Investigation on Pitting Corrosion of Nickel-Free and Manganese-Alloyed High-Nitrogen Stainless Steels

Pitting corrosion behavior of three kinds of nickel-free and manganese-alloyed high-nitrogen (N) stainless steels (HNSSs) was investigated using electrochemical and immersion testing methods. Type 316L stainless steel (316L SS) was also included for comparison purpose. Both solution-annealed and sensitization-treated steels were examined. The solution-annealed HNSSs showed much better resistance to pitting corrosion than the 316L SS in both neutral and acidic sodium chloride solutions. The addition of molybdenum (Mo) had no further improvement on the pitting corrosion resistance of the solution-annealed HNSSs. The sensitization treatment resulted in significant degradation of the pitting corrosion resistance of the HNSSs, but not for the 316L SS. Typical large size of corrosion pits was observed on the surface of solution-annealed 316L SS, while small and dispersed corrosion pits on the surfaces of solution-annealed HNSSs. The sensitization-treated HNSSs suffered very severe pitting corrosion, accompanying the intergranular attack. The addition of Mo significantly improved the resistance of the sensitization-treated HNSSs to pitting corrosion, particularly in acidic solution. The good resistance of the solution-annealed HNSSs to pitting corrosion could be attributed to the passive film contributed by N, Cr, and Mo. The sensitization treatment degraded the passive film by decreasing anti-corrosion elements and Cr-bearing oxides in the passive film.     

Monitoring localised corrosion in inhibited solutions using wire beam electrode–noise signatures method

Abstract

The objective of this work is to determine the nature of localised corrosion in inhibited solutions by establishing possible relationships between characteristic features in electrochemical noise and corrosion processes using an electrochemically integrated multielectrode system, namely the wire beam electrode (WBE) in combination with noise signatures method. Experiments have been carried out to simultaneously measure electrode potential noise and WBE current distribution maps from stainless steel (SS316L) WBE exposed to inhibited solutions containing 6%FeCl₃ solution with inorganic inhibitors including 2 wt-% sodium chromate (Na₂CrO₄), cerium chloride (CeCl₃) and lanthanum chloride (LaCl₃). Characteristic electrochemical noise signatures were found to correlate with characteristic changes in WBE current distribution maps that show corrosion rates distributions and the degree of localised corrosion. A new concept namely localisation parameter (LP) has been proposed to identify the degree of inhibition. Na₂CrO₄ effectively inhibited the pitting corrosion process and the LP successively decreased through out the corrosion process. With the presence of CeCl₃ and LaCl₃, pits on stainless steel in 6%FeCl₃ solution were not repassivated and an increase in the LP was observed for both inhibitors. The results suggest that the WBE method could be used in combination with the noise signatures as a sensitive technique for monitoring inhibiting effect on localised corrosion.     

热电厂汽轮机叶片断裂原因分析

    对某石化公司热电厂8号汽轮机的断裂叶片进行了宏观形貌、化学成分、金相组织以及扫描电镜形貌和元素成分能谱分析.结果表明,该叶片的断裂属于腐蚀疲劳失效;叶片上的点蚀坑是裂纹源;引起叶片发生点腐蚀的原因是蒸汽中存在的氯、硫等介质.     

Mikrobielle Werkstoffzerstörung – Simulation,Schadensfälle und Gegenmaßnahmen für metallische Werkstoffe: Manganoxidierende Bakterien und Lochkorrosion an Turbinenteilen aus CrNi-Stahl in einem Laufkraftwerk

Microbial deterioration of materials – simulation, case histories and countermeasures for metallic materials: Manganese oxidizing bacteria and pitting of turbine components made of CrNi steel in a hydroelectric power plant In a hydroelectric power plant pitting corrosion of the turbine runner blades (material G-X 5 CrNi 13 4) and the discharge ring (X 3 CrNi 13 4) ocurred at chloride levels of 170 mg/l maximum. Both, potentiostatic stepwise experiments and immersion tests gave no indication for susceptibility to pitting or crevice corrosion of this material in such water. Analysis of calcareous deposits found on the metal surface revealed high amounts of manganese dioxide. It is shown experimentally, that the CrNi-steel can undergo chloride induced pitting corrosion if polarized by manganese dioxide. Manganese oxidizing bacteria and possibly fungi were found to form the deposits. This case may be considered as microbiologically influenced corrosion (MIC) under aerobic conditions.     

