Microstructure and pitting corrosion resistance of annealed duplex stainless steel

The transition from metastable to stable pitting was studied in 0.5 M NaCl water solution for two cast duplex stainless steels under different microstructural conditions achieved by annealing in the range from 900 °C to 1200 °C. The ensuing microstructural changes in heat treated steels were defined and correlated with established pitting potentials (E_p) and sites of corrosion damage initiation. The variations in E_p have been discussed in terms of secondary phases precipitation. The critical condition for pit stability was quantified and used to select an appropriate microstructural state, resulting in the higher potential at which stable pit growth is first observed.     

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.     

Effect of nitrogen on corrosion behavior of 28Cr-7Ni duplex and microduplex stainless steels in air-saturated 3.5 wt% NaCl solution

The corrosion behavior of 28Cr-7Ni-O-0.34N duplex stainless steels in air-saturated 3.5-wt% NaCl solution at pH 2, 7, 10 and 27 °C was studied by the potentiodynamic method. Two types of microstructures were investigated: the as-forged duplex and microduplex (average austenite grain size 5-16 μm) structures. The austenite volume fractions of the tested steels were between 0.35 and 0.64. The nitrogen effect on corrosion behaviors of both duplex and microduplex stainless steels were the same. At pH 2, the corrosion potential increased when the nitrogen content increased, however, corrosion current density as well as corrosion rate decreased. At pH 7 and 10, the effect of nitrogen on corrosion potential and corrosion rate could not be observed. Corrosion potential at pH 10 was lower than at pH 7. Pitting potential increased when the nitrogen content in the tested steels increased at all tested pH. For the nitrogen effect on the passive current density, it seemed that only at pH 2, the average passive current densities reduced when the nitrogen content increased. Nitrogen may have participated in the passive film or has been involved in the reaction to build up passive film. The ammonium formation and nitrogen enrichment at the interface metal/passive film with adsorption mechanism were discussed. The dissolute nitrogen might have combined with the hydrogen ions in solution to form ammonium ions, resulting in increasing solution pH. The steel could then easily repassivate, hence the corrosion potential and pitting potential would increase. However, the ammonium formation mechanism could not explain the decrease of corrosion potential in basic solution. Nitrogen enrichment at the metal/passive film interface with adsorption mechanism seemed to be an applicable consideration in increasing pitting potential. However, this mechanism did not involve the ammonium ion formation. In general, for the duplex and microduplex stainless steels tested, nitrogen increased the general corrosion resistances in acid solution and pitting corrosion resistance at all solution pH. Metallographic observation in both tested duplex and microduplex steels after pitting corrosion at all tested pH revealed that, the corroded structure in the tested steels without nitrogen alloying was austenite, but those with nitrogen alloying was ferrite. Even though ferrite had a higher chromium content than austenite but higher dissolved nitrogen in austenite than in ferrite may have increased the pitting resistance equivalent number (PRE) of austenite to be higher than that of ferrite.     

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.     

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.     

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     

Inhibition effect of chromate on the passivation and pitting corrosion of a duplex stainless steel in LiBr solutions using electrochemical techniques

The electrochemical behavior of duplex stainless steel (DSS) in LiBr media was investigated by anodic cyclic polarization curves and AC impedance measurements. The effect of bromide concentration and the presence of chromate in the solutions on the corrosion behavior of AISI 2205 was studied. Cyclic polarization curve analyses showed that there was different pitting susceptibility of passive films depending on the LiBr concentration. Pitting potential decreases with LiBr concentration in a semilogarithmic scale following two different slopes. Chromate presence displaces pitting potentials towards more positive values at low LiBr concentrations but it has no effect when LiBr concentration increases.The comparative analysis carried out in LiBr and LiBr chromate-containing solutions at two different concentrations, 0.016 M and 0.032 M, verifies the assumption that halogen ions facilitate inhibitor adsorption. The addition of halides strongly increased the inhibition efficiency of chromate. The passive film becomes more resistant when bromide concentration increases, although film thickness decreases.     

0Cr25Ni7Mo4、316与304不锈钢临界点蚀温度研究

采用外加恒定电位下腐蚀电流-温度扫描方法研究了0Cr25Ni7Mo4、304和316不锈钢在1 mol/L NaCl水溶液中的点蚀行为。利用不锈钢临界点蚀温度评价了材料的耐点蚀性能.测得0Cr25Ni7Mo4和316不锈钢的临界点蚀温度分别为79.5 ℃和15 ℃,304不锈钢在0 ℃以下.对0Cr25Ni7Mo4不锈钢材料优良耐点蚀性能的原因进行了分析讨论.     

