Corrosion behavior of low alloy steel used for new pipeline exposed to H2S-saturated solution

In this paper, the corrosion behavior of low alloy steel in H₂S-saturated solution is systematically studied through immersion experiment in terms of microstructure morphology, corrosion kinetics, surface morphology, cross-sectional morphology, crystal characteristic and elemental distribution. The experimental results suggest that the corrosion rate decreased gradually with corrosion time. The corrosion products were immediately formed after the steel was immersed in corrosion solution and the structure and thickness became denser and thicker, which improved corrosion resistance. The corrosion products transformed from mackinawite, greigite and molybdenite to mackinawite, greigite, pyrrhotite and molybdenite. For the alloying elements, Cr and Mo tended to be accumulated in corrosion products compared with the steel substrate. A schematic model of corrosion process was proposed according to experimental results.     

The Influence of Sulfurization of Rust in Oil Tanks

Abstract

Hydrogen sulfide reacts with the corrosion products (Fe₂O₃) in oil tanks to form iron sulfides. The oxidation and released heat of iron sulfides can lead to spontaneous combustion of iron sulfides and fire of oil tanks. In this article, the simulating production process of iron sulfides in oil tanks and the effects of flow rate of hydrogen sulfide, environmental temperature and setting time on the quantities and types of iron sulfides are studied.     

Time-dependent corrosion behavior of electroless Ni–P coating in H2S/Cl− environment

As a mature technology, electroless Ni–P alloy coating is widely applied in the protection of chemical equipment and pipelines owing to its excellent corrosion resistance, but its application and long-term service evaluation in the field of high-sulfur oil and gas are rare. Therefore, the time-dependent corrosion behavior of Ni–P coating, which was plated on the L360 steel surface, was investigated in a saturated H₂S medium by the method of surface analysis. The results indicate that Ni–P coating with a thickness of about 52.6 μm could significantly reduce the corrosion rate compared with uncoated pipeline steel. This is related to the structure of the dense, protective film on the surface. The uncoated pipeline steel suffered local corrosion during the immersion process, and then it developed into uniform corrosion with the formation of a large number of corrosion products. In comparison, Ni–P coatings corroded relatively mildly with only a thin corroded layer. However, during prolonged corrosion testing, the corrosive medium penetrated the coating/substrate interface at inherent defects, leading to severe local corrosion of the substrate.     

Effects of Nb on stress corrosion cracking of high-strength low-alloy steel in simulated seawater

In this study, simulated heat-affected zone (HAZ) of Nb-free and Nb-bearing steel were obtained, and SEM, TEM, and slow strain rate tensile (SSRT) tests were performed to investigate the effect of Nb on the stress corrosion cracking (SCC) behavior of high-strength low-alloy (HLSA) steel in simulated seawater with or without hydrogen charging. The addition of Nb significantly refined the grains and uniformed the microstructure of HLSA. Nb hardly affected the SCC susceptibility of BM and HAZ without hydrogen-charging. However, after charging with 10 mA cm⁻², the SCC resistance of Nb-bearing steel, especially the coarse grain HAZ (CGHAZ) improved drastically, and the process of crack initiation and propagation was inhibited owing to the hydrogen trap function of NbC precipitates.     

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.     

Investigation on high temperature corrosion of water-cooled wall tubes at a 300 MW boiler

Because of the updated requirement on ultra-low NOx emission (<50 mg/Nm³), most of Chinese coal-fired boilers have to be operated at a low NOx combustion mode. However, for high-sulfur coal, water-cooled wall tubes probably suffer severe corrosion in such a strong reduction atmosphere. This work aims to investigate the high temperature corrosion behavior of water-cooled wall tubes inside a 300 MW boiler unit. A short length of corroded water-cooled wall tube was cut down and was analyzed by various characterization methods to further figure out the detailed corrosion mechanism. The typical corrosion products can be distinguished by blue, black and pale-green. Results showed that blue and black color products were mainly consisted of iron sulfides and iron oxides while the pale-green ones were identified as zinc sulfide. Along the radial direction, a layered structure of corrosion products can be observed. The formation of inner layer resulted from the reaction between iron oxide and hydrogen sulfide. The sulfur element displays a gradual increase trend while the Fe element gives out an opposite trend along the radially outward direction. The intermediate layer comes from the fly ash deposition and the outer layer is formed via condensation and deposition of ferrous sulfide gas on the water-cooled wall. The corrosion in this power plant is typical sulfide type for large amounts of Fe and S element were found in the corrosion products.     

