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.     

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.     

EIS assessment of critical pitting temperature of 2205 duplex stainless steel in acidified ferric chloride solution

In this study, critical pitting temperature (CPT) of 2205 duplex stainless steel (DSS2205) was assessed using electrochemical impedance spectroscopy (EIS) in ferric chloride solution. In order to verify the results other methods such as ASTM G 48, potentiodynamic and potentiostatic polarisation and zero resistance ammeter (ZRA) were also employed. The results show a strong close relation between the results of this method by those of previous methods. CPT of the alloy is 40 °C based on standard method and 44 °C, 49 °C according to the ZRA and potentiostatic methods. Both potentiodynamic and EIS methods give an almost identical CPT value.     

Critical pitting temperature dependence of 2205 duplex stainless steel on dichromate ion concentration in chloride medium

In this study, the influence of various concentrations of dichromate and chloride ions on critical pitting temperature (CPT) of duplex stainless steel 2205 (DSS 2205) is investigated by employing potentiodynamic and potentiostatic CPT measurement methods. Potentiostatic results indicate that by adding 0.01 M to 0.1 M NaCl solution the CPT raised by 12 °C. Based on potentiodynamic CPT measurements in the solutions with ratio equal to one for solutions containing 0.1 M NaCl + 0.1 M and 0.01 M NaCl + 0.01 M , no CPT was detected up to 75 °C.     

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.     

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.     

Corrosion of low-temperature nitrided molybdenum-bearing stainless steels

Austenitic stainless steels with up to 6.1 wt.% Mo were nitrided at 425 °C and examined in 0.1 M Na₂SO₄ without and with chlorides at pH 3.0 and 6.5. Nitrided steels exhibited an increased resistance to pitting, but at pH 3.0 they had a decreased resistance to general corrosion. After corrosion at pH 3.0 surface films contained chromium nitrides and oxides of Mo, Cr and Fe. It is proposed that the improved pitting resistance of nitrided steels is associated with the initially accelerated dissolution which leads to the accumulation of corrosion resistant CrN and of oxidised steel components.     

Critical pitting temperature (CPT) assessment of 2205 duplex stainless steel in 0.1 M NaCl at various molybdate concentrations

In this study, the influence of various concentrations of molybdate () on critical pitting temperature (CPT) of duplex stainless steel 2205 (DSS 2205) in 0.1 M NaCl solution has been investigated by employing potentiodynamic and potentiostatic CPT measurements methods. No significant increase in CPT was observed in the presence of 0.0001 and 0.001 M molybdate. However, addition of 0.01 M increases 10 °C in CPT and pitting corrosion was not observed in solution containing 0.1 M molybdate up to 85 °C. Potentiostatic CPT measurements showed CPT values of 68 and more than 85 °C in 0.01 and 0.1 M molybdate concentrations, respectively.     

Correlation between critical pitting temperature and degree of sensitisation on alloy 2205 duplex stainless steel

In this study effect of different ageing conditions on intergranular corrosion, pitting corrosion and relation between critical pitting temperature (CPT) and degree of sensitisation (DOS) was investigated by potentiostatic polarisation and double loop-EPR methods. The results showed by increasing sensitisation time, DOS increased and measured CPT value decreased. In addition the values of DOS and CPT of specimens aged at 650 °C showed almost liner relation while this correlation was diminished for the specimens aged at 800 °C. The results may be attributed to the further formation of precipitates on specimens aged at temperature of 800 °C.     

Effect of laser surface melting on intergranular corrosion behaviour of aged austenitic and duplex stainless steels

In the present study, the effect of laser surface melting (LSM) on intergranular corrosion behaviour of aged austenitic stainless steels (UNS S30400, S31603, S32100 and S34700) and aged duplex stainless steels (UNS S31803 and S32950) were investigated. LSM of the aged stainless steels was carried out using a 2.5 kW CW Nd:YAG laser. The microstructure of the aged stainless steels after LSM depends on their compositions. After LSM, the aged austenitic stainless steels mainly contain austenite (γ) with some ferrite (δ) as the minor phase, but the carbide phases are completely eliminated. For the aged duplex stainless steels after LSM, δ becomes the major phase and the δ/γ phase balance is disturbed, whereas the sigma (σ) phase is eliminated. The degree of sensitization (DOS) and corrosion morphology of the aged stainless steels before and after LSM were determined by the double loop electrochemical potentiokinetic reactivation (DL-EPR) using a potentiostat and SEM observation, respectively. Desensitization of the aged stainless steels has been successfully achieved by LSM and their intergranular corrosion resistance is found to be significantly enhanced as reflected by the decrease in DOS due to dissolution of the carbides or σ phase, which reduced Cr depletion or the possibility of solute segregation at the grain or phase boundaries, despite the presence of δ and disturbance of δ/γ phase balance.     

