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.     

Effect of Nitrogen and Sensitization on the Microstructure and Pitting Corrosion Behavior of AISI Type 316LN Stainless Steels

High-nitrogen stainless steels (SS) are receiving increased attention because of the advantages of their strength over the SS with nominal composition. However, they are susceptible to dichromium nitride (Cr₂N) precipitation during thermal exposure between 873 and 1323 K resulting in sensitization and subsequent intergranular corrosion. Round tensile specimens of AISI type 316LN SS, with three different nitrogen content 0.07, 0.14, and 0.22 wt.% in mill-annealed and sensitized (973 K for 24 h) condition were studied for their pitting corrosion behavior. The results of the potentiodynamic anodic polarization studies were correlated with the results obtained using electrochemical impedance spectroscopy (EIS) technique. Critical pitting potential (E _pp) increased with increasing nitrogen content but the same was found to decrease on aging. The parameters indicating passive film stability measured by EIS revealed faster passive film dissolution as indicated by low polarization resistance, in sensitized condition and vice-versa in mill-annealed condition. The EIS results correlated well with the variation in the respective E _pp obtained from the potentiodynamic polarization diagrams.     

Microbiologically influenced corrosion of steels by thermophilic and mesophilic bacteria

Bacterial influenced corrosion of AISI 316 stainless steels (SS) and ASTM A36 carbon steel by two strains of sulfate reducing bacteria (SRB) were analyzed. Thermophilic and mesophilic bacteria were isolated from the condensate fluid of “Los Azufres”, a geothermal electric field located in the State of Michoacan at Central Mexico. Anaerobic corrosion tests were carried out for 15, 30 and 60 days in lactate‐containing media at 50 °C and 40 °C. Scanning electron microscopy (SEM) was used to determine corrosion morphology. Pitting density was determined with an optical microscope. Corrosion potential, anodic potentiodynamic polarization curves and pH values were measured under anaerobic conditions. Results show that the microbial activity influenced the overall corrosion process, whereas, pitting corrosion and localized attack corrosion (LAC) were found. The anodic polarization curves show that passivation and activation processes should take place on the steel surface of the sample and pH decreases as the exposure time increases.     

Pitting corrosion behaviour of austenitic stainless steels with Cu and Sn additions

The influence of Cu and Sn on the pitting corrosion resistance of AISI 304 and 316 stainless steels in chloride-containing media has been investigated. The corrosion behaviour was evaluated by cyclic polarization, potentiostatic CPT measurements and electrochemical impedance spectroscopy in 3.5 wt% NaCl. The corrosion resistance was also studied in FeCl₃ under Standard ASTM G-48. According to the results, Cu addition favours pit nucleation but inhibits its growth, whereas Sn exerts the opposite effect, favouring pit growth and inhibiting its nucleation. Studies by SEM, X-ray mapping and EDS analysis showed Cu-, Cl- and O-rich corrosion products that reduce the extent of corrosion damage.     

Erosion and Corrosion Behavior of Laser Cladded Stainless Steels with Tungsten Carbide

Laser cladding of tungsten carbide (WC) on stainless steels 13Cr-4Ni and AISI 304 substrates has been performed using high power diode laser. The cladded stainless steels were characterized for microstructural changes, hardness, solid particle erosion resistance and corrosion behavior. Resistance of the clad to solid particle erosion was evaluated using alumina particles according to ASTM G76 and corrosion behavior was studied by employing the anodic polarization and open circuit potential measurement in 3.5% NaCl solution and tap water. The hardness of laser cladded AISI 304 and 13Cr-4Ni stainless steel was increased up to 815 and 725Hv_100?g, respectively. The erosion resistance of the modified surface was improved significantly such that the erosion rate of cladded AISI 304 (at 114?W/mm²) was observed ~0.74?mg/cm²/h as compared to ~1.16 and 0.97?mg/cm²/h for untreated AISI 304 and 13Cr-4Ni, respectively. Laser cladding of both the stainless steels, however, reduced the corrosion resistance in both NaCl and tap water.     

Corrosion behaviour of duplex stainless steels sintered in nitrogen

Duplex stainless steels obtained through powder metallurgy (PM) technology from austenitic AISI 316L and ferritic AISI 430L powders were mixed on different amounts to obtain biphasic structures with austenite/ferrite ratio of 50/50, 65/35 and 85/15. Prepared mixes of powders have been compacted at 750 MPa and sintered in N₂-H₂ (95% and 5%) at 1250 °C for 1 h. Corrosion behaviour, using electrochemical techniques such as anodic polarization measurement, cyclic anodic polarization scan and electrochemical potentio-kinetic reactivation test and double loop electrochemical potentio-kinetic reactivation double loop test were evaluated. For duplex stainless steels, when austenite/ferrite ratio increases the corrosion potential shifts to more noble potential and passive current density decreases. The beneficial effect of annealing solution heat treatment on corrosion behaviour was established and was compared with corrosion behaviour of vacuum sintered duplex stainless steels. The results were correlated with the microstructural features.     

