Effect of nanocrystallization on the corrosion resistance of K38G superalloy in CO + CO2 atmospheres

The corrosion resistance of the cast superalloy K38G and a sputtered nanocrystalline coating of the same material was investigated in pure CO in the temperature range, 850–1000°C and in CO-20 vol.% CO₂ at 900°C. The cast K38G alloy formed Cr₂O₃ and TiO₂ scales, and a zone of internal Al₂O₃ precipitation. Weight-gain kinetics followed the parabolic rate law under all conditions investigated. The sputtered K38G nanocrystalline coating, however, formed a single-phase Al₂O₃ scale and no internal-oxidation zone. The parabolic rate constants for nanocrystalline coating oxidation were about one order of magnitude smaller than those of the cast alloy. The changes in reaction morphology and rate are attributed to the more rapid grain-boundary diffusion of aluminum in the nanocrystalline material.     

High-Temperature Oxidation Behavior of Sputtered IN 738 Nanocrystalline Coating

A sputtered nanocrystalline coating of IN 738 alloy was obtained by means of magnetron sputtering. The isothermal oxidation behavior at 800, 900, and 1000°C and the cyclic oxidation behavior at 950°C of the coating were studied in comparison with IN 738 cast alloy. The results indicated that a double external oxide scale was formed on the nanocrystalline coating at 900, 950, and 1000°C without internal oxide and nitride. The scale consisted in an outer mixture of Cr₂O₃, TiO₂, and NiCr₂O₄ and an inner, continuous Al₂O₃ layer, which offered good adhesive and protectiveness. However, at 800°C a continuous Al₂O₃ scale could not be formed during oxidation of nanocrystalline coating and aluminum was still oxidized internally.     

The oxidation resistance of a sputtered,microcrystalline TiAl-intermetallic-compound film

The oxidation behavior of a cast TiAl intermetallic compound and its sputtered microcrystalline film was investigated at 700–900°C in static air. At 700°C, both the cast alloy and its sputtered microcrystalline film exhibited excellent oxidation resistance. No scale spallation was observed. However, at 800–900°C, the oxidation kinetics for the cast TiAl alloy followed approximately a linear rate law, which indicates that it has poor oxidation resistance over this temperature range. The poor oxidation resistance of TiAl was due to the formation of an Al₂O₃+TiO₂ scale which spalled extensively during cooling. Nevertheless, the sputtered, TiAl-microcrystalline film exhibited very good oxidation resistance. The oxidation kinetics followed approximately the parabolic rate law at all temperatures. Although the composition of the scales was the same as that of scales formed on the cast alloy, the scales formed on the sputtered microcrystalline-TiAl film are adherent strongly to the substrate. No scale spallation was found at 700–850°C, while a small amount of spallation was observed only at 900°C. This indicates that microcrystallization can improve the oxidation resistance of the TiAl alloy.     

Oxidation resistance of sputtered Ni3(AlCr) nanocrystalline coating

Isothermal and cyclic oxidation resistance at 1000°C in air were investigated for a cast Cr-containing Ni₃Al-base alloy and its sputtered nanocrystalline coating. The results indicated that both the cast Ni₃Al alloy and its sputtered coating exhibit excellent isothermal oxidation resistance as a result of the formation of Al₂O₃ scales. However, the cast alloy possesses very poor cyclic oxidation resistance because of the spallation of the initially formed Al₂O₃ scale during cooling and subsequent formation of NiO. On the contrary, the sputtered Ni₃(AlCr) nanocrystalline coating exhibits very good cyclic oxidation resistance due to the significant improvement of the adhesion of Al₂O₃.     

