Critical pitting temperature for Type 254 SMO stainless steel in chloride solutions

The variation with time of the open circuit potential of high molybdenum containing stainless steel (Type 254 SMO) was measured in 4% sodium chloride solution in the temperatures range 30-100 °C. The plot of steady state potentials as function of temperature showed an inflection at 50 °C, attributed to the decrease of oxygen solubility in test solution above 50 °C. Potentiodynamic cycling anodic polarization technique was used to determine the critical pitting potential (E_pit) and the critical protection potential (E_prot) of the steel in 4-30% NaCl solutions at temperatures between 30 and 100 °C. By plotting the two values versus solution temperature, the corresponding critical pitting (CPT) and the critical protection (CPrT) temperatures were determined. Both parameters decreased with increasing chloride content. Above the CPT, E_pit and E_prot decreased linearly with log[Cl⁻]. The addition of bromide ions to the solution shifted both E_pit and E_prot towards positive values. In 4% NaCl, E_pit increased linearly with pH in the range 1-10. The combined effect of chloride ion concentration and pH on the morphology of the pits was examined by scanning electron microscopy (SEM) following potentiodynamic cycling anodic polarization.     

Influence of input power to vibrator and vibrator-to-specimen distance of ultrasound on pitting corrosion of SUS304 stainless steel in 3.5% chloride sodium aqueous solution

The pitting corrosion of SUSU304 steel can be suppressed by the application of a 19.5 kHz ultrasound (US) in 3.5% NaCl aqueous solution. At a constant vibrator-to-specimen distance of d = 76 mm equal to the wavelength, the suppression effect increased with the input power to vibrator and the largest effect was obtained at the power of I = 8. At constant input powers of I = 2 or 8, the suppression effect decreased with the increase in the vibrator-to-specimen distance, but the largest effect was obtained at d = 68 mm in each case of I = 2 and 8.     

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.     

XPS analysis of the passive film formed on austenitic stainless steel coated with conductive polymer

Improvement of the passivation behavior of Type 304 austenitic stainless steel (SS) by coating with conductive polymers (CPs), like polyaniline (PANI) and poly(o-phenylenediamine) (PoPD), followed by exposure in an acid solution has been demonstrated. The passive films formed on SSs (after peeling off the polymer layer) are compared with those formed during anodic polarization under the same exposure condition. The passive films beneath the CPs are thicker and less hydrated than those formed on uncoated stainless steel. The polymer layer enhances the enrichment of chromium and nickel in the entire passive oxide, forming a more protective film than that formed during anodic polarization. The elemental distribution within the passive film is different in the two modes of passivation. The type of the polymer influences on the composition of the passive film. The best passivation is obtained by PoPD, with the passive film resulting in significant resistance of the SS to pitting corrosion in the 3% NaCl solution. The oxide film of this steel is characterized, in its inner and outer layers, by the highest ratio of Cr(OH)₃/Cr₂O₃ and the lowest content of iron species.     

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.     

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.     

Influence of the microstructure on the corrosion behaviour of low-carbon martensitic stainless steel after tempering treatment

The microstructure of grade X4CrNiMo16.5.1 stainless steel was studied at different scales. The chemical composition of the native passive film formed on the different phases was then determined at the microscale. The degree of homogeneity of the native passive film is discussed. Subsequently, the susceptibility to pitting corrosion of X4CrNiMo16.5.1 was quantified using the electrochemical microcell technique. The nature of precursor sites and the morphology of pits were investigated by combining scanning electron microscopy with Electron BackScatter Diffraction and potentiostatic pulse tests. The role of the microstructure and the cold-worked layer generated by polishing in pitting is discussed.     

Electrochemical polishing as a 316L stainless steel surface treatment method: Towards the improvement of biocompatibility

A 316L stainless steel (316L-SS) surface was electrochemically polished (EP) in an electrolyte of a new chemical composition at different cell voltages, with the aim of improving its corrosion resistance and biocompatibility. X-ray photoelectron spectroscopy results revealed that the EP-formed oxide films were characterized by a significantly higher atomic Cr/Fe ratio and film thickness, in comparison to the naturally-grown passive oxide film formed on the untreated (control) 316L-SS surface. As a result of the increase in the oxide film thickness and relative Cr enrichment, the EP-treated 316L-SS surfaces offered a notable improvement in general corrosion resistance and pitting potential. In addition, the attachment of endothelial cells (ECs) and smooth muscle cells (SMCs) to the 316L-SS surfaces revealed a positive effect of electropolishing on the preferential attachment of ECs, thus indicating that the EP surfaces could be endothelialized faster than the control (unmodified) 316L-SS surface. Furthermore, the EP surfaces showed a much lower degree of thrombogenicity in experiments with the platelet-rich plasma. Therefore, the use of the electrochemical polishing technique in treating a 316L-SS surface, under the conditions presented in this paper, indicates a significant improvement in the surface’s performance as an implant material.     

Metal release from various grades of stainless steel exposed to synthetic body fluids

Release rates of individual alloy constituents have been determined from seven grades of stainless steels exposed to two synthetic body fluids, used as surrogates for different areas of potential exposure in the lung: “Gamble’s solution”, (pH 7.4) that represents the interstitial fluid of the deep lung, and artificial lysosomal fluid (ALF) that represents the more acidic (pH 4.5-5) milieu of particles following their phagocytosis by macrophages. Total metal release rates from all grades of stainless steel investigated were low (<5 μg cm⁻² week⁻¹). The more acidic environment of ALF resulted in significantly higher total metal release rates (0.3-4.6 μg cm⁻² week⁻¹) compared to Gamble’s solution (<0.1 μg cm⁻² week⁻¹).     

