Pitting corrosion behaviour of austenitic stainless steels - combining effects of Mn and Mo additions

Mn and Mo were introduced in AISI 304 and 316 stainless steel composition to modify their pitting corrosion resistance in chloride-containing media. Corrosion behaviour was investigated using gravimetric tests in 6 wt.% FeCl₃, as well as potentiodynamic and potentiostatic polarization measurements in 3.5 wt.% NaCl. Additionally, the mechanism of the corrosion attack developed on the material surface was analysed by scanning electron microscopy (SEM), X-ray mapping and energy dispersive X-ray (EDX) analysis. The beneficial effect of Mo additions was assigned to Mo⁶⁺ presence within the passive film, rendering it more stable against breakdown caused by attack of aggressive Cl⁻ ions, and to the formation of Mo insoluble compounds in the aggressive pit environment facilitating the pit repassivation. Conversely, Mn additions exerted an opposite effect, mainly due to the presence of MnS inclusions which acted as pitting initiators.     

Pitting corrosion behaviour of PM austenitic stainless steels sintered in nitrogen-hydrogen atmosphere

PM 304L and 316L stainless steel have been compacted at 400, 600 and 800 MPa and sintered in vacuum and in nitrogen-hydrogen atmosphere. Postsintered heat treatments (annealing solution and ageing at 375, 675 and 875 °C) have been applied. Pitting corrosion resistance has been studied using anodic polarization measurements and the ferric chloride test. Anodic polarization curves reveal that densities and atmospheres are relevant on anodic behaviour. Pitting resistance is higher for PM 316L and for higher densities and vacuum as sintered atmosphere. Ageing heat treatments at medium and high temperatures are detrimental to passivity although susceptibility to pitting corrosion barely changes. But heat treatments at 375 °C even show certain improvement in pitting corrosion resistance. The results were correlated to the presence of precipitates and mainly to the lamellar constituent which appears in some samples sintered in nitrogen-hydrogen atmosphere. The role of nitrogen on the samples sintered under nitrogen-hydrogen atmosphere and its relation to the microstructural features was described.     

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.     

Pitting corrosion of cold rolled solution treated 17-4 PH stainless steel

In the present paper the effects the of cold rolling on pitting corrosion of 17-4 precipitation hardening stainless steel in 3.5 wt% NaCl solution was investigated. In order to clarify the effect of cold rolling the metastable pitting has been examined in more details. The results presented show that cold rolling increases the dissolution rate of metastable pitting in a manner which facilitates the transition from metastable to stable pitting. On the other hand, the frequency of occurrence of metastable pits decreases with cold working. In overall, cold rolling has no significant effect on pitting potential.     

Corrosion behaviour of duplex stainless steels sintered in nitrogen

Duplex stainless steels obtained through powder metallurgy (PM) technology from austenitic AISI 316L and ferritic AISI 430L powders were mixed on different amounts to obtain biphasic structures with austenite/ferrite ratio of 50/50, 65/35 and 85/15. Prepared mixes of powders have been compacted at 750 MPa and sintered in N₂-H₂ (95% and 5%) at 1250 °C for 1 h. Corrosion behaviour, using electrochemical techniques such as anodic polarization measurement, cyclic anodic polarization scan and electrochemical potentio-kinetic reactivation test and double loop electrochemical potentio-kinetic reactivation double loop test were evaluated. For duplex stainless steels, when austenite/ferrite ratio increases the corrosion potential shifts to more noble potential and passive current density decreases. The beneficial effect of annealing solution heat treatment on corrosion behaviour was established and was compared with corrosion behaviour of vacuum sintered duplex stainless steels. The results were correlated with the microstructural features.     

Intergranular corrosion of welded joints of austenitic stainless steels studied by using an electrochemical minicell

An intergranular corrosion study of welded joints of austenitic stainless steels (AISI 304 and 316L) has been addressed. A specific small-scale electrochemical cell (minicell) has been used. Four different weldment zones have been studied. The electrochemical methods applied were the electrochemical potentiokinetic reactivation test and electrochemical potentiokinetic reactivation double loop test. These techniques showed that the HAZ was the most critical zone to intergranular corrosion for both materials. The weld metal was susceptible to interdendritic corrosion and the fusion line showed a mixture of intergranular and interdendritic corrosion. The effect of pre- and post-welding heat treatments for AISI 316L was analyzed. The HAZ was again the most critical zone in every heat treatment condition. The results were correlated to the microstructural features of the materials.     

