Effect of water vapour on growth and adherence of chromia scales formed on Cr in high and low pO2-environments at 1000 and 1050°C

Abstract

The oxidation behaviour of pure Cr at 1000 and 1050°C was studied in Ar–O₂ and Ar–H₂–H₂O mixtures. It was found that in the low-pO₂ gases the oxide scales exhibited higher growth rates than in the high-pO₂ gases. The scales formed in the low-pO₂ gases showed substantially better adherence during cooling, than scales formed in the high-pO₂ gases. These differences in growth rate and adherence can be correlated with differences in size and location of the in-scale voids formed during the isothermal exposure. Exposures in Ar-O₂-H₂O mixtures revealed that the differences in scale growth rates as well as in scale void formation and growth are not primarily related to differences in the oxygen partial pressure of the atmosphere but to the presence of water vapour in the test gas. At sufficiently high H₂O/O₂-ratios, water vapour promotes oxide formation at the scale/metal interface thereby suppressing excessive growth of existing voids, and also as a consequence improved scale adherence. Whether the enhancement of inward scale growth is related to transport of H₂O- or H₂-molecules or due to OH^? ions, cannot be derived with certainty from the present results.     

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.     

Influence of the oxidation environment on scale morphology and oxidation rate of Fe–22Cr

Abstract

The oxidation behaviour of a commercial Fe–Cr alloy with 22 wt% Cr was investigated at 1173K in Ar–9 H₂ with 1% H₂O (pO₂ = 9.8 × 10^?19), in air with 1% H₂O (pO₂ = 0.208), and in a combination of the two atmospheres. The oxide morphology was investigated with X-ray diffraction and scanning electron microscopy. The oxide layer consisted of MnCr₂O₄ on top of Cr₂O₃.

Small oxide whiskers were present at the surface after oxidation in Ar–9 H₂ with 1% H₂O but not after oxidation in air with 1% H₂O. For samples initially oxidised in air with 1% H₂O, the oxide/alloy interface was wrinkled and covered with a SiO₂ layer. SiO₂ particles had developed at a rather flat oxide/alloy interface for samples initially oxidised in Ar–9% H₂ with 1% H₂O. The results obtained can be explained assuming that oxide growth occurs by cation diffusion only in Ar–9 H₂ with 1% H₂O, whereas both cation and anion diffusion contribute to the growth in air/H₂O.     

Effect of test atmosphere composition on high-temperature oxidation behaviour of CoNiCrAlY coatings produced from conventional and ODS powders

Abstract

The oxidation behaviour of free-standing CoNiCrAlY coatings produced by low-pressure plasma spraying using conventional powder and oxide dispersion strengthened (ODS) powder containing 2 wt. % Al-oxide dispersion was investigated. Thermogravimetric experiments at 1100 °C in Ar-20%O₂ and Ar-4%H₂-2%H₂O showed lower oxidation rates of the ODS than the conventional coating. In the latter material the scale growth was enhanced by extensive Y-incorporation of Y/Al-mixed oxide precipitates in the scale and apparently by Y-segregation to oxide grain boundaries. In the ODS coating the alumina dispersion bonded Y in the form of Y-aluminate thereby effectively suppressing scale ‘overdoping’. SEM/EBSD studies of all alumina scales revealed a columnar grain structure with the lateral grain size increasing approximately linearly with depth from the oxide/gas interface. For both coatings the alumina scale growth was slower in Ar–H₂–H₂O than in Ar–O₂. The result is believed to be related to a lower oxygen potential gradient and to slower grain boundary diffusion in the scale forming in H₂/H₂O containing gas.     

Chemical-mechanical failure of oxide scales on 9% Cr steels in air with H2O

Abstract

The oxidation behaviour of 9% Cr steels P91 and Nf616 has been investigated at 650°C in dry air and in air with water vapour, where particular attention was given to breakaway failure. Additional emphasis was given to the quantitative characterisation of the kinetics of chromium depletion in the metal subsurface zone resulting from scale growth, CrO₂H₄ evaporation, and scale cracking and healing, with scale cracking being monitored by acoustic emission measurements. While in dry air the steels show protective oxidation behaviour up to 10000 h, breakaway oxidation may occur already after 100 h in humid environments, which was correlated with the stronger Cr-depletion and the development of intrinsic oxide scale growth stresses exceeding a critical value, in the case of water vapour containing air. In the paper the different parameters that are responsible for breakaway oxidation were identified and discussed with regard to the role of water vapour in the environment. As a conclusion it turns out that breakaway is not a consequence of Intrinsic Chemical Failure (InCF) but of a Mechanically Induced Chemical Failure (MICF).     

