Uniform corrosion and intergranular corrosion behavior of nickel‐free and manganese alloyed high nitrogen stainless steels

The uniform and intergranular corrosion behavior of two kinds of nickel‐free and manganese alloyed high nitrogen stainless steels (HNSSs) were investigated. A type of 316L stainless steel (316L SS) was also included for comparison purpose. Both solution annealed (SA) and sensitization treated (ST) steels were examined. It was found that the SA HNSSs had much weaker resistance to uniform corrosion compared to the SA 316L SS. The addition of molybdenum, to some extent, improved the uniform corrosion resistance of the HNSSs. The sensitization treatment had little influence on the uniform corrosion resistance of all the steels. The HNSSs showed an obvious susceptibility to intergranular corrosion, in particular the ST HNSSs. The intergranular corrosion rates of the sensitized HNSSs were much higher than that of the sensitized 316L SS. The degree of interganular attack for the ST HNSSs was much more serious than that for the 316L SS. The addition of molybdenum obviously improved the resistance of the ST HNSSs to intergranular corrosion. The double loop electrochemical potentiokinetic reactivation tests also proved that the HNSSs were rather susceptible to the sensitization treatment compared to the 316L SS. The relatively weak resistance of the HNSSs to uniform and intergranular corrosion may be due to high manganese promoted anodic dissolution. The improvement of uniform and intergranular corrosion resistance caused by the addition of molybdenum could be attributed to the synergistic effects of molybdenum and nitrogen in the HNSSs on the formation and stability of passive film.     

不锈钢盐酸露点腐蚀行为的原位研究

利用一种新型的露点腐蚀模拟装置结合原位的电化学阻抗谱,电化学噪声等测试手段评价了304和316L两种不锈钢的盐酸露点腐蚀行为.结果表明,316L不锈钢表现出更优异的耐盐酸露点腐蚀性能,主要原因可归结为两点:一是316L不锈钢钝化膜中含有较高的Cr/(Cr+Fe) 比以及较低含量的Fe;二是316L不锈钢钝化膜中含有能改善抗点蚀性能的Mo.     

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.     

2205和316L不锈钢在氢氟酸中的电化学腐蚀行为

通过动电位极化和电化学阻抗方法考察了2205双相不锈钢和316L不锈钢在5%(体积分数)HF溶液中的电化学行为,借助Mott-Schokkty曲线分析了两种不锈钢表面钝化膜的半导体特性。结果表明：两种不锈钢在氢氟酸溶液中都能发生钝化,且2205双相不锈钢的钝化区间范围更宽,维钝电流密度更低。2205双相不锈钢表面钝化膜表现出更高的钝化膜电阻和电荷转移电阻,其抗氢氟酸腐蚀性能优于316L不锈钢,这主要与2205双相不锈钢中的Mo和Cr含量高、表面钝化膜缺陷少、钝化膜易修复等因素有关。     

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.     

Effect of p H on the Electrochemical Behaviour and Passive FilmComposition of 316L Stainless Steel

The effect of pH on the electrochemical behaviour and passive film composition of 316 L stainless steel in alkaline solutions was studied using electrochemical measurements and a surface analysis method. The critical pH of 12.5 was found for the conversion from pitting corrosion to the oxygen evolution reaction(OER). OER was kinetically faster than pitting corrosion when both reactions could occur, and OER could postpone pitting corrosion. This resulted in pitting being initiated during the reversing scan in the cyclic polarization at the critical pH. According to the X-ray photoelectron spectroscopy analysis, the content of Cr and Mo decreased with pH, while Fe content increased. This induced the degradation of the passive film, which resulted in the higher passive current densities under more alkaline conditions. The selective dissolution of Mo at high p H was found, which demonstrated that the addition of Mo in austenitic stainless steels might not be beneficial to the corrosion resistance of 316L in strong alkaline solutions.     

炼油厂冷却水系统硫酸盐还原菌对316L不锈钢点腐蚀的研究

用开路电位、动电位扫描、电化学阻抗技术和扫描电镜等方法,研究了316L不锈钢在硫酸盐还原菌(SRB)溶液中的腐蚀电化学行为,分析了炼油厂冷却水系统微生物腐蚀的特征及机制.结果表明,在含有SRB溶液中的自腐蚀电位(Ecorr)和点蚀电位(Epit)随浸泡时间的增加而负移,极化电阻(Rp)随浸泡时间的增加而减小;在含有SRB溶液中的腐蚀速率均大于在无菌溶液中;SRB的生长代谢活动影响了316L SS表面的腐蚀过程,使不锈钢表面的钝化膜层腐蚀破坏程度增加,加速了316L SS的腐蚀.     

Enhancing the localised corrosion resistance of 316L stainless steel via FBR-CVD chromising treatment

The resistance of stainless steels to localised corrosion can be adversely affected by environmental and metallurgical heterogeneities existed in complex industrial infrastructures such as seawater desalination plants exposed to aggressive evnironments. It is therefore critical to enhance the localised corrosion resistance and understand the corrosion behaviour of stainless steels in complex and aggressive industrial environmental conditions. In this work, the localised corrosion resistance of chromised stainless steel 316L (SS316L) in simulated seawater desalination systems has been investigated by electrochemical and surface analytical techniques. It has been found that chromising processes have improved the localised corrosion resistance of SS316L by reducing its susceptibility to pitting, crevice, and welding zone corrosion in simulated seawater desalination environments. This increased corrosion resistance has been explained by electrochemical polarisation studies and surface analysis showing that the chromising treatment at 1050°C resulted in a continuous and stable chromium-enriched layer on the SS316L surface.     

