Comparison of corrosion scales formed on KO8OSS and N8O steels in CO2/H2S environment

Abstract

Scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) were applied to analyse the microstructure and composition of the corrosion scale formed on KO80SS and N80 tubes with carbon dioxide (CO₂) and hydrogen sulphide (SO₂). The corrosion scales of both KO80SS and N80 tubes were of the double layer structure, and not only uniform corrosion but also localised corrosion was observed. The crystal of the surface layer is laminar. The main phase in the outer layer is calcium carbonate (CaCO₃), and the inner scale consisted of iron carbonate (FeCO₃) for KO80SS steel and FeS_0·9 with a little amount of FeCO₃ for N80 steel respectively. Additionally, the electrochemical techniques were used to investigate the characteristics of the corrosion scales. The results indicated that the polarisation resistance R_p of KO80SS steel film was nobler than that of N80 steel film. Finally, the corrosion current I_corr of KO80SS steels was lower than that of N80 steels. Corrosion scale of KO80SS tube steels is more protective to the matrix than that of N80 tube steels.     

Influence of cold gas spray parameters on the corrosion resistance of Al-Al2O3 coatings sprayed on carbon steel

ABSTRACT

This work describes the influence of standoff distance (SoD), and gas temperature on the morphology and corrosion resistance of Al-10%Al₂O₃ coatings deposited by cold gas spray (CGS) on carbon steel. The results showed that the standoff distance had little effect on the thickness and microstructure of the coating. However, a 100 °C decrease of the spraying temperature reduced the coating thickness by 300?µm. The use of electrochemical analyses and SEM images showed that all the coatings studied were able to protect the substrate during at least 1300?h of immersion, due to the dense microstructure obtained by CGS.     

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.     

Protective effect in sulfuric acid media of alumina and ceria oxide layers electrodeposited on stainless steel

The influence of thin layers of Al₂O₃ and Ce₂O₃-CeO₂, electrodeposited on stainless steel OC4004, on the corrosion behaviour of the systems Al₂O₃/SS, Ce₂O₃-CeO₂/SS and Al₂O₃-Ce₂O₃-CeO₂/SS has been studied in sulfuric acid medium. A pronounced stabilizing effect on the passive state of steel and enhancement of its corrosion resistance has been established both for the samples as deposited and for the thermally treated Ce₂O₃-CeO₂/SS systems. In comparison to them the layers of Al₂O₃ have a substantial impact on the corrosion resistance of the Al₂O₃/SS system only in the cases when the system is not subjected to thermal treatment. The consecutive deposition of Al₂O₃ and Ce₂O₃-CeO₂ films on SS gives as a result an outstanding corrosion-protective effect, whereupon the corrosion potential of the system Al₂O₃/Ce₂O₃-CeO₂/SS is shifted in positive direction with ∼ 0.3 V for the samples as deposited and with ∼ 1 V—for the thermally treated samples. The so established favourable effect has been explained by the increased concentration of chromium oxides in the surface passive film, caused by the presence of cerium oxides, as well as by their action as cathode, effective with respect to the reduction corrosion reaction, shifting strongly the potential (at which this reaction is occurring) in positive direction.     

Long term corrosion of X70 steel and iron in humid supercritical CO2 with SO2 and O2 impurities

Abstract

The corrosion of X70 steel and iron in supercritical CO₂/SO₂/O₂/H₂O environment were investigated after a 454 h exposure. Optical microscopy was applied to observe the morphology of etch pits and synthesise the three-dimensional morphology. X-ray diffraction and X-ray photoelectron spectroscopy were employed to detect the composition of product scales. Experimental results verified that the localised corrosion occurred on the X70 steel sample under corrosion product deposits. Ferrous sulphate, sulphur and iron sulphide were detected as the corrosion products.     

