Depth profile analysis of thin passive films on stainless steel by glow discharge optical emission spectroscopy

Thin passive films formed on highly corrosion-resistant type-312L stainless steel, containing 20 mass% chromium and 6 mass% molybdenum, in 2 mol dm⁻³ HCl solution at 293 K have been analyzed by glow discharge optical emission spectroscopy (GDOES). The stainless steel does not suffer pitting corrosion even in this aggressive solution, showing a wide passive potential region. The depth profiles obtained clearly show a two-layer structure of the air-formed and passive films: an outer iron-rich layer and an inner layer highly enriched in chromium. Alloy-constituting molybdenum is deficient in the inner layer of the passive films and is enriched in the outer layer, particularly at the active dissolution potential. The molybdenum species in the outer layer may retard the active dissolution of stainless steel, promoting the formation of stable passive films highly enriched in chromium. Chloride ions are present only at the outermost part of the passive films, not penetrating into the interior part.     

Depassivation-repassivation behavior of type-312L stainless steel in NaCl solution investigated by the micro-indentation

Repassivation behavior of type-312L stainless steel containing 6% of molybdenum was examined in NaCl solution using in situ micro-indentation technique, together with type-304 and 316L stainless steels. High stability of the passive film formed on the type-312L stainless steel was also examined by depth profiling analysis of passive films using glow discharge optical emission spectroscopy (GDOES). In 0.9 mol dm⁻³ NaCl solution at 296 K the type-304 and 316L stainless steels are passive only up to 0.3 V (SHE), above which pitting corrosion occurs. In contrast, no pitting corrosion occurs on type-312L stainless steel. Despite the significant difference of the pitting corrosion resistance, the repassivation kinetics of the three stainless steels, examined by micro-indentation at 0.3 V (SHE), is similar. The presence of molybdenum in the stainless steel does not influence the repassivation kinetics. The charge required to repassivate the ruptured type-312L stainless steel surface increases approximately linearly with the potential, even though the passivity-maintaining current increased markedly at potentials close to the transpassive region. Repassivation occurs without accompanying significant dissolution of steel, regardless of the stability of passive state. Depth profiling analyses of the passive films on the type-312L stainless steels formed at several potentials revealed that molybdenum species enrich in the outer layer of the passive film, below which chromium-enriched layer is present. The permeation of chloride ions may be impeded by the outer layer containing molybdate, enhancing the resistance against the localized corrosion of the type-312L stainless steel.     

An X-ray photo-electron spectroscopic study on the role of molybdenum in increasing the corrosion resistance of ferritic stainless steels in HC1

X-ray photo-electron spectroscopy has been used to investigate the correlation between composition of surface films and the beneficial effects of molybdenum addition to high purity, 30Cr ferritic stainless steels in improving the corrosion resistance properties in HCI. It has been found that the passive films formed consist mainly of hydrated chromium oxy-hydroxide and the composition of the films on 30Cr and 30Cr-2Mo stainless steels is essentially the same, except for the existence of a small amount of hexavalent molybdenum on the latter steel. The surface film formed in the active region contains a large amount of hexavalent molybdenum. The beneficial effects of molybdenum have been interpreted as follows: molybdenum eliminates the active surface sites through the formation of molybdenum oxy-hydroxide or molybdate on these site, on which it is difficult to form the stable passive film. This leads to the appearance of a homogeneous steel surface and to the formation of a homogeneous passive film.     

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.     

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.     

Influence of pH on the passivation behavior of 254SMO stainless steel in 3.5% NaCl solution

The potentiodynamic polarization measurement of 254SMO stainless steel (UNS 31254) was conducted in 3.5% NaCl solutions with pH ranging from 0.1 to 5. The results indicated that this stainless steel offered excellent pitting corrosion resistance in corrosive environments. Further, it also exhibited various features on the polarization curves in different pH solutions. The electrochemical constant-potential passivation treatment performed at different pH followed by XPS analysis revealed that the primary constituents of the outermost layer of the passive films formed in the weak (pH 5) and strong (pH 0.8) acid solutions are iron oxides and Cr₂O₃ and Cr(OH)₃, respectively. Molybdenum oxides, primarily in the six-valence state, existed in the outermost layer of the passive film. Only very weak signals corresponding to that of nickel oxides were detected in the film formed in the weak acid (pH 5) solution. The ICP-MS analyses indicated selective dissolution of a significant amount of Fe and a few Mo and Ni ions during the passivation treatment in the strong acid (pH 0.8) solution. No Cr dissolution was observed; this indicated that the Cr in the film is relatively stable. XPS depth profiling results showed that a similar bilayer-structured film was formed in both the solutions (pH 0.8 and 5); the outer layer of this film is primarily composed of Cr(OH)₃ and Mo(VI), and the inner layer, Cr₂O₃ and Mo(IV). The results of the examinations of passive film formations and dissolution by XPS and ICP-MS were consistent with the polarization curves.     

