Studies on waterline corrosion processes and corrosion product characteristics of carbon steel in 3.5 wt% NaCl solution

The waterline corrosion behaviors of carbon steel partially immersed in a 3.5 wt% NaCl solution were investigated using the wire beam electrode technique, and the effects of corrosion products on the processes of waterline corrosion were analyzed. The results demonstrated that the initial stage and development stage of waterline corrosion were mainly controlled by the concentration and diffusion of dissolved oxygen, respectively, and the deceleration stage of waterline corrosion was mainly affected by corrosion products. The main component of the yellow corrosion products was γ-FeOOH, and γ-FeOOH that exhibited a high reduction reactivity could be involved in the cathodic reaction. The black corrosion products were mainly composed of Fe₃O₄ with strong thermodynamic stability and the processes of dissolved oxygen diffusion and ion transports were obviously affected due to the continuous accumulation of Fe₃O₄ on the surface of the electrodes. Polarity reversals were observed on the single electrodes below the waterline, but the reasons for the phenomena were different from each other.     

海水飞溅区Ni-Cu-P钢的锈层和耐点蚀性能研究

在海水飞溅区对实验室冶炼的Ni-Cu-P钢、含Cu低合金钢和碳钢进行660 d的挂片实验,评价Ni-Cu-P钢的耐蚀性能;采用Fourier变换红外(FTIR)光谱、电感耦合等离子体原子发射光谱(ICP-AES)、电子探针(EPMA)、SEM和EDAX等技术,分析3种钢表面的锈层特征.结果表明,Ni-Cu-P钢表现出比...     

Corrosion behaviour investigation of 460 low alloy steels exposed in the natural deep-sea environment

ABSTRACT

The corrosion behaviours of 460 low alloy steels were investigated by the field exposure corrosion experiments with various long periods and 1200–3000?m depths in the natural deep-sea environment. XRD analysis results indicate that corrosion products of β-FeOOH, γ-FeOOH and Fe₃O₄ increase and the corrosion product of α-FeOOH decreases with the exposure sea depth extending. Electrochemical experiment results reveal the corrosion status is aggravated with the exposure sea depth extending: corrosion potentials shift negatively to a minimum self-corrosion potential of ?0.590?V (vs. SCE) and charge transfer resistances decrease to a minimum of 278?Ω?cm². Corrosion behaviours analysis shows that the average corrosion rate decreases with the time increasing and reaches a maximum value of 101?μm?a^?1. The maximum pitting depth varies between 63.0?μm and 138?μm. Gray relational analysis shows that the corrosion rate of 460 steel is most influenced by the pressure and dissolved oxygen concentration of deep sea, exhibiting a positive correlation relationship.     

硼酸缓冲溶液中pH值和腐蚀产物对低碳钢活化/钝化敏感性的影响

研究了在pH值分别为8,9和10的除氧硼酸缓冲溶液中,低碳钢腐蚀产物对其活化/钝化敏感性的影响.实验结果表明,在pH值为8时,低碳钢一直处于活性溶解状态,不受腐蚀产物影响;在pH值为9和10时,表面腐蚀产物使低碳钢钝化,其腐蚀电位最后稳定于钝化区间.XPS和XRD等分析结果表明,腐蚀产物由FeB(OH)12B4O7和γ...     

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.     

The reductive dissolution of γ-FeOOH in corrosion scales formed on cast iron in near-neutral waters

Corrosion scales which form on cast iron in oxygenated, near-neutral waters at 50°C contain green rust, Fe₂O₄ and γ-FeOOH. Upon de-oxygenation of the water, γ-FeOOH → Fe₃O₄ occurs by dissolution-precipitation as a cathodic reaction in the corrosion cell. Mechanisms of corrosion reactions are postulated in which it is proposed that the amount of γ-FeOOH is controlled by a balance between its rate of precipitation and its rate of reductive dissolution. The mechanism explains the eventual predominance of Fe₃O₄ in scales formed in oxygenated waters and the absence of γ-FeOOH from scales formed in waters with [O₂] < ～ 1 ppm.     

