Composition changes around sulphide inclusions in stainless steels, and implications for the initiation of pitting corrosion

We report high-resolution SIMS microscopy measurements, which show that many ‘MnS’ inclusions have surrounding them a narrow ‘halo’ of half-width typically 100 nm that is strongly enriched in Fe, forcing consideration of the electrochemistry of FeS as a determinant of the behaviour of the inclusion boundary. We suggest that on exposure to water a very thin and porous metal-deficient polysulphide skin forms between the bulk of the inclusion and the steel, within which a pit can be triggered. The results resolve a controversy concerning the composition of the boundary region around inclusions in stainless steel and re-emphasise its potential significance.     

Effects of copper addition on the formation of inclusions and the resistance to pitting corrosion of high performance duplex stainless steels

To elucidate the effects of copper addition on the formation of inclusions and the resistance to pitting corrosion of alloys, potentiodynamic and potentiostatic polarization tests, a SEM-EDS analysis of inclusions, and thermodynamic calculations of the formation of inclusions were conducted. The addition of copper to the base alloy increased the number and area of numerous (Mn, Cr, (Al), (Fe)) oxides and oxy-sulfides due to an increase in the activity of chromium and resulted in decreased pitting resistance. The thermodynamic prediction of the formation of inclusions was in good agreement with the experimental results.     

Effects of cerium on the compositional variations in and around inclusions and the initiation and propagation of pitting corrosion in hyperduplex stainless steels

Ce addition to a hyperduplex stainless steel increased its resistance to pitting corrosion because of the formation of stable Ce oxides and a decrease in the area of microcrevices between the matrix and inclusions that act as pit initiation sites. In addition, Cr-enriched zones were formed around Ce oxides with low Cr content in the Ce added alloy. Pitting corrosion in the base alloy initiated at the microcrevice and propagated to Cr oxides, which deteriorated the pitting corrosion resistance. However, pitting corrosion in the Ce added alloy propagated not to the stable Ce oxides but to the matrix.     

Investigation into the influence of laser melting on the sulphide inclusions in AISI 416 stainless steel

AISI 416 is a high sulphur martensitic stainless steel with elliptical shaped sulphide inclusions over 2 μm in length. After laser melting the sulphide inclusions became spherical and reduced in size to below 0.5 μm in diameter. SEM investigations showed that the total number of inclusions increased dramatically and it was calculated that the total volume of sulphur in the stainless steel had not changed during the laser treatment. The pitting potential was increased by over 200 mV with an inverse linear dependency on the average inclusion size. The frequency of metastable pitting events decreased by a factor of 100.     

In situ AFM detection of pit onset location on a 304L stainless steel

A set-up combining an AFM and an electrochemical cell has been used to study in situ the local corrosion of a 304L stainless steel in an aqueous chloride-containing solution. The focus was made on the sites where pits were initiated under controlled potential in order to establish whether or not the pits were randomly distributed at the nanoscale. Grain boundaries and surface stoichiometric inhomogeneities appeared to concentrate pit onsets significantly. The influence of the mechanical history of the material, especially soft surface strain hardening, on the location of the first pits has been shown. The study revealed that 70% of the pits initiated at strain hardened areas resulting from mechanical polishing. A plausible model has been suggested to explain such a behaviour.     

Electrochemical and XPS studies of the passive film formed on stainless steels in borate buffer and chloride solutions

The passivity of AISI 304L and AISI 316L stainless steels in a borate buffer solution, with and without the addition of chloride ions, was studied using cyclic voltammetry and potentiodynamic measurements. The passive layers formed by electrochemical oxidation at different passivation potentials on both the stainless steels were studied by X-ray photoelectron spectroscopy, their compositions were analysed as a function of depth, and the cationic fraction of the passive film was determined. The passive films established on the two stainless steels in the borate buffer solution at pH = 9.3 contained the oxides of two main elements, i.e., Fe and Cr. The oxides of the alloying elements Ni and, optionally, Mo, also contribute to the passive layer. In the presence of chloride ions a strong chromium enrichment was observed in the passive layers.     

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.     

