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.     

Corrosion behaviour of 16%Cr-4%Al and 16%Cr ODS ferritic steels under different metallurgical conditions in a supercritical water environment

The corrosion behaviour of 16%Cr and 16%Cr-4%Al ODS ferritic steels in different heat treatment conditions has been investigated in a supercritical water environment. The exposed coupons were analyzed using scanning electron microscopy (SEM), electron probe micro analysis (EPMA), Auger and X-ray diffraction analysis (XRD). It was found that the formation of oxides depends on the chemical composition and not on the metallurgical condition. The Al-free alloys formed a monolayer oxide film composed of (Cr, Fe)₂O₃. The Al-containing alloys formed an oxide film composed of an outer layer of hematite and magnetite and an inner layer of Al₂O₃. The oxidation mechanisms are discussed.     

Corrosion of 9Cr Steel in CO2 at Intermediate Temperature III: Modelling and Simulation of Void-induced Duplex Oxide Growth

9Cr–1Mo steel forms in CO₂ at 550?°C a duplex oxide layer containing an outer magnetite scale and an inner Fe–Cr rich spinel scale. The inner spinel oxide layer is formed according to a void-induced oxidation mechanism. The kinetics of the total oxide growth is simulated from the proposed oxidation model. It is found that the rate limiting step of the total oxide growth is iron diffusion through high diffusion paths such as oxide grain boundaries in the inner Fe–Cr rich spinel oxide layer. In the proposed oxidation model, a network of nanometric high diffusion paths through the oxide layer allows the very fast supply of CO₂ inside pores formed at the oxide/metal interface. Its existence is demonstrated to be physically realistic and allows explaining several observed physical features evolving in the oxide layer with time.     

Isothermal oxidation behavior of FeCo–2V intermetallic alloy

Isothermal oxidation behavior and the nature of oxide layer formed during oxidation of FeCo–2V alloy were characterized in the temperature range of 500–600 °C. Oxidation kinetics of the alloy follows a parabolic rate law. SEM and XRD studies indicate the formation of an iron rich outer oxide layer and an inner solute rich layer containing cobalt and vanadium rich oxides. The oxidation mechanism of the FeCo–2V alloy is similar to that of low alloy steels. During the initial stages, preferential oxidation of iron and cobalt occurs at the alloy surface and leads to the formation of a solute rich inner layer. Continued oxidation occurs through oxidation of iron and cobalt at the outer layer and internal oxidation of inner layer. The iron rich oxide layer formed at the surface on oxidation of FeCo alloy is semi-conducting in nature and may not provide the necessary insulating barrier required at the surface to minimize eddy current losses during A.C. applications.     

High-Temperature Oxidation Behavior of SIMP Steel at 800 °C

In this work, the high-temperature oxidation behavior of SIMP and commercial T91 steels was investigated in air at 800 °C for up to 1008 h. The oxides formed on the two steels were characterized and analyzed by XRD, SEM and EPMA. The results showed that the weight gain and oxide thickness of SIMP steel were rather smaller than those of T91 steel, that flake-like Cr₂O₃ with Mn_1.5Cr_1.5O₄ spinel particles formed on SIMP steel, while double-layer structure consisting of an outer hematite Fe₂O₃ layer and an inner Fe–Cr spinel layer formed on T91 steel, and that the location of the oxide layer spallation was at the inner Fe–Cr spinel after 1008 h, which led the ratio between the outer layer and the inner layer to decrease. The reason that SIMP steel exhibited better high-temperature oxidation resistance than that of T91 steel was analyzed due to the higher Cr and Si contents that could form compact and continuous oxide layer on the steel.     

Effect of nickel ion from autoclave material on oxidation behaviour of 304 stainless steel in oxygenated high temperature water

Characteristics of the oxide films formed on 304 stainless steel exposed to 290 °C oxygenated water in a nickel-lined autoclave were examined. The oxides evolve from dominating irregularly shaped hematite to faceted spinels with increasing immersion time. The surface layer of oxide film is first Cr-enriched and then Ni-enriched as immersion time increases. The oxides nucleate by solid-state reactions with selective dissolution of Fe and Ni, and then grow up through precipitation of cations from solution. Nickel ions dissolved from the nickel lining could promote the stability of NiFe₂O₄ spinel and influence the oxidation behaviour of 304 stainless steel significantly.     