Influence of pH on the electrochemical behaviour of a duplex stainless steel in highly concentrated LiBr solutions

The objective is to study the influence of pH on the corrosion and passive behaviour of duplex stainless steels (DSS) using potentiodynamic measurements, potentiostatic tests and electrochemical impedance spectroscopy (EIS).DSS are spontaneously passive in heavy brine LiBr solutions. Under potentiostatic conditions at applied anodic potentials within the passive domain an equivalent circuit with two time constants is the most suitable model to describe the corrosion mechanism in the interface electrolyte/passive film/metal. pH modifies the electrochemical properties of the passivity of the alloy in a 992 g/L LiBr solution reducing its resistance with the applied potential.     

Loch- und Spaltkorrosion von Chrom- und Chromnickelstählen in chloridhaltigen Lösungen

Pitting and crevice corrosion of stainless steels in chloride solutions In practice stainless steels in chloride containing waters are found to be susceptible to crevice corrosion and pitting. Corrosion tests were carried out on AISI 304 L stainless using a simulated crevice and the compositions of the electrolyte in the crevice determined. Long term potentiostatic tests were used to determine the critical potentials for crevice corrosion (U_S), for various steels in sodium chloride solutions at different concentrations and temperatures. The steels studied were 22 CrMo V 121, X 22 CrNi 17 and AISI 304 L. Like the critical pitting potential (U_L), U_S was found to have a strong dependence on the chloride content of the external solution. At higher concentrations the two potentials were similar. At lower concentrations the U_S was lower than U_L. The knowledge of these critical potentials together with well known rest potentials for a steel in an electrolyte of known concentration, allows conclusions to be drawn about its susceptibility to pitting and crevice corrosion. The method is suitable also for other passive metals.     

Depassivation-repassivation behavior of type-312L stainless steel in NaCl solution investigated by the micro-indentation

Repassivation behavior of type-312L stainless steel containing 6% of molybdenum was examined in NaCl solution using in situ micro-indentation technique, together with type-304 and 316L stainless steels. High stability of the passive film formed on the type-312L stainless steel was also examined by depth profiling analysis of passive films using glow discharge optical emission spectroscopy (GDOES). In 0.9 mol dm⁻³ NaCl solution at 296 K the type-304 and 316L stainless steels are passive only up to 0.3 V (SHE), above which pitting corrosion occurs. In contrast, no pitting corrosion occurs on type-312L stainless steel. Despite the significant difference of the pitting corrosion resistance, the repassivation kinetics of the three stainless steels, examined by micro-indentation at 0.3 V (SHE), is similar. The presence of molybdenum in the stainless steel does not influence the repassivation kinetics. The charge required to repassivate the ruptured type-312L stainless steel surface increases approximately linearly with the potential, even though the passivity-maintaining current increased markedly at potentials close to the transpassive region. Repassivation occurs without accompanying significant dissolution of steel, regardless of the stability of passive state. Depth profiling analyses of the passive films on the type-312L stainless steels formed at several potentials revealed that molybdenum species enrich in the outer layer of the passive film, below which chromium-enriched layer is present. The permeation of chloride ions may be impeded by the outer layer containing molybdate, enhancing the resistance against the localized corrosion of the type-312L stainless steel.     

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.     

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。     

Effects of molybdenum on the pitting of ferritic- and austenitic-stainless steels in bromide and chloride solutions

The effect of Mo on the pitting potential, dissolution kinetics, and repassivation behavior of high purity ferritic stainless steels, Fe-18%Cr-x%Mo, and austenitic stainless steels, Fe-18%Cr-12-15%Ni-x%Mo, was studied in solutions of bromide and of chloride. Large increases in the pitting potential of Fe-18%Cr-x%Mo in chloride solution were found with increasing Mo content, compared with the distinctly smaller increases in bromide solution. There was an excellent correlation between the increase in pitting potentials of ferritic alloys between Fe-18%Cr-2% and 5%Mo in the chloride and bromide solutions with the increased dissolution overvoltages in the saturated solution of dissolved products within artificial pits. Austenitic stainless steels also showed larger increases in pitting potential in chloride solution than in bromide solution. Higher pitting potentials were recorded for the austenitic than the ferrite steels with the same Mo content. For austenitic steels, the pitting potentials in bromide and chloride solutions were not attributable solely to the difference in dissolution rates or repassivation characteristics in saturated solution of the dissolved products. It was concluded that initiation processes play an important role in the pitting of austenitic stainless steels.     

