Effects of alloy and solution chemistry on the fracture of passive films on austenitic stainless steel

The Taguchi analysis method was used to simultaneously study the effects of alloy chemistry, pH, and halide ion concentrations on the fracture of electrochemically grown passive films using a nanoindentation technique. Three austenitic stainless steels, 304L, 316L, and 904L were potentiostatically polarized in hydrochloric acid solutions. The fracture load was dominated primarily by alloy chemistry. Passive films mechanically weaken as the atomic iron concentration increases in the film. Prolonged anodic ageing time increases the fracture load of passive films.     

Hydrogen effects on the passive film formation and pitting susceptibility of nitrogen containing type 316L stainless steels

The effects of hydrogen on the passivity and pitting susceptibility of type 316L stainless steels have been investigated with alloys containing different nitrogen contents (0.015, 0.198 and 0.556 wt.% N). The study revealed that electrochemically pre-charged hydrogen significantly reduced the pitting resistance of alloys conatining 0.015 and 0.198 wt.% nitrogen contents. In alloy with highest nitrogen content (0.556 wt.% N), an increase in the passive film current density with hydrogen was observed without affecting breakdown potential. Auger electron spectroscopy (AES) analysis of the passive film indicated the presence of nitrogen in the passive film. On other hand, for hydrogen charged samples, nitrogen was found to be significantly less in the passive film. In Electrochemical impedance spectroscopy (EIS) measurement, the decrease in semi-circle radius of Nyquist plot, and the polarization resistance, R_P associated with the resistance of the passive film was observed with hydrogen, indicating that hydrogen decreased the stability of the passive film. The present investigation indicated that precharged hydrogen deteriorated the passive film stability and pitting corrosion resistance in these alloys, and the increase in nitrogen content of the alloy offsets the deleterious effect of precharged hydrogen.     

Hydrogen uptake in austenitic stainless steels by exposure to gaseous hydrogen and its effect on tensile deformation

Hydrogen solubility and diffusivity of Fe–Cr–Ni austenitic stainless steels were measured through exposure to gaseous hydrogen at a pressure of 10 MPa over the temperature range 110–235 °C. The hydrogen solubility depended on the alloy compositions, whereas the diffusion coefficients were nearly identical at a given temperature. Hydrogen uptake in the stable austenitic steels by exposure to high-pressure gaseous hydrogen led to some loss of ductility, while their fracture surfaces showed evidence of plastic deformation. This was attributed to the enhanced inhomogeneity of plastic deformation in the presence of hydrogen and the increased stress for plastic instability with increasing hydrogen concentration.     

Determination of the critical hydrogen concentration for delayed fracture of high strength steel by constant load test and numerical calculation

The critical hydrogen concentration for hydrogen induced delayed fracture of the AISI 4135 steel at 1320 and 1450 MPa has been determined by constant load tests in combination with numerical calculations, and thus the concept of a critical hydrogen concentration has been verified. The time to fracture was obtained for circumferentially notched round bar specimens under a constant load after electrochemically pre-charged with various hydrogen contents. A numerical model was then developed for calculating the accumulated hydrogen concentration in the vicinity of the notch root, taking into account the driving effect of the hydrostatic stress on hydrogen transport. The results showed that the delayed fracture of the steel occurred when a critical hydrogen concentration at the location of the stress peak was reached by accumulation, and that the time to fracture was related to the stress-driven hydrogen accumulation process. The critical hydrogen concentration was dependent not only on the strength level, but also on the stress concentration factor of the specimens.     

Influence of stress on passive behaviour of steel bars in concrete pore solution

The influence of stress on passive behaviour of steel bars in concrete pore solution was studied with electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy. The passive ability of steel decreased as the applied load increased and higher load had much greater influence on passivation than repeated loading of small magnitude. A micro-crack model was presented to explain the damage of passive layer by loads. Lower load caused micro-cracks in the passive film which might be completely recovered after unloading. Under higher load more micro-cracks were produced in the passive film and some may penetrate the film, leading to irreversible damages.     

