Multilayer Structure of DZ445 Ni-Based Superalloy Formed by Long Time Oxidation at High Temperature

doi:10.11900/0412.1961.2021.00482

Acta Metall Sin

2023, Vol. 59

Issue (3): 387-398 DOI: 10.11900/0412.1961.2021.00482

Research paper

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Multilayer Structure of DZ445 Ni-Based Superalloy Formed by Long Time Oxidation at High Temperature

LIU Laidi¹^,², DING Biao¹^,²(

), REN Weili¹^,²(

), ZHONG Yunbo¹^,², WANG Hui³, WANG Qiuliang³

1 State Key Laboratory of Advanced Special Steel, School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China
2 Shanghai Key Laboratory of Advanced Ferrometallurgy, Shanghai University, Shanghai 200444, China
3 Institute of Electrical Engineering, Chinese Academy of Sciences, Beijing 100190, China

Cite this article:

LIU Laidi, DING Biao, REN Weili, ZHONG Yunbo, WANG Hui, WANG Qiuliang. Multilayer Structure of DZ445 Ni-Based Superalloy Formed by Long Time Oxidation at High Temperature. Acta Metall Sin, 2023, 59(3): 387-398.

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Abstract

Nickel-based superalloys have been widely used in aero engines and gas turbines because of their excellent high-temperature strength and exceptional oxidation resistance. The oxidation resistance is obtained using the thermal barrier coatings and alloying elements. In the previous investigations, the oxidation time of the nickel-based superalloys has been focused on hundreds of hours. However, in practice, the superalloys last far longer. This study investigated the superalloy DZ445's oxidation behavior at 900^oC for 300-2600 h. An oxidation film with a four-layer structure is formed after oxidation at 900^oC for 500 h and above. The outermost layer is primarily composed of NiCr₂O₄, Cr₂O₃, and TiO₂. The subouter layer consists of CrTaO₄ and TiO₂, and the subinner layer consists of Al₂O₃, NiCr₂O₄, and NiO. The innermost layer is primarily Al₂O₃. The appearances of the subouter layer and subinner layer greatly reduce the oxidation rate of the alloy, which is represented by the dramatic increase in the oxidation kinetics equation exponent and a sharp reduction of the oxidation rate constant. The formation of subouter layer changes the oxidation mechanism from outward diffusion of alloy elements to O-inward diffusion. When the subinner layer is formed, the oxidation behavior is controlled using the outward diffusion of Ni and Cr and the O-inward diffusion. The multilayer structure gave the alloy an excellent oxidation resistance capacity.

Key words: Ni-based superalloy oxidation multi-layer structure oxide film

Received: 12 November 2021

ZTFLH:

TG132.3

Fund: National Natural Science Foundation of China(51871142);Independent Research and Development Project of State Key Laboratory of Advanced Special Steel, Shanghai Key Laboratory of Advanced Ferrometallurgy, Shanghai University(SKLASS 2020-Z04);Science and Technology Commission of Shanghai Municipality(19DZ2270200)

About author: DING Biao, Tel: 15026981773, E-mail: dingbiao312@126.com
REN Weili, professor, Tel: 15902176956, E-mail: wlren@staff.shu.edu.cn;

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	Laidi LIU
	Biao DING
	Weili REN
	Yunbo ZHONG
	Hui WANG
	Qiuliang WANG

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https://www.ams.org.cn/EN/10.11900/0412.1961.2021.00482 OR https://www.ams.org.cn/EN/Y2023/V59/I3/387

Table 1 Chemical compositions of the DZ445 Ni-based superalloy

Fig.1 XRD spectra of the DZ445 Ni-based superalloy after the oxidation at 900^oC for different time

Fig.2 SEM images of the surface of the DZ445 Ni-based superalloy oxidized at 900^oC for 500 h (a), 915 h (b), 1100 h (c), 1500 h (d), 1800 h (e), 2200 h (f), and 2600 h (g) (A and B in Fig.2a indicate bright white part and dark black part of oxide film, respectively)

Table 2 Elemental compositions of the oxidation scales of DZ445 Ni-based superalloy oxidized at 900^oC for 500 h by EDS

Fig.3 SEM images of the cross-section of the DZ445 Ni-based superalloy oxidized at 900^oC for 300 h (a), 500 h (b), 915 h (c), 1100 h (d), 1500 h (e), 1800 h (f), 2200 h (g), and 2600 h (h) (P1, P2, P3, and P4 indicate the outermost layer, subouter layer, subinner layer, and innermost layer, respectively. The bright edge on the top of the outermost layer is nickel plated)

Table 3 Elemental compositions of different layers in the oxidation scales of DZ445 Ni-based superalloy oxidized at 900^oC for different time by EDS

Fig.4 Thicknesses of the oxidizing layer of the DZ445 Ni-based superalloy after oxidizing at 900^oC for different time in air

Fig.5 Isothermal oxidation kinetics curves of DZ445 Ni-based superalloy oxidized at 850^oC for 950 h, 900^oC for 2600 h, and 925^oC for 910 h

Fig.6 Double logarithmic graphs of the mass gain (ΔW) and oxidation time (t) at different temperatures

Fig.7 Logarithm of lnK plotted against the temperature reciprocal (1 / T) before and after the formation of the continuous subouter layer and subinner layer

Table 4 Oxidation kenetics equation exponent (n), oxidation rate constant (K), and activation energy (E) before and after the formation of continuous CrTaO₄ layer and subinner layer at 900^oC

Table 5 Gibbs free energies (ΔG) of various oxides formation of DZ445 Ni-based superalloy at 900^oC^[17,21,23]

Fig.8 Crystal structures of oxides CrTaO₄ (a), NiCr₂O₄ (b), Cr₂O₃ (c), and Al₂O₃ (d)

Fig.9 Concentration gradient distribution curves of alloy elements Al, Ni, and Cr from the innermost layer (or subinner layer) to the matrix after oxidation for 300 h (a) and 500 h (b)

Fig.10 Schematics of oxidation process
(a) before the formation of CrTaO₄ layer
(b) between the formation of CrTaO₄ layer and subinner layer
(c) after the formation of subinner layer

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