Formation of chromium rich oxide scales for protection against metal dusting

Abstract

Metal dusting is a disintegration of metals and alloys into graphite and metal particles, caused by strongly carburizing gas mixtures mainly in the temperature range 400–700°C. Protection of steels against metal dusting is possible through the formation of dense chromium rich oxide scales but it is not guaranteed that such scales are formed at low temperatures, even on high Cr-steels.

Surface analytical studies have been conducted on the formation and composition of the oxide scales on 9–20%Cr steels. The growth of oxide films was followed by AES for 3 hours at 10^–7 mbar O₂ great differences were observed in dependence on surface finish. On ground samples, Mn and Si appeared early and Cr-rich oxide was formed, whereas on chemically etched samples Fe-rich oxides grew.

After long term exposures (240 h) under metal dusting conditions, i.e. in CO–H₂–H₂O mixtures at 600°C, thin Cr-rich scales were observed on ground steels which were impermeable to carbon whereas on chemically etched steels thick Fe-rich scales had grown and carbon penetration was detectable. Accordingly, the oxide formation on Cr-steels at relatively low temperatures strongly depends on the surface treatment. Any surface working such as grinding and sand-blasting etc. introduces dislocations and causes a fine-grained microstructure near the surface, and the dislocations and grain boundaries act as rapid diffusion paths for supply of Cr to the surface in the first minutes of exposure, which leads to the formation of a protective oxide scale.     

Laser raman spectroscopic studies of the surface oxides formed on iron chromium alloys at elevated temperatures

Binary iron-base alloys containing chromium additions of 3, 9, 12 and 18 % were oxidized in air at elevated temperatures. Laser Raman spectroscopy has been used to determine the chemical compounds of the oxides of these alloys. It is found that the oxides formed on Fe-3Cr alloy at various elevated temperatures consist mainly of iron. However, for Cr additions ≥12 %, the surface oxide formed at 400°C consists of αFe₂O₃, Fe₃O₄ and spinel phases. With increasing oxidation temperature up to 850°C, the oxide scale consists of Cr₂O₃ and spinel phases only.     

Black oxide layer formation and banding in high chromium rolls

Abstract

In order to improve the surface quality of strip steels it is essential that surface oxide adheres to the roll surface. To understand the mechanism of banding (the detachment of oxide from the roll surface), black oxide layers on a roll surface and on a slab surface were analysed using SEM, optical microscopy, microhardness testing, energy dispersive spectrometry, and X-ray diffraction. A mathematical model for black oxide layer thickness of a high chromium iron roll was established on the basis of the oxidation mechanism and oxide layer structure. It is shown that the black oxide layers, formed on the roll surface, induce the formation of cracks which propagate easily along M₃ C and M₇ C₃ carbides resulting in their final separation from the roll surface during the rolling process.     

Photoelectrochemical investigations on individual ferritic and austenitic grains of a duplex stainless steel oxidized in water vapour

Abstract

This work presents a multiscale photoelectrochemical characterization of oxide layers, and aims mainly at introducing the mesoscopic scale (ca 30 µm). For the first time, photocurrent energy spectra could be recorded on individual ferritic and austenitic grains of a unique 2205 duplex stainless steel sample oxidized for 5 minutes at 650°C under 20% water vapour in nitrogen. These results allowed us to explain contrasting issues in the photoelectrochemical images obtained from the oxidized sample. Moreover, the bandgap energies obtained by fitting these individual mesoscopic photocurrent energy spectra with a novel approach developed in our laboratory, showed that all oxide scales were constituted of Fe₂O₃ and Cr₂O₃ and of an Fe_2-xCr_xO₃ solid solutions, but that the x-value of the latter was different depending on the metallurgic phase of the oxidized substrate. The latter results were shown to be in agreement with those of additional Raman analyses of the oxidized austenitic and ferritic grains.     

Initial oxidation of Fe–Cr alloys: in situ STM and ex situ SEM observation

Abstract

In order to understand the initial oxidation of Fe–Cr alloys a single crystal of Fe–15Cr (100) was oxidized at 440°C under controlled oxygen partial pressure in a UHV system and the surface morphology was observed using in situ STM (basic pressure 1×10^?10 mbar); in addition, polycrystalline Fe&15Cr was oxidized at 400°C in an IR-furnace in atmospheric air and the morphology was observed using ex situ SEM. The chemistry of the surface oxide layers was studied by XPS.

