Quantification of growth kinetics and adherence of oxide scales formed on Ni-based superalloys at high temperature

Cyclic and isothermal oxidation behaviors of first and fourth-generation superalloys AM1 and MCNG were investigated to evaluate the ability of the scratch test to quantify the adhesion of multi-layered oxide scales. Effects of sulfur content and of scale thickness were studied independently. Available models lead to large discrepancies in the calculated work of adhesion values with the evaluation of the residual stress being the largest source of error. Nevertheless, models can assess the effect of sulfur content and the scratch test can be used to correlate the long-term cyclic oxidation behavior and the adhesion of oxide scales

Cyclic thermogravimetry of TBC systems

The previously developed cyclic thermogravimetry analysis (CTGA) method is applied to the cyclic oxidation at 1100 °C of ZrO2–Y2O3/NiPtAl or NiCoCrAlYTa/single crystal nickel-base AM3 superalloy TBC systems. Cyclic thermogravimetry with fast heating and cooling and high accuracy in mass measurement allows to measure oxidation kinetics of the bond coating and also to detect and quantify the occurrence of the top coating cracking and spalling. The resulting data could be used later on, for time of life modelling of TBC systems

Characterization of sulfur distribution in Ni-based superalloy and thermal barrier coatings after high temperature oxidation: a SIMS analysis

Sulfur segregation was characterized by secondary ion mass spectrometry (SIMS) in uncoated single-crystal Ni-based AM1 superalloys with various S contents and on NiPtAl, NiAl and NiPt bondcoats of complete TBC systems. In spite of technical difficulties associated with diffuse sputtered interfaces, an original sample preparation technique and a careful choice of analysis conditions enabled a chemical characterization of S distribution below metal/oxide interfaces. An initial heterogeneous distribution of S in as-received high S (3.2 ppmw) AM1 was measured. After oxidation, a S depletion profile formed, with a slope that depended on the initial bulk S content. GDMS measurements enabled a quantitative distribution of S in oxidized low S (0.14 ppmw) AM1 to be constructed and discussed in relation to equilibrium surface segregation of S on Ni. The quantity of S integrated in the thermally grown oxide (TGO) was estimated and found to be very similar to that measured from depletion found in the metal. Localized S enrichments in Pt-containing coatings are related to a possible beneficial trapping mechanism of Pt on the adherence of oxide scales

Reactivity and microstructure evolution of a CoNiCrAlY/Talc cermet prepared by spark plasma sintering

A mixture of CoNiCrAlY and talc powders is considered as a new candidate composition for abradable seal coating applications. Dense specimen having the composition of 1:20 weight ratio of talc with respect to CoNiCrAlY was prepared using the Spark Plasma Sintering (SPS) technique. The aim of the present article is to investigate the reactivity and microstructure evolution of the β/γ-CoNiCrAlY based cermet. The resulting microstructures were analysed and their compositions determined using standard analytical techniques such as SEM, TEM and X-ray diffraction. After fabrication, the bulk of the material is shown to contain a continuous oxide layer of MgAl2O4 at the periphery of metallic particles, resulting from the reaction between aluminium, which has diffused from the bulk of CoNiCrAlY grains, with magnesium and oxygen delivered during the high temperature decomposition of the talc phase. Thermodynamic calculations results are found to be consistent with the experimental observations. The oxidation behaviour at a high temperature of this cermet was also investigated. It was shown that at its external surface a continuous double layer is formed — one external film at the surface of the sample made of MgAl2O4 and the second one more internal in between the later and the cermet made of α-Al2O3. The oxide scale is protective with low oxidation kinetics typical of alpha alumina growth (kP = 1.8 10 − 7mg2 cm − 4 s − 1 at 1050 °C in flowing dry air)

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 laye

High-temperature oxidation kinetics of NiAl single crystal and oxide spallation as a function of crystallographic orientation

Isothermal and cyclic high-temperature oxidation of NiAl single crystal samples are presented. Oxidations have been carried out at 900, 1050, 1100 and 1150 ◦C on (1 0 0) and (1 1 0) oriented surface. Continuous thermogravimetry in cyclic conditions allows isothermal oxidation kinetics and spalling at each cycle to be followed. Oxidation kinetics are compared between (1 0 0) surface and (1 1 0) surface. (1 0 0) oriented surfaces appeared to oxidize slightly faster than (1 1 0) oriented surfaces. Experimental results of cyclic oxidation are compared to simulated results using a previously published statistical model. Spalling increases when the average oxide scale thickness increases with the number of cycles. Longer tests are necessary to study this evolution during the ’steady-state’ but no critical oxide thickness was found

Beneficial Effect of Pt and of Pre-Oxidation on the Oxidation Behaviour of an NiCoCrAlYTa Bond-Coating for Thermal Barrier Coating Systems

