Cyclic oxidation behavior of Ni3Al-7.8% Cr-1.3% Zr-0.8% Mo-0.025% B between 900 and 1100°C

A Ni₃Al-based alloy, the composition of which was Ni-16.0% Al-7.8% Cr-1.3% Zr-0.8% Mo-0.025%B, was cyclically oxidized in the temperature range of 900 to 1100°C in air for up to 500 hr. The alloy displayed good cyclic oxidation resistance up to 1000°C, with little scale spallation. It, however, lost cyclic oxidation resistance during oxidation at 1100°C after about 200 hr, displaying large weight losses due to serious scale spallation. NiO, α-Al₂O₃, NiAl₂O₄ and ZrO₂ were formed. The oxide scales consisted primarily of an outer Ni-rich layer which was prone to spallation, and (Al, Cr, Zr, Mo, Ni)-containing internal oxides which were adherent due mainly to the formation of (Al₂O₃, ZrO₂)-containing oxides that keyed the oxide scale to the matrix alloy.     

Corrosion of a stainless steel and nickel-based alloys in high temperature supercritical carbon dioxide environment

Corrosion of four alloys has been studied in supercritical carbon dioxide at 650 °C and 20 MPa, specifically AL-6XN stainless steel and three nickel-based alloys, PE-16, Haynes 230, and Alloy 625. The tests were performed for exposure durations of up to 3000 h with samples being removed for analyses at 500 h intervals. The corrosion performance of the alloys was evaluated by weight change measurements, and the surface oxide layers were characterized by scanning electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. Weight gain measurements showed that the Al-6XN stainless steel exhibited the least corrosion resistance while the weight gains were nearly similar for the other alloys. The oxide layer in AL-6XN stainless steel was composed of large equiaxed grained outer layer of Fe₃O₄ (magnetite) and an inner layer of FeCr₂O₄. Oxide spallation was observed in this stainless steel even after 500 h exposure. In all alloys, Cr-rich oxides phases of Cr₂O₃ and Cr_1.4Fe_0.7O₃ were identified as the protective layers. In alloy PE-16 a thin layer of aluminum oxide formed that promoted the corrosion resistance of the alloy. Cr₂O₃ was identified as the main protective oxide layer in nickel base alloys Haynes 230 and 625.     

Microstructural Characteristics and Oxidation Behavior of Low-Pressure Cold-Sprayed CoNiCrAlY Coatings

CoNiCrAlY coatings were deposited by low-pressure cold spraying and subsequently heat-treated at 1050 °C for 4 h in a vacuum environment. The microstructural characteristics and oxidation behavior of CoNiCrAlY coatings were investigated. The as-sprayed coating exhibited low porosity and oxygen content. The high plastic deformation of the sprayed particles led to significant refinement of γ-matrix and dissolution of β-(Ni,Co)Al phase in the as-sprayed coating. After heat treatment, the single phase (γ) in the as-sprayed coating was converted into a γ/β microstructure, and a continuous single α-Al₂O₃ scale was formed on the coating surface. Vacuum heat treatment can postpone the formation of spinel oxides within 100 h. After being oxidized at 1050 °C for 400 h, the heat-treated coating exhibited better oxidation resistance than the as-sprayed coating. The reduced growth rate of the oxide scale and the suppression of the formation of spinel oxides can be attributed to the vacuum heat treatment, as well as the intrinsic microstructure of the cold-sprayed coating. Finally, the effects of the microstructural changes induced during the cold spraying process on the growth of the thermally grown oxide and the oxidation mechanisms of the CoNiCrAlY coatings were discussed.     

The tensile straining of oxidized Fe-Cr-Al-Y alloys

The apparent tensile fracture strains, at which cracking of α-Al₂O₃ scales formed on Fe-Cr-Al-Y alloys during oxidation in 1 atm oxygen at 1200 °C occur, have been determined by two methods at room temperature. The values are reproducible and depend on the oxidation time but are within the range 1.4% to 2.3%. These are significantly higher than other published values for thermally formed oxides. It has also been observed that an intermediate thermal cycle to room temperature during the oxidation period does not affect significantly the subsequently measured fracture strain. These relatively high values are discussed in terms of two tentative hypotheses, one relating to flaws in the oxide, the other to possible loss of cohesion of oxide which is too fine to be detected by the methods used.     

