Probing martensitic transformation, kinetics, elastic and magnetic properties of Ni2-xMn1.5In0.5Cox alloys

doi:10.1016/j.jmst.2020.01.034

Abstract

Abstract:

The martensitic transformation, kinetics, elastic and magnetic properties of the Ni_2-_xMn_1.5In_0.5Co_x (x = 0-0.33) ferromagnetic shape memory alloys were investigated experimentally and theoretically by first-principles calculations. First-principles calculations show that Co directly occupies the site of Ni sublattice, and Co atoms prefer to distribute evenly in the structure. The optimized lattice constants are consistent with the experimental results. The martensitic transformation paths are as follows: PA ↔ FA ↔ 6 M^FIM ↔ NM^FIM when 0 ≤ x < 0.25; PA ↔ FA ↔ 6 M^FM ↔ NM^FIM with 0.25 ≤ x < 0.3 and PA ↔ FA ↔ NM^FM with 0.3 ≤ x ≤ 0.33 for Ni_2-_xMn_1.5In_0.5Co_x (x = 0-0.33) alloys. The fundamental reasons for the decrease of T_M with increasing Co content are explained from the aspects of first-principles calculations and martensitic transformation kinetics. The component interval of the magnetostructural coupling is determined as 0 ≤ x ≤ 0.25 by first-principles calculations. Furthermore, the origin of the demagnetization effect during martensitic transformation is attributed to the shortening of the nearest neighboring distances for Ni-Ni (Co) and Mn-Mn. Combining the theoretical calculations with experimental results, it is verified that the T_M of the Co6 alloy is near room temperature and its magnetization difference ΔM is 94.6 emu/g. Therefore, magnetic materials with high performance can be obtained, which may be useful for new magnetic applications.

Key words: Ni-Mn-In-Co, First-principles calculations, Martensitic transformation, Kinetics, Elastic and magnetic property

Xinzeng Liang, Jing Bai, Jianglong Gu, Haile Yan, Yudong Zhang, Claude Esling, Xiang Zhao, Liang Zuo. Probing martensitic transformation, kinetics, elastic and magnetic properties of Ni_2-_xMn_1.5In_0.5Co_x alloys[J]. J. Mater. Sci. Technol., 2020, 44: 31-41.

Figures/Tables 18

Table 1 Correspondence between computational and experimental components.

	Co0	Co1	Co2	Co3	Co4	Co5	Co6
Ni_2-_xMn_1.5In_0.5Co_x	x = 0	-	x = 0.833	-	x = 0.167	-	x = 0.25	x = 0.33
Ni_50-yMn_37.5In_12.5Co_y (at.%)	y = 0	y = 1.04	y = 2.08	y = 3.13	y = 4.17	y = 5.21	y = 6.25	y = 8.33

Fig. 1. Formation energy (Ef) dependence of the occupation configuration of Co atom for Ni2-xMn1.5In0.5Cox (x = 0.083 and 0.167) alloys.

Fig. 2. Composition and possible phases dependence of the total energy for Ni2-xMn1.5In0.5Cox (x = 0-0.33) alloys.

Table 2 Optimized equilibrium lattice parameters (?) of A, 6 M and NM phases for Ni2-xMn1.5In0.5Cox (x = 0-0.33) alloys (Black italic meaning ferromagnetic state).

Co content (x)	A	6 M				NM
Co content (x)	a = b = c	a	b	c	β°	a = b	c
x = 0	5.947, 5.95 [38], 6.00 [42]	4.439	5.429	12.85	95.26	3.7892	7.118
x = 0.08	5.944	4.413	5.443	12.90	94.30	3.7896	7.103
x = 0.17	5.941	4.394	5.458	12.89	94.36	3.7961	7.084
x = 0.25	5.937, 5.95 [38]	4.240	5.828	12.68	90.83	3.7965	7.052
x = 0.33	5.932	4.238	5.840	12.66	90.91	4.2035	5.898

Fig. 3. (a) Composition dependence of formation energies Ni2-xMn1.5In0.5Cox (x = 0-0.33) alloys. (b) Composition dependence of ΔE and TM for Ni2-xMn1.5In0.5Cox (x = 0-0.33) alloys.

Fig. 4. Composition dependence of the single-crystal elastic constants C11, C12, C44 and C' for Ni-Mn-In-Co alloys.

Table 3 Calculated, experimental, and other theoretical values of the elastic constants in cubic Ni-Mn-In (Co) alloys.