X42输油管道泄漏分析

利用力学性能检测、无损探伤、腐蚀坑形貌观察和XRD相分析等研究手段,对X42输油管道试压泄露原因进行系统分析。分析结果表明:X42输油管道具有良好的强韧性能,各项力学性能指标满足管线标准要求;X42管道4点钟至8点钟位置管道内部腐蚀严重,存在明显的管道存蓄水腐蚀特征,并在管道内壁6点钟位置发现有多处点蚀坑;点蚀坑电镜分析和腐蚀产物分析表明,点蚀坑位置存在较高浓度的Cl-,点蚀坑形貌表现为典型的Cl-诱发小孔腐蚀特征。因此,X42管道试压泄漏是由于铺设后的管道内残留含较高浓度Cl-的积水,积水中的Cl-诱发孔蚀所导致。建议已完成铺设但未投用的油气管道,在封存前应进行充分排水和干燥处理,避免类似事故的发生。     

Pitting growth rate on Alloy 800 in chloride solutions containing thiosulphate: image analysis assessment

The growth rate of pits formed on Alloy 800 in chloride solutions containing various thiosulphate concentrations was assessed by potentiostatic polarisation, in situ corrosion image observation, and image analysis. The pitting growth rate was a function of solution chemistry: in chloride solution pits were small but numerous, in chloride?+?thiosulphate solution, the pits were large. Competitive adsorption on Alloy 800 of chloride and thiosulphate ions affected the pitting potential and therefore the pitting growth rate on the metal. The reduction of thiosulphate to elemental sulphur accelerated the pitting growth rate in chloride?+?thiosulphate solutions.     

AFM study of microbial colonization and its deleterious effect on 304 stainless steel by Pseudomonas NCIMB 2021 and Desulfovibrio desulfuricans in simulated seawater

The biofilm colonization dynamics of Pseudomonas NCIMB 2021 and Desulfovibrio desulfuricans (ATCC 27774) on 304 stainless steels (304 SS) was evaluated using atomic force microscopy (AFM) in simulated seawater-based media under aerobic and anaerobic conditions. Results showed that the biofilm formed on the coupon surface by the two strains of bacteria increased in the coverage, heterogeneity and thickness with exposure time, thus resulting in the deterioration of the steel substratum underneath the biofilm in the form of pitting corrosion. The depth of pits induced by D. desulfuricans was larger than that by Pseudomonas NCIMB 2021, which was mainly attributed to the enhanced corrosion of 304 SS coupons by the biogenic sulfide ions, as revealed by the results of X-ray photoelectron spectroscopy (XPS) and Tafel polarization curves. AFM was also used to determine cell attachment/detachment processes of the Pseudomonas and D. desulfuricans bacteria on the coupon surface by quantifying the tip-cell interaction forces. The interactive forces between the tip and the bacterial cell surface were considerably smaller than those between the tip and the cell-cell interface due to the accumulation of extra-cellular polymeric substances (EPS) for both strains. Furthermore, the adhesion forces over the Pseudomonas cells were verified to be more attractive than those of D. desulfuricans due to the former being a slime-producer.     

Effect of Heat Treatment on Pitting Corrosion of austenitic Cr-Ni-Mo steels in sodium chloride solution

The pitting corrosion resistance of Cr 17 Ni 12 Mo 2,5 type steel under potentiostatic polarization in a sodium chloride solution is adversely affected by previous annealing. Even though the reproducibility and accuracy of measurements are limited due to the statistical nature of pitting, the data obtained were systematically dependent on annealing temperature, time and surface roughness. The corrosion current, the number of pits or the mean area of pit opening and the corrosion rate within the pits were increased by previous annealing at 550 to 750 °C for 1–100 hrs. The highest corrosion rate estimated corresponded to heat treatments provoking severe sensitization to intergranular corrosion. The percentage area of corrosion pit openings and the estimated pit penetration rates were several times higher for as-machined than for polished surfaces. It can be assumed that pitting corrosion is little affected by the carbon content and that molybdenum depletion of grain-boundary zones is responsible for the reduced pitting resistance of annealed steels.     