Effect of Y<Subscript>2</Subscript>O<Subscript>3</Subscript> content on the oxidation behavior of Fe-Cr-Al-based ODS alloys

A study was conducted to investigate the cyclic oxidation behavior of two oxide dispersion strengthened (ODS) Fe-Cr-Al based alloys containing 0.17 wt.% and 0.7 wt.% Y₂O₃. The alloys were oxidized in air for 100 h at 1200°C based on a 24 h cycle period. X-ray diffraction (XRD) and analytical transmission electron microscopy (TEM) were used to characterize the structure, morphology, and composition of the oxide scales. Both alloys formed highly adherent and continuous layers of α-Al₂O₃ exhibiting a morphology indicative of inward scale growth. The role of Y₂O₃ was to promote adherence by segregating to the grain boundaries within the oxide. Concurrently, Y₂O₃ generated micro-porosity resulting in a scale of comparatively higher thickness in the alloy with 0.7 wt.% Y₂O₃.     

The Nature of Interfaces in Al-1050/Al-1050 and Al-1050/Mg-AZ31 Couples Joined by Magnetic Pulse Welding (MPW)

The microstructure and the phase composition of the interfaces of Al-1050/Al-1050 and Al-1050/Mg-AZ31 magnetic pulse welding (MPW) joints were characterized by SEM and TEM analyses. The mechanical properties were tested by nanoindentation. Properties of the Al-1050/Al-1050 interface joint were established. The interface is almost free from Al₃Fe precipitates, which are present in the base metal. The hardness value is higher than that of the base metal; however, values of the Young’s modulus of the interface and base metal are similar. It was suggested that the interface evolution in the Al-1050/Al-1050 system includes local melting and rapid solidification of the base materials. A wavy shaped heterogeneous interface was detected in the Al-1050/Mg-AZ31 joints. Some areas are free from visible intermetallic phases (IMPs), while others contain pockets of relatively coarse intermetallic precipitates. The presence of a relatively large fraction of globular porosity at the interface indicates that local melting takes place in the course of MPW. TEM characterization of regions free of IMPs at the interface reveals regions consisting of fcc supersaturated Al-Mg solid solution, apparently formed as a result of local mechanical alloying during MPW. In other regions, the composition and structure correspond to the Mg₁₇Al₁₂ phase, which was probably formed by local melting and rapid solidification.     

Characterization of oxide scales formed on high-velocity oxyfuel-sprayed Ni-Co-Cr-Al-Y + ReTa coatings

A high-velocity oxyfuel-sprayed 30 wt.% Ni-20 wt.% Co-30 wt.% Cr-10 wt.% Al-2 wt.% Y-4 wt.% Re-4 wt.% Ta coating was oxidized between 1000 and 1200 °C for up to 200 h in air, and the oxide scales were examined. The dense, sprayed coating consisted mainly of Cr₃Ni₂, Ni₃Al, Ni₃Ta, Ni, NiO, Al₅Y₃O₁₂, and Cr₂O₃. Intermetallics and some oxides formed during spraying. During oxidation, mainly αAl₂O₃, along with some Al₅Y₃O₁₂, CoAl₂O₄, CoCr₂O₄, Ta₂O₅, and Ta₂O_2.2 formed on the coating. The preferential oxidation of Al to form the Al-rich scales resulted in the formation of an Al-depleted region beneath the scales. Rhenium, being the most noble element, was distributed throughout the oxide scale and the coating, without forming any independent oxides.     

Structural and mechanical evaluation of the effect of oxygen boost diffusion on a gamma based titanium aluminide of Ti-45Al-2Nb-2Mn-1B

Air oxidation, vacuum heating and a subsequent oxidation (DT treatment) of Ti-45Al-2Nb-2Mn-1B (at.%) titanium aluminide resulted in several oxide layers and a hard Ti₃Al as an interlayer between the substrate and the oxide layers.Surface characterization was carried out using X-Ray Diffraction (XRD), Glow Discharge Spectroscopy (GDS), electron microscopy, microhardness tests, ball-on-disk tests and profilometry.The compositions of oxides were TiO₂ and Al₂O₃ at the surface layers after final air oxidation and Ti₃Al interlayer was enriched with oxygen.Multi step treatment improved the hardness of treated surfaces significantly in comparison with that of the sample thermally oxidized only at 800 °C (TO treatment). The hard Ti₃Al interlayer containing soluble oxygen supported the top oxide layers of the DT treated sample against indentation. Such supporting layer did not form between the soft substrate materials and the oxide layers of TO treated materials.The mean value and variation of friction coefficient on multi step treated surfaces were less than that of the untreated material. The friction behavior of worn surfaces on the multi step treated material against steel and WC-Co ball sliders was rather smoother than that of TO treated samples.Top surface layers of TO treated material were removed at very shorter sliding distances and lower loads than those of DT treated surfaces against both steel and tungsten carbide sliders.     