System	B (GPa)	G (GPa)	Y (GPa)	C^p (GPa)	υ
Ni₂MnIn	138.81	43.82	118.94	36.81	0.357
Theo.	127^a [43], 133^b
Exp.	116^c [44], 174^d [44]
Ni₂Mn_1.5In_0.5	134.34, 137.4^e [38]	43.14	116.90	31.78	0.355
Ni_1.75Mn_1.5In_0.5Co_0.25	134.9, 139.6 [38]	53.99	142.90	15.7	0.323
Ni_1.5Mn_1.5In_0.5Co_0.5	143.78, 142.7 [38]	59.40	156.63	17.54	0.318

Fig. 5. Three-dimensional surface plots of the single-crystal Young's moduli for ferromagnetic cubic Ni-Mn-In-Co alloys as a function of Co content for (a) x = 0, (b) x = 0.25, (c) x = 0.5.

Fig. 6. Total magnetic moments per formula unit as a function of Co content for Ni2-xMn1.5In0.5Cox (x = 0-0.33) alloys.

Fig. 7. Atomic magnetic moments of (a) FA, (b) 6 M, (c) NM and the nearest neighbor atomic distance (d) as a function of Co content for Ni2-xMn1.5In0.5Cox (x = 0-0.33) alloys.

Fig. 8. The total density of states (DOS) (a), spin-down total density of states (b) near Fermi energy (EF) for Ni2-xMn1.5In0.5Cox (x = 0-0.33) alloys in FA, 6 M and NM phases. The zero energy is regarded as EF.

Fig. 9. Partial density of states for Ni2-xMn1.5In0.5Cox (x = 0-0.33) alloys in (a) FA, (b) 6 M and (c) NM phases.

Table 4 Composition for Ni50-yMn37.5In12.5Coy alloys.

Nominal composition	Actual composition
Nominal composition	Ni (at.%)	Mn (at.%)	In (at.%)	Co (at.%)
Ni₅₀Mn_37.5In_12.5	49.7	37.5	12.8	0
Ni_48.96Mn_37.5In_12.5Co_1.04	48.9	36.9	12.9	1.3
Ni_47.92Mn_37.5In_12.5Co_2.08	48.1	37.0	12.8	2.1
Ni_46.87Mn_37.5In_12.5Co_3.13	46.7	37.3	12.7	3.3
Ni_45.83Mn_37.5In_12.5Co_4.17	45.7	37.1	12.9	4.3
Ni_44.79Mn_37.5In_12.5Co_5.21	44.7	37.2	12.8	5.3
Ni_43.75Mn_37.5In_12.5Co_6.25	44.0	37.1	12.8	6.1

Fig. 10. (a) Room-temperature XRD patterns for Ni50-yMn37.5In12.5Coy alloys. (b) The composition dependence of the experimental and theoretical lattice parameters (?) for FA with y = 0-8.33. (c) The composition dependence of the experimental and theoretical lattice parameters (?) for 6 M martensite with y = 0-8.33. (d) The composition dependence of the experimental and theoretical monoclinic angle (°) for 6 M martensite with y = 0-8.33.

Fig. 11. DSC curves of the martensitic transformation for Ni50-yMn37.5In12.5Coy alloys.

Table 5 The martensitic and austenitic transformation starting, finishing temperatures (Ms, Mf, As, Af,), transformation hysteresis (ΔT), enthalpy change (ΔH) and entropy change (ΔS) of Ni50-yMn37.5In12.5Coy alloys.

	M_s (K)	M_f (K)	A_s (K)	A_f (K)	ΔT(K)	ΔH(J/g)	ΔS(J/K·kg)
Ni₅₀Mn_37.5In_12.5	408	417	416	426	8.5	21.7	51.5
Ni_48.96Mn_37.5In_12.5Co_1.04	401	411	413	423	12	21.2	50.7
Ni_47.92Mn_37.5In_12.5Co_2.08	393	404	406	416	12.5	20.7	50.4
Ni_46.87Mn_37.5In_12.5Co_3.13	385	394	397	406	12	20.6	51.3
Ni_45.83Mn_37.5In_12.5Co_4.17	375	384	389	400	15	19.5	49.4
Ni_44.79Mn_37.5In_12.5Co_5.21	365	354	372	388	20.5	15.9	41.8
Ni_43.75Mn_37.5In_12.5Co_6.25	335	309	339	361	28	5.2	14.9

Fig. 12. (a) DSC curves and (b) relationship between ln(β/T2) and 10000/T of the heating path at different heating rates of Ni50Mn37.5In12.5, Ni47.92Mn37.5In12.5Co2.08 and Ni45.83Mn37.5In12.5Co4.17 alloys. The heating rates from top to bottom are 3, 5, 7, 10, 12, 15, 20 K/min, respectively.

Fig. 13. (a) M(T) curves at 0.1 T for Ni45.83Mn37.5In12.5Co4.17, Ni44.79Mn37.5In12.5Co5.21 and Ni43.75Mn37.5In12.5Co6.25 alloys. (Inset) M(T) curves at 5 T for Ni43.75Mn37.5In12.5Co6.25 alloys. (b) M(H) curves at 5 K for Ni50-yMn37.5In12.5Coy alloys.

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