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.     

Surface chemistry and corrosion behaviour of 304 stainless steel in simulated seawater containing inorganic sulphide and sulphate-reducing bacteria

Although many studies have been carried out regarding the role of sulphide anions in promoting microbial corrosion of various metal substrates, very little is known about the differences between inorganic sulphide and biogenically-derived sulphide by sulphate-reducing bacteria (SRB) and what the reasons for differing corrosion behaviour between the two types of sulphide may be towards common metals. In this study, various electrochemical and surface analytical techniques were employed to study the effect of the inorganic and biogenic sulphide (active SRB present) on the surface chemistry and corrosion behaviour of 304 stainless steels in a simulated seawater-based modified Baar’s (SSMB) medium. Clear differences in the surface chemistry of the sulphurised passive film by inorganic and biogenic sulphide (active SRB present) were quantified by X-ray photoelectron spectroscopy (XPS). The transformation of metal sulphides in abiotic and biotic sulphide solutions with the exposure time was correlated with different corrosion behaviour of 304 stainless steels.     

Effect of sulphide on the corrosion behaviour of AISI 316L stainless steel and its constituent elements in simulated Kraft digester conditions

The electrochemical behaviour of AISI 316L steel and its constituent metals in simulated Kraft digester white liquor at 170 °C has been studied by registering slow scan rate voltammograms and impedance spectra at the corrosion potential. Interpretation of the results in terms of two approaches - the Mixed-Conduction Model for passive films and a two-step dissolution reaction - allowed for the estimation of corrosion currents and polarisation resistances as depending on the material and electrolyte medium. Tentative conclusions on the effect of sulphur-containing species in the white liquor on the corrosion mechanism of the studied materials are drawn.     

Effect of surface oxide properties on corrosion resistance of 316L stainless steel for biomedical applications

Surface passivation is a promising technique for improving the corrosion resistance both in vitro and in vivo as well as the biocompatibility of 316L stainless steel. In this work, we studied the effect of different passivative processes on the in vitro corrosion resistance of 316L stainless steel wire. Characterization techniques such as anodic polarization test, scanning electron microscopy, auger electron spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy were employed to co-relate the corrosion behavior to various surface characteristics and surface treatments. Results showed that all of these surface treatments did not improve the corrosion resistance of the alloy satisfactorily except amorphous oxidation. This improvement is attributed to the removal of plastically deformed native air-formed oxide layer and the replacement of a newly grown, more uniform and compact one which is composed of nano-scale oxide particles with higher oxygen and chromium concentrations. The properties of surface oxide layer, rather than its thickness, seem to be the predominant factor to explain the improvement of in vitro corrosion resistance.     

Changes in the passive layer of corrugated austenitic stainless steel of low nickel content due to exposure to simulated pore solutions

In this work, changes undergone at the passive layer of a new type of corrugated austenitic stainless steel (low Ni, high Mn 204Cu type) when exposed to solutions simulating that contained in the pores of concrete have been studied. Changes in the nature of the passive layer have been characterized by X-ray photoelectronic spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). Particular focus has been put on the influence of the presence of chlorides and/or carbonation in the solution. Changes in the passive layer due to the passivation treatment that is often applied to corrugated stainless steels during manufacturing processes have also been considered. The results obtained on the 204Cu type steel have been compared with those obtained on more traditional, high Ni, austenitic AISI 304 grade and duplex SAF 2205 grade. During the immersion in simulated pore solutions, 204Cu type suffers more intense redox processes than other studied stainless steels. Moreover, it shows less Cr-rich protective passive layers in these media.     

Oxidation of stainless steel 304L in carbon dioxide

Oxidation of 304L stainless steel in a carbon dioxide atmosphere at 10⁵ Pa has been studied. Between 1193 and 1293 K the oxidation kinetics exhibit first a rapid increase, then a parabolic behaviour with apparent activation energy of (209 ± 8) kJ mol⁻¹ and obeys a Langmuir pressure law. After 1.15 mg cm⁻², the kinetics become almost linear.The reaction products are chromia at the grain boundaries, wüstite (Fe_1−xO) on the surface for weight gains greater than 0.30 mg cm⁻² and chromite. The very complex reaction mechanism takes into account random buckling for weight gains >1.15 mg cm⁻².     