Kinetic and metallographic study of oxidation at high temperature of cast Ni 25Cr alloy in water vapour rich air

Abstract

The high temperature oxidation behaviour of a Ni–25 wt-%Cr alloy in air enriched with water vapour (180 mbars H₂O) was studied at 1000, 1100, 1200 and 1300°C. The oxidised samples were characterised by X-ray diffraction, electron microscopy and wavelength dispersion spectroscopy. The obtained data were compared to the ones earlier obtained for the same alloy oxidised in dry air. Water vapour globally induced at all temperatures a decrease of the parabolic constant Kp and an increase in the chromia volatilisation constant Kv. The oxide scales do not present morphologic difference between the two atmospheres. After oxidation in humidified air the scale thickness is thinner and the Cr depleted depth is lower than in dry air.     

Characterization of Chromia Scales Grown on Pure Chromium in Different Oxidizing Atmospheres

Abstract

Scanning electron microscopy, X-ray diffraction, photoelectrochemistry and microphotoelectrochemistry have been used to characterize thin chromia scales, in the micrometer range, grown on pure chromium at 900°C in oxygen and in water vapour. The duplex structure formed, more easily observable in water vapour grows by the opposite transport of chromium and of oxide/hydroxide ions. The external chromia subscale exhibits the usually reported 3.5 eV bandgap whereas the internal subscale presents a reduced gap possibly due to impurity contribution. Imaging the photocurrent generated in this subscale allows the observation of good metal-oxide interface properties of samples grown in H₂O, whereas samples grown in O₂, (liable to cracking during cooling), exhibit partially disrupted zones.     

In situ ESEM investigations of the oxide growth on hot work tools steel: effect of the water vapour

Abstract

Tempered martensitic steel modified AISI H11 is used in forging processes where tool failure can result from the combination of thermo-mechanical and chemical damage. A better knowledge of the oxidation mechanisms in this material could be useful for a better appreciation of its service behaviour and lifetime. The low chromium content of this Fe–Cr type steel allows the development of mainly Fe_2–xCr_xO₃ oxides with corundum structure and leads to enhanced oxidation in the presence of water vapour.

In situ FEG–ESEM images show the scale microstructural modifications during high temperature exposure, as well as the lateral growth of oxide particles. Together with GIXRD, SEM/EDS and SIMS analysis, FEG–ESEM also allows assessment of the H₂O effect on oxidation behaviour during high temperature exposures (600 and 700°C). Water vapour induces either pores or crystallites size increase, favours faceted oxides particles with enhanced density at the highest partial pressure. At this microscopic scale, anisotropic growth of crystallites is observed, and size expansion rates are found to be linear and characteristic of each individual particle.

Temperature acts principally on oxide film microstructure. Whatever the environment, homogeneous scale growth is observed at 600°C whereas the steel surface is heterogeneously covered by oxides at 700°C.     

Effects of trace impurities on the adherence of oxide to ultra low carbon steel

The effects of trace impurities on the adherence of oxides to ultra low carbon steels were investigated. Three steels, of differing chromium, aluminium, silicon, nitrogen and oxygen content, were oxidized at 850 K in 10% CO₂-90% N₂ gas and then oxidized at 770 K in 10% CO₂-10% O₂-80% N₂ gas. Surface analysers, i.e. a Mössbauer spectrometer, Auger electron spectrometer and/or ion micro analyser, were utilized in the present study because of the very thin layer of oxides formed (1.0 to 2.0 µm). The following results were obtained. The oxide on the Al-containing steel spalled at the outer-inner oxide interface, where aluminium was enriched and many cavities appeared. The inner oxide layer, oxidized by the transport of CO₂ or O₂ gases along the outer layer grain boundaries or micropores, became thick. This generated a stress at the outer-inner layer interface with the resultant formation of cavities. On the other hand, the oxide on the Cr-containing steel showed good adherence to the metal. The inner layer, enriched with chromium, did not become thick and had no cavities at the interface. The addition of chromium to the Al-containing steel resulted in good oxide adherence because chromium acted as a barrier to the aluminium enrichment.     

