Hydrogen effects on stainless steel passive film fracture studied by nanoindentation

Hydrogen effects on the fracture stress of passive film formed on 316L stainless steel were studied by nanoindentation. Hydrogen accumulated primarily on the sample surface and in the passive film. Displacement excursion related to film fracture appeared in load-controlled load–displacement curves when electrochemically polished and anodically passivated samples were indented. The excursion disappeared after the passivation film was removed electrochemically or by nanowear. The critical load, excursion depth and length decreased with higher hydrogen concentration, along with Young’s modulus and fracture stress of the passive film.     

Comparative study of structural and semiconducting properties of passive films and thermally grown oxides on AISI 304 stainless steel

A comparative study including structural characterization and semiconducting properties of passive and thermally grown oxides on AISI 304 stainless steel is performed by near field microscopy, Auger electron spectroscopy, capacitance measurements and photoelectrochemistry. This comparative investigation is performed on thermally grown oxides at different temperatures and passive films formed at different potentials. The results obtained by characterization techniques show that the thickness of both oxides increases with increasing formation temperature and potential and allow discussing grain size and surface roughness vs. formation temperature. Capacitance measurements reveal semiconducting behavior of both iron and chromium oxides constituting whole passive and thermal oxides. These results allow extracting and discussing space charge layer thickness and doping densities of iron and chromium oxides in relation with formation conditions. The photocurrent results show a variation of the quantum efficiency with formation temperature and potential and a constant band gap value whatever the nature of the considered film. The variation of the quantum efficiency with applied potential in accordance with Pool–Frenkel model allow extracting and comparing donor densities with those obtained by capacitance measurements.     

Microstructural characteristics of the oxide scale formed on 304 stainless steel in oxygenated high temperature water

The microstructural characteristics of oxide scale formed on type 304 stainless steel in oxygenated high temperature water have been investigated. From outer to inner layer, the oxide scale consists of faceted spinel particles, irregularly shaped hematite particles and a compact layer of nano-sized spinels. Some outmost spinels formed on top of other particles are depleted in Cr, while the hematite particles tightly embedded into the inner layer contain more Cr in the inner than in the outer part. The inner nano-sized oxide grow inwards directly from the bottom of outer particles. The related oxidation mechanism is discussed.     

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.     

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.     

Direct imaging of native passive film on stainless steel by aberration corrected STEM

A cross-section of a native passive film on a commercial type 304 stainless steel was directly imaged and characterized using an aberration corrected STEM-EDS in combination with FIB sectioning. The technique demonstrated an enrichment of Cr in the lower part of the passive film, and a depletion of Cr and an enrichment of Ni in the matrix side closest to the passive film/matrix interface in accordance with previous studies, further proving the advantage of this technique with respect to spatial resolution. That is, the STEM-EDS showed a compositional profile with higher spatial resolution compared to AES which has been mainly used for this type of investigation. The technique will be applicable to the investigation of nm to sub-nm compositional fluctuation of passive films, steel surfaces adjacent to inclusions and grain boundaries postulated as an initiating site of pitting corrosion or stress corrosion cracking (SCC).     

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.     

A facile electrodeposition of hydroxyapatite onto borate passivated surgical grade stainless steel

This paper reports a successful electrodeposition method for coating hydroxyapatite (HAP) onto surgical grade stainless steel (SS). Pure HAP coatings could be achieved at −1400 mV vs SCE and the coating resistivity was assessed by potentiodynamic polarization and impedance techniques which showed that HAP coatings deposited onto the borate passivated-SS specimens possess maximum bioresistivity in Ringer’s solution. The coatings were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM) and Atomic force microscopy (AFM). The results have showed that the borate passivation followed by HAP coating performed on 316L SS could enhance the longevity of the alloy in Ringer’s solution.     