Effect of O2 on down-hole corrosion during air-assisted steam injection for heavy oil recovery

ABSTRACT

Air-assisted steam injection is used to enhance hydrocarbon recovery from heavy oil reservoirs. During this process, downhole tubular goods are subject to corrosion in a mixed oxygen-carbon dioxide-steam environment at temperature up to around 200°C causing a low-temperature oxidation phenomenon. Here we investigate the influence of the O₂/CO₂ ratio on the corrosion of P110 steel, a grade that is commonly used for oil well casings. Our findings show that corrosion is greatly influenced by the O₂ pressure but hardly at all by the CO₂ pressure. The maximum corrosion rate was in excess of 65?mm per year. However, alkalisation of the injected fluid, which promoted the formation of a protective magnetite scale, was found to greatly reduce corrosion.     

Corrosion and Stress Corrosion Cracking Behavior of X70 Pipeline Steel in a CO2-Containing Solution

The electrochemical corrosion and stress corrosion cracking (SCC) behaviors of X70 pipeline steel in CO₂-containing solution were studied by electrochemical measurements, slow strain rate tensile tests, and surface characterization. The results found that the electrochemical corrosion of X70 steel in aerated, alkaline solution is an activation-controlled process, and a stable passivity cannot develop on steel. Corrosion rate of the steel increases with the CO₂ partial pressure. The enhanced anodic dissolution due to the additional cathodic reaction in the presence of CO₂, rather than the film-formation reaction, dominates the corrosion process. The mass-transfer step through FeCO₃ deposit is the rate-controlling step in corrosion of the steel. The susceptibility of steel to SCC and the fracture brittleness increase with the CO₂ partial pressure. The enhanced fracture brittleness is attributed to the evolution and penetration of hydrogen atoms into the steel, contributing to crack propagation. The formed deposit layer is not effective in reducing hydrogen permeation due to the loose, porous structure.     

45#钢Cr-N包埋共渗涂层的组织特征及形成机理

目的研究在45~#钢表面包埋共渗沉积Cr_2N涂层提高其耐蚀性的可行性。方法采用包渗法,对在1100℃下保温不同时间,得到不同时期的氮铬共渗涂层。利用扫描电镜及能谱仪、X射线衍射仪研究氮铬共渗层的微观组织及其生长机制,利用极化曲线评估涂层耐蚀性能。结果 45~#钢氮铬包埋共渗在保温4 h时可获得最佳涂层,涂层组织为Cr_2N层(约15μm)、Cr的沉积层(约10μm)、Cr的扩散层(约15μm)。Cr_2N层呈现强烈的(002)晶面择优取向;Cr沉积层为Fe-Cr合金及铬的碳化物相(Cr_7C_3,Cr_3C_2)。在模拟燃料电池腐蚀液中,45~#钢、45涂层样品、304不锈钢自腐蚀电位和自腐蚀电流分别为-0.521 V和230.63μA·cm~(-2),-0.448 V和10.89μA·cm~(-2),-0.299 V和5.26μA·cm~(-2)。当腐蚀电位高于0.3 V时,涂层样品会二次钝化,腐蚀电流低至1.43μA·cm~(-2)。结论沉积Cr_2N的45~#钢样品相对原样其耐蚀性有很大提高,并且当腐蚀电位达到0.3 V以上时,其耐蚀性能优于304不锈钢。     

Electrochemistry of deformed smooth surfaces and short corrosion fatigue crack growth behaviour

Abstract

The polarisation characteristics for a deformed smooth surface of a 0·2% carbon steel in an artificial sea water have been determined under static and cyclic loading conditions. The influence of strain level and loading frequency on anodic and cathodic Tafel constants, corrosion current density, and corrosion potential is described. Based on these data, the conditions for corrosion fatigue testing which corresponded to a maximum synergism between surface deformation and anodic dissolution were determined. Corrosion fatigue tests, which were conducted under both constant potential and constant current density conditions have shown that a process of metal dissolution plays a determining role in the short corrosion fatigue crack growth behaviour. An experimentally based criterion is proposed involving the development of a short corrosion fatigue crack, of characteristic size, which is associated with the spacing between the major microstructural barriers. This criterion is a function of both shear stress and the parameters controlling the anodic dissolution process on a cyclically deformed smooth suiface. An expression predicting the formation of short corrosion fatigue cracks is presented which takes into account the synergistic action of shear stress and the corrosion process.     

