Stress corrosion cracking behaviour of stainless steels with respect to their use in architecture,part 2: corrosion in the passive state

Unexpected failures of 18/10 CrNi and 17/12/2 CrNiMo steels in indoor swimming pool atmospheres made it necessary to reinvestigate chloride stress corrosion cracking of stainless steels with respect to their use in arcitecture. A preceding paper presented inwestigations into stress corrosion cracking (SCC) in the active state of corrosion; the present paper deals with SCC In the passive state. The investigations showed that – in contrast to general opinion – stress corrosion cracking in the passive state can occur at temperatures well below 50°C in 18/10 CrNi and 17/12/2 CrNiMo steels, provided the corrosive medium has an extremely high chloride concentration. Other factors such as stress level, pH value or type of kation only exert a subordinate influence. Especially the high alloy austenitic steels 1.4439 and 1.4539 proved SCC-resistant under such conditions at ambient temperatures. Electrolytes with critical chloride concentrations may develop when deposits containing chlorides of sufficiently high solubility (e.g. MgCI₂, CaCl₂) are exposed to an atmoshere with critical, i.e. comparatively low humidity. Such conditions are evidently met only under very specific circumstances such as may occur in indoor swimming pools. In other structures where stainless steels have been used for decades without such damage having occurred to date, these critical conditions appear generally not to be reached.     

The influence of preceding cryoforming and testing temperature on the mechanical properties of austenitic stainless steels

The TRIP effect in austenitic stainless steels leads to temperature dependent mechanical properties. As this is caused by stress or strain induced austenite/martensite transformation a predeformation at low temperatures (cryoforming) will change the microstructure and the transformation behaviour of the remaining austenite constituent. The mechanical properties in tensile tests and the J‐integral of the chromium and nickel alloyed steels 1.4301 and 1.4571 have been tested in the temperature range from 123 to 323 K in the as‐industrially supplied condition and after 10 % cryoforming at 77 K. The temperature dependence of the elongation values and the strain hardening behaviour of the undeformed steels is much more pronounced than of the yield and tensile strength. The mechanical behaviour can be explained by differences in response to the ?‐, the α_e'‐ and the α_g'‐martensite transformation. A cryoforming changes the mechanical properties of the examined austenitic stainless steels.     

Improvement of the resistance to stress corrosion cracking in austenitic stainless steels by cyclic prestraining

Austenitic stainless steels are known to be sensitive to stress corrosion cracking (SCC) in hot chloride solutions. The aim of the present study is to find improvements in the SCC behavior of 316L-type austenitic stainless steels in 117°C MgCl₂ solutions. Previously, the authors have proposed the “corrosion-enhanced plasticity model” (CEPM) to describe the discontinuous cracking process which occurs in SCC. This model is based on localized corrosion (anodic dissolution, and hydrogen absorption)-deformation (dislocations) interactions (CDI). From the framework of this model, it is proposed that a prestraining in fatigue at saturation decreases the SCC sensitivity. This idea is experimentally confirmed for both crack initiation and crack propagation, through the analysis of the SCC behavior by slow-strain-rate tests of single and polycrystals after different prestraining conditions.     

Stress Corrosion Cracking—Crevice Interaction in Austenitic Stainless Steels Characterized By Acoustic Emission

