Influence of chemical composition on the pitting corrosion resistance of non-standard low-Ni high-Mn-N duplex stainless steels

The pitting corrosion resistance of a new family of duplex stainless steels has been evaluated. These non-standard duplex stainless steels are characterised by low Ni content and high N and Mn levels. Potentiodynamic polarisation scans in NaCl solution have been carried out to determine pitting potentials. A crevice-free cell has been used to perform the electrochemical tests.An exponential equation is obtained in the regression analysis between the pitting potential and chemical composition which allows an estimate of the pitting resistance of these new duplex stainless steels.     

Stainless steel reinforcing bars – reason for their high pitting corrosion resistance

In harsh chloride bearing environments stainless steel reinforcing bars offer excellent corrosion resistance and very long service life for concrete structures, but the high costs limit a more widespread use. Manganese bearing nickel‐free stainless steels could be a cost‐effective alternative. Whereas the corrosion behavior of stainless steels in alkaline solutions, mortar and concrete is quite well established, only little information on the reasons for the high pitting resistance are available. This work reports the results of pitting potential measurements in solutions simulating alkaline and carbonated concrete on black steel, stainless steel DIN 1.4301, duplex steel DIN 1.4462, and nickel‐free stainless steel DIN 1.4456. Duplex and nickel‐free stainless steels are fully resistant even in 4 M NaCl solutions with pH 13 or higher, the lower grade DIN 1.4301 shows a wide scatter between fully resistant and pitting potentials as low as +0.2 V SCE. In carbonated solutions with pH 9 the nickel‐free DIN 1.4456 shows pitting corrosion at chloride concentrations ≥3 M. This ranking of the pitting resistance can be rationalized based on XPS surface analysis results: both the increase of the Cr(III)oxy‐hydroxide and Mo(VI) contents in the passive film and a marked nickel enrichment beneath the film improve the pitting resistance. The duplex DIN 1.4462 shows the highest pitting resistance, which can be attributed to the very high Cr(III)oxy‐hydroxide, to a medium Mo(VI) content in the film and to a nickel enrichment beneath the film. Upon time, the protective properties of the surface film improve. This beneficial effect of ageing (transformation of the passive film to a less Fe²⁺ containing, more hydrated film) will lead to higher pitting potentials. It can be concluded that short‐term solution experiments give conservative results in terms of resistance to chloride‐induced corrosion in reinforced concrete structures.     

Effect of alloying elements on the contact resistance and the passivation behaviour of stainless steels

The effects of alloying elements (Cr, Mo) on the passivation and the transpassive transition behaviour of various commercial stainless steels, which are candidate materials for the bi-polar plates in polymer electrolyte membrane fuel cell, were investigated via a contact electric resistance (CER) technique with graphite counter part. The contact resistance, too high for a semi-conductor film with high donor density, is not the inherent ohmic resistance of the passive film. The CER potentials decrease linearly with the pitting resistance equivalent number (PREN). The passive films of stainless steels with high PREN are more readily removed compared to those with low PREN in terms of the charge necessary to remove the passive films. The change in transpassive transition behaviour of the stainless steels from that of iron to that of chromium went on steeply with an increase in the PREN.     

Study of the correlation between pitting corrosion and the component ratio of the dual phase in duplex stainless steel welds

Three duplex stainless steel weldments were produced by changing the chromium element to study the correlation between the pitting corrosion characteristics and the component ratio of the dual phase. The pit morphologies showed that metastable pits were generated at a lower pitting resistance equivalent number (PREN) phase. The secondary austenite phases seemed to serve as a path for the corrosive environment regardless of the ferrite number (FN). There is some discrepancy between the measured values (pitting potential (E_p) through polarization test) and expected values (sequence ranked by PREN of weaker phase) in 1 mol l⁻¹ NaCl solution at 60 °C.     

Long-term corrosion behaviour of stainless reinforcing steel in mortar exposed to chloride environment

Long-term corrosion behaviour of six stainless reinforcing steels embedded in mortar and exposed to chloride media was monitored by electrochemical impedance spectroscopy at the open circuit potential during the period of 2 years. Corrosion behaviour of studied steels was divided into two phases characterized by different interfacial behaviour: (i) passive phase and (ii) pitting propagation phase. After 2 years, duplex steel 1.4362 showed very good corrosion performance similar to austenitic steel 1.4401. Steel types with low Ni content but with high N and Mn content, 1.4597 and 1.4162, showed lower corrosion resistance compared to austenitic steel 1.4301.     

