior of mild steel has been investigated during the wet and dry cyclic transitions containing Cr³⁺ ion added as sulfate in order to gain a better understanding of the influence of Cr on the atmospheric corrosion of steels. The corrosion rate during drying is greatly suppressed by the existence of Cr³⁺ ion in the electrolyte covered with the surface. Lower corrosion rates are observed during drying even if the surface have been polarized to negative potentials below −200 mV_SHE during the wet corrosion conditions in which the surface-covered electrolyte contains Cr³⁺ ion. This corrosion behavior is identical to the case of Cr-containing steel for the wet and dry cyclic transitions without the addition of Cr³⁺ ion. The composition of rust layer after the wet and dry cyclic transitions is composed of α-FeOOH, γ-FeOOH and Fe_3−δO₄ for both cases of non-Cr³⁺ and Cr³⁺-containing condition, and no significant difference in the mass fraction of the above rust substances between two conditions is observed by means of Mössbauer spectroscopy. The only difference in the rust layer is that the rust formed under the wet and dry cyclic transitions containing Cr³⁺ ion contains a certain amount of Cr near the steel/rust interface. Those results suggest that the role of Cr during the wet and dry cyclic transitions is the inhibition of the rust reduction and the formation of Fe²⁺-state intermediate by the existence of Cr in the rust layer. This can lead to the inhibition of the oxygen reduction during drying.     

Mechanisms of corrosion layer formation during zirconium immersion in a (Fe)-bearing glass melt

The kinetics and mechanism of pure zirconium corrosion in an iron-bearing borosilicate glass melt are investigated from 1230 to 1418 °C. The influence of immersion time and temperature on the corrosion layer morphologies is discussed. The corrosion mechanism is a multi-step process and is described using the Zr-Si-O-B phase diagram. Boron and silicon species contained in the melt are reduced at the zirconium contact and ZrSi_sB_b intermetallic compounds are formed while the Zr substrate is oxidized into ZrO_x. When the local melt fO₂ value induces the Fe⁰ precipitation, complex ZrSi_sB_bFe_f compounds are formed. The last step consists in the oxidation of ZrO_x into ZrO₂.     

A3钢在富营养化东湖水中初期腐蚀研究

    以A3钢为研究对象,采用失重实验和电化学技术研究了A3钢在富营养化东湖水中的腐蚀行为.结果表明：A3钢在实验过程中腐蚀电流随时间增长逐渐减小;自腐蚀电位先降后升,而极化电阻逐渐增大,说明电极表面刚开始处于活化状态,然后电极表面“保护膜”不断生长,将电极表面覆盖,减缓了基体的腐蚀;电化学方法计算出富营养化水中A3钢的腐蚀电流与线性极化电阻的比例常数B值为23.6242;通过XPS分析得出A3钢腐蚀产物的成分为FeOOH,Fe³⁺与C、N、S结合的有机产物和FeSO₄,其中Fe²⁺/Fe³⁺=0.24.     

Sodium phthalamates as corrosion inhibitors for carbon steel in aqueous hydrochloric acid solution

Three compounds of N-alkyl-sodium phthalamates were synthesized and tested as corrosion inhibitors for carbon steel in 0.5 M aqueous hydrochloric acid. Tests showed that inhibitor efficiencies were related to aliphatic chain length and dependent on concentration. N-1-n-tetradecyl-sodium phthalamate displayed moderate efficiency against uniform corrosion, 42–86% at 25 °C and 25–60% at 40 °C. Tests indicated that compounds behave as mixed type inhibitors where molecular adsorption on steel followed Langmuir isotherm, whereas thermodynamic suggested that a physisorption process occurred. XPS analysis confirmed film formation on surface, where Fe⁺² complexes and Fe⁺² chelates with phthalamates prevented steel from further corrosion.     

