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.     

Corrosion resistance of different steel grades in the geothermal fluid of Molasse Basin

Long‐term corrosion resistance of carbon steels grade API L80 and API Q125 has been evaluated by means of electrochemical measurements and exposure tests in the Molasse Basin, one of the most important geothermal fluids in Europe. In addition, the localized corrosion resistance of the duplex stainless steel alloy 2205 and the austenitic stainless steel grade 316L was determined at 100 and 150 °C. In general, investigated materials showed a remarkable resistance to uniform and localized corrosion. Their corrosion behaviour at service conditions is discussed in this paper.     

Studies on Stress Corrosion Cracking of Super 304H Austenitic Stainless Steel

Stress corrosion cracking (SCC) is a common mode of failure encountered in boiler components especially in austenitic stainless steel tubes at high temperature and in chloride-rich water environment. Recently, a new type of austenitic stainless steels called Super304H stainless steel, containing 3% copper is being adopted for super critical boiler applications. The SCC behavior of this Super 304H stainless steel has not been widely reported in the literature. Many researchers have studied the SCC behavior of steels as per various standards. Among them, the ASTM standard G36 has been widely used for evaluation of SCC behavior of stainless steels. In this present work, the SCC behavior of austenitic Fe-Cr-Mn-Cu-N stainless steel, subjected to chloride environments at varying strain conditions as per ASTM standard G36 has been studied. The environments employed boiling solution of 45 wt.% of MgCl₂ at 155 °C, for various strain conditions. The study reveals that the crack width increases with increase in strain level in Super 304H stainless steels.     

Corrosion‐technical properties of high‐strength stainless steels for the application in prestressed concrete structures

Experience with prestressed concrete over about half a century has indicated that the corrosion resistance of conventional prestressing steel does not always satisfy, especially the prestressing steels are susceptible to chloride attack (de‐icing salts) and hydrogen (hydrogen‐induced stress corrosion cracking). On the other hand corrosion agents, such as chloride, condensation water, can penetrate in the concrete and arrive at the surface of steels. Hence, corrosion damage of prestressing steels can happen and, in the extreme cases, the prestressed concrete structure collapsed resulting from the failure of the tendon. In this paper, consideration is made to use high‐strength stainless steels as prestressing tendon with bond in concrete. The high‐strength stainless steels of qualities 1.4301 (X5CrNi18‐10), 1.4401 (X5CrNiMo17‐12‐2), 1.4436 (X3CrNiMo17‐13‐3) and 1.4439 (X3CrNiMoN17‐13‐5) with sequence of increasing austenite stability were investigated. For application in prestressing tendon with bond in concrete the cold‐drawn high‐strength stainless steel of quality 1.4401 is an optimal proposition regarding its satisfactory resistance against pitting corrosion and stress corrosion cracking (SCC) in structure‐related corrosive conditions. The lower alloyed steel 1.4301 has an insufficient resistance against the chloride‐induced corrosion because of the lack of molybdenum and the content of deformation martensite due to the strong cold‐drawing of its unstable austenitic structure.     

22Cr双相不锈钢与304L、316L钢在氯化物溶液中耐应力腐蚀性能的比较

采用恒载荷法、恒应变法研究了22Cr双相不锈钢在不同Cl-浓度、不同温度的氯化物渗液中耐应力腐蚀的性能,并与316L和304L普通奥氏体不锈钢进行了对比.结果表明,22Cr双相不锈钢在氯化物环境中具有更好的应力腐蚀破裂(SCC)抗力.     

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.     

