脉冲电流对无氧铜杂质元素Pb分布的影响

熊姣; 李琨; 杨湘杰

doi:10.3969/j.issn.1674-6457.2026.04.019

PDF(4044 KB)

精密成形工程 ›› 2026, Vol. 18 ›› Issue (4) : 186-195. DOI: 10.3969/j.issn.1674-6457.2026.04.019

铜合金成形

脉冲电流对无氧铜杂质元素Pb分布的影响

熊姣^1,2, 李琨^2,3, 杨湘杰^2,3,*

作者信息 +

Effect of Pulsed Electric Current on the Distribution of Pb Impurities in Oxygen-free Copper

XIONG Jiao^1,2, LI Kun^2,3, YANG Xiangjie^2,3,*

Author information +

文章历史 +

摘要

目的系统探究脉冲电流（PEC）这一物理场辅助技术对无氧铜熔体中Pb杂质的净化效果,揭示其迁移规律与作用机理,以开发高效绿色的净化新工艺。方法以含1%（质量分数）Pb的无氧铜为研究对象,在高频感应炉中熔化后,施加不同参数（电极插入深度、脉冲电流大小、脉冲频率）的脉冲电流进行处理。采用金相显微镜（OM）、扫描电镜（SEM）和X射线荧光光谱仪（XRF）等手段对处理后样品的微观组织、Pb杂质的尺寸、面积占比及空间分布进行系统表征与定量分析。结果脉冲电流能有效驱动Pb杂质克服中心偏析,实现向阳极及熔体底部的定向迁移,从而在材料中心与阴极区域形成净化区。参数优化实验发现,当电极插入深度为石墨坩埚深度的1/4、脉冲电流为150 A、脉冲频率为1 500 Hz时,净化效果最优,中心区域Pb去除率最高,可达58.75%。其微观机理主要归因于电迁移力引发的电迁移效应与由电流密度梯度导致的电自由能下降。然而,当电流或频率超过临界阈值时,强烈的焦耳热效应会诱发熔体无序对流,反而导致净化效率下降。结论脉冲电流技术可有效实现无氧铜熔体中Pb杂质的定向迁移与选择性净化。杂质迁移受电迁移力和电流密度梯度力的协同驱动,且存在最优工艺窗口。本研究明确了该技术的关键工艺参数与作用机理,为高性能无氧铜的绿色制备提供了理论依据与实践指导。

Abstract

The work aims to systematically investigate the purification effect of pulsed electric current (PEC), an auxiliary physical field technology, on Pb impurities in an oxygen-free copper melt, to reveal the migration behavior and underlying mechanism of Pb and to develop an efficient and green purification process. With oxygen-free copper containing 1 wt.% Pb as the research object, the melt prepared in a high-frequency induction furnace was treated with PEC at varying parameters (electrode insertion depth, pulsed current intensity and frequency). The microstructure, size, area fraction and spatial distribution of Pb impurities in the treated samples were systematically characterized and quantitatively analyzed through optical microscopy (OM), scanning electron microscopy (SEM) and X-ray fluorescence (XRF) spectrometry. The PEC effectively drived Pb impurities to overcome central segregation, achieving directional migration towards the anode and the bottom of the melt, thereby forming purified zones in the central and cathode areas. Parameter optimization experiments revealed that the optimal purification efficiency was achieved with an electrode insertion depth as 1/4 of the depth of the graphite crucible, a pulsed current of 150 A, and a frequency of 1 500 Hz, resulting in a maximum Pb removal rate of 58.75% in the central region. The underlying mechanism was primarily attributed to the combined driving forces of electromigration (electron wind force) and the reduction in electrochemical free energy induced by the current density gradient. However, when the current or frequency exceeded critical thresholds, the intense Joule heating effect induced disordered convection within the melt, consequently reducing the purification efficiency. Pulsed electric current technology can effectively achieve directional migration and selective purification of Pb impurities in oxygen-free copper melts. The impurity migration is driven synergistically by electromigration force and current density gradient force, with an optimal processing window existing. This research clarifies the key process parameters and mechanism of this technology, providing a theoretical basis and practical guidance for the green preparation of high-performance oxygen-free copper.

