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.     

Hydrogen permeation behaviour of X56 steel in simulated atmospheric environment under loading

Abstract

The hydrogen permeation behaviour of X56 steel under loading in a simulated atmospheric environment was investigated. The results show that the hydrogen permeation current increases as the elastic deformation of the steel increases. In addition, the hydrogen permeation current decreases with an increase in plastic deformation. Cracking of the passive film and the reduced specimen thickness after deformation are proposed as reasons for the decrease in permeation. Thus, during plastic deformation, there is a competition between dislocation trapping and dislocation transport of hydrogen, which affects the overall hydrogen permeation current.     

Hydrogen entry into steel during atmospheric corrosion process

Hydrogen entry and permeation into iron were measured by an electrochemical method during atmospheric corrosion reaction. The hydrogen permeation was enhanced on passive films because the hydrogen adsorption increased by the hydrogen evolution mechanism which is different from that on a bear iron surface. The permeation rate during a wet and dry corrosion cycle showed a maximum in the drying process depending upon the surface pH and the corrosion potential. The pollutant such as Na₂SO₃ which decreases the pH and the corrosion potential causes an increase in the permeation rate. The mechanism of the change in the permeation rate during the wet and dry cycles is explained by the polarization diagram of the electrode covered by thin water layer.     

Hydrogen permeation behavior of nickel electroplated AISI 4340 steel

The role of the electroplated nickel layer on hydrogen permeation through AISI 4340 steel was investigated by a electrochemical hydrogen permeation test. The permeation test, composed of three steps, was conducted to measure the hydrogen diffusivity and surface hydrogen concentration. A constant current of 20 mAcm^-2 and a constant potential of -100 mV vs. Ag/AgCl electrode were applied to the hydrogen entry and exit cells, respectively. The thickness of the electroplated nickel layer on AISI 4340 steel increased in a linear fashion with an increase in electroplating time. The nickel coated layer contributed to a decrease in the hydrogen permeability of nickel coated AISI 4340 steel specimens. This is due to the fact that the surface hydrogen concentration and hydrogen diffusivity in nickel coated layer were lower than those of AISI 4340 steel substrate. Especially, low hydrogen diffusivity decreased significantly with hydrogen permeability. The critical effective hydrogen diffusivity for barrier of nickel electroplated AISI 4340 steel specimens was higher than the hydrogen diffusivity of AISI 4340 steel specimen. It is proposed then that the thin nickel layer on AISI 4340 steel acts as a barrier for hydrogen permeation through AISI 4340 steel.     

Hydrogen permeation in high strength steel under load in aqueous environment

Abstract

The hydrogen assisted cracking problem is one of the major causes of the failure occurring in the high strength steel structures used in various industries. In aqueous environment, hydrogen is generated by the hydrogen reduction reaction on the steel surface. With depletion of the high quality resources in oil and gas industry, the hydrogen assisted cracking problem becomes severe in sour environment, which contains high amount of H₂S. Understanding on the hydrogen permeation behaviour is crucial to deal properly with the hydrogen related problems since they are primarily determined by the hydrogen uptake and transport in the steel. The Devanathan–Stachurski method is widely used to evaluate electrochemically the hydrogen permeation behaviour. This method has been successfully used for the steel with no load. Under loading condition, this electrochemical test method has been modified to accommodate the externally applied load. However, the data require careful examination to validate the technical importance because of the stability and homogeneity of palladium layer coated on the steel surface under load. In this paper, the hydrogen permeation test method under loading condition will be reviewed for the high strength steels used in oil and gas industry. The factors affecting the hydrogen permeation in the high strength steel will be discussed in terms of the applied stress level and the sulphide film forming on the steel surface in sour environment.     

Atmospheric corrosion monitoring of a weathering steel under an electrolyte film in cyclic wet–dry condition

Electrochemical Impedance Spectroscopy (EIS) and film thickness measurements have been employed to study the corrosion monitoring of steel under an electrolyte film in wet–dry cycles simulating a coastal atmosphere. The results indicate that within each cycle, the corrosion rate increases during drying process due to an increase in Cl⁻ concentration and an enhancement of oxygen diffusion by thinning out of the electrolyte. As corrosion process proceeds, the corrosion rate increases greatly and reaches a maximum. During subsequent corrosion stage, the corrosion rate decreases greatly and keeps at a low value due to the formation of a stable rust layer.     

