Early stages of the oxidation of a FeCrAlRE alloy (Kanthal AF) at 900 °C: A detailed microstructural investigation

Early stages of the evolution of Al₂O₃ scales formed on a FeCrAlRE alloy (Kanthal AF) have been investigated by analytical TEM. The samples were oxidized isothermally at 900 °C in dry O₂ or O₂ + 40% H₂O for 1 h or 24 h. All oxide scales exhibited a two-layered structure, with a continuous inward growing α-Al₂O₃ inner layer and an outward growing outer layer. After 1 h, the outer oxide layer consisted of γ-Al₂O₃ in both environments. After 24 h exposure in dry O₂, the γ-Al₂O₃ in the outer oxide layer was partly transformed to α-Al₂O₃ and spinel oxide (Mg_1−xFe_xAl₂O₄). In contrast, the γ-Al₂O₃ in the outer layer was not transformed after 24 h in O₂ + 40% H₂O, showing that water vapour stabilizes γ-Al₂O₃. All oxide scales contained a Cr-rich band, a product of the initial oxidation. The inner α-Al₂O₃ layer is suggested to nucleate on Cr₂O₃ or Cr_2−xFe_xO₃ in the initial oxide.     

High-Temperature Oxidation of Fe3Al and Fe3Al–Zr Intermetallics

The oxidation behavior of Fe₃Al and Fe₃Al–Zr intermetallic compounds was tested in synthetic air in the temperature range 900–1200 °C. The addition of Zr showed a significant effect on the high-temperature oxidation behavior. The total weight gain after 100 h oxidation of Fe₃Al at 1200 °C was around three times more than that for Fe₃Al–Zr materials. Zr-containing intermetallics exhibited abnormal kinetics between 900 and 1100 °C, due to the presence and transformation of transient alumina into stable α-Al₂O₃. Zr-doped Fe₃Al oxidation behavior under cyclic tests at 1100 °C was improved by delaying the breakaway oxidation to 80 cycles, in comparison to 5 cycles on the undoped Fe₃Al alloys. The oxidation improvements could be related to the segregation of Zr at alumina grain boundaries and to the presence of Zr oxide second-phase particles at the metal–oxide interface and in the external part of the alumina scale. The change of oxidation mechanisms, observed using oxygen–isotope experiments followed by secondary-ion mass spectrometry, was ascribed to Zr segregation at alumina grain boundaries.     

Cyclic oxidation behavior and thermal barrier effect of YSZ-(Al2O3/YAG) double-layer TBCs prepared by the composite sol-gel method

Novel YSZ (6 wt.% yttria partially stabilized zirconia)-(Al₂O₃/YAG) (alumina-yttrium aluminum garnet, Y₃Al₅O₁₂) double-layer ceramic coatings were fabricated using the composite sol-gel and pressure filtration microwave sintering (PFMS) technologies. The thin Al₂O₃/YAG layer had good adherence with substrate and thick YSZ top layer, which presented the structure of micro-sized YAG particles embedded in nano-sized α-Al₂O₃ film. Cyclic oxidation tests at 1000 °C indicated that they possessed superior properties to resist oxidation of alloy and improve the spallation resistance. The thermal insulation capability tests at 1000 °C and 1100 °C indicate that the 250 μm coating had better thermal barrier effect than that of the 150 μm coating at different cooling gas rates. These beneficial effects should be mainly attributed to that, the oxidation rate of thermal grown oxides (TGO) scale is decreased by the “sealing effect” of α-Al₂O₃, the “reactive element effect”, and the reduced thermal stresses by means of nano/micro composite structure. This double-layer coating can be considered as a promising TBC.     

Characterization of the alumina scale formed on a commercial MCrAlYHfSi coating

A commercial NiCoCrAlYHfSi coating deposited on a Ni-base superalloy substrate was characterized before and after high temperature oxidation. The combination of Y, Hf and Si additions is reported to improve coating performance. Advanced characterization techniques including scanning-transmission electron microscopy were used to study the segregation behavior of Y and Hf ions to the alumina grain boundaries after 200 h at 1050 °C and 100 and 200 h exposures at 1100 °C. After both exposure times, two distinct oxide layers were observed. The outer transient layer included many Y- and Hf-rich oxide particles. The inner layer consisted of columnar α-Al₂O₃ grains normal to the surface of the coating. Segregation of Y and Hf ions was found on the alumina grain boundaries as has been observed in model alloys with similar compositions. Isothermal exposures for up to 200 h at 1050° and 1100 °C caused a minimal increase in surface roughness. However, 200 1-h cycles at 1100 °C resulted in a more significant increase in surface roughness.     