导出引用

熊姣, 李琨, 杨湘杰. 脉冲电流对无氧铜杂质元素Pb分布的影响[J]. 精密成形工程. 2026, 18(4): 186-195 https://doi.org/10.3969/j.issn.1674-6457.2026.04.019

XIONG Jiao, LI Kun, YANG Xiangjie. Effect of Pulsed Electric Current on the Distribution of Pb Impurities in Oxygen-free Copper[J]. Journal of Netshape Forming Engineering. 2026, 18(4): 186-195 https://doi.org/10.3969/j.issn.1674-6457.2026.04.019

中图分类号： TG146.2

参考文献

[1] WANG Z W, LI Z, BU J J, et al.One-Step Direct Desulfurization of Cuprous Sulfide for Copper Recovery via Electrolysis in Deep Eutectic Solvent[J]. Separation and Purification Technology, 2022, 303: 122133.
[2] GONG A, CAO C F, YAN K, et al.A Novel Method for Rapid and Highly Selective Removal of Arsenic from Copper Electrolyte Using Zirconium Salts[J]. Chemical Engineering Journal, 2024, 481: 148460.
[3] QIN Z L, XIAO J H, DU T Y, et al.Eco-Friendly Iron Extraction from Fe-Containing Copper Smelting Slag via Reduction Roasting with Coal and Magnetic Separation: Experimental and Mechanism Insights[J]. Journal of Environmental Chemical Engineering, 2024, 12(5): 114117.
[4] 孙志成. 新能源用高纯无氧铜材生产工艺及性能研究[D]. 南昌: 南昌大学, 2024.
SUN Z C.Research on the Production Process and Performance of High-Purity Oxygen-Free Copper for New Energy[D]. Nanchang: Nanchang University, 2024.
[5] ZHANG Z H, LIU H T, HUA Y X, et al.Study on the Effect of Phosphorus on Anti-Softening Performance of Oxygen-Free Copper[J]. Journal of Materials Research and Technology, 2024, 33: 2612-2623.
[6] 张勇, 赵冬伟, 舒波. 再生铜产业发展现状及发展机遇[J]. 云南科技管理, 2023, 36(2): 1-5.
ZHANG Y, ZHAO D W, SHU B.Present Situation and Development Opportunities of Recycled Copper Industry[J]. Yunnan Science and Technology Management, 2023, 36(2): 1-5.
[7] 张学友, 王海北, MA Hao.铜产业的双碳目标实现路径与方法[J]. 矿冶, 2024, 33(3): 456-465.
ZHANG X Y, WANG H B, MA H.Paths and Methods for Achieving Carbon Peaking and Carbon Neutrality in the Copper Industry[J]. Mining and Metallurgy, 2024, 33(3): 456-465.
[8] 周伟, 刘璐华, 杨庆, 等. 外加电流对钢中夹杂物影响的研究进展[J]. 江西冶金, 2023, 43(6): 465-475.
ZHOU W, LIU L H, YANG Q, et al.Research Progress of the Effect of External Currents on Inclusions in Steel[J]. Jiangxi Metallurgy, 2023, 43(6): 465-475.
[9] 钟云波, 任忠鸣, 邓康, 等. 交变磁场净化金属液时金属液紊流的形成及其控制[J]. 中国有色金属学报, 2001, 11(4): 541-546.
ZHONG Y B, REN Z M, DENG K, et al.Formation and Control of Turbulent in Metal Melts Purified by Alternating Magnetic Field[J]. The Chinese Journal of Nonferrous Metals, 2001, 11(4): 541-546.
[10] XIANG S Q, MA R, ZHANG X F.Removing Hydrogen in Solid Metal Using Electric Current Pulse[J]. Journal of Alloys and Compounds, 2020, 845: 156083.
[11] MAKAROV S, LUDWIG R, RESNICK J, et al.The Effect of a Short Pulse of Current on Small Particles in a Conducting Fluid[J]. Journal of Nondestructive Evaluation, 1999, 18(3): 99-102.
[12] KOROVIN V M.Pressure Pulse Induced by a Pulsed Electric Current in a Cylindrical Liquid Conductor[J]. Technical Physics, 2005, 50(7): 815-820.
[13] GUO J D, WANG X L, DAI W B.Microstructure Evolution in Metals Induced by High Density Electric Current Pulses[J]. Materials Science and Technology, 2015, 31(13): 1545-1554.
[14] ZHANG G Z, YAN L G, ZHANG X F.Inclusion Removal in Molten Magnesium by Pulsed Electric Current[J]. ISIJ International, 2020, 60(5): 815-822.