Alumina Scale Formation on a Powder Metallurgical FeCrAl Alloy (Kanthal APMT) at 900–1,100 °C in Dry O2 and in O2 + H2O

A Rapidly Solidified Powder (RSP) metallurgical FeCrAl alloy, Kanthal APMT, was exposed in dry and humid O₂ for 72 h at 900–1,100 °C. The formed oxide scales were characterized using gravimetry in combination with advanced analysis techniques (SEM, EDX, TEM, XRD, AES and SIMS). The oxide scales were at all exposures composed of two-layered α-Al₂O₃ scales exhibiting a top layer of equiaxed grains and a bottom layer containing elongated grains. A Cr-rich zone, originating in the native oxide present before exposure, separated these two layers. The top α-Al₂O₃ layer is suggested to have formed by transformation of outwardly grown metastable alumina, while the inward-grown bottom α-Al₂O₃ layer had incorporated small Zr-, Hf- and Ti-rich oxide particles present in the alloy matrix. The scale also contained larger Y-rich oxide particles. Furthermore, in the temperature range studied, the presence of water vapour accelerated alloy oxidation somewhat and affected scale morphology.     

The Protectiveness of Thermally Grown Oxides on Cold Sprayed CoNiCrAlY Bond Coat in Thermal Barrier Coating

This paper presents the results of an oxidation behavior study for a thermal barrier coating (TBC) with air plasma sprayed yttria-stabilized zirconia top coat and CoNiCrAlY bond coat deposited using low pressure plasma spray (LPPS) and cold spray (CS). The TBC is subjected to isothermal oxidation and creep tests at 900?°C and evaluated using scanning electron microscopy, energy dispersive x-ray spectrometry transmission electron microscopy and electron backscatter diffraction. The thermally grown oxide (TGO) developed in the TBC with the LPPS bond coat was composed of only ??-Al₂O₃ and the TGO developed in the TBC with a CS bond coat is composed of ??-Al₂O₃ and ??-Al₂O₃. Despite the presence of this metastable ?? phase, the TGO in the CS specimens exhibits a dense microstructure and lower amounts of mixed oxides. The correlation between ??-Al₂O₃ and the formation of mixed oxides was investigated through the measurement of ??-Al₂O₃ thickness ratio and mixed oxides coverage ratio. It was found that the mixed oxides coverage ratio is inversely proportional to the ??-Al₂O₃ thickness ratio.     

High temperature oxidation of Ni-20Cr-12.5Al coatings containing 1% dispersed oxides

Oxidation studies were conducted on plasma sprayed coatings of Ni-20Cr-12.5Al containing one of the following: 1% MgO, 1% La₂O₃, 1% Y₂O₃, and 0.8% Y. The alloy powders containing dispersed oxides were prepared by a variety of processes employing attrition and ball milling. The TEM characterization of the plasma sprayed deposits of Ni-20Cr-12.5Al-1Y₂O₃ indicated that the oxide particles ranged from almost pure aluminum oxide to various compounds of aluminum and yttrium oxide. In cyclic tests conducted at 1150 and 1225°C, the coating containing 1% Y₂O₃ appeared to provide the best oxidation resistance. The oxidation resistance appeared to be influenced by the size and distribution of the oxide particles.     