Tribocorrosion behaviour of low temperature plasma carburised 316L stainless steel in 0.5 M NaCl solution

Experiments have been carried out to study the tribocorrosion behaviour of low temperature plasma carburised 316L stainless steel under unidirectional sliding in 0.5 M NaCl solution, using a pin-on-disk tribometer integrated with a potentiostat for electrochemical control. It is found that the carburised layer exhibits much better resistance to material removal than the untreated specimen, particularly at anodic potentials. No corrosion pits are observed inside the wear track on the carburised specimen at anodic potentials as high as 750 mV (SCE). The results are discussed in terms of the relative contribution of wear and corrosion to overall material removal by tribocorrosion.     

Environmental factors affecting pitting corrosion of type 304 stainless steel investigated by electrochemical noise measurements under potentiostatic control

Electrochemical noise measurements on anodically polarised type 304 stainless steel surfaces in contact with buffer solutions of neutral pH were performed to study the effect of chloride ions in the nucleation of pitting corrosion. Passive layer stability and susceptibility to pitting corrosion after pickling and passivation at different environmental conditions were also investigated by means of electrochemical current noise measurements under cathodic and anodic polarisation. According to the obtained experimental results pits nucleate independently on the presence of chloride ions. It has been also shown that protectiveness of stainless steel surfaces after pickling strongly depends on the relative humidity of the environment in which the surface is subsequently passivated.     

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.     

Explanation of the effect of high chloride concentration on the critical pitting temperature of stainless steel

We correlate the effect of high chloride concentration on the critical pitting temperature (CPT) of type 316L stainless steel with its effect on the critical pit solution chemistry as determined by the artificial pit technique. It is shown that the change in CPT with bulk chloride concentration (0.5-9 mol kg⁻¹) can be correlated with a change in the ratio of C^∗/C_s, where C^∗ is the critical dissolved alloy cation concentration to sustain pitting, and C_s is the solubility of FeCl₂ at the pit surface. A complicating factor is that natural pits can only grow with C^∗ = C_s at the lower chloride concentrations, but can grow without the salt film at very high chloride concentrations; this transition is believed to occur close to 5 or 6 m bulk chloride concentration. The dependence of C_s on bulk chloride concentration is given a new interpretation based on a common-ion effect operating within an altered local chemistry with complexation.     

Influence of cold working on the pitting corrosion resistance of stainless steels

This paper addresses the influence of cold rolling and tensile deformation on the pitting corrosion resistance of AISI 304 and AISI 430 stainless steels, investigated using some electrochemical techniques specifically designed for the different pitting stages to be analyzed separately. Cold work is shown to act differently depending on the pitting stage under consideration. (i) The pit initiation frequency shows a maximum after 20% cold-rolling reduction or 10% tensile deformation. This maximum is also observed on the ferritic grade, contradicting the hypothesis of a direct effect of strain-induced martensite, and is more likely related to the dislocations pile-ups. (ii) The pit propagation rate increases monotonously with cold rolling reduction, and pit repassivation ability decreases (leading to a larger number of stable pits), suggesting that the overall dislocation density is the controlling factor in these stages. Last, the significance of pitting potential measurements is discussed in the light of the effect of the cold-rolling reduction on the measured values.     

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.     

Laser Raman microscopic studies of passive films formed on type 316LN stainless steels during pitting in chloride solution

The surface films formed on type 316LN stainless steels (SS) with different nitrogen contents, during potentiodynamic polarization in acidified 1 M NaCl solution, were characterized by Laser Raman Spectroscopy (LRS). LRS confirmed the presence of oxides and oxychlorides of iron and chromium, hydrated chlorides and nitrates in the film. Raman mapping showed increasing nitrate content in the film with increasing nitrogen content. The film on the uncorroded material showed the presence of chromium and molybdenum oxides. The improvement in pitting corrosion resistance of type 316LN SS with increasing nitrogen content was attributed to increased amount of nitrates in the passive film.     

