The influence of platinum on the maintenance of α-Al2O3 as a protective scale

The influence of externally located platinum on the isothermal stability of -Al₂O₃ scales formed at high temperatures has been examined. It has been observed that a nickel-base alloy forms an external scale of -Al₂O₃ during oxidation at 1200°C, but this scale breaks down isothermally, enabling a faster-growing Cr₂O₃-rich scale to develop. However, in the presence of platinum metal alongside the specimen in the furnace hot zone, the breakdown of the -Al₂O₃ scale is postponed for a substantial period of time. It appears that platinum, as the volatile species PtO₂, is incorporated into the growing -Al₂O₃ scale where it either influences the stress relief mechanism at temperature or reduces oxidation growth stress generation and thus significantly enhances the isothermal stability of the scale.     

The high-temperature corrosion behavior of Nb-Al alloys in a H2/H2S/H2O gas mixture

The corrosion behavior of pure Nb and three Nb Al alloys containing 12.5, 25, and 75 at.% Al was studied over the temperature range of 800–1000°C in a H₂/H₂S/H₂O gas mixture. Except for the Nb-12.5Al alloy consisting of a two phase structure of -Nb and Nb₃Al, other alloys studied were single phase. The corrosion kinetics followed the parabolic rate law in all cases, regardless of temperature and alloy composition. The parabolic rate constants increased with increasing temperature, but fluctuated with increasing Al content. The Nb-75Al alloy exhibited the best corrosion resistance among all alloys studied, whose corrosion rates are 1.6–2.2 orders of magnitude lower than those of pure-Nb (depending on temperature). An exclusive NbO₂ layer was formed on pure Nb, while heterophasic scales were observed on Nb-Al alloys whose compositions and amounts strongly depended on Al content and temperature. The scales formed on Nb-12.5Al consisted of mostly NbO₂ and minor amounts of Nb₂O₅, NbS2, and -Al₂O₃, while the scales formed on Nb-25Al consisted of mostly Nb₂O₅ and some -Al₂O₃. The scales formed on Nb-75Al consisted of mostly -Al₂O₃ and Nb₃S₄ atT 900°C, and mostly -Al₂O₃ , Nb₃S₄ and some AlNbO₄ at 1000°C. The formation of -Al₂O₃ and Nb₃S₄ resulted in a significant reduction of the corrosion rates.     

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.     

Improvement in the Oxidation Resistance of an Al-Deposited Fe–Cr–Al Foil by Preoxidation

The oxidation kinetics of conventional Fe–20Cr–5Al (in mass %) foil, Al-deposited foil and Al-deposited and preoxidized foil was studied at 1373 K in air. All the foils were 50-m thick and contained minor additions of rare-earth elements. The oxide scales were observed with SEM and TEM combined with EDS and were characterized with X-ray diffractometry and electron diffraction. The deposition of Al onto the foil from the vapor phase improves oxidation resistance. The details regarding this matter were reported elsewhere. The combination of the Al deposition and the subsequent preoxidation at 1173 K for 90 ks in air further increases the oxidation resistance, i.e., the smallest parabolic rate constant among the three kinds of foils, and excellent scale adherence. Preoxidation enhances the growth of -Al₂O₃, which transforms to -Al₂O₃ during subsequent oxidation. However, such -Al₂O₃ grains are much larger than those formed on the conventional foil of similar chemical composition. Small closed voids and small spinel-type, oxide particles appear in -Al₂O₃ grains with the progress of oxidation. The former is explained in terms of the volume decrease accompanying the phase transformation and the latter by the low solubility of Fe in -Al₂O₃.     

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.     

Phase equilibria in the subsolidus region of the NiO-α-Al2O3 system between 1000 and 1920°C

Nickel spinel, Ni_1–xAl_2(1+x/3)O₄, is the only intermediate compound in the quasibinary NiO--Al₂O₃ system at temperatures between 1000 and 1920°C. The spinel equilibrated with NiO occurs at its stoichiometric composition, NiAl₂O₄, independent of temperature. An alumina rich spinel, 0.17 x 0.62, equilibrated with -Al₂O₃ increases in alumina content with increasing temperature. Aluminum oxide solubility in NiO increases from 1 mole % at 1000°Cto 3 mol % at 1800°C. Nickel oxide solubility in -Al₂O₃ was found to increase from 2 mole % at 1000°C to 3 mole % at 1920°C.     

