High-temperature oxidation of duplex stainless steels S32101 and S32304 in air and simulated industrial reheating atmosphere

High-temperature oxidation of duplex stainless steels S32101 and S32304 was performed under three conditions: isothermal oxidation at 1050 °C in air and simulated industrial reheating atmosphere and in situ oxidation in air during the continuous heating to 1050 °C. Breakaway oxidation was found in S32101 but not in S32304, before which the weight gain per unit area was in parabolic relation to time. A triplex oxide layer of S32101 and a duplex-layer of S32304 oxidized for 120 min were observed, respectively. The initial oxidation phase was austenite for S32101 and ferrite for S32304 due to different manganese content.     

Effect of “475 °C embrittlement” on duplex stainless steels localized corrosion resistance

The influence of the 475 °C ageing treatment on the localized corrosion resistance of austenitic-ferritic (duplex) stainless steels has been investigated by means of double loop electrochemical potentiodynamic reactivation (DL-EPR) and potentiostatic tests. The effect of different ferrite/austenite (α/γ) volume fractions has been also considered. For this purpose, two different 22 Cr 5 Ni duplex stainless steels, with different α/γ ratios (respectively equal to 1 and 1.5) have been investigated. The ageing treatment at 475 °C was conducted up to 1000 h. The resulting microstructural modifications were analyzed with transmission electron microscopy observation. The microstructure resulting from solid state transformations, like spinodal decomposition and G-phase precipitation, were characterized and the relevant mechanisms identified. An evident influence of the ferrite and austenite volume fraction on the G-phase formation and spinodal decomposition kinetics were found. The effects on the localized and selective corrosion attack susceptibility were also investigated.     

Cyclic oxidation of yttria dispersed austenitic stainless steels

Cyclic oxidation of austenitic steels (Fe-20Ni-14Cr-2.5Mo-2Mn-2.5Al-wt.%) dispersed with 0, 0.5 and 5 wt.% yttria was carried out at 800 °C in air. The scale surface and cross-section were characterized using X-ray diffraction, scanning electron microscopy (SEM), electron probe microanalysis (EPMA) and X-ray photoelectron spectroscopy (XPS). Yttria additions improve the resistance to spallation. The increase in the resistance to spallation appears to be related to the presence of mixed oxides between yttria and base metal oxides.     

Oxidation of Cr2AlC at 1300 °C in air

High purity, dense Cr₂AlC compounds were synthesized via a powder metallurgical route, and their oxidation behavior was investigated at 1300 °C in air for up to 336 h. A thin external oxide layer formed, which consisted primarily of not Cr₂O₃ but Al₂O₃. Since Al was consumed to produce the Al₂O₃, Al-depletion and Cr-enrichment occurred underneath the Al₂O₃ layer. This led to the formation of a Cr₇C₃ layer containing voids. These grew during oxidation, eventually destroying the Cr₇C₃ layer formed on the unoxidized Cr₂AlC matrix.     

The high-temperature oxidation of bulk nanocrystalline 304 stainless steel in air

The high-temperature oxidation of bulk nanocrystalline 304 stainless steel (BN-SS304) and its conventional polycrystalline counterpart (CP-SS304) in air at 900 °C for 24 h were studied by thermogravimetric analysis, X-ray photoelectron spectroscopy and scanning electron microscope. We studied the valence electron configurations of BN-SS304, CP-SS304 and their oxide scales by ultra-violet photoelectron spectroscopy. The high-temperature oxidation resistance of BN-SS304 was enhanced in both initial and isothermal oxidation, which was attributed to its larger work function and more chemical stability, its more chemically stable and compact oxide scale, its weaker O₂ adsorption and diffusion, its weaker Cr and Mn atoms diffusions.     