Annealing temperature effect on the pitting corrosion resistance of plasma arc welded joints of duplex stainless steel UNS S32304 in 1.0 M NaCl

Pitting corrosion resistance of 2304 duplex stainless steels after autogenous plasma-arc welding and subsequent short-time post-weld heat treatment at different temperatures, determined by critical pitting temperature in 1.0 M NaCl solution, has been investigated. The results showed that the as-welded joint displayed impaired pitting corrosion resistance and that pitting preferentially occurred at ferrite grain in heat-affected zone near the fusion line. Short-time annealing treatment at 1020–1120 °C has a beneficial effect on the pitting corrosion resistance of welded joint. The most favorable annealing temperature for the analyzed welded joints was found to be 1080 °C, at which the joint restored the pitting corrosion resistance lost during welding entirely.     

两种船体钢耐点蚀性能的电化学噪声评估

运用电化学噪声(EN)测量技术和极化曲线技术检测两种船体钢A和B在0.5mol/L NaHCO3+3%NaCl溶液中的腐蚀状况,结果表明,两种钢的噪声图谱都表现出了明显的点蚀特征;在点蚀诱导期,B钢电位噪声波动的幅度和暂态峰的密集程度均比A钢大,而且诱导期持续时间较短;对噪声电阻的分析也表明,在该试验体系中A钢表面状态更稳定。极化曲线的分析结果表明A钢的点蚀电位较高、极化电阻较大、腐蚀电流较小,耐点蚀性能更好,这与电化学噪声分析的结论一致。     

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。     

Zu einem Phänomen der Lochkorrosionsbegrenzung bei hochlegierten Sonderedelstählen und NiCrMo-Legierungen in Chloridlösungen

On a phenomenon of the limitation of pitting corrosion at high alloyed special stainless steels and NiCrMo-alloys in chloride solutions Testing the pitting corrosion resistance of high alloyed special stainless steels and NiCrMo-alloys in chloride solutions there was observed a limitation of the pitting corrosion range toward more positive potentials. Above this limitation, the so-called pitting corrosion limitation potential, the pit initiation by all means is prevented, but the growth of pits which had been initiated before in the pitting corrosion range not necessarily comes to a stop. Therefore current density-potential curves which are obtained by downward polarization after an initial potential jump into the transpassive region and chronopotentiostatic tests are more suitable to investigate this phenomenon than cyclic polarization measurements and potentiostatic alteration tests. There is indicated a dependence of this phenomenon on temperature. The phenomenon of a limitation of the pitting corrosion range toward more positive potentials has been found until now at alloy 926, alloy 31, alloy 28, alloy 59 and alloy C-276.     

Corrosion behavior of iron-based alloys in the LiBr + ethylene glycol + H2O mixture

The corrosion resistance of 1018 carbon steel, 304 and 316 type stainless steels in the LiBr (55 wt.%) + ethylene glycol + H₂O mixture at 25, 50 and 80 °C has been studied using electrochemical techniques which included potentiodynamic polarization curves, electrochemical noise and electrochemical impedance spectroscopy techniques. Results showed that, at all tested temperature, the three steels exhibited an active-passive behavior. Carbon steel showed the highest corrosion rate, since both the passive and corrosion current density values were between two and four orders of magnitude higher than those found for both stainless steels. Similarly, the most active pitting potential values was for 1018 carbon steel. For 1018 carbon steel, the corrosion process was under a mixed diffusion and charge transfer at 25 °C, whereas at 50 and 80 °C a pure diffusion controlled process could be observed. For 316 type stainless steel, at 25 and 50 °C a species adsorption controlled process was observed, whereas at 80 °C a diffusion controlled mechanism was present. Additionally, at 25 °C, the three steels were more susceptible to uniform type of corrosion, whereas at 50 and 80 °C they were very susceptible to localized type of corrosion.     

Cl离子对 304、316不锈钢临界点蚀温度的影响

采用外加恒定电位下腐蚀电流-温度扫描的方法分别研究了304、316不锈钢在不同浓度NaCl水溶液中的临界点蚀温度.得到了材料临界点蚀温度随Cl-浓度变化的关系曲线.在分析温度与Cl-浓度分别对钝化膜影响的基础上阐述了二者对不锈钢点蚀的综合作用机理.