Comparative corrosion resistance of plasma-based low-energy nitrogen ion implanted austenitic stainless steel

A high nitrogen face-centered-cubic phase (γ_N) was obtained on the nitrided surface of 1Cr18Ni9Ti austenitic stainless steel by plasma-based low-energy nitrogen ion implantation. No pitting corrosion for the γ_N phase was confirmed by electrochemical polarization measurement in 3% NaCl solution. The protective passive film with a duplex character, iron hydroxide/oxides in the outer region and chromium hydroxide/oxides and iron oxides accompanying chromium and iron nitrides in the inner region, was by 2-3 times thicker than that of original stainless steel. The thick iron hydroxide/oxides region formed on the chromium hydroxide/oxides region due to the increase of alkalinity in the solution, leading to barrier against penetration of localized attack of the aggressive ions. The equivalent general corrosion resistance for the γ_N phase was observed in 0.5 mol/l H₂SO₄ solution relative to the original stainless steel. The passive film formed on the γ_N phase in 0.5 mol/l H₂SO₄ solution was similar to that of original stainless steel. The different role of nitrogen was proposed in pitting corrosion resistance and general corrosion resistance of austenitic stainless steel.     

Passivity of stainless steel in sulphuric acid under chemical oxidation

The main purpose of the present work was to study the passivity of stainless steel in sulphuric acid under chemical oxidation with H₂O₂ solution. Potentiodynamic polarisation and open circuit potential (OCP) measurements indicated that H₂O₂ facilitates the increase of OCP of stainless steel which shifts from active region into passive region. The X-ray photoelectron spectroscopy results suggested that a passive film, composed of oxyhydroxides, Cr₂O₃, Cr(VI) species, NiO, and sulphate (FeSO₄, Cr₂(SO₄)₃·xH₂O), is achieved after H₂SO₄–H₂O₂ passivation. The passive mechanism under H₂O₂ oxidation was discussed and the corrosion resistance of passive film was compared with that of the passive films produced by HNO₃ passivity and H₂SO₄ potentiostatic passivity. The results of electrochemical impedance spectroscopy, cyclic voltammetry, and anodic polarisation experiments confirmed that the chemical oxidation with H₂O₂ solution is capable of improving the corrosion resistance of stainless steel significantly and the passive film is more stable than those produced by other passivating methods.     

Electrochemical study on hot corrosion of Si-modified aluminide coated In-738LC in Na2SO4-20 wt.% NaCl melt at 750 °C

The corrosion performance of the slurry Si-modified aluminide coating on the nickel base superalloy In-738LC exposed to low temperature hot corrosion condition has been investigated in Na₂SO₄-20 wt.% NaCl melt at 750 °C by combined use of the anodic polarization and characterization techniques.The coated specimen showed a passive behavior up to −0.460 V vs. Ag/AgCl (0.1 mol fraction) reference electrode, followed by a rapid increase in anodic current due to localized attack in the higher potential region. In the passive region, the anodic dissolution of constituents of the coating occurred through the passive film, probably SiO₂, at slow rate of 20-30 μA/cm². The passive current for the Si-modified coating was two orders of magnitude smaller than that for bare In-738LC, which is known as Cr₂O₃ former in this melt. This indicates that the SiO₂ film is chemically more stable than Cr₂O₃ film under this condition. However, pitting-like corrosion commenced around −0.460 V and proceeded at the high rate of 100 mA/cm² in the higher potential region than +0.400 V. The corrosion products formed on the coating polarized in different anodic potentials were characterized by SEM, EDS and XRD. It was found from the characterization that oxidation was dominant attack mode and no considerable sulfidation occurred at 750 °C. The SiO₂ oxide was not characterized in the passive region because the thickness of the passive film was extremely thin, but was detected as the primary oxide in the localized corrosion region, where the selective oxidation of Al was observed by further progress of the corrosion attack front into the inner layer of coating.     