Stress corrosion cracking (SCC) susceptibility of austenitic EN1.4301 (AISI 304) and EN1.4404 (AISI 316L) stainless steels was studied using the constant load method and polymer (PTFE) crevice former in order to study the effects of crevice on SCC susceptibility. The uniaxial active loading tests were performed in 50 pct CaCl2 at 373 K (100 °C) and in 0.1 M NaCl at 353 K (80 °C) under open-circuit corrosion potential (OCP) and electrochemical polarization. Pitting, crevice, and SCC corrosion were characterized and identified by acoustic emission (AE) analysis using ∆t filtering and the linear locationing technique. The correlation of AE parameters including amplitude, duration, rise time, counts, and energy were used to identify the different types of corrosion. The stages of crevice corrosion and SCC induced by constant active load/crevice former were monitored by AE. In the early phase of the tests, some low amplitude AE activity was detected. In the steady-state phase, the AE activity was low, and toward the end of the test, it increased with the increasing amplitude of the impulses. AE allowed a good correlation between AE signals and corrosion damage. Although crevice corrosion and SCC induced AE signals overlapped slightly, a good correlation between them and microscopical characterization and stress-strain data was found. Especially, the activity of AE signals increased in the early and final stages of the SCC experiment under constant active load conditions corresponding to the changes in the measured steady-state creep strain rate of the specimen. The results of the constant active load/crevice former test indicate that a crevice can initiate SCC even in the mild chloride solution at low temperatures. Based on the mechanistic model of SCC, the rate determining step in SCC is thought to be the generation of vacancies by selective dissolution, which is supported by the low activity phase of AE during the steady-state creep strain rate region.     

The correlation of microstructure and stress corrosion fracture of HY-130 steel weldments

Microstructure is among the most important factors known to affect the stress corrosion cracking (SCC) susceptibility of medium and high strength steels. Multipass welding can produce various microstructures in the weld and heat affected zone on quite a fine scale, so that intimately mixed fracture modes are observed on SCC specimens of such welds. Performance of these welds mirrors the different SCC susceptibilities of the different microstructures. Detailed metallographic observations have been carried out to demonstrate the correlation between the microstructural features and SCC fracture of HY-130 steel weldments. It is shown that the refined microstructures were most resistant to SCC and the accompanying fracture mode was microvoid coalescence. Those microstructures giving rise to the more brittle fracture modes and thus less resistant to SCC were associated with the columnar/coarse equiaxed grain structures of untempered (or slightly tempered) martensite and/or bainite. These results were used as the basis for suggested welding practice to improve the SCC resistance of HY-130 and other medium strength steel weldments. Formerly Post-doctoral Associate at Carnegie-Mellon University     

New Stainless Steel Solutions as Economic Alternatives to Classical 1.4301 Austenitic Grades

In the recent situation of a historically high nickel price, austenitic stainless steels, such as 1.4301, became too expensive compared to their actual technical value in many applications. This paper presents two new stainless steel grades developed by ArcelorMittal to replace 1.4301. The first one is a 20%Cr ferritic grade. The second one is a low‐Ni Cu‐bearing austenitic grade. The choices in the compositions are described as a function of the technical requirements, economical target and the production process limitations. The final properties are discussed as a function of the composition and compared with 1.4301 and other existing stainless steels. Finally, the complementarities of these two new grades are highlighted in regard to the different application markets considered.     

Initiation of stress corrosion cracking for pipeline steels in a carbonate-bicarbonate solution

The linearly increasing stress test (LIST) was used to study the stress corrosion cracking (SCC) behavior of a range of pipeline steels in carbonate-bicarbonate solution under stress rate control at different applied potentials. Stress corrosion cracking, at potentials below -800 mV(SCE), was attributed to hydrogen embrittlement. Stress corrosion cracking, in the potential range from about-700 to -500 mV(SCE), was attributed to an anodic dissolution mechanism. In the anodic potential region, the SCC initiation stress was larger than the yield stress and was associated with significant plastic deformation at the cracking site. The relative SCC initiation resistance decreased with in-creasing yield strength. In the cathodic potential region, the SCC initiation stress was smaller than the yield stress of steel; it was approximately equal to the stress at 0.1 pct strain(@#@ Σ_0.1pct) for all the steels. The original surface was more susceptible to SCC initiation than the polished surface.     