The influence of yttrium additions on the oxidation resistance of a directionally solidified Ni-Al-Cr3C2 eutectic alloy

Isothermal oxidation of a directionally solidified Ni-Al-Cr₃C₂ eutectic alloy results in development of an external -Al₃O₃-rich scale. However, this scale breaks down after relatively short times at temperature and a less protective Cr₂O₃-rich scale is formed, together with substantial internal oxide in the alloy. In an attempt to maintain the external -Al₂O₃-rich scale and prevent damaging subscale oxidation, modified yttrium-containing directionally solidified alloys have been developed. The oxidation resistance of these alloys at 1000 and 1100°C in flowing air has been investigated and found to be considerably better than that of the corresponding yttrium-free alloy. At both temperatures an external -Al₂O₃-rich scale is produced and is retained for much longer periods than on the yttrium-free alloys during isothermal and thermal cycling oxidation. Some scale breakdown does occur during thermal cycling at 1100°C, but -Al₂O₃ is able to re-form as the surface oxide. However, although external -Al₂O₃-rich scales are retained for long periods on these alloys, some oxide penetration into the alloy beneath these scales does occur where coarse carbide fibers intersect the alloy surface. This is associated with relatively poor scale integrity at these intersections.     

Oxidation Behavior of a Single-Crystal Ni-Base Superalloy in Air—II: At 1000, 1100, and 1150°C

The oxidation behavior of a single-crystal (SC) Ni-base superalloy was studied over the temperature range from 1000–1150°C and analysed by TGA, XRD, EDAX, and SEM. The results indicated that the SC Ni-base superalloy exhibited parabolic oxidation kinetics, which were controlled by the growth of the inner -Al₂O₃ layer. A mixed scale formed on the SC Ni-base superalloy after prolonged oxidation. The scale consisted of an outer layer of spinel, a sublayer of mainly -Al₂O₃ with small amount of spinel adjoined by a very thin and even discontinuous layer of CrTaO₄-rich oxide, and an inner -Al₂O₃ layer. The inner -Al₂O₃ layer provided good protection. No internal oxides or nitrides were observed below the inner -Al₂O₃ layer after 1000 hr at 1000°C, and after 200 hr at 1100 and 1150°C.     

The effect of various oxide dispersions on the phase composition and morphology of Al2O3 scales grown on β-NiAl

A series of oxide-dispersed-NiAl alloys were oxidized in order to explore the effect of various cation dopants on the - phase transformation in the Al₂O₃ scale and the effect of phase composition on the scale microstructure. Larger ions such as Y, Zr, La, and Hf appeared to slow the- to-Al₂O₃ phase transformation, while a smaller ion, Ti, appeared to accelerate the transformation.     

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.     

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.     

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.     

TEM Study of the Effect of Y on the Scale Microstructures of Cr2O3- and Al2O3-Forming Alloys

This study was undertaken to investigate and compare the effects of a yttrium addition on the oxide scale development of -Cr₂O₃- and -Al₂O₃-forming alloys under isothermal oxidation conditions. The alloys had a nominal composition (in wt.%) of Ni–30Cr, Ni–30Cr–0.5Y, Ni–30Cr–5Al, and Ni–30Cr– 5–Al–0.5Y. They were oxidized in air for 50 hr at 1000°C. The scale microstructures were characterized using cross-sectional transmission-electron microscopy combined with energy-dispersive X-ray spectroscopy. It was observed that the scale thickness decreases and the scale adherence increases due to the Y addition. The growth direction of -Cr₂O₃ scale changes from predominately outward to inward while countercurrent diffusion within -Al₂O₃ is replaced by inward diffusion due to Y modification. It is considered that the ability of Y to scavenge sulfur from the alloy and its segregation to the oxide grain boundaries primarily account for most of its beneficial effects.     