Short Term Oxidation Behavior of Si-Free Low-Cr Alloy Sputtered Coating

A sputtered coating of a low-Cr alloy without Si was deposited on the cast alloy with the same composition. The short term (100 h) oxidation behavior of the sputtered coating and the cast alloy was evaluated in air at 800 °C. The results indicated that the sputtered coating exhibited a higher oxidation resistance than the cast alloy. It was found that the mass gain of the cast alloy increased continuously with oxidation time and was higher than that of the sputtered coating, which demonstrated only a slight increase in mass gain with oxidation time after 5 h thermal exposure. During the initial thermal exposure of 0.5 h, the oxide scale formed on the cast alloy consisted of Fe₂O₃ and (Fe,Co,Cr)₃O₄ spinel with a small amount of Cr. However, (Fe,Co,Cr)₃O₄ spinel and Fe₂O₃ were thermally grown on the sputtered coating. After oxidation for 100 h, the oxide scale formed on the cast alloy consisted of Co₃O₄ and (Fe,Co)₃O₄ with internal oxide of Cr, while a double-layer oxide consisting of an outer (Fe,Co,Cr)₃O₄ spinel layer and an inner Cr₂O₃ layer was developed on the sputtered coating.     

Metallic yttrium additions to high temperature alloys: Influence on Al2O3 scale properties

In the present study, the effect of adding yttrium to alloys is investigated. The microstructure of the cast Fe-25Cr-4Al-0.5Y alloy used in the study shows that the vttrium is present in different shapes and sizes as the intermetallic phase, (Fe, Cr)₄(Al, Y), previously unreported in the literature. Upon oxidation in dry oxygen in the 1100–1200 °C temperature range, a columnar, fine-grained (0.5–1 m) -Al₂O₃ scale is formed which grows predominantly by inward oxygen grain-boundary transport. The intermetallic phase, during incorporation into the oxide scale, is converted into Y₃Al₅O₁₂, the chromium and iron from the intermetallic diffusing back into the metal matrix. The Y₃Al₅O₁₂ phase saturates the oxide scale with yttrium, which segregates to oxide grain boundaries. The microstructural features of the oxide scale resemble those of the scale formed on the yttria-dispersed alloy we investigated earlier. The improved adherence of the oxide scale is a consequence of yttrium doping, which facilitates the formation of a fine-grained scale in which oxide growth stresses can be relieved by diffusional plastic flow. Further, yttrium suppresses Al transport in the oxide scale and prevents Al₂O₃ nucleation within the scale, a process which can generate compressive stresses in the scale. The yttrium doping in the oxide scale is somewhat more efficient when it is present as a dispersoid in the metal.     

Oxidation Behavior of Cast Ni3Al Alloys and Microcrystalline Ni3Al+5% Cr Coatings with and without Y Doping

Ni₃Al+5% Cr and Ni₃Al+5% Cr+0.3% Y (wt.%) microcrystalline coatings were produced using a close-field, unbalanced magnetron-sputter deposition (CFUMSD) technique. Isothermal and cyclic-oxidation tests were carried out to assess the oxidation resistance of the coatings. The results showed that Al₂O₃ formed on the coatings as the main oxidation products, with the formation of - and -Al₂O₃ scales at 900 and 1200°C, respectively. The spallation resistance of the Al₂O₃ scales formed on the coatings was superior to the oxide scales formed on cast Ni₃Al. After oxidation, interfacial voids were observed on the oxide–metal interface of the cast alloy while no voids were found on the coating surfaces. On the basis of the enhancement of Al diffusion, because of the high density of grain boundaries in the coatings, oxidation mechanisms were proposed.     

Effect of Nanocrystallization on the Oxidation Behavior of a Ni–8Cr–3.5Al Alloy

Magnetron-sputter deposition was used to produce a Ni–8Cr–3.5Al(wt.%) nanocrystalline coating on substrates of the same alloy. Theoxidation behavior of the cast Ni–8Cr–3.5Al alloy and itssputtered coating were investigated at 1000°C in air. Complex,layered-oxide scales composed of Cr₂O₃ outer layer,mixed spinel NiAl₂O₄ and NiCr₂O₄middle layer, and -Al₂O₃ inner layer were formedon the Ni–8Cr–3.5Al nanocrystalline coating during 200-hroxidation, whereas Cr₂O₃, with some NiCr₂O₄external layer with internal Al₂O₃, formed on the castalloy. Because of the formation of this -Al₂O₃inner layer on the coating, the sputtered Ni–8Cr–3.5Al coatingshowed better oxidation resistance than the cast alloy. The effect ofnanocrystallization on oxide formation is discussed. It was indicated thatthe formation of this -Al2O3 inner layer was closely related to therapid diffusion of Al through grain boundaries in the nanocrystallinecoating and the relatively high Cr content in Ni–8Cr–3.5Al.     