Nanostructure and local properties of oxide layers grown on stainless steel in simulated pressurized water reactor environment

The morphology and local electrical resistance of duplex oxide films formed on 316L stainless steel at 325 °C in simulated primary coolant of pressurized water reactor have been investigated at the nanometre scale with Conductive Atomic Force Microscopy. The electrical resistance varies over ∼1 order of magnitude for most oxide grains and over 2–3 orders of magnitude locally at grains and grain boundaries. This is rationalized in terms of local variation of the composition and thus resistivity of the mixed Fe(II)–Cr(III) barrier inner layer of the oxide films with grain boundaries of the outer layer possibly promoting Cr(III) enrichment.     

Microstructural analysis and corrosion behaviour of D9 stainless steel - Zirconium metal waste form alloys

Metal waste form (MWF) alloys of D9 stainless steel with 5-20 wt.% zirconium (Zr) were cast and used for the present work. The microstructural analysis by scanning electron microscopy of as-cast MWF alloys showed the presence of two distinctly different phases. Phases identified by X-ray diffraction techniques are mostly iron-based γ-austenite, Fe-Zr and Ni-Zr-type intermetallics. Corrosion properties evaluated by potentiodynamic polarization method in de-mineralized water at pH 1, 5, and 8 showed lower breakdown potential at pH 1 compared to pH 5 and 8. Impedance study showed a single semicircle curve with high polarization resistance indicating stable passive film under all conditions.     

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.     

The effect of annealing on the corrosion behaviour of 444 stainless steel for drinking water applications

In this study, the corrosion behaviour of annealed and not annealed AISI 444 ferritic stainless steel in tap water with and without addition of selected concentrations of chloride ions was investigated. Cyclic potentiodynamic macro (large area) and micro (small area) polarization measurements (CPP), salt spray test, SEM and EDS analysis were employed to evaluate the pitting and crevice corrosion susceptibility of annealed and not annealed AISI 444. The results obtained indicate that annealing does not improve the resistance to pitting and crevice corrosion. Moreover, micro CPP indicates local susceptibility to pitting on both annealed and not annealed materials; such susceptibility was not evident from macropolarization tests.     

Fatigue strength of 316L-type stainless steel in simulated body fluids

The fatigue strength of commercial SUS316L stainless steel was studied in PBS(−) (phosphate buffer solution) with different dissolved oxygen contents and CPBS (a 0.9 mass% NaCl-containing citric phosphate buffer solution) with different pH levels, i.e., 5.0, 6.0, and 7.5. The results obtained are as follows. (1) The fatigue behaviour in PBS(−) was hardly affected by the dissolved oxygen content. (2) The fatigue strength in a high-cycle region was much lower in CPBS of pH 7.5 than in PBS(−) of pH 7.5. (3) The fatigue strength in CPBS decreased with decreasing pH from 7.5 to 5.0.     

Zinc treatment effects on corrosion behavior of 304 stainless steel in high temperature, hydrogenated water

Trace levels of soluble zinc(II) ions (30 ppb) maintained in mildly alkaline, hydrogenated water at 260 °C were found to lower the corrosion rate of austenitic stainless steel (UNS S30400) by about a factor of five, relative to a non-zinc baseline test [S.E. Ziemniak, M. Hanson, Corros. Sci. 44 (2002) 2209] after 10,000 h. Characterizations of the corrosion oxide layer via grazing incidence X-ray diffraction and X-ray photoelectron spectroscopy in combination with argon ion milling and target factor analysis, revealed that miscibility gaps in two spinel binaries—Fe(Fe_1−mCr_m)₂O₄ and (Fe_1−nZn_n)Fe₂O₄—play a significant role in determining the composition and structure of the corrosion layer(s). Although compositions of the inner and outer corrosion oxide layers represent solvus phases in the Fe₃O₄-FeCr₂O₄ binary, zinc(II) ion incorporation into both phases leads to further phase separation in the outer (ferrite) layer. Recrystallization of the low zinc content ferrite solvus phase is seen to produce an extremely fine grain size (∼20 nm), which is comparable in size to grains in the inner layer and which is known to impart resistance to corrosion. Zinc(II) ion incorporation into the inner layer creates additional corrosion oxide film stabilization by further reducing the unit cell dimension via the substitution reaction

