High temperature oxidation of FeCrAl‐alloys – influence of Al‐concentration on oxide layer characteristics

The superior high temperature oxidation resistance of FeCrAl alloys relies on the formation of a dense and continuous protective aluminium oxide layer on the alloy surface when exposed to high temperatures. Consequently, the aluminium content, i.e. the aluminium concentration at the alloy–oxide layer interface, must exceed a critical level in order to form a protective alumina layer. In the present study the oxidation behaviour of six different FeCrAl alloys with Al concentrations in the range of 1.2–5.0 wt% have been characterised after oxidation at 900 °C for 72 h with respect to oxide layer surface morphology, thickness and composition using scanning electron microscopy, energy dispersive X‐ray spectroscopy and Auger electron spectroscopy. The results show that a minimum of 3.2 wt% Al in the FeCrAl alloy is necessary for the formation of a continuous alumina layer. For Al concentrations in the range of 2.0–3.0 wt% a three‐layered oxide layer is formed, i.e. an oxide layer consisting of an inner alumina‐based layer, an intermediate chromia‐based layer and an outer iron oxide‐based layer. In contrast, the 1.2 wt% Al FeCrAl alloy is not able to form a protective oxide layer inhibiting extensive oxidation.     

A new austenitic alumina forming alloy: an aluminium‐coated FeNi32Cr20

The FeCrAl alloys owe their low oxidation rate to the formation of a slow growing α‐aluminium oxide scale. Therefore they are used, for example, as a substrate material in metal‐supported automotive catalytic converters. Increasing exhaust gas temperatures mean that, in addition to the oxidation properties, high temperature mechanical properties should also be improved. Compared to the ferritic FeCrAl alloys, austenitic alloys possess the required high mechanical strength at higher temperatures. However for most commercially available materials the oxidation resistance is not sufficient due to a low aluminium content. High aluminium contents are avoided in austenitic alloys, since they cause severe workability problems, even at aluminium contents, which are below the necessary amount to get a pure alumina scale. The newly developed material Nicrofer 3220 PAl (coated FeNiCrAl) consists of an austenitic FeNi32Cr20 alloy coated with aluminium on both sides. It combines the outstanding oxidation resistance of an alumina forming FeCrAl alloy with the advantage of the high temperature strength of an austenitic alloy. Additionally the oxidation is even lower than the oxidation of the commercial grade Aluchrom YHf (FeCr20Al6)—conventional homogenous FeCrAl. Aluminium coated FeNiCrAl can easily be formed into its final shape. Prior to service, an in situ heat treatment is recommended in order to optimize the properties.     

Oxidation of alumina formers at 1173 K: effect of yttrium ion implantation and yttrium alloying addition

The oxidation behaviour of three alumina forming FeCrAl alloys has been investigated during isothermal exposures in air at 1173 K. Two of them were Kanthal A1, differing by the presence or not of implanted yttrium. The third one, Kanthal AF contains alloying additions of yttrium. Kinetic results indicate that only yttrium implantation significantly reduces the growth rate of the oxide scale during the early oxidation stage. For longer oxidation times, the reactive element markedly influences the oxidation rate and the composition of the oxide scale, whatever its introduction mode in the alloy. In situ X-ray diffraction shows that yttrium suppresses the formation of transition alumina and promotes the growth of α-Al₂O₃, thereby leading to the earlier formation of a protective oxide scale.     

High-Temperature Oxidation Behavior of ODS–Fe3Al

The high-temperature oxidation behavior of an oxide dispersion-strengthened (ODS) Fe₃Al alloy has been studied during isothermal and cyclic exposures in oxygen and air over the temperature range 1000 to 1300°C. Compared to commercially available ODS–FeCrAl alloys, it exhibited very similar short-term rates of oxidation at 1000 and 1100°C, but at higher temperatures the oxidation rate increased because of increased scale spallation. Over the entire temperature range, the oxide scale formed was -Al₂O₃, with the morphological features typical of reactive-element doping and was similar to those formed on the ODS–FeCrAl alloys. Although initially this scale appeared to be extremely adherent to the Fe₃Al substrate, an undulating metal–oxide interface formed with increasing time and temperature, which led to cracking of the scale in the vicinity of surface undulations accompanied by a loss of small fragments of the full-scale thickness. In some instances, the surface undulations appeared to have resulted from gross outward local extrusion of the alloy substrate. Similar features developd on the FeCrAl alloys, but they were typically much smaller after a given oxidation exposure. The ODS–Fe₃Al alloy has a significantly larger coefficient of thermal expansion (CTE) than typical FeCrAl alloys (approximately 1.5 times at 900°C) and this appears to be the major reason for the greater tendency for scale spallation. The stress generated by the CTE mismatch was apparently sufficient to lead to buckling and limited loss of scale at temperatures up to 1100°C, with an increasing amount of substrate deformation at 1200°C and above. This deformation led to increased scale spallation by producing an out-of-plane stress distribution, resulting in cracking or shearing of the oxide.     