Effect of NiAl Microcrystalline Coating on the High-Temperature Oxidation Behavior of NiAl–28Cr–5Mo–1Hf

The effect of an NiAl microcrystalline coating prepared by magnetron sputtering on the high-temperature oxidation behavior of NiAl–28Cr–5Mo–1Hf was investigated in static air at 1000–1150°C. The additions of Cr, Mo, and Hf changed the single -phase structure into a multiphase structure [-NiAl, -Cr(Mo), and Heusler phase]. The NiAl–28Cr–5Mo–1Hf alloy formed a nonprotective mixed scale of Al₂O₃+Cr₂O₃+HfO₂ and exhibited relatively large weight gains. The large weight gains were attributed to extensive internal oxidation. The sputtered NiAl microcrystalline coating remarkably improved the oxidation resistance of NiAl–28Cr–5Mo–1Hf due to the formation of a compact and adherent Al₂O₃ scale at all test temperatures. It was found that the --Al₂O₃ transformation caused the anomalous behavior of the oxidation–kinetics curves of the NiAl microcrystalline coating in the temperature range 1000–1150°C. A change in the morphology of scales occurred with the transformation.     

Oxidation Behavior of a Single-Crystal Ni-Base Superalloy in Air. I: At 800 and 900°C

The oxidation behavior of a Single-crystal Ni-base superalloy was studied using discontinuous thermogravimetric analysis (TGA) and prolonged exposure in air at 800 and 900°C. The mass gain of specimens at 900°C was found to be lower than that of specimens at 800°C because of the formation of a protective inner -Al₂O₃ layer at 900°C. A subparabolic time dependence (n=0.16 at 800°C and n=0.10 at 900°C) of the oxide growth rate was determined at both temperatures. At 800°C, the superalloy exhibited nonuniform oxidation—in some areas a thin scale with an outer NiO layer and an inner layer of an Al-rich oxide was found and, in other areas, complex oxides [CrTaO₄, NiCr₂O₄, (Ni,Co)Al₂O₄, etc.] below the NiO outer layer formed by growing into the superalloy. The scale formed at 900°C is more uniform than that formed at 800°C, consisting of several layers: an NiO outer layer, spinel-rich sublayer, a CrTaO₄-rich layer, and an -Al₂O₃ inner layer. The -Al₂O₃ inner layer provides good oxidation protection and the specimen mass gain is low for test up to 1925 hr.     

纳米晶化对Ni-25Cr-5Al-1S合金热生长氧化膜粘附性的影响

比较研究了高S铸态合金Ni-25Cr-5Al-1S(mass%)及其溅射纳米涂层在1000℃的氧化行为,结果表明:铸态合金在20小时恒温氧化中生长的氧化膜在冷却时发生严重剥落,氧化膜/基体界面局部区域S含量较高;而溅射纳米涂层没有发生氧化膜剥落现象,涂层/氧化膜界面上明显无S的存在.这说明Ni-25Cr-5Al-1S合金纳米化可以有效抑制S对氧化膜/合金界面结合的"毒化效应",提高了氧化膜的粘附性.     

