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Title: Processing, characterisation and oxidation study of the nickel aluminides (βNiAl) for thermal barrier coating applications
Author: Chandio, Ali Dad
ISNI:       0000 0004 5993 8431
Awarding Body: University of Manchester
Current Institution: University of Manchester
Date of Award: 2015
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Superalloys used in aeroengines are designed to offer superior strength at increasingly higher operating temperatures. In order to optimise the working efficiency and provide additional protection to the components such as turbine blades; a thermal barrier coating (TBC) system is applied. The TBC is a multilayer system consisting of mainly two layers i.e. bond coat (BC) and topcoat (TC). In addition, a third layer grows between the TC and BC during oxidation known as a reaction layer or thermally grown oxide (TGO). The function of the TC (usually, yttria stabilised zirconia (YSZ)) is to provide thermal insulation to aeroengine parts or reduce their surface temperatures; whereas, the BC provides binding between the TC and the substrate, and oxidation resistance to the underlying alloy by forming an adherent and continuous oxide i.e. α-Al2O3. During service, in the absence of mechanical damage to the TBC, most failures are attributed to the BC performance. The most frequently adopted BCs are; β-(Pt, Ni)Al, Pt-γ-Ni/γ’-Ni3Al and MCrAlY. In addition, reactive elements (REs) are incorporated in the BCs due to their ability to enhance oxidation resistance significantly. In the present study βNiAl based coatings/BCs and alloys with and without REs (Zr and Hf) and Pt were prepared. For the coatings CMSX-4 single crystal superalloy was used as a substrate material and pack aluminising/cementation or in-situ chemical vapour deposition (CVD) as a coating process. The isothermal oxidation testing was carried out at 1150oC for 50 and 100 hours in air. The preparation and oxidation performance of a δNi2Al3 coating was carried out, as, this is a starting material for βNiAl matrix based coatings/or BCs. The oxidation of δNi2Al3 coating showed large volumetric changes (thickness variations), multiphase TGO, TGO/coating interface melting and spallation during oxidation. In contrast, the ‘simple βNiAl’ coating (or βNiAl matrix) was found to exhibit comparably enhanced thermal stability than that of the δNi2Al3 coating. Moreover, a detailed study of the simple βNiAl coating was also carried out in order to understand the oxidation performance. The coating before oxidation in the as-deposited condition was found to contain residual compressive stresses of 140 – 200 MPa. In contrast, after oxidation analysis exhibited substantial interdiffusion between the coating and the substrate resulting in a large reduction of the Al content and influx of substrate elements into the coating. This in turn caused coating transformation from βNiAl to the γ’-Ni3Al phase and formation of a multiphase TGO (TiO2, NiAl2O4, and ϴ-Al2O3 intrusion in α-Al2O3). Moreover, the degree of the TGO spallation and residual stresses increased with the oxidation time. In order to enhance the oxidation performance of the βNiAl coatings, the substrate pre-treatment was carried out i.e. CMSX-4 superalloy was electrolytically etched to remove the γ-Ni phase and fabricate βNiAl coatings on the remaining γ’-Ni3Al. This coating is termed as E-βNiAl. In comparison to simple βNiAl, the E-βNiAl coating showed improved spallation resistance. However, E-βNiAl revealed increased surface area due to etching of the substrate and triggered fast TGO growth rates when tested in an un-polished condition. Furthermore, simple βNiAl coatings were doped with Zr and Hf separately using a two-step aluminising method. The appropriate addition of either Zr or Hf was found to reduce the substrate elements (W, Ta, Cr and Ti etc.) in the coating before and after oxidation. After oxidation, examination of the presence of Zr or Hf in the coating was found to confirm the commonly reported beneficial effects. The TGOs grown on these coatings were almost pure α-Al2O3 which subsequently reduced growth and stresses. In addition to Zr/& Hf doped coatings, a study on Hf and Zr doped βNiAl bulk alloys was also carried out in order to understand the dopant effects on the oxidation resistance of βNiAl alloys in the absence of interdiffusion (as in case of coatings). In general, the commonly reported oxidation benefits were confirmed by the addition of these elements such as reduced TGO growth, oxide pegging, a columnar morphology of the TGO and segregation of REs at alumina grain boundaries etc. In addition, two more beneficial effects are suggested to be the ‘TGO crack filling up (or crack-healing)’ and formation of the ‘dense-TGO’. Within this study, the investigation of commercially available Pt-βNiAl BC was also carried out in air and vacuum atmospheres. The results demonstrated that the initial chemistry and elemental distribution (particularly Al/& Pt) was found to affect the TGO growth and phases significantly. In addition to its well established beneficial effects, the main effect of a Pt addition is suggested to be the stabilisation of the βNiAl structure even at a lower Al content.
Supervisor: Xiao, Ping Sponsor: NED University of Engineering & Technology, Karachi, Pakistan ; University of Manchester
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Thermal Barrier Coatings ; Nickel Aluminides ; Bond Coat ; REs-modifed ßNiAl Coatings and Alloys ; Pt-ßNiAl Bond Coat