Effects of pH and chloride concentration on pitting corrosion of AA6061 aluminum alloy

Effects of pH solution and chloride (Cl⁻) ion concentration on the corrosion behaviour of alloy AA6061 immersed in aqueous solutions of NaCl have been investigated using measurements of weight loss, potentiodynamic polarisation, linear polarisation, cyclic polarisation experiment combined with open circuit potential transient technique and optical or scanning electron microscopy.The corrosion behaviour of the AA6061 aluminum alloy was found to be dependant on the pH and chloride concentration [NaCl] of solution. In acidic or slightly neutral solutions, general and pitting corrosion occurred simultaneously. In contrast, exposure to alkaline solutions results in general corrosion. Experience revealed that the alloy AA6061 was susceptible to pitting corrosion in all chloride solution of concentration ranging between 0.003 wt% and 5.5 wt% NaCl and an increase in the chloride concentration slightly shifted both the pitting E_pit and corrosion E_cor potentials to more active values. In function of the conditions of treatment, the sheets of the alloy AA6061 undergo two types of localised corrosion process, leading to the formation of hemispherical and crystallographic pits.Polarisation resistance measurements in acidic (pH = 2) and alkaline chloride solutions (pH = 12) which are in good agreement with those of weight loss, show that the corrosion kinetic is minimised in slightly neutral solutions (pH = 6).     

Corrosion behaviour of stainless steel exposed to highly concentrated chloride solutions

The characteristics of pitting corrosion of Type 304L stainless steel (SS) exposed to highly concentrated chloride solutions were studied through the evaluation of the corrosion potential, the pitting potential, the structure of the passive layer and the statistics of pitting depth and density. Both as-received and weld metal samples were studied. The weld metal sample was machined from the welding zone of a butt weld of Type 304L SS. The results showed an accelerated anodic dissolution and depressed film resistance at the welding zone, but no dramatic change on pitting corrosion was observed from the statistics of pitting during the test duration up to 720?h. The pitting corrosion resistance was significantly affected by the chloride concentration and slightly affected by the temperature under the investigated conditions.     

Enhancement of Corrosion Resistance of Type 304 Stainless Steel Through a Novel Thermo-mechanical Surface Treatment

The paper describes a novel thermo-mechanical surface treatment approach, involving conventional shot blasting followed by laser surface heating, to engineer microstructural modification in type 304 austenitic stainless steel for enhancing its corrosion resistance. Thermo-mechanical surface treatment resulted in the formation of fine recrystallized grains with some strain-induced martensite on the modified surface. Surface treatment of type 304 stainless steel brought about significant improvement in its resistance against uniform as well as pitting corrosion. Electrochemical impedance spectroscopic studies showed improved polarization resistance (R _p) value for thermo-mechanically treated surface indicating formation of a more protective passive film than that formed on the untreated surface. In contrast to untreated type 304 stainless steel specimens where pits preferentially initiated at the site of Al₂O₃ inclusions, thermo-mechanically treated specimen exhibited only general dissolution with a few repassivated and shallow pits. Grain refinement and dispersion of alumina inclusions on the modified surface are considered to be the key factors responsible for improvement in uniform and pitting corrosion resistance of type 304SS.     

Pitting corrosion on 316L pipes in terephthalic acid (TA) dryer

Grade 316L is a type of austenitic stainless steel with ultra‐low carbon content and it exhibits superior corrosion resistance. However, pitting is always observed in 316L steel when it is exposed to media containing halide ions. In the present study, we found that in the presence of acetate acid (HAc) containing chloride or bromide ions, pitting occurred on the surface of the rotary steam pipes with the matrix material of 316L steel in terephthalic acid (TA) dryer. In order to identify the causes of the failure, metallographic structures and chemical compositions of the matrix material were inspected by an optical microscope (OM) and a photoelectric direct reading spectrometer. Beside these, scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) as well as ion chromatography (IC) were used to analyze the micromorphologies of the corrosion pits and the chemical compositions of the corrosion deposits within them. Analysis of the results revealed the sources of halide ions and the factors accelerating the corrosion rate. Beside these, detailed mechanisms of pitting were discussed and six out of all the seven theoretical morphologies of pitting features were obtained in practice.     

