Unveiling the mechanism of yttrium significantly improving high-temperature oxidation resistance of super-austenitic stainless steel S32654

doi:10.1016/j.jmst.2022.01.001

Abstract

Abstract:

Aiming at serious catastrophic oxidation problem of super-austenitic stainless steel S32654, the influence of different rare earth elements on its oxidation behavior was comparatively investigated at 1200 °C. The mechanism of Y significantly improving high-temperature oxidation resistance of S32654 was unveiled. The results demonstrated that Y played much better beneficial roles than Ce and La in the initial formation of oxide layer: (1) Y promoted Cr segregation to steel surface to combine with O; (2) its preferential oxidation provided nucleation cores for Cr₂O₃. Both roles jointly promoted the selective oxidation of Cr and then the formation of protective Cr-rich oxide layer. This provided good prerequisites for inhibiting the formation and volatilization of MoO₃. Additionally, Y cation segregation to oxide grain boundaries further promoted the selective oxidation of Cr and Si to form more protective oxide layer. These beneficial roles of Y essentially eliminated the synergistic effects of MoO₃ volatilization and lamellar Cr₂N precipitation on catastrophic oxidation. Accordingly, the oxidation resistance of Y-bearing S32654 was improved by 22%-45%.

Key words: Super-austenitic stainless steel, Rare earth elements, Yttrium, Oxidation, MoO₃ volatilization, Cr₂N precipitation

Shucai Zhang, Huabing Li, Zhouhua Jiang, Hao Feng, Zhejian Wen, Junyu Ren, Peide Han. Unveiling the mechanism of yttrium significantly improving high-temperature oxidation resistance of super-austenitic stainless steel S32654[J]. J. Mater. Sci. Technol., 2022, 115: 103-114.

Figures/Tables 14

Table 1. Chemical compositions of experimental super-austenitic stainless steels S32654 (wt.%).

Steel	C	Si	Mn	P	S	Cr	Ni	Mo	Cu	N	Ce	La	Y	Fe
RE-free	0.013	0.40	3.00	0.005	0.002	24.51	22.48	7.29	0.51	0.50	-	-	-	Bal.
0.01Ce	0.015	0.39	3.03	0.005	0.002	24.48	22.51	7.28	0.48	0.50	0.01	-	-	Bal.
0.01La	0.014	0.41	3.05	0.005	0.002	24.50	22.49	7.30	0.50	0.50	-	0.01	-	Bal.
0.01Y	0.015	0.40	3.02	0.005	0.002	24.52	22.53	7.33	0.49	0.50	-	-	0.01	Bal.

Fig. 1. Macro-morphologies of S32654 samples before and after oxidation at 1200 °C for 1-5 h.

Fig. 2. Weight losses of S32654 samples after isothermal oxidation at 1200 °C for 1-5 h.

Fig. 3. XRD patterns of S32654 samples after oxidation at 1200 °C for 1 h: (a) surface oxide layer and (b) residual oxide layer.

Fig. 4. SEM surface morphologies of S32654 samples after oxidation at 1200 °C for 1 h: (a) RE-free, (b) 0.01Ce, (c) 0.01La and (d) 0.01Y.

Table 2. Chemical compositions of typical oxides in the surface oxide layer of S32654 samples after oxidation at 1200 °C for 1 h.

EDS point	Fe	Cr	Ni	Mo	Mn	O
A₁	45.23	7.58	21.53	0.00	1.95	23.71
A₂	43.09	9.08	21.23	0.00	2.21	24.39
A₃	44.03	8.13	19.29	0.00	1.81	26.74
A₄	43.52	9.52	20.45	0.00	1.45	25.06
B₁	23.91	2.59	9.04	36.79	5.52	22.15
B₂	21.65	2.79	7.51	34.59	5.66	27.80
B₃	22.81	2.18	7.98	32.51	6.54	27.98
B₄	24.12	3.47	9.21	28.86	4.54	29.80

Fig. 5. SEM cross-section morphologies and EDS element maps of S32654 samples after oxidation at 1200 °C for 1 h: (a) RE-free, (b) 0.01Ce, (c) 0.01La and (d) 0.01Y.

Fig. 6. Simulational models of FeCrMo(O) structure: (a) the surface without Cr atom and the sub-surface without RE atom (1, 2 and 3 indicate the exchange positions of Cr and Mo atom) and (b) the surface with 50% Cr atom and the sub-surface with one or two RE atoms (1 and 2 indicate the positions where the first and second RE atoms are introduced).

Fig. 7. The addition of RE atom on the segregation and binding energy: (a) the segregation energy of Cr towards the surface and (b) the binding energy between O and the surface.

Fig. 8. The addition of RE atom on the Cr-O bond length and the charge-density diagram.

Fig. 9. Standard Gibbs free energies of Ce, La, Y and the main alloying elements in S32654 reacting with O2.

Fig. 10. SEM surface morphologies of S32654 samples after oxidation at 1200 °C for 3 min: (a) RE-free, (b) 0.01Ce, (c) 0.01La and (d) 0.01Y.

Table 3. Ionic radius of trivalent rare earth cation and volume of RE2O3 [54,55].

RE³⁺	Ionic radius (pm)	Coordination number	RE₂O₃	Volume (Å³)	Space group
Ce³⁺	102.0	6	Ce₂O₃	77.169	$P\bar{3}m1$
La³⁺	103.2	6	La₂O₃	83.017	$P\bar{3}m1$
Y³⁺	90.0	6	Y₂O₃	69.708	$P\bar{3}m1$

Fig. 11. TEM bright-field images and EDS spectra of the oxide grain boundaries in the S32654 samples after oxidation at 1200 °C for 2 min: (a) 0.01Ce, (b) 0.01La and (c) 0.01Y.

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