Combined pre-annealing and pre-oxidation treatment for the processing of thermal barrier coatings on NiCoCrAlY bond coatings

A combined pre-annealing and pre-oxidation treatment was developed for the processing of partially yttria stabilized (PYSZ) thermal barrier coatings (TBC) on top of NiCoCrAlY bond coatings (BC). To develop this pre-treatment, the influence of the oxygen potential during pre-annealing and pre-oxidation on the life span and failure mechanisms of the entire high temperature coating system upon thermal cycling was investigated. The results of this study showed that the service life of the coating system depended strongly on the composition and microstructure of the thermally grown oxide (TGO) after pre-oxidation. The longer life spans were obtained if the TGO thickened very slowly during thermal cycling due to a large α-Al₂O₃ grain size. Such a slow-growing TGO corresponded with a pre-treatment for which θ-Al₂O₃ was formed during pre-oxidation and for which the yttrium was located within a high density of pegs along the TGO/BC interface after pre-oxidation. If the yttrium was present on top of the TGO after pre-oxidation, a thick mixed alumina-zirconia layer formed upon thermal cycling. This mixed oxide layer contributed significantly to the total oxide layer thickness, resulting in short life spans. The formation of NiAl₂O₄ spinel in between the TBC and the α-Al₂O₃ should be avoided, since this can lead to premature failure along the spinel/α-Al₂O₃ interface.     

On the Microstructure of the Initial Oxide Grown by Controlled Annealing and Oxidation on a NiCoCrAlY Bond Coating

Different pre-annealing and pre-oxidation treatments were conducted on a dual phase γ+β Ni–21Co–18Cr–22Al–0.2Y (at.%) bond coating for 1 hr at 1373 K (i) with or without a native oxide upon heating, (ii) in two different atmospheres upon heating, and (iii) under various oxygen partial pressures (pO₂) in the range of 0.1–10⁵ Pa during oxidation. The chemical composition, structure, morphology and phase constitution of the resulting oxide layers were investigated using a range of analytical techniques. It is found that the exclusive formation of a continuous α-Al₂O₃ layer without the simultaneous formation of NiAl₂O₄ spinel was promoted for oxidation at low pO₂. The formation of metastable θ-Al₂O₃ was suppressed for a low fraction of the β phase, coupled with a high fraction of segregated Y at the initial bond coat surface. Initial Y segregation and incorporation of Y₂O₃ and Y₃Al₅O₁₂ within the developing oxide layer was promoted in the absence of a native oxide and for heating in an inert atmosphere. The development of protrusions (i.e. pegs) at the oxide/coating interface, as a result of the incorporation of internal Y₂O₃ precipitates by the inward growing oxide layer, was most pronounced upon heating in an inert atmosphere, followed by oxidation at an intermediate pO₂.     

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.     

The Effect of Heat Treatment on the Oxidation Behavior of HVOF and VPS CoNiCrAlY Coatings

Free-standing VPS and HVOF CoNiCrAlY coatings were produced. The as-sprayed HVOF coating retained the γ/β microstructure of the feedstock powder, and the VPS coating consisted of a single (γ) phase. A 3-h, 1100 °C heat treatment in vacuum converted the single-phase VPS coating to a two-phase γ/β microstructure and coarsened the γ/β microstructure of the HVOF coating. Oxidation of free-standing as-sprayed and heat-treated coatings of each type was carried out in air at 1100 °C for a duration of 100 h. Parabolic rate constant(s), K _p, were determined for free-standing, as-sprayed VPS and HVOF coatings as well as for free-standing coatings that were heat treated prior to oxidation. The observed increase in K _p following heat treatment is attributed to a sintering effect eliminating porosity from the coating during heat treatment. The lower K _p values determined for both HVOF coatings compared to the VPS coatings is attributed to the presence of oxides in the HVOF coatings, which act as the barrier to diffusion. Oxidation of the as-sprayed coatings produced a dual-layer oxide consisting of an inner α-Al₂O₃ layer and outer spinel layer. Oxidation of the heat-treated samples resulted in a single-layer oxide, α-Al₂O₃. The formation of a thin α-Al₂O₃ layer during heat treatment appeared to prevent nucleation and growth of spinel oxides during subsequent oxidation.     

Spinel formation in thermal barrier systems with a Pt-enriched γ-Ni + γ′-Ni3Al bond coat

The oxidation of electron beam physical vapour deposited thermal barrier coatings with a Pt-enriched γ-Ni + γ′-Ni₃Al bond coat was investigated. Due to the growth of the thermally grown oxide (TGO), γ-Ni formed underneath the TGO as a result of Al depletion. Phase characterisation by X-ray diffraction, as well as microstructural observations, indicated that a NiAl₂O₄ spinel phase formed at the TGO/bond coat interface after prolonged oxidation. It is proposed that the formation of spinel occurs when local cracks present at the interface and the underlying bond coat is Al-depleted. The cracks provide a direct path for oxygen and nickel oxide forms at the bond coat surface. With further oxidation, the spinel forms at the interface through solid state reaction between the TGO and nickel oxide.     