Effect of Al and Ce oxide layers electrodeposited on OC4004 stainless steel on its corrosion characteristics in acid media

The changes in the corrosion characteristics of stainless steel OC4004 in 0.1 M HNO₃ after electrodeposition of thin Al and Ce oxide films on it has been investigated. The Ce₂O₃–CeO₂ layers have been found to possess a pronounced stabilizing effect on the steel passive state and on its corrosion resistance, respectively, whereas the Al₂O₃ layers do not improve considerably the corrosion behaviour of the SS/Al₂O₃ system. A twice-lower corrosion current was observed with a ternary SS/Al₂O₃/Ce₂O₃–CeO₂ system in the passive region, while the zones of potentials, where the steel is in a stable passive state, are not changed. The obtained results permit the assumption that the cerium oxides layer acts as an effective cathode playing a determining role with respect to the improvement of the corrosion behavior of the steel. It has been concluded that when the SS/Al₂O₃/Ce₂O₃–CeO₂ system is used in media containing nitric acid, the corrosion will proceed at potentials where the passive state of steel would not be disturbed.     

Stress corrosion cracking of 304L stainless steel in molten salts media

A tensile apparatus with constant strain rate, suitable for corrosion tests in molten salts has been used to determine the mechanical characteristics of 304L stainless steel in molten NaClCaCl₂ at 570°C fromα= f [(Δl)/(l₀) %]curves for different strain rates. Potentiometric measurements, executed simultaneously, have determined the electrochemical conditions during mechanical testing. Results show a strain rate field in which the stress corrosion cracking occurs.     

Optical spectroscopic and electrochemical characterization of oxide films on a ferritic stainless steel

Colored oxide films that form on ferritic stainless steel in a high-temperature, oxidizing environment and correspond to different chemical compositions can cause a deterioration of pitting resistance and corrosion performance. Herein, optical spectroscopic and electrochemical techniques have been used to reveal the relationship between color, chemical composition, and corrosion resistance of oxide films formed in the temperature range from 400°C to 800°C for 30 min and at 800°C for 10, 20, 30, and 60 min. The substrate with a thin and dense passivation film leads to a low pitting potential but high corrosion resistance. Oxide films of yellowish or brownish color formed below 600°C are mainly iron oxides, which correspond to low corrosion resistance. No passivation characteristics can be observed for polarization curves of oxide films formed at 500°C and 600°C. The color of oxide films varies from blue to dark gray with the increase of oxidation time at 800°C. Corrosion resistance changes with different proportions of Fe₃O₄, Cr₂O₃, and FeCr₂O₄. The gray oxide films formed at 800°C for 30 min exhibit the lowest pitting susceptibility and the highest corrosion resistance.     

Corrosion Inhibition of 304 Stainless Steel by Nano-Sized Ti/Silicone Coatings in an Environment Containing NaCl and Water Vapor at 400–600°C

The corrosion behavior of 304 stainless steel (SS) and its corrosion inhibition by brushing nano-sized Ti/silicone coatings on its surface in an environment containing a solid NaCl deposit and water vapor at 400–600°C was studied. Results indicated that water vapor or NaCl, especially water vapor plus NaCl accelerated the corrosion of the steel markedly. The corrosion scales of the uncoated steel had a duplex structure at 400–500°C and internal oxidation occurred for the uncoated steel at 600°C in an environment containing NaCl and water vapor. The corrosion of the 304SS was inhibited efficiently by the coatings at 400–500°C, and the coated steel suffered corrosion to some extent and most of the coatings were destroyed at 600°C. X-ray diffraction (XRD) indicated that the corrosion products of the uncoated steel were mainly Fe₂O₃, Cr₂O₃, NiO or Na₂CrO₄, and the coatings consisted mainly of TiO₂ and SiO₂ after exposure at 400–500°C. The good corrosion resistance of the nano-sized Ti/silicon coatings was attributed to the formation of SiO₂, and TiO₂ that resulted from the decomposition of the organic components in the coating and fast oxidation of nano-Ti powder respectively during the experiments, TiO₂ mixed together with SiO₂ and formed a new coating on the steel surface that played an important role in the protection of the steel.     

