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.     

核电厂水池覆面用不锈钢钢板在硼酸水溶液中的点蚀行为

采用电化学方法研究了温度、Cl~-以及SO_4~(2-)含量对不锈钢板S30403、S32101和S32205在硼酸溶液中点蚀行为的影响。结果表明:3种材料的点蚀电位(Eb)和再钝化电位(Er)均随Cl~-含量的升高而降低,S32205不锈钢的点蚀电位和再钝化电位普遍高于S32101和S30403不锈钢的;存在临界温度(约60℃),当温度高于临界温度,S32205不锈钢的点蚀电位大幅降低,再钝化电位的临界温度介于40~60℃;SO_4~(2-)含量对3种材料点蚀电位和再钝化电位的影响不明显。S32205不锈钢的耐点蚀性能优于S32101和S30403不锈钢的,而S32101和S30403不锈钢的耐点蚀性能相当。     

Novel strategies for assessing the pitting corrosion resistance of stainless steel surfaces

Pitting corrosion is one of the most common mechanisms of surface damage on stainless steels. Electrochemical methods have been preferentially applied for the evaluation of the pitting corrosion resistance of stainless steels in the laboratory. Nevertheless, some of them are not reliable enough and in general the application of electrochemical methods in the field becomes difficult because of required deep understanding of corrosive phenomena and measurement technology. Therefore, new approaches for the evaluation of the pitting corrosion susceptibility of stainless steel surfaces in the laboratory as well as in the field are necessary. In the present paper two novel strategies including electrochemical noise measurements under anodic polarization for laboratory testing, and an indicator test to assess the susceptibility of stainless steel surfaces to pitting corrosion in the field are introduced. Experimental results concerning the influence of surface treatments on the pitting corrosion resistance on stainless steels have confirmed that final surface condition has a significant effect on their future pitting corrosion susceptibility. In addition, the pitting corrosion resistance of stainless steel surfaces was observed being specifically dependent on the achieved surface topography and in some cases independent on the roughness parameters of the surface.     

Corrosion behaviour of Lotus-type porous high nitrogen nickel-free stainless steels

Corrosion behaviour of three austenitic Lotus-type porous high nitrogen Ni-free stainless steels exposed to an acidic chloride solution has been investigated by electrochemical tests and weight loss measurements. Polarization resistance indicates that the corrosion rate of Lotus-type porous high nitrogen Ni-free stainless steels is an order of magnitude lower than that of Lotus-type porous 316L stainless steel in acidic environment. The localised corrosion resistance of the investigated high nitrogen Ni-free stainless steels, measured as pitting potential, E_b, also resulted to be higher than that of type 316L stainless steel. The influences of porous structure, surface finish and nitrogen addition on the corrosion behaviour were discussed.     

Importance of initial surface film in the degradation of stainless steels by atmospheric exposure

The surface compositions of stainless steels types 304, 316, 430, and 444 combined with four types of surface finishes, 2B finish, hairline polishing, mirror polishing, and bright annealing, were measured by ICP-AES, EPMA, and XPS before exposure. The surface finish that most enriched the chromic species in the surface film was mirror polishing, followed by bright annealing, 2B finish, and hairline polishing. The order of corrosion-resistance was type 444, type 316, type 304, and type 430. The surface compositions were correlated with the rating number and pitting depth after exposure to atmospheric environments. The rating number had a high positive correlation with the concentration of Cr in the surface film, and had a slight correlation with the near-surface composition measured by EPMA at 12 kV, but did not show any correlation with bulk composition within the composition range covered in the present work. This same trend was observed for pitting depth. It was concluded that the cationic concentration of Cr in the surface film before atmospheric exposure is the prime factor in controlling the resistance of stainless steels to atmospheric corrosion.     

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.     

焊接氧化皮对奥氏体不锈钢孔蚀性能的影响

采用电化学测试技术,在NaCl介质中焊接氧化皮对3种奥氏体不锈钢的耐孔蚀性能进行了探讨.结果表明,有焊接氧化皮部位较比母材更易产生孔蚀,去除氧化皮则改善耐蚀性能.有焊接氧化皮的不锈钢耐孔蚀性能依NK1<316<304次序变劣.通过表面SIMS分析,发现焊接氧化皮合金表面贫乏铬,从而导致耐孔蚀性能下降.有焊接氧化皮NK1不锈钢耐孔蚀性能之所以优于304不锈钢,是由于表面膜中富集铜元素,并参与了成膜过程,改善了表面电化学行为,增强了表面膜抵抗侵蚀性离子破坏的能力.     