Localized corrosion properties of low interstitial ferritic,high purity austenitic and high chromium duplex stainless steels

Within the framework of a research aimed at characterizing the behaviour of new materials to pitting and crevice corrosion, an investigation has been made, using electrochemical techniques, of the following materials: ELI ferritic stainless steels (18 Cr-2 Mo-Ti; 21 Cr-3 Mo-Ti; 26 Cr-1 Mo); high chromium duplex stainless steel (Z 5 CNDU 21-08) and high chromium-nickel austenitic stainless steel (Z 2 CNDU 25-20); commercial austenitic stainless steels (AISI 304 L and 316 L) and laboratory heats of austenitic stainless steels with low contents of interstitials (LTM/18 Cr- 12 Ni, LTM/16 Cr- 14 Ni-2 Mo). It was possible to graduate a scale of resistance to pitting and crevice corrosion in neutral chloride solutions at 40 C; in particular the two experimental austenitic stainless steels LTM/18 Cr- 12 Ni and LTM/16 Cr- 14 Ni-2 Mo are at the same level as the AISI 316 L and 18 Cr-2 Mo-Ti, respectively. An occluded cell was developed and used for determining the critical potential for crevice corrosion (E_{localized corrosion}). For the steels under investigation E_{localized corrosion} is less noble than E_pitting especially for ELI ferritic 18 Cr-2 Mo-Ti and 21 Cr–3 Mo-Ti.     

Oberflächenbehandlung als Korrosionsschutzmaßnahme von nichtrostenden Stählen

Surface treatment as corrosion protection measure of stainless steels The pickling behaviour of several stainless austenitic steels and of one steel with ferritic/austenitic grain structure were investigated in pickling solutions of different compositions based on hydrofluoric acid. Because of uncertainties in practical applications, the influence of temperature, time and acid content on the mass loss is of high interest. In another series of experiments, aqueous solutions of citric acid were tested for their suitability as pickling chemicals for the materials X 6 CrNiTi 18 10 (AISI 321) and X 6 CrNiMoTi 17 12 2 (AISI 316 Ti). Finally, the pickling procedures based on nitric acid/hydrofluoric acid mixtures were compared with mechanical cleansing methods and with pickling procedures based on aqueous citric acid solutions as well, to elucidate their influence on the corrosion resistance of the treated materials. The valuation followed a pitting corrosion test in sodium chloride solutions of different concentrations after Herbsleb and Schwenk. Pickling with hydrofluoric acid solutions is superior to other cleansing procedures, if corrosive environments are present. The ecologically beneficial citric acid solutions are only able to remove the annealing colours from stainless steels.     

节镍型不锈钢的耐腐蚀性能比较

通过3.5%NaCl溶液中动电位极化曲线测定和中性盐雾试验,对200系列奥氏体不锈钢和400系列铁素体不锈钢两类节镍型不锈钢与304不锈钢的耐腐蚀性能进行了对比研究。结果显示,400系列铁素体不锈钢的耐点蚀性能优于200系列奥氏体不锈钢,两种节镍型不锈钢的耐点蚀性能均不如304不锈钢好;200系列奥氏体不锈钢的耐均匀腐蚀性能最差,443不锈钢耐均匀腐蚀性能与304不锈钢相当,439不锈钢比304不锈钢耐均匀腐蚀性能稍差。201、202、304、439和443不锈钢在3.5%NaCl溶液中的点蚀电位分别为(vs.SCE)-32 mV、-22 mV、312mV、165 mV和227 mV,腐蚀速率分别为0.0071 mm/a、0.0062 mm/a、0.0026 mm/a、0.0038 mm/a和0.0024mm/a。     

改性纳米SiC粉体强化铸造奥氏体不锈钢耐点蚀性能的研究

在生产条件下采用冲入法制备了改性纳米SiC粉体强化奥氏体不锈钢试样,用化学浸泡和电化学检测两种方法研究了纳米SiC粉体对不锈钢耐点蚀性能的影响。结果表明,经改性纳米SiC粉体强化处理后的不锈钢组织明显细化,成分偏析引起的铁素体析出减少;当纳米SiC粉体加入量为0.1 mass%时,不锈钢的点蚀速率降低了 16%,电极电位提高了3倍。能谱分析表明,经强化处理,不锈钢中的Cr成分偏析减轻,有效改善了晶界等易发生点蚀部位的贫Cr现象。     

The effect of CeCl3 inhibitor on the localized corrosion of stainless steel in chloride solutions