Corrosion resistance of low‐nickel duplex stainless steel rebars

The use of stainless steel bars in reinforced concrete structures may be an effective method to prevent corrosion in aggressive environments where high amounts of chlorides may penetrate in the concrete cover. For an estimation of the service life of structures where stainless steel bars are used, the chloride threshold for these rebars should be defined, and the influence of chemical composition and metallurgical factors that may affect the corrosion resistance (strengthening, welding, etc.) should be assessed. To reduce the cost of stainless steel reinforcement, duplex stainless steels with low nickel content have been recently proposed as an alternative to traditional austenitic steels, even though, few results are available regarding their corrosion performance in chloride contaminated concrete. This paper deals with the corrosion resistance of low‐nickel duplex stainless steel rebars (1.4362 and 1.4162) as a function of the chloride content. Comparison is made with traditional austenitic steels. An attempt to define a chloride threshold for the different stainless steels is made by comparing the results of several test procedures both in concrete and in solution.     

Die Oberflächenbehandlung von Schweißverbindungen hochkorrosionsbeständiger 6% Mo-Stähle und Nickel-Basis-Legierungen

Surface treatments of high alloy 6 Mo stainless steel and nickel alloy weldments High alloy stainless steels (6% Mo) and a high nickel alloy (alloy 625) weldment have been tested in order to answer the question whether post-treatment of the weldment has an effect on the corrosion resistance, especially on pitting corrosion. Therefore, the critical pitting temperature of weldments was tested in acidic chloride solution (standard tests). As a result grinding with rough emery paper as well as sand blasting lowers the localized corrosion resistance in the weldment area, while pickling has a positive effect, especially after blasting. Pickling can be done either by a solution of nitric + hydrofluoric acid or by a commercial pickling paste. In any event pickling is recommended as a final surface treatment for high alloy stainless steels and nickel alloys, especially in case of prevailing highly corrosive conditions such as pitting and crevice corrosion.     

Korrosionsverhalten hochchromhaltiger,ferritischer, chemisch beständiger Stähle

Corrosion behaviour of high chromium ferritic stainless steels Ferritic steels developed for seawater desalination and containing 20 to 28% chromium, up to 5% Mo and additions of nickel and copper have been tested with respect to their corrosion behaviour, in particular in chloride containing media. The materials in the sensibilized state were tested for inter-crystalline corrosion susceptibility in the Strauß-, Streicher-, nitric acid hydrofluoric acid- and Huey-Tests. No intercrystalline corrosion was encountered in the case of the steels with 28% Cr and 2% Mo. The resistance to pitting was assessed on the basis of rupture potentials determined by potentiokinetic tests. The resistance of the steels with 20% Cr and 5% Mo or 28% Cr and 2% Mo is superior to that of the molybdenum containing austenitic types. Addition of nickel yields a significant increase in crevice corrosion resistance; the same applies to resistance in sulfuric acid. In boiling seawater all the materials tested are resistant to stress corrosion cracking. No sign of any type of corrosion was found on nickel containing steels after about 6000 hours exposure to boiling 50% seawater brine even under salt deposits.     

Selektive Korrosion von Duplexstahl. Teil 2: Lokale Korrosionserscheinungen an Duplexstahl X2CrNiMoN22‐5‐3 unter Einwirkung von Chloriden und mechanisches Verhalten in Abhängigkeit vom Gefügezustand

Selective corrosion of duplex stainless steel. Part 2: Localized corrosion manifestations under exposure of chlorides on duplex stainless steel X2CrNiMoN22‐5‐3 and mechanical behavior in dependence of the microstructure In completion to part 1 of this paper this part deals with interrelations between localized corrosion manifestations, mechanical properties and the microstructure of duplex stainless steel X2CrNiMoN22‐5‐3. The pit formation on duplex stainless steels is substantially determined by the distribution of the alloying elements within single phases and by defects in the oxide layer. The positive properties of molybdenum become ineffective at thicker oxide layers due to the fact, that molybdate, which is responsible for inhibition of pitting, can not be formed. Depletion areas caused by precipitations are preferential attack places for corrosion. The influence of chlorides for duplex stainless steels in rolled and welded conditions is characterized by a logarithmic dependence.     