Preparation of the single crystal in the UHV system did not lead to segregation of Cr to the surface during heating. In situ STM investigation showed that oxidation of Fe–Cr commenced by nucleation of Cr oxide on the surface, due to selective oxidation of Cr. When the Cr at the surface and at the interface was completely consumed by nucleation of Cr oxide, Fe oxidized and covered the initial Cr oxide nuclei, resulting in an Fe oxide layer on the surface. Ex situ experiments showed that initial oxidation of the mechanically prepared polycrystalline alloy depended on the defect distribution in the surface. It started with formation of whisker-type Fe oxides along defects and proceeded with spherical-type nucleation and growth of Fe oxide. In both experiments, the final product on the surface was Fe₂O₃.     

Influence of different annealing processes under various atmospheres on the oxidation behaviour of γ-TiAl

Abstract

A detailed study of the oxidation behaviour of bare γ-TiAl based alloy Ti–45Al–8Nb under various conditions, such as different atmospheres, pressures, temperatures (900°C, 1000°C) and times (100–200 h) is presented. Under high vacuum conditions (10^–6 mbar) a continuous zone of α-₂Ti₃Al was formed at the surface with an oxygen-enriched phase on top. No oxide scale formation was obvious. During thermal treatment under Ar-atmosphere at low vacuum pressure (approximately 50 mbar) mainly nitrides (TiN, Ti₂AlN) and Al₂O₃ particles were formed at the surface with an α-₂layer below. Annealing γ-TiAl in hydrogen atmosphere (about 1040 mbar) led to the formation of a thick reaction zone. A TiO₂ layer was formed on top, followed by a mixed oxide scale. Beneath that scale a thick region with alumina, σ–Nb₂Al and α-₂Ti₃Al was observed.

Moreover, the oxidation behaviour of several thermally pre-treated samples was tested by cyclic oxidation at 900°C in air. The microstructure of the oxide scale formed after testing can be compared with that of non pre-treated material. γ-TiAl annealed under high vacuum conditions exhibits the lowest oxidation rate, while the mass gain of specimens pre-treated under Ar-atmosphere increased rapidly in the first cycles. All pre-treated specimens exceeded a lifetime of 600 cycles at minimum. The reference material failed after 520 cycles.     

Preparation and characterization of chromium oxide supported on zirconia

Chromium oxide/zirconia was prepared by dry impregnation of powdered Zr(OH)₄ with an aqueous solution of (NH₄)₂CrO₄. The characterization of prepared samples was performed using Fourier-transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and differential thermal analysis (DTA), and by measurement of the surface area. The addition of chromium oxide to zirconia shifted the transitions of ZrO₂ from the amorphous to the tetragonal phase and from the tetragonal to the monoclinic phase to higher temperatures due to the strong interaction between chromium oxide and zirconia; and the specific surface area of the samples increased in proportion to the chromium-oxide content. Since the ZrO₂ stabilizes supported chromium oxide, chromium oxide was well dispersed on the surface of zirconia, and -Cr₂O₃ was only observed at calcination temperatures above 1173 K. Upon the addition of only small amounts of chromium oxide (1 wt % Cr) to ZrO₂, both the acidity and acid strength of the samples increased remarkably, showing the presence of two kinds of acid sites on the surface of CrOx/ZrO₂ (Brönsted and Lewis acid sites).     

The effect of H2-anneal on the adhesion of Al2O3 scales on a Fe3Al-based alloy

Abstract

The cyclic (1,100°C, air) and isothermal (1,000°C, O₂) oxidation behavior of a Fe-28Al-5Cr (at%) alloy, with and without a prior H₂-anneal heat treatment at 1,200°C for 100 h, was studied. Changes in interfacial chemistry were evaluated using Scanning Auger Microscopy after removal of the oxide film in ultra high vacuum. This was achieved by making a scratch on the specimen surface, which caused spallation of the film at various locations along the scratch. The scale thickness and the temperature drop at which spallation took place during cooling were utilized to semi-quantitatively compare the adherence of the scales. Porosity at the scale–alloy interface and the scale microstructure were determined from scanning electron microscope observations. It was found that H₂-anneal greatly improved scale adhesion and resulted in a pore-free and sulfur-free interface. The effects were similar to that of a 0.1 at% Zr-containing alloy, except that the improvement in scale adhesion was not as great as that from Zr doping. This implies that oxide/alloy interfaces are not intrinsically strong and the effect of reactive elements, such as Zr, is more than preventing impurity from segregating to the interface. Results are also compared with the effect of H₂-anneal on other model alloys, such as NiCrAl, FeCrAl and NiAl, and on single crystal superalloys.     

