Corrosion failures of AISI type 304 stainless steel in a fertiliser plant

A urea plant, operating on ammonia and carbon dioxide (CO₂) gases, had to be shutdown due to corrosion in the intercooler and aftercooler of its CO₂ gas cleaning circuit. Extensive general corrosion of AISI type 304 stainless steel parts, such as sealing strips, fins, demisters and the shell, of these two components which were in contact with the duplex stainless steel tubes, caused the shutdown of the fertiliser plant within 6 months. Investigations of the corrosion products by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) techniques showed the presence of carbon and ammonia based compounds, thus suggesting the role of ammonia and CO₂ gases, or the product of their reactions, in the corrosion of type 304 stainless steel. Electrochemical polarisation studies showed that duplex stainless steel possessed a more positive open circuit potential and a nobler critical pitting potential than type 304 stainless steel thus confirming that the corrosion of type 304 stainless steel was caused by the galvanic action with the duplex stainless steel heat transfer tubes. Hence, it was recommended that (i) the same material (type 304 stainless steel) be used for all parts of the intercooler and aftercooler to avoid galvanic corrosion, (ii) condense water carried over by CO₂ gas by cooling it to low temperatures immediately after it comes out from the scrubber, (iii) slight modification of the process to add up to 0.8% oxygen in the CO₂ gas before entry into the intercooler, which will help in retaining/formation of an effective passive film on type 304 stainless steel.     

Enhanced localized and uniform corrosion resistances of bulk nanocrystalline 304 stainless steel in high-concentration hydrochloric acid solutions at room temperature

The localized and uniform corrosion resistances of bulk nanocrystalline 304 stainless steel (NC-304SS) produced by severe rolling technique, and its conventional polycrystalline 304 stainless steel (CC-304SS) counterpart, were investigated in high-concentration hydrochloric acid solutions at room temperature. NC-304SS can scarcely suffer from localized corrosion in 4 mol/L and 5 mol/L HCl solutions during 5-day immersion tests, and in 1–3 mol/L HCl solutions during thirty-five-day immersion tests. The corrosion rate of NC-304SS was also less than that of CC-304SS during these immersion tests. The improved localized and uniform corrosion resistances of NC-304SS were explained in terms of the adsorption and chemical activity of Cl^? on NC-304SS and CC-304SS characterized by X-ray photoelectron spectroscopy, and the valence electron configurations of NC-304SS and CC-304SS were characterized by ultra-violet photoelectron spectroscopy rather than conventional electrochemical results.     

The abrasive corrosion behavior of plasma-nitrided alloy steels in chloride environments

Both corrosion and abrasive corrosion behavior of plama-nitrided type 304 and 410 stainless steels and 4140 low alloy steel were investigated in 3% NaCl solution (pH = 6.8) by electrochemical corrosion measurements. Surface morphology and alloying elements after corrosion and abrasion corrosion tests were examined by scanning electron microscopy and energy dispersive analysis of X-rays. The results indicated that the plasma-nitrided SAE 4140 steel containing -(Fe,Cr)_{2 – 3}N and -(Fe,Cr)₄N surface nitrides which produce a thick and dense protective layer exhibited a significant decrease of corrosion currents by inhibition of the anodic dissolution of iron, whereas the plasma-nitrided type 304 and 410 stainless steels containing the segregation of chromium nitride CrN exhibited a extensive pitting corrosion by acceleration of the anodic dissolution of iron. It is concluded that the susceptibility to pitting is consistent with the degree of chromium segregation, and decreases as follows: 304 stainless steel > 410 stainless steel > 4140 steel. Also, the results of abrasive corrosion testing for the plasma-nitrided alloys are strongly related to the subtleties of the nitrided microstructures resulting in a pitting and spalling type of abrasive corrosion of type 304 and 410 stainless steels, and excellent abrasive corrosion resistance for SAE 4140 steel.     