Influence of sigma-phase formation on the localized corrosion behavior of a duplex stainless steel

Because of their austenitic-ferritic microstructures, duplex stainless steels offer a good combination of mechanical and corrosion resistance properties. However, heat treatments can lower the mechanical strength of these stainless steels as well as render them susceptible to intergranular corrosion (IGC) and pitting corrosion. In this study, a low-carbon (0.02%) duplex stainless steel is subjected to various heat treatments at 450 to 950 °C for 30 min to 10 h. The heat-treated samples then undergo ASTM IGC and pitting corrosion tests, and the results are correlated with the microstructures obtained after each heat treatment. In the absence of Cr₂₃C₆ precipitation, σ-phase precipitates render this duplex stainless steel susceptible to IGC and pitting corrosion. Even submicroscopic σ-phase precipitates are deleterious for IGC resistance. Longer-duration heat treatments (at 750 to 850 °C) induce chromium diffusion to replenish the chromium-depleted regions around the σ-phase precipitates and improve IGC resistance; pitting resistance, however, is not fully restored. Various mechanisms of σ-phase formation are discussed to show that regions adjacent to σ-phase are depleted of chromium and molybdenum. The effect of chemical composition (pitting resistance equivalent) on the pitting resistance of various stainless steels is also noted.     

Influence of nickel additions on the corrosion behaviour of low nitrogen 22% Cr series duplex stainless steels

Four 22% Cr duplex stainless steel alloys containing varying nickel contents of approximately 5%, 7%, 9% and 13% were melted in a vacuum induction furnace, hot rolled, solution annealed and water quenched. Their corrosion behaviour was investigated in sulphuric acid and sodium chloride solutions using potentiodynamic polarization and chronoamperometric techniques. Increasing nickel contents have an appreciable influence on the observed corrosion behaviour. Polarization curves show similarities in the uniform corrosion behaviour of the alloys in the various solutions, but significant differences in their pitting resistance in chloride environments. Alloy 2209 (22% Cr - 9% Ni) generally exhibited the highest resistance to uniform corrosion, while alloy 2213 (22% Cr - 13% Ni) displayed the best pitting corrosion resistance. X-ray diffraction analysis of the surfaces of the alloys after corrosion in the different media revealed different corrosion products. Scanning electron micrographs revealed that the alloys were differently attacked by chloride ions, with different pit depths and morphologies. The corrosion behaviour exhibited by the alloys was attributed to the influence of nickel on phase modification, microstructural refinement, and the types of films formed in different environments. Uniform corrosion behaviour of the alloys was concluded to be predominantly controlled by phase composition and ratio, while pitting resistance was chiefly controlled by an alloy’s nickel contents.     

Corrosion behaviour of sensitized and unsensitized Alloy 900 (UNS 1.4462) in concentrated aqueous lithium bromide solutions at different temperatures

Duplex stainless steels can undergo microstructural changes if they are heated improperly. When that happens, duplex stainless steels are sensitized and intermetallic phases appear. The high Chromium and Molybdenum content promotes the formation of secondary phases as a consequence of the heat treatment. These secondary phases, which are rich in alloying elements, such as Cr and Mo, deplete these elements from the neighbouring phases, leading to a reduction in corrosion resistance. In order to study the influence of the secondary phases on the corrosion parameters, samples of duplex stainless steel, Alloy 900 (UNS 1.4462), have been heated in argon atmosphere at 825 °C for 1 h. The corrosion behaviour of sensitized and unsensitized Alloy 900 has been analyzed in a concentrated aqueous lithium bromide (LiBr) solution of 992 g/L by means of cyclic potentiodynamic curves. Secondary phase presence reduces the pitting potential value of Alloy 900. Besides, the pitting potential decreases with temperature. On the other hand, the corrosion potential and open circuit potential values increase with temperature and sensitization.     

