Effects of bond coat preoxidation on the properties of ZrO2-8wt.% Y2O3/Ni-22Cr-10Al-1Y thermal-barrier coatings

Plasma-sprayed thermal barrier coatings (TBCs) consist of an intermediate MCrAlY bond coat to protect the substrate superalloy from oxidation/hot corrosion and a thermal insulating zirconia-based ceramic top coat. This system is developed for advanced turbine-engine, hot-section components. In this study the as-sprayed Ni-22Cr-10Al-1Y bond coat was subjected to preoxidation treatment at 1000° C for 1, 50, 100, and 200 hr, also at 1100°C, 1200°C and 1300°C for 1 hr to form an oxide scale before subsequent deposition of a ZrO₂-8wt.% Y₂O₃ top coat. The oxidation kinetics were measured, and the phase constitution and morphology of pregrown oxides on the Ni-22Cr-1Y bond coat were analyzed by x-ray diffractometer and SEM/EDS to elucidate the improvement and degradation mechanisms of the new system. The results of the experiments in this study showed that the tentative ZrO₂-8wt.% Y₂O₃ TBC specimens with preoxidized Ni-22Cr-10Al-1Y bond coat, when properly processed, exhibited lower oxidation rates and generally longer lifetime compared with traditional TBC specimens.     

Cyclic and isothermal oxidation behavior on some Ni-Cr alloys

Additions of 3 wt.% Mn and 3 wt.% Si were made to Ni-20Cr. These alloys, along with Ni-20Cr and Ni-40Cr were oxidized for 100 1-hr cycles at 1100°C and 50 1-hr cycles at 1200° C. Oxidation behavior was judged by sample weight and thickness change, metallography, x-ray diffraction, and electron microprobe analysis. These tests showed that Ni-40Cr and Ni-20Cr-3Si were about the same and were the most oxidation-resistant alloys. Ni-20Cr-3Mn was not as oxidation resistant, especially at 1200° C. Ni-20Cr was far less oxidation resistant than any of the other alloys. The Ni-40Cr and Ni-20Cr-3Si relied on a protective layer of Cr₂O₃ for their oxidation resistance. A SiO₂ layer was noted beneath the Cr₂O₃ layer on the Ni-20Cr-3Si, but had apparently only a second-order effect. The source of improved protection of the Ni-20Cr-3Mn was apparently the formation of a relatively adherent MnCr₂O₄ layer at the metal-oxide interface.     

Oxidation and sulfidation behavior of Fe-20Cr-16Ni-4Al-1Y2O3 oxide-dispersion-strengthened alloy

High-temperature oxidation and sulfidation studies were conducted on an oxide-dispersion-strengthened alloy of composition Fe-20Cr-16Ni-4Al-1Y₂O₃. The oxidation studies were conducted in air and low-PO₂ environments over a temperature range of 650–1200°C. Results are also reported on the sulfidation resistance of preformed oxide scales and the influence of reoxidation of preformed sulfide scales. Detailed microstructural results and x-ray diffraction analysis data are presented to substantiate the corrosion behavior of the alloy over the wide range of conditions anticipated in fossil-energy systems. Data are also presented on the corrosion behavior of the alloy in oxygen/sulfur mixed gas atmospheres, and the results are used to compare the corrosion behavior of the present alloy with other chromia- and alumina-forming alloys.     

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.     

A TEM study of the oxide scale development in Ni-Cr-Al alloys

In the present study the isothermal oxidation behaviours of Ni-10Cr-5Al, Ni-20Cr-5Al and Ni-30Cr-5Al alloys were investigated. The alloys were oxidised in air for 50 h at 1000 °C. Analytical transmission electron microscopy was used to characterize the morphology, structure and composition of the oxide scale. The oxide formed adjacent to the alloy was α-Al₂O₃ such that the higher was the Cr content of the alloy the easier was its formation. The Ni-30Cr-5Al alloy formed a complete layer of α-Al₂O₃ in the initial stages of oxidation through ‘oxygen gettering’ by Cr. A decrease in scale thickness and an increase in scale adherence were observed with an increase in Cr content from 10 to 30 wt.%.     

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.     

Oxidation of Fe-8Cr-14Ni-Al-Si-Mn from 700 to 1000°C

This paper reports an investigation into reducing the Cr concentration in commercial-grade stainless steels while maintaining oxidation protection at elevated temperatures. Aluminum and Si were added as partial substitute alloy elements to enhance the reduced operation protection resulting from Cr concentration reduced by approximately 50 pct of that found in stainless steels. The goal of this study was to determine the oxidation mechanism of such an Fe, Al-Si alloy: Fe-8Cr-14Ni-1Al-3.5Si-1Mn. During the initial oxidation period the protection resulted from a thin film of Al₂O₃ over an Fe and Cr spinel. Long-term oxidation protection resulted from the gradual formation of a Cr sesquioxide (Cr₂O₂) inner oxide layer. Eventually an outer oxide layer formed that was a mixed composition spinel of Cr and Mn (MnO · Cr₂O₃). The Al₂O₃, which was part of the original protective layer flaked off early in the oxide testing, and the aluminum oxide that formed later appeared as an internal oxide precipitate.     