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.     

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.     

Electrochemical behaviour of high nitrogen stainless steel in acidic solutions

The electrochemical behaviour of high nitrogen stainless steel in acidic solutions was studied by potentiodynamic polarization, EIS, Mott-Schottky and XPS. The passive film formed in neutral NaCl solution was very stable, but the stability of the film decreased with the addition of H₂SO₄ into the solution. The passive film formed in acidic Na₂SO₄ has a superior protective ability than that in acidic NaCl solution. The stability of the film formed in tested solution decreased with increase of applied potentials. The film formed on steel surface was of n-type semiconductor. Chloride penetration mechanism was proposed for the observed passive film breakdown.     

Effect of marine Pseudoalteromonas sp. on the microstructure and corrosion behaviour of 2205 duplex stainless steel

The effects of isolated marine Pseudoalteromonas sp. on the microstructure and corrosion behaviour of 2205 duplex stainless steel were investigated using electrochemical and surface analysis methods. Electrochemical studies demonstrated a negative shift in corrosion potential and an increase in corrosion current density in the presence of bacteria. EDS results showed a high concentration of chloride ions in the biofilm structure and a decrease in Cr content beneath the biofilm layer and near cracks. These results could lead to localised corrosion on metal surfaces. FESEM images illustrated the process of bacterial attachment on the metal surfaces at different exposure times.     

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.     

Effect of ageing heat treatments on the microstructure and intergranular corrosion of powder metallurgy duplex stainless steels

The influence of ageing heat treatments (675 and 875 °C for 1.5 to 48 h) on the microstructure and intergranular corrosion resistance of sintered in nitrogen duplex stainless steels was investigated. The materials were obtained by sintering mixtures of austenitic AISI 316L and ferritic AISI 430L powders. Corrosion behaviour was evaluated by using electrochemical techniques. The beneficial effect of nitrogen on corrosion behaviour of solution annealed samples was established. During ageing, secondary phases were precipitated and the intergranular and transgranular corrosion resistance significantly decreased though repassivation was observed in specimens aged at 875 °C for times up to 8 h.     

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.     

The corrosion behaviour of austenitic and duplex stainless steels in artificial saliva with the addition of fluoride

The evolution of the passive films on 2205 duplex stainless steel (2205 DSS) and AISI 316L stainless steel in artificial saliva, and with the addition of fluoride, was studied using electrochemical impedance spectroscopy (EIS) and potentiodynamic measurements. The extent of the passive range increased for the 2205 DSS compared to the AISI 316L in both solutions. The formation of the passive film was studied by EIS at the open-circuit potential (OCP). The passive layers were studied at the OCP by X-ray photoelectron spectroscopy (XPS). The passive films on both materials predominantly contained Cr-oxides, whereas the Fe species were markedly depleted.     

Electrochemical reactivation methods applied to PM austenitic stainless steels sintered in nitrogen-hydrogen atmosphere

Exposure methods (ASTM A262 Practice A and Modified Strauss Test) and electrochemical reactivation methods such as EPR and EPRDL was applied to PM 304L and PM 316L stainless and comparisons with wrought stainless steels were made. Sintering in vacuum and nitrogen-hydrogen atmosphere was chosen. The latter was the focus of the work and the former was used on comparative basis. It was seen how nitrogen in PM stainless steels plays a relevant role both when is dissolved and when is in intermetallic precipitates. A set of heat treatments were applied: annealing and sensitizing at 375, 675 and 875 °C. The results indicate that the electrochemical reactivation methods are suitable to evaluate the degree of sensitization of PM austenitic stainless steels.