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。     

Pitting corrosion of welded joints of austenitic stainless steels studied by using an electrochemical minicell

A pitting corrosion study of welded joints of austenitic stainless steels (AISI 304 and 316L) has been addressed. A specific small-scale electrochemical cell (minicell) has been used. Four different weldment zones have been studied. The electrochemical methods applied were the potentiodynamic anodic polarization test and cyclic potentiodynamic polarization measurements. These techniques showed that the HAZ was the most critical zone for pitting corrosion for both materials. The results were correlated to the microstructural features of the materials. Finally, a comparative study between minicell and lacquer coating techniques has been done. The results show that it is advisable to use the minicell device if reliable results are wanted.     

Remaining Strengths and Pitting Resistance of AISI 316 After a Fire Attack: Implications for Use as Concrete Rebars

This study has looked into the tensile and the corrosion behavior of the AISI 316 austenitic stainless steel subjected to annealing temperature between 600 and 900 °C for up to 7 days. Discussion of results centers on using AISI 316 as concrete reinforcing bars. At a given temperature within this range, the tensile behavior is almost unaffected for annealing up to 7 days. However, there is a drastic change in fractography with annealing temperature. There is no relationship between the degree of sensitization and anodic polarization parameters. No relationship exists between annealing temperature and anodic polarization parameters, too. In comparison with ordinary carbon steel, the presence of Ca(OH)₂ is much more beneficial to the pitting resistance of AISI 316.     

Corrosion resistance properties of glow-discharge nitrided AISI 316L austenitic stainless steel in NaCl solutions

Glow-discharge nitriding treatments can modify the hardness and the corrosion resistance properties of austenitic stainless steels. The modified layer characteristics mainly depend on the treatment temperature. In the present paper the results relative to glow-discharge nitriding treatments carried out on AISI 316L austenitic stainless steel samples at temperatures ranging from 673 to 773 K are reported. Treated and untreated samples were characterized by means of microstructural and morphological analysis, surface microhardness measurements and corrosion tests in NaCl solutions. The electrochemical characterization was carried out by means of linear polarizations, free corrosion potential-time curves and prolonged crevice corrosion tests. Nitriding treatments performed at higher temperatures (>723 K) can largely increase the surface hardness of AISI 316L stainless steel samples, but decrease the corrosion resistance properties due to the CrN precipitation. Nevertheless nitriding treatments performed at lower temperatures (?723 K) avoid a large CrN precipitation and allow to produce modified layers essentially composed by a nitrogen super-saturated austenitic metastable phase (S-phase) that shows high hardness and very high pitting and crevice corrosion resistance; at the same polarization potentials the anodic current density values are reduced up to three orders of magnitude in comparison with untreated samples and no crevice corrosion event can be detected after 60 days of immersion in 10% NaCl solution at 328 K.     

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.     

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.     

On the corrosion mechanism of AISI 204Cu stainless steel in chlorinated alkaline media

Electrochemical techniques (CV, SECM, CPT) and surface analysis techniques (EDX, SEM) have been employed to assess the corrosion behaviour of the AISI 204Cu stainless steel. The behaviour of this steel has been compared with that of AISI 304 and AISI 434 stainless steels in chlorinated alkaline media. All samples performed well at room temperature under potentiodynamic polarisation up to a chloride to hydroxyl ratio of 10. At this ratio the AISI 204Cu and the AISI 434 steels presented pitting potential at +0.47 V vs. SCE and +0.31 V vs. SCE, respectively. Moreover, the critical pitting temperature was higher for the AISI 204Cu steel than for the AISI 434 steel, respectively 58 °C and 28 °C.In terms of corrosion performance of the AISI 204Cu stainless steel can be classified better than the AISI 434 steel and worse than the AISI 304 steel.Local electrochemical and chemical examinations allowed evidencing the local activity of some pits over long period, and to conclude that the improved corrosion performance of the low nickel alloy AISI 204Cu stainless steel should be ascribed to copper cementation at active corrosion sites.     

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.     