Effect of internal oxidation pretreatments and Si contamination on oxide-scale growth and spalling

Internal oxidation pretreatments carried out in quartz capsule with a Rhines pack were found to have a profound effect on the subsequent oxidation behavior of alloys. Specimens of Co-15 wt.% Cr, Co-25 wt.% Cr, Ni-25 wt.% Cr, and Ni-25 wt.% Cr-1 wt.% Al were tested at 1100°C after pre-oxidation treatments. Even without the development of internal oxide particles, pretreated binary CoCr and NiCr alloys oxidized with significantly lower rates. Selective oxidation of chromium was observed on the non-Cr₂O₃-forming Co-base alloys, whereas on the Cr₂O₃-forming Ni-base alloys, elimination of base-metal oxide, reduction in the Cr₂O₃ growth rate, and better scale adhesion were found. These effects were more apparent with pre-oxidation temperatures greater than 1000°C and with longer pretreatment times. Contaimination of Si from the quartz is believed to be the cause.     

Oxidation behavior of Ni-Cr-1ThO2 alloys at 1000 and 1200°C

The oxidation behavior of Ni-13.5-33.7Cr-1ThO₂ alloys in flowing oxygen at 150 Torr was investigated in the temperature range 1000–1200°C. Gravimetric measurements of the oxidation kinetics have been combined with microstructural studies of the reacted samples in order to evaluate the reaction mechanisms. The oxide products formed on the alloys were a function of Cr content, sample surface preparation, reaction time, and temperature. The presence of ThO₂ appears to produce two effects during alloy oxidation. First, enhanced Cr diffusion to the alloy surface results in rapid formation of a Cr₂O₃ subscale beneath NiO on Ni-13.5Cr-1ThO₂ and selective oxidation of Cr for Ni-22.6Cr-1ThO₂. Second, the mechanism of formation of Cr₂O₃ is apparently different from that for simple Ni-Cr alloys, resulting in about an order of magnitude reduction in the Cr₂O₃ growth rate. The oxidationvaporization of Cr₂O₃ to CrO₃ becomes rate controlling for the higher Cr alloys after only a few hours of exposure at 1200°C.     

Kinetics of Fe-30% Ni-12.5% Co invar alloy during high temperature oxidation

The oxidation behavior of Fe-30% Ni-12.5%Co Invar alloy possessing low thermal expansion-high strength has been studied by exposing it in temperature ranges of 1000–1200 in an air atmosphere. The formed oxide scale consisted of two layers, an outer layer and an inner layer, and the oxidation mechanism showed uniform growth for all oxidation conditions. The growth rate of the scale had a parabolic relationship with oxidation time, and the estimated activation energy for the growth of the whole oxide layer was approximately 19.84 kcal/mol. The outer scale consisted of five oxide layers, whose outermost scale consisted of major phase CoFe₂O₄ containing a particulate Fe₂O₃ phase. The oxide scale of Fe-30 Ni-12.5% Co had different compositions and phases from the Fe-30%Ni alloy investigated in previous studies. Especaally, when the alloy was exposed for a longer oxidation time and at a higher temperature, the volume fraction ratio of CoFe₂O₄ to Fe₂O₃ was found to increase     

Effect of yttrium on the sulfidation behavior of Ni-Cr-Al alloys at 700°C

The sulfidation of Ni-10Cr-5Al, Ni-20Cr-5Al, and Ni-50Cr-5Al, and of the same alloys containing 1% Y, was studied in 0.1 atm sulfur vapor at 700°C. The sulfidation process followed linear kinetics for all the alloys except Ni-50Cr-5Al-1Y, and possibly Ni-50Cr-5Al, which followed the parabolic law. The reaction rates decreased with increasing chromium content in alloys without yttrium, and the addition of yttrium reduced the rates by at least a factor of two for the alloys containing 10 and 20% Cr and by an order of magnitude for Ni-50Cr-5Al. Alloys containing 10 and 20% Cr (with and without yttrium) formed duplex scales consisting of an outer layer of NiS_1.03 and an inner lamellar layer of a very fine mixture of Cr₂S₃ and A1₂O₃ in a matrix of NiS_1.03. The two alloys containing 50% Cr formed only a compact layer of Cr₂S₃, which was brittle and spalled during cooling. The lamellae in the duplex scales were parallel to the specimen surface and bent around corners. The lamellae were thicker than those on Ni-Al binary alloys. The lamellae were also thicker in scales on the 20% Cr alloy than on the 10% Cr alloy. The presence of yttrium refined the lamellae and increased the lamellae density near the scale/metal interface in the 10% alloy, but in the 20% Cr alloy the lammellae were thicker and more closely spaced. Platinum markers were found in the inner portion of the exterior NiS_1.03 layer close to the lamellar zone. A counter-current diffusion mechanism is proposed involving outward cation diffusion and inward sulfur diffusion, although diffusion was not rate controlling for alloys containing 10 and 20% Cr. Auger analysis of scales formed on Ni-50Cr-1Y showed an even distribution of yttrium throughout the layer of Cr₂S₃, suggesting that some yttrium dissolved in the sulfide. The reduced sulfidation rate of samples containing yttrium is explained by the possible dissolution of yttrium as a donor. The presence of Y⁴⁺ would then decrease the concentration of interstitial chromium ions in the N-type layer of Cr₂S₃, which would decrease the reaction rate.     