Die Lochkorrosionsanfälligkeit des Vergütungsstahles X20Cr13 in Natriumchloridlösungen

Pitting corrosion susceptibility of the heat treatable steel X20Cr13 in sodium chloride solutions For blades in steam trubines it is common to use the heat-treatable steels with 13% Cr (X20Cr13). Cracking of blades in the region of the turbine, where the steam starts to get wet, have often been referred to be caused by corrosion fatigue. The fatigue cracks sometimes start at inclusions in the material, but more often at pits caused by pitting corrosion. Pitting is brought about by chloride containing blade deposits. To examine the pitting behaviour of the steel in NaCl-solutions we measured the mixed-potential, the potentiostatic piting potential, the mass-loss and the pits per area as depending on temperature (20–80°C), pH (5–7–9), oxygen content (20 μg/kg up to saturation with oxygen) and chloride content (8×10^?5 mole/l up to saturation with NaCl 5,4 mole/l). The results show that steel X20Cr13 suffers pitting corrosion because of it's low Cr content in all technical possible NaCl solutions down to a Cl content of 10^?5 mole/l at the mixed potential.     

Untersuchungen über die Lochfraßkorrosion des passiven Eisens in chlorionenhaltiger Schwefelsäure

Investigation into pitting corrosion of passive iron in sulphuric acid containing chloride ions Pitting corrosion of metallic materials is generally connected with presence of a surface layer giving rise to a local differentiation of the electrochemical behaviour of the metal surface. The pitting corrosion by halogen ions on passive metals is investigated using passive iron in chloride ion-containing sulphuric acid as the model system. Quantitative data are presented concerning the mechanism and kinetics of the individual processes giving rise to pitting corrosion in a chloride ion concentration range covering three powers of ten, and in the whole potential range of iron passivity, from the Flade potential to the transpassive breakthrough potential. Pit formation normally follows a linear kinetic law, the rate depending in particular from the chloride ion concentration and from the thickness of the passive layer. The growth of pit diameters follows a linear kinetic law, too; the dissolution current density in the pits depends from the chloride ion concentration. Comparative investigations carried out on active iron, and potential distribution as measured in the pits show that the metal is active in the pits, too. The heterogeneous mixed electrode condition — active pit/passive metal surface — is stabilised by resistance polarisation. The investigations so far do not permit any statement concerning the specific effect of the chloride ions.     

Preconditioning of AISI 304 stainless steel surfaces in the presence of flavins—Part II: Effect on biofilm formation and microbially influenced corrosion processes

Biofilm formation and microbially influenced corrosion of the iron-reducing microorganism Shewanella putrefaciens were investigated on stainless steel surfaces preconditioned in the absence and presence of flavin molecules by means of XANES (X-ray absorption near-edge structure) analysis and electrochemical methods. The results indicate that biofilm formation was promoted on samples preconditioned in electrolytes containing minute amounts of flavins. On the basis of the XANES results, the corrosion processes are controlled by the iron-rich outer layer of the passive film. Biofilm formation resulted in a cathodic shift of the open circuit potential and a protective effect in terms of pitting corrosion. The samples preconditioned in the absence of flavins have shown delayed pitting and the samples preconditioned in the presence of flavins did not show any pitting in a window of −0.3- to +0.0-V overpotential in the bacterial medium. The results indicate that changes in the passive film chemistry induced by the presence of minute amounts of flavins during a mild anodic polarization can change the susceptibility of stainless steel surfaces to microbially influenced corrosion.     

Structure–property quantification of corrosion pitting under immersion and salt-spray environments on an extruded AZ61 magnesium alloy

Extruded AZ61 magnesium coupons were exposed to immersion and cyclical salt spray environments over 60 h in order to characterize their corrosion rates. The characteristics of general corrosion, pitting corrosion, and intergranular corrosion were quantified at various intervals. General corrosion was more prevalent on the immersion surface. In addition, more pits formed on the immersion surface due the continuous exposure to water and chloride ions. However, the pits on the salt spray surface showed larger surface areas, larger volumes, and covered more area on the micrographs as compared to the pits on the immersion surface, due to the dried pit debris that trapped chloride ions within the pits.     