Effects of non-metallic inclusions on the initiation of pitting corrosion in 11% Cr ferritic stainless steel examined by micro-droplet cell

This paper explores the effects of non-metallic inclusions (NMIs) on the initiation of pitting corrosion in type 409L stainless steels refined by the argon oxygen decarburization (AOD) and vacuum oxygen decarburization (VOD) processes. The dominant NMIs in the AOD and VOD samples were (Ti, Ca)-oxides and Ti-nitrides, respectively. In-situ electrochemical noise (EN) and micro-electrochemical analyses were conducted to investigate quantitatively the inherent effects of the NMIs on the pitting corrosion of the alloys. Pitting corrosion was initiated mostly around the (Ti, Ca)-oxides in the AOD samples, while little such corrosion occurred around the Ti-nitrides in the VOD samples. In addition, the pitting resistance of the AOD samples increased with increasing Ti content and decreasing Ca content in the (Ti, Ca)-oxides.     

Effect of austenite stability on the pitting corrosion resistance of cold worked stainless steels

The influence of cold rolling on the pitting resistance of stainless steels is investigated with respect to the austenite stability. A maximum in pitting initiation frequency for 20% reduction is confirmed whatever the austenite stability, but the value of this maximum fairly correlates to the amount of deformation-induced martensite. A direct influence of dislocations piling-up and an indirect role of martensite as a pile-up stabilizer is postulated. In the potentiostatic regime, cold work is shown to lower the repassivation ability and to increase the number of stable pits. Then, addition of alloying elements (such as copper) affects the pitting resistance not only for chemical but also for mechanical reasons (such as their effect on the staking fault energy and austenite stability), confirming the decisive role of microstructure in pitting corrosion of industrial alloys.     

Corrosion behaviour of low temperature plasma carburised 316L stainless steel in chloride containing solutions

The electrochemical corrosion behaviour of the carburised (expanded austenite) layer on 316L austenitic stainless steel produced by low temperature plasma carburising has been studied in 0.5 M NaCl and 0.5 M HCl + 0.5 M NaCl solutions. The present work focuses on the variation of the corrosion behaviour of the carburised layer with depth from the surface and the effect of carbon concentration on electrochemical behaviour. The results show that the carburised layer has excellent resistance to localised corrosion. There exists a critical carbon concentration, above which the expanded austenite possesses excellent resistance to both metastable pit formation and pit growth.     

The influence of the cathodic process on the interpretation of electrochemical noise signals arising from pitting corrosion of stainless steels

The use of electrochemical noise (EN) measurements for the investigation and monitoring of corrosion has allowed many interesting advances in the corrosion science in recent years. A special advantage of EN measurements includes the possibility to detect and study the early stages of localized corrosion. Nevertheless, the understanding of the electrochemical information included in the EN signal is actually very limited. The role of the cathodic process on the EN signals remains uncertain and has not been sufficiently investigated to date. Thus, an accurate understanding of the influence of the cathodic process on the EN signal is still lacking. On the basis of different kinetics of the oxygen reduction it was established that the anodic amplitude of transients arising from pitting corrosion on stainless steel can be decreased by the corresponding electron consumption of the cathodic process. Therefore, the stronger the electron consumption, the weaker the anodic amplitude of the EN signal becomes. EN signals arising from pitting corrosion on stainless steel can be measured because the cathodic process is inhibited by the passive layer. This was confirmed by means of EN measurements under cathodic polarisation. Since the cathodic process plays a decisive role on the form of transients arising from pitting corrosion, its influence must be considered in the evaluation and interpretation of the EN signals.     

Pitting corrosion behaviour of austenitic stainless steels with Cu and Sn additions

The influence of Cu and Sn on the pitting corrosion resistance of AISI 304 and 316 stainless steels in chloride-containing media has been investigated. The corrosion behaviour was evaluated by cyclic polarization, potentiostatic CPT measurements and electrochemical impedance spectroscopy in 3.5 wt% NaCl. The corrosion resistance was also studied in FeCl₃ under Standard ASTM G-48. According to the results, Cu addition favours pit nucleation but inhibits its growth, whereas Sn exerts the opposite effect, favouring pit growth and inhibiting its nucleation. Studies by SEM, X-ray mapping and EDS analysis showed Cu-, Cl- and O-rich corrosion products that reduce the extent of corrosion damage.     

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.