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.     

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.     

The high-temperature oxidation of Ni-20%Cr alloys containing various oxide dispersions

The oxidation behavior of Ni-20%Cr alloys containing approximately 3 vol.% Y₂O₃, ThO₂, and A1₂O₃ as dispersed particles has been examined in the temperature range 900 to 1200° C in slowly flowing oxygen at 100 Torr. The results show that the oxidation behavior of the Y₂O₃-, ThO₂-, Al₂O₃-, and Ce0₂-containing alloys is very similar and that some anomalies in the behavior of the ThO₂-containing alloy might be explained by the slower rate of chromium diffusion in this coarse-grained alloy. Two Al₂O₃-containing alloys were studied. One with a relatively coarse dispersoid size behaved in a manner analogous to a dispersion-free Ni-30% Cr alloy at 1100°C. The other alloy contained a dispersion of fine Al₂O₃ particles and behaved exactly like the Y₂O₃-containing alloy at 1000 and 1100°C, but at 1200° C oxidized at a faster rate. It has been shown that the adherent scales on dispersion-containing alloys have a stabilized fine grain size, whereas the nonadherent scales on dispersion-free alloys undergo grain growth.This work has been supported by the Naval Air Systems Command under Contract No. N00019-72-C-0190.     

Effect of Ti and Ta on the oxidation of a complex superalloy

The oxidation behaviors of a series of directionally solidified Ni-base superalloys were studied at 1000 and 1100°C. These alloys are based on a composition of Ni-4.2Co-4.8Cr-12.8Al-1.6W3.1Mo-1.0Re (at.%), with additions of Ta and Ti. Both Ta and Ti partition to alloy phases in a manner similar to Al. With addition of 1 at. % of Ta, the oxidation resistance is improved significantly, while 1 at. % of Ti appears to have no effect. Raising the concentration of Ta and Ti to 3 at. % degrades the oxidation resistance, the degradation is especially severe with 3 at. % of Ta. At only 1 at. % of Ta and Ti, both alloys establish a protective layer of Al₂O₃. The loss of the oxidation resistance at 3 at. % addition of Ta and Ti is related to the formation of complex oxides which are less protective. Detailed analysis of the oxide phases are conducted using a combination of X-ray diffraction and SEM. Characterizations of the oxidation behaviors are made under isothermal and cyclic conditions. The discrepancies between data obtained under both conditions were noted.     

The effect of yttrium and thorium on the oxidation behavior of Ni-Cr-Al alloys

The effect of quaternary additions of 0.5% Y and 0.5 and 1.0% Th to a base alloy of Ni-10Cr-5Al on the oxidation behavior and mechanism was studied during oxidation in air over the range of 1000–1200°C. The presence of yttrium decreased the oxidation kinetics slightly, whereas the addition of thorium caused a slight increase. Oxide scale adherence was markedly improved by the addition of the quaternary elements. Although a number of oxides formed on yttrium-containing alloys, quantitative x-ray diffraction clearly showed that the rate-controlling step was the diffusion of oxygen through short-circuit paths in a thin layer of alumina that formed parabolically with time. Mixed oxides containing both aluminum and yttrium formed by the reaction of Y₂O₃ to form YAlOP₃ initially, and Y₃Al₅O₁₂ (YAG) after longer times. Although the scale adherence of the yttrium-containing alloy was considerably better than the base alloys, spalling did occur that was attributed to the formation of the voluminous YAG particles that grew in a mushroom-like manner, lifting the protective scale off the substrate locally. The YAG particles formed primarily at grain boundaries in the substrate in which the yttrium originally existed as YNi₉. This intermetallic compound reacted to form Y₂O₃, liberating metallic nickel that subsequently reacted to form NiO or NiAl₂O₄ spinel or both. The Y₂O₃ reacted with aluminum to ultimately form the YAG mushrooms. Thorium did not form any mixed oxides; the only oxide involving thorium was ThO₂, which existed as small particles at the oxide-metal interface. A highly beneficial effect of the thoria particles in reducing film spalling was observed. Scale spalling in the base alloy was attributed to void formation at the oxide-metal interface, the voids forming by condensation of excess vacancies from the Kirkendall effect associated with fast back-diffusion, of nickel into the substrate as aluminum was preferentially oxidized and diffused slowly outward. The mechanism of improved scale adherence in the quaternary alloys was the elimination of voids by annihilation of the Kirkendall vacancies at vacancy sinks introduced by the noncoherent interfaces between yttrium and thorium-containing intermetallics or oxides or both.This work is based on a portion of the dissertation of Arun Kumar in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Engineering, University of California, Los Angeles.Supported by NASA-Ames under grant No. NGR 05-007-352.     