XPS studies on passive film formed on stainless steel in a high-temperature and high-pressure methanol solution containing chloride ions

The composition and structure of passive film formed on 316L SS immersed in an anhydrous methanol solution (water content < 0.05 wt%) containing 0.42 wt% LiCl at 323-473 K were investigated by X-ray photoelectron spectroscopy (XPS), and compared with those of film formed in an aqueous solution. The passive film formed in the methanol solution was mainly composed of Fe and Cr oxides, and it possessed a double-layered structure consisting of an Fe oxide-rich outer layer and a Cr oxide-rich inner layer. Dissolution of the Fe-rich layer and densification of the Cr-rich inner layer were observed, especially at high temperatures. However, these were suppressed in an aerated methanol solution at 423 K or below, probably due to the barrier effect of adsorbed oxygen. No Ni compound contributed to composing the passive film, even at higher temperatures. The ratio of OH⁻ to O²⁻ was small and decreased with an increase in temperature (the presence of oxygen suppressed the decrease, especially at 423 K or below). The chloride ions were concentrated in the Fe-rich outer layer, and they penetrated more deeply than that in the aqueous solution into the passive film formed in the methanol solution.     

Corrosion behavior of the composite ceramic coating containing zirconium oxides on AM30 magnesium alloy by plasma electrolytic oxidation

The deterioration process of a plasma electrolytic oxidation (PEO) coating containing zirconium oxides on AM30 magnesium alloy in 3.5 wt.% NaCl solution have been investigated. The coating consists of an outer porous layer and an inner dense layer. The content of MgF₂ is high in the pores and an MgO-rich layer is evident in the inner layer. The corrosion resistance of the outer layer gradually decreases in the initial immersion stage (96 h) due to the decomposition of MgO, and the deterioration of the inner layer is delayed by the blocking effect of the outer layer.     

High temperature corrosion of pure Fe, Cr and Fe-Cr binary alloys in O2 containing trace KCl vapour at 750 °C

Pure Fe, Cr and Fe-Cr binary alloys were corroded in O₂ containing 298 ppm KCl vapour at 750 °C. The corrosion kinetics were determined, and the microstructure and the composition of oxide scales were examined. During corrosion process, KCl vapour reacted with the formed oxide scales and generated Cl₂ gas. As Cl₂ gas introduced the active oxidation, a multilayer oxide scales consisted of an outmost Fe₂O₃ layer and an inner Cr₂O₃ layer formed on the Fe-Cr alloys with lower Cr concentration. In the case of Fe-60Cr or Fe-80Cr alloys, monolayer Cr₂O₃ formed as the healing oxidation process. However, multilayer Cr₂O₃ formed on pure Cr.     

Evolution of surface chemistry and morphology of oxide scale formed during initial stage oxidation of modified 9Cr–1Mo steel

Initial stage oxidation characteristics of the modified 9Cr–1Mo steel in ambient air at 650 °C have been investigated, for exposure times ranging from 5 to 500 h. Oxygen flux from the gas phase causes high initial oxidation rate, but the growth kinetics do not follow parabolic law. In “as-received” condition, binary oxides of Fe and Cr were found as native oxides. Upon oxidation, segregation of Mn resulted in the formation of MnCr₂O₄ along with FeCr₂O₄ and binary oxides of Fe, Cr and Mn. Thus, the initial oxide scale constitutes multiple oxides with delineated interface, unlikely to have a layered structure.     

Characterisation of oxide films formed on Co–29Cr–6Mo alloy used in die-casting moulds for aluminium

Oxide films formed at 700 °C on Co–29Cr–6Mo alloy were characterised extensively to improve the corrosion resistance of the alloy to liquid Al, enabling its use in Al die-casting moulds. Film of duplex layer consisting of an outer CoO-rich layer and an inner Cr₂O₃-rich layer was observed in samples subjected to oxidation for 4 h. With an increase in duration of oxidation, CoO was gradually replaced by Cr₂O₃, resulting in a single-layered oxide film dominantly composed of Cr₂O₃. The oxide film evolved with duration of oxidation treatment indicating the possibility of optimising films for Al die-casting moulds.     