铁闪锌矿的Leptospirillum ferrooxidans菌浸出及电化学性能(英文)

采用纯种L.ferrooxidans菌研究矿浆浓度、pH及外加Fe3+离子对铁闪锌矿生物浸出的影响。结果表明,锌的浸出率随着矿浆浓度的降低而增加。在生物浸出过程中调节pH值到1.6对铁闪锌矿的溶解有促进作用。外加Fe3+离子加速了铁闪锌矿的生物浸出,但当外加Fe3+离子浓度超过2.5g/L时,促进作用变弱。这是因为高浓度的Fe3+离子会对细菌生长产生抑制作用且促进黄钾铁矾的生成。在L.ferrooxidans菌存在条件下,利用电化学测试方法进一步了解有、无外加Fe3+离子时铁闪锌矿的溶解过程。实验数据表明,外加Fe3+离子可以增加腐蚀电流密度,有利于锌的提取。交流阻抗谱表明,添加Fe3+离子后没有改变反应过程的控制步骤。     

Gamma-radiation-induced corrosion of carbon steel in neutral and mildly basic water at 150 °C

The effect of γ-radiation on the kinetics of carbon steel corrosion has been investigated by characterizing the oxide films formed on steel coupons at 150 °C and at two pH values. Results show that continuous irradiation enhances surface oxide formation with the type of oxide formed dependant on the solution pH. For experiments at 150 °C and a [OH⁻] equivalent to that for pH_{25 °C} = 10.6, the surface oxide on carbon steel after γ-irradiation was non-porous and uniform, and no localized corrosion was observed. This oxide, however, appears to be susceptible to brittle fracture during cooling. Raman spectroscopy of the surface film indicates that it is a mixture of the phases of Fe₃O₄ and γ-Fe₂O₃. In contrast, at 150 °C with [OH⁻] equivalent to neutral pH_{25 °C}, metal dissolution is significant and the surface oxide film is very porous. Raman spectra show that this oxide film is also composed of a mixture of Fe₃O₄ and γ-Fe₂O_3. The results from this work combined with previously reported electrochemical studies of the same system as a function of pH and temperature can be used to deconvolute the effects of radiation, pH and temperature on the nature of the corrosion process.     

Corrosion of X65 steel in CO2-saturated oilfield formation water in the absence and presence of acetic acid

Electrochemical corrosion behavior of X65 steel in CO₂-saturated formation water in the absence and presence of acetic acid was studied by electrochemical measurements, scanning vibrating micro-electrode (SVME), localized electrochemical impedance spectroscope (LEIS) and surface analysis techniques. It is found that, when steel is immersed in formation water, the dissolution of Fe dominates the anodic process and the steel is in active dissolution state. Adsorption of intermediate product on the electrode surface results in generation of an inductive loop in the low frequency range of EIS plot. As corrosion proceeds, the concentration of Fe²⁺ in the solution increases. When the product of [Fe²⁺] × [] exceeds solubility product of FeCO₃, FeCO₃ will deposit on the electrode surface, and protects the steel substrate from further corrosion. The steel is in a “passive” state. When the electrode surface is completely covered with FeCO₃ film, the inductive loop in the low frequency range disappears. In the presence of acetic acid in formation water, the cathodic reaction will be enhanced due to the direct reduction of undissociated acetic acid. Addition of acetic acid degrades the protectiveness of corrosion scale, and thus, enhances corrosion of steel by decreasing the FeCO₃ supersaturation in solution.     

Effect of Fe-Zn alloy layer on the corrosion resistance of galvanized steel in chloride containing environments

In this study, the effect of Fe-Zn alloy layer that is formed during galvanizing process on the corrosion behavior of galvanized steel has been investigated. The galvanostatic dissolution of galvanized steel was carried out in 0.5 M NaCl solution to obtain the Fe-Zn alloy layer on the base steel. The alloy layer was characterized to be composed of FeZn₁₃, FeZn₇ and Fe₃Zn₁₀ intermetallic phases, which constitute the zeta, delta1 and gamma layers of galvanized steel, respectively. It was observed that the alloy layer has similar cathodic polarization behavior but different anodic polarization behavior compared to galvanized steel. The anodic current plateau of alloy layer was up to 100 times lower than that of galvanized coating. Corrosion test performed in wet-dry cyclic condition has shown that the alloy layer has lower corrosion rate as compared to galvanized steel. From the results of corrosion test of alloy layer and base steel, it was concluded that Zn²⁺ has positive effect on the protectiveness of the zinc corrosion products. The measurement of surface potential over the alloy/steel galvanic couple has confirmed the galvanic ability of alloy layer to protect both the alloy layer itself and the base iron during initial stage of atmospheric corrosion.     