Localised corrosion of highly alloyed stainless steels in an ammonium chloride and diethylamine chloride aqueous solution

This paper studies the pitting corrosion of highly alloyed stainless steels (SS) immersed in an ammonium chloride and diethylamine chloride aqueous solution at temperatures of 25, 40, 60 and 80°C. Four materials were tested: UNS S 31726 SS, UNS S 31254 SS, UNS S 32550 SS and titanium, for comparative purposes. Gravimetric, after immersion up to 103 days, polarisation curves, impedance, SEM, EDX and optical microscopy were the techniques used. UNS S 31726 SS shows the lowest corrosion resistance. UNS S 31254 and UNS S 32550 SSs show similar behaviour. Titanium presents impedance data three orders higher than the other SS materials. The SS materials present a pseudoinductive behaviour on impedance data, associated with an adsorption process of the amine compound which decreases as the temperature increases.     

Mechanism of Pitting Corrosion of Copper in Supply Waters

Abstract

Detailed examination of a large number of copper water tanks and pipes showing pitting corrosion (taken from certaind is districts to which pitting is confined) revealed features that could not be reconciled with the conventiona1 explanation based on the presence of large cathodic areas surrounding small anodic corrosion Sites. A new theory of pitting corrosion of copper is proposed which explains the features observed Pitting arises when a pocket of cuprous chloride forms beneath a porous electrically conducting membrane (usually cuprous oxide). The anodic and cathodic processes occur on the inner andouter surfaces of the memberane. Dissolution of copper occurs by reaction with the anodic product beneath the membrane and deposition of calcium carbonate occurs by reaction of hardness salts in the water with the cathodic product above the membrane.

Pockets of cuprous chloride capable of developing into corrosion pits can only form if the potential of the copper rises above 90mV EH during the period of film formation. Control of the potential below this value by coupling to a small sacrificial aluminium anode has been shown to prevent formation of pits in copper tanks and cylinders in service.     

The protection potential of aluminium

The corrosion behaviour of aluminium is investigated in chloride solutions at potentials below the critical pitting potential. Potentiodynamic and steady-state polarization data are presented and analyzed. Pit propagation is shown to continue as the applied potential drops below this critical value. The dissolution front shifts from macroscopic pits to more occluded, microscopic sites, which are known to branch out from the main pits in the form of crystallographic pits and tunnels. The protection potential is shown to be ca. 100 mV more active than the critical pitting potential and appears to be independent of the extent of pit propagation within the limits of experimental error. Polarization data are interpreted in terms of metal dissolution kinetics and diffusion. Results are compared to the available data for steel.     

Corrosion of aluminium,stainless steels and AISI 680 nickel alloy in nitrogen‐based fuels

Nitrogen‐based compounds can potentially be used as alternative non‐carbon or low‐carbon fuels. Nevertheless, the corrosion of construction materials at high temperatures and pressures in the presence of such fuel has not been reported yet. This work is focused on the corrosion of AISI Al 6061, 1005 carbon steel (CS), 304, 316L, 310 austenitic stainless steels (SS) and 680 nickel alloy in highly concentrated water solution of ammonium nitrate and urea (ANU). The corrosion at 50 °C and ambient pressure and at 350 °C and 20 bar was investigated to simulate storage and working conditions. Sodium chloride was added to the fuel (0–5 wt%) to simulate industrial fertilizers and accelerated corrosion environment. Heavy corrosion of CS was observed in ANU solution at 50 °C, while Al 6061, 304 and 316L SS showed high resistance both to uniform and pitting corrosion in ANU containing 1% of sodium chloride. Addition of 5% sodium chloride caused pitting of Al 6061 but had no influence on the corrosion of SS. Tests in ANU at 350 °C and 20 bar showed pitting on SS 304 and 316L and 680 nickel alloy. The highest corrosion resistance was found for SS 310 due to formation of stable oxide film on its surface.