304不锈钢表面化学钝化膜对Sn粘附行为的影响

为了研究化学酸洗钝化在低熔点金属Sn与304不锈钢粘附过程中的作用,通过浸泡腐蚀实验分析了液态Sn与U型弯曲后的酸洗钝化不锈钢的交互作用行为,探讨了Sn粘附对不锈钢基体浸泡腐蚀性能的影响.实验结果表明:Sn与304不锈钢相互作用在界面处形成了片状(Fe,Cr)Sn2化合物冶金层,酸洗钝化处理改变了冶金结合,使液态Sn与304不锈钢界面成为直接物理接触;U型弯曲破坏了钝化膜的完整性,未能阻止Sn与不锈钢的界面冶金结合,但降低了界面化合物层的厚度.浸泡腐蚀实验结果表明,Sn粘附层促进了不锈钢基体腐蚀.     

模拟2倍浓缩海水中聚环氧琥珀酸和Na2MoO4对304不锈钢的缓蚀作用

为开发适用于循环冷却海水／不锈钢体系的绿色缓蚀剂,采用电化学阻抗谱、极化曲线及表面腐蚀形貌分析,研究了聚环氧琥珀酸（PESA）、Na2MoO4在模拟2倍浓缩海水中对304不锈钢的缓蚀作用。结果表明：在模拟2倍浓缩海水中,PESA与Na2MoO4均能在304不锈钢表面形成保护膜,产生缓蚀作用;PESA为阳极吸附型缓蚀剂,...     

Behaviour of 316 Ti stainless steel in deuterium oxide with chloride

Since tritiated water contains deuterium oxide, we require a better understanding of stainless steel corrosion in tritiated water and thus we have compared the behaviour of 316 Ti stainless steel in ²H₂O and H₂O with and without chloride. This was done by anodic polarization curves, cyclic voltammetry and electrochemical impedance spectroscopy. The corrosion potential of 316 Ti stainless steel in deuterium oxide changes and is related to pH modification due to the dissociation constant of this aqueous medium which shows the importance of pH in passivity. Without chloride, the insulating properties of the passive oxide layer depending on the pH and passive potentials are enhanced with ²H₂O. With deuterium oxide containing chloride at near neutral pH, the repassive potential is lower than that obtained with H₂O, consequently localized corrosion in grain boundaries and pit propagation, which lead to crevice corrosion, are greater. The critical pitting potential is in transpassivity indicating that pitting is less likely to occur. Comparison with and without Cl^- for the passive potentials near the corrosion potential, shows that although chloride reduces the insulation provided by the passive oxide layer it is still greater than that obtained with H₂O. This revised version was published online in November 2006 with corrections to the Cover Date.     

Influence of laser surface alloying with chromium and nickel on corrosion resistance of type 304L stainless steel

Abstract

The influence of laser surface alloying (LSA) with Cr and Cr + Ni on the corrosion behaviour of type 304L stainless steel (SS) was investigated using potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS) in chloride (0·5M NaCl) and acidic (1 N H₂SO₄) media. Surface alloying was carried out by laser cladding type 304L SS substrate with premixed powders of AISI type 316L SS and the desired alloying elements. The results indicated that Cr surface alloyed specimen exhibited a duplex (γ + α) microstructure with Cr content of ～24 wt-%, whereas Cr + Ni surface alloyed specimen was associated with austenitic microstructure with Cr and Ni contents of ～22 wt-% each. The potentiodynamic polarisation results in chloride solution indicated that LSA with Cr + Ni considerably enhanced the pitting corrosion resistance compared with LSA with Cr alone. In acidic media, such beneficial effects were not observed. Electrochemical impedance spectroscopy results showed an increase in semicircle arc for both chloride and acidic media for both Cr and Cr + Ni clad samples indicating improvement in the oxide film stability compared with untreated specimen. The polarisation resistance was higher and capacitance values of the laser clad specimen were lower than those in the untreated specimen. The microstructural changes and compositional variations produced by LSA are correlated to the corrosion behaviour.     

