Investigation of the deterioration of passive films in H_2S-containing solutions

The effect of H_2S on the corrosion behavior of 316 L stainless steel was investigated using electrochemical methods by changing the gas condition from CO_2 to H_2S and then back to CO_2. The presence of H_2S showed an acceleration effect on the corrosion of 316 L stainless steel in comparison with CO_2. The acceleration effect remained even after the complete removal of H_2S by CO_2, indicating that the passive film was irreversibly damaged. X-ray photoelectron spectroscopy(XPS) analysis indicated that the passive film was composed of Cr_2O_3, Fe_2O_3, and FeS_2 after being immersed in H_2S-containing solutions. The semiconducting property of the passive film was then investigated by using the Mott–Schottky approach. The presence of sulfides resulted in higher acceptor and donor densities and thus was responsible for the deterioration of passive films.

Influence of chromium on the initial corrosion behavior of low alloy steels in the CO_2–O_2–H_2S–SO_2 wet–dry corrosion environment of cargo oil tankers

The influence of Cr on the initial corrosion behavior of low-alloy steels exposed to a CO2–O2–H2S–SO2 wet–dry corrosion environment was investigated using weight-loss measurements, scanning electron microscopy, N2 adsorption tests, X-ray diffraction analysis, and electrochemical impedance spectroscopy. The results show that the corrosion rate increases with increasing Cr content in samples subjected to corrosion for 21 d. However, the rust grain size decreases, its specific surface area increases, and it becomes more compact and denser with increasing Cr content, which indicates the enhanced protectivity of the rust. The results of charge transfer resistance(Rct) calculations indicate that higher Cr contents can accelerate the corrosion during the first 7 d and promote the formation of the enhanced protective inner rust after 14 d; the formed protective inner rust is responsible for the greater corrosion resistance during long-term exposure.

Effect of H_2S concentration on the corrosion behavior of pipeline steel under the coexistence of H_2S and CO_2

The effect of H2S concentration on H2S/CO2 corrosion of API-X60 steel was studied by scanning electron microscopy, a weight-loss method, potentiodynamic polarization tests, and the electrochemical impedance spectroscopy technique. It is found that the corrosion process of the steel in an environment where H2S and CO2 coexist at different H2S concentrations is related to the morphological structure and stability of the corrosion product film. With the addition of a small amount of H2S, the size of the anode reaction region is decreased due to constant adsorption and separation of more FeS sediment or more FeHS+ ions on the surface of the steel. Meanwhile, the double-layer capacitance is diminished with increasing anion adsorption capacity. Therefore, the corrosion process is inhibited. The general corrosion rate of the steel rapidly decreases after the addition of a small amount of H2S under the coexistence of H2S and CO2. With a further increase in H2S concentration, certain parts of the corrosion product film become loose and even fall off. Thus, the protection provided by the corrosion product film worsens, and the corrosion rate tends to increase.

Electrochemical impedance spectroscopy study on the corrosion of the weld zone of 3Cr steel welded joints in CO_2 environments

The welded joints of 3Cr pipeline steel were fabricated with commercial welding wire using the gas tungsten arc welding(GTAW) technique. Potentiodynamic polarization curves, linear polarization resistance(LPR), electrochemical impedance spectroscopy(EIS), scanning electron microscopy(SEM), and energy-dispersive spectrometry(EDS) were used to investigate the corrosion resistance and the growth of a corrosion film on the weld zone(WZ). The changes in electrochemical characteristics of the film were obtained through fitting of the EIS data. The results showed that the average corrosion rate of the WZ in CO2 environments first increased, then fluctuated, and finally decreased gradually. The formation of the film on the WZ was divided into three stages: dynamic adsorption, incomplete-coverage layer formation, and integral layer formation.