Effect of hydrogen on the fracture behavior of high strength steel during slow strain rate test

The effect of hydrogen on the fracture behavior of the quenched and tempered AISI 4135 steel at 1450 MPa has been investigated by means of slow strain rate tests on smooth and circumferentially-notched round-bar specimens. Hydrogen was introduced into specimens by electrochemical charging and its content was measured by thermal desorption spectrometry (TDS) analysis. Results showed that the steel had high hydrogen embrittlement susceptibility. For both smooth and notched specimens, the fracture mode was changed from microvoid coalescence (MVC) to brittle intergranular (IG) fracture after the introduction of a small amount of diffusible hydrogen. Fracture initiated in the vicinity of the notch root for notched specimens, while it started from around the center in smooth specimens. The fracture stress decreased with increasing diffusible hydrogen content, and the decreasing trend was more prominent for specimens with a higher stress concentration factor. Taking into account the stress-driven hydrogen diffusion and accumulation in the vicinity of the notch root, the local diffusible hydrogen concentration and local fracture stress in notched specimens have been calculated. According to numerical results, the relationship between the local fracture stress and local diffusible hydrogen concentration was independent of stress concentration factor, which could account for the effect of hydrogen on the fracture stress of the steel.     

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.     

An XPS and ISS investigation of passive layers on binary Fe-Al alloys

Passive layers have been formed electrochemically under inert conditions on sputter-cleaned Fe-Al alloys. The aluminum content was 8, 15 and 22 at%, which meets the homogeneity region of α-Fe in the Fe-Al phase diagram. The addition of aluminum reduces the active dissolution current density remarkably compared with that of pure iron. X-ray photoelectron spectroscopy (XPS) studies show an accumulation of aluminum oxide within the center of the passive layer, which is confirmed by elastic-ion scattering spectroscopy (ISS) and XPS depth profiles. Angular-resolved XPS measurements suggest a continuous structural change of the chemical film during its growth. A discussion of the investigations is presented on the basis of a model of oxide growth.     

Direct modification of a passivated iron electrode with alkyltriethoxysilanes for preventing passive film breakdown in a borate buffer containing 0.1 M of chloride ion

A passive film on an iron electrode was modified with alkyltriethoxysilanes directly. In order to examine the protective ability of the modified passive film against breakdown, the pitting potential, E_pit was measured by anodic polarization of the modified electrode in a borate buffer solution (pH 8.49) containing 0.1 M of Cl⁻. The value of E_pit for the modified electrode shifted in the positive direction from that of the unmodified electrode, indicating prevention of passive film breakdown. The modified passive film was not broken down in the passive and transpassive regions of polarization curve in some cases. However, many current spikes appeared in the all curves of the modified electrodes. The modified surface of passivated electrode was characterized by X-ray photoelectron and FTIR reflection spectroscopies and contact angle measurement. There were defects and clusters of associated water within the modified film and hence, Cl⁻ could permeate through the defects, leading to appearance of current spikes and occurrence of breakdown.     

Effect of hydrogen on the properties and fracture characteristics of TRIP 800 steels

The paper describes effect of hydrogen on the properties and fracture characteristics of two variants of TRIP 800 C–Mn–Si steels. The effect of hydrogen was studied by means of tensile tests on specimens previously charged by hydrogen. Hydrogen provoked embrittlement in both variants but only for very high hydrogen content. Hydrogen embrittlement manifested itself mainly by a loss of plasticity. Both steel variants were able to absorb a large amount of hydrogen, up to 50 ppm. Concerning fractographic characteristics, steels containing higher hydrogen content displayed transgranular cleavage fracture. In exceptional cases, an irreversible embrittlement was revealed initiating on non-metallic inclusions.     

States and transport of hydrogen in the corrosion process of an AZ91 magnesium alloy in aqueous solution

Mott–Schottky measurement and secondary ion mass spectroscopy (SIMS) were used to investigate the states and transport of hydrogen during the corrosion behavior of an AZ91 magnesium alloy in 0.1 M sodium sulfate solution. The results showed that when samples were immersed or charged in solution, hydrogen atoms diffused into the film and reacted with vacancy to cause the increases of the carrier concentration (excess electron or hole carrier) and diffusion rate of hydrogen. Some hydrogen atoms diffused to interior of matrix and enriched in β phase while others resorted in the corrosive film. With the increase of immersion or charging time, magnesium hydride would be brittle fractured when the inner stress caused by hydrogen pressure and expansion stress of formation of magnesium hydride was above the fracture strength, which provided the direct experimental evidence of the hydrogen embrittlement (HE) mechanism of magnesium and its alloys. After immersion in solution, the transfer of excess electrons to the interfaces of corrosion film and solution would destroy the charge equilibrium in the film and stimulate the adsorption of , which resulted in the initiation of localized corrosion; after cathodic charging and then immersion, the enrichment of hydrogen atoms at interior of corrosion film would combine into hydrogen gas to form high pressure and result in the rupture of corrosion film, and localized corrosion initiated and developed at surface. Therefore, localized corrosion nucleated earlier on the charged samples than on the uncharged samples. Hydrogen invasion accelerated the corrosion of matrix.     