Isothermal Oxidation Behavior of Ti-50Al Alloy with Y Additions at 800 and 900°C

The isothermal-oxidation behavior of Al-rich TiAl alloys containing Y up to 1.0 at.% was studied in synthetic air with a flow of 200–250 mL/min at 800 and 900°C. Oxidation kinetics and scale adherence were studied in terms of the morphological features and microstructural evolution of the oxide scale. In the specimens oxidized at 800°C, all alloys containing 0.3–1.0 at.%Y showed reduced mass gain compared to the Y-free alloy, especially for the 0.3 at.%Y alloy. Under isothermal exposure at 900°C, the addition of small amounts of Y (0.1 and 0.3 at.%) was effective in enhancing the oxidation resistance. The alloys with higher Y contents (0.6 and 1.0 at.%), on the contrary, had a reverse effect on the oxidation resistance by providing rapid diffusion paths in the form of coarse Y₂O₃ particles close to the substrate. The improvement of oxidation resistance of the alloy with Y additions was due partly to the improved adhesion of the scale and due partly to the formation of a continuous α-Al₂O₃ layer in the outer scale. Y segregation and/or Y₂O₃ precipitation at the oxide grain boundaries was effective in decreasing the oxidation rate and refining the oxide grains. The thinner scale was responsible for relaxing the thermal stress and, thus the cohesion between the scale and substrate was greatly improved in Y-containing alloys.     

Investigation on the corrosion and oxidation resistance of Ni-Al2O3 nano-composite coatings prepared by sediment co-deposition

Ni-Al₂O₃ composite coatings were prepared by using sediment co-deposition (SCD) technique from a Watt's type electrolyte containing nano-Al₂O₃ particles. The corrosion resistance and high temperature oxidation resistance of resulting composite coatings were investigated. It was found that the incorporation of nano-Al₂O₃ particles in Ni matrix refined the Ni crystal and changed the preferential orientation of composite coatings. Meanwhile, the corrosion and oxidation resistance were improved after the incorporation of nano-Al₂O₃ particles into Ni matrix. The nano-Al₂O₃ content in deposits plays an important role for improving the corrosion and oxidation protection. The corrosion and oxidation resistance of Ni-Al₂O₃ nano-composite coatings produced via SCD technique are superior to that of CEP technique. Compared to pure Ni and Ni-Al₂O₃ composite coatings fabricated using CEP technique, the Ni-7.58 wt.% Al₂O₃ composite coating obtained by SCD technique exhibits better corrosion resistance and enhanced high temperature oxidation resistance. Moreover, the mechanism of corrosion and high temperature oxidation resistance of Ni-Al₂O₃ nano-composite coatings are discussed.     

Roles of Nb on the oxidation characteristics and oxide scale evolution of Fe-25Cr-35Ni-2.5Al-XNb alloys at 1000°C and 1100°C

The oxidation characteristics of Fe-25Cr-35Ni-2.5Al-_XNb (0, 0.6, and 1.2 wt%) alumina-forming austenitic alloys at 1000°C and 1100°C in air were investigated. Results show that Nb has an important effect on the high-temperature oxidation resistance. A bilayer oxide scale with a Cr₂O₃-rich outer layer and Al₂O₃-rich internal layer forms on the surface of the Nb-free alloy and exhibits a poor oxidation resistance at 1000°C and 1100°C. With Nb addition, both the 0.6Nb-addition and 1.2Nb-addition alloys exhibit better oxidation resistance at 1000°C. Because of the third element effect, Nb addition reduces the critical Al content and forms a single external protective Al₂O₃ scale, which greatly improves the oxidation resistance. After oxidation at 1100°C, niobium oxides (mainly Nb₂O₅) are formed on the surface of the 1.2Nb-addition alloy and destroy the integrity of the Al₂O₃ scale, which causes the formation of Cr-rich oxide nodules and eventually develops to be a loose bilayer oxide scale with NiCr₂O₄, Cr₂O₃, and Fe₂O₃ outer layers and Al₂O₃ inner layer.     

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.