KCl-induced high temperature corrosion of the austenitic Fe-Cr-Ni alloys 304L and Sanicro 28 at 600 °C

The influence of KCl(s) on the high temperature oxidation of the austenitic alloys 304L and Sanicro 28 at 600 °C in O₂ + H₂O environment is reported. 0.10 mg/cm² KCl(s) was added before exposure. The samples are investigated by grazing angle XRD, SEM/EDX, and AES. In the absence of KCl, both alloys show protective behaviour in dry O₂. In O₂ + H₂O environment, alloy 304L suffers local breakaway corrosion while Sanicro 28 still shows protective behaviour. The oxidation of both alloys is strongly accelerated by KCl. KCl reacts with chromium in the normally protective corundum-type oxide, forming K₂CrO₄. This depletes the scale in chromia and leads to the formation of a non-protective, iron-rich scale. The significance of KCl-induced corrosion in real applications is discussed and the oxidation behaviour of the two steels is compared.     

Microstructural investigation of the breakdown of the protective oxide scale on a 304 steel in the presence of oxygen and water vapour at 600 °C

This article focuses on the detailed microstructural investigation of the oxide scale formed on a 304 steel in the presence of oxygen and water vapour (40%) at 600 °C. The work has been carried out using a combination of microanalytical techniques including FIB, TEM, EDX and electron diffraction. The local breakdown of the initially protective oxide scale and the growth of island/crater oxide morphology are described. Special consideration is given to the influence of the microstructure of the steel and the oxide scale on the breakdown behaviour.     

A fundamental study of Fe-Cr binary alloy-oxide film interfaces at 288 °C by computational chemistry calculations

A quantum chemical molecular dynamics method was used in order to understand the oxide film degradation mechanism at metal/metal-oxide interfaces. The present study shows that oxygen diffusivity in the metal is significantly higher at a Fe-Cr/Fe₂O₃ interface compared to a Fe-Cr/Cr₂O₃ interface. This indicates that Cr₂O₃ enables protection of the surface for a longer period of time than Fe₂O₃ in a high temperature environment. Applied tensile strain enhances the oxygen mobility towards the metal surface. This process helps to increase the oxidation of the metal surface by forming metal oxygen bonds. Atomic charge analysis reveals that the oxygen atoms are negatively charged and the chromium atoms are more highly positively charged than iron ones. The negatively charged oxygen atoms are able to make covalent bonds with the positive metal atoms. This charge transfer process facilitates the formation of metal-oxygen bonds and weakens the metallic bonds.     

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.     

Corrosion behaviour of corrugated lean duplex stainless steels in simulated concrete pore solutions

This work studies the corrosion behaviour of two corrugated lean duplex stainless steels (SAF 2001 and 2304 grades) in eight alkaline solutions (carbonated and non-carbonated, saturated Ca(OH)₂ solutions with different chloride contents). 2001 stainless steel is a new grade in market because of its composition. 2304 is a grade previously studied under different conditions. However, its use as reinforcement in concrete is new. Studies are carried out by polarization curves following scanning electronic microscopy (SEM) and optical observations. Results are compared to those of carbon steel and austenitic AISI 304 and duplex SAF 2205 under similar conditions. After corrosion tests in alkaline media with chloride, ferrite tends to corrode selectively in 2304 duplex, while austenite corrodes selectively in 2001 under the same conditions. The influence of the duplex microstructure on attack development and morphology is analyzed. The electrochemical parameters obtained from the polarization curves suggest 2001 could replace 304 keeping the structure its corrosion performance (and with clear economical advantages). 2304 shows better corrosion behaviour than the more expensive 304, but somewhat lower than the excellent behaviour shown by 2205.     

Effect of ageing heat treatments on the microstructure and intergranular corrosion of powder metallurgy duplex stainless steels

The influence of ageing heat treatments (675 and 875 °C for 1.5 to 48 h) on the microstructure and intergranular corrosion resistance of sintered in nitrogen duplex stainless steels was investigated. The materials were obtained by sintering mixtures of austenitic AISI 316L and ferritic AISI 430L powders. Corrosion behaviour was evaluated by using electrochemical techniques. The beneficial effect of nitrogen on corrosion behaviour of solution annealed samples was established. During ageing, secondary phases were precipitated and the intergranular and transgranular corrosion resistance significantly decreased though repassivation was observed in specimens aged at 875 °C for times up to 8 h.     