EIS study on 2024‐T3 aluminum alloy corrosion in simulated acid rain under cyclic wet‐dry conditions

The wet‐dry cycle corrosion processes of 2024‐T3 aluminum alloys under different pH environments were investigated using electrochemical impedance (EIS) technique in conjunction with SEM method. The results show that, during the dry period of each cycle, the electrode potential was relatively stable and the corrosion processes can be studied using EIS technique. In the case of pH 3.5 and during the entire corrosion process, the Nyquist plot was composed of a high‐frequency capacitive arc due to corrosion reaction and a low‐frequency capacitive arc due to the formation of corrosion products layer, and the corrosion rate during the same cycle was almost the same. In the case of pH 4.5 and during the first several cycles, the Nyquist plot was composed of nearly only one capacitive arc due to the corrosion reaction, and the corrosion rate during the same cycle increased with time. Additionally, the EIS features of the entire corrosion processes of 2024‐T3 aluminum alloy were interpreted theoretically.     

低碳钢焊接接头氢渗透与氢损伤行为分析

对退火态低碳钢焊接接头进行了电解充氢,得到了接头不同位置产生氢损伤的微观组织,用电化学方法测量了焊后接头不同位置的氢渗透曲线,计算了接头不同位置的扩散系数、稳态平均氢浓度和扩散氢含量,解释了低碳钢焊接接头的不同位置充氢产生氢气泡、氢鼓泡及氢致裂纹数目差异的机理.结果表明,母材处表征扩散系数远小于焊缝处,平均氢浓度远大于焊缝处,导致母材处的氢渗透与损伤行为较明显,表面溢出氢气泡和近表面产生的氢鼓泡数目远多于焊缝处,然而焊缝处由于塑韧性较母材差,焊接残余应力较大,产生较多氢致裂纹,多位于氢浓度较大的近表面,内部由于拘束较大而产生少数细长裂纹.     

Long‐term atmospheric corrosion monitoring

The paper presents the analysis of corrosion rates of carbon steel, zinc, aluminium and copper after long‐term exposition as a function of time and environmental parameters. All experimental methodologies on the test sites were carried out according to ISO standards. The analysis of trends of environmental pollution and corrosion rates was performed for one year exposition of metals on three sites (urban/industrial, urban and rural atmosphere) in Poland. The corrosivity changes as a result of a reduction of corrosion rates of metals used are relatively smaller then the reduction of pollution. By using the equation C = Atⁿ, where C – corrosion rate after t years, A – corrosion rate after the first year of exposition, and results of long‐term corrosion rates, exponent n was determined for the different metals and sites from log‐log plots.     

低碳贝氏体钢在干燥和高湿环境中的腐蚀行为

测试低碳贝氏体钢分别于干燥和高湿环境的电化学阻抗谱(EIS)和极化曲线,并观察其表面形貌,对比研究了低碳贝氏体钢在两种环境中的腐蚀行为.结果表明,低碳贝氏体钢在两种环境中的腐蚀速率均是先增至峰值后减小.高湿环境中试样的腐蚀速率峰值出现早于干燥环境中试样.峰值前高湿环境中试样的腐蚀速率高于干燥环境中试样的腐蚀速率,峰值后高湿环境中试样的腐蚀速率低于干燥环境中试样的腐蚀速率.     

Electrochemical corrosion behavior of bronze materials in an acid-containing simulated atmospheric environment

The present work investigates the corrosion behavior of bronze materials under thin electrolyte layers (TELs) in a simulated atmospheric environment containing formic and acetic acid by electrochemical measurements as well as surface characterization. The results show that the corrosion of bronze under TEL is significantly faster than that in the bulk solution, and the corrosion rate of bronze is the highest when the thickness of TEL is about 100 μm. Formic acid is observed to be more corrosive than acetic acid. Copper formate and copper acetate hydrate appear in the corrosion products formed on the surface of bronze, suggesting that the organic acid participates in the corrosion process of bronze materials in the simulated atmospheric environment.     

Hydrogen permeation measurements in natural sea environment

The specially designed, fully equipped, and computerized devices for the underwater long‐term measurements have been used to study the hydrogen permeation rate through the structural steels under natural sea water conditions. By applying constant cathodic potentials, the polarization current and the hydrogen permeation rate were recorded. The temperature and the concentration of S^?2 ions in sea water were also measured. After the tests, the concentration of residual hydrogen in samples and the chemistry of the membrane surface were analyzed. The obtained permeation data were compared with the S^?2 content in sea water and with the chemistry and appearance of formed deposits. The effect of SRB on the hydrogen permeation through structural steels is dependent on the site of the sample placing and on the sea water temperature. At a lower water temperature, the low hydrogen absorption was measured due to a lower activity of SRB. The highest hydrogen uptake accompanied by the highest content of S in corrosion and cathodic deposits was observed for membranes situated on the sea bed. The electric field of cathodically protected wall did not affect the hydrogen absorption. The hydrogen uptake recorded under the natural sea conditions can be higher than that measured in the laboratory tests, which should be taken into account while servicing marine constructions, especially embedded ones.     