The early stages of development of α-Al2O3 scales on Fe-Cr-Al and Fe-Cr-Al-Y Alloys at high temperature

The development ofthe oxides on Fe-14%Cr-4%Al, Fe-27%Cr-4%Al, and similar alloys containing 0.008% Y, 0.023% Y, and 0.8% Y has been investigated during the early stages of oxidation in 1 atm oxygen at 1000 and 1200°C. In all cases, a steady-state -Al₂O₃layer is established rapidly, after some initial formation of transient oxides rich in iron and chromium. For the yttrium-free alloys the steady-state situation is achieved more rapidly for the higher chromium-containing alloy and at the higher temperature. The amount of transient oxide formed is also determined by the specimen surface topography since the development of the -Al₂O₃ layer is less rapid at the base of alloy asperities than at a flat alloy-oxide interface. Following establishment of the complete -Al₂O₃layer, the oxide develops a convoluted oxide morphology at temperature, due to high compressive growth stresses in the oxide. These arise following reaction between oxygen ions diffusing inward down the oxide grain boundaries and aluminum ions diffusing outward through the bulk oxide. This results in lateral growth of the oxide and plastic deformation and movement of the alloy in a direction parallel to the alloy-oxide interface. The addition of yttrium to the alloys promotes the selective oxidation of aluminum. Also, the yttrium is incorporated into the growing oxide where it changes the mechanism of growth, reducing the production of the high compressive growth stresses and thus the development of the convoluted oxide morphology.     

High temperature corrosion of hot-dip aluminized steel in Ar/1%SO<Subscript>2</Subscript> gas

Carbon steels were hot-dip aluminized in Al or Al-1at%Si baths, and corroded in Ar/1%SO₂ gas at 700-800 °C for up to 50 h. The aluminized layers consisted of not only an outer Al(Fe) topcoat that had interdispersed needle-like Al₃Fe particles but also an inner Al-Fe alloy layer that consisted of an outer Al₃Fe layer and an inner Al₅Fe₂ layer. The Si addition in the bath made the Al(Fe) topcoat thin and nonuniform, smoothened the tongue-like interface between the Al-Fe alloy layer and the substrate, and increased the microhardness of the aluminized layer. The aluminized steels exhibited good corrosion resistance by forming thin α-Al₂O₃ scales, along with a minor amount of iron oxides on the surface. The interdiffusion that occurred during heating made the aluminized layer thick and diffuse, resulting in the formation of Al₅Fe₂, AlFe and AlFe₃ layers. It also smoothened the tongue-like interface, and decreased the microhardness of the aluminized layer. The non-aluminized steel formed thick, nonadherent, nonprotective (Fe₃O₄, FeS)-mixed scales.     

In Situ Study of Oxidation-Induced Growth Strains In a Model NiCrAlY Bond-Coat Alloy

Synchrotron radiation has been used to study in situ the evolution of growth strains in an Al₂O₃ scale (the so-called TGO or thermally grown oxide) on a model bond-coat alloy (Ni-19.7 Cr-19.2 Al-0.1 Y at.%) as oxide growth proceeds in air at 950–1100°C, and the changes in these strains due to thermal-expansion mismatch as the samples are cooled. Tensile growth stresses develop in the oxide scales during the initial stages of oxidation, a result of initially formed transition aluminas converting to the stable α-Al₂O₃ form, but large residual compressive stresses are present at room temperature due to thermal-expansion mismatch between the scale and the bond-coat.     

Effect of bond-coat pre-aluminization and pre-oxidation duplex pretreatment on the performance of ZrO2-8 wt.% Y2O3/Co-29Cr-6Al-1Y thermal-barrier coatings

A modification to the conventional thermal-barrier coating (TBC) system was made. In this study, the low-pressure, plasma-sprayed Co-29Cr-6Al-1Y bond coat received a duplex pretreatment of bond-coat pre-aluminizing and pre-oxidation prior to overlaying the air-plasma sprayed ZrO₂-8 wt.% Y₂O₃ top coat. The effects of this treatment on the properties of the TBC system were evaluated by thermal-cyclic test at 1050° C in air. The results of cyclic-oxidation tests showed that the proposed processes could remarkably improve the performance of ZrO₂-8 wt.% Y₂O₃/Co-29Cr-6Al-1Y TBC. The improvement was attributed to a modification of bond-coat oxides and the associated reduction of the oxidation rate of the MCrAlY bond coat.     

