Stress corrosion cracking and hydrogen embrittlement of sensitized austenitic stainless steels in boiling saturated magnesium chloride solutions

Stress corrosion cracking (SCC) and hydrogen embrittlement (HE) of the sensitized stainless steels of type 304, 310 and 316 were investigated as a function of test temperature in boiling saturated magnesium chloride (MgCl₂) solutions under a constant applied stress condition. The test temperature dependence of fracture appearance and three parameters of time to failure (t_f), steady-state elongation rate (l_ss) and transition time to time to failure ratio (t_ss/t_f) suggests that type 304 suffered SCC and HE, while type 316 suffered only HE and type 310 SCC. It was also found that the test temperature dependence of three parameters for the sensitized type 304 and 310 was almost similar to that of the solution annealed stainless steels, whereas that of type 316 showed a clear difference between sensitized and solution annealed specimens. The relationships between the logarithms of the time to failure and the steady-state elongation rate became a straight line for all stainless steels. However, its slope depended upon the fracture mode; −2.0 for SCC and −1.5 for HE. This showed that the steady-state elongation rate was the parameter for predicting the time to failure for the stainless steels in the MgCl₂ solutions. The results obtained were explained in terms of martensite transformation, hydrogen entry site, sensitization, and so on.     

On the stress corrosion cracking and hydrogen embrittlement of sensitized austenitic stainless steels in boiling saturated magnesium chloride solutions: Effect of applied stress

Stress corrosion cracking (SCC) and hydrogen embrittlement (HE) of sensitized stainless steels of types 304, 310 and 316 were investigated as a function of applied stress at different test temperatures in boiling saturated magnesium chloride (MgCl₂) solutions under a constant applied stress condition. The stress dependence of fracture appearance and three parameters of time to failure (t_f), steady-state elongation rate (l_ss) and transition time to time to failure ratio suggests that types 304 and 310 suffered SCC, while type 316 suffered only HE. It was also found that the applied stress dependence of three parameters for the sensitized types 304 and 310 was almost similar to that of the solution-annealed stainless steels, whereas that of type 316 showed a clear difference between sensitized and solution-annealed specimens. The relationships between the logarithms of the time to failure and the steady-state elongation rate became a straight line for all stainless steels. However, its slope depended upon the fracture mode: −2.0 for SCC and −1.5 for HE. This showed that the steady-state elongation rate was a good parameter for predicting the time to failure for the stainless steels in the MgCl₂ solutions. The results obtained were explained in terms of martensite transformation, hydrogen entry site, and sensitization.     

The effect of test temperature on SCC behavior of austenitic stainless steels in boiling saturated magnesium chloride solution

The stress corrosion cracking (SCC) of the austenitic stainless steels of types 304, 310 and 316 was investigated as a function of test temperature in boiling saturated magnesium chloride solution (MgCl₂) using a constant load method. Both of types 304 and 316 exhibited similar corrosion elongation curves, while the corrosion elongation curve of type 310 was different from those of types 304 and 316, in terms of the three parameters such as time to failure (t_f), steady-state elongation rate (l_ss) and transition time to time to failure ratio (t_ss/t_f) obtained from the corrosion elongation curves for these stainless steels. The relationship between the time to failure and a reciprocal of test temperature fell in two straight lines on a semi-logarithmic scale as well as the relationship between the steady-state elongation rate and a reciprocal of test temperature. These regions were considered to correspond to a SCC-dominated region and a hydrogen embrittlement (HE)-dominated region from the value of (t_ss/t_f) and the fracture appearance. The relationship between the steady state elongation rates versus time to failure on a logarithmic scale became a straight line, whereas the slopes of the line for the stainless steels were different with the different fracture mechanism such as SCC and HE. It was found that the linearity of the relationship can be used to predict the time to failure for the stainless steels in the corrosive environment. In addition, type 310 did not suffer from HE, which means that type 310 showed only SCC. This would be explained by whether or not a formation of α′-martensite takes place.     