The Corrosion of Titanium Aluminides in H2/H2S/H2O Atmospheres at 800–1000°C

The corrosion behavior of three Ti–Al intermetallics containing 20, 30, and 40 wt.% Al was studied over the temperature range 800–1000°C in a H₂/H₂S/H₂O gas mixture. Ti–20Al and Ti–40Al alloys had the single-phase structure of Ti₃Al and TiAl, respectively, while Ti–30Al was a two-phase mixture of Ti₃Al+TiAl. The corrosion kinetics followed the parabolic rate law in all cases, regardless of temperature and alloy composition. The parabolic rate constants increased with increasing temperature, but decreased with increasing Al content. The Ti–40Al alloy exhibited the best corrosion resistance among all alloys studied. The scales formed on Ti–Al intermetallics were heterophasic and duplex, consisting of an outer-scale layer of pure -TiO₂ and an inner layer of -TiO₂ with minor amounts of -Al₂O₃ and Ti_l-xS. The amount of -Al₂O₃, which increased with increasing Al content, is responsible for the reduction of the corrosion rates as compared with those of pure Ti oxides.     

X-ray topographic study of β-NiAl upon growth of an α-Al2O3 film

The Berg-Barrett X-ray topographic method was employed as a microstructural technique to seek correlations of the metal substructure to the morphological features of -Al₂O₃ films grown on -NiAl. An analysis of diffraction micrographs using {112} and {002} reflections from individual grains in -NiAl revealed its subgrain structure to a depth of 30 . The dimensions of these subgrains were directly related to the density of oxide ridges in the -Al₂O₃ films and to the dimensions and shapes of cavities at the NiAl-Al₂O₃ interface.     

On the transient oxidation of a Ni-15Cr-6Al alloy

Stages in the development of a protective -Al₂O₃ scale on a Ni-15Cr-6Al (wt.%) alloy have been examined. It is shown that prior to the formation of a continuous -Al₂O₃ layer, a transient stage of oxidation occurs that consists of a rapid uptake of oxygen with conversion of a thin surface layer of alloy to predominantly spinel and the subsequent development of a discrete layer of Cr₂O₃. It is also shown that during the transient period of oxidation metastable phases of aluminum oxide are formed which transform to -Al₂O₃ upon incorporation into the external oxide scale.     

Effect of Palladium Incorporation on Isothermal Oxidation Behavior of Aluminide Coatings

A (Ni, Pd)Al coating has been prepared by low-pressure pack cementation on the nickel-base superalloy IN738 with a preplating of Pd–20 wt.% Ni alloy. The coating consists mainly of a single phase of -Pd(Ni)Al in the outer part and -Ni(Pd)Al in the inner part. The oxidation behavior of the (Ni,Pd)Al coating at 900–1100°C was studied by TGA, XRD, and SEM/EDS. Results show that the transformation of - to -Al₂O₃ is more rapid on the (Ni,Pd)Al coating than that on a simple NiAl coating. The addition of Pd to the aluminide coating facilitates the transformation of - to -Al₂O₃e oxide scale formed and accelerates the diffusion of Ti from the substrate to the coating surface simultaneously.     

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.     

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.     

Application of an acoustic-emission technique to the high-temperature oxidation of Fe-Cr-Al alloys

Acoustic-emission analysis combined with thermogravimetry has been used to investigate the oxidation behavior of undoped and doped Fe-Cr-Al alloys. It was demonstrated that acoustic-emission signals which were detected upon isothermal oxidation of undoped Fe-20Cr-5Al arise from buckling of the finegrain -Al₂O₃ layer. The acoustic-emission signals which were detected upon isothermal oxidation of Fe-18Cr-12Al are attributed to repeated cracking of the coarse-grain -Al₂O₃ layer. The mass-gain curve results from superimposed diffusion-controlled oxide growth and accelerated oxide growth after cracking of the oxide layer. The present study shows that acoustic-emission analysis is very useful as it complements thermogravimetric results. The advantage of acoustic-emission analysis is that it reveals cracking and spalling of the oxide layer, which is not recorded by thermogravimetry.