用第二阳极电流峰法评定奥氐体不锈钢晶间腐蚀敏感性

<正> 一、前言 检验奥氏体不锈钢晶间腐蚀的敏感性,国内外沿用的标准实验方法,有10％草酸电解侵蚀试验、硫酸锎—硫酸—铜屑试验(Strauss试验)、65％硝酸试验(Huey试验)等。草酸电解法适宜用于筛选试验,Strauss法和Huey法试验时间都很长,而且要用繁琐的失重法评定晶间腐蚀程度。所以,人们一直寻求既准确又快速、简便的试验方法。 近年来,各国在用电化学方法预测不锈钢晶间腐蚀敏感性的研究方面十分活跃,如EPR法,第二阳极电流峰法、恒电位侵蚀法等。本文采用动电位阳极化曲线上第二电流峰值法来检验不同敏化程度的几种不锈钢的晶间腐蚀敏感性,并与试样表面金相形貌及标准的CuSO_4+H_2SO_4+铜屑方法试验结果进行比较,旨在确定第二阳极电流峰法的适用性及其灵敏程度。     

Effect of alloyed molybdenum on corrosion behavior of plasma immersion nitrogen ion implanted austenitic stainless steel

Plasma immersion ion implantation (PIII) of nitrogen has been performed on two austenitic stainless steels (with and without Mo addition) at three different temperatures namely, 250, 380 and 500 °C for 3 h. Grazing angle X-ray diffraction (GXRD) was carried out on the surface of the steels (both PIII treated and untreated). GXRD results suggest that PIII is more effective in Mo containing stainless steel (SS). The electrochemical corrosion studies examined through both by DC polarization and EIS technique in 3.5 wt.% NaCl reveals that, 3 h N-implantation at 250 and 380 °C improves the corrosion and pitting resistance of both the austenitic stainless steels under investigation. The effect N implantation on pitting resistance is seen more in the presence of Mo, than when it is not present in the SS. It is further emphasized that the pitting resistance of the alloys significantly deteriorates, when they are implanted at 500 °C.     

The electrochemical behavior of austenitic stainless steel with different degrees of sensitization in the transpassive potential region in 1 M H2SO4 containing chloride

This paper investigates electrochemical methods to estimate the degree of sensitization (DOS) for as-rolled and solution-treated austenitic stainless steels (AISI 304). The change in DOS was introduced by heat treatment of various time periods at 700 °C, and the electrochemical experiments were conducted at 27 °C in 1 M H₂SO₄ + 0.2 wt.% NaCl. The results show that there is no obvious difference in the anodic polarization curves of the specimens with the differences in DOS. However, the DOS of specimens can be clearly differentiated with AC impedance response in a particular transpassive potential region. In the transpassive potential region of the anodic polarization curve, as overpotential is increased beyond the breakdown potential, three types of anodic dissolution, passive dissolution, grain-boundary attack, and pitting can be characterized. The DOS can only be correctly evaluated with AC impedance response in the middle of the transpassive potential region, where anodic dissolution is of grain-boundary attack type, from 1.05 to 1.1 V. The chromium-depleted zone was preferentially attacked and an intergranular corrosion was found for the serious sensitized specimen after AC impedance test. The healing effect was observed in as-rolled specimens as the specimens were heated more than 72 h, but the effect was not found in the solution-treated specimens sensitized for up to 480 h at 700 °C.     

Enhanced corrosion resistance of interstitially hardened stainless steel: Implications of a critical passive layer thickness for breakdown

Immense interstitial hardening of 316L austenitic stainless steel via low-temperature paraequilibrium carburization also leads to greatly improved corrosion resistance. Both the hardening and the improved corrosion resistance owe their origin to a “colossal” supersaturation of interstitial carbon. The corrosion resistance of stainless steel involves a Cr₂O₃-rich passive film, and the composition and thickness of the passive film developed during anodic polarization at various potentials were determined for both carburized and non-treated steels using grazing incidence X-ray photoelectron spectroscopy. Passive oxide film breakdown is a necessary step in pitting corrosion, and appears to occur in these steels at a critical film thickness of ≈3 nm. We suggest that this breakdown is of chemomechanical origin. Long wavelength thickness perturbations occur during film growth to reduce the strain energy density in the passive film arising from intrinsic and electric field-induced stresses. At the critical thickness, the localized thinning is sufficient to lead to dielectric breakdown and nucleation of pitting corrosion. The improved corrosion resistance for the carburized material results from thinner passive films at a given potential and hence a delay in the detrimental effect of the thickness perturbations.     

Effect of the Heat Treatment on the Corrosion Resistance of Duplex Stainless Steels

Duplex stainless steels (DSS) are biphasic austenitic-ferritic steels in which the best combination of mechanical and corrosion resistance properties is achieved for an almost equal volume fraction of the phases. In this work, the effect of secondary phases precipitation on the corrosion resistance of four DSS grades (2101, 2304, 2205 and 2507), after isothermal aging in the critical temperature range 750-900 °C, was studied. The corrosion resistance was investigated by potentiodynamic polarization tests in both 0.6 M NaCl solution (pH 7) and in an acid chlorinated solution (pH 3) at room temperature. Moreover, the critical pitting temperature was determined according to ASTM G150. The results showed that secondary phases precipitation mainly influenced the resistance to corrosion of the lean duplex grades.     

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.