Oxidation behavior of NixFe1−x(OH)2 in Cl-containing solution

The addition of Ni leads to the formation of protective rust layer on steel and subsequently high corrosion resistance of steel in Cl⁻-containing environment. α-FeOOH, β-FeOOH, γ-FeOOH and Fe₃O₄ are formed mainly on steels exposed to Cl⁻-containing atmosphere. It is expected that systematic investigation of the effect of Ni(II) on the formation process of each oxide in solution should lead to elucidation of the role of Ni in the formation of anticorrosive oxide layer. This study reports the oxidation behavior of Ni_xFe_1−x(OH)₂ in Cl⁻-containing solution at two different pH regions (condition I under which solution pH is allowed to decrease and condition II under which solution pH is maintained at 8) where γ-FeOOH and Fe₃O₄ are predominantly formed, respectively, upon the oxidation of Fe(OH)₂. In the presence of Ni(II) in the starting solution, the formation of Ni(II) doped β-FeOOH with very low crystalline was facilitated and the formation of γ-FeOOH was suppressed with increasing Ni(II) content and with increasing oxidation rate of Fe(II). Ni(II) was found to have Fe₃O₄-suppressing effect under condition II.     

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.     

A study of the evolution of rust on Mo–Cu-bearing fire-resistant steel submitted to simulated atmospheric corrosion

The corrosion evolution of a Mo–Cu-bearing fire-resistant steel in a simulated industrial atmosphere was investigated by corrosion weight gain, XRD, EPMA, XPS, and polarization curves. The results indicate that the corrosion kinetics is closely related to the rust composition and electrochemical properties. As the corrosion proceeds, the relative content of γ-FeOOH and Fe₃O₄ decreases and α-FeOOH increases, and the rust layer becomes compact and adherent to steel substrate. Molybdenum and copper enrich in the inner rust layer, especially at the bottom of the corrosion nest, forming non-soluble molybdate and Cu(I)-bearing compounds responsible for enhanced corrosion resistance of the rust layer.     

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.     

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.     

Corrosion resistance and mechanical properties of low-alloy steels under atmospheric conditions

The corrosion resistance and mechanical strength of four newly developed low-alloy steels (LAS) were compared with a carbon steel (SS400) and a weathering steel (Acr-Ten A) using a laboratory-accelerated test that involved cyclic wet/dry conditions in a chloride environment (5 wt.% NaCl). The new LAS were designated 1605A, 1605B, 1604A, and 1604B. After 72 cycles of cyclic corrosion tests, the susceptibility of the steels to corrosion could be listed in the following order based on their weight loss (from high to low): SS400 > Acr-Ten A > 1604B ? 1604A > 1605B ? 1605A. The change in mechanical properties by corrosion was the least for SS400, Acr-Ten A was second, and effects of corrosion on the mechanical properties of the other four low-alloy steels were similar. Finally, the characteristics of the rust layers on each LAS sample were observed by SEM, and analyzed by FTIR and EPMA. The results indicated that most of the rust layers on the test steels were composed of a loose outer rust layer and a dense inner rust layer. The outer rust layer of each steel was composed of α-FeOOH, γ-FeOOH, magnetite (Fe₃O₄), H₂O, and amorphous ferric oxyhydroxide (FeO_x(OH)_3−2x, x=0-1), while the inner rust layer was composed mainly of Fe₃O₄ with a little α-FeOOH. In addition, it was apparent that the copper and chromium alloying additions were enriched, respectively, at the rust-layer/substrate interface and in the rust layers. Finally, combining the results of the accelerated tests and the rust layer analysis showed that low-alloy steels, such as 1605A and 1605B, have better weathering steel properties than Acr-Ten A for use in the humid and salty weather.     

Ex-situ and in-situ X-ray diffractions of corrosion products freshly formed on the surface of an iron-silicon alloy

Ex-situ X-ray diffraction measurements of a small amount of samples extracted from wet corrosion products freshly formed on a pure iron and iron-2 mass% silicon surfaces have been conducted using synchrotron radiation for clarifying the formation process of corrosion products. The results showed that γ-FeOOH was formed on the outer side of wet corrosion products formed on the surface of the pure iron by sodium chloride solution, while γ-FeOOH, α-FeOOH, Fe₃O₄, and green rusts were formed on the inner side. On the other hand, in comparison to the case of the pure iron, a significant formation of β-FeOOH was observed in the iron-silicon alloy. Influences of silicon alloying on corrosion products formed by aqueous solution containing sulfate ions were also observed. Furthermore, in-situ diffraction measurements by a conventional X-ray source were conducted for analyzing corrosion products formed on the pure iron and iron-silicon alloy surfaces by cyclic exposure to wet and dry atmospheres. The results obtained by the in-situ diffraction and ex-situ diffraction measurements on the corrosion products were consistent.     

