Effect of Cu content on microstructure and mechanical properties of in-situ β phases reinforced Ti/Zr-based bulk metallic glass matrix composite by selective laser melting (SLM)

doi:10.1016/j.jmst.2020.06.024

Abstract

Abstract:

In this study, non-toxic in-situ β phases of reinforced Ti/Zr-based bulk metallic glass matrix composites (BMGCs) of (Ti_0.65Zr_0.35)_100-_xCu_x (x = 5, 10, 15 at.%) are fabricated via selective laser melting. The effect of Cu content on phase formation, microstructure, and mechanical properties is investigated. The average volume fraction and width of the β phase decreases with increasing Cu content, while a more amorphous phase and the (Ti, Zr)₂Cu phase forms. In the center zone of the molten pool, the β phase grows in the direction of the temperature gradient, and the amorphous phase distributes among the β phases. This occurs using: sphere morphology (for x = 5), a more continuous elongated sphere and network morphology (for x = 10), and network morphology (for x = 15), respectively. In the edge zone of the molten pool, due to the smaller cooling rate and the existence of a partially molten zone, the β phase becomes coarser, and an amorphous phase forms for more continuous networks. Furthermore, the hardness improves significantly with increasing Cu content. No crack is found for x = 5. Although the average volume fraction of the β phase for x = 5 is about 90 %, the compression yield strength is 1386 ± 64 MPa, reaching to an average level of conventionally fabricated counterparts, due to finer microstructure, and twinning and martensitic transformation of the β phase.

Key words: Metallic glass, Amorphous phase, β Phase, Bulk metallic glass matrix composites (BMGCs), Additive manufacturing (AM), Selective laser melting (SLM)

Xuehao Gao, Xin Lin, Qiaodan Yan, Zihong Wang, Xiaobin Yu, Yinghui Zhou, Yunlong Hu, Weidong Huang. Effect of Cu content on microstructure and mechanical properties of in-situ β phases reinforced Ti/Zr-based bulk metallic glass matrix composite by selective laser melting (SLM)[J]. J. Mater. Sci. Technol., 2021, 67: 174-185.

Figures/Tables 16

Fig. 1. OM images of horizontal sections of Cu5, Cu10 and Cu15.

Fig. 2. XRD results of Cu5, Cu10 and Cu15.

Fig. 3. DSC results of Cu5, Cu10 and Cu15.

Table 1 DSC results of Cu5, Cu10, Cu15.

Sample	T_g (K)	T_x (K)	ΔT= T_x-T_g (K)	ΔH (J/g)
Cu5	543	613	70	11.93
Cu10	536	598	62	11.34
Cu15	514	591	77	3.75

Fig. 4. SEM-BSE images of (A, D) Cu5 sample, (B, E) Cu10 sample and (C, F) Cu15 sample in (A, B, C) center zone of molten pool and (D, E, F) edge zone of molten pool (the edge zone is between the red dotted lines).

Table 2 Microstructure characteristics of Cu5, Cu10, Cu15.

	Sample	Volume fraction of β phase (%)	Volume fraction of amorphous phase (%)	Average width of β phase (μm)	Average width of amorphous phase (μm)
Cu5	Center zone	92 ± 1.4	8 ± 1.4	0.57 ± 0.05	0.15 ± 0.02
Cu5	Edge zone	89.5 ± 1.9	10.5 ± 1.9	1.17 ± 0.13	0.16 ± 0.02
Cu10	Center zone	78.2 ± 3.9	21.8 ± 3.9	0.5 ± 0.07	0.19 ± 0.03
Cu10	Edge zone	77.8 ± 1.8	22.2 ± 1.8	1.11 ± 0.11	0.28 ± 0.02
Cu15	Center zone	58.4 ± 5.4	41.6 ± 5.4	0.4 ± 0.05	0.18 ± 0.02
Cu15	Edge zone	62.7 ± 4.2	37.3 ± 4.2	0.74 ± 0.06	0.29 ± 0.04

Fig. 5. (A) Average volume fraction variation of β phase and amorphous phase in center zone and edge zone with the content of Cu element; (B) Average width variation of β phase in center zone and edge zone with the content of Cu element; (C) Average width variation of amorphous phase in center zone and edge zone with the content of Cu element.

Fig. 6. (A) Bright-field TEM image and SAED image of the microstructure in Cu5 sample; (B) HRTEM image in the interface of the amorphous and (Ti, Zr)2Cu phase, corresponding to image A-ⅰ; (C) Bright-field TEM image, SAED image and HRTEM image of intragranular twins of β phase in Cu5 sample; (D) Bright-field TEM image and SAED image of the microstructure in Cu10 sample; (E) HRTEM image in the interface of the amorphous and β phase, corresponding to image D-ⅲ; (F) Bright-field TEM image and SAED image of (Ti, Zr)2Cu phase in Cu10 sample; (G) Bright-field TEM image and SAED image of the microstructure in Cu15 sample; (H) HRTEM image in the interface of the amorphous and martensite phase, corresponding to image G-ⅵ; (K) Bright-field TEM image and SAED image of martensite phase in Cu15 sample.

Table 3 EDS results of Cu5, Cu10, Cu15 (at.%).

Sample	β phase			Amorphous phase
	Ti	Zr	Cu	Ti	Zr	Cu
Cu5	63.4 ± 0.5	27.9 ± 0.3	8.8 ± 0.2	31.9 ± 0.6	36.2 ± 0.7	31.9 ± 0.5
Cu10	57.8 ± 0.3	34.2 ± 0.3	8 ± 0.01	31.1 ± 0.1	39.3 ± 0.32	29.6 ± 0.39
Cu15	64.8 ± 0.7	28.2 ± 0.7	7 ± 0.3	34.9 ± 0.3	34.6 ± 1.2	30.5 ± 1.2

Table 4 Results of Vickers hardness test (HV).

Cu5	Cu10	Cu15
364 ± 6	408 ± 10	437 ± 10

Table 5 Compression results of Cu5 sample.

Elastic modulus (GPa)	Yield strength (MPa)	Maximum strength (MPa)	Fracture strain (mm/mm)
28.3 ± 1.3	1386 ± 64	1810 ± 87	17.6% ± 2.8 %

Fig. 7. (A) Compression engineering stress-strain curves of Cu5 sample; (B) Fracture surface of Cu5 sample; (C) Vein pattern; (D) Regional enlarged view of vein pattern; (E) Droplet pattern; (F) Regional enlarged view of droplet pattern.

Fig. 8. Pseudo binary phase diagram of (Ti0.65Zr0.35)100-xCux.

Fig. 9. (A) Schematic of three dimensional morphology of the molten pool in SLM; (B) Schematic of top view of molten pool in SLM (x-y cross section; green arrows n1 and n2 is solidification interface normal direction in point b and d respectively, θ1 and θ2 is the angle between solidification interface normal and laser scanning direction in point b and d respectively, θ2>θ1); (C) Schematic of front view of molten pool in SLM (x-z cross section; red arrows represent temperature gradient of molten pool G); (D) Schematic of variations of temperature with time at different positions in the molten pool (the curve 1-2 corresponds to a-b curve of B ; the curve 3-4 corresponds to c-d curve of B).

Fig. 10. (A) Comparison of yield strength and fracture strain; (B) Comparison of maximum strength and fracture strain.

Fig. 11. (A) Comparison of yield strength and average volume fraction of β phase; (B) Comparison of yield strength and average width of β phase.

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