结构钢在模拟海洋大气环境中的腐蚀行为研究

利用模拟海洋大气环境的加速腐蚀实验,对比研究了两种结构钢(低碳铁素体钢和耐候钢09CuPCrNi)朝天面与朝地面的腐蚀行为及相应锈层,结果表明两种结构钢的朝地面均比朝天面腐蚀严重.电化学阻抗谱(EIS)结果表明朝天面锈层对氯离子的阻碍能力高于朝地面锈层,X射线衍射(XRD)结果表明朝天面锈层中X射线无定形锈含量高于朝地面锈层,N2吸附结果表明朝天面锈层比朝地面锈层致密.两面腐蚀条件的差异造成了两面锈层相组成和致密度的不同,从而导致相应锈层保护性能的区别.提出锈层孔隙模型,解释了锈层保护性能差异的原因是锈层干/湿交替频率的不同.     

The atmospheric corrosion kinetics of low carbon steel in a tropical marine environment

The atmospheric corrosion kinetics of low carbon steel exposed for up to 36 months in marine and industrial sites was studied by weight loss measurements. The results show that the mechanism and kinetics of the atmospheric corrosion process presents transition behaviour in marine environments with high chloride ion content and high relative humidity, whereas no transition appears in industrial environment. The average corrosion velocity in marine site reaches a maximum during the period of transition and then fluctuates in a certain range; however, the instantaneous corrosion velocity follows different exponential functions before and after the period of transition.     

Long-term atmospheric corrosion of mild steel

A great deal of information is available on the atmospheric corrosion of mild steel in the short, mid and even long term, but studies of the structure and morphology of corrosion layers are less abundant and generally deal with those formed in just a few years. The present study assesses the structure and morphology of corrosion product layers formed on mild steel after 13 years of exposure in five Spanish atmospheres of different types: rural, urban, industrial and marine (mild and severe). The corrosion layers have been characterised by X-ray diffraction (XRD) and scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS). Long-term corrosion is seen to be more severe in the industrial and marine atmospheres, and less so in the rural and urban atmospheres. In all cases the corrosion rate is seen to decrease with exposure time, stabilising after the first 4–6 years of exposure. The most relevant aspects to be noted are (a) the great compaction of the rust layers formed in the rural and urban atmospheres, (b) the formation of hematite and ferrihydrite phases (not commonly found) in the industrial and marine atmospheres, respectively and (c) identification of the typical morphological structures of lepidocrocite (sandy crystals and flowery plates), goethite (cotton balls structures) and akaganeite (cotton balls structures and cigar-shaped crystals).     

Electrochemical monitoring of atmospheric corrosion phenomena

An atmospheric corrosion monitor (ACM) which consists of $\text{Cu}\text{Zn}$ or Cu/steel couples, has been used to study various aspects of atmospheric corrosion. Calibration of ACM's is carried out under 1 ml of distilled water. Measurements under 10^?510^?1N KCl show that the conductivity of the electrolyte is not an important parameter in determining the amount of current flow. A detailed study was related to the effect of salt particles on atmospheric corrosion. While no current flow and no corrosion occurred on clean surfaces up to r.h. ≈ 95%, large increases of the galvanic current were observed when salt particles were placed on the ACM surface provided that the relative humidity in the test cell was higher than the r.h. value of a saturated solution of the salt particle applied. The ACM has also been used to monitor changes in the composition of gaseous atmospheres (air, N₂, N₂ plus SO₂). Outdoor exposure of the $\text{Cu}\text{Zn}$ and Cu/steel ACM suggests that this instrument can be used not only to monitor time-of-wetness, but also the corrosivity of a test environment.     

模拟海洋大气环境对XCS-lode钢与30CrNi3Mo钢腐蚀行为的影响

采用盐雾腐蚀试验方法,研究了模拟海洋大气环境下XCS-lode钢与30CrNi3Mo钢的腐蚀性能,通过极化曲线及电化学阻抗谱(EIS)试验研究了两种钢在腐蚀行为上的差异.结果表明:XCS-lode钢相比30CrNi3Mo钢具有更高的自腐蚀电位,XCS-lode钢腐蚀产物膜的阻抗明显大于30CrNi3Mo钢,XCS-lo...     

The atmospheric corrosion of unprotected carbon steel – a comparison between field study and laboratory test

A comparison is made between the atmospheric corrosion of unprotected carbon steel in outdoor exposures and results from laboratory tests. The atmospheric corrosion in the outdoor exposures is expressed as a function of certain atmospheric parameters (e.g. SO₂ concentration). In the laboratory tests the atmosphere consisted of air containing known amounts of SO₂ and water vapour. The experiments were carried out in such a way that both supply and deposition of SO₂ was known. There was good agreement between the empirical formula and the results from the laboratory tests provided that the supply of SO₂ in the laboratory test was below ca. 0.5 μg · h^?1 · CM^?2.