Pitting Potential of stainless steels in artificial sweat

The pitting potentials of 12/12, 316 PX, AISI 303, 304, 316F and 316L austenitic stainless steels were determined in artificial sweat (perspiration) at room temperature. Two compositions of sweat were used: the BAM composition which contains two malodorous organic acids and the composition proposed in an ISO standard which does not contain them. The quasi-potentiostatic method (10 mV potential steps per min), potentiodynamic technique (1 V/min linear sweep) and scratch test were used on mechanically polished and HNO₃-passivated surfaces. The aggressivity of the two artificial sweats with respect to stainless steels was found to be practically the same. The pitting potentials and the classification of the stainless steels according to their pitting potential values were found to depend on the surface preparation and, to a lesser extent, on the test method. The experimental techniques were often complementary and a combination of two or three methods in conjunction may increase the confidence with which the conclusions can be applied. The lowest pitting corrosion resistance was found for AISI 303 and the highest for AISI 316L. As expected stainless steels with the lowest concentration of nonmetallic inclusions (sulfides and oxides) exhibited the best pitting corrosion resistance.     

Effects of chloride and crevice on corrosion resistance of stainless steels buried in soil within Seoul Metropolitan

Field and laboratory tests were conducted to find the factors affecting corrosion of stainless steels in soil. During one-year exposure, corrosion occurred within a joint and on the surface of type 304 pipe with the joint, which was buried at the site with a high chloride concentration of about 3680 ppm; however, corrosion was not observed at any of the other sites independent of the stainless steel grade and the presence of joints. At some sites, a seasonal fluctuation of corrosion potential was observed in the soil though corrosion did not occur. This observation may be due to the activity of sulfate reducing bacteria because a decrease of corrosion potential with the inoculated bacteria did not cause corrosion of stainless steels. These results indicate that both the level of chloride and the presence of crevices are the main factors affecting corrosion of stainless steels in soil but that the activity of bacteria is not. From measurements of pitting potential, a guideline for stainless steel use in soil is drawn as follows: Corrosion of stainless steels in soil occurs when the pitting potential of stainless steel under crevices in synthetic ground water that contains the same chloride concentration as the soil is less than the saddle potential. Finally, the guideline for stainless steels applications was provided in this paper according to this criterion.     

Electrochemical investigations of pitting corrosion

By using chronopotentiostatic and stepwise potential change experiments with potentiokinetic and galvanostatic testing, the following types of pitting corrosion of stainless steels in chloride-containing solutions have been investigated: sulphate inhibition of pitting; 35%Cr-Fe alloy; Cr-Ni-Mo stainless steels. The circuit resistance was found to be of fundamental importance. The pit passivation potential depends on the intensity of a corrosion attack before potential change only in the case of inhibited solutions. In uninhibited solutions passivation and formation potentials are nearly equal only in the case of potentiostatic circuit conditions. The Cr-Fe alloy and the Cr-Ni-Mo stainless steels show a potential range of repassivating pitting. Of practical interest is the critical potential of stable pitting which decreases with increasing circuit resistance. The beneficial effect of Mo is only valid for the pitting potential obtained potentiostatically and not at higher circuit resistances. Considering the practical meaning of the addition of Mo it may be concluded that this element is probably essentially connected with repassivation of pits and conditioning effects of the passive layer.     

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。     

衣康酸介质中Cl^—和NO3^—对不锈钢点蚀电位的影响

利用动电位法测定３１６Ｌ奥氏体不锈钢和Ｒ１双相不锈钢在Ｃ５Ｈ６Ｏ４－Ｃｌ＾－－ＮＯ３＾－水溶液体系中的阳极极化曲线和点蚀电位,探讨了衣康酸（Ｃ５Ｈ６Ｏ４）介质中Ｃｌ＾－和ＮＯ３＾－对点蚀的影响。结果表明：（１）Ｃｌ＾－浓度［Ｃｌ＾－］的提高导致不锈钢点蚀电位Ｅｂ降低,其关系为Ｅｂ＝ａ－ｂｌｇ［Ｃｌ＾－］。同样条件下,Ｒ１不锈钢的点蚀电位比３１６Ｌ不锈钢高３００￣４００ｍＶ;（２）在含Ｃｌ＾－的衣康     

Real time pit initiation studies on stainless steels: The effect of sulphide inclusions

It has long been accepted that manganese sulphide favours pitting on stainless steels. However, there are different standpoints on the most important mechanism for pit initiation; due to dissolution of sulphide inclusions, chromium depletion around the inclusion or mechanical rupture of the passive film by metal chlorides. Analysing the pitting potential and metastable pitting rates on different grades of stainless steels has rationalised the effect of sulphide content on pitting corrosion resistance. In situ atomic force microscopy (AFM) has been used in conjunction with conventional electrochemical techniques for imaging real time pit initiation events.     

