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Surface & Coatings Technology 205 (2010) 12411244

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Surface & Coatings Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s u r f c o a t

Simultaneous synthesis by spark plasma sintering of a thermal barrier coating system with a NiCrAlY bond coat
Jianrong Song a,b, Kaka Ma a, Lianmeng Zhang b, Julie M. Schoenung a,
a b

Department of Chemical Engineering and Materials Science, University of California-Davis, One Shields Avenue; Davis, CA 95616, USA Department of Materials Science and Engineering, Wuhan University of Technology, 122 Luoshi Rd.; Wuhan, Hubei 430070, China

a r t i c l e

i n f o

a b s t r a c t
As-fabricated thermal barrier coating (TBC) systems generally consist of a superalloy substrate, a MCrAlY bond coat (M = Ni, Co, Fe), and a ceramic (usually partially stabilized zirconia) top coat. The conventional methods for producing the two coating layers generally derive from thermal spray and physical vapor deposition techniques. Thermal exposure leads to the formation of an additional layer: the thermally grown oxide (TGO) between the bond coat and top coat. In the present work, a TBC system is synthesized through the application of spark plasma sintering (SPS), which provides not only the opportunity to synthesize all three layers at once, but the process is quite rapid and can produce dense layers. More specically, this paper describes the application of this method to an yttria-stabilized ZrO2 (YSZ) top coat and a NiCrAlY bond coat on a Ni-base Hastelloy X substrate. A one-micron thick Al2O3 TGO layer is also created from the reaction between an Al foil layer inserted in the stack prior to sintering and the ZrO2 in the top coat. The effects of select process conditions are considered. The resulting multi-layer system is characterized with optical microscopy, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), energy dispersive X-ray analysis (EDAX) and X-ray diffraction (XRD). Differential thermal analysis (DTA) is used to investigate the reaction between the Al foil and the YSZ top coat. 2010 Elsevier B.V. All rights reserved.

Available online 20 August 2010 Keywords: Thermal barrier coatings In-situ TGO Spark plasma sintering Simultaneous synthesis

1. Introduction Yttria-stabilized zirconia (YSZ) thermal barrier coatings (TBCs) have been widely used in gas turbine engine applications to protect the blade alloy in the hot section [1]. The YSZ TBCs can be considered as a four-layer material system, consisting of: (1) a superalloy substrate; (2) an oxidation-resistant metallic bond coat, usually MCrAlY or platinum aluminized coating; (3) a thermally grown oxide (TGO), typically -alumina, usually formed during heat treatment and/or in service; and (4) the YSZ ceramic top coating, usually 68 wt. % yttria-stabilized zirconia deposited either by plasma spraying or electron beam physical vapor deposition [2]. Development of such complex TBCs usually requires multiple fabrication steps, each of which needs to be optimized to produce the desirable material structure and associated properties [3]. Spark plasma sintering (SPS) is a novel sintering technique with the characteristics of higher heating rate and shorter dwell times when compared to conventional pressure-assisted sintering methods [4], which enhances sintering activity and leads to limited grain growth [5]. In previous studies, SPS has been explored as a new

method for coating fabrication, demonstrating the capability of fabricating coatings with a wide range of dened compositions or building complex multilayered structures [6]. Multi-layer coatings with combinations of Pt-modied Ni aluminides, MCrAlY and YSZ/Pt/ Al have been successfully fabricated by SPS [7]. NiCoCrAlYTa single and multilayered coatings were applied on a nickel base superalloy substrate by SPS, resulting in homogenous structures with good adherence and excellent high temperature properties [6,8]. However, the fabrication of YSZ TBCs with an in-situ synthesized Al2O3 TGO intermediate layer has not been previously reported. In the current research, the SPS technique was utilized to simultaneously produce 7YSZ/Al2O3/NiCrAlY multi-layer coatings on superalloy substrates, with the Al2O3 TGO layer being synthesized in-situ from Al foil during the fabrication process, thus eliminating the need for multiple process steps.