The nature of the third-element effect in the oxidation of Fe-xCr-3 at.% Al alloys in 1 atm O2 at 1000 °C

The oxidation of an Fe-Al alloy containing 3 at.% Al and of four ternary Fe-Cr-Al alloys with the same Al content plus 2, 3, 5 or 10 at.% Cr has been studied in 1 atm O₂ at 1000 °C. Both Fe-3Al and Fe-2Cr-3Al formed external iron-rich scales associated with an internal oxidation of Al or of Cr+Al. The addition of 3 at.% Cr to Fe-3Al was able to stop the internal oxidation of Al only on a fraction of the alloy surface covered by scales containing mixtures of the oxides of the three alloy components, but not beneath the iron-rich oxide nodules which covered the remaining alloy surface. Fe-5Cr-3Al formed very irregular external scales where areas covered by a thin protective oxide layer alternated with others covered by thick scales containing mixtures of the oxides of the three alloy components, undergrown by a thin layer rich in Cr and Al, while internal oxidation was completely absent. Conversely, Fe-10Cr-3Al formed very thin, slowly-growing external Al₂O₃scales, providing an example of third-element effect (TEE). However, the TEE due to the Cr addition to Fe-3Al was not directly associated with a prevention of the internal oxidation of Al, but rather with the inhibition of the growth of external scales containing iron oxides. This behavior has been interpreted on the basis of a qualitative oxidation map for ternary Fe-Cr-Al alloys taking into account the existence of a complete solid solubility between Cr₂O₃ and Al₂O₃.     

The corrosion behavior of Fe-Cr alloys containing Co,Mn, and/or Ni and of a Co-base alloy in the presence of molten (Li,K)-carbonate

The corrosion behavior or commercial Fe ana Co base alloys and Fe-Cr model alloys with different contents of Co and/or Mn was investigated by continuous exposure tests in the presence of a thin carbonate film. All alloys studied form multi-layered corrosion scales consisting of outer Li containing oxides and inner Cr rich oxides, i.e. spinels or LiCrO₂. The LiCrO₂ is formed on alloys with high Cr contents (≤ 20 wt.%), whereas mixed (Fe,M)_3-x Cr_xO₄ spinels (M = Co, Mn, Ni) were found on alloys with lower Cr content (15–20 wt.%). Insoluble Cr containing oxides occur only in the inner layers of the corrosion scale, whereas on the surface of corroded specimens soluble chromates were detected. Alloys with Mn contents greater than 15 wt.% form Mn₂O₃ in the initial stages of the experiments, this oxide reacts with the melt and formation of Li₂MnO₃ takes place. In exposure tests up to 500 h Fe-Cr alloys with low contents of Mn and Co (10 wt.% Co or Mn) form iron rich oxides (LiFeO₂ and LiFe₅O₈) with varying amounts of dissolved Mn or Co. In the later corrosion stages outward diffusion of Mn and/or Co takes place and LiCoO, and Li₂MnO₃ are formed on top of LiFeO₂, whereby the concentration of Mn and/or Co in the inner layers (LiFeO₂ and spinel) decreases. The outer Li containing oxides LiFeO₂, LiCoO₂ and Li₂MnO₃ are nearly insoluble in the melt and when present at the surface protect the metallic material from further corrosive attack. Fe-Cr model alloys containing Co and Mn form multi-layered corrosion layers after 2000 h of exposure. These layers consist of four oxides in the following sequence from the metal-scale to the scale-melt interface: (Fe,Cr,Co,Mn)₃O₄ spinel, LiFeO₂, Li₂MnO₃ and LiCoO₂.     

Oxidation of a quaternary three-phase Cu-20Ni-20Cr-5Fe alloy at 700-900 °C in 1 atm of pure O2

The oxidation of a quaternary Cu-Ni-Cr-Fe alloy containing approximately 20 at.% Ni, 20 at.% Cr and 5 at.% Fe, balance Cu (Cu-20Ni-20Cr-5Fe), was studied at 700-900 °C in 1 atm of pure oxygen. The alloy is composed of a mixture of three phases, where the lightest α phase with the largest Cu content forms the matrix, while the other two, much richer in Cr, form a dispersion of isolated particles. At variance with the ternary three-phase Cu-20Ni-20Cr alloy examined previously, which was unable to form protective chromia scales over the alloy surface even after an extended period of oxidation, the present alloy formed complex external scales containing mixtures of the oxides of the various components plus a deep internal region containing a mixture of alloy and oxide phases. With time, a very irregular and thin but essentially continuous chromia layer formed at the bottom of the mixed internal oxidation region, producing a gradual decrease of the oxidation rate. Thus, the addition of 5 at.% Fe to Cu-20Ni-20Cr alloy is able to decrease the critical Cr content required to form the most stable oxide and promotes the formation of a continuous chromia scale under a lower Cr content in spite of the simultaneous presence of three different phases.     