Stainless steels have been used extensively in many sectors such as medical and household appliances as well as construction. This has been primarily due to their high resistance to corrosion attacks, reasonable cost, and excellent mechanical properties. However, when placed in corrosive media stainless steel is susceptible to localized corrosion attacks, especially when placed in chloride solutions. The paper explores the issue of corrosion liability of austenitic (AISI 316) and duplex (UNS S32205) stainless steels in et aconditions of seawater environment as well as under the influence of an inhibitor in the same environmental conditions. The behavior of stainless steels was examined via electrochemical testing relying on DC and AC techniques, optical metallographic analysis, scanning electron microscopy, and X‐ray diffraction analysis. Duplex stainless steel showed better resistance to localized corrosion but a higher tendency toward general corrosion in all examined solutions. Cerium chloride in a chloride solution showed inhibiting properties for both the AISI 316 and the UNS S32205.     

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。     

不同热处理态的304和321奥氏体不锈钢在氯化铵环境中的应力腐蚀行为对比研究

目的 对比研究原始、固溶和敏化态的304和321奥氏体不锈钢在模拟加氢催化氯化铵环境中的应力腐蚀（SCC）行为及机理。方法 将304和321奥氏体不锈钢经过热处理制备成固溶和敏化态试样,采用U形弯试样在模拟加氢催化氯化铵环境中浸泡的应力腐蚀试验方法对其进行研究,通过观察U形弯弧顶的腐蚀形貌和开裂时间,并结合腐蚀及裂纹的SEM照片和电化学测试结果进行分析。结果 原始和固溶状态304不锈钢U形弯试样在氯化铵溶液环境中开裂时间为25 d左右,断口形貌分别为穿晶断口和沿晶断口;敏化态试样18 d后发生开裂,断口形貌为穿晶和沿晶的混合断口。原始和固溶态321不锈钢U形弯试样在该环境中经过39 d均无应力腐蚀裂纹;敏化试样经30 d后产生宏观开裂。电化学测试结果显示,不同热处理态的304不锈钢在氯化铵溶液中均具有明显的点蚀敏感性,321不锈钢在该环境中耐点蚀和应力腐蚀的能力优于304不锈钢。结论 不同状态的304不锈钢在高温氯化铵环境中具有较强的应力腐蚀倾向,特别是敏化态试样;321不锈钢在该环境中的应力腐蚀敏感性相对较小,但敏化处理显著增加了其沿晶应力腐蚀倾向,而固溶态试样具有明显的沿晶腐蚀特征。     

Corrosion resistance of stainless steel pipes in soil

To be able to give safe recommendations concerning the choice of suitable stainless steel grades for pipelines to be buried in various soil environments, a large research programme, including field exposures of test specimens buried in soil in Sweden and in France, has been performed. Resistance against external corrosion of austenitic, super austenitic, lean duplex, duplex and super duplex steel grades in soil has been investigated by laboratory tests and field exposures. The grades included have been screened according to their critical pitting‐corrosion temperature and according to their time‐to‐re‐passivation after the passive layer has been destroyed locally by scratching. The field exposures programme, being the core of the investigation, uses large specimens: 2 m pipes and plates, of different grades. The exposure has been performed to reveal effects of aeration cells, deposits or confined areas, welds and burial depth. Additionally, investigations of the tendency of stainless steel to corrode under the influence of alternating current (AC) have been performed, both in the laboratory and in the field. Recommendations for use of stainless steels under different soil conditions are given based on experimental results and on operating experiences of existing stainless steel pipelines in soil.     

Corrosion behavior of a superduplex stainless steel in chloride aqueous solution

Super duplex stainless steels (SDSS) have been widely used as structural materials for chemical plants (especially in those engaged in phosphoric acid production), in the hydrometallurgy industries, and as materials for offshore applications due to their excellent corrosion resistance in chloride environments, compared with other commercial types of ferritic stainless steels. These alloys also possess superior weldability and better mechanical properties than austenitic stainless steels. However, due to their two-phase structure, the nature of which is very dependent on their composition and thermal history, the behavior of SDSS regarding localized corrosion appears difficult to predict, especially in chloride environments. To improve their final properties, the effect of the partition of the alloying elements between the two phases, and the composition and microstructure of each phase are the key to understanding the localized corrosion phenomena of SDSS. This paper concerns the effects of the SDSS microstructure and heat treatment on the SDSS corrosion resistance in aqueous solutions, containing different amounts of NaCl at room temperature.     