Effects of Ce and Si additions to CoNiCrAlY bond coat materials on oxidation behavior and crack propagation of thermal barrier coatings

In thermal barrier coating (TBC) systems, thermally grown oxide (TGO) forms at the interface between the top coat and the bond coat (BC) during service. Delamination or spallation at the interface occurs by the TGO formation and growth. Therefore, modifications of the BC materials are one means to inhibit the TGO formation and to improve the crack resistance of TBCs. In this study, morphologies of TGO were controlled by using Ce and Si additions to conventional CoNiCrAlY BC material. The evaluation of the crack resistance was carried out using acoustic emission methods under pure bending conditions. As a result, when the BCs of TBCs with Ce added were aged at 1373 K over 10 h, the morphologies of the TGO were changed drastically. The BC materials of TBCs coated with Ce added indicated an improved crack resistance with high-temperature exposure. It is expected that the morphologies can improve the crack resistance of TBCs. This article was originally published inBuilding on 100 Years of Success: Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, 2006.     

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.     

Thermal Cycling Behavior of Thermal Barrier Coatings with HVOF NiCrAlY Bond Coat

Thermal Barrier Coatings with HVOF NiCrAlY Bond Coat is prepared on nickel-based superalloy substrates. The lifetime of the coating is about 1630 h for 1-h cycle at 1050 °C. Growth of the TGO (thermally grown oxide) approximately follows a parabolic kinetics, and the TGO presents a bi-layered structure. Failure of the coating occurs near the interface between the mixed oxides layer of TGO and top coat. A finite element method is employed to analyze the stress distribution in the coating. The results show that maximum stresses occur at the top coat/TGO interface near the edge of the coating. The maximum radial stress for TGO consisting of spinel and Al₂O₃ is about five times larger than that of Al₂O₃, while the maximum axial stress is about ten times larger. The mixed oxide layer of TGO plays an important role in the premature failure of TBCs.     

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.     

Cyclic-Oxidation Behavior of Thermal-barrier Coatings Exposed to NaCl Vapor

A Ni–24Cr–6Al–0.7Y (NiCrAlY) coating was deposited on a nickel-base superalloy by low-pressure plasma spraying, and the top coating, ZrO₂ partially stabilized with Y₂O₃ (7.5 wt%), was deposited on the NiCrAlY coating by air-plasma spraying. The cyclic-oxidation behavior of the NiCrAlY + YSZ coating exposed to NaCl vapor was investigated under atmospheric pressure at 1,050 °C, 1,100 °C and 1,150 °C. The cyclic-oxidation life of the NiCrAlY + YSZ coating in the presence of NaCl vapor was shortened compared with that in air. The higher the temperature is, the shorter the cyclic oxidation life. The oxide scale formed at the interface between the bond coat and the ceramic layer after exposure to NaCl vapor consisted of voluminous and non-protective NiO, Al₂O₃ and NiCr₂O₄ spinel. The failure of the TBC exposed to NaCl vapor occurs within the top coat and close to the YSZ/thermal growth oxide interface. The failure mechanism has been discussed based on the experimental results and thermodynamics.     

Proto-TGO formation in TBC systems fabricated by spark plasma sintering

Thermal barrier coatings (TBC) are commonly used in modern gas turbines for aeronautic and energy production applications. The conventional methods to fabricate such TBCs are EB-PVD or plasma spray deposition. Recently, the spark plasma sintering (SPS) technique was used to prepare new multilayered coatings. In this study, complete thermal barrier systems were fabricated on single crystal Ni-based superalloy (AM1®) substrate in a one-step SPS process. The lifetime of TBC systems is highly dependent on its ability to form during service a dense, continuous, slow-growing alumina layer (TGO) between an underlying bond coating and a ceramic top coat. In the present paper, we show that such kind of layer (called proto-TGO in the following) can be in situ formed during the SPS fabrication of TBC systems. This proto-TGO is continuous, dense and its nature has been determined using TEM-EDS-SAD and Raman spectroscopy. This amorphous oxide layer in the as-fabricated samples transforms to α-Al₂O₃ during thermal treatment under laboratory air at 1100 °C. Oxidation kinetics during annealing are in good agreement with the formation of a protective α-Al₂O₃ layer.     