Corrosion of stainless steels and carbon steel by molten mixtures of commercial nitrate salts

The isothermal corrosion behavior of two stainless steels and a carbon (C) steel in mixtures of NaNO₃ and KNO₃ was evaluated to determine if the impurities found in commodity grades of alkali nitrates aggravate corrosivity as applicable to an advanced solar thermal energy system. Corrosion tests were conducted for approximately 7000 hours with Types 304 and 316 stainless steels at 570 °C and A36 C steel at 316 °C in seven mixtures of NaNO₃ and KNO₃ containing variations in impurity concentrations. Corrosion tests were also conducted in a ternary mixture of NaNO₃, KNO₃, and Ca(NO₃)₂. Corrosion rates were determined by descaled weight losses while oxidation products were examined by scanning electron microscopy (SEM), electron microprobe analysis (EPMA), and x-ray diffraction (XRD). The nitrate mixtures were periodically analyzed for changes in impurity concentrations and for soluble corrosion products. Results of these tests indicated that the short-term corrosion rates of the stainless steel specimens in many of the mixtures could be described in terms of parabolic kinetics. However, no single rate law could be assigned to the corrosion kinetics resulting from exposure in all of the mixtures. For engineering applications, corrosion rates over the entire exposure period are best described as linear with respect to time. In the binary nitrate mixtures, the annualized rates of metal loss were found to be between 6 and 15 μm/year for the stainless steel specimens at 570 °C depending on the particular mixture. Metal loss for the C steel specimens immersed in these same mixtures at 316 °C extrapolated to approximately 1–4 μm/year. SEM and XRD revealed that the complex, multiphase surface oxides formed on the stainless steel coupons were composed primarily of iron-chromium spinel, iron oxides, and sodium ferrite. Magnetite was the principal corrosion product formed on the carbon steel specimens. Overall, for the typical range of impurities in commercially available nitrate salts, corrosion rates for solar thermal energy applications remained acceptable for all of the materials examined.     

玻璃Cr2O3陶瓷涂层表面液态重金属润湿角的测量与表征

金属材料的腐蚀性能与其表面润湿特性有着密切的关系。采用亚音速火焰喷涂技术制备了玻璃-Cr2O3陶瓷涂层,设计了一套运行在高温环境中且密封的专用试验平台,研究经过不同保温时间后,重金属在45钢与喷有玻璃-Cr2O3陶瓷涂层的45钢表面的润湿角及相关现象的变化。结果表明:相同质量的重金属液滴在45钢表面的润湿角为18°,在玻璃-Cr2O3陶瓷涂层表面的润湿角为114°,玻璃-Cr2O3陶瓷涂层抗液态重金属润湿性能较好。固化后重金属颗粒与试样之间的接触面积及剪切强度均有所不同,304不锈钢与颗粒剪切强度为1.42MPa,而涂层与颗粒剪切强度为0.21MPa。     

Fe3C influence on the corrosion rate of mild steel in aqueous CO2 systems under turbulent flow conditions

The corrosion and corrosion inhibition of mild steel in CO₂ saturated solutions were studied under turbulent flow conditions at different pH. Electrochemical measurements using a.c. and d.c. techniques in uninhibited solutions of pH 3.8 indicated the formation of protective surface films (FeCO₃) in short immersion times. However, as the exposure time was increased the corrosion rate always increased, an effect attributed to the increased surface area of Fe₃C residue from corrosion of the steel. At pH 5.5, the corrosion rate always increased with time, behaviour also associated with the presence of Fe₃C surface film. The huge cathodic area of Fe₃C seems to have a more important impact on the electrochemical behaviour than the poorly formed FeCO₃ products. The effect of Fe₃C on inhibition by a quaternary amine inhibitor at pH 3.8 is to increase the corrosion rate as the pre-corrosion time is increased. The Fe₃C causes either (a) a cathodic area increase reflected in the corrosion rate increase with time or (b) a potential gradient in the pores of the Fe₃C layer that prevents positively charge amine ions from reaching all anodic sites.     

