Understanding the effect of nitrogen in austenitic stainless steel on the intergranular stress corrosion crack growth rate in high temperature pure water

Understanding the effect of nitrogen content on the crack growth rate (CGR) due to intergranular stress corrosion cracking (IGSCC) in high temperature (288 °C) pure water, in non-sensitised and strain-hardened stainless steel (SS) type 304 LN was the focus of this study. Non-sensitised SS containing two different levels of nitrogen (0.08 and 0.16 wt.%) in the solution annealed condition was strain-hardened by cross-rolling at 200 °C (warm rolling). It has earlier been reported that SS with a higher nitrogen level in the warm rolled condition has a higher CGR in high temperature pure water. Tensile testing was carried out using both the SS in the warm rolled as well as in the solution annealed condition at 288 °C. Samples were prepared for transmission electron microscopy (TEM) from the warm rolled SS and from the tensile tested (at 288 °C) specimens. TEM studies indicated that twinning and shear band formation were the major modes of deformation due to rolling at 200 °C and these feature were observed to terminate at grain boundaries, leading to regions of higher strain and stresses at grain boundaries. Higher nitrogen SS has higher grain boundary strain and stresses making the grain boundary regions more susceptible to IGSCC, resulting in higher CGR values. At 288 °C dislocation entanglement and cross-slip were the predominant modes of deformation.     

Predicting crack growth rate vs. temperature behaviour of Type 304 stainless steel in dilute sulphuric acid solutions

The coupled-environment fracture model for intergranular stress corrosion cracking of Type 304 stainless steel in boiling water reactor primary (water) heat transport circuits containing relatively pure water has been extended to incorporate the effects of sulphuric acid additions to the coolant and to include thermal activation of the crack tip strain rate. These extensions allow comparisons to be made between theoretically estimated and experimentally determined crack growth rates (CGRs) over a considerable temperature range after calibration at a single temperature. The model predicts, in agreement with experiment, that the CGR passes through a maximum with increasing temperature at a temperature of about 180 °C. The temperature dependence of the CGR is attributed to the competing effects of temperature on the thermally activated processes that occur at the crack tip and the properties (including ECP and conductivity) of the external environment.     

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.     

High corrosion resistance of austenitic stainless steel alloyed with nitrogen in an acid solution

Passivity of austenitic stainless steel containing nitrogen (ASS N25) was investigated in comparison with AISI 316L in deareated acid solution, pH 0.4. A peculiar nature of the passivation peak in a potentiodynamic curve and the kinetic parameters of formation and growth of the oxide film have been discussed. The electronic-semiconducting properties of the passive films have been correlated with their corrosion resistance. Alloying austenitic stainless steel with nitrogen increases its microstructure homogeneity and decreases the concentration of charge carriers, which beneficially affects the protecting and electronic properties of the passive oxide film.     

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.     

Predicting the mechanisms and crack growth rates of pipelines undergoing stress corrosion cracking at high pH

A fundamentally based mathematical model was developed with the goal to predict, as a first step, the crack growth rate (CGR) of high pH stress corrosion cracking (SCC) of buried steel pipelines. Two methods were used to predict CGRs and for both methods the model has included the film rupture and repassivation mechanism. The two methods are distinguished by the expression used to determine the active anodic current density at the crack tip. In the first method, this current density is expressed by the anodic polarization curve with a large peak current density and the prediction tends to yield a larger CGR and a lower pH at the crack tip. By contrast, when the Butler–Volmer equation is used to express the crack tip anodic current density, with a predicted low CGR the chemistry at the tip does not appear to have any significant change due to the high buffer of the solution.The predicted mechanism responsible for the steady-state crack growth is shown to be the balance between the increasing stress intensity factor as the crack grows, which tends to increase the crack tip strain rate and thus the CGR, and the change of the crack tip condition, which, for large CGRs, is the significant shift in the more negative direction of the crack tip potential, and for low CGRs, the increase of ferrous ion concentration, and either tends to decrease CGR.Limitations currently existing in the model and proposal for further development of the model are discussed.     

Quantitative analysis of Cr-depleted zone morphology in low carbon martensitic stainless steel using FE-(S)TEM

A new type of intergranular stress corrosion cracking (IGSCC) has been observed in low carbon martensitic stainless steel at heat affected zone (HAZ). Nano level microstructural analysis was carried out to investigate IGSCC factors. It was found that cracks propagate along prior austenite grain boundaries where a row of carbides had been formed. Cr-depleted zones at the grain boundaries were characterized by a STEM-EDX analysis and that morphology was obtained by deconvoluting this results. It is concluded that Cr-depleted zones only a few nanometers in width are enough to cause IGSCC at HAZ in this steel under certain circumstances.     

