He'nan KMD Advanced Materials and Technology Co.,Ltd.,Xinxiang453000,China
Citations
MENG Fanjian,LI Linjie,LIU Aikui,DONG Xuemao,LIU Zhaoyang,LIU Yan,ZHANG Ying,LU Changjian,GAO Xiaowei. Effect of Mg addition on microstructure and mechanical properties of C19400 alloy[J]. Copper Engineering,2026(2):20-26.
Abstract
This study aims to investigate the influence of Mg addition on the microstructure and properties of C19400 alloy, providing a potential approach for performance enhancement. To this end, C19400 alloys with varying Mg contents were fabricated under identical processing conditions, and then the alloys with different Mg contents were processed by thermomechanical treatment. Microstructure, mechanical properties, electrical conductivity, softening temperature, and bending performance of the alloys in different processing states were examined. Results revealed that Mg addition suppressed the precipitation of secondary phase, leading to a finer and more homogeneous dispersion. Under the same deformation and heat treatment conditions, tensile strength and hardness of the alloys increased with Mg content. Moreover, Mg-containing C19400 alloys exhibited superior high-temperature softening resistance, with the softening temperature reaching 490 ℃. Bending performance of Mg-containing C19400 alloys was significantly improved compared with the Mg-free alloys with the same thickness.
Keywords
C19400 alloy;Mg;mechanical property;high temperature softening resistance;bending property;
C19400合金是全球首款应用于引线框架的铜合金材料,由美国奥林公司于1970年研发成功,该材料的问世迅速推动了铜合金引线框架材料的研发热潮[ SHI G D,CHEN X H,JIANG H,et al. Strengthening mechanisms of Fe nanoparticles for single crystal Cu-Fe alloy[J]. Materials Science and Engineering:A,2015,636:43-47. 陈一萱,邹存磊,李长鸣,等. 高性能Cu-Fe-C复合材料研究进展[J]. 铜业工程,2025(3):44-52. 1-2]。该合金属于Cu-Fe-P系合金,其突出特点是具有较好的强度、电导率和塑性,生产工艺简单,性价比高,在航空航天、电子和汽车制造等领域获得广泛应用[ LI R G,KANG H J,CHEN Z N,et al. A promising structure for fabricating high strength and high electrical conductivity copper alloys[J]. Scientific Reports,2016,6:20799. GENG Y F,BAN Y J,WANG B J,et al. A review of microstructure and texture evolution with nanoscale precipitates for copper alloys[J]. Journal of Materials Research and Technology,2020,9(5):11918-11934. KIM H G,HAN S Z,EUH K,et al. Effects of C addition and thermo-mechanical treatments on microstructures and properties of Cu-Fe-P alloys[J]. Materials Science and Engineering:A,2011,530:652-658. LU D P,WANG J,ZENG W J,et al. Study on high-strength and high-conductivity Cu-Fe-P alloys[J]. Materials Science and Engineering:A,2006,421(1/2):254-259. WEN C Y,QIU Y,ZHANG Z G,et al. Deformation behavior of heterogeneous lamellar Cu-Fe-P immiscible alloys with enhanced strength and ductility produced by laser powder bed fusion[J]. Journal of Alloys and Compounds,2024,971:172675. XIE M,LI F,ZHOU S F,et al. Effect of laser energy density on microstructure and properties Cu-Fe-P immiscible alloys fabricated by laser selective melting:heterogeneous and high strength and magnetic[J]. Journal of Materials Research and Technology,2023,26:2759-2769. 3-8]。Fe在Cu中的溶解度(质量分数)较低,在635 ℃时可达0.15%,在1050 ℃时可达3.5%,Fe元素的添加不仅能细化晶粒,还能延缓再结晶过程,进而改善铜合金的力学性能,尽管它会降低铜的导电性和导热性,但仍值得关注; 而P在Cu基体中的溶解度有限,最大值为1.75%,在室温下几乎为0,该元素的存在能防止Fe氧化形成夹杂及氢脆,是优质的脱氧剂,还能提高焊接性和抗氧化性。C19400合金的显微组织主要由α-Cu基体和析出相(α-Fe,γ-Fe,Fe2P,Fe3P等[ 刘宇宁,莫永达,向朝建,等. C19400合金半蚀刻后表面粗糙度的影响因素[J]. 腐蚀与防护,2024,45(9):74-79. 9])组成。