Breakdown of the protective oxide on 11 % Cr steel at high temperature in the presence of water vapor and oxygen,the influence of chromium vaporization

Abstract

We report on the effect of water vapor and oxygen on the oxidation of a ferritic/martensitic 11 % Cr steel (CrMoV11 1). The influence of pH₂O, exposure time, gas velocity and temperature was investigated. The samples were exposed to dry O₂, O₂+10 or 40 % H₂O for up to 336 hours. Total pressure was 1 atm (1.02 × 10⁵ Pa). The gas velocity was between 0.05 and 10 cm/s while temperature was in the range 450–700°C. The samples are investigated by thermogravimetry, GI-XRD, SEM/EDX, GDOES, FIB and TEM/EDX. Oxidation is strongly affected by the vaporization of CrO₂(OH)₂ in H₂O/O₂ environment. The mechanism of vaporization of CrO₂(OH)₂ from a Cr₂O₃ surface is modelled by DFT calculations. In the absence of chromium vaporization the alloy forms a protective oxide consisting of a corundum-type solid solution (Fe_1–xCr_x)₂O₃. The vaporization of chromium tends to deplete the oxide in chromium. In some cases the oxide remains protective in spite of chromium depletion while in other cases there is a transition to breakaway oxidation. In the latter case a thick layered scale forms, consisting of an outer hematite part and an inner iron-chromium spinel. Oxidation behavior in an O₂+H₂O environment is to a large extent determined by the ability of the metallic substrate to supply the oxide with chromium by diffusion in order to compensate for the losses by vaporization. The corrosivity of the environment increases with the concentration of water vapor and oxygen, with the gas velocity and with temperature.     

Deposition of nanocrystalline nonstoichiometric chromium oxide coatings on the surface of multiwalled carbon nanotubes by chromium acetylacetonate vapor pyrolysis

Nanocrystalline coatings of nonstoichiometric chromium oxide have been obtained for the first time on the surface of multiwalled carbon nanotubes (MWCNTs) by the method of metalorganic chemical-vapor deposition using chromium acetylacetonate as a precursor. The new hybrid nanomaterial (Cr₂O_2.4/MWCNT) has been characterized by X-ray diffraction, scanning electron microscopy, and thermogravimetric analysis. It is established that oxidation of the hybrid nanomaterial in air under soft conditions (at 380°C) leads to the formation of nanocrystalline chromium oxide (Cr₂O₃) on the surface of MWCNTs.

     

Growth of ZnO nanostructure on Cu0.62Zn0.38 brass foils by thermal oxidation

Cu_0.62Zn_0.38 brass foil was heated at temperatures of 400–700 °C in flowing N₂–5%O₂ at a pressure of 1 atm. for 1–24 h. The oxidized specimens were characterized with a scanning electron microscope, an X-ray diffractometer and a transmission electron microscope. The results show that hexagon ZnO nanowires and nanowalls grew on convoluted oxide scales when brass foils were oxidized at 500 and 600 °C. Thermodynamics of forming ZnO is analyzed based on oxidation theory of an alloy. Pilling–Bedworth ratio of Cu–Zn alloy is calculated based on the volume differences between the formed oxide and the consumed metal. The growth stresses caused by Pilling–Bedworth ratio of the alloy and stress relief of oxide scale at different oxidation temperature are analyzed. The mechanism of forming nanostructural ZnO on the convoluted oxide scales is explained by the change in the growth stresses and stress relief of oxide scale during thermal oxidation.     

Oxidation behavior of a new Fe–Ni–Cr-based alloy in pure steam at 750 °C

The isothermal oxidation of a new Fe–Ni–Cr-based alloy has been investigated in pure steam at 750 °C for exposure time up to 500 h using secondary electron microscope (SEM)/ X-ray energy-dispersive spectroscopy (EDS) and X-ray diffraction (XRD). Results showed that the alloy was oxidized approximately following a parabolic law with a parabolic rate constant k_p of 2.36 × 10^?13 g²/m⁴/s. As revealed by SEM/EDS and XRD results, a duplex-layered external oxide scale was formed, consisting of a thin outer layer of Ni(Fe, Al)₂O₄ and a thicker inner layer of (Cr, Mn)₂O₃. Underneath the external oxide scale, the internal oxidation of Ti to be TiO₂ occurred particularly along the grain boundaries of the matrix alloy. Internal oxide of Al₂O₃ was also observed but at a deeper depth. Based on the detailed compositional and microstructural characterization of the oxidized zone, the mechanism of the external and internal oxidation in steam is presented.     