Experimental study and numerical simulation on the SSCC in FV520B stainless steel exposed to H2S+Cl− Environment

Constant displacement loading tests using wedge opening loading specimens were carried out in aqueous hydrogen sulfide solution containing sodium chloride to investigate the susceptibility of stress corrosion cracking (SCC) of FV520B precipitation hardening martensitic stainless steel. Results of the SCC tests indicated that the stress corrosion critical stress intensity factor (K_ISCC) dramatically decreased in the corrosion medium investigated and decreased with the increasing of H₂S concentration. Microstructures of fracture surfaces were analyzed using a scanning electron microscope (SEM) with an energy dispersive X-ray spectroscopy (EDS). The fracture surface was typical of sulfide stress corrosion fracture. In addition, large amount of intermittent arc-crack on the side surfaces around the tip of main crack formed even no main crack propagated.A sequentially coupling finite element analysis (FEA) program was utilized to simulate the stress field and calculate the diffused hydrogen concentration distribution of specimen exposed to the corrosion medium investigated. The FEA results indicated that corrosion pit affected the stress and diffusion hydrogen distribution around the corrosion pit where large stress gradients formed. Side surface cracks initiated from those corrosion pits and propagated under the synergy of stress and hydrogen. The effect of the corrosion pit on hydrostatic stress distribution was limited in superficial zone near the side surface, thus side surface cracks propagated along the hoop direction rather than along the direction of specimen thickness. Based on the morphology observation and FEA results, it can be concluded that the SCC mechanism of FV520B steel was hydrogen embrittlement mainly and combination of anodic dissolution. Simultaneously, corrosion pitting was the precondition of side surface crack formation while the stress induced hydrogen diffusion was the dominant factor.     

Influence of fuel ashes on corrosion of surface coatings cladded by CMT method

The aim of the present research was to investigate the influence of different biomasses and sewage sludge ash (at 650°C for 1000 h and 2000 h, respectively) on the surface of weld cladded (Cold Metal Transfer technique, CMT) stainless steels 309 and 310. The biomass ashes were rich in K₂O, CaO, SiO₂, whereas sewage sludge ash in P₂O₅, CaO, Fe₂O₃, and SiO₂. Characterization of the stainless steel cross-section and surface after the corrosion process inducted by the presence of ash were carried out by scanning electron microscopy (SEM) with EDAX analysis. Phase analysis of corrosion products was made by X-ray diffraction (XRD). Chromium, nickel, and iron oxides were the main oxides which occurred after the corrosion test. It has been proved that biomass ashes have the corrosive properties (because of their chemical composition) and are more aggressive than the sewage sludge ash for that kind of materials.     

Characteristics of scales from the Milos geothermal plant

Samples of scales have been studied using X-ray diffraction, elemental analysis and scanning electron microscopy. Analyses have also been made of brine and steam samples. The scale consists of heavy metal sulfides and silicon compounds which account for 90–100% of the deposited mass. The composition of the scale depends on the location with respect to the fluid flashing point. Samples in the vicinity of this point largely consist of metal sulfides (PbS, ZnS and CuFeS₂), while the percentage of silica and possibly of other silicon compounds tends to increase farther downstream.In all the samples, a significant part of the iron is not in the form of sulfide and is possibly bound into the silica matrix by some kind of “ion-bridging”. It is also observed that a silicon — rich layer adheres to the metal surface, even in places where sulfides are the main contituents of the scale.     

Corrosion and interfacial contact resistance of nanocrystalline β-Nb2N coating on 430 FSS bipolar plates in the simulated PEMFC anode environment

The corrosion of metallic bipolar plates in the proton exchange membrane fuel cells (PEMFCs) anode environment would degrade the performance and shorten the lifespan of the fuel cell. Hence, it is essential to develop a conductive coating with good corrosion resistance. Herein we demonstrate a dense, defect-free, and well-adhered nanocrystalline β-Nb₂N coating prepared on 430 ferritic stainless steel (430 FSS) via disproportionation of Nb(Ⅳ) species in molten salts. The corrosion mechanism of bare and β-Nb₂N coated 430 FSS in the simulated PEMFC anode environment is also studied by electrochemical techniques including potentiodynamic polarization, potentiostatic polarization, and electrochemical impedance spectroscopy. Results show that β-Nb₂N coating can significantly improve the corrosion resistance of the steel alloy with acceptable contact resistance. In addition, no obvious degradation is observed for the β-Nb₂N coating after potentiostatic polarization measurement for 500 h. This work offers a promising strategy to develop the corrosion protective coating on metallic bipolar plates for PEMFCs.     