Characterization of AISI 4340 corrosion products using Raman spectroscopy

Most of the currently available corrosion product characterization techniques require extensive samples preparation methods and cannot be employed under aqueous conditions. Raman spectroscopy possesses the advantage of characterization of the corrosion products under practical operation conditions, including aqueous, without any sample preparation procedures. The present study examines the corrosion characteristics of AISI-4340 steel at aqueous and atmospheric environments using Raman spectroscopy. FeO, Fe₂O₃, and Fe₃O₄ were observed as the main corrosion products. The measured oxides thicknesses ratio were compared to the theoretic value obtained from Tammann equation.     

The role of rusts in corrosion and corrosion protection of iron and steel

The processes of atmospheric corrosion of iron and steel and the properties of corrosion products (rusts) are modeled based on a quantitative evaluation of the chemical reactions pertaining to corrosion to elucidate the conditions with which corrosion-protective rust films form. Based on the model, it is suggested that in the initial stage of corrosion, in the rusts, the pH of the aquatic system is maintained at 9.31 owing to an equilibrium with iron(II) hydroxide and the rate of air-oxidation at this pH is very fast, and that dense, self-repairing rust films form, protecting the underlying iron and steel. However, after corrosion stops, the rust film deteriorates due to the dissolution and shrinkage by aging, and the deteriorated rust film separates the anode and cathode reaction products (Fe²⁺ and OH⁻ ions) to cause crevice corrosion. The air-oxidation of iron(II) in anode channels without the presence of OH⁻ ions results in strongly acidic solutions (pH 1.41), causing acid-corrosion. It is proposed that good catalysts (e.g. copper(II) and phosphate ions) accelerate the air-oxidation at low pH, delaying the crevice- and acid-corrosion stages. Further, it is argued that iron compounds with negative charges due to the non-stoichiometric proportions of the lattice oxide ions and metal ions (solid oxoanions of iron) exhibit stable cation-selective permeability even with a drop in pH. Rust films including such compounds would stop the passage of aggressive anions and act to protect iron and steel.     

Long-term anticorrosion behaviour of polyaniline on mild Steel

Anticorrosion performances of polyaniline emeraldine base/epoxy resin (EB/ER) coating on mild steel in 3.5% NaCl solutions of various pH values were investigated by electrochemical impedance spectroscopy (EIS) for 150 days. In neutral solution (pH 6.1), EB/ER coating offered very efficient corrosion protection with respect to pure ER coating, especially when EB content was 5-10%. The impedance at 0.1 Hz of the coating increased in the first 1-40 immersion days and then remained constant above 10⁹ Ω·cm² until 150 days, which in combination with the observation of a Fe₂O₃/Fe₃O₄ passive film formed on steel confirmed that the protection of EB was mainly anodic. In acidic or basic solution (pH 1 or 13), EB/ER coating also performed much better than pure ER coating. However, these media weakened the corrosion resistance due to breakdown of the passive film or deterioration of the ER binder.     

Corrosion of carbon steel in concentrated LiNO3 solution at high temperature

The corrosion of carbon steel in concentrated LiNO₃ solution at high temperature was investigated by a weight loss method. Results showed that increasing temperature and pH would increase the corrosion rate, and increasing concentration and adding Li₂CrO₄ would reduce the corrosion rate. The corrosion in LiNO₃ solution was general corrosion and the corrosion products were composed of Fe₃O₄ and Fe₂O₃. A compact passive layer comprising of Cr₂O₃, Fe₃O₄ and Fe₂O₃ was observed with adding Li₂CrO₄, and it could effectively depress the corrosion. The carbon steel corrosion in LiNO₃ solution was much smaller than that in LiBr solution.     