Stress corrosion cracking of stainless steels in NaCl solutions

The metallurgical influences on the stress corrosion resistance of many commercial stainless steels have been studied using the fracture mechanics approach. The straight-chromium ferritic stainless steels, two-phase ferritic-austenitic stainless steels and high-nickel solid solutions (like alloys 800 and 600) investigated are all fully resistant to stress corrosion cracking at stress intensity (K₁) levels ≤ MN • m-^3/2 in 22 pct NaCl solutions at 105 °C. Martensitic stainless steels, austenitic stainless steels and precipitation hardened superalloys, all with about 18 pct chromium, may be highly susceptible to stress corrosion cracking, depending on heat treatment and other alloying elements. Molybdenum additions improve the stress corrosion cracking resistance of austenitic stainless steels significantly. The fracture mechanics approach to stress corrosion testing of stainless steels yields results which are consistent with both the service experience and the results from testing with smooth specimens. In particular, the well known “Copson curve” is reproduced by plotting the stress corrosion threshold stress intensity (AT_ISCC) vs the nickel content of stainless steels with about 18 pct chromium. Formerly with the BBC Brown Boveri Company, Baden, Switzerland     

Effect of different Cr contents on tensile and corrosion behaviors of 0.13 pct N-containing CD4MCU cast duplex stainless steels

The tensile and corrosion behaviors of 0.13 pct N-containing CD4MCU cast duplex stainless steels with different Cr contents ranging from 23 to 28 pct were examined in the present study. The polarization tests were conducted in 3.5 pct NaCl + 5 pct H₂SO₄ aqueous solution for general corrosion resistance, and the in-situ slow strain rate (SSR) tests were also conducted in air and 3.5 pct NaCl + 5 pct H₂SO₄ aqueous solution to quantify the resistance to stress corrosion cracking (SCC) of the three materials. A substantial microstructural change in 0.13 pct N-containing CD4MCU cast duplex stainless steel was observed with different Cr contents, which in turn affected the tensile and corrosion behaviors significantly. Tensile behavior of 0.13 pct N-containing CD4MCU cast duplex stainless steel, for example, varied in a nonlinear manner with different Cr contents due to the volume change of hard ferritic phase and the presence of the second precipitates of soft austenitic phase in the ferrite matrix. The beneficial effect of Cr for improving the general corrosion and the SCC resistances was largely overshadowed by this variation in microstructural characteristics. The relationship between the microstructural evolution and the tensile and corrosion behavior of 0.13 pct N-containing CD4MCU cast duplex stainless steels with different Cr contents was discussed based on the optical microscopy and scanning electron microscopy (SEM) micrographic and fractographic observations.     

Stress corrosion cracking of pressure vessel steels in high-temperature caustic aluminate solutions

Stress corrosion cracking (SCC) behavior of three kinds of low alloy pressure vessel steels in high-temperature (200 °C to 300 °C) caustic aluminate (AIO_-2) solutions has been studied by slow strain rate tests (SSRT). The results indicate that these pressure vessel steels are susceptible to SCC in caustic aluminate solution and that the SCC susceptibility increases with increasing temperature between 200 °C to 300 °C. Sulfide content and stringered sulfide inclusions severely and anisotrop-ically affect the caustic SCC of these low alloy steels. The inclusions in the rare-earth-treated steel are predominantly globular rare-earth sulfides or oxysulfides, resulting in improved transverse prop-erties. The effect of inclusions on SCC behavior correlates with the projected area of inclusions perunit volume at the crack tip,A _v , on the plane perpendicular to the tensile direction. The susceptibility to SCC increases with increasingA _v .     

合金元素对油船用低合金钢腐蚀行为的影响

采用恒温浸泡的标准试验方法,考察了4种不同合金体系船体钢在强酸性氯离子介质中的腐蚀行为,探讨了合金元素对钢腐蚀行为的影响,结果表明:Cu和Ni对钢的耐蚀性有显著影响,随着Cu、Ni含量的增加,钢的耐蚀性逐渐提高,自腐蚀电位提高,电流密度显著降低,界面电荷传递电阻明显增大。Cu是提高钢在强酸性氯离子环境中耐蚀性的主要元素,其主要机理为其以再沉积颗粒(100~500nm)的方式在钢的表面富集,并具有较高的稳定性,该沉积颗粒钝化了钢基体,降低了钢的溶解速度。Ni元素在钢中的存在显著提高了钢的基体电位,降低了材料的腐蚀敏感性,但Ni元素在锈层中的富集特征不明显。     