On the Plasma （ion） Carburized Layer of High Nitrogen Austenitic Stainless Steel

The manganese concentration of austenltic stainless steel decreases from the inner layer towards the surface of the plasma (ion) carburized layer due to the evaporation of manganese from the specimen surface. The carbon concentration in the carburized layer is influenced by alloyed elements such as Cr, Ni, Si, and Mo, as well as Nitrogen. This study examined the effects of nitrogen on the properties of the carburized layer of high nitrogen stainless steel. Plasma (ion) carburizing was carried out for 14.4 ks at 1303 K in an atmosphere of CH4 H2 gas mixtures under a pressure of 350 Pa. The plasma carburized layer of the high nitrogen stainless steel was thinner than that of an austentric stainless steel containing no nitrogen. This suggested that the nitrogen raised the activity of carbon in the plasma carburized layer, GDOES measurement indicated that the nitrogen level in the layer did not vary after plasma (ion) carburizing.     

Influence of grain size on nitrogen diffusivity in austenitic stainless steel

Ion nitriding of austenitic stainless steel with the aim to improve the tribological properties while retaining the excellent corrosion resistance is a well-established method. At the same time, strongly varying microstructures can be obtained depending on the pretreatment. In this work, the influence of prior heat treatment in the temperature range between 950 and 1200 °C on the microstructure, especially the grain size, and the corresponding observed nitrogen diffusivity in austenitic stainless steel DIN 1.4301 (AISI 304, X6CrNi18.10) after nitrogen plasma immersion ion implantation (PIII) is studied. Cross-section and plan view samples were prepared and investigated. With increased annealing temperature, both larger grains and slower diffusion was observed, despite diffusion ranges much smaller than the average grain size. Another, still hidden effect of dislocation densities or other defects on both secondary parameters is suggested.     

On the corrosion mechanism of AISI 204Cu stainless steel in chlorinated alkaline media

Electrochemical techniques (CV, SECM, CPT) and surface analysis techniques (EDX, SEM) have been employed to assess the corrosion behaviour of the AISI 204Cu stainless steel. The behaviour of this steel has been compared with that of AISI 304 and AISI 434 stainless steels in chlorinated alkaline media. All samples performed well at room temperature under potentiodynamic polarisation up to a chloride to hydroxyl ratio of 10. At this ratio the AISI 204Cu and the AISI 434 steels presented pitting potential at +0.47 V vs. SCE and +0.31 V vs. SCE, respectively. Moreover, the critical pitting temperature was higher for the AISI 204Cu steel than for the AISI 434 steel, respectively 58 °C and 28 °C.In terms of corrosion performance of the AISI 204Cu stainless steel can be classified better than the AISI 434 steel and worse than the AISI 304 steel.Local electrochemical and chemical examinations allowed evidencing the local activity of some pits over long period, and to conclude that the improved corrosion performance of the low nickel alloy AISI 204Cu stainless steel should be ascribed to copper cementation at active corrosion sites.     

Effect of nitrogen addition to shielding gas on residual stress of stainless steel weldments

Abstract

The objective of the present study was to investigate the effect of nitrogen additions to the shielding gas on the ferrite content and residual stress in austenitic stainless steels. Autogenous gas tungsten arc (GTA) welding was applied on austenitic stainless steels 304 and 310 to produce a bead on plate weld. The delta ferrite content of the weld metals was measured using a Ferritscope. The residual stress in the weldments was determined using the hole drilling strain gauge method. The present results indicated that the retained delta ferrite content in type 304 stainless steel weld metals decreased rapidly as nitrogen addition to the argon shielding gas was increased. The welding residual stress increased with increasing quantity of added nitrogen in the shielding gas. It was also found that the tensile residual stress zone in austenitic stainless steel weldments was extended as the quantity of added nitrogen gas in the argon shielding gas was increased.     