Zinc treatment effects on corrosion behavior of 304 stainless steel in high temperature, hydrogenated water

Trace levels of soluble zinc(II) ions (30 ppb) maintained in mildly alkaline, hydrogenated water at 260 °C were found to lower the corrosion rate of austenitic stainless steel (UNS S30400) by about a factor of five, relative to a non-zinc baseline test [S.E. Ziemniak, M. Hanson, Corros. Sci. 44 (2002) 2209] after 10,000 h. Characterizations of the corrosion oxide layer via grazing incidence X-ray diffraction and X-ray photoelectron spectroscopy in combination with argon ion milling and target factor analysis, revealed that miscibility gaps in two spinel binaries—Fe(Fe_1−mCr_m)₂O₄ and (Fe_1−nZn_n)Fe₂O₄—play a significant role in determining the composition and structure of the corrosion layer(s). Although compositions of the inner and outer corrosion oxide layers represent solvus phases in the Fe₃O₄-FeCr₂O₄ binary, zinc(II) ion incorporation into both phases leads to further phase separation in the outer (ferrite) layer. Recrystallization of the low zinc content ferrite solvus phase is seen to produce an extremely fine grain size (∼20 nm), which is comparable in size to grains in the inner layer and which is known to impart resistance to corrosion. Zinc(II) ion incorporation into the inner layer creates additional corrosion oxide film stabilization by further reducing the unit cell dimension via the substitution reaction

0.2Zn²⁺(aq)+Fe(Fe_0.35Cr_0.65)₂O₄(s)?0.2Fe²⁺(aq)+(Zn_0.2Fe_0.8)(Fe_0.35Cr_0.65)₂O₄(s)     

Effect of common water contaminants on the corrosion of aluminium alloys in ethylene glycol-water solution

The effects of common water contaminants of chloride (Cl⁻), cupric (Cu²⁺) and ferric (Fe³⁺) ions, in four different mixture combination of Fe³⁺ + Cu²⁺, Cl⁻ + Fe³⁺, Cl⁻ + Cu²⁺ and Cl⁻ + Fe³⁺ + Cu²⁺, were examined on the corrosion behaviour of aluminium alloys in ethylene glycol-water solution, using mass loss technique. The highest material losses were recorded for the two alloys in ethylene glycol solution containing the combination of the chloride and the two heavy metal ions. The corrosivity of the solution in the presence of the combination of ions was in the order of Cl⁻ + Fe³⁺ + Cu²⁺ > Cl⁻ + Cu²⁺ > Cl⁻ + Fe³⁺ > Fe³⁺ + Cu²⁺. The results gave first-order kinetics with respect to aluminium in ethylene glycol solution-ion systems. Alloy 3SR exhibits maximum corrosion in all the solutions. It is concluded that the two commercial alloys in the solution polluted with all the three ions would not be able to survive for reasonable period of time without corrosion inhibitor.     

Influence of Zn on oxide films on Alloy 690 in borated and lithiated high temperature water

To clarify the corrosion control effect of Zn injection into hydrothermal environments, the oxide films on Alloy 690 in the deaerated borated and lithiated water have been investigated using potentiodynamic polarization curves, electrochemical impedance spectra at 300 °C and ex-situ X-ray photoelectron spectroscopy. With Zn injection in the solution, ZnCr₂O₄ and ZnFe₂O₄ were formed in the inner and outer layers of the oxide films on Alloy 690, respectively, through exchange reactions between Zn²⁺ and Fe²⁺/Ni²⁺. A simple model for oxide film structure change and the mechanism of corrosion inhibition by Zn injection is proposed and discussed.     

Inhibitoren der Korrosion 20(1)–Über die zeitliche Abhängigkeit der analytischen Zusammensetzung der Korrosionsprodukte des Eisens von der Menge an verbrauchtem Sauerstoff

Analytical composition of the corrosion products of iron as a function of time and of the oxygen consumed Using a modified standard method of analysis it is possible to analyze mixtures containing Fe⁰, Fe²⁺ and Fe³⁺. This method is used to study corrosion systems catalyzed by chlorides. According to the results obtained the amount of Fe²⁺ is approx constant at pH 7, irrespective of the oxygen quantityt consumed, Fe⁰ being oxidized to give Fe²⁺ and the latter being oxidized, at a comparable rate, to give Fe³⁺. At pH 3, however, Fe²⁺ is obtained almost exclusively, and beyond pH Fe³⁺ becomes predominating.     