Aqueous corrosion behaviour of sintered stainless steels manufactured from mixes of gas atomized and water atomized powders

The electrochemical corrosion improvement of a powder metallurgical (PM) stainless steel is studied in this work. Water atomized (WA) ferritic AISI 434L powders have been mixed with gas atomized (GA) austenitic (AISI 316L type) and ferritic (AISI 430L type) powders and processed through the traditional PM route. The addition of GA powder to the usual WA powder decreases the mean size of the pores of the sintered stainless steels. As the bigger pores are the ones that are able to act as crevices, unlike the smaller ones - that act as closed porosity, reduction in the number of big pores tends to improve the corrosion behaviour of PM stainless steels. Reductions of the corrosion rate (i_corr) and increases of the corrosion potential (E_corr) have been measured in neutral media, with and without chlorides. Moreover, the additional beneficial effect of achieving a duplex microstructure through the addition of GA austenitic powders to the WA ferritic powders has also been verified.     

Microstructural evolution and localized corrosion resistance of an aged superduplex stainless steel

The present investigation was undertaken to analyze the effects of isothermal ageing treatments, carried out between 700 and 900 °C for a variety of times up to two weeks and followed by water quenching, on the microstructure and on the localized corrosion resistance of a superduplex stainless steel, SAF 2507.The quantitative metallography coupled with X-ray diffraction techniques was adopted to follow the microstructural evolution, together with SEM microscopy.Electrochemical potentiodynamic tests, as cyclic polarization curves recorded in sodium chloride solutions, together with weight loss measurements were employed to evaluate the susceptibility of the aged specimens to pitting corrosion.The influence of the transformation of ferrite into secondary austenite and sigma phase and of other microstructural variations, as chromium nitrides precipitation, on the stability of the passive film is shown. The susceptibility of the aged alloy to pitting corrosion phenomena, is related to sigma phase precipitation in association to the secondary austenite formation, which lead to a noticeable Cr depletion at grain boundaries.     

Comparison of influences of NaCl and CaCl2 on the corrosion of 11% and 17% Cr ferritic stainless steels during cyclic corrosion test

During the drying stage of the cyclic corrosion test on ferritic stainless steels in the NaCl environment, the current abruptly increased and then decreased to nearly zero, indicating that pits are initiated as the salt concentration is increased, which are then repassivated when the surface is completely dry. During the wet stage, the current remained high, suggesting that pits mainly propagate during the wet stage. In contrast, in the cyclic corrosion test in the CaCl₂ environment, the current was highest during the drying stage, indicating that the electrolyte is not completely dried and corrosion mainly propagates during the drying stage.     

Studies of the tensile and corrosion fatigue behaviour of austenitic stainless steels

Corrosion fatigue behaviour of four types of austenitic stainless steels were investigated in boiling 45% magnesium chloride solution at a stress ratio of 0.25 and a frequency of 0.1 Hz. Type 316LN stainless steel possessed the best resistance and type 304 stainless steel had the lowest resistance to corrosion fatigue. XPS studies on the fracture surface indicated that the presence of nitrogen as ion in the surface film of type 316LN stainless steel gave it the highest resistance to corrosion fatigue. Fractographic examination showed wholly transgranular cracking in all cases.     

Corrosion behaviour of corrugated lean duplex stainless steels in simulated concrete pore solutions

This work studies the corrosion behaviour of two corrugated lean duplex stainless steels (SAF 2001 and 2304 grades) in eight alkaline solutions (carbonated and non-carbonated, saturated Ca(OH)₂ solutions with different chloride contents). 2001 stainless steel is a new grade in market because of its composition. 2304 is a grade previously studied under different conditions. However, its use as reinforcement in concrete is new. Studies are carried out by polarization curves following scanning electronic microscopy (SEM) and optical observations. Results are compared to those of carbon steel and austenitic AISI 304 and duplex SAF 2205 under similar conditions. After corrosion tests in alkaline media with chloride, ferrite tends to corrode selectively in 2304 duplex, while austenite corrodes selectively in 2001 under the same conditions. The influence of the duplex microstructure on attack development and morphology is analyzed. The electrochemical parameters obtained from the polarization curves suggest 2001 could replace 304 keeping the structure its corrosion performance (and with clear economical advantages). 2304 shows better corrosion behaviour than the more expensive 304, but somewhat lower than the excellent behaviour shown by 2205.     