Multiphase Nb–TiCo alloys: The significant impact of surface corrosion on the structural stability and hydrogen permeation behaviour

Multiphase Nb_xTi_(100-x)/2Co_(100-x)/2 (x = 30–60) alloys are a promising material for hydrogen separating membranes. These alloy membranes exhibit a rapid decline in hydrogen permeation flux within ∼12 h when operated at 773 K. To address this issue, a dense oxide (e.g. Nb₂O₅, TiO₂ and CoO) layer was prepared between a Pd coating layer and an Nb–TiCo substrate by surface corrosion for improving their thermal stability, and the corrosion resistance of Nb–TiCo alloys was investigated. An increase in the Nb content (x) lowers the corrosion resistance of these alloys, but makes it easier to form the above oxide layer. Substantial enhancement of hydrogen permeability and thermal stability at 773 K was observed for the alloys (x = 30 and 40) after corrosion, which can be ascribed to an increase in hydrogen diffusivity. This improved permeability and stability are closely related to the formation of the above surface oxide layer that impeded interdiffusion between the Pd film and Nb–TiCo substrates. This study demonstrates that insertion of a diffusion barrier between the Pd and Nb-based substrates by surface corrosion is a viable approach to enhance the high-temperature stability of Pd-coated Nb–TiCo alloys, an aspect not widely explored in Nb-based hydrogen separation and purification membranes.     

Microstructure and properties of intercritically reheated coarse-grained heat affected zone in pipeline steel after secondary thermal cycle

As a kind of high strength microalloyed steel, pipeline steel has high strength and toughness. However, the formation of the intercritically reheated coarse-grained heat affected zone (ICCGHAZ) during the welding process is an important limitation affecting its performance. Herein, microstructural transformation in the ICCGHAZ of X100 pipeline steel after a secondary thermal cycle and hydrogen sulfide stress corrosion cracking (SSCC) resistance of the transformed microstructure are investigated. The microstructure of X100 pipeline steel after the secondary thermal cycle is similar to that after the primary thermal cycle, comprising lath bainite and granular bainite. With an increase in t_8/5 (time required for the material to cool from 800 °C to 500 °C), the M-A constituents that continuously precipitate along the prior austenite grain boundaries in the second thermal cycle are coarsened and form a necklace-type structure. A variation in t_8/5 does not significantly affect the crystallographic characteristics of the ICCGHAZ. The stress corrosion test shows that the resistance to SSCC decreases and cleavage fracture characteristics become more noticeable with an increase in t_8/5.     

燃煤电站锅炉高温腐蚀特征的研究

采用金相显微镜、X射线衍射、X射线荧光探针、场发射扫描电子显微镜-能谱分析和孔径测试等微观分析手段,对某燃煤电站锅炉水冷壁的腐蚀产物进行了系统分析,结果表明腐蚀产物呈层状结构,其外层疏松多孔,内层结构致密;腐蚀产物主要组成为铁硫化物,铁氧化物和少量的硅酸盐组分,由内而外腐蚀产物的元素分布规律为硅、铝含量呈上升趋势,硫、铁含量呈下降趋势;矿物组成主要为腐蚀生成的铁硫化物矿物、铁氧化物矿物以及来自飞灰颗粒的硅铝酸盐矿物。综合分析其组成和微区特征,其水冷壁的腐蚀类型为硫化物型腐蚀。     

Oxidation behavior of nickel coating on ferritic stainless steel interconnect for SOFC application

The oxidation behavior of nickel coated ferritic stainless steel SS441 has been investigated. A nickel coating layer is deposited on the steel which is employed in a solid oxide fuel cell stack as interconnect. The nickel film is about 8 μm thick and is topped by an additional 4 μm thick La_0.67Sr_0.33MnO₃ (LSM) film on the interconnect cathode-contacting surface for the prevention of chromium evaporation from the steel substrate. A 10,000-h 800 °C isothermal ageing on 10 × 10 mm² steel coupons shows a continuous growth of oxide scales up to ∼200 μm in thickness on the surface, consisting of a 100 μm thick iron oxide layer followed by a complex Fe–Ni–Cr spinel structure. A single-cell stack is tested at 800 °C for up to 1226 h and an average degradation rate of 7.5% kh⁻¹ is observed. Oxidation characteristics of the coating system are analyzed after testing. A Fe–Ni spinel phase is found covering most of the surface area. This is attributed to the intensive interdiffusion of iron and nickel during the stack operation and the high intersolubility of the two elements. In both the tests of the steel coupons and the stack, LSM film structures are damaged by the thermally grown Fe–Ni oxides, and the expected Cr-preventing function is limited. The Fe–Ni spinel layer initially forms an effective obstacle against Cr out-migration. However, the increasing content of iron in the spinel phase induces oxide scale spallation afterwards. Though the fast grown Fe–Ni oxide scale can serve as an effective barrier against chromium out-migration, the iron-enriched scale structure is susceptible to corrosion attacks after an extended stack operation period.     

The dependence of anti-corrosion behaviors of iron sulfide films on different reactants

As the product of hydrogen sulfide corrosion, iron sulfide compound can be used as hydrogen permeation barrier. In this study, chemical vapor deposition was used to synthesize iron sulfide films on the surface of X80 steel with different sulfur sources, and the effects of different sulfur sources on the products were studied. The film was characterized by its morphology, composition and performance. The results show that the hydrogen resistance of our product and the bonding degree between the substrate and the film are strongly relevant with the compactness of the films. When we used TBDS as sulfur source, the highest impendance and the smallest hydrogen permeation current (0.53 μA/cm²) was obtained, which is due to the better adhesion and dense structure compare to the other two sulfur sourses.     