Metal ion release from electric guitar strings in artificial sweat

The aim of this study was to monitor the dissolution of metal ions from electric guitar strings. For characterization of investigated strings, two independent methods of analysis were chosen: ICP-OES and AAS. Electric guitar strings consisted of two separate parts: Sn-plated steel core wire which was hexagonal in cross section and Ni-plated steel wrap which was round in cross section. Dissolution of Ni²⁺, Mn²⁺, Si⁴⁺, Sn²⁺ and Fe³⁺ ions from electric guitar strings E6 and D4 were measured as a function of time in artificial sweat solution, at temperature of 37 °C according to the EN 1811:1999 standard test procedure. The determination of the amount of the metal ions released in the corrosive solutions was carried out by means of inductively coupled plasma-optical emission spectroscopy (ICP-OES). The mechanism of metal ions eluted in artificial sweat is discussed. The concentrations of dissolved metal ions in corrosive solution from E6 and D4 strings are decreasing in the following order: Fe³⁺ > Sn²⁺ > Mn²⁺ > Si⁴⁺ > Ni²⁺. Among all investigated metal ions, nickel is far the most allergenic. Since the amounts of the eluted Ni²⁺ did not exceed 0.5 μg cm⁻² week⁻¹, the investigated electric guitar strings should not induce contact dermatitis.     

转鼓和搅拌槽反应器中氧化亚铁硫杆菌氧化Fe2+的比较（英文）

研究转鼓和搅拌槽反应器中氧化亚铁硫杆菌在不同Al2O3粉末含量下对Fe2+的氧化。结果表明:未添加Al2O3粉末时,氧化亚铁硫杆菌在搅拌槽中的生物活性比在转鼓中的生物活性高。当Al2O3粉末含量从0增加到50%(质量分数)时,Fe2+的生物氧化速率从0.23g/(L·h)显著降低到0.025g/(L·h),可能是搅拌槽中的固体颗粒碰撞和研磨作用导致氧化亚铁硫杆菌失活。转鼓中Al2O3的含量增加对氧化亚铁硫杆菌的生物活性仅有较小的负面影响,这是由于两个反应器不同的混合机制所致。在相同的Al2O3含量下,Fe2+在转鼓反应器中的生物氧化速率比在搅拌槽中的生物氧化速率更高,尤其在较高的固体含量下,表明转鼓反应器能允许较高的固体含量和维持较高的生物活性。由于Al2O3粉末与真实硫化矿具有不同的物理化学性质,因此转鼓反应器用于硫化矿生物浸出的可行性还需进一步验证。     

Corrosion behavior of cold rolled steel in peracetic acid solutions

The corrosion behavior of cold rolled steel in different concentrations of peracetic acid (PAA) has been studied by electrochemical technique at 0 °C, 10 °C, 20 °C and 30 °C, respectively. Electrochemical parameters like corrosion potential, corrosion current density and corrosion rate were determined. The results show that concentrations of PAA and test temperatures can affect the corrosion rate obviously. The corrosion rate increases with increase of the concentration of PAA at each temperature, but the maximum corrosion rate appears at 20 °C at each same concentration of PAA. The characteristic chemical reactions were used to investigate the form of Fe ions dissolved in PAA solutions. It was found that the Fe³⁺ ions were the dominant corrosion products. A probable corrosion mechanism is presented to explain the experimental results.     

Glass coatings on stainless steels for high-temperature oxidation protection: Mechanisms

The oxidation behavior of a martensitic stainless steel with or without glass coating was investigated at 600–800 °C. The glass coating provided effective protection for the stainless steel against high-temperature oxidation. However, it follows different protection mechanisms depending on oxidation temperature. At 800 °C, glass coating acts as a barrier for oxygen diffusion, and oxidation of the glass coated steel follows linear law. At 700 or 600 °C, glass coating induces the formation of a (Cr, Fe)₂O₃/glass composite interlayer, through which the diffusion of Cr³⁺ or Fe³⁺ is dramatically limited. Oxidation follows parabolic law.