High temperature oxidation of AlCrFe complex metallic alloys

Isothermal oxidation of Al₆₅Cr₂₇Fe₈ and Al₈₀Cr₁₅Fe₅ was studied in the 600–1080 °C range. Formation of transient alumina layers is obtained up to 900 °C. On Al₆₅Cr₂₇Fe₈ transient to α-phase transformations occur when performing oxidation at 1000 °C, together with the possible appearance of (Al_0.9Cr_0.1)₂O₃. At 1080 °C, direct formation of α-alumina is obtained. On Al₈₀Cr₁₅Fe₅, spallation of the oxide layer during the cooling stage is observed following oxidation at 800 and 900 °C, revealing thermal etching of the underneath alloy surface. At 1050 °C the α-Al₂O₃ scale is directly formed but plastic deformation and recrystallization of the underneath alloy into several intermetallic phases is observed.     

High temperature scaling of Ni-xSi-10 at.% Al alloys in 1 atm of pure O2

The oxidation of Ni-xSi-10Al alloys (with x = 0, 2, 4 and 6 at.%), has been studied at 900 and 1000 °C in 1 atm of pure O₂ to examine the effect of different silicon additions on the behavior of ternary Ni-Si-10Al alloys. The kinetic curves of Ni-10Al are approximately parabolic at both 900 and 1000 °C. Conversely, the kinetics of the ternary alloys at both temperatures correspond generally to a rate decrease faster than predicted by the parabolic rate law, except for the oxidation of Ni-6Si-10Al at 1000 °C, which exhibits a single nearly-parabolic stage. Oxidation of the binary alloy formed at both temperatures an internal oxidation zone beneath a layer of NiO. Oxidation of Ni-2Si-10Al at both temperatures and of the other two alloys at 900 °C formed initially a zone of internal oxidation of Al + Si. However, a layer of alumina forming at the front of internal oxidation after some time blocked the internal oxidation and produced a gradual conversion of the metal matrix of this region into NiO, with a simultaneous decrease of the oxidation rate. Conversely, the oxidation of Ni-4Si-10Al and Ni-6Si-10Al at 1000 °C did not produce an internal oxidation, but formed an alumina layer directly on the alloy surface after an initial stage when also Ni was oxidized. Therefore, silicon exerts the third-element effect by reducing the critical Al content needed for the transition from its internal to its external oxidation with respect to the corresponding Ni-Al alloy. This result is interpreted by means of an extension to ternary alloys of Wagner’s criterion for the same transition in binary alloys based on the attainment of a critical volume fraction of internal oxide.     

High-temperature oxidation behavior of pure Ni3Al

The high-temperature oxidation behaviour of pure Ni₃Al alloys in air was studied above 1000°C. In isothermal oxidation tests between 1000 and 1200°C, Ni₃Al showed parabolic oxidation behavior and displayed excellent oxidation resistance. In cyclic oxidation tests between 1000 and 1300°C, Ni₃Al exhibited excellent oxidation resistance between 1000 and 1200°C, but drastic spalling of oxide scales was observed at 1300°C. When Ni₃Al was oxidized at 1000°C, Al₂O₃ was present as -Al₂O₃ in a whisker form. But, at 1100°C the gradual transformation of initially formed metastable -Al₂O₃ to stable -Al₂O₃ was observed after oxidation for about 20 hr. After oxidation at 1200°C for long times, the formation of a thick columnar-grain layer of -Al₂O₃ was observed beneath a thin and fine-grain outer layer of -Al₃O₃. The oxidation mechanism of pure Ni₃Al is described.     

Early high temperature oxidation behaviour of Ti(C,N)-based cermets in air

Isothermal oxidation behaviour of two Ti(C,N)-based cermets (TiC-10TiN-16Mo-6.5WC-0.8C-0.6Cr₃C₂-(32-x)Ni-xCr, x = 0 and 6.4 wt%) was investigated in air at 800-1100 °C up to 2 h. Mass gains exhibited neither linear nor parabolic law during isothermal oxidation. The oxide scales formed at 800-1100 °C were multi-layered, consisting of NiO outerlayer, NiTiO₃ interlayer and TiO₂-based innerlayer. The internal oxidation zones formed at 1000-1100 °C consisted of Ti-based, Ni-based and Mo-based complex oxides. Cermet with 6.4 wt% Cr exhibited superior oxidation resistance, due to the presences of Cr_0.17Mo_0.83O₂ in TiO₂-based innerlayer of the oxide scale and Cr-rich Ti-based complex oxide in the internal oxidation zone.     