周期干湿浸条件下P265GH钢和Q235钢的大气腐蚀行为简

以NaCl+NaHSO3为腐蚀介质,通过浸渍干湿复合循环实验及腐蚀失重分析,并利用SEM,XRD和FTIR技术,研究了Q235碳钢和P265GH低合金钢的大气腐蚀行为。结果表明,两种钢的腐蚀遵从相同的动力学规律,腐蚀产物中均存在大量致密的α-FeOOH和非晶态δ-FeOOH,锈层具有很好的保护性,使得腐蚀速率降低。实验开始阶段两种钢的腐蚀量基本相同,但随着腐蚀的进行两者差距增大,P265GH低合金钢较Q235碳钢的失重小、锈层致密、耐腐蚀性好。     

Microstructure and corrosion performance of X100 steel in the oilfield produced water

ABSTRACT

The corrosion performances of X100 steels in the oilfield produced water with different temperature (30°C, 40°C, 60°C) under the simulated working conditions were studied by potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) test. Energy dispersive spectroscopy (EDS) was used to measure the element composition of the sample after corrosion. The phase and chemical compositions of the specimens were analyzed by X-ray diffraction (XRD) and Raman spectrometry. The electrochemical results showed that the corrosion resistance of the specimen exposed for 24 hours increased with the increase of the testing temperature, indicating the better protective effect due to the corrosion product film formed under high temperature despite the impact of turbulence. The corrosion products consist of Fe₃O₄, Fe₂O₃, α-FeOOH, and γ-FeOOH. The corrosion mechanism model of X100 steel was established and the corrosion behavior was analyzed under simulated working conditions.     

N80 钢抗固液两相冲刷腐蚀行为的研究

目的 研究 N80 钢在含有石英砂的不同浓度 NaCl 溶液中的冲刷腐蚀行为。 方法 采用扫描电子显微镜( SEM) 、能谱分析( EDS) 等手段分析腐蚀产物的结构及相组成,通过失重法计算腐蚀速率。 结果 腐蚀产物主要为 FeO 及 Fe₃O₄。 结论 随 NaCl 浓度的增加,N80 钢的腐蚀速率加快,当 NaCl 质量分数超过 7% 时,出现明显的点蚀。     

Corrosion resistance and corrosion behavior of high-copper-bearing steel in marine environments

Thus far, research on the corrosion resistance of copper-containing steel has been limited to Cu content of less than 1%, and the corrosion resistance of antibacterial Cu-containing steel with Cu content above 3% has not been reported. In this study, 0Cu3 carbon steel (CS), 0Cr15Cu3 stainless steel (SS), and Q345 CS were investigated. The corrosion resistance and corrosive behavior of high-copper (high-Cu)-bearing steel in a marine environment were examined by scanning electron microscopy, energy dispersive spectrometry, X-ray diffraction, electrochemical impedance spectroscopy, and potentiodynamic polarization. Coupon test results showed that the Cu in the 0Cr15Cu3 SS and 0Cu3 CS can promote the formation of stable α-FeOOH from γ-FeOOH in the outer rust layers, and make the rust layers more thick and dense. In the electrochemical experiment, the impedance loop diameters and R_ct values of the 0Cr15Cu3 SS and 0Cu3 CS were higher than those of Q345, while the I_corr was less than that of Q345, which indicates that the anticorrosion property of these two types of high-Cu-bearing steel was higher than that of Q345. The aim of this study was to define the properties of corrosion resistance and corrosive behavior in high-Cu-bearing steels to promote their application in marine engineering.     

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.     

Characterization of the rust formed on weathering steel exposed to Qinghai salt lake atmosphere

The product formed on weathering steel exposed to salt lake atmosphere for 12 months was investigated by X-ray diffraction (XRD), infrared transmission spectroscopy (IRS), scanning electron microscopy (SEM), electron probe micro analyzer (EPMA) and electrochemical techniques. The rust was mainly composed of β-FeOOH, Fe₈(O,OH)₁₆Cl_1.3 and a little γ-FeOOH. Amorphous δ-FeOOH was only on skyward surface. The rust layer suppressed anodic reaction and facilitated the cathodic reaction. The very small value of rust resistance R_r in this work indicated that the rust had poor protective ability. Cl element was rich in the whole rust layer and played an important role in accelerating the corrosion of weathering steel in salt lake atmosphere.     

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.