The oxidation behaviour of a thermal barrier coating (TBC) system is a major concern as the growth of the thermally grown oxide (TGO) layer on the bondcoating creates stresses that greatly favour the thermal barrier spallation. To delay the loss of the thermal protection provided, research has focused on the bondcoating composition and microstructure as well as on the parameters required for a suitable pre-oxidation treatment before the deposition of the ceramic top coat. Platinum is known to enhance the oxidation/corrosion resistance of MCrAlY coatings. The effect of Pt on the oxidation behaviour of a NiCoCrAlYTa coating was assessed in this study. In addition, pre-oxidation treatments were conducted to determine if the oxidation behaviour of the modified NiCoCrAlYTa coating could be further improved

Thermal barrier systems and multi-layered coatings fabricated by spark plasma sintering for the protection of Ni-base superalloys

Aeronautic gas turbine blades, vanes and combustion chambers are protected against high temperature oxidation and corrosion by single or multilayered coatings. These include environmental coatings, generally based on Pt-modified Ni aluminides or MCrAlY overlays (where M = Ni and/or Co), thermal barrier coating (TBC) systems including a ceramic thermally insulating layer, and abradable seals. The present work shows the ability of the Spark Plasma Sintering technique to rapidly develop new coatings compositions and microstructures. This technique allows combining powders and metallic foils on a superalloy substrate in order to obtain multilayered coatings in a single short production step. Fabrication of MCrAlY overlays with local Pt and/or Al enrichments is shown, as well as fabrication of coatings made of z-PtAl2, e-PtAl, α-AlNiPt2, martensitic and b−(Ni,Pt)Al or Pt-rich g/g’ phases, including their doping with reactive elements. The fabrication of a complete TBC system with a porous and adherent Yttria Stabilized Zirconia (YSZ) layer on a bond-coating is also demonstrated, as well as the fabrication of a CoNiCrAlY-based cermet coating for abradable seal application. Difficulties of fabrication are reviewed, such as Y segregation, risks of carburization, local over-heating, or difficulty to coat complex shaped parts. Solutions are given to overcome these difficulties

Thermal cycling behavior of EBPVD TBC systems deposited on doped Pt-rich γ–γ′ bond coatings made by Spark Plasma Sintering (SPS)

In the last decade, an increasing interest was given to Pt-rich γ–γ′ alloys and coatings as they have shown good oxidation and corrosion properties. In our previous work, Spark Plasma Sintering (SPS) has been proved to be a fast and efficient tool to fabricate coatings on superalloys including entire thermal barrier coating systems (TBC). In the present study, this technique was used to fabricate doped Pt-rich γ–γ′ bond coatings on AM1® superalloy substrate. The doping elements were reactive elements such as Hf, Y or Zr, Si and metallic additions of Ag. These samples were then coated by electron beam physical vapour deposition (EBPVD) with an yttria partially stabilized zirconia (YPSZ) thermal barrier coating. Such TBC systems with SPS Pt rich γ–γ′ bond coatings were compared to conventional TBC system composed of a β-(Ni,Pt)Al bond coating. Thermal cycling tests were performed during 1000-1 h cycles at 1100 °C under laboratory air. Spalling areas were monitored during this oxidation test. Most of the Pt rich γ–γ′ samples exhibited a better adherence of the ceramic layer than the β-samples. After the whole cyclic oxidation test, cross sections were prepared to characterize the thickness and the composition of the oxide scales by using scanning-electron microscopy. In particular, the influence of the doping elements on the oxide scale formation, the metal/oxide roughness, the TBC adherence and the remaining Al and Pt under the oxide scale were monitored. It was shown that RE-doping did not improve the oxidation kinetics of the studied Pt rich γ–γ′ bond coatings, nevertheless most of the compositions were superior to “classic” β-(Ni,Pt)Al bond coatings in terms of ceramic top coat adherence, due to lower rumpling kinetics and better oxide scale adherence of the γ–γ′-based systems

Effect of modification by Pt and manufacturing processes on the microstructure of two NiCoCrAlYTa bond coatings intended for thermal barrier system applications

Few studies have already shown that Pt influences the diffusion of aluminium and therefore the microstructure of β-NiAl or γ-Ni/γ′-Ni3Al materials. Besides, several works have revealed that the addition of Pt to MCrAlY (M = Ni and/or Co) improves the oxidation/corrosion behavior of the material. Nevertheless, very few data have been published on the microstructure of such modified MCrAlYs. Then, the present work deals with the addition of Pt to two NiCoCrAlYTa coatings that differ by their manufacturing process. Characterization is carried out in order to understand the influence of Pt diffusion but also the effect of the manufacturing process on the final microstructure. The collected data from XRD, SEM, EDS and TEM analyses reveal that an Al uphill diffusion occurs during heat treatment due to the presence of the Pt layer. The Al diffusion from the NiCoCrAlYTa bulk to the Pt-rich surface is so extensive that no more β-phase remains within the core of the coating. Pt may also dissolve TaC, precipitates largely present in the non-modified NiCoCrAlYTa coatings. In addition to Pt, the microstructure of the NiCoCrAlYTa prior to Pt deposition and heat treatment, dependent on the NiCoCrAlYTa manufacturing process, greatly influences the final microstructure