Microstructure, Mechanical Properties and Corrosion Resistance of the Mo0.5V0.5NbTiZrx High-Entropy Alloys with Low Thermal Neutron Sections

doi:10.1007/s40195-024-01728-7

Abstract

Abstract:

High-entropy alloys exhibit significant potential for application in the nuclear industry owing to their exceptional resistance to irradiation, excellent mechanical properties, and corrosion resistance. In this work, the Mo_0.5V_0.5NbTiZr_x (x = 0-2.0) high-entropy alloys containing alloying elements with low thermal neutron absorption cross section were designed and prepared. The crystal structure, microstructure, mechanical properties and corrosion resistance of the studied alloys were investigated. All the alloys possess a body-centered cubic crystal structure, which is consistent with the CALPHAD (acronym of CALculation of PHAse Diagram) modeling results. The addition of Zr does not alter the crystal structure of the Mo_0.5V_0.5NbTiZr_x alloys; however, it leads to an increase in the lattice constant as Zr content increases. The addition of Zr initially enhances the yield strength, but subsequently leads to a decline as the Zr content increases further. Specifically, the corrosion resistance of the Mo_0.5V_0.5NbTiZr_x alloys in superheated steam at 400 °C and 10.3 MPa decreases with the increase of Zr content. The effect of Zr content on the phase formation, mechanical properties and corrosion resistance of the Mo_0.5V_0.5NbTiZr_x high-entropy alloys are discussed. This study has successfully developed a novel Mo_0.5V_0.5NbTiZr_0.25 high-entropy alloy, which demonstrates exceptional properties including high yield strength, excellent ductility, and superior anti-corrosion performance. The findings of this research have significant implications for the design of high-entropy alloys in nuclear applications.

Key words: High-entropy alloys, Phase formation, Mechanical properties, Corrosion resistance

Chao Xiang, En-Hou Han, Zhiming Zhang, Huameng Fu, Haifeng Zhang, Jianqiu Wang, Guodong Hu. Microstructure, Mechanical Properties and Corrosion Resistance of the Mo_0.5V_0.5NbTiZr_x High-Entropy Alloys with Low Thermal Neutron Sections[J]. Acta Metallurgica Sinica (English Letters), 2024, 37(10): 1643-1656.

Figures/Tables 16

Fig. 1 a ΔHmix-δ; b ΔSmix-δ; c Ω-δ plots for the MoVNbTiZrx, Mo0.5VNbTiZrx, Mo0.5V0.5NbTiZrx, Mo0.5VNb0.5TiZrx, and Mo0.5V0.5Nb0.5TiZrx (x = 0, 0.25, 0.5, 0.75, 1.0, 1.5 and 2.0) alloy systems. The content of Zr increases from left to right in each plot

Table 1 Density (ρ), atomic radius (r), melting point (Tm), lattice constant (a), Vickers hardness (HV), Young’s modulus (E), thermal neutron absorption cross section (σA) of the pure Mo, V, Nb, Ti, and Zr elements [3,40,41,50]

Element	ρ (g/cm³)	r (Å)	T_m (°C)	a (Å)	HV (kgf/mm²)	σ_A (barn)
Mo	10.28	1.36	2623	3.147	156	2.48
V	6.11	1.32	1910	3.024	64	5.08
Nb	8.57	1.43	2477	3.301	135	1.15
Ti	4.51	1.46	1668	3.276	99	6.09
Zr	6.51	1.6	1855	3.582	92	0.185

Fig. 2 a Non-equilibrium solidification simulation for the Mo0.5V0.5NbTiZrx (x = 0, 0.25, 0.5, 0.75, 1.0, 1.5, and 2.0) alloys using Scheil-Gulliver models. Calculated equilibrium phase diagrams for the b Zr0, c Zr0.25, d Zr0.5, e Zr0.75, f Zr1.0, g Zr1.5, and h Zr2.0 alloys

Table 2 Calculated liquidus temperature (Tliq), solidus temperature (Tsol), decomposition temperature (Tdec), the ratio ((Tsol−Tdec)/Tdec)) value, equilibrium phase constitution and volume fraction at 500 °C of the Mo0.5V0.5NbTiZrx (x = 0, 0.25, 0.5, 0.75, 1.0, 1.5 and 2.0) alloys

Alloy	T_liq (°C)	T_sol (°C)	T_dec (°C)	(T_sol−T_dec)/T_dec	Phase constitution and volume fraction
Zr0	2162	1997	595	0.62	BCC#1 (0.78) + HCP (0.22)
Zr0.25	2110	1897	795	0.55	BCC#1 (0.58) + BCC#2 (0.38) + HCP (0.04)
Zr0.5	2066	1835	926	0.43	BCC#1 (0.49) + BCC#2 (0.51)
Zr0.75	2027	1797	1011	0.38	BCC#1 (0.44) + BCC#2 (0.56)
Zr1.0	1991	1773	1069	0.34	BCC#1 (0.40) + BCC#2 (0.60)
Zr1.5	1929	1746	1140	0.30	BCC#1 (0.34) + BCC#2 (0.66)
Zr2.0	1877	1733	1177	0.28	BCC#1 (0.29) + BCC#2 (0.71)