Effect of welding process on the microstructure and properties of dissimilar weld joints between low alloy steel and duplex stainless steel

To obtain high-quality dissimilar weld joints, the processes of metal inert gas (MIG) welding and tungsten inert gas (TIG) welding for duplex stainless steel (DSS) and low alloy steel were compared in this paper. The microstructure and corrosion morphology of dissimilar weld joints were observed by scanning electron microscopy (SEM); the chemical compositions in different zones were detected by en-ergy-dispersive spectroscopy (EDS); the mechanical properties were measured by microhardness test, tensile test, and impact test; the corro-sion behavior was evaluated by polarization curves. Obvious concentration gradients of Ni and Cr exist between the fusion boundary and the type II boundary, where the hardness is much higher. The impact toughness of weld metal by MIG welding is higher than that by TIG weld-ing. The corrosion current density of TIG weld metal is higher than that of MIG weld metal in a 3.5wt% NaCl solution. Galvanic corrosion happens between low alloy steel and weld metal, revealing the weakness of low alloy steel in industrial service. The quality of joints pro-duced by MIG welding is better than that by TIG welding in mechanical performance and corrosion resistance. MIG welding with the filler metal ER2009 is the suitable welding process for dissimilar metals jointing between UNS S31803 duplex stainless steel and low alloy steel in practical application.

Cathodic reaction mechanisms in CO2 corrosion of low-Cr steels

The cathodic reaction mechanisms in CO2 corrosion of low-Cr steels were investigated by potentiodynamic polarization and galvanostatic measurements.Distinct but different dominant cathodic reactions were observed at different p H levels.At the higher p H level(p H>~5),H2 CO3 reduction was the dominant cathodic reaction.The reaction was under activation control.At the lower pH level(pH<~3.5),H+reduction became the dominant one and the reaction was under diffusion control.In the intermediate area,there was a transition region leading from one cathodic reaction to another.The measured electrochemical impedance spectrum corresponded to the proposed cathodic reaction mechanisms.

Passivity breakdown of 13Cr stainless steel under high chloride and CO_2 environment

Herein, the effect of high chloride ion(Cl^-) concentration on the corrosion behavior and passive film breakdown of 13Cr martensitic stainless steel under CO_2 environment was demonstrated. The Cl^- concentration was varied from 30 to 150 g/L and cyclic potentiodynamic polarization was conducted to investigate the influence of the Cl^- concentration on the corrosion potential(E_(corr)), passive breakdown potential(E_(pit)), and repassivation potential(E_(rep)). The results of the polarization curves revealed that 13Cr stainless steel is susceptible to pitting under high Cl^- concentration. The passive breakdown potential and repassivation potential decreased with the increase of Cl-concentration. The semiconducting behavior of the passive film was investigated by Mott-Schottky analysis and the point defect model(PDM). It was observed that the iron cation vacancies and oxygen vacancies were continuously generated by autocatalytic reactions and the higher Cl^- concentration resulted in higher vacancies in the passive film. Once the excess vacancies condensed at the metal/film interface, the passive film became locally detached from the metal, which led to the breakdown of the passive film.

Environmental boundary and formation mechanism of different types of H2S corrosion products on pipeline steel

To establish an adequate thermodynamic model for the mechanism of formation of hydrogen sulfide(H_2S) corrosion products,theoretical and experimental studies were combined in this work. The corrosion products of API X60 pipeline steel formed under different H_2S corrosion conditions were analyzed by scanning electron microscopy,energy-dispersive X-ray spectroscopy,and X-ray diffraction. A thermodynamic model was developed to clarify the environmental boundaries for the formation and transformation of different products. Presumably,a dividing line with a negative slope existed between mackinawite and pyrrhotite. Using experimental data presented in this study combined with previously published results,we validated the model to predict the formation of mackinawite and pyrrhotite on the basis of the laws of thermodynamics. The established relationship is expected to support the investigation of the H_2S corrosion mechanism in the oil and gas industry.

Corrosion behavior of low alloy steels in a wet–dry acid humid environment

The corrosion behavior of corrosion resistant steel(CRS) in a simulated wet–dry acid humid environment was investigated and compared with carbon steel(CS) using corrosion loss, polarization curves, X-ray diffraction(XRD), scanning electron microscopy(SEM), electron probe micro-analysis(EPMA), N_2 adsorption, and X-ray photoelectron spectroscopy(XPS). The results show that the corrosion kinetics of both steels were closely related to the composition and compactness of the rust, and the electrochemical properties of rusted steel. Small amounts of Cu, Cr, and Ni in CRS increased the amount of amorphous phases and decreased the content of γ-Fe OOH in the rust, resulting in higher compactness and electrochemical stability of the CRS rust. The elements Cu, Cr, and Ni were uniformly distributed in the CRS rust and formed CuFeO_2, Cu_2O, CrOOH, NiFe_2O_4, and Ni_2O_3, which enhanced the corrosion resistance of CRS in the wet–dry acid humid environment.