A hydrogen embrittlement mechanism for sensitized types 304, 316 and 310 austenitic stainless steels in boiling saturated magnesium chloride solutions

We have already proposed a mechanism for intergranular hydrogen embrittlement (IG-HE) for solution annealed austenitic stainless steels (types 304, 316 and 310) in HCl solutions and in boiling saturated magnesium chloride solutions. The proposed IG-HE mechanism was based on martensite transformation, hydrogen-enhanced local plasticity (HELP), grain boundary sliding (GBS). Recently, it was reported that the fracture susceptibility and fracture mode for sensitized steels in boiling saturated magnesium chloride solution under an open-circuit condition were significantly different from those observed for solution annealed steels. In the present paper, the hydrogen embrittlement behavior of sensitized types 304, 316 and 310 in boiling saturated magnesium chloride solutions was explained in more details in terms of an inhibiting effect of chloride ions, martensite transformation, Cr depletion, HELP, the degree of corrosiveness through the comparison with those for the solution annealed steels. Furthermore, a transgranular HE (TG-HE) cracking mode that was not observed for the solution annealed steels was discussed as well as IG-HE. Then a TG-HE mechanism for sensitized austenitic stainless steels was proposed, while the IG-HE mechanism for solution annealed austenitic stainless steels which was discussed in details was applied to IG-HE of sensitized austenitic stainless steels. It was also pointed out that the occurrence of both TG-HE and IG-HE was explained with an identical concept.     

Characterization and perspective of stress corrosion cracking of austenitic stainless steels (type 304 and type 316) in acid solutions using constant load method

The stress corrosion cracking (SCC) of the commercial austenitic stainless steels, type 304 and type 316 has been extensively investigated as functions of applied stress, sensitizing temperature, sensitizing time and the environmental factors such as pH, anion concentration, anion species (chloride ions and sulfate ions), test temperature, applied potential and inhibitor concentrations of chromate and molybdate by using a constant load method. We have found that the steady state elongation rate obtained from corrosion elongation curve becomes a relevant parameter for predicting time to failure and also for criterion on assessment of whether SCC takes place or not. The value of t_ss/t_f is also found to become an indicator for assessment of whether SCC takes place or not. Furthermore, from the results obtained, it is deduced that a unified SCC mechanism is qualitatively proposed to explain both of transgranular SCC (TGSCC) and intergranular SCC (IGSCC), where the unified SCC mechanism is basically based on a film rupture- formation event at crack tips.     

Impact of temperature excursion on stress corrosion cracking of stainless steels in chloride solution

The impact of a temperature excursion on the subsequent stress corrosion crack growth at the normal operating temperature has been investigated for 321 stainless steel (UNS32100) and 316L stainless steel (UNS31603) using precracked compact tension specimens. Although the data are preliminary the indication is that once crack growth has initiated in 321 SS at the elevated temperature, 130 °C in this study, the crack growth may be sustained at the lower temperature (40 °C), at least over the exposure time of about 700 h. However, the growth rate of 316L SS at the lower temperature was significantly lower than for 321 SS and tended to zero after 2000 h. For the 316 SS a temperature transient should not impact on structural integrity, provided it is short in duration.     

Effect of N and C on stress corrosion cracking susceptibility of austenitic Fe18Cr10Mn-based stainless steels

Stress corrosion cracking (SCC) susceptibility of austenitic Fe18Cr10Mn alloys with 0.3N, 0.6N and 0.3N0.3C was investigated in aqueous chloride environment using a slow strain rate test method. The SCC susceptibility of Fe18Cr10Mn alloys in 2 M NaCl solution at 50 °C under constant anodic potential condition decreased with increase in N content from 0.3 to 0.6 wt%, and with addition of 0.3 wt% C to the Fe18Cr10Mn0.3N alloys. The present study strongly suggested that the beneficial effects of N and C on the SCC behavior of Fe18Cr10Mn alloys would be associated with the resistance to pitting corrosion initiation and the repassivation kinetics.     