TEM analysis of the microstructure of thermal barrier coatings after isothermal oxidation

Thermal barrier coatings (TBCs) are extensively used to protect metallic components in applications where the operating conditions include an aggressive environment at high temperatures. The most important factor controlling TBC durability is the nucleation, and subsequent thickening, of a thermally grown oxide (TGO) layer which is formed during high-temperature oxidation. For this reason, the aim of this work is to analyse the TGO microstructure evolution during isothermal oxidation to explain the macroscopic oxidation behaviour. To this end, transmission electron microscopy (TEM) was used to evaluate the TGO fine microstructure. ZrO₂(Y₂O₃) top coat and NiCrAlY bond coating were air plasma sprayed onto an Inconel 600 Ni base alloy. The TBCs were isothermally oxidized in air at 950 and 1050 °C for 24, 48, 72, 144 and 336 h and the principal differences in TGO composition were analysed. α-Al₂O₃ was the main TGO constituent in the TBC treated at 950 °C. On the other hand, Al was rapidly consumed in the TBC oxidized at 1050 °C leading to the formation of NiAl₂O₄ spinels, after 72 h exposure, and NiO, after 336 h. The TGO growth kinetics followed a power law, controlled by Al³⁺ diffusion, in the samples treated at 950 °C. However, two different power laws fitted the TGO growth kinetics in the coatings treated at 1050 °C as the diffusion of Ni²⁺ is relevant after 72 h exposure.     

Effect of Y Distribution on the Oxidation Kinetics of NiCoCrAlY Bond Coat Alloys

The relation between the Y distribution in the alloy and the growth kinetics of the developing oxide scale was studied for the thermal oxidation of two Ni–20Co–19Cr–24Al–0.2Y (at.%) alloys at 1,373 K: (i) a coarse-grain cast alloy with large Ni₅Y intermetallic precipitates, and (ii) a fine-grain freestanding coating with small Ni₅Y precipitates. Using a combination of experiments and model calculations, it is shown that the average growth kinetics of a NiCoCrAlY alloy are dependent on the size and distribution of Y-rich oxide inclusions (pegs) in the α-Al₂O₃ oxide layer. Alumina scales containing a high density of small Y-oxide inclusions grow faster than α-Al₂O₃ scales containing only a few, large Y-oxide inclusions. Upon oxidation of the freestanding coating, the Y-oxide inclusions in the scale attain their maximum size after the Y in the coating is completely consumed. After this point, a decrease in the average oxidation kinetics occurs.     

Carburization Behavior of Electrodeposited Ni3 Al–CeO2-Base Coatings on Fe–Ni–Cr Alloys

The cyclic carburization of electrodeposited pure and CeO₂-dispersed Ni₃Al intermetallic coatings on Fe–Ni–Cr alloys has been investigated at 850 and 1050°C for periods up to 500 h in a reducing 2%CH₄–H₂ atmosphere. At 850°C, all Ni₃Al-base-coating samples showed excellent carburization resistance and slow mass increases due to the formation of a thin γ-Al₂O₃ scale and a low carbon activity (a _c = 0.73). At 1050°C and a high carbon activity (a _c = 3.21), all coatings are superior to the uncoated Fe–Ni–Cr alloy in terms of carburization resistance. A thin α-Al₂O₃ scale slowly formed on all Ni₃Al coatings effectively blocked the carbon attack. The addition of CeO₂ particles in the Ni₃Al coatings significantly mitigated the cracking of the α-Al₂O₃ scale and the resultant internal oxidation and carburization. For all coatings, Ni-rich particles were found to be formed on the α-Al₂O₃ scale during oxidation, which had led to the deposition of catalytic coke.     

High-Temperature-Oxidation Behavior of Iron–Aluminide Diffusion Coatings

Aluminide diffusion coatings were oxidized in air under atmospheric pressure under isothermal and cyclic conditions. The high-temperature efficiency of the pack-aluminized alloys was tested by comparing their oxidation behavior in the temperature range 800–1080°C. The k _p values deduced from the parabolic plots of weight-gain curves showed that α-Al₂O₃ composed the major phase of the oxide scale on samples oxidized at T > 1000°C. For lower temperatures, transient-alumina phases were observed. The aluminide materials also exhibited excellent resistance to cyclic oxidation at 1000°C. The second aim of this study was to dope the aluminide compounds obtained by a pack-cementation process with yttria, which was introduced by metal-organic chemical-vapor deposition (MOCVD). The beneficial effect of the reactive-element-oxide coating is strongly dependent on its mode of introduction, since the oxidation resistance is drastically increased when the Y₂O₃ coating was applied prior to the aluminization process. When applied after the aluminization, the reactive element gave negative effects on the high-temperature oxidation behavior of the iron aluminides. The oxide morphologies, X-ray diffraction patterns and two-stage experiments helped to understand the oxide-scale-growth mechanisms.     