高温浓硫酸中氟离子掺入对不锈钢耐蚀性能的影响

采用浸泡法和电化学测试方法结合扫描电镜和能谱仪研究了高温浓硫酸中氟离子的掺入对304、2507以及904L三种不锈钢耐蚀性能的影响.结果表明:氟离子的掺入对三种不锈钢在浓硫酸中的腐蚀具有抑制作用,综合来看,904L具有更为稳定的耐蚀性能;三种不锈钢在高温浓硫酸中由于生成了热力学不稳定的硫化镍而产生了活化转钝化现象,而掺入氟离子会和硫离子发生竞争使其排挤出电极表面,氟离子与镍离子结合形成另外一种更稳定的阻挡层使不锈钢耐蚀性提高.      

Effect of N addition on tensile and corrosion behaviors of CD4MCU cast duplex stainless steels

The effect of N addition on the microstructure, tensile, and corrosion behaviors of CD4MCU (Fe-25Cr-5Ni-2.8Cu-2Mo) cast duplex stainless steel was examined in the present study. The slow strain rate tests were also conducted at a nominal strain rate of 1 × 10⁻⁶/s in air and 3.5 pct NaCl+5 pct H₂SO₄ solution for studying the stress corrosion cracking (SCC) behavior. It was observed that the volume fraction of austenitic phase in CD4MCU alloy varied from 38 to 59 pct with increasing nitrogen content from 0 to 0.27 wt. pct. The tensile behavior of CD4MCU cast duplex stainless steels, which tended to vary significantly with different N contents, appeared to be strongly related to the volume changes in ferritic and austenitic phases, rather than the intrinsic N effect. The improvement in the resistance to general corrosion in 3.5 pct NaCl+5 pct H₂SO₄ aqueous solution was notable with 0.13 pct N addition. The further improvement was not significant with further N addition. The resistance to SCC of CD4MCU cast duplex stainless steels in 3.5 pct NaCl+5 pct H₂SO₄ aqueous solution, however, increased continuously with increasing N content. The enhancement in the SCC resistance was believed to be related to the volume fraction of globular austenitic colonies, which tended to act as barriers for the development of initial pitting cracks in the ferritic phase into the sharp ones.     

Effect of cold work on stress corrosion cracking behavior of types 304 and 316 stainless steels

The influence of cold work (prestraining) in the range 2.3 to 56 pct on stress corrosion cracking (SCC) properties of types 304 and 316 stainless steels in boiling MgCl2 solution at 154 °C was investigated using a constant load method. In both materials, SCC initiation was in transgranular mode. Transition in stress corrosion cracking mode from transgranular to intergranular, as the crack proceeds, was observed at all cold work levels in 316 stainless steel and at cold work levels of 26 pct and 56 pct in 304 stainless steel. Both prestraining and increase in the initial applied stress facilitated the transition in crack morphology to intergranular mode. Increased tendency to intergranular SCC at high applied stresses and in cold worked specimens appears to be mechanistically analogous.     

Effect of cold work on stress corrosion cracking behavior of types 304 and 316 stainless steels

The influence of cold work (prestraining) in the range 2.3 to 56 pct on stress corrosion cracking (SCC) properties of types 304 and 316 stainless steels in boiling MgCl2 solution at 154 °C was investigated using a constant load method. In both materials, SCC initiation was in transgranular mode. Transition in stress corrosion cracking mode from transgranular to intergranular, as the crack proceeds, was observed at all cold work levels in 316 stainless steel and at cold work levels of 26 pct and 56 pct in 304 stainless steel. Both prestraining and increase in the initial applied stress facilitated the transition in crack morphology to intergranular mode. Increased tendency to intergranular SCC at high applied stresses and in cold worked specimens appears to be mechanistically analogous.     

Stress corrosion cracking of stainless steels

The similarities and differences in the stress corrosion cracking response of ferritic and austenitic stainless steels in chloride solutions will be examined. Both classes of materials exhibit a cracking potential: similar transient response (to loading) of the potential in open circuit tests or the current in potentiostatic tests and similar enrichment of chromium and depletion of iron in the film associated with localized corrosion processes. The ferritic steels are more resistant to localized corrosion than are the austenitic steels, which is responsible for the difference in the influence of prior thermal and mechanical history on cracking susceptibility of the two types of steel. Similarities in the fractography of stress corrosion cracks and those produced by brittle delayed failure during cathodic charging of the ferritic steels indicate that hydrogen embrittlement is involved in the failure process.     

