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.     

The stress corrosion cracking behavior of austenitic stainless steels in boiling magnesium chloride solutions

The change in the mechanism of stress corrosion cracking with test temperature for Type 304, 310 and 316 austenitic stainless steels was investigated in boiling saturated magnesium chloride solutions using a constant load method. Three parameters (time to failure; t_f, steady-state elongation rate; l_ss and transition time at which a linear increase in elongation starts to deviate; t_ss) obtained from the corrosion elongation curve showed clearly three regions; stress-dominated, stress corrosion cracking-dominated and corrosion-dominated regions. In the stress corrosion cracking-dominated region the fracture mode of type 304 and 316 steels was transgranular at higher temperatures of 416 and 428 K, respectively, but was intergranular at a lower temperature of 408 K. Type 310 steel showed no intergranular fracture but only transgranular fracture. The relationship between log l_ss and log t_f for three steels became good straight lines irrespective of applied stress. The slope depended upon fracture mode; −2 for transgranular mode and −1 for intergranular mode. On the basis of the results obtained, it was estimated that intergranular cracking was resulted from hydrogen embrittlement due to strain-induced formation of martensite along the grain boundaries, while transgranular cracking took place by propagating cracks nucleated at slip steps by dissolution.     

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.     

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.     

Metal dissolution and maximum stress during SCC process of ferritic (type 430) and austenitic (type 304 and type 316) stainless steels in acidic chloride solutions under constant applied stress

By using a constant load method and inductive coupled plasma (ICP) spectrometer, the metal dissolution and maximum stress (σ_m^air) of type 430 ferritic stainless, and type 304 and type 316 austenitic stainless steels during stress corrosion cracking (SCC) process were investigated under a constant applied stress condition in 0.82 kmol/m³ hydrochloric acid (HCl) and 0.82 kmol/m³ acidic chloride (pH 1.0) solutions. The σ_m^air of the specimens interrupted at various elongations up to failure under the same constant applied stress condition was measured at room temperature and air atmosphere by using an Instron type tensile machine. The metal dissolution behaviour of the stainless steels changed at the transition time (t_ss) in the corrosion elongation curve; that is, the dissolution rate before t_ss was larger than that after t_ss. The σ_m^air decreased gradually with increasing elongation, but showed a rapid small reduction at t_ss and then decreased with elongation with a sudden reduction around fracture. The results obtained were discussed in terms of the amount of metal ions per the number of cracks, selective dissolution, reduction in cross sectional area and so on.     

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 susceptibility of sensitized type 316 stainless steel in sulphuric acid solution

The stress corrosion cracking (SCC) of a commercial austenitic stainless steel type 316 was investigated as a function of sensitizing temperature (800-1300 K) and test temperature (333-373 K) in 0.82 kmol/m³ sulphuric acid solution by using a constant load method, to compare with that already obtained in 0.82 kmol/m³ hydrochloric acid solution. The three parameters (l_ss, steady state elongation rate, t_ss, transition time, t_f, time to failure) were obtained from corrosion elongation curve and were divided into three regions of applied stress, irrespective of sensitizing temperature, which are dominated by either stress, SCC or corrosion. In the SCC-dominated region, the logarithm of l_ss was a linear function of the logarithm of t_f regardless of applied stress and test temperature for each sensitized specimens, showing that l_ss became a useful parameter for prediction of t_f, although the slope depended upon sensitizing temperature. The maximum applied stress, the minimum applied stress and the value of t_ss/t_f in the SCC-dominated region depended upon sensitizing temperature. Specifically, at a sensitizing temperature of around 950 K the maximum applied stress was smaller at a test temperature of 353 K, but larger at a test temperature of 333 K than that of the solution annealed specimens. In addition, sulphate ions were found to become more aggressive than chloride ions for the SCC susceptibility of the specimens with the most severe sensitization. On the basis of the results obtained, the effect of sensitization on SCC, the role of sulphate ions and an intergranular mechanism were discussed in comparison to the results of the sensitized specimens obtained in 0.82 kmol/m³ HCl solution.     

Effect of metallurgical variables on the stress corrosion crack growth behaviour of AISI type 316LN stainless steel

Mill-annealed AISI type 316LN stainless steels, received from two different sources (one indigenous (SS-2) and the other foreign (SS-1)), were tested for stress corrosion cracking (SCC) resistance in a boiling acidified environment of NaCl. SCC results indicated a remarkably lower value of plateau crack growth rate (PCGR) and higher values of K_ISCC and J_ISCC for SS-2, which was attributed to the lower effective grain boundary energy resulting from a higher amount of copper in it. Cold working reduced K_ISCC and PCGR; while thermal aging and welding decreased K_ISCC and increased PCGR vis-à-vis the annealed material.     

Stress corrosion cracking of type 304 austenitic stainless steel in sulphuric acid solution including sodium chloride and chromate

The stress corrosion cracking (SCC) of a commercial austenitic stainless steel type 304 was investigated as functions of chloride concentration, chromate concentration and test temperature under a constant applied stress condition in 0.82 kmol/m³ sulphuric acid solution by using a constant load method. From the dependence of the three parameters (, steady state elongation rate; t_ss, transition time; t_f, time to failure) obtained from corrosion elongation curve on chloride/chromate concentrations and test temperature, a parameter for predicting time to failure and critical values of chromate concentration and test temperature, below which little SCC takes place, were estimated. In addition, a transgranular SCC mechanism was qualitatively inferred and then the effect of chromate and chloride on SCC behavior was discussed.     

