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.     

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.     

High-Temperature Oxidation of Ni Coated with La2O3 by Atomic-Layer Chemical-Vapor Deposition (ALCVD)

The effects of superficial (30–100 nm) La₂O₃ surface coatings on the oxidation kinetics of Ni from 700 to 1100°C in air and the oxide morphology of the NiO scales have been investigated. The parabolic rate constant is lower than for uncoated Ni by a factor of 5 to 10. The oxide morphology changes with the La₂O₃ coatings: The oxide scale consists of an outer fine-grain layer with an inner region of coarser, but still equiaxed, grains. SIMS shows that the majority of the La remains at the surface where a highly oxygen-defective spinel, La₂Ni₄O₇, was found by TEM. Two-stage oxidation followed by SIMS profiling reveals that the oxide growth occurs inside the scales.     

Analysis of Pore Formation at Oxide–Alloy Interfaces—I: Experimental Results on FeAl

Pores, or voids, at oxide–alloy interfaces are commonly observed after high temperature oxidation when the alloy does not contain a reactive element. In order to understand the pore-nucleation and growth processes, the density, size and depth of interfacial pores on Fe–40 at.%Al as a function of oxidation time at 1000°C were examined. Scanning-electron microscopy (SEM) and atomic force microscopy (AFM) were used to characterize the pores after removal of the surface Al₂O₃ scale. The nucleation of pores was most rapid during the initial stage of oxidation where cation-transported-alumina growth dominates. Pore growth involves widening as well as deepening, where the deepening rate is slower for larger pores. Growth is accomplished by aluminum evaporation after 20 min or by surface diffusion before that time. Pore shape within an alloy grain stays constant and is dictated by the balance of surface and interface energies.     

Formation of Al2O3 Scales on Single-Phase RuAl Produced by Reactive Sintering

The oxidation behavior of single-phase RuAl produced by powder metallurgy combined with arc melting was investigated. Oxidation was conducted at 1000°C; oxide scale growth and phase formation were studied using scanning-electron microscopy (SEM) and x-ray diffraction (XRD). A dense protective scale with an Al–depleted sublayer was formed during oxidation. The oxide scale is the stable -Al₂O₃. The oxide-scale morphology shows the presence of whiskers, with a needle-like form, which suggests that the growth of the oxide scale is produced by outward diffusion of Al. At the beginning, oxidation follows a parabolic law, but, after 100 hr of oxidation; the growth rate is slower than expected from a parabolic law.     

High-temperature corrosion of dilute chromium-lanthanum alloys

The kinetics of oxidation in air of chromium-lanthanum alloys have been investigated in the temperature range 1100–1400°C. The positive effect of lanthanum on the heat resistance of chromium was established and is explained as a result of the formation of a barrier oxide film consisting of Cr₂O₃ and LaCrO₃. The dispersed particles of lanthanum chromite distributed on grain boundaries form diffusion barriers that change the oxidation law from parabolic to logarithmic. An empirical equation which quantitatively describes masstransport processes with decreasing effective diffusion area and simultaneous sublimation of scales is proposed.     

Effect of theθ-α-Al2O3 transformation on the oxidation behavior ofβ-NiAl + Zr

Isothermal oxidation of NiAl + Zr has been performed over the temperature range of 800–1200°C and studied by TGA, XRD, and SEM. A discontinuous decrease in growth rate of two orders of magnitude was observed at 1000° C due to the formation of -Al₂O₃ from -Al₂O₃. This transformation also resulted in a dramatic change in the surface morphology of the scales, as a whisker topography was changed into a weblike network of oxide ridges and radial transformation cracks. It is believed that the ridges are evidence for a shortcircuit outward aluminum diffusion growth mechanism that has been documented in a number of¹⁸O tracer studies.     

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.     

Effect of Cr,Co, and Ti additions on the high-temperature oxidation behavior of Ni3Al

The oxidation behavior of Ni₃Al+2.90 wt.% Cr, Ni₃Al+3.35 wt% Co, and Ni₃Al+2.99 wt.% Ti alloys was studied in 1 atm of air at 1000, 1100, and 1200°C. Isothermal tests revealed parabolic kinetics for all three alloys at all temperatures. Cyclic oxidation for 28 two-hour cycles produced little spallation at 1000°C, but caused partial spallation at 1100°C. Especially, at 1200°C severe spallation in all three alloys was observed. Although additions of Cr, Co, or Ti to Ni₃Al alloys slightly increased the isothermal-oxidation resistance, the additions tended to decrease the cyclic-oxidation resistance. The major difference in the oxidation of the three alloys compared with the oxidation of pure Ni₃Al alloys was the existence of small -Al₂O₃ particles in the middle of the -Al₂O₃ scale and the formation of irregularly shaped Kirkendall voids at the alloy-scale interface.     

