Liquid-Solid Phase Separation Process of Pb-Al Alloy Under the Effect of Electric Current Pulses

doi:10.11900/0412.1961.2022.00505

Acta Metall Sin

2024, Vol. 60

Issue (12): 1710-1720 DOI: 10.11900/0412.1961.2022.00505

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Liquid-Solid Phase Separation Process of Pb-Al Alloy Under the Effect of Electric Current Pulses

LI Yanqiang¹^,², ZHAO Jiuzhou¹^,²(

), JIANG Hongxiang¹^,², ZHANG Lili¹, HE Jie¹^,²

1 Shi -changxu Innovation Center for Advanced Materials, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
2 School of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China

Cite this article:

LI Yanqiang, ZHAO Jiuzhou, JIANG Hongxiang, ZHANG Lili, HE Jie. Liquid-Solid Phase Separation Process of Pb-Al Alloy Under the Effect of Electric Current Pulses. Acta Metall Sin, 2024, 60(12): 1710-1720.

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Abstract

The Pb-Al alloy, which undergoes liquid-solid (L-S) phase separation, can potentially serve as a high-performance and low-cost anode material for hydrometallurgy and a grid material for lead-acid batteries. For this purpose, a microstructure containing uniformly dispersed micro/nano Al-rich particles in the Pb matrix is desired. However, during cooling of the Pb-Al alloy melt, Al-rich particles nucleate from the matrix melt first, grow, and migrate in the melt until they are caught by the solidification interface. Consequently, Pb-Al alloys often exhibit a solidification microstructure with coarse Al-rich particles or significant phase segregation. Recent studies have shown that the application of electric current pulses (ECPs) during solidification can effectively modify the microstructure evolution. This research aims to investigate the possibility of controlling the L-S phase separation process and microstructure of Pb-Al alloys. To achieve this, continuous solidification experiments were carried out on Pb-Al L-S phase separation alloy while subject to ECPs. A theoretical model describing the microstructure formation during the L-S phase separation process of the alloy under the effect of ECPs was proposed. The microstructure evolution was simulated according to the experimental conditions, and the effect of ECPs on the L-S phase separation process of the alloy was analyzed. It was demonstrated that ECPs can effectively reduce the energy barrier for the nucleation of Al-rich particles during the L-S phase separation process of Pb-Al alloy, enhance the particles' nucleation rate, and reduce the average radius, thereby promoting the formation of a composite containing in situ micro/nano Al-rich particles embedded in the Pb matrix. The peak current density (j_max) has two critical values ( $j c 1$ and $j c 2$ ). When $j m a x ≤ j c 1$ , ECPs have a negligible effect on the nucleation behavior of Al-rich particles. When $j c 1 < j m a x < j c 2$ , the nucleation rate and number density of the Al-rich particles increase rapidly with increasing $j m a x$ . When $j m a x ≥ j c 2$ , the nucleation rate and number density increase continuously with increasing $j m a x$ , but at a lower rate. Furthermore, the electromagnetic force causes migration of the Al-rich particles toward the center of the sample, resulting in the emergence of an Al-poor layer on the surface of the sample and promoting the formation of a special composite composed of a Pb-rich shell and an in situ Al-rich particles reinforced Pb matrix core.

Key words: electric current pulse immiscible alloy liquid-solid phase separation nucleation simulation

Received: 11 October 2022

ZTFLH:

TG111.4

Fund: National Key Research and Development Program of China(2021YFA0716303);National Natural Science Foundation of China(51971227);National Natural Science Foundation of China(51974288);National Natural Science Foundation of China(52174380);China Manned Space Engineering Project, Space Utilization System of China Manned Space Engineering(KJZ-YY-NCL06);Scientific Instrument Developing Project of Chinese Academy of Sciences(YJKYYQ20210012)

Corresponding Authors: ZHAO Jiuzhou, professor, Tel: (024)23971918, E-mail: jzzhao@imr.ac.cn

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https://www.ams.org.cn/EN/10.11900/0412.1961.2022.00505 OR https://www.ams.org.cn/EN/Y2024/V60/I12/1710

Fig.1 Schematic of the Bridgman-type solidification setup equipped with the ECPs producing device and the L-S phase separation process in a continuous solidifying Pb-Al alloy (rOz—the coordinate system, ECP—electric current pulse, L-S—liquid-solid)

Fig.2 Backscattered electron (BSE) images of the microstructures of the Pb-0.15Al alloys continuously solidified under the effect of ECPs with peak current densities (j_max) being 0 A/m² (a), 4 × 10⁸ A/m² (b), 8 × 10⁸ A/m² (c), and 1.2 × 10⁹ A/m² (d), respectively