The effect of sensitizing temperature on stress corrosion cracking of type 316 austenitic stainless steel in hydrochloric acid solution

The stress corrosion cracking (SCC) of a commercial austenitic stainless steel type 316 was investigated as a function of sensitizing temperature (750-1300 K) and test temperature (333-373 K) in 0.82 kmol/m³ hydrochloric acid (HCl) solution by using a constant load method. From the applied stress dependence of three parameters (i_ss: steady state elongation rate, t_ss: time interval of SCC-dominated failure, t_f: time to failure), the relationships between applied stress and the three parameters were divided into three regions that are dominated by either stress, SCC or corrosion. In the SCC-dominated region, the logarithm of i_ss was a linear function of the logarithm of t_f irrespective of applied stress and test temperature, although its slope depended upon sensitizing temperature. This result showed that the i_ss became a useful parameter for prediction of t_f as well as the case of the solution annealed specimens. Furthermore, at the most severe sensitization with a sensitizing temperature of around 1000 K, the slope of the linear function of log i_ss vs. log t_f showed a minimum, the value of t_ss/t_f was a maximum and the fracture appearance was an intergranular mode. On the basis of the results obtained, the effect of sensitization on SCC was discussed in comparison to the results for the solution annealed type 316 and a qualitative intergranular SCC (IGSCC) mechanism was inferred.     

Stress corrosion cracking mechanism of prestressing steels in bicarbonate solutions

Prestressing steels occasionally fail by a process named “stress corrosion cracking”. This process has not been fully elucidated and several theories exists in order to explain the cases in which real structures have collapsed. This paper briefly mentions the different theories and identifies the progress in understanding whether it is necessary to use a testing method, which is able to separate the different steps and mechanisms contributing to the failures.This paper presents the methodology used for inducing controlled localized attack to study the susceptibility of the high strength steels resistance to stress corrosion cracking (SCC). The method is designed to study the growth of cracks initiated from a mechanical notch; the crack is not produced by fatigue.It consists of several stages: coating of the bar with epoxy resin, generation of a small notch, constant load and controlled potential test in the media, mechanical test in air and fractographic study. It allows us to calculate the crack propagation rate and the fracture toughness in the same test.Finally, it has been possible to apply the surface mobility mechanism (SMM) in order to identify the SCC mechanism that operates.     

Effect of austenite instability on the hydrogen-enhanced crack growth of austenitic stainless steels

Fatigue crack growth tests were performed to assess the fatigue behavior of AISI 316L and 254 SMO stainless steels (SSs) in air and gaseous hydrogen. 254 SMO SS generally exhibited a greater resistance to fatigue crack growth than 316L. Sensitization treatment had only a marginal effect on the fatigue crack growth behavior of both alloys in air. Moreover, 316L SS exhibited significant hydrogen-enhanced crack growth but 254 SMO, even sensitized 254 SMO specimens, did not. A thin layer of strain-induced martensite was formed on the fatigue-fractured surface of the 316L SS, and its content increased when raising the stress ratio. The thin martensite layer was responsible for the hydrogen-enhanced fatigue crack growth of the 316L SS. By contrast, the extremely stable austenite was responsible for the low susceptibility of 254 SMO SS to hydrogen-accelerated crack growth. The trapping of hydrogen at the grain boundaries and the transformed martensite in the sensitized 316L specimens led to increased fatigue crack growth rates and intergranular fracture of the material.     