Fig. 3 Composition versus temperature of a BCC#1 phase and b BCC#2 phase of the Zr0.25 alloy. Composition versus temperature of c BCC#1 phase and d BCC#2 phase of the Zr1.5 alloy

Fig. 4 a X-ray diffraction patterns of the Mo0.5V0.5NbTiZrx (x = 0, 0.25, 0.5, 0.75, 1.0, 1.5 and 2.0) alloys after HIP and annealing at 1200 °C for 24 h, b the enlarged (110) peaks of the BCC phase

Fig. 5 SEM backscattered electron images of the annealed Mo0.5V0.5NbTiZrx alloys with lower (left) and higher (right) magnifications: a Zr0, b Zr0.25, c Zr0.5, d Zr0.75, e Zr1.0, f Zr1.5, g Zr2.0

Table 3 Chemical composition (in at%) of the annealed Mo0.5V0.5NbTiZrx alloys measured by EDS

Alloy	Region	Mo	V	Nb	Ti	Zr
Zr0	Nominal	16.67	16.67	33.33	33.33	-
	Overall	16.32 ± 0.19	16.25 ± 0.51	34.03 ± 0.21	33.40 ± 0.48	-
	Dendrite	22.29 ± 0.32	14.16 ± 0.27	35.33 ± 0.54	28.22 ± 0.23	-
	Interdendrite	18.03 ± 0.36	17.76 ± 0.54	32.14 ± 0.51	32.07 ± 0.24	-
Zr0.25	Nominal	15.38	15.38	30.77	30.77	7.70
Zr0.25	Overall	14.74 ± 0.45	14.85 ± 0.37	30.04 ± 0.13	29.98 ± 0.42	10.39 ± 0.08
Zr0.5	Nominal	14.28	14.28	28.58	28.58	14.28
Zr0.5	Overall	16.26 ± 0.18	13.60 ± 0.52	30.21 ± 0.49	25.38 ± 0.06	14.55 ± 0.43
Zr0.75	Nominal	13.33	13.33	26.67	26.67	20.00
Zr0.75	Overall	13.67 ± 0.19	12.01 ± 0.11	26.78 ± 0.23	26.05 ± 0.27	21.48 ± 0.23
Zr1.0	Nominal	12.50	12.50	25.00	25.00	25.00
Zr1.0	Overall	12.33 ± 0.35	11.40 ± 0.48	24.90 ± 0.09	24.87 ± 0.53	26.49 ± 0.35
Zr1.5	Nominal	11.11	11.11	22.22	22.22	33.34
Zr1.5	Overall	9.90 ± 0.31	10.66 ± 0.11	20.78 ± 0.30	21.94 ± 0.30	36.72 ± 0.39
Zr2.0	Nominal	10.00	10.00	20.00	20.00	40.00
Zr2.0	Overall	9.29 ± 0.73	9.64 ± 0.45	19.22 ± 0.18	19.30 ± 0.27	42.55 ± 0.13

Fig. 6 SEM/EDS mappings of Mo, V, Nb, Ti and Zr for the Mo0.5V0.5NbTiZrx alloys: a Zr0, b Zr0.25, c Zr0.5, d Zr0.75, e Zr1.0, f Zr1.5, g Zr2.0

Fig. 7 Calculated theoretical densities and experimental densities of the Mo0.5V0.5NbTiZrx (x = 0, 0.25, 0.5, 0.75, 1.0, 1.5 and 2.0) alloys

Fig. 8 Experimental hardness of the Mo0.5V0.5NbTiZrx (x = 0, 0.25, 0.5, 0.75, 1.0, 1.5 and 2.0) alloys

Fig. 9 a Engineering stress-strain curves, and b yield strength (σ0.2), compressive strength (σp), and fracture strain (εf) for the Mo0.5V0.5NbTiZrx (x = 0, 0.25, 0.5, 0.75, 1.0, 1.5 and 2.0) alloys

Fig. 10 Fracture morphologies of a-c Zr0 alloy, and d-f Zr0.25 alloy. Both alloys show a mixed fracture mode of transgranular fracture and intergranular fracture, and slip bands are seen from c and f

Fig. 11 Fracture morphologies of a Zr0.5; b Zr0.75; c Zr1.0; d Zr1.5; and e Zr2.0 alloys. These five alloys also exhibit a mixed fracture mode of transgranular and intergranular fractures. However, the slip bands are not observed

Fig. 12 Weight gain of the Zr0, Zr0.25, Zr0.5, Zr0.75, Zr1.0, Zr1.5 and Zr2.0 alloys after corrosion tests in superheated steam at 400 °C and 10.3 MPa for 30 days. The results were compared with the Zr-4 alloy

Fig. 13 Surface and cross-sectional morphologies of the Zr0, Zr0.5, Zr1.0, and Zr2.0 alloys after corrosion tests in superheated steam at 400 °C and 10.3 MPa for 30 days a-c Zr0 alloy, d-f Zr0.5 alloy, g-i Zr1.0 alloy, j-l Zr2.0 alloy

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