Surface physico-chemistry study of an austenitic stainless steel: Effect of simple cold rolling treatment on surface contamination

The surface physico-chemistry properties of stainless steel and the effects of a cold rolling treatment were investigated. X-ray photoelectron spectroscopy (XPS) analyses were carried out on rolled surfaces at different rates. Thus, by characterizing passive film chemistry and contamination layer, the modifications due to this treatment were quantified, in particular an increase of the ratio (Fe/Cr)_oxide is evidenced with the level of the cold rolling treatment. Moreover, based on an angle resolved analysis, a new model where the contamination layer is represented as isolated parts was developed in order to describe the geometry of this carbon contamination. XPS experiments show an iron enrichment of the passive film during the cold rolling treatment, which seems to be explained by a surface heating during the mechanical treatment. Therefore, the new island model puts in evidence the effects of ageing time and surface condition on the geometry of carbon contamination. Hence, cold rolling increases the thickness and the recovery of carbon contamination on the stainless steel surface.     

Influence of long-term ageing in solution containing chloride ions on the passivity and the corrosion resistance of duplex stainless steels

The influence of long-term ageing in NaCl on the passivity and the electrochemical behavior of UNS S32304 is studied. The passive film thickness, the Cr/Fe ratio and the chloride content were significantly increased after ageing. The chloride distribution depends on residual stresses, sample microstructure and surface preparation. Local electrochemical measurements revealed that pitting potentials are between 250–550 mV vs. SCE after electropolishing. The higher the chloride content, the lower the local pitting potential. It was also shown that the presence of chloride was balanced by the enrichment in chromium after ageing. Then no pitting potential could be measured.     

Weld oxide formation on lean duplex stainless steel

Weld oxides have a strong influence on corrosion resistance, but have hitherto only been studied to a limited extent for duplex stainless steels. X-ray photoelectron spectroscopy (XPS) has here been used to study heat tint formed on gas tungsten arc (GTA) welds on the commercial duplex grades LDX 2101 (EN 1.4162/UNS S32101) and 2304 (EN 1.4362/UNS S32304) welded with and without nitrogen additions to the shielding gas. The process of heat tint formation is discussed in terms of transport phenomena to explain the effect of atmosphere, temperature and composition. The oxides formed were found to be enriched in manganese and corrosion testing shows that nitrogen has a strong influence on the weld oxide. A mechanism is proposed including evaporation from the weld pool and subsequent redeposition.     

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.     

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.     

XPS analysis of manganese in stainless steel passive films on 1.4432 and the lean duplex 1.4162

Passive films were compared on two stainless steels: the recent lean duplex EN 1.4162 and EN 1.4432 (316L). For alloys with significant amount of manganese and nickel, the Mn 2p_3/2 peak will overlap with the Ni-LMM. To resolve this overlap, Ni 2p_3/2 to Ni-LMM intensity ratios were recorded on 1.4432, compensated for overlayer thickness, and then used to fix the Ni-LMM intensities in the Mn 2p spectra on the duplex material. Manganese was found in oxidation states II and V/VI; its film content was not dependent on the bulk composition.     

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.     

Inhibition effect of chromate on the passivation and pitting corrosion of a duplex stainless steel in LiBr solutions using electrochemical techniques

The electrochemical behavior of duplex stainless steel (DSS) in LiBr media was investigated by anodic cyclic polarization curves and AC impedance measurements. The effect of bromide concentration and the presence of chromate in the solutions on the corrosion behavior of AISI 2205 was studied. Cyclic polarization curve analyses showed that there was different pitting susceptibility of passive films depending on the LiBr concentration. Pitting potential decreases with LiBr concentration in a semilogarithmic scale following two different slopes. Chromate presence displaces pitting potentials towards more positive values at low LiBr concentrations but it has no effect when LiBr concentration increases.The comparative analysis carried out in LiBr and LiBr chromate-containing solutions at two different concentrations, 0.016 M and 0.032 M, verifies the assumption that halogen ions facilitate inhibitor adsorption. The addition of halides strongly increased the inhibition efficiency of chromate. The passive film becomes more resistant when bromide concentration increases, although film thickness decreases.     

In situ synchrotron X-ray micro-tomography study of pitting corrosion in stainless steel

Pitting corrosion of stainless steel has been investigated with high-resolution in situ X-ray microtomography. The growth of pits at the tip of stainless steel pins has been observed with 3D microtomography under different conditions of applied current and cell potential. The results demonstrate how pits evolve in stainless steel, forming a characteristic “lacy” cover of perforated metal. In addition, it is shown how the shape of pits becomes modified by MnS inclusions.     

Annealing temperature effect on the pitting corrosion resistance of plasma arc welded joints of duplex stainless steel UNS S32304 in 1.0 M NaCl

Pitting corrosion resistance of 2304 duplex stainless steels after autogenous plasma-arc welding and subsequent short-time post-weld heat treatment at different temperatures, determined by critical pitting temperature in 1.0 M NaCl solution, has been investigated. The results showed that the as-welded joint displayed impaired pitting corrosion resistance and that pitting preferentially occurred at ferrite grain in heat-affected zone near the fusion line. Short-time annealing treatment at 1020–1120 °C has a beneficial effect on the pitting corrosion resistance of welded joint. The most favorable annealing temperature for the analyzed welded joints was found to be 1080 °C, at which the joint restored the pitting corrosion resistance lost during welding entirely.