Influence of the applied stress rate on the stress corrosion cracking of 4340 and 3.5NiCrMoV steels under conditions of cathodic hydrogen charging

Stress corrosion cracking (SCC) of as-quenched 4340 and 3.5NiCrMoV steels was studied under hydrogen charging conditions, with a cathodic current applied to the gauge length of specimens subjected to Linearly Increasing Stress Test (LIST) in 0.5 M H₂SO₄ solution containing 2 g/l arsenic trioxide (As₂O₃) at 30 °C. Applied stress rates were varied from 20.8 to 6 × 10⁻⁴ MPa s⁻¹. Both the fracture and threshold stress decreased with decreasing applied stress rate and were substantially lower than corresponding values measured in distilled water at 30 °C at the open circuit potential. The threshold stress values correspond to 0.03–0.08 σ_y for 4340 and 0.03–0.2 σ_y for the 3.5NiCrMoV steel. SCC velocities, at the same applied stress rate, were an order of magnitude greater than those in distilled water. However, the plots of the crack velocity versus applied stress rate had similar slopes, suggesting the same rate-limiting step. The fracture surface morphology was mostly intergranular, with quasi-cleavage features.     

Role of nitrite addition in chloride stress corrosion cracking of a super duplex stainless steel

This paper presents the role of addition of nitrite ions in susceptibility of a super duplex stainless steel, SAF 2507 to stress corrosion cracking (SCC) in chloride environment, which has a particular industrial relevance. Slow strain rate testing (SSRT) in 30 wt.% MgCl₂ solution established SCC susceptibility, as evidenced by post-SSRT fractography. However, the addition of nitrite has interesting influence. At their lower concentrations, nitrite additions seem to decrease SCC susceptibility, whereas, at a higher concentration, it has an accelerating effect on SCC. Attempts have been made to understand this behaviour on the basis of the role of nitrite in passivation and pitting characteristics of SAF 2507 in chloride solution.     

Controlling grain boundary energy to make austenitic stainless steels resistant to intergranular stress corrosion cracking

Intergranular corrosion and intergranular stress corrosion cracking are the two localized corrosion mechanisms that are of concern to the typical applications of austenitic stainless steels in industries. Until recently, the common understanding was that a higher frequency of random boundaries increases the susceptibility, caused by a sensitization heat treatment or by operating temperatures, of austenitic stainless steels to both intergranular corrosion and intergranular stress corrosion cracking. A recent study demonstrated that extreme randomization of grain boundaries leads to a considerable improvement of resistance to both sensitization and intergranular corrosion. This work is a continuation of Ref. 1 and relates the effects of grain boundary randomization to intergranular stress corrosion cracking: the results show a trend consistent with earlier observations on intergranular corrosion. It is shown that there is improvement in resistance to intergranular stress corrosion cracking with extreme randomization of grain boundaries.     

A new aspect on intergranular hydrogen embrittlement mechanism of solution annealed types 304, 316 and 310 austenitic stainless steels

The objective of this paper is to propose a new intergranular hydrogen embrittlement mechanism of solution annealed austenitic stainless steels (types 304, 316 and 310) on the basis of the results already reported. An intergranular hydrogen embrittlement (IG-HE) took place for type 316 at potentials less noble than the open-circuit potential in a HCl solution, and for types 304 and 316 at a lower test temperature under an open-circuit condition in saturated boiling magnesium chloride solutions by using a constant load method, while type 310 suffered only a transgranular stress corrosion cracking (TG-SCC) in both solutions under the same experimental conditions, but not IG-HE. In addition, TG-SCC occurred for types 304 and 316 under an open-circuit condition in the HCl solution irrespective of test temperature and in saturated boiling magnesium chloride solutions at higher test temperatures. Thus, the occurrence of IG-HE depended upon the material and test temperature. The new IG-HE mechanism was developed that explains the results obtained in terms of martensite transformation, hydrogen-enhanced local plasticity (HELP), grain boundary sliding (GBS) and so on.     