Influences of oxygen on corrosion characteristics of TiO2/316L stainless steel in supercritical water

Supercritical water gasification (SCWG) is a promising technology for converting organic wastes to hydrogen. Less amount of oxygen is beneficial for increasing hydrogen generation rate. However, the corrosion rate of reactor material would be accelerated. TiO₂ coating with a thickness of 0.1 mm was prepared on the surface of 316L stainless steel (SS316L) to improve its corrosion resistance in supercritical water (SCW). The corrosion performances of TiO₂/SS316L were tested in a bath SCW reactor at 400 °C, 25 MPa. The influences of oxygen concentration (0–1000 mg/L) on surface morphologies and corrosion depths were studied thoroughly. Results indicated that the surface of TiO₂/SS316L exhibited cracks and pores after exposed in SCW. And the average corrosion rates accelerated at higher oxygen concentrations. The interface between the coating and medium was relatively smooth and there was no obvious change in the thickness of the coating with oxygen concentration of 0 and 500 mg/L. While for that with 1000 mg/L oxygen, the surface of TiO₂/SS316L exhibited reticulate crack. The cross section showed a serrate structure, and only 0.08 mm thick of the coating was remained. In addition, the corrosion mechanism of coating was discussed.     

Corrosion study of SS430/Nb as bipolar plate materials for PEMFCs

Niobium-coated 430 stainless steel (SS430/Nb) specimens were evaluated as possible bipolar plate materials in conditions that resemble a typical PEMFC environment with respect to their interfacial contact resistance (ICR) and corrosion resistance. Results show that SS430/Nb demonstrated to have low ICR values and very good corrosion resistance in comparison with commercial steel and Ni-based alloys. In addition, the ICR values are also comparable with those of graphite.     

Corrosion of construction materials of separator in molten carbonates of alkali metals

The mitigation of steels and alloys corrosion is one of the great challenges for application of high-temperature devices in contact with molten salts. The current research estimates corrosion resistance of the following construction materials: Crofer APU 22, austenitic steel 12Cr18Ni10Ti and two types of austenitic nickel-chromium alloy: CrNi78Ti, CrNi78Ti + 5% wt. W. The measurements are performed by exposition of samples within 24 h in the molten mixture of carbonates of lithium and potassium at 650 °C. The rates and mechanism of materials corrosion under these conditions are determined. The process occurring on the surface while contact of the materials and steels with carbonate melt are investigated.Accurate quantitative data on materials interaction with alkali carbonate melt have been obtained by gravimetrical and physico-chemical methods. The high-temperature corrosion of Fe and Ni austenitic materials has turned dramatically different from both their low-temperature corrosion and each other. There are mixed passivating oxide films on the surface of the only iron-based materials.In addition, the resulting layers of corrosion products are well bonded to the substrate and have protective properties and can be used as protective coatings in molten salts of other compositions, including alkali metal fluorides.     

Oxygen ingress into geothermal steam and its effect on corrosion of low carbon steel at Broadlands,New Zealand

Oxygen injected into high pressure (650 kPa) geothermal steam containing high H₂S levels drastically increased the corrosion rate of carbon steel. At increasing oxygen levels, formerly protective scales were replaced by semi-protective corrosion products identified as pyrrhotite, marcasite, pyrite and magnetite. Corrosometer probes were used to determine corrosion rates, but hydrogen probes and chemical analysis were also employed to diagnose corrosion mechanisms. Oxygen appeared to act as a cathodic depolarizer in addition to its oxidizing action on hydrogen sulphide to S, H₂O, SO₄^2? and polysulphides.     

Effect of corrosion inhibitors on hydrogen uptake by Al from NaOH solution

Corrosion rate, hydrogen permeation rate (hydrogen uptake) and stress corrosion cracking of Al were studied in NaOH solutions, pure and with the addition of H₃BO₃, EDTA, KMnO₄ and As₂O₃. The presence of the studied species in electrolyte and the implantation of Al surface with B⁺ ions inhibited corrosion. Hydrogen uptake was found to be promoted or inhibited by means of studied species, depending on the method of their introduction into the base solution and on the applied polarization. The observed different influence of corrosion inhibitors on the hydrogen uptake was associated with the different chemical composition and structure (revealed by XPS analysis) of the surface films, formed on Al under the various conditions. Under similar polarization conditions, the presence of H₃BO₃ in the base solution similarly affected the hydrogen uptake by Al and the susceptibility to stress corrosion cracking of the metal.