Sulfidation–Oxidation Behavior of FeCrAl and TiCrAl and the Third-Element Effect

Short-term sulfidation–oxidation exposures were conducted under high pS₂ and low pO₂ conditions for TiCrAl and FeCrAl alloys at 600 and 800 °C. Low mass gains and submicron Al-and Ti-rich oxide scales were formed on TiCrAl at 600 °C, while high mass gains and FeS-based scale formation were observed for FeCrAl. Based on the good behavior of TiCrAl, third-element effect additions of Cr are not inherently detrimental under sulfidation–oxidation conditions. Rather, differences in the mechanistic action of the third-element addition of Cr between FeCrAl and TiCrAl alloys and its relevance to low oxygen potential sulfidation–oxidation environments were the key factors in determining whether or not a protective alumina scale was established.     

The Initial Oxide Scale Development on a Model FeNiCrAl Alloy at 900 °C in Dry and Humid Atmosphere: A Detailed Investigation

The investigated alumina forming FeNiCrAl model alloy shows protective oxidation behavior in dry and humid environment at 900 °C. Hence, this type of alloy may replace conventional chromia forming austenitic alloys in aggressive oxidizing/reducing environments. A detailed investigation of the oxide scale development reveals a complex initial scale development. Firstly, at alloy grain boundaries, a thin Al rich oxide forms which is replaced by transient alumina platelets in dry and equiaxed α-Al₂O₃ crystallites in humid atmosphere. The scale at alloy grain centers develops via a layered scale of external chromia:Fe/Ni metal inclusions:internal alumina to a layered external spinel:internal alumina scale in dry atmosphere. In humid condition an additional oxide feature appears on the center of large alloy grains i.e. thick oxide protrusions. Despite the initially different phase compositions a continuous protective α-Al₂O₃ scale forms both atmospheres.     

A TEM study of the oxide scale development in Ni-Cr-Al alloys

In the present study the isothermal oxidation behaviours of Ni-10Cr-5Al, Ni-20Cr-5Al and Ni-30Cr-5Al alloys were investigated. The alloys were oxidised in air for 50 h at 1000 °C. Analytical transmission electron microscopy was used to characterize the morphology, structure and composition of the oxide scale. The oxide formed adjacent to the alloy was α-Al₂O₃ such that the higher was the Cr content of the alloy the easier was its formation. The Ni-30Cr-5Al alloy formed a complete layer of α-Al₂O₃ in the initial stages of oxidation through ‘oxygen gettering’ by Cr. A decrease in scale thickness and an increase in scale adherence were observed with an increase in Cr content from 10 to 30 wt.%.     

Influence of the mode of introduction of a reactive element on the high temperature oxidation behavior of an alumina‐forming alloy. Part II: Cyclic oxidation tests

Several routes of yttrium introduction were applied to test the high temperature oxidation performance of a FeCrAl alloy. Isothermal oxidation tests were described in a previous paper (Part I of this paper in this journal, 2004, 55, 352). Cyclic oxidation tests were performed in air under atmospheric pressure on blank specimens, Y₂O₃ sol‐gel coated‐, Y₂O₃ metal‐organic chemical vapor deposited (MOCVD)‐, yttrium ion implanted‐alloys, as well as on a steel containing 0.1 wt. % of yttrium as an alloying element. For the 20 hours cycles, all the samples, except FeCrAl‐0.1Y, exhibit weight losses after a few cycles, indicating drastic spallation of the oxide scales. The MOCVD coated specimen has the highest weight loss. The oxidation kinetics of the FeCrAl‐0.1Y alloy obey a parabolic law, indicating that the alumina scale formed on its surface is protective even after more than 1200 hours of oxidation (> 50 cycles). The 100 hours cycle oxidation tests give similar results. The FeCrAl‐0.1Y alloy exhibits the best oxidation behavior with very little spallation after more than 2000 hours (85 days) of oxidation at 1100°C (20 cycles). Most of the other samples exhibit severe oxide scale spallation followed by an increase of their oxidation rate related to the formation of non‐protective iron oxides.     