2. Experimental procedure This work was conducted using 20 mm diameter discs, prepared from a HASTELLOY X alloy plate by electrical discharge machining (EDM), as substrates. Commercial Ni22Cr10Al1Y (wt.%) powder (Ni-343 alloy) from Praxair Surface Technologies-Tafa was used for the bond coat. The average particle size for this powder was 12 m

Corresponding author. Tel.: +1 530 752 5840; fax: +1 530 752 9554. E-mail address: (J.M. Schoenung). 0257-8972/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.surfcoat.2010.08.064


J. Song et al. / Surface & Coatings Technology 205 (2010) 12411244

microscopy (HR-TEM). Differential thermal analysis (DTA) was conducted with a Thermogravimetric Analyzer (TGA 7 from Perkin Elmer Inc.). The X-ray diffraction (XRD) patterns were generated with a Philips X-ray diffractometer. 3. Results and discussion In the SPS process, the densication of the sample can be observed through the displacement of the plungers. Through the plungers displacement detector, the relationship between densication and temperature is described, as shown in Fig. 1. Positive values for displacement correspond to samples' shrinkage. For temperatures greater than 567 C, the temperature of the sample is measured by an infrared high precision thermometer. In the present study, it is observed that shrinkage only occurs in the temperature range of 572 C to 607 C, which is due to the melting of Al foil. Throughout the rest of the temperature range, expansion is observed. The change in displacement is determined by the consolidation behavior of the green body and the thermal expansion of the dense body [9]. In these multiple coating samples, the thermal expansion of dense superalloy substrate plays a critical role in the displacement change (i.e., expansion) during the SPS process. Fig. 2a shows the as-sintered TBC on the substrate, and Fig. 2b shows a schematic illustration with the dimensions of the sample. The top coat of the as-sintered TBC appeared black, due to the reduction of the YSZ. The top coat changed to white (the normal color of YSZ) after annealing the sample at 900 C in air for 1 h. From the radial direction, there are four layers in the TBC system (as shown in Fig. 2b): 7YSZ top coat (~500 m thick), Al2O3 TGO (~1 m thick), NiCrAlY bond coat (~150 m thick), and Hastelloy X substrate (5 mm). This conguration of layers is essentially equivalent to that of a conventional sprayed TBC system after mild thermal exposure [10]. Fig. 3 shows the backscattered electron image of a representative cross section of the TBC sample produced by SPS, and higher magnication images of the interfacial regions. The relative density of the 7YSZ top coat and NiCrAlY bond coat was determined by using image analysis software. The relative density of the 7YSZ top coat is approximately 75%, as evidenced by the porosity (the black regions in the top coat), which is easily distinguished in secondary electron images (not shown here). The NiCrAlY bond coat layer is fully dense and consists of three phases, as determined through EDAX and HRTEM with electron diffraction (not shown here): -Ni(Cr) solid solution (dark gray), -NiAl (light gray), and a CrO phase (black spots). The CrO phase, although not commonly described within this alloy system, has been observed in our previous work [11] and was conrmed by HR-TEM. The stability and role of this phase is being further investigated, but is beyond the scope of the present study. It is further observed that, as expected and previously noted [12], there is

Fig. 1. Temperature and displacement curve in SPS process.

and the average grain size was 1 m. The top coat was fabricated from commercial 7YSZ (7 wt.% yttria-stabilized zirconia) powder from Inframat Corporation with an average particle size of 100 m and an average grain size of 20 nm. Pure Al foil with a thickness of 7 m was positioned between the 7YSZ powder and the NiCrAlY powder in order to generate the Al2O3 TGO and to keep the interface at and homogeneous after sintering. The powders were carefully weighed and poured into a graphite die (the inner diameter was 20 mm) after rst inserting the superalloy disc. A hydrostatic pressure of 25 MPa was applied to increase the green density prior to sintering. The sample was sintered by SPS (SPS 825 S system fabricated by DR. Sinter Inc.) under a uniaxial 30 MPa and a vacuum of 4 Pa, both of which were maintained throughout the sintering process. The pulse duration was 3.3 ms, and one pulse sequence contained 12 pulses, while the interval between pulse sequence was 6.6 ms. The pulse-sequence current averaged 2000 A during the sintering process. The heating rate was 100 C/min, and the sintering temperature was 1100 C. The soaking time was 1 min at 600 C and 3 min at 1100 C. After sintering, the surfaces of the samples were polished with ne grit to remove the region into which the carbon had diffused. The microstructure of the sintered coating samples was characterized by optical microscopy and further analysis was performed with a Phillips FEI XL30-SFEG scanning electron microscope (SEM) equipped with an energy dispersive X-ray spectroscopy (EDAX) system and JEOL JEM-2500 high-resolution transmission electron