Corrosion properties of active screen plasma nitrided 316 austenitic stainless steel

AISI 316 austenitic stainless steel has been plasma nitrided using the active screen plasma nitriding (ASPN) technique. Corrosion properties of the untreated and AS plasma nitrided 316 steel have been evaluated using various techniques, including qualitative evaluation after etching in 50%HCl + 25%HNO₃ + 25%H₂O, weight loss measurement after immersion in 10% HCl, and anodic polarisation tests in 3.5% NaCl solution. The results showed that the untreated 316 stainless steel suffered severe localised pitting and crevice corrosion under the testing conditions. AS plasma nitriding at low temperature (420 °C) produced a single phase nitrided layer of nitrogen expanded austenite (S-phase), which considerably improved the corrosion properties of the 316 austenitic stainless steel. In contrast, AS plasma nitriding at a high temperature (500 °C) resulted in chromium nitride precipitation so that the bulk of the nitrided case had very poor corrosion resistance. However, a thin deposition layer on top of the nitrided case, which seems to be unique to AS plasma nitriding, could have alleviated the corrosion attack of the higher temperature nitrided 316 steel.     

Effect of hydrogen on tensile behaviour of micrometre-sized specimen fabricated from a metastable austenitic stainless steel

This study was conducted by micro mechanical testing and scanning white-light interferometry (SWLI) to clarify the intrinsic effect of hydrogen on tensile properties of a metastable austenitic stainless steel. The stress–strain behaviour of the micrometre-sized specimens exhibited two distinct strain hardening stages controlled by dislocation gliding and martensitic transformation. In-situ SWLI of the micrometre-sized specimens during the tensile test revealed that plasticity localization caused by hydrogen is predominantly responsible for the hydrogen embrittlement (HE) of the austenite stainless steel.     

Role of water chemistry and microstructure in stress corrosion cracking in the fusion boundary region of an Alloy 182-A533B low alloy steel dissimilar weld joint in high temperature water

Stress corrosion cracking (SCC) in the fusion boundary (FB) region of an Alloy 182-low alloy steel (LAS) dissimilar weld joint in 288 °C water was investigated by experiments and finite element simulation. Creviced bent beam and crack growth rate (CGR) experiments showed that, while the FB was a barrier to SCC growth, further crack growth into LAS was activated by a combined effect of sulfate and dissolved oxygen in water. Finite element simulation suggested that a positive gradient of hardness as the crack approached to the FB in dilution zone caused decreased CGR. Role of microstructure and water chemistry in SCC was discussed.     

Brittle to ductile transition in nickel free high nitrogen austenitic stainless steels

Abstract

The brittle to ductile transition (BDT) in nickel free high nitrogen austenitic stainless steel was investigated. Falling weight impact tests at 176, 273 and 336 K revealed that Fe–25Cr–1·1N (wt-%) austenitic steel exhibits a sharp BDT in spite of being a face centred cubic alloy. The plastic deformation observed following the impact tests indicated that the BDT is induced by poor ductility at low temperatures, as is the case with ferritic steels. To measure the activation energy for the BDT, the strain rate dependence of the BDT temperature was examined using four-point bending tests. The BDT temperature was found to be weakly dependent on strain rate. Arrhenius plots of the BDT temperature against strain rate showed that the activation energy for the BDT of Fe–25Cr–1·1N steel is much higher than that of low carbon ferritic steels. The origins of this distinctive BDT and the large value for its activation energy in this high nitrogen steel are discussed in terms of the reduction in dislocation mobility at low temperatures because of the interactions between the glide dislocations and the solute nitrogen atoms.     

Kinetics of nitrogen absorption in molten aisi 316 stainless steel during immersion nitrogen blowing

Nitrogen absorption in molten metal for stainless steel AISI316 has been investigated by immersion nitrogen blowing through an immersed alumina nozzle with an internal diameter of 3 mm. Based on these experimental data, some kinetic parameters of nitrogen absorption, such as reaction order, rate constant and apparent activation energy of nitrogen absorption reaction, have been obtained. Effect of stirring by immersion nitrogen blowing through an immersed alumina nozzle on nitrogen absorption reaction has been observed. Results show the following: (1) Nitrogen absorption reaction is the −1.5th order reaction. The rate constant k _N is of the order of 10⁻⁵ wt%^2.5·min⁻¹. Nitrogen absorption reaction for AISI 316 has negative apparent activation energy of −92.40 kJ·mol⁻¹. This indicates that the nitrogen absorption reaction has a complex and multistep reaction mechanism. (2) The rate of nitrogen absorption reaction in molten stainless steel is mixture control by the adsorption of monatomic nitrogen on the surface of molten stainless steel and mass transfer in molten metal. (3) A rate equation of nitrogen absorption reaction has been derived based on a mixed control mechanism by both the -1st order nitrogen absorption reaction and mass transfer in molten metal.     

