Magnetic transformation of Mn from anti-ferromagnetism to ferromagnetism in FeCoNiZMnx (Z = Si, Al, Sn, Ge) high entropy alloys

doi:10.1016/j.jmst.2020.06.040

Abstract

Abstract:

We design high entropy alloys (HEAs) with different induction elements (Si/Al/Sn). In order to keep the crystal structure invariant and to investigate how the increment in saturation magnetization (M_s) is caused only by the change of electron spin state, each set of HEAs contains a different amount of Mn. Synergistic effects among induction elements that induce the magnetic transformation of Mn from anti-ferromagnetism to ferromagnetism are found. M_s of added Mn reduces when a particular induction element (Si_0.4/Al_0.4/Sn_0.4) exists, while a larger increment of M_s appears when two induction elements coexist, Si_0.4Al_0.4 (25.79 emu/g) and Sn_0.4Al_0.4 (15.43 emu/g). This is reflected in the microcosmic magnetic structure for the emergence of closed domains due to large demagnetization energy, which is confirmed by the Lorentz transmission electron microscope (LTEM) data. The calculated magnetic moments and the exchange integral constants from density functional theory based on the Exact Muffin-Tin Orbits formalism reveal that the magnetic state and the strength of ferromagnetic and anti-ferromagnetic coupling determine the variation of M_s in different chemical environments. The difference in energy levels of coexisting multiple induction elements also leads to a larger increment of M_s, Si_0.4Al_0.4Sn_0.4 (29.78 emu/g), and Si_0.4Al_0.4Ge_0.4Sn_0.4 (31.00 emu/g).

Key words: High entropy alloy, Magnetic transformation, Density functional theory, Magnetic moment, Exchange integral constants

Bin Zhang, Yuping Duan, Haifeng Zhang, Shuo Huang, Guojia Ma, Tongmin Wang, Xinglong Dong, . Magnetic transformation of Mn from anti-ferromagnetism to ferromagnetism in FeCoNiZMn_x (Z = Si, Al, Sn, Ge) high entropy alloys[J]. J. Mater. Sci. Technol., 2021, 68: 124-131.

Figures/Tables 7

Fig. 1. XRD patterns of (a) FeCoNiSi0.4Mnx, (b) FeCoNiAl0.4Mnx, and (c) FeCoNiSi0.4Al0.4Mnx HEAs with different Mn contents.

Table 1 The experimental and calculated LCs for FeCoNiSi0.4Mnx, FeCoNiAl0.4Mnx, and FeCoNiSi0.4Al0.4Mnx HEAs with different Mn contents.

Sample	Mn content (x)	LC (exp.)	Ratio (%)	LC (cal.)	Ratio (%)
FeCoNiSi_0.4Mn_x (FCC)	0	3.559	-	3.551	0.22
	0.4	3.567	0.22	3.555	0.34
	0.8	3.574	0.42	3.545	0.81
FeCoNiAl_0.4Mn_x (FCC)	0	3.579	-	3.590	-0.31
	0.4	3.590	0.31	3.575	0.42
	0.8	3.596	0.47	3.561	0.97
FeCoNiSi_0.4Al_0.4Mn_x (BCC)	0	2.841	-	2.843	-0.07
	0.2	2.844	0.11	2.847	-0.11
	0.4	2.863	0.77	2.851	0.42
	0.6	2.866	0.88	2.854	0.42
	0.8	2.870	1.02	2.857	0.45

Fig. 2. Curves of Ms with changing Mn contents for (a) FeCoNiSi0.4Mnx, (b) FeCoNiAl0.4Mnx, (c) FeCoNiSi0.4Al0.4Mnx, (d) FeCoNiAl0.4Sn0.4Mnx, (e) FeCoNiSi0.4Al0.4Sn0.4Mnx, and (f) FeCoNiSi0.4Al0.4Ge0.4Sn0.4Mnx HEAs. The three color charts indicate the corresponding increment of Ms with adding different Mn content into the original HEAs: aqua, $\Delta M_{s}$ (1) = Ms (x = 0.4) - Ms (x = 0); olive, $\Delta M_{s}$ (2) = Ms (x = 0.8) - Ms (x = 0.4); violet, $\Delta M_{s}$ (3) = Ms (x = 0.8) - Ms (x = 0).

Fig. 3. (a, d) Over-focused LTEM images for FeCoNiSi0.4Al0.4 and FeCoNiSi0.4Al0.4Mn0.4 HEAs with the corresponding SAED in the inset; (b, c) the in-plane magnetization distribution map for FeCoNiSi0.4Al0.4 HEA; (e) the enlarged picture for the olive green box in (d) with the corresponding under-focused magnetic domains images in the inset; (f) the magnetization distribution map for FeCoNiSi0.4Al0.4Mn0.4 HEA. (c, f) are the images for two samples after clockwise rotation of 45°. The green arrows represent the magnetization direction at each point.

Fig. 4. (a) Total DOS and (b) Mn d Partial DOS (PDOS) for FeCoNiSi0.4Mnx (top), FeCoNiAl0.4Mnx (middle), and FeCoNiSi0.4Al0.4Mnx (bottom) HEAs. The black, red, and blue curves represent the DOS of HEAs with the content of Mn of 0, 0.4, and 0.8.

Fig. 5. Magnetic moments of individual atoms and total magnetic moment in FeCoNiSi0.4Mnx (a-f), FeCoNiAl0.4Mnx (g-l), and FeCoNiSi0.4Al0.4Mnx (m-r) HEAs calculated from DFT at zero temperature. The magnetic moments of Si and Al are not presented here.

Fig. 6. Magnetic exchange interactions for FeCoNiSi0.4Mnx (a-c), FeCoNiAl0.4Mnx (d-f), and FeCoNiSi0.4Al0.4Mnx (g-i) HEAs as a function of the coordination shell, respectively. The enlarged pictures from the 2nd to 5th coordination shell are presented in Fig. S14.

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