Fig. 2. (a) The morphology of the as-sintered TBC on the superalloy substrate; (b) schematic illustration showing layers and approximate thickness values.

J. Song et al. / Surface & Coatings Technology 205 (2010) 12411244


Fig. 3. A representative microstructural image of the top coat, bond coat, alumina TGO layer, and the interfacial regions between layers.

no internal oxidation since there are no splat boundaries and the oxygen concentration during sintering is very low due to the vacuum applied during SPS. It is clear to see in the high magnication images that there are no pores, cracks or reaction products at the interfaces; rather, these interfaces are clean and homogeneous, which should result in good interfacial adhesion. The thin black layer in Fig. 3 is the Al2O3 TGO intentionally created through the reaction of the Al foil with ZrO2 in the 7YSZ top coat. In a conventional TBC, this layer would develop during thermal exposure, but can be non-uniform in both composition and thickness [13]. Here, the TGO layer is of uniform composition and thickness, which is benecial for reduced stress concentrations and improved thermal fatigue [14]. The reaction between the Al foil and the ZrO2 in the 7YSZ top coat was studied in more detail by using DTA and XRD. A mixture of Al foil and 7YSZ powder was loaded into a crucible, and heated to 1400 C at a rate of 10 C/min in a owing ultra-high purity argon atmosphere (99.999% pure). The DTA curve is shown in Fig. 4. During heating, there was an endothermic trough at 655.8 C, indicating the melting

of the Al foil. The exothermic peak observed at 1043.1 C corresponds to the reaction between the Al and the ZrO2. Due to the excess of Al in the system, on cooling there was an exothermic peak at 618.2 C, corresponding to the solidication of Al. It is noted that the intensity of this exothermic peak was lower than that of the melting endothermic trough due to the reaction of some Al with the ZrO2. Fig. 5 shows the phase identication results for the reaction product as determined by XRD. The peaks for Zr and Al2O3 are clearly observed in the XRD pattern, as well as peaks for the residual Al and ZrO2. The results indicate that the Al was indeed oxidized by the ZrO2 as described by the following chemical equation: Al + ZrO2 Zr + Al2O3. The chemical reduction of Zr is consistent with the observation that the top coat was black after sintering [15], but then became white after the short-term anneal in oxygen (leading to the reoxidation of the Zr). To further verify that the Al was not simply reacting with oxygen in the system, an additional DTA test without the ZrO2 present was carried out, the results of which did not exhibit the reaction peak.

Fig. 4. DTA curve for the Al foil and the 7YSZ powder.

Fig. 5. The XRD patterns for the reaction product.


J. Song et al. / Surface & Coatings Technology 205 (2010) 12411244

4. Conclusions Multiple-layer TBCs consisting of 7YSZ/Al2O3/NiCrAlY layers on a Ni superalloy substrate were produced simultaneously by using SPS at 1100 C under 30 MPa uniaxial pressure. Commercially available feedstock powders were used for the YSZ and NiCrAlY layers; the onemicron thick Al2O3 layer, however, was the product of the reaction between an Al foil layer and the ZrO2 in the 7YSZ top coat, as studied by DTA and XRD. The microstructures of the as-sintered layers are similar to those in conventional TBCs made through thermal spray methods; the Al2O3 layer is at and homogeneous. Acknowledgements Financial support was provided by the U.S. Ofce of Naval Research (ONR) through Grant N00014-06-1-0506 and the China Scholarship Council (CSC) through the Government-sponsored Overseas Study Program.

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