Plasma-Auftragschweißen mit CrNiMoN-legierten Duplex-Werkstoffen

Plasma arc surfacing with CrNiMoN-alloyed duplex stainless steels This paper presents results of researching the Plasma-Hot-Wire-Surface-Welding process with duplex stainless steels X2CrNiMoN22-5-3 and X2CrNiMoN25-7-4. This includes the determination of the microstructure as well as the mechanic-technological and corrosion properties of the layers. The welding parameters have been optimized first in order to produce claddings of a thickness between 2–3 mm. Primary, the welding process influence regarding the degree of dilution on the ferrite-austenitecontent has been investigated. The rate of cooling t_12/8 and t_8/5 have been evaluated during duplex claddings of one and two layer. The results correspond to rate of cooling of PHA-weldings with duplex stainless steels without any dispersion. These results were confirmed by metallographic investigations of one and two layer duplex claddings. Layer analysis shows the homogeneity of the layer composition. Bending tests with normal and side bending samples of one and two layer revealed the excellent bonding between substrate and cladding. In the chemical corrosion experiments the claddings show approximately the similar pitting behaviour as the by rolling manufactured reference material. The surface quality of the X2CrNiMoN22-5-3 claddings is significant to the pitting behaviour. One and two layer claddings of X2CrNiMoN25-7-4 shows, independent of their initial conditions, the same pitting resistance as the reference material. It has been proved by SEP 1877 and EPR (electrochemical potentiodynamic reactivation) tests, that PHA-claddings are resistant against intercrystalline corrosion.     

Pitting and crevice corrosion of superaustenitic stainless steels

Superaustenites are mainly used in offshore applications, oil production and chemical industry. Most important types of localised corrosion of these steels are pitting and crevice corrosion. Investigated materials were N08028, S31254 and three modified alloys. Chromium content of investigated alloys varied between 20 and 27%, molybdenum between 3.2 and 6.0%, nitrogen between 0.1 and 0.36% and copper between 0 and 1.1%. For means of comparison stainless steel AISI 316L has been included in the study. Pitting and crevice corrosion of these highly corrosion resistant steels has been investigated by use of standardized tests. Critical pitting temperature and critical crevice temperatures were determined according to ASTM G 48, Methods C and D, respectively. Electrochemical measurements for determination of pitting potentials were done according to ASTM G 61 as well as for determination of critical pitting temperatures according to ASTM G 150. Results are presented as function of MARC (Measure of alloying for resistance to corrosion) defined by Speidel since linear correlation coefficients were higher when compared to conventional PREN. Results obtained by different testing methods must not be compared directly. Every test however is sensitive to microstructural defects like precipitations and segregations that decrease corrosion resistance. The higher alloyed a material is, the higher is its tendency to form microstructural defects, and the more difficult is it to reach its theoretical corrosion resistance at given chemical composition.     

新型双相抗点蚀铸造不锈钢的组织及耐蚀性能研究

采用金相显微镜、X射线衍射、电子探针、扫描电镜（SEM）和扫描隧道显微镜（STM）研究了新型超低碳、低铬镍、高硅双相铸造不锈钢的组织及其点蚀行为，结果表明，新钢种具有比C15钢更好的抗点蚀性能。     

Austenitic-ferritic stainless steels: A state-of-the-art review

Austenitic-ferritic stainless steels, more commonly known as duplex stainless steels, or DSS for short, consist of two basic phases. One is austenite, A, and the other is ferrite, F, present in about equal amounts (but not less than 30% each). The two phases owe their corrosion resistance to the high chromium content. Compared to austenitic stainless steels, ASS, they are stronger (without sacrificing ductility), resist corrosion better, and cost less due to their relatively low nickel content. DSS can be used in an environment where standard ASS are not durable enough, such as chloride solutions (ships, petrochemical plant, etc.). Due to their low nickel content and the presence of nickel, DSS have good weldability. However, they have a limited service temperature range (from −40 to 300°) because heating may cause them to give up objectionable excess phases and lower the threshold of cold brittleness in the heat-affected zone of welded joints. State-of-the art DSS are alloyed with nitrogen to stabilize their austenite, and in this respect the nitrogen does the job of nickel. Also, nitrogen enhances the strength and resistance to pitting and improves the structure of welds. Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 10, pp. 20–29, October, 1997.     