Mechanism of isothermal oxidation of the intel-metallic TiAl and of TiAl alloys

The oxidation behavior of Ti36Al, Ti35Al-0.1C, Ti35Al-1.4V-0.1C, and Ti35 Al-5Nb-0.1C (mass-%) in air and oxygen has been studied between 700 and 1000°C with the major emphasis at 900°C. Generally an oxide scale consisting of two layers, an outward- and an inward-growing layer, formed. The outward-growing part of the scale consisted mainly of TiO₂ (rutile), while the inward-growing part is composed of a mixture of TiO₂ and -Al₂O₃. A barrier layer of Al₂O₃ on TiAl between the inner and the outer part of the scale was visible for up to 300 hr. Under certain conditions, the Al₂O₃ barrier dissolved and re-precipitated in the outer TiO₂ layer. This shift leads to an effect similar to breakaway oxidation. Only the alloy containing Nb formed a longlasting, protective Al₂O₃ layer, which was established at the metal/scale interface after an incubation period of 80–100 hr. During this time, Nb was enriched in the subsurface zone up to approximately 20 w/o. The growth of the oxide scale on TiAl-V obeyed a parabolic law, because no Al₂O₃ barrier layer formed; large Al₂O₃ particles were part of the outward-growing layer. A brittle 2-Ti₃Al-layer rich in O formed beneath the oxide scale as a result of preferential Al oxidation particularly when oxidized in oxygen. Oxidation in air can lead also to formation of nitrides beneath the oxide scale. The nitridation can vary between the formation of isolated nitride particles and of a metal/Ti₂AlN/ TiN/oxide, scale-layer system. Under certain conditions, nitride-layer formation seemed to favor protective Al₂O₂₃ formation at the metal/scale interface, however, in general nitridation was detrimental with the consequence that oxidation was generally more rapid in air than in oxygen.     

Microstructural aspects of low-pressure plasma-sprayed CoNiCrAlY coating on Hastelloy X

A Co-32Ni-21Cr-8Al-0.5Y alloy coating was plasma sprayed on Hastelloy X. The microstructure of the coating layer consists of γ phase solid solution, γ′ phase, and Y-rich intermetallic phase. This coating exhibits excellent oxidation and sulfidation resistance after exposure in air and in sodium sulfate at 1,000°C for 60 h, due to the formation of α-Al₂O₃ oxide scale. However, the presence of chloride in the sodium sulfate leads to rupture of the aluminium oxide scale, and this results in the precipitation of chlorides and sulfides within the coating layer.     

Isothermal Oxidation Behavior of NiCoCrAlTaY Coating Deposited by High Velocity Air-Fuel Spraying

The performance of thermal barrier coatings is influenced by the high temperature oxidation behavior of the bond coat. In this paper, NiCoCrAlTaY bond coat was deposited by high velocity air-fuel (HVAF) spraying, and the microstructure and surface morphology of the bond coat before and after oxidation were examined to aim at developing high performance thermal barrier coatings. Results showed that the HVAF sprayed NiCoCrAlTaY coating presented a dense microstructure and some partially melted particles with a near spherical morphology were deposited on the coating surface. A uniform ??-Al₂O₃ scale was formed on the HVAF sprayed MCrAlY coating surface after the pre-oxidation treatment in an argon atmosphere. A small fraction of nodular-shaped mixed oxides was formed when the MCrAlY coating was oxidized for 100?h at 1000?°C. The amount of the mixed oxides increased less significantly after 200?h oxidation. A homogeneous ??-Al₂O₃ oxide scale was maintained over the large particles on the bond coat surface after 200?h oxidation at 1000?°C in air. A model is proposed to explain the formation of nodular-shaped mixed oxides.     

The Effect of Implanted Al and/or Y on the Scale Formation on Low-Al Fe20Cr2Al Alloy

The very early stages of the oxidation of an Fe20Cr2Al alloy, unmodified and ion-implanted by aluminium, yttrium and a combination of both elements, Al and Y, were studied at 1100 °C in oxygen using two-stage-oxidation exposures with ¹⁸O₂ as a tracer and subsequent characterisation of the scales using SIMS analyses of distribution of oxygen isotopes and oxide-related negative ion clusters, SEM observations of the surface morphology and photoluminescence spectroscopy analysis of the phase composition. The scales formed in all cases, except for the Al-implanted alloy, exhibited layered structures, with the outer part comprising Fe- and Cr-rich oxide, and the inner part being Al₂O₃, which grew due to a mixed outward–inward mechanism . The alumina sub-layers contained the transient oxides and α-Al₂O₃. Implanted Al significantly affected the mechanism of the scale growth, providing that the scale consisted essentially of α-Al₂O₃, and grew via a mixed inward-outward mechanism typical for scales on alumina formers.