Oxidation behaviour of the alloy IC-6 and protective coatings

In this work, NiCoCrAlY coatings were deposited on a new Ni-base alloy, IC-6. The oxidation kinetic curves of alloy IC-6, K17 and NiCoCrAlY coatings on alloy IC-6 at 900-1100 °C were obtained. The results indicated that the oxide scales consisted of α-Al₂O₃, NiAl₂O₄, NiO, as well as a small amount of NiMoO₄ and MoO₂. These scales occurred after alloy IC-6 exposure at 900 °C for 100 h. The weight loss occurred when alloy IC-6 were exposed at 1050 and 1100 °C due to the formation of volatile MoO₃. After the NiCoCrAlY coating was deposited, the scales mainly contained α-Al₂O₃, when the specimens were oxidized at 900 °C, and α-Al₂O₃and Cr₂O₃ at 1050 °C. The formation of α-Al₂O₃ and Cr₂O₃ scales on NiCoCrAlY coating was directly responsible for improving oxidation resistance of the alloy IC-6.     

A fundamental aspect of the growth process of alumina scale on a metal with dispersion of CeO2 nanoparticles

The dispersion of CeO₂ nanoparticles resulted in a decrease of the oxidation rate of an ultrafine-grained Ni₂Al₃ at 1000 °C. The reason is explained as follows. During oxidation many Ce ions are released from the CeO₂ nanoparticles that are enveloped by the inward growing α-Al₂O₃ from the scale/metal interface due to an increased solubility. The Ce ions transport outward along grain boundaries of the scale, retarding the diffusion of Al ions for the thickening of the outer θ-Al₂O₃. This explanation is consistent with an observation that many CeO₂ nano-precipitates appeared mainly in the near-surface zone of the formed alumina scale.     

Oxidation resistance and corrosion behavior of hot-dip aluminized coatings on commercial-purity titanium

Aluminizing is an effective method to protect alloys from oxidation and corrosion. In this article, the microstructure, morphology, phase composition of the aluminized layers and the oxide films were investigated by SEM, EDS and X-ray diffraction. The high temperature oxidation resistance and electrochemical behavior of hot dip aluminizing coatings on commercial-purity titanium had been studied by cyclic oxidation test and potentiodynamic polarization technique. The results show that the reaction between the titanium and the molten aluminum leads to form an aluminum coating which almost has the composition of the aluminum bath. After diffusion annealing at 950 °C for 6 h, the aluminum coating transformed into a composite layer, which was composed of an inner layer and an outer layer. The inner layer was identified as Ti₃Al or Ti₂Al phase, and the outer layer was TiAl₃ and Al₂O₃ phase. The cyclic oxidation treatment at 1000 °C for 51 h shows that the oxidation resistance of the diffused titanium is 13 times more than the bare titanium. And the formation of TiAl₃, θ-Al₂O₃ and compact α-Al₂O₃ at the outer layer was thought to account for the improvement of the oxidation resistance at high temperature. However, the corrosion resistance of the aluminized titanium and the diffused titanium were reduced in 3.5 wt.% NaCl solution. The corrosion resistance of the aluminized titanium was only one third of bare titanium. Moreover, the corrosion resistance of the diffused titanium was far less than bare titanium.     

High temperature oxidation behavior of Ni-Cr-Al based powder porous metal

This study investigated the high temperature oxidation behavior of newly developed Ni-Cr-Al powder porous metal. High temperature isothermal oxidation tests were conducted at 900, 1000 and 1100 °C temperatures for 24 h under an atmosphere of 79% N₂ + 21% O₂ gas. Oxidation weight gain vs. time curves represented typical oxidation behavior of parabolic shape. Weight gain increased with increasing oxidation temperature. Ni-Cr-Al porous metal mainly created oxides such as α-Al₂0₃, Cr₂O₃, NiCr₂O₄. The α-Al₂0₃ oxide could be still maintained up to 1100 °C oxidation temperature as a thick and stable protective layer. It was noted that Ni-Cr-Al porous metal had better high temperature oxidation resistance than those of other Ni-based and Fe-based porous metals. The catastrophic degradation of oxidation resistance especially at very high temperature was not observed up to 1100 °C in this porous metal. The micro-mechanism of high temperature oxidation of Ni-Cr-Al porous metal was also discussed.     

High temperature oxidation of γ/γ′-strengthened Co-base superalloys

Isothermal oxidation was carried out on new γ/γ′ Co-base superalloys of the system Co–Al–W–B. Appropriate B-contents lead to improved oxidation resistance and oxide layer adhesion. Oxidation at 800 and 900 °C results in formation of Co₃O₄, CoO, and complex oxides (containing Co, Al, and W). A continuous and protective inner alumina layer forms only at 800 °C. Furthermore, oxidation leads to phase transformation (γ/γ′ to γ/Co₃W microstructure) at the matrix/oxide layer interface due to Al-depletion. The effect of additional alloying elements such as Ta, Cr, Nb, Si, V, Mo, and Ir on the oxidation behaviour was also investigated.     

