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Acta Metall Sin  2015, Vol. 51 Issue (6): 693-700    DOI: 10.11900/0412.1961.2014.00498
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MICROSTRUCTURE AND OXIDATION BEHAVIOR OF ZrSi2-NbSi2 MULTILAYER COATINGS ON AN Nb-Ti-Si-Cr BASE ULTRAHIGH TEMPERATURE ALLOY
Xuan LI,Xiping GUO(),Yanqiang QIAO
State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi'an 710072
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Xuan LI, Xiping GUO, Yanqiang QIAO. MICROSTRUCTURE AND OXIDATION BEHAVIOR OF ZrSi2-NbSi2 MULTILAYER COATINGS ON AN Nb-Ti-Si-Cr BASE ULTRAHIGH TEMPERATURE ALLOY. Acta Metall Sin, 2015, 51(6): 693-700.

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Abstract  

The rather poor oxidation resistance of Nb-Si base ultrahigh temperature alloys has seriously limited their practical applications at high temperatures. Niobium disilicide coatings, especially those modified by reactive elements (RE) such as Zr and Y, have been shown to possess good anti-oxidation properties at high temperatures due to the formation of a protective RE-containing SiO2 scale. Halide activated pack cementation (HAPC) is one of the most widely used techniques for preparing protective coatings on Nb-Si base ultrahigh temperature alloys, because compact coatings and metallurgical substrate/coating bonds can be obtained with using this technique. However, only a very limited amount of Zr and Y can be diffused into the coatings by a single co-deposition pack cementation process as a result of their large atomic radii and high melting points. To solve this problem, a method such as magnetron sputtering, which can be used for producing overlay coatings with different composition ratios of coating elements, seems to be feasible. In the present study, ZrSi2-NbSi2 multilayer coatings were prepared on an Nb-Ti-Si-Cr base ultrahigh temperature alloy by first magnetron sputtering 2 μm thick Zr-film, and then Si-Y co-deposition at respectively 1150, 1250 and 1350 ℃ by HAPC process. The structures and formation processes, as well as the static oxidation behavior of the coatings were investigated. The results show that the coating prepared at respectively 1150, 1250 and 1350 ℃ had similar structures, consisting of a ZrSi2 outer layer, a (Nb, X)Si2 (X=Ti, Cr, Zr and Hf) middle layer and a (Ti, Nb)5Si4 inner layer. However, the higher co-deposition temperature (1350 ℃) could cause cracks at the interfaces between the constituent layers of the coatings. The formation of the coating was dominated by inward diffusion of Si, accompanied with a certain degree of outward diffusion of Nb, Ti and Cr from the base alloy during the second Si-Y co-deposition process. The oxidation tests demonstrated that the ZrSi2-NbSi2 multilayer coating possessed excellent oxidation resistance. After oxidation, a dense scale consisting of SiO2, TiO2, ZrSiO4 and Cr2O3 formed on the coating, which can protect the base alloy from oxidation at least for 100 h at 1250 ℃ in air.

Key words:  Nb-Ti-Si-Cr base ultrahigh temperature alloy      ZrSi2-NbSi2 multilayer coating      structural formation      oxidation-resistant performance     
Fund: Supported by National Natural Science Foundation of China (Nos.51371145, 51431003 and U1435201), Programme of Introducing Talents of Discipline to Universities of China (No.B080401) and Fund of State Key Laboratory of Solidification Processing in NWPU (No.116-QP-2014)

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https://www.ams.org.cn/EN/10.11900/0412.1961.2014.00498     OR     https://www.ams.org.cn/EN/Y2015/V51/I6/693

Fig.1  Preparation processes of the Zr-Y modified slicide compound coatings
Fig.2  Cross-sectional SEM-BSE images (a, c, e) and element concentration profiles (b, d, f) of the ZrSi2-NbSi2 multilayer coatings prepared at 1150 ℃ (a, b), 1250 ℃ (c, d) and 1350 ℃ (e, f) for 4 h (X=Ti, Cr, Zr, Hf) (Vertical arrow in Fig.2a represents the analyses direction for the elements in Fig.2b, and inset in Fig.2c shows the enlarged view of square area)
Point Nb Si Ti Al Cr Zr Y Hf
1 0.8 66.2 3.9 - 2.3 25.5 0.7 0.6
2 4.5 67.3 9.9 0.4 10.2 5.9 0.7 1.1
3 15.9 65.1 8.0 - 8.1 1.1 0.6 1.2
  
Fig.3  XRD spectra on the surface, middle layer and inner layer of the ZrSi2-NbSi2 multilayer coating prepared at 1250 ℃ for 4 h
Fig.4  Cross-sectional SEM-BSE image (a) and element concentration profile (b) of the interface between the Zr film and base alloy after inter-diffusion at 1250 ℃ for 4 h (Vertical arrow in Fig.4a represents the analyses direction for the elements in Fig.4b)
Fig.5  SEM-BSE image (a) and XRD spectrum (b) of the surface of ZrSi2-NbSi2 multilayer coating after oxidation at 1250 ℃ for 100 h (Inset shows the macrograph morphology of the coated specimen after oxidation)
Fig.6  Low (a) and locally high magnified (b) cross-sectional SEM-BSE images of the coating after oxidation at 1250 ℃ for 100 h
Fig.7  Calculated free energy changes for 1 mole of ZrO2 to react with 1 mole of SiO2 at different temperatures (ΔG0—standard Gibbs free energy of formation of compound)
Constituent phase Si Zr Ti Al Cr Nb Y O
SiO2 22.6 - 1.1 4.0 0.2 - 0.7 71.4
ZrSiO4 14.4 14.1 1.0 1.1 0.4 0.6 0.3 68.1
TiO2 0.4 1.1 22.4 0.7 0.4 1.1 - 73.9
Cr2O3 2.9 - 0.8 3.5 29.5 0.3 - 63.0
  
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