Co2 corrosion inhibition of X-120 pipeline steel by a modified imidazoline under flow conditions

A study of the effect of flow conditions on the performance of a carboxyethyl-imidazoline as CO₂-corrosion inhibitor for API X-120 pipeline steel has been evaluated. Testing techniques include polarization curves, linear polarization resistance, electrochemical impedance spectroscopy and electrochemical noise measurements under stirred conditions (0, 250, 500, 1000 and 2500 rpm). All these techniques show that for the uninhibited solution, corrosion rate increases with an increase in the rotation speed, but for the inhibited solution, the lowest corrosion rate is obtained at 500 rpm, and it increases at lower or higher rotation speeds.     

Laboratory investigation on the condensation and corrosion rates of top of line corrosion in carbon steel: a case study from pipeline transporting wet gas in elevated temperature

A glass cell was designed to simulate the condition for top of line corrosion encountered in wet gas transportation pipelines. Aqueous solution of 3 wt-% NaCl saturated with CO₂ at atmospheric pressure was employed. Effect of temperature gradient in the formation of condensation and its rate was investigated. API 5L Grade X65 carbon steel material was used as the working electrode for the experiment. The condensation rate was measured for the temperature gradient of 20°C, 30°C and 50°C under atmospheric condition for 24?h duration of the experiment. The corrosion rate of the specimens was measured using weight loss and Linear Polarisation Resistance (LPR) techniques. The LPR probe was immersed in the collected condensed water from the experiment to calculate the corrosion rate. The measured corrosion rate from the weight loss technique was in agreement with the corrosion rate measured from LPR. The corrosion rate measurement was repeated with the addition of 1000?ppm of pH modifying agent. This study indicates that the corrosion rate of pipeline and piping when subject to temperature gradient of 50°C and above is very high and alarming.     

Electrochemical corrosion behaviour of a Ti‐IF steel and a SAE 1020 steel in a 0.5 M NaCl solution

Investigations concerning the electrochemical corrosion behaviour of low carbon (LC) and ultra‐low carbon (ULC) steels are relatively scarce and limited. The present study aims to compare electrochemical impedance parameters and potentiodynamic polarization curves of an LC steel and an ULC Ti‐interstitial free (IF) steel evidencing the effects of carbon content and pearlite fraction on the electrochemical corrosion behaviour. Corrosion tests were carried out in a 0.5 M NaCl solution at 25 °C with a pH range between 6.5 and 6.8. It was found that the IF steel sample presents an electrochemical corrosion resistance, which is slightly higher than that of the LC steel sample.     

Corrosion behavior of UCX,KHR35, and KHR45 alloys in molten nitrates

The corrosion behavior of three high-Ni, high-Cr alloys, that is, UCX, KHR35, and KHR45 alloys, in a mixture of 60% NaNO₃–40% KNO₃ at 600°C has been evaluated by using weight loss tests, potentiodynamic polarization curves, and electrochemical impedance spectroscopy measurements. Cr contents ranged between 23.25 and 43.2 wt.%, whereas Ni ranged between 36.6 and 50.3 wt.%. For comparison, the same studies were performed on 304-type stainless steel (304SS). Tests were complemented with detailed scanning electronic microscope and X-ray diffraction studies. Results showed that that the three high-Ni, high-Cr alloys had lower weight loss than that for 304SS. Polarization tests indicated the formation of a passive layer in all cases. Electrochemical impedance spectroscopy data have shown that the corrosion mechanism for all the alloys was charge transfer from the alloy to the molten salt. Finally, X-ray patterns showed the presence of Cr₂O₃ in all tested alloys, which is responsible for the observed passive behavior and their corrosion resistance.