Cyclic oxidation behaviour of electrodeposited Ni3Al-CeO2 base coatings at 1050 °C

This paper presents the cyclic oxidation behaviour of electrodeposited pure, nano CeO₂ (9-15 nm)- and micron CeO₂ (5 μm)-modified Ni₃Al coatings on Fe-Ni-Cr substrate at 1050 °C for periods up to 500 h. The pure Ni₃Al coating had a marginal resistance to cyclic oxidation at 1050 °C, while the CeO₂-dispersed Ni₃Al coatings showed much better cyclic oxidation resistance. This difference was attributed to many beneficial effects of CeO₂ including changing the growth mechanism of α-Al₂O₃ scale, reducing the growth rate of the scale, improving mechanical properties of the scale, and reducing void formation at the scale/coating interface and at the scale-grain boundaries.     

Oxidation Behavior and Breakdown of an Aluminide Coating on DZ40M Alloy at High Temperatures

DZ40M alloy is a new Co-base superalloy, which is suitable for the blade material of gas turbines. In this paper, isothermal oxidation of an aluminide coating on this alloy was examined at 900–1100°C in air. It was observed that the weight gain at lower temperatures (900 and 1000°C) was greater than that at the higher temperature (1050°C), which was due to the formation of both -Al₂O₃ and -Al₂O₃ at 900 and 1000°C but only -Al₂O₃ at 1050 and 1100°C.     

In-situ measurements by impedance spectroscopy of highly resistive α-alumina

In-situ impedance spectroscopy has been used for characterisation of oxides at elevated temperatures. However, for highly resistive oxides, the influence of electrode contact and leakage currents due to gas phase and surface conduction needs to be taken into account. In this study, IS measurements of pure and dense α-alumina (α-Al₂O₃) samples were performed in the temperature range 400-1000 °C with different types of electrode contact, in air and in nitrogen. The results show that above 700 °C the influence is negligible, whereas at lower temperatures the surface leakage current was substantial, and a so-called guard electrode recommendable.     

Oxidation performance of Mo3Si with Al additions

The Mo₃Si alloys with different aluminum contents were fabricated by the arc-melting and drop-casting technique, heat treated and then exposed to air at 700, 800, 900 and 1000 °C in order to assess their oxidation behavior. Line scan studies led to the assumption that the oxide scale thermally grown at 1000 °C was composed of SiO₂ which was located closer to the alloy matrix and Al₂O₃ around the outer surface of the oxidized sample, while the Mo oxide volatilized at this oxidation temperature. The results also showed that the unalloyed sample (Mo₃Si) underwent a pest reaction in a short time of exposure, while the sample with 16 at.% Al exhibited the best oxidation behavior, which could be attributed to the formation of SiO₂ and Al₂O₃ in the oxide scale.     

Cyclic oxidation of Ti3AlC2 at 1000–1300 °C in air

The cyclic-oxidation behavior of Ti₃AlC₂ was investigated at 1000–1300 °C in air for up 40 cycles. It was revealed that Ti₃AlC₂ had excellent resistance to thermal cycling. The cyclic oxidation of Ti₃AlC₂ basically obeyed a parabolic law. In all cases, the scales were dense, resistant to spalling and highly stratified. The inner continuous α-Al₂O₃ layer was well adhesive, while the outermost layer changed from rutile TiO₂ at temperatures below 1100 °C to Al₂TiO₅ at 1200 and 1300 °C, respectively. At 1300 °C, a mechanical-keying structure of inner Al₂O₃ to the Ti₃AlC₂ substrate formed, which improved the resistance to scale-spallation.     

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.     

Oxidation properties of Fe-5Cr-4Al (wt.%) alloys in oxygen at temperatures 1000°C–1320°C

Oxidation kinetics of a parent Fe-5Cr-4Al alloy subjected to two types of anneals were investigated at temperatures ranging from 1000°C to 1320°C. The alloy annealed at 850°C exhibited a rapid transient oxidation stage associated with growth of nodules containing iron oxides and internal precipitation of -Al₂O₃ in the alloy beneath these nodules. The nodules nucleated and grew from sites located in the regions of the alloy grain boundaries during the period of rapid alloy grain growth. Nodular growth virtually ceased when a continuous -Al₂O₃ film formed at the nodule-alloy interface. The alloy subjected to anneal at 1000°C and at the reaction temperature to stabilize the alloy grain size tended upon oxidation to form a protective -Al₂O₃, layer by parabolic kinetics at temperatures to 1250°C. If this alloy was oxidized in stages at 1000°C, a protective -Al₂O₃ scale was formed up to 1320°C. The temperature coefficient of the parabolic oxidation kinetics was consistent with diffusion processes at boundaries of the -Al₂O₃ grains playing an essential role during growth of this protective oxide layer.