Microbially influenced corrosion of stainless steel by marine bacterium Vibrio natriegens: (I) Corrosion behavior

The microbially influenced corrosion of stainless steel (SS) by marine bacterium Vibrio natriegens (V. natriegens) was investigated using surface analysis (atomic force microscopy (AFM), scanning electron microscopy (SEM), and energy dispersive X-ray analysis (EDXA)) and electrochemical techniques (the open circuit potential, electrochemical impedance spectroscopy (EIS), and potentiodynamic polarization curves ). AFM images corroborated the results from the EIS models which show biofilm attachment and subsequent detachment over time. The SEM images revealed the occurrence of micro-pitting corrosion underneath the biofilms on the metal surface after the biofilm removal. The presence of carbon, oxygen, phosphor and sulfur obtained from EDXA proved the formation of biofilm. The electrochemical results showed that the corrosion of SS was accelerated in the presence of V. natriegens based on the decrease in the resistance of the charge transfer resistance (R_ct) obtained from EIS and the increase in corrosion current densities obtained from potentiodynamic polarization curves.     

Pitting corrosion resistance of laser surface alloyed 304 stainless steel

Abstract

The pitting corrosion resistance of AISI 304 stainless steel (SS), which was laser melted in both nitrogen and argon atmosphere, was studied using the potentiodynamic anodic polarisation method. An attempt was made to introduce nitrogen onto the surface layers by melting in nitrogen atmosphere and argon atmosphere using a continuous wave CO₂ laser as the heat source at a power output of 3·06 kW at the laser head. The pitting corrosion resistance was determined by measuring the critical pitting potential during anodic polarisation. Secondary ion mass spectrometry (SIMS) was carried out on the laser melted surface to characterise the chemical composition. It was found that the pitting corrosion resistance of 304 SS was improved when laser surface melting was carried out in argon and was improved further when melting was carried out in nitrogen atmosphere. However, the improvement in pitting corrosion resistance in laser melted material was observed only in the reabraded condition and the pitting corrosion resistance in the as melted condition was lower than for the unmelted 304 SS. The improvement in localised corrosion behaviour was attributed to the increase of nitrogen content which was incorporated onto the surface layer during laser surface melting and this was confirmed using SIMS.

MST/1530     

Microstructure and corrosion behaviour of FeCoNiCuSnx high entropy alloys

Abstract

The FeCoNiCuSn_x alloys with different Sn contents are prepared, the microstructure and the corrosion behaviour of the alloys are investigated. When Sn content is lower than 0.09, FeCoNiCuSn_x alloys consist of a single FCC phase. While Sn content of the alloy is 0.09, a small quantity of BCC structure is present. The FeCoNiCuSn_x alloys have a wider passive region in the NaOH solution. FeCoNiCuSn_x alloys exhibit a better corrosion resistance in NaCl solution than 304 stainless steel, the corrosion resistance of FeCoNiCuSn_0.04 alloy is best among all the alloys. The corrosion resistance of FeCoNiCuSn_x alloys in NaOH solution is lower than that of 304 stainless steel, the corrosion resistance of FeCoNiCuSn_0.03 alloy is best among all FeCoNiCuSn_x alloys.     

Corrosion behaviour of amorphous Ni–Si thin films on AISI 304L stainless steel

Abstract

Nanoscale Ni – Si thin films are widely used in commercial microelectronic devices because of their promising electrical properties as well as their chemical stability. However, their application in corrosive environment has not been frequently addressed in the literature. In this study, amorphous Ni_0.66Si_0.33, Ni_0.40Si_0.60, and Ni_0.20Si_0.80 thin films are prepared on AISI 304L stainless steel by means of ion-beam sputter (IBS) deposition and their corrosion behaviour is studied using potentiodynamic polarisation measurements. The electrochemical measurements were conducted in 0.05M HCl solution at room temperature. By means of optical interferometer, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), the surface morphology and chemical composition of the thin films were examined before and after the electrochemical measurement. The evaluated results showed that the Ni–Si thin films may exhibit improved corrosion resistance over the 304L substrate provided that Si content is high enough to facilitate the formation of a Si-rich passive film.     