Influence of Reactive Element Oxide Coatings on the High Temperature Oxidation Behavior of Alumina-Forming Alloys

Reactive-element-oxide coatings were processed by a metal-organic chemical-vapor-deposition technique on the surface of a model FeCrAl alloy. The high-temperature performances of Nd₂O₃-, Y₂O₃-coated and uncoated alloys were tested in air under atmospheric pressure at 1050, 1100 and 1200° C. The coated samples did not exhibit the expected reactive-element effects since the oxidation rates were not decreased, and the oxide-scale adherence was only slightly improved. The study of the oxide-scale morphology revealed very convoluted oxide scales, except for alumina scales formed on uncoated materials at 1100 and 1200° C. Two-stage oxidation experiments showed that the reaction proceeded by a mixed anionic–cationic diffusion process; consequently, the growth of alumina within the existing alumina layer results in convoluted scales. It is proposed that the weak incorporation of the reactive elements within the thermally growing alumina scales was responsible for the limited reactive element effects, when reactive-elements were applied as oxide coatings on alumina-forming steels.     

Effect of Nb on oxidation behavior of high Nb containing TiAl alloys

The isothermal oxidation behavior of Ti-45Al-8Nb and Ti-52Al-8Nb alloys at 900 °C in air was investigated. The early oxidation behaviors were studied by using XPS and AES. And the microstructure and the composition of the oxidation scale were studied by using XRD and SEM. The results show that the oxidation behavior of TiAl alloy is significantly improved by Nb addition. Nb substitutes for Ti in TiO₂ as a cation with valence 5, and thus to suppress TiO₂ growth. The (Ti,Nb)O₂-rich layer is a dense and chemically uniform which is more protective than the TiO₂ layer. Nb addition also lowers the critical Al content to form an external alumina. Nb₂Al phase is formed in the metallic matrix at the oxide–metal interface on the high Nb containing TiAl alloys.     

Effect of Titanium Addition on Alumina Growth Mechanism on Yttria-Containing FeCrAl-Base Alloy

FeCrAl-base alloys are well known for their excellent oxidation resistance due to formation of a slowly growing alumina surface scale during high-temperature service. The actual scale growth mechanism and especially adherence are strongly affected by the presence of oxygen-active elements such as yttrium, titanium or hafnium. In the present study, the effect of titanium addition on the scale growth mechanisms of an yttrium oxide dispersion-strengthened FeCrAl base alloy was studied during oxidation at 1200 °C in Ar–O₂. For microstructural characterization results of scanning electron microscopy and electron backscatter diffraction were combined with X-ray diffraction data. Scale growth mechanisms were investigated by two-stage oxidation using ¹⁸O tracer with subsequent scale analyses using secondary neutrals mass spectrometry. The scale on the alloy without intentionally added titanium grew virtually exclusively by oxygen diffusion along oxide grain boundaries and exhibited a columnar structure with the grain size increasing in growth direction. The addition of titanium resulted in formation of an outer oxide zone of equiaxed grains on top of the inner columnar part. The equiaxed grains increased in size with increasing exposure time. Comparison with the tracer studies revealed that the titanium-induced equiaxed zone was the result of outer scale growth. Mechanisms for the initiation of outward aluminium transport are discussed. Indications were found that the effect of titanium on the scale growth mechanisms already occurred for titanium additions as low as 0.02 wt%.     

Computational modeling of mixed oxidation-carburization processes: Part 1

Heat-resistant alloys used in mixed-oxidant environments rely on the formation of a chromia, alumina, or silica surface film for corrosion resistance and the presence of second-phase precipitates in the matrix often for their strength properties. The growth of the oxide film on such alloys is often accompanied by the dissolution of precipitates in the alloy subsurface region. Continued oxidation combined with oxide-scale spallation tends to decrease the content of the oxide-forming constituent to such a level that protective scaling can no longer occur and severe degradation can develop. In the present work, the initial corrosion processes involving the complex coupling between oxide scale growth and precipitate dissolution is simulated computationally. As an example, a Ni-Cr alloy containing Cr ₂₃ C ₆ precipitates was exposed to an oxidizing-carburizing environment. An approach combining finite difference and Newton-Raphson methodologies is developed to model this diffusion/ dissolution process, incorporating the point-defect-chemistry aspects of the oxide scale. The model is able to predict the chemical and microstructural evolution of high-chromium austenitic alloys during the initial stages of oxidation-carburization.     