Comparison Study on the Semiconductive and Dissolution Behaviour of 316L and Alloy 625 in Hydrochloric Acid Solution

The corrosion behaviour of 316L and Alloy 625 was investigated using cyclic polarization,electrochemical impedance spectroscopy,X-ray photoelectron spectroscopy,Auger electron spectroscopy and induced coupled plasma-optical emis sion spectrometer.The results indicated that Alloy 625 showed better corrosion resistance than 316L and the prolonging immersion time could enhance corrosion resistance of the two alloys.The passive film formed on the surface of 316L exhibited an electronic structure of p-p heterojunction,with Fe3O4 and Cr2O3 enriched in the outer and inner layers,respectively.However,Alloy 625 presented the electronic structure of n-p heterojunction dominated by the outer Fe2O3/NiFe2O4 and inner Cr2O3.This resulted in the opposite semiconductive properties of the passive films formed on the two materials.In the acid solutions,Fe and Mo suffered from selective dissolution while Cr and Ni were relatively stable.The corrosion rates were mainly dominated by the dissolution of iron.Alloy 625 presented better corrosion resistance than 316L due to the obviously lower content of Fe and the higher content of Cr and Ni in the passive film.The continuously selective dissolution of iron resulted in the increase in Cr/Fe ratio in the passive film,which was responsible for the enhancement in corrosion resistance.

Effect of p H on the Electrochemical Behaviour and Passive FilmComposition of 316L Stainless Steel

The effect of pH on the electrochemical behaviour and passive film composition of 316 L stainless steel in alkaline solutions was studied using electrochemical measurements and a surface analysis method. The critical pH of 12.5 was found for the conversion from pitting corrosion to the oxygen evolution reaction(OER). OER was kinetically faster than pitting corrosion when both reactions could occur, and OER could postpone pitting corrosion. This resulted in pitting being initiated during the reversing scan in the cyclic polarization at the critical pH. According to the X-ray photoelectron spectroscopy analysis, the content of Cr and Mo decreased with pH, while Fe content increased. This induced the degradation of the passive film, which resulted in the higher passive current densities under more alkaline conditions. The selective dissolution of Mo at high p H was found, which demonstrated that the addition of Mo in austenitic stainless steels might not be beneficial to the corrosion resistance of 316L in strong alkaline solutions.

Effect of Small Content of Chromium on Wet–Dry Acid Corrosion Behavior of Low Alloy Steel

Effect of small content of chromium(Cr) on wet–dry acid corrosion behavior of low alloy steels has been investigated.The results show that the corrosion resistance of the steels increased with increasing Cr content from 0.10 to0.50 wt%.Higher content of Cr promotes initial corrosion and accelerates the formation of dense and protective rust in long-term corrosion.The enhanced protectiveness of the rust is closely related to its composition.High content of Cr increases the content of amorphous phases and decreases the content of c-Fe OOH in the rust,resulting in the high compactness of the rust and low electrochemical activity in acid condition.Cr dopes in rust and depresses the transformation from amorphous phases to a-Fe OOH,as well as the growth process of Fe OOH particles,which is responsible for the enhanced compactness of rust in long-term corrosion.

Effects of W and Mo Additions on Wet-dry Acid Corrosion Behavior of Low-Alloy Steels Under Different O_2 Concentrations

Effects of W and Mo additions on wet-dry acid corrosion behavior of low-alloy steels under different O_2 concentrations were investigated. The results showed that W and Mo-containing steels presented excellent wet-dry corrosion resistance under O_2 concentrations of both 1 and 5%. The roles of W and Mo played in increasing corrosion resistance of the steels were different. W could improve the thermodynamic stability of the steel substrate, while Mo could promote the formation of protective rust. Interaction between W, Mo and O_2 concentration greatly influenced wet-dry acid corrosion of low-alloy steels. W addition was more effective for depressing charge transfer process at the rust/substrate interface and presented higher enhanced effect on increasing corrosion resistance than Mo under O_2 concentration of 1%.Mo was more effective on increasing rust compactness and showed higher enhanced effect on increasing corrosion resistance than W under O_2 concentration of 5%.