Influence of nitridation on the oxidation of a 304 steel at 800 °C

This paper presents a study on the oxide growth on a AISI 304 chromia-forming alloy, in air at 800 °C. After the nitridation treatment was performed on the steel surface, a γ_N solid solution is detected. In this case, no nitride formation in the alloy surface could be observed. In situ X-ray diffraction has been used to follow the oxides evolution at testing temperature. At the beginning of the oxidation test, CrN is formed together with Fe₂O₃. Nevertheless, Cr₂O₃ quickly appears and leads to a protective oxide scale formation growing according to a parabolic rate law. During oxidation in situ X-ray diffraction also shows that Fe₂O₃ is transformed into FeCr₂O₄. Our results show that nitridation increases the high temperature oxidation resistance of 304 steels at 800 °C.     

Glass coatings on stainless steels for high-temperature oxidation protection: Mechanisms

The oxidation behavior of a martensitic stainless steel with or without glass coating was investigated at 600–800 °C. The glass coating provided effective protection for the stainless steel against high-temperature oxidation. However, it follows different protection mechanisms depending on oxidation temperature. At 800 °C, glass coating acts as a barrier for oxygen diffusion, and oxidation of the glass coated steel follows linear law. At 700 or 600 °C, glass coating induces the formation of a (Cr, Fe)₂O₃/glass composite interlayer, through which the diffusion of Cr³⁺ or Fe³⁺ is dramatically limited. Oxidation follows parabolic law.     

Influence of grain size on the oxidation behavior of NbCr2 alloys at 950-1200 °C

The oxidation behavior of mechanically alloyed microcrystalline NbCr₂ intermetallics was investigated at 950-1200 °C in air by SEM in comparison with coarse-grain cast alloys. Results indicate that the mechanically alloyed alloys possess a better oxidation resistance and are less permeable to nitrogen than the cast alloys. At 1200 °C, the mechanically alloyed NbCr₂ alloys show a better resistance to scale spallation than the cast materials. The differences observed above are attributed to the finer grains increasing the relaxation of the oxide scale stress and improving the adhesion of the oxide layer on the matrix.     

Notched tensile tests of cold-rolled 304L stainless steel in 40 wt.% 80 °C MgCl2 solution

The effects of cold-rolling (20% thickness reduction) and sensitization treatment (600 °C/10 h) on the microstructure, tensile properties and susceptibility to stress corrosion cracking of 304 stainless steel in 80 °C MgCl₂ (40 wt.%) solution were investigated. The increase in hydrogen traps, which retarded hydrogen diffusion to the strained region, accounted for the low loss in notched tensile strength (NTS) of such a cold-rolled specimen, as compared to the solution-treated specimen in the corrosive environment. By contrast, the high NTS loss of sensitized specimens in MgCl₂ solution was attributed mainly to the formation of stress-induced martensite near grain boundary regions.     

Wet oxidation of stainless steels: New insights into hydrogen ingress

It is well established that hydrogen derived from water vapor can penetrate oxidizing alloys with detrimental effect. However, the complexities of tracking hydrogen in these materials have prevented the direct profiling of hydrogen ingress needed to understand these phenomena. Here we report hydrogen profiles in industrially-relevant alumina- and chromia-forming steels correlated with the local oxide-metal nano/microstructure by use of SIMS D₂O tracer studies and experimental protocols to optimize D retention. The D profiles unexpectedly varied markedly among the alloys examined, which indicates mechanistic complexity but also the potential to mitigate detrimental water vapor effects by manipulation of alloy chemistry.     

Sulphidation/oxidation behaviour of TiAlCr and Al2Au coated Ti45Al8Nb alloy at 750 °C

In this paper, we present the sulphidation/oxidation behaviour of a Ti45Al8Nb (at%) alloy coated with different protective surface films. Two intermetallic coatings are considered; TiAlCr and Al₂Au deposited by physical vapour deposition. The coated alloy was subjected to a H₂/H₂S/H₂O yielding pS₂ - 10⁻¹ Pa and pO₂ - 10⁻¹⁸ Pa potentials at 750 °C for up to 1000 h. The corrosion kinetics were determined by means of discontinuous gravimetry and the as-received and exposed samples were characterised using scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and X-ray diffraction analysis (XRD). The materials showed the development of a multilayered structure. In the case of the TiAlCr coated Ti45Al8Nb - base alloy, Al₂O₃, TiO₂ and Cr₂S₃ developed. For the Al₂Au coated Ti45Al8Nb samples an Al₂O₃ scale containing TiO₂ nodules was observed at the surface.     