The effects of reactive element additions and sulfur removal on the adherence of alumina to Ni- and Fe-base alloys

The effects of reactive element additions to alumina-forming alloys (single-crystal Ni-base and ferritic Fe-Cr-Al alloys) and the effect of hydrogen annealing to remove sulfur on the oxide adherence to these alloys have been studied. The results have shown that desulfurization by hydrogen annealing can result in improvements in cyclic oxidation comparable to that achieved by doping with reactive elements. The results have also shown that there is less stress generation during the cyclic oxidation of Y-doped FeCrAl compared to Ti-doped or desulfurized FeCrAl. This indicates that the growth mechanism, as well as the strength of the oxide/alloy interface, influences the ultimate oxidation morphology and stress state which will certainly affect the length of time the alumina remains protective. It has been shown to be possible to estimate the amount of sulfur available to segregate to the alloy/oxide interface and how this is influenced by reactive element additions or hydrogen annealing. If these calculations can be made more quantitative it should be possible to engineer alumina-forming alloys for optimum resistance to cyclic oxidation e.g. by combining an appropriate desulfurization treatment and choice of reactive element addition.     

Effect of Si and Y<Subscript>2</Subscript>O<Subscript>3</Subscript> Additions on the Oxidation Behavior of Ni–<Emphasis Type="Italic">x</Emphasis>Al (<Emphasis Type="Italic">x</Emphasis> = 5 or 10 wt%) Alloys at 1150 °C

The effect of Si and Y₂O₃ additions on the oxidation behavior of Ni–xAl (x = 5 or 10 wt%) alloys at 1150 °C was studied. The addition of Y₂O₃ accelerates oxidation rate of alloys, especially growth rate of NiO, but improves adherence of the scale to the substrate. The addition of Si facilitates the selective oxidation of Al, suppresses the formation of NiO and therefore reduces the critical Al content to form continuous layer of alumina scale. Higher Al content decreases the oxidation rate of alloys in binary Ni–Al alloys and increases the oxidation rate of alloys in ternary Ni–Al–Si alloys. The effect of third-element Si is more significant and beneficial than that of Al content in ternary Ni–Al–Si alloys.     

The prediction of breakaway oxidation for alumina forming ODS alloys using oxidation diagrams

The oxidation induced loss in wall thickness of alumina forming high temperature alloys is in most cases not a limiting factor for component life because of the slow growth rates of the alumina surface scales. However, scale growth and repealing after spalling lead to depletion of the scale forming element, aluminium, in the bulk alloy. If, during long time service at high temperatures, the concentration of aluminium has decreased beneath a critical level, the protective alumina scale can no longer be formed and oxidation of the base elements Fe, Ni or Co occurs, leading to a catastrophic breakaway oxidation of the component. A model is presented which allows the calculation of the time at which this breakaway occurs using FeCrAl based ODS alloys as an example. The parameters which are necessary for the calculations, such as scale growth rates, scale spalling und bulk aluminium diffusion can be determined from relatively short time laboratory experiments. The calculated und measured results for the commercial ODS alloys ODM 751, PM 2000 und MA 956 at 11.00 und 1200°C are presented in form of Oxidation Diagrams in which the time to breakaway oxidation is plotted as a function of component wall thickness. On the basis of the theoretical considerations possible measures for increasing the oxidation limited life of the mentioned alumina forming alloys are discussed.     

Criteria for the formation of protective Al2O3 scales on Fe-Al and Fe-Cr-Al alloys

The conditions for the formation of external alumina scales on binary Fe-Al alloys and the nature of the third-element effect due to chromium additions have been investigated by studying the oxidation at 1000 °C in 1 atm O₂ of a binary Fe-10 at.% Al alloy (Fe-10Al) and of two ternary Fe-Cr-10 at.% Al alloys containing 5 and 10 at.% chromium (Fe-5Cr-10Al and Fe-10Cr-10Al, respectively). An Al-rich scale developed initially on Fe-10Al was subsequently replaced by a multi-layered scale containing mixtures of Fe and Al oxides plus a large number of Fe-rich oxide nodules: internal aluminum oxidation was essentially absent from this alloy. Addition of 5 at.% chromium to Fe-10Al did not suppress the formation of nodules, but they were eventually healed by the growth of an alumina layer at their base, resulting in a significant reduction of the oxidation rate. Finally, the alloy with 10 at.% Cr formed continuous external alumina scales without any Fe-rich nodule. Thus, the addition of sufficient amounts of chromium to Fe-10Al produces a third-element effect as expected. However, the process found in this alloy system does not involve a prevention of the internal oxidation of Al. Instead, it shows a transition from the growth of mixed Fe- and Al-rich external scales directly to an external Al₂O₃ scale formation. An interpretation of this kind of mechanism involving a third-element is presented along with a prediction of the critical Al contents required to produce the various possible scaling modes on binary Fe-Al alloys.     