Sensitization Behaviour of Manganese‐Alloyed Austenitic Stainless Steels

Manganese is an essential alloying element in advanced austenitic stainless steels with specific properties such as high resistance to harsh corrosive environments, high strength or low material costs. These materials are often used for welded constructions which have to be highly corrosion resistant. Hence it has to be ensured that the heat input during welding does not initiate the precipitation of chromium carbide resulting in a susceptibility to intergranular corrosion. This leads to the question whether the sensitization behaviour of manganese‐alloyed austenitic stainless steels is comparable to that of the well‐known conventional chromium nickel austenites. In the present work the effect of heat‐input on the susceptibility of the CrNi‐steel 1.4301 and the CrNiMn‐steel 1.4376 to intergranular corrosion (IGC) was considered. Investigations were carried out by corrosion testing in the so‐called Strauss‐Test to elucidate the effect of the annealing temperatures on the microstructure. Furthermore, the influence of heat treatment on the mechanical properties was evaluated by tensile testing. As a result, it could be demonstrated that manganese‐alloyed austenitic stainless steels like grade 1.4376 exhibit a sensitization behaviour very similar to the conventional austenitic steel grades. The same kinds of tests on intergranular corrosion resistance can be applied for both types of materials.     

Stress corrosion cracking behavior of PH13-8Mo stainless steel in Cl-solutions

The stress corrosion cracking (SCC) behavior of PH13-8Mo precipitation hardening stainless steel (PHSS) in neutral NaCl solutions was investigated through slow-strain-rate tensile (SSRT)test at various applied potentials.Fracture morphology,elongation ratio,and percentage reduction of area were measured to evaluate the SCC susceptibility.A critical concentration of 1.0mol/L neutral NaCl existed for SCC of PH13-8Mo steel.Significant SCC emerged when the applied potential was more negative than-0.15 VSCE,and the SCC behavior was controlled by an anodic dissolution (AD) process.When the applied potential was lower than-0.55 VSCE,an obvious hydrogen-fracture morphology was observed,which indicated that the SCC behavior was controlled by hydrogen-induced cracking (HIC).Between-0.15 and-0.35 VSCE,the applied potential exceeded the equilibrium hydrogen evolution potential in neutral NaCl solutions and the crack tips were of electrochemical origin in the anodic region;thus,the SCC process was dominated by the AD mechanism.     

Thermodynamic analysis on the role of hydrogen in anodic stress corrosion cracking

A synergistic effect of hydrogen and stress on a corrosion rate was analyzed with thermodynamics. The results showed that an interaction of stress and hydrogen could increase the corrosion rate remarkably. Stress corrosion cracking (SCC) of austenitic stainless steel (ASS) was investigated in boiling chloride solution to confirm the analysis. Hydrogen could be introduced into the specimen and concentrated at the crack tip during SCC in boiling LiCl solution (143°C). The concentrating factor is about 3 which is consistent with calculated results according to stress induced diffusion.     

Localised corrosion behaviour of high and low nitrogen Cr-Mn steels

It is well established that addition of nitrogen to steels improves the pitting corrosion resistance of steels. To elucidate the role of nitrogen, electrochemical and surface analytical studies were carried out on Cr-Mn steels with low (0.0075 %) and high (0.9 %) nitrogen contents. The incubation time for pitting, measured in sodium sulphate solutions containing different concentrations of chloride was higher for the high nitrogen steel. The pit initiation process was found to be first order with respect to chloride concentration. The passive current density was one order lower than that of nitrogen free steel. The grain broundary attack observed in low nitrogen steel was not present in high nitrogen steel. XPS analysis indicated nitrogen enrichment at the surface in the passive layer. This may be one reason for the higher pitting resistance of nitrogen containing steel besides formation of ammonium ions and rising pH.