The oxidation of TiC in dry oxygen, wet oxygen, and water vapor

Isothermal oxidation of TiC was studied using powder sample at 300–400°C in Ar/O₂ = 95/5 kPa (dry oxidation) and Ar/O₂/H₂O = 90/5/5–10 kPa (wet oxidation), and at 520–650°C in Ar/H₂O = 95/5–15 kPa (H₂O oxidation) by monitoring weight changes. The phases produced were identified by X-ray analysis and the oxidized sample was observed by scanning and transmission electron microscopy. The dry, wet and H₂O oxidation of TiC was found to be described by a one-dimensional diffusion-controlling equation. It was revealed that the oxidation was divided into three steps, slow step I, fast step II, and slow step III. Water vapor in the wet oxidation accelerated these three steps, particularly step II. Non-isothermal oxidation of TiC was also performed to simultaneously monitor the evolved gases (CO/CO₂, H₂, CH₄) with weight changes by thermogravimetry and mass analysis. The accelerating effect of water vapor on oxidation of TiC was discussed from kinetic and thermoanalytical viewpoints.     

Effect of oxygen partial pressure on the oxidation behaviour of an yttria dispersion strengthened NiCr-base alloy

An yttria dispersion strengthened NiCr-base alloy was studied with respect to isothermal oxidation behaviour at 1000 °C and 1050 °C in high- and low-pO₂ gases, i.e. Ar–O₂ and Ar(−H₂)–H₂O. The scale growth kinetics, morphology and composition were studied by thermogravimetry in combination with SEM/EDX and SNMS. Due to Y doping the surface scale is very protective and initially grows predominantly by inward oxygen diffusion. Local formation of mainly outwardly growing oxide nodules occurs after longer oxidation times and is related to metallic protrusions formed as a result of internal oxidation of the minor alloying addition aluminium. The differences in scale morphology in the various environments are related to the effect of the gas composition on scale grain size and on the relative amounts of inward scale growth. Possibly the pO₂ dependence of the Ti-solubility in the chromia scale and/or hydrogen doping of the oxide plays an additional role in the scale growth process.     

Effect of component thickness on lifetime and oxidation rate of chromia forming ferritic steels in low and high pO2 environments

Abstract

Long term oxidation tests were carried out with a high-Cr ferritic steel at 800°C and 900°C in simulated cathode and anode gas of a solid oxide fuel cell (air and an Ar/H₂/H₂O mixture respectively). It was found that with decreasing sample thickness the life time of the steel decreases due to breakaway phenomena. This effect is caused by faster exhaustion of the chromium reservoir from the bulk alloy in the case of thinner components. During air exposure the oxidation rates increase with decreasing specimen thickness and this has to be taken into account in the calculation of the Cr-reservoir exhaustion. This thickness dependence is not found during the exposures in simulated anode gas. Hence, especially for thin walled components, the oxidation rates in anode gas are substantially smaller and thus the life times are longer than during air exposure. The differences in oxidation behaviour in the two environments are discussed on the basis of scale formation mechanisms involving microcrack formation in the surface oxide scale and depletion of major and minor alloying additions in the bulk alloy.     

Oxidation of Fe–Si alloys in CO2–H2O atmospheres

Abstract

Iron and model alloys containing 1, 2, and 3wt% Si were reacted with dry and wet CO₂ gases at 800°C. All oxidised in dry CO₂ according to approximately linear kinetics. Additions of H₂O accelerated the reaction until steady-state parabolic kinetics were achieved. However, the effect of H₂O was small in the steady-state reaction stage of Fe – 3Si. Alloy reaction products were a duplex scale consisting of an outer FeO+Fe₃O₄ layer and an inner FeO+Fe₂SiO₄ layer, plus an internal oxidation zone, in all gases. In Fe – 1Si, amorphous SiO₂ precipitates in the internal oxidation zone grew with rod-like morphologies in all gases. However, internal amorphous SiO₂ precipitates grown in Fe – 2Si and Fe – 3Si formed network patterns. Internal penetration rates were initially rapid in Fe – 1Si, but slowed considerably at longer times. In Fe – 3Si, the internal oxidation zone grew wider in the first 20 h of reaction, and then remained constant in dry gas. In the wet gases this zone subsequently diminished, and disappeared after 50 h reaction.     