High-temperature oxidation of nickel-based alloys and estimation of the adhesion strength of resulting oxide layers

The kinetics of isothermal oxidation (1100°C) of commercial nickel-based alloys with different content of sulfur (0.22–3.2 wt ppm) is studied. The adhesion strength in a metal/oxide system is estimated as a function of sulfur content and duration of high-temperature exposure. The scratch-test technique is proposed to quantitatively estimate the work of adhesion of resulting oxide films. It is found that the film microstructure is composed of an inner α-Al₂O₃ layer and an outer NiAl₂O₄ spinel layer, which are separated by discrete inclusions of TiO₂. Residual stresses in the oxide film are experimentally determined by X-ray diffraction.     

Residual Stress Evolution and Failure Modes in a Thermal Barrier Coating Deposited on a Curved Substrate

A set of thermal barrier coated (TBC) specimens was made from CMSX-4 superalloy containing curved surfaces that are representative of typical turbine blades with a bond coat (BC) of HVOF ‘Amdry 995’ and a top coat (TC) that was air plasma sprayed 7 wt% Y₂O₃ stabilised ZrO₂. The specimens were thermally oxidised at 925 °C for times between 100 and 10,000 h. The residual stresses, both in the TC and the thermally grown oxide (TGO) that formed between the TC and BC upon thermal exposure, were measured on the cross-sections using Raman spectroscopy and photo-stimulated luminescence spectroscopy, respectively. A constraint upon the residual stress in the TC in the vicinity of the interface was found to be due to the growth of TGO. The corresponding microstructural evolution of the TBC and TGO was investigated using scanning electron microscopy to assist understanding of the residual stress distribution within the TC thickness and the undulating TGO. The effect of substrate curvature on the strain levels in the TC was evaluated and considered with respect to the macro-scale failure modes of the coating system.     

Improvement of the adhesion of a ceramic coating on a ceramic substrate

The structure and adhesion of an alumina coating on a ceramic substrate with NiCrAlY alloy bond coating was investigated by heating at 1573 and 1673 K in the air. Phases of NiO, NiCrO₃, NiAl₂O₄, αAl₂O₃, and Ni were revealed in a 100 μm thick bond coating on heating at 1573 and 1673 K. A veined structure was also detected in the coating heated at 1573 K. The adhesion strength of the coating was improved and reached approximately 20 MPa on heating at 1573 and 1673 K for 14.4 ks in air although the strength of the as-sprayed coating was only 2 MPa. The improvement of adhesion strength may arise from the formation of NiAl₂O₄ with a spinel structure at the interfaces of the top coating/bond coating/substrate coating system. The adhesion strength of the coating improved on decreasing the bond coating thickness and reached approximately 45 MPa for a 20 μm thick bond coating which was heated at 1673 K. Only NiAl₂O₄ oxide was formed in the bond coating.     

Electrochemical Corrosion of HVOF-Sprayed NiCoCrAlY Coatings in CO<Subscript>2</Subscript>-Saturated Brine

The effect of pre-oxidation treatment and surface preparation of optimized NiCoCrAlY coatings deposited by high-velocity oxygen fuel (HVOF) spraying and exposed to a low-temperature corrosive environment is reported herein. Coatings with two surface finish conditions (as-sprayed and ground) were heat treated under two different oxygen partial pressures (air and argon). The electrochemical corrosion behavior was evaluated in CO₂-saturated brine via potentiodynamic polarization, polarization resistance, and electrochemical impedance measurements. The results show that the grinding process and pre-oxidation treatment in argon enhanced growth and formation of α-Al₂O₃ scale. The potentiodynamic polarization results show that both pre-oxidation and surface treatment had a positive influence on the corrosion resistance of the coating. The reduction of the porosity and the formation of a dense, uniform, and adherent oxide scale through pre-oxidation treatment led to an increase of the corrosion resistance due to a decrease in active sites and blocking of diffusion of reactive species into the coating. However, according to the results, complete transformation from metastable alumina phases to α-Al₂O₃ in addition to formation and growth of dense α-Al₂O₃ is required to ensure full protection of the coating and base material over long periods.     

预氧化处理对热障涂层热冲击性能及残余应力的影响

采用等离子喷涂工艺在镍基高温合金基体上制备了热障涂层(底层为MCrAlY,面层为ZrO2+ 8％ Y2O3),通过控制高真空烧结炉的氧分压对涂层进行预氧化处理,分析了预氧化处理对热障涂层热冲击性能和涂层应力状态的影响.结果表明,预氧化处理提高了粘接层的致密度,涂层组织变得均质化,降低了粘结层由于凸起尖角产生复杂应力的概率;有效干预热生长氧化物(TGO)的生长过程,降低了TGO的生长速度;热障涂层残余应力随热冲击次数的增加而增大,但经过预氧化处理的涂层应力增长幅度较缓慢,经过400次热冲击后的残余应力为492.5 MPa,未经过预氧化处理涂层热冲击350次后应力值为650.1 MPa.