Analysis of sensitization phenomenon in friction stir welded 304 stainless steel

This study evaluates the degree of sensitization (DOS) of 304 stainless steel joined by friction stir welding (FSW). Single-loop electrochemical potentiokinetic reactivation tests were performed using a 0.5 mol/L H₂SO₄ + 0.01 mol/L KSCN solution. Sensitization was promoted by exposition of the stainless steel at temperatures between 400°C and 850°C. The microstructure was characterized using optical microscopy to identify the weld zone and the base metal. The samples treated at 550°C showed the most severe intergranular corrosion. The DOS was lower in the weld zone than in the base metal after heat treatments. This reduction in the DOS for the weld zone indicates that FSW is a beneficial process in joining stainless steel.     

Evaluation of temperature effect on the corrosion process of 304 stainless steel in high temperature water with electrochemical noise

The effect of temperature on corrosion process of 304 stainless steel (SS) in high temperature water was investigated by electrochemical noise (EN), scanning electron microscope (SEM), Raman spectrum and X-ray photoelectron spectroscopy (XPS). The experimental results showed that the corrosion process could be divided into two stages (passivity and active dissolution) with the increasing temperature. At 100 °C, the oxide film was a single layer mainly consisting of Cr₂O₃. However, at 250 °C, it became a double layer with an inner layer of Cr–Fe spinel compound and an out precipitated layer. The related growth mechanisms of the oxide film were also discussed.     

Influence of the microstructure on the corrosion resistance of plasma‐nitrided austenitic stainless steel 304L and 316L

Austenitic stainless steels are widely used in medical and food industries because of their excellent corrosion resistance. However, they suffer from weak wear resistance due to their low hardness. To improve this, plasma nitriding processes have been successfully applied to austenitic stainless steels, thereby forming a thin and very hard diffusion layer, the so‐called S‐phase. In the present study, the austenitic stainless steels AISI 304L and AISI 316L with different microstructures and surface modifications were used to examine the influence of the steel microstructure on the plasma nitriding behavior and corrosion properties. In a first step, solution annealed steel plates were cold‐rolled with 38% deformation degree. Then, the samples were prepared with three kinds of mechanical surface treatments. The specimens were plasma nitrided for 360 min in a H₂–N₂ atmosphere at 420 °C. X‐ray diffraction measurements confirmed the presence of the S‐phase at the sample surface, austenite and body centered cubic (bcc)‐iron. The specimens were comprehensively characterized by means of optical microscopy, scanning electron microscopy, glow discharge optical emission spectroscopy, X‐ray diffraction, surface roughness and nano‐indentation measurements to provide the formulation of dependencies between microstructure and nitriding behavior. The corrosion behavior was examined by potentio‐dynamic polarization measurements in 0.05 M and 0.5 M sulfuric acid and by salt spray testing.     

Deposition of diamond-like carbon films on the inner surface of narrow stainless steel tubes

Diamond-like carbon (DLC) films were deposited on the inner surface of 304-type stainless steel tube with an inner diameter of 10 mm by DC glow discharge plasma. The influence of the deposition time, pressure and the ratios of CH₄ in CH₄/Ar gas mixture on the DLC film deposition were investigated. The images of Scanning Electron Microscopy (SEM) show that the DLC films are featureless and free of porosity. Fibre-like structure was recognized on the film surface by Atomic Force Microscopy (AFM). The film deposition rate decreases with increasing the deposition time. Relative higher deposition rate (40 nm/min) can be obtained at 20-30 Pa, higher and lower pressure will significantly decrease the deposition rate. Raman spectrum analysis shows that the films deposited in 30 min at 20-30 Pa have more sp³ content. The corrosion resistance of the films was measured by potentiodynamic polarization test. The DLC films deposited on the inner surface of the 304-type stainless steel tube significantly improve its corrosion resistance.     