Corrosion behaviour of intermetallic aluminide coatings on nitrogen-containing austenitic stainless steels

The present work reports the effect of aluminide layers on the aqueous corrosion behaviour of four different 316L stainless steels containing various nitrogen contents (0.015%, 0.1%, 0.2% and 0.56% N). Diffusion annealed aluminide layers are generated over the surface by heat treatment of the aluminium precoated alloys at 750 °C for 25 h in nitrogen atmosphere. X-ray diffraction patterns of the surface modified samples showed the presence of AlN, Al₁₃Fe₄ and FeAl₂ phases. Diffusion of aluminum into the alloy, and the formation of AlN by the reaction of aluminium with matrix nitrogen, was identified using secondary ion mass spectrometry (SIMS). The nitrogen peak in the diffused layer was found to increase with increasing nitrogen content of the base alloy. SEM observation of cross-sectionally mounted alloys showed the presence of spherical AlN phase in addition to iron aluminide intermetallic phases. The role of such a composite surface layer containing intermetallic aluminides and nitride on the corrosion resistance of austenitic stainless steels in 0.5 M NaCl and 0.5 M sulphuric acid is discussed in greater detail based on open circuit potential (OCP)–time measurements, potentiodynamic polarisation studies and electrochemical impedance spectroscopy (EIS) investigations. The aluminide layered alloy with 0.1% N content showed better corrosion performance. The presence of nitrogen was found to have a positive effect in enhancing the hardness of the composite layer. Role of matrix nitrogen on the microstructure and microchemical distribution at the surface, and its role on corrosion resistance in acidic and chloride media are discussed in detail.     

Potentiodynamic polarization behaviour of AISI type 316 stainless steel in NaCl solution

Potentiodynamic polarization behaviour of AISI type 316 SS in NaCl solution was investigated in terms of the potential scan rate effect. The critical pitting potential, E_pit, of the stainless steel appeared to be strongly dependent on the potential scan rate. A cumulative anodic electric charge density of the steel was defined as the total charge density from the open circuit potential, E_ocp, and calculated using the potentiodynamic polarization curves. It was found that, plotted as a function of the polarization time, the values of the cumulative charge density consisted of two lines with different slopes. It was confirmed that the deflection of the cumulative charge density vs. time plots corresponded to E_pit and the values of the cumulative charge density at the deflection were little dependent on the applied scan rate. The cumulative charge density at the deflection was defined as a critical electric charge density for the stable pitting. Also, it was suggested that this electric charge density should be associated with the critical condition for the stable pitting and the critical electric charge for stable pitting should be a representative parameter for the pitting resistance of a material.     

Effect of Geobacter sulfurreducens on the microbial corrosion of mild steel, ferritic and austenitic stainless steels

The influence of Geobacter sulfurreducens was tested on the anaerobic corrosion of four different steels: mild steel 1145, ferritic steel 403 and austenitic steels 304L and 316L. Within a few hours, the presence of cells induced a free potential (E_oc) ennoblement around +0.3 V on 1145 mild steel, 403 ferritic steel and 304L austenitic steels and slightly less on 316L. The kinetics of E_oc ennoblement depended on the amount of bacteria in the inoculum, but the final potential value depended essentially on the nature of the material. This effect was due to the capacity of G. sulfurreducens to create a direct cathodic reaction on steel surfaces, extracting the electrons directly from material. The presence of bacterial cells modified the corrosion features of mild steel and ferritic steel, so that corrosion attacks were gathered in determined zones of the surface. Local corrosion was significantly enhanced on ferritic steel. Potential ennoblement was not sufficient to induce corrosion on austenitic steels. In contrast G. sulfurreducens delayed the occurrence of pitting on 304L steel because of its capability to oxidize acetate at high potential values. The electrochemical behaviour of 304L steel was not affected by the concentration of soluble electron donor (acetate, 1–10 mM) or the amount of planktonic cells; it was directly linked to the biofilm coverage. After polarization pitting curves had been recorded, microscopic observations showed that pits propagated only in the surface zones where cell settlement was the densest. The study evidenced that Geobacter sulfurreducens can control the electrochemical behaviour of steels in complex ways that can lead to severe corrosion. As Geobacteraceae are ubiquitous species in sediments and soils they should now be considered as possible crucial actors in the microbial corrosion of buried equipment.     