In vitro electrochemical investigations of advanced stainless steels for applications as orthopaedic implants

Potentiodynamic anodic polarization experiments on advanced stainless steels (SS), such as nitrogenbearing type 316L and 317L SS, were carried out in Hank’s solution (8 g NaCl, 0.14 g CaCl₂, 0.4 g KC1, 0.35 g NaHCO₃, 1 g glucose, 0.1 g NaH₂PO₄, 0.1 g MgCl₂, 0.06 g Na₂HPO₄ 2H₂O, 0.06 g MgSO₄ 7H₂O/1000 mL) in order to assess the pitting and crevice corrosion resistance. The results showed a significant improvement in the pitting and crevice corrosion resistance than the commonly used type 316L stainless steel implant material. The corrosion resistance was higher in austenitic stainless steels containing higher amounts of nitrogen. The pit-protection potential for nitrogen-bearing stainless steels was more noble than the corrosion potential indicating the higher repassivation tendency of actively growing pits in these alloys. The accelerated leaching study conducted for the above alloys showed very little tendency for leaching of metal ions, such as iron, chromium, and nickel, at different impressed potentials. This may be due to the enrichment of nitrogen and molybdenum at the passive film and metal interface, which could have impeded the releasing of metal ions through passive film.     

不锈钢海水潮汐区16年腐蚀行为

在青岛、厦门和榆林3个试验站的潮汐区对5种不锈钢暴露16年，总结其腐蚀行为和规律。在潮汐区暴露的不锈钢受点蚀和缝隙腐蚀破坏。不锈钢在潮汐区暴露1至4年的点蚀速度较大，以后点蚀速度减慢。耐点蚀性能较好的不锈钢，耐缝隙腐蚀性能也较好。不锈钢在潮汐区的腐蚀随暴露地点的海水温度升高而加重。增加Cr含量、添加Mo能明显提高不锈钢在潮汐区的耐蚀性。Ni对提高的耐蚀性有效，但影响效果较小。海生物污损能引起不锈钢的局部腐蚀，它对不锈钢在潮汐区的腐蚀有显著影响。     

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.     

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.     

940X新型不锈钢的耐蚀性能

通过盐雾试验和点腐蚀电位测试,对比了新型940X不锈钢和9Cr18不锈钢的耐蚀性能.结果表明,在NaCl溶液中940X不锈钢的耐全面腐蚀和耐点腐蚀的性能比9Cr18的高.并结合化学成分及金相能谱分析了940X不锈钢的耐蚀机理.     

点蚀敏感性的评价新方法——极限零概率点蚀电位法

对1Cr13不锈钢点蚀电位的离散分布进行统计分析,利用点蚀发生概率、门槛电流密度和电极电位的关系,结合直线外延法推测出在极限门槛电流密度下,零概率点蚀电位,即极限零概率点蚀电位,可以作为评价材料耐点蚀性能的参数。     

Electrochemically induced surface annealing without electrolyte immersion and its influence on pitting resistance

The martensite in metastable-austenite-stainless-steels may decrease the corrosion resistance of the steels. Electrochemically induced surface annealing (EISA) can decrease the content of martensite in the steels, so it can promote the pitting resistance of the steels. But EISA treatment has to be operated on the condition of electrolyte immersion, which is an obstacle for its actual application. In this paper AISI304L stainless steel samples were treated with a no-immersion device. The martensite content of the steel decreased after the treatment, but the hardness of the steel almost had no change. The EISA effect was achieved with the no-immersion device. After the corrosion in a 3.5% NaCl aqueous solution, the EISA treated samples had less, smaller and shallower pits than the untreated samples had. The pitting potential of the EISA treated samples was almost equal to that of the untreated samples, and the open circuit potential of the EISA treated samples was higher than that of the untreated samples. The no-immersion EISA treatment promotes the pitting resistance of metastable-austenite-stainless-steels.