High-temperature oxidation of rhodium

The oxidation kinetics of Rh were measured in air at 1 atm. in the temperature range 600–1000°C. The oxidation weight gain proceeds logarithmically at the lower temperatures (600°C, 650°C) followed by a transition to power law behavior at the higher temperatures (800°C). The logarithmic growth kinetics result from thickening of a hexagonal Rh₂O₃ scale. The transition from logarithmic to power law growth kinetics occurs in the range 700–800°C, and reflects thickening of hexagonal and orthorhombic Rh₂O₃ scales. Above 800°C, the growth kinetics result from thickening of a predominately orthorhombic Rh₂O₃ scale. At 1000°C the oxide becomes volatile, leaving the metal surface exposed.     

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.     

Oxidation of the intermetallics MoSi2 and TiSi2—A comparison

The oxidation behavior of two MoSi₂ variants, one Mo-rich and one Si-rich, and TiSi₂ was investigated between 1000 and 1400°C in air, oxygen and an 80/20-Ar/O₂ mixture. A protective SiO₂ scale develops on MoSi₂ in all atmospheres in the temperature range investigated. The SiO₂ modification changes around 1300°C from tridymite to cristobalite. This change in SiO₂ modification seems to cause an enhanced formation of SiO₂ and evaporation of MoO₃. The SiO₂ grows at the MoSi₂-scale interface. In air a two-layer scale grows on TiSi₂ between about 1000 and 1200°C with an inner inwards growing fine-grain mixture of SiO₂ + TiO₂ and an outer outward-growing TiO₂ partial layer. TiN formation in the transient oxidation is responsible for the formation of the inner mixed partial layer because in N -free atmospheres a scale of a SiO₂ matrix with some Ti oxide precipitates inside is formed. A one-layer scale structure similar as that in N-free atmosphere is found on TiSi₂ in air at T > 1200°C. In oxygen the TiO₂ precipitates grow as needles mostly oriented perpendicular to the surface. Due to the faster oxygen transport in TiO₂ compared with SiO₂, these TiO₂ needles act as oxygen pipes, causing an enhanced oxidation of TiSi₂ in front of these needles. The SiO₂ scale dissolves about 1–2% TiO₂. This doping causes a mixed oxygenand Si transport with the consequence that the SiO₂ scale on TiSi₂ grows partly by oxygen transport inwards and Si transport outwards. The SiO₂ modification is cristobalite over the entire temperature range investigated.     

Oxidation Behavior of Ti--50Al Intermetallics with Thin TiAl3 Film at 1000°C

Isothermal oxidation tests at 1000°C in air indicate that the Ti--50Al alloy with about 8 m TiAl₃ layer on the surface can resist the oxidation for 10 hr. From the FESEM and EPMA/EDS results, the rapid oxidation behavior is attributed to the formation of oxide nodules through the protective Al₂O₃ and TiAl₂ layers on the outer surface. Upon increasing the oxidation time at 1000°C, the size and the number of oxide nodules increase. After 3 hr of oxidation at 1000°C, a laminated layer is formed in between the oxide nodule and substrate, which consists of two nearly parallel phases. The EDS results suggest that these two phases are Ti--Al--O compounds. After 20 hr oxidation, the oxidation nodules and laminated layers disappear and a complex oxide scale is formed which is similar to the bare Ti--50Al oxidized at 1000°C.     

The high-temperature oxidation behavior of vanadium-aluminum alloys

The oxidation behavior in air of pure vanadium, V-30Al, V-30Al-10Cr, and V-30Al-10Ti (weight percent) was investigated over the temperature range of 700–1000° C. The oxidation of pure vanadium was characterized by linear kinetics due to the formation of liquid V₂O₅ which dripped from the sample. The oxidation behavior of the alloys was characterized by linear and parabolic kinetics which combined to give an overall time dependence of 0.6–0.8. An empirical relationship of the form: W/A=Bt + Ct^1/2 + D was found to fit the data well, with the linear contribution suspected to be from V₂O₅ formation for V-30Al and V-30Al-10Cr, and a semi-liquid mixture of V₂O₅ and Al₂O₃ for V-30Al-10Ti. The parabolic term is presumed related to the formation of a solid mixture of V₂O₅ and Al₂O₃ for V-30Al and V-30Al-10Cr, and TiO₂ for V-30Al-10TiThe addition of aluminum was found to reduce the oxidation rate of vanadium, but not to the extent predicted by the theory of competing oxide phases proposed by Wang, Gleeson, and Douglass. This was attributed to the formation of a liquid-oxide phase in the initial stages of exposure from which the alloys could not recover. Ternary additions of chromium and titanium were found to decrease the oxidation rate further, with chromium being the most effective. The oxide scales of the alloys were found to be highly porous at 900° C and 1000° C, due to the high vapor pressure of V₂O₅ above 800° C.     