Corrosion behaviour of nitrogen ion implanted AISI type 304L stainless steel in nitric acid medium

The effects of nitrogen ion implantation on corrosion behaviour of 304L stainless steel in 1 N HNO₃ medium were investigated using surface analytical and electrochemical techniques. Nitrogen ion was implanted at 70 keV in the dose range of 1 × 10¹⁵, 1 × 10¹⁶, 1 × 10¹⁷ and 2.5 × 10¹⁷ N⁺/cm², respectively. Grazing incidence X-ray diffraction results for unimplanted and up to dose of 1 × 10¹⁶ N⁺/cm² showed co-existence of γ-Fe and α′-Fe and, at higher doses (1 × 10¹⁷ and 2.5 × 10¹⁷) preferential formation of chromium nitride was observed. X-ray photoelectron spectroscopy investigation confirmed the formation of chromium nitride at higher doses. Electrochemical corrosion investigation revealed nobler open circuit potential, decrease in corrosion current densities, passive current densities and increase in polarization resistance with increase in dose rate. Surface morphology analysis after polarization study using atomic force microscope showed grain boundary dissolution for unimplanted specimens and resistance to surface dissolution with increase in dose rate for implanted specimens.     

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.     

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.     

Composition and structure of coloured oxide films on stainless steel formed by triangular current scan and cathodic hardening treatment

The influence of the electrochemical hardening treatment on the composition and structure of coloured porous films formed by triangular current scan on AISI 304 stainless steel has been examined by impedance spectroscopy and also by SEM, AES, XPS and AFM. It was observed that the films, originally consisting of a porous chromium-iron oxide, became more compact and enriched in chromium after the hardening treatment. The development of a high frequency semi-circle in the impedance spectra is explained by the formation of an outer oxide layer.     

Effect of solution concentration on semiconducting properties of passive films formed on austenitic stainless steels

The semiconductor properties of passive films formed on AISI 316L in three acidic solutions were studied by employing Mott-Schottky analysis in conjunction with the point defect model (PDM). Based on PDM, the key parameters for passive film growth are the diffusivity and density of the defects within the film. The results indicated that donor densities are in the range 1-4 × 10²¹ cm⁻³ and increased with solution concentration. By assuming that the donors are oxygen ion vacancies and/or cation interstitials, the diffusion coefficient of the donors in three acidic solutions are calculated to be approximately 1-5 × 10⁻¹⁶ cm²/s.     

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.     

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.     

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.     

Effects of temperature on the oxide film properties of 304 stainless steel in high temperature lithium borate buffer solution

The paper mainly investigated the effects of temperature on the oxide film properties of 304SS in lithium borate buffer solution by electrochemical measurements and XPS analysis. As temperature increased, the protective property of the film degraded and structure varied from a single layer to a double-layer. Whatever the temperature, the oxide film exhibited an n-type and p-type semiconductor in the potential range above and below the flat band potential, respectively. The electronic properties were assigned to a Fe–Cr spinel inner layer and a defective Fe–Cr oxide outer layer. The related growth mechanisms of the oxide film were also discussed.     

The semiconducting properties of passive films formed on AISI 316 L and AISI 321 stainless steels: A test of the point defect model (PDM)

The semiconductor properties of passive films formed on AISI 316L in 1 M H₂SO₄ in three temperatures and AISI 321 in 0.5 M H₂SO₄ were studied by employing Mott–Schottky analysis in conjunction with the point defect model (PDM). Based on the Mott–Schottky analysis in conjunction with PDM, it was shown that the calculated donor density decreases exponentially with increasing passive film formation potential. Also, the results indicated that donor densities increased with temperature. By assuming that the donors are oxygen ion vacancies and/or cation interstitials, the diffusion coefficients of the donors for two stainless steels are calculated.     

Soft X-ray absorption spectroscopy study of the effects of Si, Ce, and Mo ion implantation on the passive layer of AISI 304 stainless steel

The chemical modifications introduced in the passive layer of AISI 304 stainless steel after Si, Ce, and Mo ion implantation were investigated and compared with non-implanted steel by soft X-ray absorption spectroscopy. The influence of ion implantation on the passive properties was evaluated by measuring soft X-ray absorption spectra at the Cr, Fe, Ni, Mn and Si 2p in addition to oxygen 1s thresholds. All ion implanted samples show a relative Cr-enrichment at the surface as compared with non-implanted samples. Fe 2p as well as O 1s spectral changes reveal chemical differences in the passive layer as a function of the element ion-implanted.     

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.