Characterization of the alumina scale formed on coated and uncoated doped superalloys

To investigate the mechanisms by which Y and La dopants affect the oxidation behavior of Ni-base single‐crystal superalloys, the oxide scales formed on two variants of a commercial X4 alloy, each with and without a MCrAlYHfSi coating were characterized. The alloy systems were oxidized for 100 h at 1100 °C and then examined using analytical transmission electron microscopy. Without a coating, a duplex scale was formed on the superalloy surface comprised of an outer Ni‐rich spinel‐type layer and an inner columnar α‐Al₂O₃ layer. In this case, Hf and Ti were found segregated to the alumina grain boundaries in the outer part of the scale on both alloys but only Hf was detected near the metal–alumina interface. There was no evidence of Ta, Y or La segregation to the alumina scale grain boundaries after this exposure. The scale formed on the alloys with the thermally sprayed coating was primarily alumina, and Y and Hf segregated to the alumina grain boundaries for both alloys. There was evidence of Ti-rich oxides in the outer part of the scale indicating that Ti had diffused through the coating into the thermally grown oxide but La was not found.     

Internal oxidation of Fe-Al alloys in the α-phase region

The internal oxidation behavior of Fe-0.069, 0.158, and 0.274 wt% Al alloys was investigated in the -phase region. The internal oxidation experiments have been made over the temperature range from 1023 to 1123 K using a mixture of iron and its oxide powders. A parabolic rate law holds in the present alloys, where the rate constant, K_p, depends upon the oxidation temperature as well as the aluminum content. The internal oxidation of Fe-Al alloys is, therefore, controlled by a diffusion process of oxygen in the alloy. The oxide formed in the oxidation layer is the stoichiometric FeAl₂O₄ (hercynite). The aluminum concentration, N _Al ^Io , in the oxidation layer was calculated by taking account of counterdiffusion of aluminum. Furthermore, the oxygen concentration, N _O ^S , at the specimen surface was evaluated on the basis of thermodynamics. Using these estimated values of K_p, N _Al ^IO , and N _O ^S , the diffusion coefficient of oxygen, D _O ^IO , in the oxidation layer, where the oxide particles were dispersed, was also calculated. D _O ^IO increases as the volume fraction of the oxide, f^IO, increases. The diffusion coefficient of oxygen, D_O, in -iron was determined by extrapolating D _O ^IO to f^IO=0.     

TEM investigations of the early stages of TiAl oxidation

The early stages of TiAl oxidation at 900°C and 1000°C in air have been investigated by transmission electron microscopy (TEM). The investigations revealed that at the beginning of oxidation, i.e., after 4 min, TiO₂ and Al₂O₃ grow in a preferential orientation on the -TiAl substrate. After 4 h of oxidation an oxide scale structure can already be found similar to that known from long-term oxidation. In addition, besides -Al₂O₃, the formation of a second aluminum oxide phase and of titanium nitrides is observed. The processes at the metal-oxide interface of oxidation in the early stages, consisting of a repeated cycle of Al₂O₃ formation, Al₂O₃ dissolution, outward migration of Al through the scale, and reprecipitation of Al₂O₃ in the outer scale, are described by a model. The four stages observed in the kinetics of TiAl oxidation are explained on the basis of the results obtained and the structure of the oxide scale.     

The oxidation of high-purity iron-chromium-aluminum alloys at 800°C

A systematic study is presented of the oxidation of pure iron-chromium-aluminum alloys at 800°C, in pure oxygen, at a pressure of 200 Torr. Oxidation characteristics are described with reference to kinetic measurements, scale topographies and morphologies, and also possible growth mechanisms. An oxide map is used to show that alloys may be classified into four categories depending on the external scale that forms: Fe₂O₃, Cr₂O₃, Al₂O₃, or Al₂O₃ with iron-oxide nodules. Alloys containing less than 2–2.5 wt. % aluminum formed either Fe₂O₃ or Cr₂O₃ as an external scale, depending on the chromium content, and internal, rod-like protrusions of Al₂O₃. At higher aluminum concentrations, Al₂O₃ was always present as an external scale, although this was interspersed by iron-oxide nodules at chromium concentrations of less than 5 wt. %. A model based on Wagner's secondary getter concept is proposed for eliminating nodule nucleation. Evidence is also present that indicates that at 800°C, alumina scale decohesion occurs prior to void formation and that voids are the result of thermal etching beneath lifted scales.     