[15] FENG Y, LIU C H, HUANG X S, et al.Purification of Mg-Gd-Zr Alloys with Pulsed Electric Current[J]. Metallurgical and Materials Transactions B, 2023, 54(5): 2467-2478.
[16] REN S F, YAN L G, ZHANG X F, et al.Separation of Impurity Iron from Polysilicon by Pulsed Electric Current[J]. JOM, 2020, 72(11): 4101-4108.
[17] SUN Y M, HUANG X S, LIU C H, et al.Impurity Iron Separation from Molten Secondary Aluminum by Pulsed Electric Current[J]. Journal of Alloys and Compounds, 2023, 934: 167903.
[18] HUANG X S, ZHAO H L, WANG C Y, et al.One-Step Separation of Hazardous Element Lead in Brass Alloy by Physical External Field[J]. Journal of Cleaner Production, 2020, 276: 123358.
[19] 高翔宇, 严仁杰, 张涛, 等. 电脉冲诱导下AZ31镁合金动态再结晶与β-Mg₁₇Al₁₂相低温溶解的协同机制影响[J]. 精密成形工程, 2025, 17(7): 62-68.
GAO X Y, YAN R J, ZHANG T, et al.Synergistic Mechanisms of Electropulsing-Induced Dynamic Recrystallization and Low-Temperature Dissolution of β-Mg₁₇Al₁₂ Phase in AZ31 Magnesium Alloy[J]. Journal of Netshape Forming Engineering, 2025, 17(7): 62-68.
[20] 王志强, 钟嘉珉, 李宗安, 等. 固态电迁移提纯稀土金属的国内外研究进展[J]. 中国稀土学报, 2022, 40(6): 956-975.
WANG Z Q, ZHONG J M, LI Z A, et al.Research Progress of Purification of Rare Earth Metals by Solid-State Electrotransport in China and Overseas[J]. Journal of the Chinese Society of Rare Earths, 2022, 40(6): 956-975.
[21] ZHOU M C, DAI Y X, LIU C H, et al.Migration Behavior of Impurity Iron in Silicon Melt under Pulsed Electric Current[J]. Acta Metallurgica Sinica (English Letters), 2024, 37(5): 889-903.
[22] ZHANG B Y, HUANG X S, ZHANG X F, et al.Purification of Cu-Zn Melt Based on the Migration Behavior of Lead and Bismuth under Pulsed Electric Current[J]. Journal of Cleaner Production, 2023, 396: 136577.
[23] LIU C H, MA H, HUANG X, et al.Controlling the Spatial Distribution and Alignment of Inclusions in Sulfur Containing Steel by Pulsed Electric Current[J]. Journal of Materials Research and Technology, 2025, 35: 5084-5096.
[24] SCHAICH W L.Theory of the Driving Force for Electromigration[J]. Physical Review B, 1976, 13(8): 3350-3359.
[25] HO P S, KWOK T.Electromigration in Metals[J]. Reports on Progress in Physics, 1989, 52(3): 301-348.
[26] QIN R S, BHOWMIK A.Computational Thermodynamics in Electric Current Metallurgy[J]. Materials Science and Technology, 2015, 31(13): 1560-1563.
[27] TU K N, LIU Y X, LI M L.Effect of Joule Heating and Current Crowding on Electromigration in Mobile Technology[J]. Applied Physics Reviews, 2017, 4: 011101.
[28] TU K N.Recent Advances on Electromigration in Very-Large-Scale-Integration of Interconnects[J]. Journal of Applied Physics, 2003, 94(9): 5451-5473.
[29] 周亚冲. 脉冲电流对Ti-6Al-4V合金相变行为的影响与电致强化机理研究[D]. 长春: 吉林大学, 2023.
ZHOU Y C.Study on Phase Transformation Behavior of Ti-6Al-4V Alloy and Its Strengthening Mechanism via Electropulsing Treatment[D]. Changchun: Jilin University, 2023.
[30] SAMUEL E I, BHOWMIK A, QIN R S.Accelerated Spheroidization Induced by High Intensity Electric Pulse in a Severely Deformed Eutectoid Steel[J]. Journal of Materials Research, 2010, 25(6): 1020-1024.
[31] GAO Y, WANG Q, MA N, et al.Effect of High-Density Pulse Current on the Microstructure and Mechanical Properties of Hypereutectic Al-Si Alloy[J]. Journal of Materials Processing Technology, 2016, 233: 114-120.