Oxidation Behaviors of Different Grades of Ferritic Heat Resistant Steels in High-Temperature Steam and Flue Gas Environments

For steam tubes used in thermal power plant, the inner and outer walls were operated in high-temperature steam and flue gas environments respectively. In this study, structure, microstructure and chemical composition of oxide films on inner and outer walls of ex-service low Cr ferritic steel G102 tube and ex-service high Cr ferritic steel T91 tube were analyzed. The oxide film was composed of outer oxide layer, inner oxide layer and internal oxidation zone. The outer oxide layer on the original surface of tube had a porous structure containing Fe oxides formed by diffusion and oxidation of Fe. More specially, the outer oxide layer formed in flue gas environment would mix with coal combustion products during the growth process. The inner oxide layer below the original surface of tube was made of Fe-Cr spinel. The internal oxidation zone was believed to be the precursor stage of inner oxide layer. The formation of internal oxidation zone was due to O diffusing along grain boundaries to form oxide. There were Fe-Cr-Si oxides discontinuously distributed along grain boundaries in the internal oxidation zone of G102, while there were Fe-Cr oxides continuously distributed along grain boundaries in that of T91.     

Oxidation of Binary FeCr Alloys (Fe?C2.25Cr, Fe?C10Cr, Fe?C18Cr and Fe?C25Cr) in O2 and in O2?+?H2O Environment at 600???C

The oxidation behaviour of the binary alloys Fe?C2.25Cr, Fe?C10Cr, Fe?C18Cr and Fe?C25Cr (wt%) in dry and wet O₂ at 600???C is investigated by isothermal exposures of carefully polished samples for up to 168?h. The oxidized samples are investigated gravimetrically and the oxides formed are studied by X-ray diffraction. X-ray photoelectron spectroscopy is used for depth profiling of the thin oxides. The scale surface is imaged by SEM. Cross-sections through the scale are analyzed by SEM/EDX for imaging and for measuring the chemical composition. The oxidation behavior of the four FeCr alloys is intermediate between those of iron and chromium. Fe?C2.25Cr oxidizes in a way similar to iron in both environments, forming a poorly protective scale consisting of FeCr spinel at the bottom, magnetite in the middle and a hematite cap layer. In dry O₂, Fe?C10Cr, Fe?C18Cr and Fe?C25Cr form a thin and protective (Fe,Cr)₂O₃ oxide similar to the chromia film formed on pure chromium. In wet O₂, Fe?C10Cr, Fe?C18Cr and Fe?C25Cr initially form the same kind of protective oxide film as in dry conditions. After an incubation time that depends on alloy chromium content, all three alloys go into breakaway oxidation and form thick, poorly protective scales similar to those formed on Fe?C2.25Cr. Breakaway oxidation in wet O₂ is triggered by the evaporation of CrO₂(OH)₂ from the protective (Fe,Cr)₂O₃ oxide.     

Structural mechanism of scale for 12Cr–W–Mo–Co steels with enhanced oxidation resistance

The phase constituent, morphologies, layer structures of the scale of 12Cr–W–Mo–Co heat resistant steel (HRS) formed in dry air and air with 10% vapour were systematically investigated. The interface between the scale and ferritic/martensitic matrix of this HRS was also studied. For the scale formed in air, single particle- and sheet-shaped oxide layer, which are composed of (Fe, Co, Cr)₂O₃, were formed. The scale combines with steel matrix via coherent or semi-coherent structure. For the scale formed in air with 10% vapour, the oxides take the shape of particulate. Layering phenomenon has been observed, i.e. the external layer is composed of (Fe, Co)₂O₃/(Fe, Co)₃O₄, the internal layer with spinel (Fe, Co, Cr)₃O₄ and the transition layer with Cr rich and Cr poor regions. The interface between the transition layer and the matrix is tight and steady, but the region linking the internal scale and transition layer is shaky and brittle. Both the oxidation processes in air and air with 10% vapour are considered to be controlled by diffusion mechanism.     

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.     

Electrochemical and XPS studies of the passive film formed on stainless steels in borate buffer and chloride solutions

The passivity of AISI 304L and AISI 316L stainless steels in a borate buffer solution, with and without the addition of chloride ions, was studied using cyclic voltammetry and potentiodynamic measurements. The passive layers formed by electrochemical oxidation at different passivation potentials on both the stainless steels were studied by X-ray photoelectron spectroscopy, their compositions were analysed as a function of depth, and the cationic fraction of the passive film was determined. The passive films established on the two stainless steels in the borate buffer solution at pH = 9.3 contained the oxides of two main elements, i.e., Fe and Cr. The oxides of the alloying elements Ni and, optionally, Mo, also contribute to the passive layer. In the presence of chloride ions a strong chromium enrichment was observed in the passive layers.