Investigation on carbon dioxide corrosion behaviour of HP13Cr110 stainless steel in simulated stratum water

The carbon dioxide corrosion behaviour of HP13Cr110 stainless steel in simulated stratum water is studied by potentiodynamic curve and electrochemical impedance spectroscopy (EIS); the micro-structure and composition of the corrosion scale formed at high-temperature and high-pressure are analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results show that 13Cr stainless steel is in passive state in the stratum water, the passive current density increases and the passive potential region decreases with increasing temperature. The corrosion scale formed at high-temperature and high-pressure is mainly composed of iron/chromium oxides and a little amount of FeCO₃.     

Fabrication of continuous mesoporous organic–inorganic nanocomposite films for corrosion protection of stainless steel in PEM fuel cells

The organic–inorganic composite film was deposited on the 304 stainless steel as bipolar plate material for proton exchange membrane fuel cells by spin-coating method. As shown by XRD, N₂ adsorption–desorption and TEM, the composite films exhibit ordered mesoporous structures. The corrosion tests in 0.5 M H₂SO₄ system displayed that, compared with 304SS, the composite films made corrosion potential shifted to positive direction by 250–1000 mV (SCE) and corrosion current decreased by 1–3 orders of magnitude. Wherein, the C-50–60% composite film showed the optimal protective performance, its corresponding potentiostatic polarization process was extremely stable in the simulated fuel cells environment.     

Photoelectrochemical investigation of ac modulated passive films on 304 stainless steel in weak alkaline and neutral solutions

Abstract

A photoelectrochemical investigation has been carried out on an ac modulated passive film on AISI 304 stainless steel in 0·1M Na₂ B₄O₇ and 0·5M Na₂ SO₄ solutions. The results of the photocurrent measurements indicate that the photoresponse is determined by defects in the electronic structure of the films when the defects lead to localised states in the band gap region and that the photoresponse is sensitive to the passive condition and testing solutions. It is concluded that the passive film on 304 stainless steel is in a highly disordered amorphous state.     

Effect of Al and Ce oxide layers electrodeposited on OC4004 stainless steel on its corrosion characteristics in acid media

The changes in the corrosion characteristics of stainless steel OC4004 in 0.1 M HNO₃ after electrodeposition of thin Al and Ce oxide films on it has been investigated. The Ce₂O₃–CeO₂ layers have been found to possess a pronounced stabilizing effect on the steel passive state and on its corrosion resistance, respectively, whereas the Al₂O₃ layers do not improve considerably the corrosion behaviour of the SS/Al₂O₃ system. A twice-lower corrosion current was observed with a ternary SS/Al₂O₃/Ce₂O₃–CeO₂ system in the passive region, while the zones of potentials, where the steel is in a stable passive state, are not changed. The obtained results permit the assumption that the cerium oxides layer acts as an effective cathode playing a determining role with respect to the improvement of the corrosion behavior of the steel. It has been concluded that when the SS/Al₂O₃/Ce₂O₃–CeO₂ system is used in media containing nitric acid, the corrosion will proceed at potentials where the passive state of steel would not be disturbed.     

Effect of ZnO on the corrosion of zinc,Q235 carbon steel and 304 stainless steel under white light illumination

This paper discusses the effects of the coupling of ZnO–Zn, Q235 carbon steel, and 304 stainless steel on their corrosion in 3.5% NaCl under white light illumination. In the presence of Na₂S, ZnO provided photoelectrochemical cathodic protection for the coupled metals. In the absence of Na₂S, ZnO could only provide photoelectrochemical cathodic protection for 304 stainless steel. Under white light illumination, the open circuit potential of ZnO photoelectrode shifted in the negative direction. ZnO provided photoelectrochemical cathodic protection to the metals only when the open circuit potential of ZnO photoelectrode was more negative than that of the metals.     

Passivity of polycrystalline NiMnGa alloys for magnetic shape memory applications

The corrosion and passivation behaviour of bulk polycrystalline martensite Ni₅₀Mn₃₀Ga₂₀ and austenite Ni₄₈Mn₃₀Ga₂₂ alloys was compared in electrolytes with different pH values. Linear anodic and cyclic potentiodynamic polarisation methods and anodic current transient measurements have been conducted for the alloys and their constituents to analyze free corrosion, anodic dissolution and passive layer formation processes. Electrochemically treated alloy surfaces were characterized with scanning electron microscopy (SEM) and angle-resolved x-ray photoelectron spectroscopy (XPS). The electrochemical response of both alloys is in principal similar and is dominated by the Ni oxidation. In acidic solutions (pH 0.5 and 5) a slightly higher reactivity is detectable for the martensitic alloy which is mainly attributed to enhanced dissolution processes at the multiple twin boundaries. In weakly acidic to strongly alkaline solutions (pH 5-11) both alloys exhibit a low corrosion rate and a stable anodic passivity. While air-formed films comprise NiOOH, Ga₂O₃ and MnO₂, passive films formed in near neutral media (pH 5-8.4) are composed of Ni(OH)₂, NiOOH and Ga₂O₃ in the outer region and of NiO, MnO₂ and MnO in the metal-near region.     