Hydrogen-induced cracking of pure titanium in sulphuric acid and hydrochloric acid solutions using constant load method

The hydrogen-induced cracking (HIC) of the commercial pure titanium (Ti) has been investigated as functions of applied stress and test temperature in sulphuric acid and hydrochloric acid solutions by using a constant load method. From the results obtained, HIC was hydrogen embrittlement (HE) related to the fracture of hydride. We have also found that the steady state elongation rate obtained from corrosion elongation curve becomes a relevant parameter for predicting time to failure and a criterion to assess whether HIC takes place or not. A parameter, t_sst_f⁻¹ was also found to become an indicator to assess whether HE takes place or not. Furthermore, it was deduced that HIC was qualitatively explained in terms of hydride formation and a localized deformation, which was basically based on a hydride formation-rupture event at crack tips.     

Environment-induced cracking of Al–Cu alloy (AA2017P-T3) under constant load in distilled water and sodium chloride solutions

The environment-induced cracking (EIC) of a commercial Al–Cu alloy has been investigated as functions of applied stress, chloride ion concentration and test temperature in distilled water and sodium chloride solutions by using a constant load method. The effect of chloride ion on EIC is complex. The EIC susceptibility increased, unchanged and then decreased with increasing the chloride ion concentration. However, whenever EIC takes place with and without chloride ion, the fracture appearance and the value of t_ss (transition time to deviation from linear elongation)/t_f (time to failure) are the same, and further the relationship between log t_f and log l_ss (steady state elongation rate) becomes the identical straight line irrespective of applied stress, chloride ion concentration and test temperature. The latter means that l_ss becomes a relevant parameter for predicting t_f. It has been concluded that EIC of Al–Cu alloy takes place by hydrogen embrittlement (HE) associated with the fracture of hydride, and a HE mechanism is qualitatively proposed to explain the results obtained.     

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.     

The stress corrosion cracking of welded austenitic stainless steels in MgCl2 solutions in the presence of NaI additions

The influence of Nal additions on the stress corrosion cracking (SCC) of Type 304L and 316L welded stainless steels in 42 wt% aqueous MgCl₂ solution at 154°C has been investigated. The results indicate clearly that addition of 1 N NaI to the boiling MgCl₂ solution prevents SCC of the welded steels. The I⁻ can act as an effective cathodic inhibitor. The correlation between mechanical properties, fracture morphology and the mechanism of the inhibition behaviour of I⁻ on SCC is discussed.     

Oxidation resistance of sintered stainless steels: effect of yttria additions

The porosity of sintered stainless steels modifies their oxidation behavior, as compared to that of wrought stainless steels. This work studies the oxidation behavior of three sintered stainless steels: one ferritic (AISI 434L) and two austenitic (AISI 316L and 304L). 304L with yttria additions is also been studied to explore the possibility of reducing the oxidation rate of austenitic stainless steels by using this reactive element. The results demonstrate the influence of the formation of NiFe₂O₄ on the high-temperature behavior of sintered austenitic stainless steels and the effectiveness of yttria additions in increasing the oxidation resistance at 800 °C.     

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.     

Determination of threshold stress intensity for chloride stress corrosion cracking of solution-annealed and sensitized austenitic stainless steel by circumferential notch tensile technique

This paper discusses a new approach to determination of threshold stress intensity factor for stress corrosion cracking (K_ISCC) of stainless steel in 42% MgCl₂ environment at 154 °C. K_ISCC of solution-annealed and sensitized AISI 304 stainless steel in chloride environment has been determined using circumferential notch tensile (CNT) technique. K_ISCC data generated using CNT technique have been compared with those generated using traditional techniques such as compact tension and double cantilever beam (reported in the literature). The results presented here validate the ability of CNT technique for determination of K_ISCC of sensitized as well as solution-annealed austenitic stainless steel. This paper also discusses the mechanistic aspects of the difference in fractographic features of the sensitized and solution-annealed stainless steel.     

Evaluation of stress corrosion cracking phenomenon in an AISI type 316LN stainless steel using acoustic emission technique

This paper deals with the analysis of the acoustic emission (AE) signals to determine the micro-process during stress corrosion cracking (SCC) of AISI type 316LN stainless steel that cause the AE, and thus the mechanism of the SCC process. AE with amplitudes ranging from 27.6 to 46.5 dB with different counts, energy and rise times occurred during SCC of type 316LN stainless steel in 45% MgCl₂ at 413 K. The analysis of the AE signals in conjunction with fractography indicated that a surge in the AE counts and energy indicated initiation of SCC. AE was found to be continuous prior to the initiation. The time gap between AE events increased during initiation. AE events occurred in bursts during crack growth. Plastic deformation ahead of the crack tip was determined to be the major source of AE during propagation of SCC in type 316LN stainless steel. The cracking was found to initiate and propagate in the transgranular mode.     

Correlation between the degree of sensitization and stress corrosion cracking susceptibility of type 304H stainless steel

Austenitic stainless steel 304H is extensively used in the super heater tubes of power boiler due to its superior mechanical properties at elevated temperatures. However, its relatively high carbon content increases the susceptibility to sensitization and subsequent stress corrosion cracking.This work is concerned with investigation of the sensitization and stress corrosion cracking (SCC) of austenitic stainless steel grade 304H. Electrochemical potentiokinetic reactivation (EPR) test was used to evaluate the degrees of sensitization (DOS) of the studied alloy at various temperatures and periods of time. DOS increased with increasing sensitization time and temperature. This was confirmed by microstructure examination after EPR test. Boiling magnesium chloride (MgCl₂) test was used to evaluate the susceptibility of 404H stainless steel to stress corrosion cracking. DOS and test stress level had negative effects on time to failure in boiling MgCl₂. The correlation between DOS and SCC was also discussed.     

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.