Laser Raman microscopic studies of passive films formed on type 316LN stainless steels during pitting in chloride solution

The surface films formed on type 316LN stainless steels (SS) with different nitrogen contents, during potentiodynamic polarization in acidified 1 M NaCl solution, were characterized by Laser Raman Spectroscopy (LRS). LRS confirmed the presence of oxides and oxychlorides of iron and chromium, hydrated chlorides and nitrates in the film. Raman mapping showed increasing nitrate content in the film with increasing nitrogen content. The film on the uncorroded material showed the presence of chromium and molybdenum oxides. The improvement in pitting corrosion resistance of type 316LN SS with increasing nitrogen content was attributed to increased amount of nitrates in the passive film.     

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.     

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.     

Effect of GTAW remelting on the corrosion performance of AISI 316L cladding

Gas tungsten arc welding (GTAW) process was used for remelting of the top clad layers of austenitic stainless steel 316L deposited on low-carbon steel using gas metal arc welding (GMAW) process. Different electrochemical techniques were used for assessing and comparing sensitization and pitting corrosion performance of these clads (both in the as-welded as well as aged condition), besides comparing their passive film characteristics. Top clad layer remelting was influential upto a penetration depth of around 2.34 mm. Aging of clads at 750°C/24 hr accelerated the precipitation of carbides, which suppressed partially due to their remelting as indicated by electron probe microanalysis studies. Due to this GTAW remelted clads exhibited a relatively lesser degree of sensitization and higher pitting corrosion resistance as compared to the conventional GMAW clads. X-ray photoelectron spectroscopy studies revealed a relatively higher concentration of O, Cr, Ni, and Mo in the passive film of remelted clad surfaces than the conventional ones, which accounted for enhanced protectiveness of passive film on remelted surfaces as indicated by electrochemical impedance spectroscopy studies.     

316L不锈钢波纹管海水腐蚀失效机理对比分析

316L不锈钢是一种耐蚀性和加工性优异的奥氏体不锈钢。在海洋环境使用过程中发现经钝化处理的316L不锈钢波纹管在短时间内出现穿孔,而经表面黑化处理的波纹管出现缓慢的均匀腐蚀,没有出现点蚀穿孔现象。为了弄清波纹管穿孔的原因及机理,采用扫描电镜、数码显微镜及金相显微镜分别对黑化处理及钝化处理的不锈钢腐蚀形貌及金相组织结构进行观察。利用X射线衍射仪(XRD)和化学成分分析技术分别对腐蚀产物的相结构及不锈钢材料的成分进行分析。结果表明,酸洗后钝化膜的破裂和海水中氯离子的残留是形成点蚀穿孔的主要原因;表面黑化之后的波纹管由于表面形成了疏松的物质,在海水中为均匀腐蚀,其腐蚀的速度远低于点蚀速度。     

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.     

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.     

核级316NG控氮奥氏体不锈钢的局部腐蚀行为

采用电化学测试法、点腐蚀试验法、盐雾腐蚀试验法和慢应变速率测试法,分别对比研究了核级316NG控氮奥氏体不锈钢和321奥氏体不锈钢的局部腐蚀行为,并利用扫描电子显微镜、光学显微镜等分别观察腐蚀后不锈钢的表面形貌。结果表明:316NG和321不锈钢晶间腐蚀再活化率分别为3.83%和4.47%,点腐蚀速率分别为10.74g/(m2·h)和45.97g/(m2·h),盐雾腐蚀速率分别为2.14×10-2 g/(m2·h)和12.32×10-2 g/(m2·h),应力腐蚀开裂敏感指数分别为0.078和0.10;316NG不锈钢中N和Mo元素提高了其耐局部腐蚀性能,因此其耐局部腐蚀性能均优于核电站结构材料321不锈钢的。     

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.     

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.     

Hydrogen effects on the passive film formation and pitting susceptibility of nitrogen containing type 316L stainless steels

The effects of hydrogen on the passivity and pitting susceptibility of type 316L stainless steels have been investigated with alloys containing different nitrogen contents (0.015, 0.198 and 0.556 wt.% N). The study revealed that electrochemically pre-charged hydrogen significantly reduced the pitting resistance of alloys conatining 0.015 and 0.198 wt.% nitrogen contents. In alloy with highest nitrogen content (0.556 wt.% N), an increase in the passive film current density with hydrogen was observed without affecting breakdown potential. Auger electron spectroscopy (AES) analysis of the passive film indicated the presence of nitrogen in the passive film. On other hand, for hydrogen charged samples, nitrogen was found to be significantly less in the passive film. In Electrochemical impedance spectroscopy (EIS) measurement, the decrease in semi-circle radius of Nyquist plot, and the polarization resistance, R_P associated with the resistance of the passive film was observed with hydrogen, indicating that hydrogen decreased the stability of the passive film. The present investigation indicated that precharged hydrogen deteriorated the passive film stability and pitting corrosion resistance in these alloys, and the increase in nitrogen content of the alloy offsets the deleterious effect of precharged hydrogen.     

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.