The effect of denitrifying Fe-oxidizing bacteria TPH-7 on corrosion inhibition of sodium molybdate

The corrosion process characteristics in the presence of thermophilic strain TPH-7 were investigated. The results showed that (1) by adding Na₂MoO₄ to the sterilized solution, the steel could be well protected with the increasing of the concentration from 0 to 100 mg/l, which caused the decreasing of corrosion current; (2) in the solution with strain TPH-7 and Na₂MoO₄, corrosion product formed and corrosion current decreased slightly. Based on the SEM observation, strain TPH-7 would adhere to the steel surface to interfere with the corrosion inhibition process of steel by molybdate. Therefore, 100 mg/l Na₂MoO₄ could not inhibit the MIC caused by strain TPH-7.     

Über das Permeationsverhalten von Wasserstoff in einem stabilaustenitischen nichtrostenden Stahl

Permeation behaviour of hydrogen in a stable austenitic stainless steel Electrochemical method was used to study the effects of the passive film, polarization potential and the pH value in the solution on the permeation behaviour of hydrogen in the stable austenitic stainless steel 310. The diffusion coefficient of hydrogen at 25°C in this steel was determined to be (1.2 ± 0.1) ± 10⁻¹² m²s⁻¹, and that of the passive film was estimated to be about 10⁻²¹ m²s⁻¹. The saturated hydrogen permeation current was increased with the decrease of the pH-value in the solution; it was also increased not only with the increase of cathodic polarization potential, but also with the increase of the anodic polarization potential if it is above the breakdown potential of the passive film.     

Effects of Ti addition on microstructure and the associated corrosion behavior of a 22Cr-5Ni duplex stainless steel

The effects of Ti addition on microstructure and the associated electrochemical properties of 22Cr-5Ni duplex stainless steel were evaluated using X-ray diffraction, X-ray electron probe microanalysis, electron backscattered diffraction, scanning Kelvin probe force microscopy, scanning electron microscopy–energy-dispersive X-ray spectroscopy, electrochemical techniques, and X-ray photoelectron spectroscopy. The results indicated that the addition of a minor amount of Ti refined the grains, improved the pitting potential, and lowered passive current densities remarkably. However, excessive content could cause an imbalance of phase proportion of ferrite and austenite phases and precipitation of the coarse TiN particles. The films on the base and Ti-containing alloy have a similar chemical composition, but the addition of Ti enriched the chromium in the passive film. In particular, the ratio of Cr₂O₃ and Mo⁶⁺ increased, which helped to form a comparatively homogeneous and stable passive film on the duplex stainless steel.     

Effect of citrate ions on the electrochemical behaviour of low-carbon steel in borate buffer solutions

The electrochemical behaviour of cold-rolled low carbon steel was studied on both active and passive potential regions in borate buffer solutions with and without the addition of sodium citrate (NaCit). In the active region anodic charges increased significantly and R_CT values decreased with citrate, due to the formation of soluble complexes. In the passive potential region the film formed at +0.4 V in borate buffer solution with and without 0.010 M NaCit is probably enriched by Fe₃O₄ oxide, while films formed at +0.8 V are probably enriched by γ-Fe₂O₃. The equivalent circuit [R_s(R_CTQ)] fitted all experimental impedance data.     

Photocurrent and capacitance investigations into the nature of the passive films on austenitic stainless steels

Photocurrent and capacitance measurements of semiconductor passive films formed on metals and alloys can be used to study the electronic properties and reveal indirect information about structure and composition. The current work used these techniques to investigate the electronic properties of the passive films formed on three austenitic stainless steels, types 304L, 316L and 254SMO, in borate. Evidence was found for the existence of a large number of localised mid bandgap states, consistent with amorphous oxides. However, the flat-band potentials of the austenitic stainless steel passive films were found to be independent of both composition and measuring frequency. The most credible explanation for the bandgap values determined from photocurrent measurements is that the passive films are formed as dual layers, iron oxide outer layer and chromium oxide inner layer. This model does not need to evoke the potential dependent bandgaps used by previous authors.