0.2Zn²⁺(aq)+Fe(Fe_0.35Cr_0.65)₂O₄(s)?0.2Fe²⁺(aq)+(Zn_0.2Fe_0.8)(Fe_0.35Cr_0.65)₂O₄(s)     

The behaviour of praseodymium 4-hydroxycinnamate as an inhibitor for carbon dioxide corrosion and oxygen corrosion of steel in NaCl solutions

Praseodymium 4-hydroxycinnamate (Pr(4OHCin)₃) was investigated as a novel corrosion inhibitor for steel in NaCl solutions, and found to be effective at inhibiting corrosion in both CO₂-containing and naturally-aerated systems. Surface analysis results suggest that the corrosion inhibition ability of Pr(4OHCin)₃ in the naturally-aerated corrosion system could be attributed to the formation of a continuous protective film. For the CO₂-containing system, the corrosion inhibition efficiency of Pr(4OHCin)₃ was predominantly because of formation of protective inhibiting deposits at the active electrochemical corrosion sites, in addition to a thinner surface film deposit.     

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.     

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.     

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.     

Determination of threshold stress intensity for chloride stress corrosion cracking of solution-annealed and sensitized austenitic stainless steel by circumferential notch tensile technique

This paper discusses a new approach to determination of threshold stress intensity factor for stress corrosion cracking (K_ISCC) of stainless steel in 42% MgCl₂ environment at 154 °C. K_ISCC of solution-annealed and sensitized AISI 304 stainless steel in chloride environment has been determined using circumferential notch tensile (CNT) technique. K_ISCC data generated using CNT technique have been compared with those generated using traditional techniques such as compact tension and double cantilever beam (reported in the literature). The results presented here validate the ability of CNT technique for determination of K_ISCC of sensitized as well as solution-annealed austenitic stainless steel. This paper also discusses the mechanistic aspects of the difference in fractographic features of the sensitized and solution-annealed stainless steel.     

Oxidation of 316 stainless steel in supercritical water

The oxide scales of 316 stainless steel (316 SS) have been examined after exposure to supercritical water (SCW) with 2.0% H₂O₂ for up to 250 h. The exposed samples were analyzed using weight measurement, scanning electron microscopy (SEM), and X-ray diffraction analysis (XRD). It was found that mass gain of all samples increased with increasing temperature and exposure time. Higher temperature SCW resulted in rougher surfaces and thicker oxide scales. Duplex layer oxide structures with Ni-enrichment at the oxide/metal interface developed on all samples exposed to SCW, which were identified as Fe₂O₃/Fe₃O₄ + spinel/Cr₂O₃/Ni-enrichment/316 SS from the outer to inner layer. The possible oxidation mechanisms are also discussed.     

Effects of nitrogen on the passivity of Fe-20Cr alloy

Influences of nitrogen on the passivity of Fe-20Cr-(0, 1.1)N alloys were examined by in situ electrochemical techniques. Nitrogen was incorporated in the form of (Fe, Cr)-nitrides in the passive film, and Cr was enriched in the film of the alloy with nitrogen. Photocurrent analysis demonstrated that the structure of passive film formed on Fe-20Cr-1.1N alloy is Cr-substituted γ-Fe₂O₃ with (Fe, Cr)-nitrides. Mott-Schottky analysis revealed that the film formed on Fe-20Cr-1.1N contained higher Cr⁶⁺ and lower Cr³⁺ vacancy concentrations compared with that on Fe-20Cr alloy. All of these results were associated with the enhanced protectiveness of the film on Fe-20Cr-1.1N.