Oxidation of silicon carbide in a wet atmosphere

The effects of water vapour on oxidation of pressureless-sintered silicon carbide containing alumina as a densifying aid were studied in a wet air flow with 10, 20, 30 and 40vol% H₂O at 1300° C for 100h. The oxidation kinetics were determined in a wet air flow with 20 vol % H₂O and in a dry air flow at 1300° C for times up to 360 h. The weight gain on oxidation showed an increasing tendency with increasing water vapour content. Water vapour in the atmosphere strongly influenced oxidation and accelerated the reaction. Oxidation in a wet atmosphere proceeded in a diffusion-controlled manner, in the same process as that for the dry atmosphere. No remarkable differences were noticed in the microstructure of the oxide layer and the surface roughness between the samples oxidized under the four wet conditions, but the surface roughness increased with increasing oxidation time. Water vapour evidently accelerated the devitrification of amorphous silica and promoted oxidation. Oxidation in a wet atmosphere (10 to 40 vol % H₂O for 100 h and 20 vol % H₂O up to 360 h) had a slight degrading effect on the flexural strength. The microstructure or surface roughness of the oxide layer formed during oxidation presumably had very little effect on the room-temperature strength.     

Influence of chromium diffusion and different surface finishes on the oxidation behaviour of chromium steels

Abstract

The present contribution is focused on the systematic investigation of the effects of different surface finishes (ground, polished, electropolished) on the oxidation behaviour of chromium steels. The specimens were oxidized in a H2–2.5%H₂O atmosphere at 872 K for 1 h to 100 h. Depth profiles were recorded by secondary neutral mass spectrometry (SNMS) to determine the elemental composition of the oxide scale and the diffusion profiles below the scale. The surface finish was found to influence both the thickness of the oxide scale and the depletion of the selectively oxidized elements.     

Oxidation of FeCrAl foils at 500–900°C in dry O2 and O2 with 40% H2O

Abstract

High temperature resistant FeCrAl alloys are frequently used in high temperature applications such as heating elements and metal based catalytic converter bodies. When exposed to high temperatures an adherent, slowly growing, dense aluminium oxide layer forms on the surface, which protects the underlying alloy from severe degradation. The composition, structure and properties of the formed oxide layer are strongly dependent on the alloy composition, temperature and oxidation environment. In this study, the Sandvik 0C404 FeCrAl alloy, in the form of 50 μm thick foils, was exposed isothermally in the temperature range 500–900°C for 168 hours in dry O₂ and in O₂ with 40 vol.% H₂O. The surface morphology, composition and microstructure of the grown oxide scales were characterized by using scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), grazing incidence X-ray diffraction (GIXRD), Auger electron spectroscopy (AES), and time of flight secondary ion mass spectrometry (TOF-SIMS). The oxidation process was faster at 900°C than at 500 and 700°C. At 500°C a thin (10–20 nm) mixed oxide of Fe, Cr and Al was formed. Exposure at 700°C resulted in a similar (40–50 nm) duplex oxide, in both dry O₂ and in O₂ with 40 vol.% H₂O. These oxide scales consisted of an inner and an outer relatively pure alumina separated by a Cr-rich band. This type of duplex oxide scale also formed at 900°C with a thin inward growing α–Al₂O₃ at the oxide/metal interface and an outward growing layer outside a Cr-rich band. However, at 900°C the outward growing layer showed two types of oxide morphologies; a thin smooth base oxide and a much thicker nodular oxide grown on top of substrate ridges. In dry O₂ atmosphere, the main part of this outward growing layer had transformed to α–Al₂O₃. Only in the outer part of the thick oxide nodules, metastable alumina was found. When exposed in the presence of water vapour the main part of the metastable alumina remained untransformed.     