Application of Self Assembled 6-aminohexanol layers for corrosion protection of 304 stainless steel surface

Grafting of 6-aminohexanol onto a 304 stainless steel substrate was performed with the assistance of polydopamine self assembly. The surface structure of the films was characterized using optical and scanning electron microscopy and X-ray energy dispersive spectroscopy confirmed the establishment of organic films. The corrosion resistance properties were characterized using the electrochemical impedance spectroscopy and potentiodynamic polarization curve measurements. Enhanced corrosion resistance performance was mainly ascribed to the compact film structure and the blocking characteristics against electron transfer of the modified 304 stainless steel substrate.     

An investigation of the electrolytic solution effects on stainless steel electrode for dye-sensitized solar cells

In the field of dye-sensitized solar cells (DSSCs) the tendency is nowadays to replace the classical conducting glass by a metallic substrate (i.e. stainless steel 304L) as the counter-electrode. However the electrolytic solution (iodide/triiodide in an organic solvent) may be aggressive for stainless steel. An electrolytic solution optimization should improve the long-term stability and increase the cell performance. For this purpose, the electrolytic solution was submitted to different treatments (i.e. deoxygenation, dehydration and dehydration–deoxygenation) in order to increase the corrosion resistance of stainless steel (304L) electrode by eliminating the dissolved oxygen and water.     

The corrosion behaviours of polyaniline coated stainless steel in acidic solutions

Polyaniline (PANI) coating on stainless steel (SS) using oxalic acid as supporting electrolyte was obtained by using cyclic voltammetry technique. The corrosion performances of these PANI coated electrodes (SS/PANI) were determined in 0.05 M sulphuric acid and in 0.1 M hydrochloric acid solutions with electrochemical impedance spectroscopy and anodic polarization curves. The results clearly showed that SS/PANI immersed in sulphuric acid appeared to have better protective effect on the corrosion of SS than that of hydrochloric acid. The PANI coating was found to be stable and protective for extended immersion period in 0.05 M H₂SO₄.     

Dissolution and repair of passive film on Cu-bearing 304L stainless steels immersed in H2SO4 solution

The antibacterial Cu-bearing 304L stainless steel is a new kind of structural and functional integrated metal material. In this work, evolution behavior of passive film of different heat treated Cu-bearing 304L stainless steel immersed in 0.5?M H₂SO₄ solution was investigated by using electrochemical measurements, atomic force microscopy (AFM) observation and X-ray photoelectron spectroscopy (XPS) analysis. The results show that the solution and aging treated samples have the similar polarization behaviors. The passive film impedance experiences an initial decrease within 7?days followed by a subsequent increase, while the defect density of passive film presents the opposite trend. Meanwhile, the evolution of surface morphology and the estimated thickness of the passive film confirm that it experiences initial dissolution and follow-up repair. Furthermore, the Cr³⁺ content in passive film undergoes sequential reduction to increase, however the variation tendency of Cu²⁺ content is just opposite, indicating that the content variation of Cr and Cu in passive film reflects the competitive process of film dissolution and repair. In addition, compared with solution treated samples, aged samples have a bigger i_corr value and the rougher passive film. This indicates that the passive film of solution treated steel is more compact and stable.     

Corrosion behaviour of single (Ti) and duplex (Ti–TiO2) coating on 304L stainless steel in nitric acid medium

Sputter deposited single titanium (Ti) layer, and duplex Ti–TiO₂ coating on austenitic type 304L stainless steel (SS) was prepared, and the corrosion performance was evaluated in nitric acid medium using surface morphological and electrochemical techniques. Morphological analysis using atomic force microscope of the duplex Ti–TiO₂ coated surface showed minimization of structural heterogeneities as compared to single Ti layer coating. The electrochemical corrosion results revealed that, titanium coated 304L SS showed moderate to marginal improvement in corrosion resistance in 1 M, and 8 M nitric acid, respectively. Duplex Ti–TiO₂ coated 304L SS specimens showed improved corrosion resistance as compared to Ti coating from dilute (1 M) to concentrated medium (8 M). The percentage of protection efficiency for base material increases significantly for duplex Ti–TiO₂ coating as compared to single Ti layer coating. The oxidizing ability of nitric acid on both the coatings as well as factors responsible for improvement in protection efficiency are discussed and highlighted in this paper.