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.     

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.     

Sol-gel thermal barrier coatings: Optimization of the manufacturing route and durability under cyclic oxidation

A new promising and versatile process based on the sol-gel transformation has been developed to deposit yttria-stabilised thermal barrier coatings. The non-oriented microstructure with randomly structured pore network, resulting from the soft chemical process, is expected to show satisfactory thermo-mechanical behaviour when the TBC is cyclically oxidized. First stage of the research consists of optimizing the processing route to generate homogeneous microstructure and controlled surface roughness. The objective is to reduce, as much as possible, the size and depth of the surface cracks network inherent to the process. Indeed, the durability of the TBC when cyclically oxidized strongly depends on the sharpness of those cracks that concentrate thermo-mechanical stresses and generate detrimental propagation resulting in spallation. Cyclic oxidation tests are performed using a cyclic oxidation rig instrumented with CCD cameras to monitor in a real time basis the mechanism of crack propagation and spallation. The impact of various parameters either directly related to the processing route, e.g. the intimate microstructure of the TBC and the TBC thickness, or to the thermal loading, e.g. the oxidation temperature and the cumulated hot time, on the durability of the TBC is investigated.     

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 bond-coating creates stresses that greatly favour the thermal barrier spallation. To delay the loss of the thermal protection provided, research has focused on the bond-coating 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.     

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.     

Subsurface microstructural changes in a cast heat resisting alloy caused by high temperature corrosion

A cast HP ModNb alloy (Fe-25Cr-35Ni-1Nb, wt.%) was oxidised and carburised in CO-CO₂ corresponding to a_C = 0.1 and p_O2 = 3 × 10⁻¹⁶ atm at 1080 °C. Formation of an external, chromium-rich oxide scale led to depletion of this metal in a deep alloy subsurface zone. Within that zone, secondary chromium-rich carbides dissolved, primary carbides oxidised, solute silicon and aluminium internally oxidised, and extensive porosity developed. Pore volumes correspond to the difference between metal loss by scaling and metal displacement by internal oxidation, assuming the scale-metal interface to be fixed. The pores are concluded to be Kirkendall voids.     

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.