TEM investigation of the oxide scales formed on a FeCrAlRE alloy (Kanthal AF) at 900°C in dry O2 and O2 with 40% H2O

Abstract

The base oxide scales on a commercial FeCrAl alloy oxidized isothermally at 900°C in dry O₂ or O₂ with 40% H₂O were studied in detail using analytical electron microscopy. Electron transparent cross-section foils prepared with a FIB/SEM in-situ lift-out technique were investigated using STEM/EDX and CBED. The oxide scales on the samples exposed to dry O₂ are slightly thinner than the scales formed in O₂+H₂O. The oxide scales exhibit a multilayered structure, with a Cr-rich layer in the middle, indicating the original metal/gas interface. An almost pure inner α-Al₂O₃ layer, containing columnar grains, was formed by inward oxygen diffusion, after exposures in both the dry and wet atmospheres. The outer oxide layer consisted of γ-Al₂O₃ in the wet case and of α-Al₂O₃/MgAl₂O₄ in the dry case. It is suggested that the α-Al₂O₃/MgAl₂O₄ phases resulted from a phase transformation of initially grown γ-Al₂O₃. The observations indicate that water vapour may stabilize the γ-Al₂O₃ phase.     

Mechanisms of chromia scale failure during the course of 15–18Cr ferritic stainless steel oxidation in water vapour

Abstract

Breakaway oxidation of 15–18 % Cr ferritic stainless steels occurring in water vapour is described in the temperature range 800–1000°C. The failure of the protective chromia scale leads to iron oxide(s) nodule formation with accelerated kinetics. Characterisation of the (Fe,Cr)₂O₃ initial oxide scale by Raman spectroscopy and photoelectrochemistry shows chemical evolution with oxidation time, with increasing Cr/Fe ratio before haematite suddenly appears at the steel-oxide interface. The mechanisms for such a phenomenon are discussed, first on a thermodynamic point of view, where it is shown that chromium (VI) volatilisation or chromia destabilisation by stresses are not operating. It is rather concluded that mechanical cracking or internal interface decohesion provide conditions for haematite stabilisation. From a kinetic point of view, rapid haematite growth in water vapour compared to chromia is thought to be the result of surface acidity difference of these two oxides.     

Oxidation and diffusion study on AlCrVN hard coatings using oxygen isotopes O and O

The present work aims to investigate the oxidation behaviour of AlCrVN hard coatings of equal composition but of different crystal structure. In order to gain more information about the mechanisms that are active during oxidation, a two-stage oxidation procedure has been applied where different isotopes, ¹⁶O and ¹⁸O, were introduced in each step. The analysis by means of secondary ion mass spectrometry depth profiling with its inherent isotope selectivity provided information on the general oxidation behaviour as well as the oxygen diffusion during the oxidation process. The single-phase coating with its face-centred cubic (fcc) structure presents a higher oxidation resistance as compared to the dual-phase coating containing a wurtzite and an fcc phase. After the annealing treatment the surface of the latter is entirely covered by VO₂ and V₂O₅ as evidenced by Raman spectroscopy. The single-phase coating, on the other hand, reveals unoxidised coating material and AlVO₄ crystals. However, even though exhibiting a significantly different oxidation resistance, the oxygen diffusion is similar. In both cases the peak values of ¹⁸O, which was introduced in the second stage, were found near the oxide-nitride interface indicating that O atoms diffused through the already formed oxides. Additional experiments using a gas mixture comprising natural water vapour H₂¹⁶O and ¹⁸O₂ revealed that mainly the presence of molecular oxygen causes oxidation as with increasing water vapour partial pressure the oxide layer thickness was significantly reduced.     

Effects of Si,Mn, and water vapour on the microstructure of protective scales grown on Fe–20Cr in CO2 gas

Abstract

Model alloys Fe–20Cr–0.5Si and Fe–20Cr–2Mn (wt-%) were exposed to Ar–20CO₂ and Ar–20CO₂–20H₂O at either 818 or 650°C. In dry gas, protective scales on Fe–20Cr–0.5Si consisted of an outer Cr₂O₃ layer and an inner SiO₂ layer. In wet gas, additional chromia whiskers were formed on top of the duplex scale. Chromia grains formed in wet gas were much smaller than those in dry gas. A TEM analysis revealed that phase constitutions of the protective scale on Fe–20Cr–2Mn were not uniform: Mn₃O₄ and MnCr₂O₄ above alloy grain boundaries and Mn₃O₄, Cr₂O₃ and MnCr₂O₄ on alloy grains. Formation of different oxides and morphologies are discussed in terms of changes in diffusion paths and thermodynamics caused by the presence of carbon and hydrogen.