Desmutting of aluminium alloy 2024-T3 using rare earth electrolyte

Abstract

The desmutting of 2024-T3 aluminium alloy using a new rare earth desmutting solution has been studied by SEM and X-ray photoelectron spectroscopy (XPS). It was evident from SEM that, during desmutting, there was dissolution and etching of both the intermetallics and the basic oxide scale left after alkaline cleaning. In addition, copper from the intermetallics was deposited as a residue on the surface of the desmutted alloy. The residue, in the form of precipitates ～200 nm in size, proved to be copper with an oxide coating. The addition of oxidants such as hydrogen peroxide (H₂O₂ ) and potassium persulphate (K₂ S₂O₈ ) removed these precipitates. It was apparent from XPS that the surface was coated with a thin 6 nm aluminium oxide after desmutting.     

Effect of minute element addition on the oxidation resistance of FeCoCrNiAl and FeCoCrNi2Al high entropy alloy

The effect of Ti_0.1 and Ti_0.1Si_0.1 addition on the high temperature isothermal oxidation behavior of dense FeCoCrNiAl and FeCoCrNi₂Al high entropy alloy (HEA) consolidated by vacuum hot pressing were investigated by X-ray diffraction, Scanning Electron Microscopy and Raman Spectroscopy. Mechanical properties such as hardness, Young’s modulus, and thermal properties such as differential scanning calorimetry (DSC) and coefficient of thermal expansion (CTE) were also investigated. The weight gain recorded after isothermal oxidation for 5,25,50 and 100 h at 1050 °C was found to be parabolic in nature. X-ray diffraction analysis (XRD), as well as Raman spectroscopy analysis of HEA’s oxidized at 1050 °C for 100 h, shows the formation of the Al₂O₃ phase. A homogeneous thin oxide scale without any discontinuity was observed throughout the cross-section. Ti and Si addition in 0.1 at. % improves mechanical properties, oxidation resistance, and reduces waviness of the oxide scale.     

Oxidation of potential SOFC interconnect materials,Crofer 22 APU and Avesta 353 MA,in dry and humid air studied in situ by X-ray diffraction

Abstract

Several stainless steels have been developed for the use as interconnect materials in solid oxide fuel cells in order to reduce costs, while maintaining the required performance. The materials however, are subjected to humid air, at high temperatures up to 800°C leading to enhanced oxidation. High temperature X-ray diffraction, combined with field emission – scanning electron microscopy, has been applied to study in situ the influence of water vapour on the chromia scale formation on the ferritic Crofer 22 APU and the austenitic Avesta 353 MA alloys in comparison to their dry air oxidation behaviour. Both materials form at 800°C, during the first 100h exposure, Cr₂O₃ and MnCr₂O₄, the latter mostly in the surface region of the oxide scale. Additionally, Crofer 22 APU forms internal Al₂O₃ precipitates, while on Avesta 353 MA a SiO₂ layer is found beneath the outer oxide scale. High temperature XRD indicates stress formation and relaxation in the Cr₂O₃ scale formed in humid air, especially for Crofer 22 APU.     

Cyclic oxidation of FeCrAlY/Al2O3 composites

Abstract

Three-ply composites consisting of a FeCrAlY matrix and continuous single crystal Al₂O₃ (sapphire) fibers were cyclically oxidized at 1,000° and 1,100°C for up to 1,000 1-h cycles. FeCrAlY matrix only samples were also fabricated and tested for comparison. Fiber ends were exposed at the ends of the composite samples. Following cyclic oxidation, cracks running parallel to and perpendicular to the fibers were observed on the large surface of the composite. In addition, there was evidence of increased scale damage and spallation around the exposed fiber ends, particularly around the middle ply fibers. This damage was more pronounced at the higher temperature. The exposed fiber ends showed cracking between fibers in the outer plies, occasionally with Fe and Cr-rich oxides growing out of the cracks. Large gaps developed at the fiber–matrix interface around many of the fibers, especially those in the outer plies. Oxygen penetrated many of these gaps resulting in significant oxide formation at the fiber–matrix interface far within the composite sample. Around several fibers, the matrix was also internally oxidized showing Al₂O₃ precipitates in a radial band around the fibers. The results show that these composites have poor cyclic oxidation resistance due to the CTE mismatch and inadequate fiber–matrix bond strength at temperatures of 1,000°C and above.     

Adhesion of thermal barrier coatings systems after long term oxidation : influence of preoxidation temperature and surface state of the bond coat

Abstract

The aim of this study was to determine the effect of the pre-oxidation temperature and surface state of the bond coat on the microstructure of the oxide scale formed at the first stages of oxidation and on its adhesion after subsequent long-term oxidation (1000 h) at 1100–C. Short-term isothermal oxidations of 1 h were performed at several temperatures (900–C, 1100–C) on a Pt-modified NiAl bond coat with two different surface states (as-aluminized or grit-blasted) deposited on a superalloy (AM1). The adherence of the different systems after an additional isothermal ageing treatment in air at 1100–C for 1000 h, was compared in order to deduce the initial oxide scale leading to the best resistance to spallation. Characterization was performed using SEM and analytical TEM. The crystalline structure and the morphology of the as-formed oxide scale were studied as a function of the different parameters.     