Analytical Electron-Microscopy Study of the Breakdown of α-Al2O3 Scales Formed on Oxide Dispersion-Strengthened Alloys

Alumina scales formed during cyclic oxidation at 1200°C on three Y₂O₃–Al₂O₃-dispersed alloys: Ni₃Al, -NiAl, and FeCrAl (Inco alloy MA956) were characterized. In each case, the Y₂O₃ dispersion improved the -Al₂O₃ scale adhesion, but in the case of Ni₃Al, an external Ni-rich oxide spalled and regrew, indicating a less-adherent scale. A scanning-transmission electron microscope (STEM) analysis of the scale near the metal–scale interface revealed that the scale formed an ODS FeCrAl showed no base metal-oxide formation. However, the scale formed on ODS Ni₃Al showed evidence of cracking and Ni-rich oxides were observed. The microstructures and mechanisms discussed may be relevant to a thermal-barrier coating with an Al-depleted aluminide bond coat nearing failure.     

The Oxidation behavior of ODS iron aluminides

Oxide-dispersed Fe-28at.% Al-2%Cr alloys were produced by a powder metallurgy technique followed by hot extrusion. A variety of stable oxides were added to the base alloy to assess the effect of these dopants on the oxidation behavior at 1200°C in air and O₂. An Al₂O₃ dispersion flattened the α-Al₂O₃ scale, but produced none of the other reactive element effects and had an adverse influence on the long-term oxidation behavior. A Y₂O₃ dispersion improved the alumina scale adhesion relative to a Zr alloy addition at 1200 and 1300°C. However, the Y₂O₃ dispersion was not as effective in improving scale adhesion in Fe₃Al as it is in FeCrAl. This inferior performance is attributed to a larger amount of interfacial void formation on ODS Fe₃Al.     

A Simple Expression for Predicting the Oxidation Limited Life of Thin Components Manufactured from FCC High Temperature Alloys

Chromia and alumina forming high temperature alloys suffer from breakaway oxidation if the concentration of the preferred scale forming element in the alloy decreases below the level required to sustain growth of the protective oxide scale. In thin components, the breakaway may occur even before oxide spallation starts to contribute to alloy depletion. In the present paper a simplified method is developed to predict the time to breakaway as a function of oxidation rate, initial concentration and diffusivity of the scale forming element in the alloy as well as component thickness. The first approach used is an approximation of the analytical solution previously derived by Whittle. The second method is based on a numerical solution and an exploration of the way in which the time to breakaway varies with the above mentioned parameters. Comparison with literature data reveals that for a number of applications good agreement between calculated and measured lifetimes can be achieved using both approaches. The lifetime equation derived using the numerical approach has the advantage that it allows prediction of breakaway oxidation in a larger range of experimental and alloy composition related parameters. It not only describes the behaviour of materials with a face centered cubic lattice but also includes the limiting case in which solute diffusion is fast compared to surface recession rate, as in, for example, the oxidation of ferritic alumina forming FeCrAl alloys at high temperatures.     

Oxygen solubility and a criterion for the transition from internal to external oxidation of ternary alloys

Smith's model is expanded in order to derive expressions to quantitatively describe the oxygen-solubility behavior in ternary alloys as a function of alloy composition. Multicomponent-diffusion theory is used to establish a criterion for the onset of internal oxidation beneath the external scale when oxidizing conditions favor formation of the oxide of the least-noble metal in a ternary alloy. The oxygen-solubility model and the criterion are applied to the oxidation of Ni–Cr–Al alloys in 76 torr of oxygen at 1100 and 1200°C, predicting the minimum Al concentrations required to form a protective Al₂O₃ scale. It shows that sufficient Cr additions would significantly reduce the oxygen solubility and also alter the oxygen distribution in the ternary alloys, avoiding the oxygen supersaturation necessary for the onset of internal oxidation. These two factors make it easier to establish the protective Al₂O₃ scale.