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.     

Oxidation Behavior of a Sputtered Ni–5Cr–5Al Nanocrystalline Coating

A NiO-forming Ni–5Cr–5Al (at.%) alloy has been developed anddeposited as a sputtered nanocrystalline coating. The oxide formation andoxidation behavior of this coating have been studied at 1000°C inair. The oxidation rate markedly decreased with time and the oxidationkinetics obeyed the fourth power law. Complex oxide scales, consisting ofNiO, NiAl₂O₄ and -Al₂O₃,were formed during 200 hr oxidation. The outer oxide layer consisted of NiOand NiAl₂O₄ and an inner oxide layer of-Al₂O₃. The sputtered Ni–5Cr–5Alnanocrystalline coating showed good oxidation resistance due to theformation of an -Al₂O₃ inner layer andexcellent adhesion of the complex oxide scales.     

TEM studies of oxidized NiAl and Ni3Al cross sections

Cross sections of oxide scale/(Ni-Al) intermetallics were prepared by a new method and studied using primarily transmission electron microscopy (TEM). The cross sections were prepared by encasing an oxidized metal specimen sandwich in a low-melting-temperature zinc alloy. Observations of oxidized zirconium-doped -NiAl cross sections revealed crystallographic voids beneath an adherent Al₂O₃ scale. The oxide-metal interface was incoherent, but a high dislocation density in the metal near the interface suggested that a large tensile stress was induced by the attached oxide scale. A duplex Al₂O₃-NiAl₂O₄ scale formed on zirconium-doped and zirconium/boron-doped -Ni₃Al alloys. Additional results are presented involving oxidation mechanisms and oxide-metal interface structures.     

Oxidation behavior of an Fe-38Ni-13Co-4.7Nb-1.5Ti-0.4Si superalloy at high temperature in Ar-H2O atmospheres

The oxidation of an Fe-38Ni-13Co-4.7Nb-1.5Ti-0.4Si superalloy (Incoloy 909 type alloy), was investigated at temperatures between 1000 K and 1400 K in Ar-(1, 10%)H₂0 atmosphere using metallographic, electron probe microanalysis, and X-ray diffraction techniques. The oxide scales consist of an external scale and an internal scale which has an intergranular scale (above 1200 K) and an intergranular scale. The oxide phases in each scale are identified as-Fe₂,O₃ (below 1200 K) or FeO (above 1300 K) and CoO · Fe₂O₃ and FeO · Nb₂O₅, respectively. The morphologies, the oxide phases and the oxidation rates do not depend on the partial pressure of H₂O in the range between one and ten percent in Ar gas. The rate constants for the intergranular-scale formation in this alloy are about one-tenth as large as those in Fe-36%Ni alloy reported previously. At all the temperatures the scales grow according to a parabolic rate law and the apparent activation energies for the processes are estimated.     

Evaluation of High Temperature Oxidation Behaviour of Nanostructured Cr/Co–Al Coatings

The high temperature oxidation behavior of sputtered Cr/Co–Al coatings fabricated by DC/RF magnetron sputtering on a superalloy substrate has been studied in the present work. The microstructural features and phase formation of the as-deposited coatings were characterized by FE-SEM, AFM, and XRD, respectively. Weight-change measurements were made to calculate the cyclic oxidation kinetics of the coated superalloy exposed to air at 900 °C. It was observed that the corrosion rate of sputtered Cr/Co–Al coated superalloy is lower than that of the uncoated superalloy owing to the formation of continuous, dense, adherent and protective oxide scales over the surface of the coatings. The protective oxide scales in the corroded coatings were basically the thin layer of Cr₂O₃, CoO, Al₂O₃ and CoCr₂O₄, which provide protection to the base superalloy at high temperature.