The oxidation of Fe3Al–(0, 2, 4, 6%)Cr alloys at 1000 °C

Thermomechanically treated Fe₃Al–(0, 2, 4, 6at.%)Cr alloys were isothermally oxidized at 1000 °C in air, and their oxidation characteristics were studied using thermogravimetric analyzer, X-ray diffractometer, scanning electron microscope, electron probe microanalyzer, and TEM/EDS. It was found that Cr decreased the oxidation resistance of Fe₃Al alloys to a certain extent. The oxide scales that formed on the unalloyed Fe₃Al alloys consisted primarily of α-Al₂O₃ containing a small percentage of dissolved iron ions. Less than 1% of dissolved chromium ions was additionally present in the oxide scale formed on the Fe₃Al–Cr alloys. An Al-free, Fe-enriched zone was formed beneath the oxide scale, owing to Al consumption to form the oxide scale. The oxide scale on all alloys had poor adherence.     

On the early stages of scale development on Ni–22Al–30Pt with and without Hf additions at 1150°C

Abstract

Platinum modified Ni –Al-based alloys play an important role in the aeronautical industry as materials applied as Bond Coats (BCs) in thermal barrier coating systems (TBC), which provide protection against high temperature oxidation. Therefore, it is crucial for the assessment of the performance of the TBC to understand the oxidation behaviour of the Bond Coat material and the properties of the thermally grown oxide developing on it.

This paper reports on the scale growth mechanism of Pt-modified γ′-Ni₃Al-based alloys with and without Hf additions at the early stages of oxidation. Samples were oxidized at 1150°C for up to 50 min. The consecutive stages of the scale evolution were followed by a systematic approach using a two-stage oxidation treatment in atmospheres containing different amounts of ¹⁸O₂ oxygen isotope. The scale growth mechanism was followed with the aid of the in-depth analysis of elemental distribution, in particular of the oxygen isotopes, across the scale using secondary ion mass spectrometry (SIMS). The surface morphology of the scales was observed using scanning electron microscopy, while its local phase composition was determined using photoluminescence spectroscopy. In addition, the imaging SIMS was used to generate distribution maps of the oxygen isotopes. Because of the limited lateral resolution of the SIMS technique (down to 0.5 μm) they were conclusive only for the most prolonged exposures (50 min).

Typical stages of scale evolution were observed for the growing scales: initially flat layers were formed, followed by more or less developed blade-like surface grains, phase-transformation-related cracks and round patches and, finally, ridges. The latter were only found on the Hf-free material. The scale growth mechanism evolved from an initially predominant outward growth mechanism towards an increasing contribution of the inward mechanism. The relative extents of the outward and inward growth mechanisms depended strongly on the surface fraction of patches and through-scale cracks. The phase composition analyses showed that cracks and patches are regions where the transient aluminas were preferentially transformed into the α-Al₂O₃ phase which is the required protective scale. The ridges formed in cracks essentially consisted of α-Al₂O₃. For the most of studied exposure periods both types of phases: transient aluminas and α-Al₂O₃ co-existed in the scales.

The results obtained indicate that: (i) phase transformations occur locally and not simultaneously in the entire scale; (ii) Hf additions retard the phase transformation; (iii) the phase transformation is completed only on Hf-free material and not after oxidation for 50 min; (iv) the two-stage oxidation approach should be carefully applied to study the growth mechanism of evolving scales in which regions of different phase compositions develop.     

Oxidation of silicon nitride sintered with ceria and alumina

Abstract

Sinter-hipped silicon nitride with additions of ceria and alumina has been subjected to oxidation for up to 72 h at various temperatures. Within the experimental temperature range (1250–1425°C), a parabolic weight gain was observed with an activation energy of 350 kJ mol^?1 for the process. On oxidation there formed an oxide scale whose morphology depended on temperature and cooling rate, and a subscale, at the interface between the substrate and the oxide scale, consisting of β3-Si₃MN₄ grains, a Ce-rich silicate glass, and Si₂N₂0. The morphology and phase content of the oxide products were characterised by X-ray diffractometry and electron microscopy. Detailed analyses by SEM showed that the oxide scales were not homogeneous, but exhibited several layers with important microstructural and compositional variations through their thickness.

MST/1107