Fig.3 2D size distributions of the Al-rich particles in the Pb-0.15Al alloys continuously solidified under the effect of ECPs with j_max being 0 A/m² (a), 4 × 10⁸ A/m² (b), 8 × 10⁸ A/m² (c), and 1.2 × 10⁹ A/m² (d), respectively

Fig.4 Average 2D radius ( $R ¯ 2 D$ ) of the Al-rich particles in Pb-0.15Al alloys vsj_max

Fig.5 BSE images of the surface microstructures of the Pb-0.15Al alloys solidified without ECPs (a) and with the ECPs of j_max = 8 × 10⁸ A/m² (b)

Parameter	Value	Unit
Dynamic viscosity of Pb $η m$	0.0004636exp(1036.7 / T)	Pa·s
Thermal conductivity of liquid Pb $k m$	15.88	W·m^-1·K^-1
Density of liquid Pb $ρ m$	10670 - 1.32(T - 600.4)	kg·m^-3
Density of solid Al $ρ β$	2700	kg·m^-3
Specific heat of liquid Pb $c p m$	127.61	J·kg^-1·K^-1
Latent heat of solidification of Pb $L$	24700	J·kg^-1
Electrical conductivity of liquid Pb $σ e m$	(0.0479T + 66.6)^-1	10^-8 S·m^-1
Electrical conductivity of solid Al $σ e β$	[15(exp(0.00057T)–1)]^-1	10^-8 S·m^-1

Table 1 Thermophysical property parameters of Pb-Al system^[28]

Fig.6 Supercooling ( $Δ T$ ) and supersaturation ( $S$ ) of the matrix melt, and nucleation rate ( $I$ ), number density ( $N$ ), and average radius ( $R ¯$ ) of the Al-rich particles in front of the solidification interface along the central $z$ axis for Pb-0.15Al alloys solidified without ECPs (a), and the enlargement of the microstructure evolution in the nucleation region of the Al-rich particles (b)

Fig.7 Calculated temperature profile (solid lines) along the central z axis in front of the solidification interface when solidifying Pb-0.15Al alloys at the rate of 10 mm/s with the ECPs of different j_max together with the experimental results (symbols) without ECPs (T_s(C₀)—solubility line temperature of initial composition alloy, T_eu—eutectic reaction temperature of Al-Pb alloy)

Fig.8 Temperature and flow fields of the melt in front of the solidification interface when solidifying Pb-0.15Al alloys without ECPs (a) and with the ECPs of j_max = 8 × 10⁸ A/m² (b), the maximum of the melt convection rate (V_c,max) vsj_max (c), and z-component of the melt convection velocity (V_cz) along the central z-axis (d) (Q_e—Joule heat of ECPs, f_e—electromagnetic force of ECPs)

Fig.9 Variations of $N$ and $R ¯$ (a) and the volume fraction ( $ϕ$ ) (b) of the Al-rich particles in the solidified Pb-0.15Al alloys along radial direction ( $Δ G V, e$ —electromagnetic energy of ECPs)

Fig.10 r-component of the average size particles' move-ment velocity at the position of r = 2 mm ( $u r (R ¯, r = 2 m m)$ ) along the central z axis when solidifying Pb-0.15Al alloy with the ECPs of different j_max

Fig.11 Curves of $N I$ , $N I I$ , $N I + N I I$ , and $R ¯ 2 D$ vs $j m a x$ ( $N I$ —number density of the Al-rich particles nucleated during the period of the current density j > 0; $N I I$ —number density of the Al-rich particles nucleated during the period of j = 0; j_c1 and j_c2—critical values of j_max)

Fig.12 Curves of $T$ , $S$ and $I$ vs $z$ with j_max values being 0 A/m² (a), 4 × 10⁸ A/m² (b), 6 × 10⁸ A/m² (c), and 8 × 10⁸ A/m² (d), respectively ( $I I$ —Al-rich particles' nucleation rate at the moment of $j = j m a x$ ; $I I I$ —Al-rich particles' nucleation rate during the period of $j = 0$ . The parameter with subscript “max” refers to the maximum value for the corresponding parameter)

Fig.13 Curves of $Δ T$ , $S$ , $I$ , $N$ , and $R ¯$ vs $z$ for Pb-0.15Al alloys solidified under the effect of ECPs (a, b), and the radius distribution function ( $f$ ) of the Al-rich particles at the positions of Nos.1~6 as marked in Figs.13a and b (c) with j_max = 8 × 10⁸ A/m² (Fig.13b is the local enlargement of Fig.13a)

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