Enhanced crystallization resistance and thermal stability via suppressing the metastable superlattice phase in Ni-(Pd)-P metallic glasses

doi:10.1016/j.jmst.2019.11.005

Abstract

Abstract:

Virtually, glass formation is to avoid crystallization during solidification, i.e., a consequence of the competition between the undercooled liquid and primary crystalline phases. It is found that the crystallization resistance of the binary Ni-P system was drastically enhanced with alloying of Pd and correspondingly, the critical size for glass formation increased significantly from the micrometer to millimeter scale. Thermodynamically, the introduction of Pd could effectively increase the atomic size mismatch and heat of mixing, which are beneficial to stabilize the supercooled liquid. Kinetically, the introduction of Pd not only successfully suppresses the formation of metastable superlattice phase, which is prone to nucleation and growth in the supercooled liquid state, but also changes the crystallization mechanism from the primary to eutectic mode. The current finding sheds light on understanding glass formation of the most studied Pd-Ni-P system and the glass-forming ability in general.

Key words: Metallic glass, Glass-forming ability, Thermal stability, Nanocrystallization, Metastable superlattice phase

Qing Du, Xiongjun Liu, Yihuan Cao, Yuren Wen, Dongdong Xiao, Yuan Wu, Hui Wang, Zhaoping Lu. Enhanced crystallization resistance and thermal stability via suppressing the metastable superlattice phase in Ni-(Pd)-P metallic glasses[J]. J. Mater. Sci. Technol., 2020, 42: 203-211.

Figures/Tables 11

Fig. 1. (Color online) X-ray diffraction patterns obtained from the as-cast Ni80P20 and Pd40Ni40P20 samples.

Fig. 2. (Color online) DSC curves for (a) crystallization,(c) melting and (d) solidification processes of the Pd40Ni40P20 and Ni80P20 MGs; (b) TMDSC curves for the Ni80P20 MG.

Table 1 Thermodynamical parameters and calculated criteria for glass-forming ability between Ni80P20 and Pd40Ni40P20 MGs.

Metallic glass	T_g (K)	T_x (K)	T_m (K)	T_l (K)	T_s (K)	ΔT_x (K)	T_rg	γ
Ni₈₀P₂₀	595 (TMDSC)	617	1162	1208	1059.1	22	0.51	0.342
Pd₄₀Ni₄₀P₂₀	572	659	885	1010	822.2	87	0.64	0.417

Fig. 3. (Color online) X-ray diffraction patterns for the (a) Ni80P20 and (b) Pd40Ni40P20 MGs during crystallization at different temperatures.

Fig. 4. (Color online) TEM and HRTEM observations of crystallized Ni80P20 and Pd40Ni40P20 MGs. (a), (c) TEM bright-field images of Ni80P20 MG after Peak 1and Peak 2; (b), (d)HREM images of the corresponding regions in (a) and (c); (e), (f) TEM images of Pd40Ni40P20 MG after Peak 1and Peak 2.

Fig. 5. (Color online) DSC curves of the (a) Ni80P20 and (b) Pd40Ni40P20 MGs under non-isothermal conditions at different heating rates.

Fig. 6. (Color online) Kissinger plots for the Ni80P20 and Pd40Ni40P20 MGs, (a) Tx, (b) TP1 and (c) TP2.

Table 2 Apparent activation energies for crystallization of the Ni80P20 and Pd40Ni40P20 MGs calculated by the Kissinger model.

Metallic glass	B (K/min)	T_x (K)	T_P1 (K)	T_P2 (K)	E_x (kJ/mol)	E_P1 (kJ/mol)	E_P2 (kJ/mol)	E_C (kJ/mol)
Ni₈₀P₂₀	5	608.1	618.4	683.1	223.6	235.9	194.9	654.4
	10	617.2	628.3	696.7
	20	625.6	636.8	709.6
	40	636.9	646.7	724.8
Pd₄₀Ni₄₀P₂₀	5	649.2	663.3	697.0	236.2	348.2	254.0	838.4
	10	657.8	670.0	706.9
	20	666.7	677.4	718.2
	40	680.1	684.8	730.2

Fig. 7. (Color online) Crystallized volume fraction for the (a, c) Peak 1 and (b, d) Peak 2 of the Ni80P20 MG and Pd40Ni40P20 MG, respectively, as function of temperature at different heating rates.

Fig. 8. (Color online) Variations of the crystallization rate for the (a, c) Peak 1 and (b, d) Peak 2 of the Ni80P20 MG and Pd40Ni40P20 MG, respectively, as function of temperature at different heating rates.

Table 3 JMA kinetic parameters of the Ni80P20 and Pd40Ni40P20 MGs.

Metallic glass	Stage	B (K/min)	(dx/dt)_p (s^-1)	K_p (s^-1)	K₀ (s^-1)	n	<n>
Ni₈₀P₂₀	Peak 1	5	0.0067	0.0062	5.22E+17	2.92	3.1 ± 0.2
		10	0.0132	0.012	4.91E+17	2.98
		20	0.0263	0.0233	5.23E+17	3.05
		40	0.0555	0.0452	5.13E+17	3.32
	Peak 2	5	0.0031	0.0042	3.36E+12	2.02	2.0 ± 0.1
		10	0.0062	0.008	3.30E+12	2.08
		20	0.0111	0.0155	3.45E+12	1.93
		40	0.0215	0.0297	3.31E+12	1.95
Pd₄₀Ni₄₀P₂₀	Peak 1	5	0.0063	0.0079	2.09E+25	2.16	2.4 ± 0.3
		10	0.0122	0.0155	2.18E+25	2.13
		20	0.0269	0.0304	2.16E+25	2.39
		40	0.0635	0.0595	2.17E+25	2.88
	Peak 2	5	0.0039	0.0052	5.69E+16	2.01	2.2 ± 0.1
		10	0.0085	0.0102	5.99E+16	2.24
		20	0.0164	0.0197	5.88E+16	2.25
		40	0.0306	0.0382	5.66E+16	2.17

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