Influence of Powder Particle Size on the Oxidation Behavior of a PM Ni3Al Alloy

The influence of particle size on the oxidationbehavior of Ni₃Al prepared by powdermetallurgy (PM) was investigated in the temperaturerange of 535 to 1020°C for exposures up to 200 hr.Four alloys were obtained, each one processed with a differentpowder particle size fraction (<25, 25-50, 50-100,and 100-200 m). For temperatures below 730°C,the scale consists of an outer NiO layer, a thindiscontinuous intermediate nickel layer, and an internaloxidation zone. The lowest oxidation rate corresponds tothe material with the smallest particle size. Thisresults from its higher grain-boundary density; the boundaries act as easy-diffusion paths foraluminum leading to the rapid formation of a continuousinner alumina layer. At temperatures above 730°C, athree layered scale is observed consisting of an outer NiO layer, an intermediate layer that,depending on temperature, consisted of a mixture ofnickel and aluminum oxides orNiAl₂O₄, and an inner layer ofAl₂O₃, which accounts for thehigher oxidation resistance. The oxidation attack is characterized byintrusions of the scale into the alloy, the intrusionnumber increasing as the particle size decreases. It isassumed that oxide particles and impurities present at the original particle boundaries facilitatealumina growth along these regions. Thus, the lowestoxidation rate for the highest temperature rangecorresponds to the largest particle-sizematerial.     

High-temperature oxidation resistance of sputtered micro-grain superalloy K38G

The oxidation of sputtered and cast superalloy K38G specimens was studied. The sputtered alloy was microcrystalline, with an average grain size <0.1 m. The mass gains of the sputtered alloy were much less than those of the cast alloy at 800, 900, and 1000°C up to 500 hr, and were even less than those of pack aluminide on the cast alloy. K38G is a chromia-forming cast nickel-base superalloy, so the oxide scale formed on it is composed of Cr₂O₃, TiO₂, Al₂O₃, and a spinel. The oxide scale formed on the sputtered alloy was Al₂O₃. This scale is thin, compact, and adherent. This result implied that micro crystallization reduced the critical aluminum content necessary to form alumina on the surface of this superalloy. No oxide spoliation, as typically observed for cast of aluminized alloys, occurred on the sputtered superalloy. The reduction of the critical aluminum content for the formation of alumina and the improvement of the spoliation resistance may be attributed to the microcrystalline structure formed during sputtering. The numerous grain boundaries favor outward aluminum grain-boundary diffusion, provide increased nucleation sites, and reduced stresses in the oxide scales.     

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.     

High-temperature oxidation behavior of a Ni-Cr-Al-Fe-Y alloy

A study was conducted to examine the isothermal oxidation behavior of a wrought Ni-Cr-Al-Fe-Y alloy in air at temperatures in the range of 950–1150°C. Oxidation kinetics were determined from weight-change measurements. Analytical electron microscopy, scanning electron microscopy, and x-ray diffraction were used to characterize the morphology, structure, and composition of the oxide scale. Overall oxidation of the alloy was found to follow parabolic kinetics. Under steady-state conditions, the oxidation reaction appeared to be controlled by diffusional transport in an adherent Y-modified -Al₂O₃ scale with an activation energy of about 400 KJ/mol. Yttrium was found to preferentially segregate to grain boundaries of -Al₂O₃ which maintained a fine columnar grain structure about 0.05–0.2 m in size. Based upon the results obtained, it was suggested that the role of Y was to promote the formation of a thin layer of -Al₂O₃ with improved mechanical strength.     

The effect of an Al2O3 dispersion on the adhesion of Al2O3 scales on aluminized Co-10% Cr alloys

The beneficial effect of dispersions of reactive-metal oxide particles on the adhesion of Cr₂O₃ and Al₂O₃ scales formed on heat-resisting alloys is wellknown. It has been shown that an Al₂O₃ dispersion in an alloy can improve the adhesion of a Cr₂O₃ scale, and it is of particular interest in assessing the various theoretical proposals for the effect to determine whether such a dispersion can affect the adhesion of an Al₂O₃ scale. In this investigation, a Co–10% Cr–1 % Al alloy was first internally oxidized to form an Al₂O₃ dispersion. This alloy was then aluminized so that on subsequent oxidation an Al₂O₃ scale developed. It was shown that the dispersion did indeed improve the scale adhesion. The implications of this result are discussed.     

Effects of Chromium on the Oxidation Performance of β-FeAlCr Coatings

-FeAl coatings containing various Cr contents of 6.5–45 wt.%were produced with a closed-field, unbalanced magnetron sputter (CFUMS)deposition technique. Cyclic oxidation tests at 1100°C in air for100 1-hr cycles and isothermal exposures at 1000°C in pure O₂ for100 hr were carried out with the coatings and an as-cast FeAlspecimen. All of the coatings showed good scale-spallation resistanceduring cyclic oxidation and the coating with 6.5 wt.% Cr exhibited thelowest oxidation rates in both cyclic and isothermal oxidationexposures. After oxidation, fine-grain ridge-type oxide scales formed onthe coatings, while the oxide scale formed on the cast FeAl showed alarge quantity of -Al₂O₃ blades and large interfacial voids on thebase–alloy surface. The transformation from to -Al₂O₃was accelerated due to the presence of Cr in the coatings. The fasttransformation considerably reduced oxidation rates, suppressed fastoutward Al diffusion for the growth of a -Al₂O₃ scale, and preventedthe formation of interfacial voids that played a major role in causing thescale spallation.