Direct Alloying of Immiscible Tungsten and Copper Based on Nano Active Structure and Its Thermodynamic Mechanism

doi:10.11900/0412.1961.2022.00003

Acta Metall Sin

2023, Vol. 59

Issue (5): 679-692 DOI: 10.11900/0412.1961.2022.00003

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Direct Alloying of Immiscible Tungsten and Copper Based on Nano Active Structure and Its Thermodynamic Mechanism

WANG Hanyu, LI Cai, ZHAO Can, ZENG Tao, WANG Zumin, HUANG Yuan(

)

School of Materials Science and Engineering, Tianjin University, Tianjin 300354, China

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WANG Hanyu, LI Cai, ZHAO Can, ZENG Tao, WANG Zumin, HUANG Yuan. Direct Alloying of Immiscible Tungsten and Copper Based on Nano Active Structure and Its Thermodynamic Mechanism. Acta Metall Sin, 2023, 59(5): 679-692.

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Abstract

W is usually used as plasma-facing components in nuclear fusion reactors because of its high melting point, low sputtering yield, high-temperature strength, and low tritium retention properties. On the other hand, Cu and its alloys show excellent thermal conductivity making them ideal as a heat sink material in reactors. Therefore, W-Cu layered composites have important applications in nuclear fusion reactors. Due to the immiscibility between W and Cu, direct alloying between them without using interlayer metals is critical for the preparation of such layered composites. In this study, a nanoporous active structure was used to induce and promote the direct alloying of the W-Cu system. Direct alloying consists of three steps. First, a nanoporous active layer is prepared on the surface of a W foil via two-step anodizing and deoxidized annealing in a hydrogen atmosphere. Second, a Cu coating layer is deposited on the nanoporous W by electroplating. Finally, the obtained W-Cu electrodeposited sample is annealed at temperatures close to the melting point of Cu (i.e., 980^oC). The established thermodynamic model for the direct alloying of immiscible metal systems is used for the direct alloying of W and Cu based on a nanoporous active structure. There are two problems with this model. First, the surface energy results are arbitrary due to the selection of the number of surface atomic layers. Second, the unit scale in thermodynamic calculations. To solve these problems, the calculation methods for surface energy and pressure energy are improved in this work, which makes the thermodynamic calculation for the direct alloying of W-Cu based on a nanoporous active structure feasible. The results show that a nanoporous active structure is formed on the surface of W after nanotreatment. The characterization results of the W/Cu interface show that the diffusion distance between the two metals is about 27 nm and the direct alloying between W and Cu is successful. The average shear strength of the W-Cu layered composites was 101 MPa. This is a 16% increase compared with W-Cu layered composites without a nanoporous structure. The thermodynamic calculation results show that the surface energy of the W-Cu system is greatly improved due to the nanoporous active structure prepared on the W surface. The surface energy can be used as the main thermodynamic driving force for the direct alloying of W-Cu systems. There are different reasons why nanotreatment increases W surface energy. One reason is the increase of crystal planes with high surface energy via nanotreatment of the W surface, and another is the shape of the nanoporous structure.

Key words: immiscible W-Cu system nanoporous structure direct alloying thermodynamic model surface energy

Received: 04 January 2022

ZTFLH:

TG146.4

Fund: National Key Research and Development Program of China(2018YFB0703904);National Key Research and Development Program of China(2017YFE0302600)

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	WANG Hanyu
	LI Cai
	ZHAO Can
	ZENG Tao
	WANG Zumin
	HUANG Yuan

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https://www.ams.org.cn/EN/10.11900/0412.1961.2022.00003 OR https://www.ams.org.cn/EN/Y2023/V59/I5/679

Fig.1 Surface SEM images and corresponding EDS results (insets) (a, c) and cross-section SEM images of W plate (b, d) with nanoporous structure layer prepared through two-step anodizing process without (a, b) and with (c, d) deoxidation process

Fig.2 Linear sweep voltammetry (LSV) curves of the nanoporous W plate and the pretreated W plate (RHE—reversible hydrogen electrode)

Fig.3 High-angle annular dark field (HAADF) image of W/Cu interface (a), atomic fraction along the red arrow marked in Fig.3a (b), and elemental mappings of W (c) and Cu (d)
Color online

Fig.4 HRTEM image of W/Cu interface (Inset I shows the fast Fourier transform (FFT) pattern from the darker area and inset II shows the brighter one, d—interplanar spacing)

Fig.5 Stress-strain curves of shear strength of W/Cu layered composites prepared based on nano active structure (a) and pretreated W block (b)

Fig.6 SEM image of shear fracture surface (W side) of the W/Cu layered composite (a); EDS analysis results of the region marked with rectangles I (b), II (c), and III (d)

Fig.7 SEM image of shear fracture surface (Cu side) of the W/Cu layered composite (a), and EDS analysis result of the region marked with the rectangle in Fig.7a (b)

Fig.8 XRD spectra of W without nanopores (a), nanoporous W (b), and Cu plating layer (c)

Table 1 Surface energy (E_surf) of crystal faces contained on the surface of W and Cu based on the first-principles and new formula of surface energy

Element	V^2/3	$n w s - 1 / 3$	φ	γ	E	K	G	S_f	γ^S,0	ρ	M	T_m
	cm²	(d.u.)^1/3	V		GPa	GPa	GPa	10⁵ m²	mJ·m^-2	g·cm^-3	g·mol^-1	K
Cu	3.70	1.47	4.45	0.343	129.8	137.8	48.3	1.67	1825	8.96	63.55	1356
W	4.50	1.81	4.80	0.280	411.0	160.6	311.0	2.03	3675	19.32	183.84	3680

Table 2 Parameters used in thermodynamic calculation for the W-Cu direct alloying^[25,42]

Fig.9 Calculated energy curves of W-Cu direct alloying processes based on nano active structure for the W-Cu systems (Δ $G a l l o y i n g c$ —Gibbs free energy for the formation of W/Cu crystalline phase, Δ $G a l l o y i n g a$ —Gibbs free energy for the formation of W/Cu amorphous phase, E_initial,W—initial energy of W-Cu system without nano-treatment, E_initial,nano—initial energy of W-Cu system with nano-treatment)
(a) without pressure
(b) under 106 MPa pressure

Fig.10 Origin shape of W nanoporous with convex structure (a), concave structure (b, c), structural diagram and cross-section of simplified geometric models of Figs.10a and c (d, e), and geometry model for the W plate without nano-treatment (f) (D—nanopore diameter, d_surf—the thickness of the surface layer in a metal that provides surface energy, h₀—the height of a cylinder in the convex or concave structure, h₁—the height of a cone in the convex or concave structure, h₂—obtained from h₁ ± d_surf, R₁—the bottom radius of cylinder and cone in the convex or concave structure, R₂—obtained from R₁ ± d_surf, a—the side length of the model of W plate without nano-treatment)

Fig.11 Fine-scale density profiles (ρ(Z)) for W and Cu near and at the W/Cu interface constructed through direct alloying at different temperatures

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