The effect of large heat input on the microstructure and corrosion behaviour of simulated heat affected zone in 2205 duplex stainless steel

In the simulated heat affected zone of 2205 duplex stainless steels, effects of large welding heat inputs on the microstructure and corrosion behaviour were investigated. Reformed austenite content increased with the coarsening of grain boundary austenite (GBA) and the growth of intragranular austenite (IGA) and Widmanstatten austenite (WA), thus improving the low temperature toughness and affecting corrosion state. Reduction of chromium nitrides contributed to better resistance to pitting corrosion. Moreover, the pitting corrosion and intergranular corrosion were improved resulting from the formation of more GBA and WA. The specimen with a Δt_8/5 of 100 s presents better comprehensive performance.     

Investigation of the HCl (g) attack on pre-oxidized pure Fe, Cr, Ni and commercial 304 steel at 400 °C

The paper presents the results from an investigation studying the ability of pre-oxidized metals and alloys to withstand chlorine attack in the form of gaseous HCl. The materials under investigation were pure Fe (s), Cr (s), Ni (s), and a commercial 18Cr-10Ni-Fe (304) alloy. The samples were pre-oxidized in different well defined environments, dry 10 vol.% O₂ (g) + N₂ (bal.), 10 vol.% O₂ (g) + 5 vol.% H₂O (g) + N₂ (bal.) and 10 vol.% O₂ (g) + 250 vppm SO₂ (g) + N₂ (bal.) for 24 h at 400 °C using a horizontal tube furnace. Afterwards the oxide films were characterized by GI-XRD, FEG-SEM, XPS and ToF-SIMS. The samples were then exposed further in 10 vol.% O₂ (g) + 500 vppm HCl (g) + x (x = 5 vol.% H₂O (g), 250 vppm SO₂ (g)) + N₂ (bal.). The exposure time was 100 h and after the exposures during the cool down process the reaction chamber was flushed with dry 10 vol.% O₂ (g) + N₂ (bal.). The corroded samples were then examined by the same techniques mentioned before. HCl (g) showed mainly to be aggressive toward the Fe (s) samples that form a relatively thick and porous oxide scale consisting of layered Fe₂O₃ (s)/Fe₃O₄ (s) during pre-oxidation, and the aggressiveness did not depend on the pre-oxidation conditions. All the other materials formed thin and dense oxides (20-100 nm) during pre-oxidation, and they did not suffer accelerated oxidation caused by HCl (g) during the subsequent exposure. The only exception was Ni (s) that had been pre-oxidized in an atmosphere containing SO₂ (g), in this case Ni sulphides and sulphates were formed during pre-oxidation which in turn caused accelerated oxidation to Ni when subsequently exposed to HCl (g). HCl (g) readily reacts with NiSO₄ (s) and Ni₃S₂ (s) and forms NiCl₂ (s) and SO₃ (g).     

Corrosion behaviour of duplex stainless steels sintered in nitrogen

Duplex stainless steels obtained through powder metallurgy (PM) technology from austenitic AISI 316L and ferritic AISI 430L powders were mixed on different amounts to obtain biphasic structures with austenite/ferrite ratio of 50/50, 65/35 and 85/15. Prepared mixes of powders have been compacted at 750 MPa and sintered in N₂-H₂ (95% and 5%) at 1250 °C for 1 h. Corrosion behaviour, using electrochemical techniques such as anodic polarization measurement, cyclic anodic polarization scan and electrochemical potentio-kinetic reactivation test and double loop electrochemical potentio-kinetic reactivation double loop test were evaluated. For duplex stainless steels, when austenite/ferrite ratio increases the corrosion potential shifts to more noble potential and passive current density decreases. The beneficial effect of annealing solution heat treatment on corrosion behaviour was established and was compared with corrosion behaviour of vacuum sintered duplex stainless steels. The results were correlated with the microstructural features.