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.     

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.     

The role of corrosion-resistant alloying elements in passivity

Passivity of alloys containing corrosion-resistant elements were reviewed. Chromium and valve metals except aluminum form stable oxyhydroxide films even in aggressive hydrochloric acids. Molybdenum forms a passive MoO₂ film in the active region of stainless steels and hence decreases the active dissolution current. In the passive region of transition metals and valve metals, molybdenum is generally in the transpassive state and dissolved. However, if the outer oxyhydroxide film is stable the inner MoO₂ film is protected by the outer oxyhydroxide film and the MoO₂ film acts as the effective barrier against diffusion of matters through the film. Thus the passive current density of 30Cr-2Mo ferritic stainless steel is more than two orders of magnitude lower than that of 30Cr steel without molybdenum in 1 M HCl.     

Observation of passive films on Fe–20Cr–xNi (x = 0, 10, 20 wt.%) alloys using TEM and Cs-corrected STEM–EELS

The structure and composition of passive film formed on Fe–20Cr–xNi (x = 0, 10, 20 wt.%) alloys in deaerated pH 8.5 borate buffer solution was examined by transmission electron microscope and Cs-corrected scanning transmission electron microscope-electron energy loss spectroscopy. Thickness of the passive film on each alloy was measured to be 2.5–2.7 nm and the passive film was enriched with Cr. The passive film formed on the alloys exhibited an amorphous structure, as confirmed by the lack of diffraction contrast and by the fast Fourier transform images taken within a region of the passive film on each alloy.     

Passivity breakdown and stress corrosion cracking of stainless steel

Passivity breakdown of stainless steel is an important initial process for starting stress corrosion cracking. It was found that small amount of impurities in environments affects the initiation process, but do not affect the propagation process of SCC. The environmental effect on the initiation process is rationally explained by introducing “bound water model” of passive film and HSAB (Hard and Soft Acid and Base) rule. Background of the issue including bound water model and HSAB rule was discussed.     

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).     

Effects of the solution temperature and the pH on the electrochemical properties of the surface oxide films formed on Alloy 600

The surface oxide films on Alloy 600 have been investigated as a function of the solution temperature and the pH by using a cyclic voltammetry, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and a depth profiling by Auger electron spectroscopy (AES). H₃BO₃, Na₂SO₄ and NaOH aqueous solutions with temperatures in the range of 30–300 °C were used as the test solutions. As the solution temperature of the 0.5 M H₃BO₃ increased, the thickness of the passive film increased but the resistance of the passive film was diminished, which is coincident with a solution temperature dependency of the passive current in the potentiodynamic curve. The inner oxide film on Alloy 600 was distinguishable from the Cr-rich outer oxide film above 100 °C. From the Mott–Schottky relation, the oxide formed in 0.5 M H₃BO₃ at 300 °C showed a p-type semiconductor property, accompanied by a Cr-rich oxide film throughout the whole oxide film unlike the n-type oxide films up to 250 °C. The oxide resistance of the passive film decreased in the order of 0.5 M H₃BO₃, 0.1 M NaOH and 0.5 M Na₂SO₄, which is consistent with the pH dependency of the passive current. Ni-rich oxide films of a p-type were formed in the 0.5 M Na₂SO₄ or 0.1 M NaOH.     

Hydrogen embrittlement susceptibility and permeability of two ultra-high strength steels

Slow displacement rate tensile tests were carried out in a saturated H₂S solution to investigate the effect of hydrogen embrittlement on notched tensile strength (NTS) and fracture characteristics of two ultra-high strength steels (PH 13-8 Mo stainless steel and T-200 maraging steel). Hydrogen permeation properties were determined by an electrochemical permeation method. The results of permeation tests indicated that over-aged specimens showed a lower diffusivity/hydrogen flux and higher solubility than those solution-annealed. The great increase in reverted austenite (irreversible hydrogen traps) together with numerous precipitates at the expense of dislocations (reversible) in the over-aged specimen led to such a change in permeability. Ordinary tensile tests indicated that four tested specimens had roughly the same yield strength level. Hence, the hydrogen embrittlement susceptibility of the material could be related to their permeation properties. The uniform distribution of strong hydrogen traps in over-aged specimens instead of weak traps in the solution-annealed impeded the hydrogen transport toward the strained region, thus, the resistance to sulfide stress corrosion cracking was improved in over-aged specimens.     

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.