Comparative corrosion resistance of plasma-based low-energy nitrogen ion implanted austenitic stainless steel

A high nitrogen face-centered-cubic phase (γ_N) was obtained on the nitrided surface of 1Cr18Ni9Ti austenitic stainless steel by plasma-based low-energy nitrogen ion implantation. No pitting corrosion for the γ_N phase was confirmed by electrochemical polarization measurement in 3% NaCl solution. The protective passive film with a duplex character, iron hydroxide/oxides in the outer region and chromium hydroxide/oxides and iron oxides accompanying chromium and iron nitrides in the inner region, was by 2-3 times thicker than that of original stainless steel. The thick iron hydroxide/oxides region formed on the chromium hydroxide/oxides region due to the increase of alkalinity in the solution, leading to barrier against penetration of localized attack of the aggressive ions. The equivalent general corrosion resistance for the γ_N phase was observed in 0.5 mol/l H₂SO₄ solution relative to the original stainless steel. The passive film formed on the γ_N phase in 0.5 mol/l H₂SO₄ solution was similar to that of original stainless steel. The different role of nitrogen was proposed in pitting corrosion resistance and general corrosion resistance of austenitic stainless steel.     

Electrochemical behaviour enhancement of stainless steels by a SiO2 PACVD coating

Amorphous silica coatings have been deposited by plasma assisted chemical vapor deposition (PACVD) process on M2 steel and 304 stainless steel substrates. The chemical inertia of the coating has been established by resonant quartz crystal microbalance (RQCM), and no porosity has been observed at the AFM scale. The barrier effect has been evaluated on M2 steel by applying the concept of dipolar relaxation. The protection is very efficient, and no deleterious galvanic coupling with the uncoated metallic surface can occur.

A coated stainless steel was also investigated in NaCl solution in order to understand how the passive properties are influenced by such a barrier coating. When deposited on stainless steel, coated part keeps the beneficial passive behaviour inherent to the substrate. They evidence almost no corrosion. The silica based layer behaves as a quasi perfect dielectric. The corrosion rate is then greatly reduced, and the pitting resistance is improved. The excellent localized corrosion protection has been explained by a tiny porosity rate, and a limited access of chloride ions through open pores.     

Microstructure and mechanical properties of austenitic stainless steels after cold rolling

The effect of austenite stability on the evolution of microstructure and mechanical properties of three austenitic stainless steels during cold rolling has been studied. Samples of different grain sizes have been used to characterize the microstructures during deformation. In the case of 304/8% Ni and 304/10% Ni stainless steels, the transformation microstructures consist of mechanical twins: ε-martensite and α′-martensite. No hexagonal close-packed (hcp) ε-martensite was detected in 316 stainless steel. The volume fraction of α′-martensite formed increases with increasing strain in 304 and 316 stainless steels for a given grain size. The amount of α′ phase increases with a decrease in grain size in 304 stainless steel, while the formation of this phase has been found to be grain size insensitive in 316 stainless steel. The strain-hardening behavior exhibited by the three stainless steels used in this study indicates the contribution of both α′-martensite and grain size strengthening in the case of both 304 stainless steels, while only grain size contribution was found in the case of 316 stainless steel.     

Transient and steady state crack growth kinetics for stress corrosion cracking of a cold worked 316L stainless steel in oxygenated pure water at different temperatures

The stress corrosion cracking (SCC) growth kinetics for a cold worked 316L stainless steel was continuously monitored in high purity water at different temperatures and dissolved oxygen (DO) levels under a K (or K_max) of 30 MPa m^0.5. The total SCC test time was more than 8000 h to make sure the steady state crack growth rate under each test condition could be reached. Crack growth rate (CGR) increases with increasing temperature in the range 110-288 °C. A typical intergranular-cracking mode is identified. Depending on the previous test condition, especially the temperature, three kinds of crack growth kinetics, i.e., increasing with testing time then becoming steady, being constant during the whole period, or decreasing with test time then becoming steady, are identified and discussed. Time-dependent and testing history-dependent crack growth modes were confirmed in two series of tests in 2 ppm DO and 7.5 ppm DO pure water. The apparent activation energies are calculated and compared with other data in different environments under different applied loading levels for understanding the cracking mechanism.