Microstructure and pitting corrosion of similar and dissimilar stainless steel welds

Abstract

Pitting Corrosion behaviour of similar and dissimilar metal welds of three classes of stainless steels, namely, austenitic stainless steel (AISI 304), ferritic stainless steel (AISI 430) and duplex stainless steel (AISI 2205), has been studied. Three regions of the weldment, i.e. fusion zone, heat affected zone and unaffected parent metal, were subjected to corrosion studies. Electron beam and friction welds have been compared. Optical, scanning electron microscopy and electron probe analysis were carried out to determine the mechanism of corrosion behaviour. Dissimilar metal electron beam welds of austenitic–ferritic (A–F), ferritic–duplex (F–D) and austenitic–duplex stainless steel (A–D) welds contained coarse grains which are predominantly equiaxed on austenitic and duplex stainless steel side while they were columnar on the ferritic stainless steel side. Microstructural features in the central region of dissimilar stainless steel friction welds exhibit fine equiaxed grains due to dynamic recrystallisation as a result of thermomechanical working during welding and is confined to ferritic stainless steel side in the case of A–F, D–F welds and duplex stainless steel side in the case of D–A welds. Beside this region bent and elongated grains were observed on ferritic stainless steel side in the case of A–F, D–F welds and duplex stainless steel side in the case of D–A welds. Interdiffusion of elements was significant in electron beam welding and insignificant in friction welds. Pitting corrosion has been observed to be predominantly confined to heat affected zone (HAZ) close to fusion boundary of ferritic stainless steel interface of A–F electron beam and D–F electron beam and friction weldments. The pitting resistance of stainless steel electron beam weldments was found to be lower than that of parent metal as a result of segregation and partitioning of alloying elements. In general, friction weldments exhibited better pitting corrosion resistance due to lower incidence of carbides in the microstructure.     

真空度对2205双相钢在热浓缩海水中点蚀行为的影响

目的研究真空度对2205双相不锈钢在海水淡化环境中耐点蚀性能的影响。方法在1.5倍人工浓缩海水中,采用循环阳极极化曲线与电化学阻抗谱等电化学方法,研究了2205双相不锈钢的点蚀和再钝化行为,并通过扫描电子显微镜对极化后试样的腐蚀形貌进行分析。结果测试了七种不同真空状态下2205双相不锈钢的循环阳极极化曲线和电化学阻抗谱,发现随着真空度的升高,试样的自腐蚀电位和点蚀电位均不断降低,分别约从-256 m V和605 m V下降到-485 m V和363 m V(均vs.SCE),点蚀倾向明显增大。同时,Nyquist曲线中的半圆弧逐渐变得扁平,Bode图中的相位角约从80°下降到77°,但是点蚀电位与再钝化电位之差逐渐升高。不同真空度下循环阳极极化后,试样表面的点蚀坑形貌不完全相同,蚀坑数量随着真空度的升高而明显减少,当真空度升高为0.72时,点蚀坑尺寸明显减小。结论随着真空度的逐渐升高,不锈钢钝化膜的致密性和保护性降低,电化学阻抗值逐渐减小,耐点蚀性能变差,但是再钝化性能却有所增强。循环阳极极化后试样的腐蚀程度减小。     

节镍型双相不锈钢的研究进展

高氮低镍双相不锈钢具有较高的强度和优良的耐局部腐蚀性能。同时,以低成本的锰、氮代替昂贵的镍可以大大降低生产成本。分析了锰、氮代镍的一些冶金学问题,并对目前国内外节镍型双相不锈钢的研究进展作了大致的介绍。     

Effect of annealing temperature on pitting behavior and microstructure evolution of hyper‐duplex stainless steel 2707

Hyper‐duplex stainless steel (HDSS) 2707 is a competitive material for application in extremely caustic environments. In this study, different annealing temperatures ranging from 1020°C to 1200°C were examined by electrochemical tests and microstructure analysis. The microstructure characterization indicated that precipitations were detected when the annealing temperature was below 1050°C and a relatively balanced austenite–ferrite phase structure was obtained at 1100°C. Through electrochemical measurements in NaBr solution, it was revealed that with the increase of temperature the pitting resistance of HDSS 2707 first rose then declined, peaking at 1100°C. The highest critical pitting temperature was about 67°C. In addition, the pitting position shifted from austenite phase to austenite–ferrite boundary and finally to ferrite interior with the annealing temperature increasing, which was in agreement with the pitting resistance equivalent values (PREN) of the two phases.