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.     

A comprehensive assessment of the performance of corrosion resistant alloys in hot acidic brines for application in oil and gas production

Four stainless steels and alloys (17-4 PH, X4CrNiMo 16-5-1, F6NM and UNS N09935) were evaluated in relation to their application in the oil and gas industry. These materials were tested in solutions exhibiting a range of chloride concentrations, pH values and temperatures of interest for the oil and gas producing environments. The pitting sensitivity was investigated by means of potentiodynamic polarisation measurements, based on the ASTM G61 standard, in conjunction with a morphological study performed by scanning electron and optical microscopy. The resistance to stress corrosion cracking (SCC) was evaluated in compliance with the ASTM G123 standard. Erosion–corrosion was assessed by exposing the materials under electrochemical control to a flux of erodent glass microspheres in a rotating disc electrode device. A ranking of the materials resistance was derived, based on appropriate parameters, devised to effectively and synthetically represent the complex sets of environments of interest for the relevant application. Our results showed, as expected, that UNS N09935 displays the best performance with respect to pitting resistance and susceptibility to SCC as well as a very good resistance to erosion–corrosion. Among the other investigated materials, 17-4 PH showed higher resistance to pitting, X4CrNiMo 16-5-1 and F6NM longer time to SCC failure while 17-4 PH and X4CrNiMo 16-5-1 exhibited superior ability to withstand erosion–corrosion damaging.     

Spannungsrißkorrosion nichtrostender austenitischer Chrom-Nickel-Stähle bei Raumtemperatur

Stress corrosion cracking of austenitic chromium-nickel stainless steels at ambient temperature For the chloride-induced SCC with transgranular crack path in austenitic 18Cr10Ni stainless steel, a critical temperature between 45 and 50°C exists. This critical temperature, however, is valid only for the passive state of the steel in nearly neutral, chloride-containing aqueous environments. In the active state, SCC with transgranular crack mode can occur at temperatures down to ambient temperature. The active state is caused by highly acidic, high-chloride containing aqueous corrosive media. Adherent aqueous films with these properties can grow on the surface of structural components inside swimming-pools when the water is disinfected by addition of chlorine. Under these conditions, failure of austenitic CrNi and CrNiMo stainless steels by SCC with transgranular crack path at ambient temperature is possible and actually occurred. SCC with preferentially intergranular crack path can also occur at ambient temperature when austenitic stainless steels with a sensitized microstructure are used. Under these conditions, the corrosion attack is caused by non-specific aggressive environments, e.g., adherent aqueous films not containing chloride ions. The crack mode, intergranular or mixed, depends on the stress level.     

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.     

Corrosion behaviour of carbon S-phase created on Ni-free biomedical stainless steel

Following the success of forming a carbon S-phase (expanded austenite) surface layer on medical grade Ni-free austenitic stainless steel by DC plasma carburising, the established commercial carburising process Kolsterising® was performed on both Ni-containing (AISI 304) and Ni-free austenitic stainless steels. While the Ni-containing stainless steel responded very well to Kolsterising®, the Ni-free alloy did not. The carbon absorption and the hardness of the Kolsterised® Ni-free alloy are inferior to Kolsterised® AISI 304 Ni-containing stainless steel, however, the hardness of the untreated Ni-free alloy was doubled by Kolsterising®. The response of both Kolsterised® Ni-free and Ni-containing alloys to pitting, crevice corrosion and intergranular corrosion resistance was similar. From this work it can be concluded that the Kolsterised® austenitic stainless steels do not suffer from intergranular corrosion but are susceptible to intragranular pitting when tested in boiling sulphuric acid and copper sulphate solution. It was also observed that Kolsterising® improves significantly the pitting and crevice corrosion resistance of the alloys used in this study.