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.
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 900oC for 300-2600 h. An oxidation film with a four-layer structure is formed after oxidation at 900oC 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.
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)
Table 1 Chemical compositions of the DZ445 Ni-based superalloy
Fig.1 XRD spectra of the DZ445 Ni-based superalloy after the oxidation at 900oC for different time
Fig.2 SEM images of the surface of the DZ445 Ni-based superalloy oxidized at 900oC 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)
Area
O
Al
Cr
Ni
Ti
Ta
Co
A
61.83
2.04
17.00
11.32
5.94
0.08
1.79
B
60.28
25.25
4.40
7.96
1.08
0.03
1.00
Table 2 Elemental compositions of the oxidation scales of DZ445 Ni-based superalloy oxidized at 900oC for 500 h by EDS
Fig.3 SEM images of the cross-section of the DZ445 Ni-based superalloy oxidized at 900oC 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)
Oxide layer
Time / h
Al
Cr
Ta
Ti
Ni
O
Co
P1
300
1.11
32.03
0.00
2.05
1.77
62.64
0.40
500
3.32
19.35
0.18
3.59
10.65
58.36
4.56
915
0.69
28.19
0.06
1.60
5.38
62.54
1.54
1100
3.30
21.54
0.17
2.31
10.64
57.94
4.09
1500
1.76
16.81
0.12
7.12
14.59
55.35
4.24
1800
5.43
16.38
0.18
4.59
8.49
61.37
3.57
2200
2.69
20.75
0.07
1.52
11.36
58.75
4.87
2600
2.20
21.02
0.22
1.80
10.29
62.13
2.34
P2
300
4.58
11.30
6.14
8.11
1.13
68.61
0.15
500
2.63
10.42
6.49
7.64
5.98
65.13
1.72
915
1.09
6.72
9.37
8.36
4.51
69.75
0.23
1100
4.22
6.69
7.29
6.79
3.45
71.07
0.50
1500
1.36
10.97
6.95
8.65
7.00
63.13
1.96
1800
2.12
9.64
7.54
8.21
3.28
68.16
1.05
2200
1.53
8.89
7.14
8.03
4.85
68.33
1.23
2600
0.73
6.53
9.26
8.58
3.75
70.90
0.25
P3
300
-
-
-
-
-
-
-
500
24.43
3.55
0.82
1.21
11.94
56.75
1.32
915
14.27
3.04
1.14
1.03
15.43
64.82
0.28
1100
27.66
1.46
0.38
0.44
9.71
59.57
0.77
1500
23.14
3.90
0.21
0.28
17.83
53.29
1.34
1800
22.94
4.47
0.83
1.27
10.50
58.72
1.27
2200
21.70
4.67
0.20
0.62
15.97
55.44
1.40
2600
20.97
3.02
0.49
0.42
12.67
61.35
1.07
P4
300
36.55
0.77
0.18
0.24
2.62
59.12
0.51
500
33.37
2.30
0.32
0.41
3.14
59.47
0.99
915
34.07
1.97
0.19
0.30
4.56
58.05
0.88
1100
35.85
1.18
0.15
1.54
0.79
60.35
0.13
1500
35.53
1.52
0.06
0.29
3.90
57.92
0.78
1800
35.24
1.90
0.07
0.90
1.53
60.12
0.24
2200
33.48
1.30
0.11
0.57
4.41
59.45
0.69
2600
33.84
1.97
0.17
0.74
1.74
61.34
0.20
Table 3 Elemental compositions of different layers in the oxidation scales of DZ445 Ni-based superalloy oxidized at 900oC for different time by EDS
Fig.4 Thicknesses of the oxidizing layer of the DZ445 Ni-based superalloy after oxidizing at 900oC for different time in air
Fig.5 Isothermal oxidation kinetics curves of DZ445 Ni-based superalloy oxidized at 850oC for 950 h, 900oC for 2600 h, and 925oC 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
Time
n
K
E / (kJ·mol-1)
Before the formation of CrTaO4 layer
2.17
1.0 × 10-2 mg2·cm-4·h-1
325
Between the formation of subouter and subinner layer
4.17
1.93 × 10-3 mg3·cm-6·h-1
424
After the formation of subinner layer
25.00
3.5 × 10-5 mg25·cm-50·h-1
485
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 900oC
Oxide
ΔG
Oxide
ΔG
NiO
-279.2
NiCr2O4
-826.2
Cr2O3
-547.1
CrTaO4
-580.3
TiO2
-733.4
CoO
-274.9
Al2O3
-869.2
WO2
-379.7
Ta2O5
-613.5
MoO2
-382.9
Table 5 Gibbs free energies (ΔG) of various oxides formation of DZ445 Ni-based superalloy at 900oC[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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