Selection of Trace Interface Active Element for Zn-Pb Monotectic Alloy
Received date: 2024-04-08
Revised date: 2024-07-20
Online published: 2025-02-20
Supported by
National Key Research and Development Program of China(2021YFA0716303);China Manned Space Station Project(KJZ-YY-NCL-1-02);China Manned Space Station Project(KJZ-YY-NCL-1-06);Natural Science Foundation of Liaoning Province(2023-MS-023)
Zn-Pb alloy is an excellent electrochemical material, provided that Pb-rich particles are well dispersed within the Zn-based matrix. When used as the anode in Zn-MnO2 batteries, the Zn-Pb alloy effectively inhibits hydrogen evolution corrosion, enhances cycling stability, and improves Coulombic efficiency, thus significantly increasing the battery's durability. However, Zn-Pb alloy is a typical monotectic alloy, characterized by liquid-liquid phase transformation during solidification. In this transformation, a homogeneous monotectic alloy melt separates into two liquid phases, resulting in a phase-segregated microstructure that limits the alloy's application. Extensive research has been conducted on the solidification of monotectic alloys. The use of external fields such as ultrasound, electric fields, magnetic fields, and composite electric-magnetic fields to control the solidification structure has been explored. Studies have also investigated the impact of nucleating agents on the solidification process and microstructure. In addition, alloying with a third element to control the solidification process has proven effective. Results indicate that the microstructure evolution during the liquid-liquid phase transition involves complex kinetic behaviors, including nucleation, growth, Ostwald ripening, motion, collision-coagulation of minority phase droplets, and their interaction with the solidification front. The nucleation and migration of minority phase droplets have a dominant influence on the solidification microstructure of monotectic alloys. Adding interface active elements to the alloy melt reduces the liquid/liquid interfacial energy, increasing the nucleation rate and reducing the Marangoni migration velocity of minority phase droplets. This promotes the formation of a well-dispersed microstructure in Zn-Pb alloys. According to the Gibbs isothermal adsorption equation, an element can act as an interface active element if it segregates at the interface between the two liquid phases at the onset of the liquid-liquid phase transition. In this study, solidification experiments were conducted with Zn-4.0%Pb (mass fraction) alloy micro-alloyed with different trace elements to evaluate their effects on the liquid-liquid phase transition. The results indicate that trace elements Sn and In significantly refine Pb-rich particles, while the effects of Cu and Bi are negligible. An analytical model was developed to calculate the segregation behavior of trace elements at the Zn-rich liquid/Pb-rich liquid interface in the Zn-Pb alloy. Calculations reveal that Sn and In segregate to the liquid/liquid interface and act as interface active elements, facilitating effective refinement of Pb-rich particles. In contrast, Cu and Bi cannot act as interface active elements. The segregation behavior of trace elements is closely related to their interactions with Zn and Pb; trace elements can only act as interface active elements if they exhibit weak attraction or repulsion toward both Zn and Pb.
Key words： monotectic alloy; interface active element; trace element; solidification
YANG Linjie , ZHANG Lili , ZHAO Jiuzhou , JIANG Hongxiang , HE Jie . Selection of Trace Interface Active Element for Zn-Pb Monotectic Alloy[J]. Acta Metall Sin, 2026 , 62(3) : 532 -540 . DOI: 10.11900/0412.1961.2024.00101
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