Effect of the micro-plasma arc welding technique on the microstructure and pitting corrosion of AISI 316L stainless steels in heavy LiBr brines

The effects of the micro-plasma arc welding technique on the microstructure and pitting corrosion of different zones of an AISI 316L stainless steel were studied using different microscopy and electrochemical techniques. Galvanodynamic measurements and laser scanning confocal microscope were used to evaluate the corrosion evolution in situ. Results show, in general, the worst corrosion behaviour for the heat affected zone. Furthermore, there is a relation between the effects of the micro-plasma arc welding process on the materials microstructure and their pitting corrosion resistance. The weld zone was always in the cathodic position of the possible galvanic pairs.     

Influence of ultrasound on pitting corrosion and crevice corrosion of SUS304 stainless steel in chloride sodium aqueous solution

The change of polarization curves and surface morphologies of SUS304 stainless steel was investigated in 3.5 mass% NaCl solution with or without the application of ultrasound (US). As the result, both the pitting corrosion and the crevice corrosion were largely suppressed by the application of US. The reason is attributed to the decrease in the concentration of hydrogen and chloride ions in pits or in the crevice by removing the corrosion product and stirring the liquid there.     

Corrosion assessment of nitric acid grade austenitic stainless steels

The corrosion resistance of three indigenous nitric acid grade (NAG) type 304L stainless steel (SS), designated as 304L1, 304L2 and 304L3 and two commercial NAG SS designated as Uranus-16 similar to 304L composition and Uranus-65 similar to type 310L SS were carried out in nitric acid media. Electrochemical measurements and surface film analysis were performed to evaluate the corrosion resistance and passive film property in 6 N and 11.5 N HNO₃ media. The results in 6 N HNO₃ show that the indigenous NAG 304L SS and Uranus-65 alloy exhibited similar and higher corrosion resistance with lower passive current density compared to Uranus-16 alloy. In higher concentration of 11.5 N HNO₃, transpassive potential of all the NAG SS shows a similar range, except for Uranus-16 alloy. Optical micrographs of all the NAG SS revealed changes in microstructure after polarization in 6 N and 11.5 N HNO₃ with corrosion attacks at the grain boundaries. Frequency response of the AC impedance of all the NAG SS showed a single semicircle arc. Higher polarization resistance (R_P) and lower capacitance value (CPE-T) revealing higher film stability for indigenous NAG type 304L SS and Uranus-65 alloy. Uranus-16 alloy exhibited the lowest R_P value in both the nitric acid concentration. Auger electron spectroscopy (AES) study in 6 N and 11.5 N HNO₃ revealed that the passive films were mainly composed of Cr₂O₃ and Fe₂O₃ for all the alloys. The corrosion resistance of different NAG SS to HNO₃ corrosion and its relation to compositional variations of the NAG alloys are discussed in this paper.     

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.     

Acoustic emission during pitting corrosion of 304 stainless steel

Acoustic emission (AE) during pitting corrosion of 304 stainless steel (304 SS) in H₂SO₄ solutions with different pH values and Cl⁻ concentrations was studied. Two types of AE signals are detected in all solutions. Each type of signals is characterized by AE parameters (rise time, counts number, duration and amplitude) and waveform carefully. It is believed that the hydrogen bubbles evolution inside the pits is the AE source.     

Effect of nickel alloying on crevice corrosion resistance of stainless steels

The crevice corrosion behaviour of stainless steels containing 25 mass% Cr, 3 mass% Mo and various amounts of Ni was investigated in natural seawater. The results showed that ferritic steels containing nickel were more resistant to corrosion than both ferritic steels without nickel and austenitic steels. The superiority of the Ni bearing ferritic steel over the other steels was in close agreement with the depassivation pH of those steels in acidic chloride solutions. The results showed that the addition of Ni to ferritic steel was effective in decreasing the depassivation pH and the dissolution rate in acidic chloride solutions at crevices.