Microstructure and stress corrosion cracking in simulated heat-affected zones of duplex stainless steels

The effects of nitrogen content and the cooling rate on the reformation of austenite in the Gleeble simulated heat-affected zone (HAZ) of 2205 duplex stainless steels (DSSs) were investigated. The variation of stress corrosion cracking (SCC) behavior in the HAZ of 40 wt% CaCl₂ solution at 100 °C was also studied. Grain boundary austenite (GBA), Widmanstatten austenite (WA), intergranular austenite (IGA) and partially transformed austenite (PTA) were present in the HAZ. The types and amounts of these reformed austenites varied with the cooling rate and nitrogen content in the DSS. U-bend tests revealed that pitting corrosion and selective dissolution might assist the crack initiation, while the types and amounts of reformed austenite in the HAZ affected the mode of crack propagation. The presence of GBA was found to promote the occurrence of intergranular stress corrosion cracking. WA, IGA and PTA were found to exhibit a beneficial effect on SCC resistance by deviating the crack propagation path.     

Stress corrosion cracking study of microalloyed pipeline steels in dilute NaHCO3 solutions

Studies were carried out to evaluate the stress corrosion cracking (SCC) behavior of a X-70 microalloyed pipeline steel, with different microstructures by using the slow strain rate testing (SSRT) technique at 50 °C, in NaHCO₃ solutions. Both anodic and cathodic potentials were applied. Additionally, experiments using the SSRT technique but with pre-charged hydrogen samples and potentiodynamic polarization curves at different sweep rates were also carried out to elucidate hydrogen effects. The results showed that the different microstructures in conjunction with the anodic applied potentials shift the cracking susceptibility of the steel. In diluted NaHCO₃ solutions cathodic potentials close to their rest potential values decreased the SCC susceptibility regardless the microstructure, whereas higher cathodic potentials promote SCC in all steel conditions. Certain microstructures are more susceptible to present anodic dissolution corrosion mechanism. Meanwhile concentrated solution did not promotes brittle fracture.     

Stress corrosion cracking of gas-tungsten arc welds in continuous-cast AZ31 Mg alloy sheet

AZ31 Mg alloy sheet was welded using a gas-tungsten arc (GTA) process over inserts containing 2.3–9.3 wt.% Al. The welded specimens were susceptible to SCC in distilled water, with susceptibility increasing with decreasing weld metal Al (or β particle) concentration. Primary stress corrosion cracks initiated at the weld metal–HAZ interface by stress-assisted localised dissolution and propagated through the weld and base metals by transgranular and intergranular H-assisted fracture (TG-HAF and IG-HAF) respectively. The IG fracture mode may be intrinsic to the texture imparted upon the base metal by rolling. The increase in SCC susceptibility with decreasing weld metal Al concentration is contrary to the purported roles of β particles in promoting localised corrosion and as crack nucleation sites, but corresponds with increases in weld – base metal galvanic current density and weld metal localised corrosion susceptibility.     

Effect of weld metal chemistry on stress corrosion cracking behavior of AISI 444 ferritic stainless steel weldments in boiling chloride solution

The influence of the weld metal chemistry on the susceptibility of AISI 444 ferritic stainless steel (FSS) weldment to stress corrosion cracking (SCC) in hot chloride was investigated by constant load tests and metallographic examination. Two types of filler metal of austenitic stainless steel (E316L and E309L) were used in order to produce fusion zones of different chemical compositions. The SCC test results showed that the interface between the fusion zone (FZ) and the heat affected zone (HAZ) was the most susceptible region to SCC. Results also showed that the AISI 444 stainless steel weldment with E309L weld metal presented the best SSC resistance. Microstructural examinations indicated that the cracks initiated in the weld metal and propagated to the HAZ of the AISI 444 FSS, where the fracture occurred and it was observed a considerable amount of precipitates. Additionally, the higher SCC resistance of the AISI 444 FSS weldment with E309L weld metal may be attributed to the presence of a discontinuous delta‐ferrite network in its microstructure, which acted as a barrier to cracks propagation from the fusion zone to the HAZ/fusion zone interface of AISI 444 FSS. Fractrography analyses showed that the transgranular quasi‐cleavage fracture mode was predominant in the AISI 444 weldment with E316L weld metal and the mixed fracture mode was the predominant in the AISI 444 weldment with E309L weld metal.