众所周知,合金性能的优化主要依赖于形变热处理和微合金化两种技术。其中,微合金化对性能的优化归因于所添加元素对基体的增强,即形成新的析出相或抑制时效过程中析出相的粗化。对于铜合金板带材,在Cu基体中添加Mg,Mn,Ni,Si,Co,Te和Ag等微合金化元素,并对合金化元素含量进行合理控制,可以改变铜合金的相变和晶界行为,进而增强其力学性能、折弯性能及抗软化性能[ GENG Y F,BAN Y J,WANG B J,et al. A review of microstructure and texture evolution with nanoscale precipitates for copper alloys[J]. Journal of Materials Research and Technology,2020,9(5):11918-11934. 4, LIU K M,LU D P,ZHOU H T,et al. Effect of Ag micro-alloying on the microstructure and properties of Cu-14Fe in situ composite[J]. Materials Science and Engineering:A,2010,527(18/19):4953-4958. PANG Y J,CHAO G H,LUAN T Y,et al. Microstructure and properties of high strength,high conductivity and magnetic Cu-10Fe-0.4Si alloy[J]. Materials Science and Engineering:A,2021,826:142012. CUI J G,ZHOU R,YANG W D,et al. Effect of Mg on microstructure and properties of Cu-Ni-Fe-P alloy with high strength and high conductivity[J]. Materials Today Communications,2024,41:110513. 裴锋,田旭,薛莹妤,等. 渗碳体石墨化制备无铅石墨黄铜的腐蚀性能[J]. 南昌大学学报(理科版),2024,48(1):36-41. 王芸,王嘉慧,艾云龙,等. Al0.15MoNbTaTiVZrx难熔高熵合金的组织与力学性能[J]. 南昌航空大学学报(自然科学版),2024,38(4):58-66. 兰利亚,李耀群,杨海云. 铜及铜合金精密带材生产技术[M]. 北京:冶金工业出版社,2009. 10-15]。其中,Mg作为一种低成本的合金元素,具有大规模工业应用的潜力[ MONZEN R,WATANABE C. Microstructure and mechanical properties of Cu-Ni-Si alloys[J]. Materials Science and Engineering:A,2008,483:117-119. 16]。该元素的添加可以提高Cu-Fe系合金在变形过程中微观组织的稳定性[ SUN Y Q,PENG L J,HUANG G J,et al. Effects of Mg addition on the microstructure and softening resistance of Cu-Cr alloys[J]. Materials Science and Engineering:A,2020,776:139009. ZENG H,SUI H,WU S J,et al. Evolution of the microstructure and properties of a Cu-Cr-(Mg) Alloy upon thermomechanical treatment[J]. Journal of Alloys and Compounds,2021,857:157582. 17-18],并可抑制Cu基体的再结晶,降低Fe的极限固溶度,细化析出的Fe相,使Fe相分布更加均匀,进而提高合金的力学性能和软化温度。相关研究表明:Mg的添加可使Cu-30Fe合金屈服强度提高40%[ JEONG Y B,JO H R,PARK H J,et al. Mechanical properties and microstructural change in (Cu-Fe) immiscible metal matrix composite:Effect of Mg on secondary phase separation[J]. Journal of Materials Research and Technology,2020,9(6):15989-15995. 19]; 可使Cu-6.5Fe-0.3Mg合金的屈服强度、抗拉强度、伸长率和电导率分别提高至635 MPa,704 MPa,5.1%和60.2%IACS[ YUAN D W,ZENG H,XIAO X P,et al. Effect of Mg addition on Fe phase morphology,distribution and aging kinetics of Cu-6.5Fe alloy[J]. Materials Science and Engineering:A,2021,812:141064. 20]; 可细化Cu-Ni-Fe-P合金的晶粒尺寸和(Ni,Fe)2P析出相[ CUI J G,ZHOU R,YANG W D,et al. Effect of Mg on microstructure and properties of Cu-Ni-Fe-P alloy with high strength and high conductivity[J]. Materials Today Communications,2024,41:110513. 12],从而提高合金的强度。然而,关于Mg元素添加对C19400合金组织和性能影响的研究较少。
显微组织分析。采用Nikon ECLIPSE MA200光学显微镜(OM)对样品显微组织进行观察。试样制备。 先使用不同粒径SiC砂纸和直径约50 nm的Al2O3悬浮液以同一方向研磨和抛光,直到观察面达到镜面光洁度; 之后使用95 ml C2H5OH+5 ml HCl+5 g FeCl3溶液浸蚀样品表面10~15 s; 浸蚀后立刻冲洗并烘干。
对含Mg和无Mg的铸态C19400合金试样分别进行微观组织观察,结果如图1所示。可知,C19400合金的显微组织主要由Cu基体和灰白色的析出相组成。其中无Mg合金的析出相尺寸更大、更聚集。这是由于Mg与P的强相互作用能抑制Fe2P析出相的粗化,同时形成弥散分布的Mg2P颗粒,增强析出相的钉扎效应[ JEONG Y B,JO H R,PARK H J,et al. Mechanical properties and microstructural change in (Cu-Fe) immiscible metal matrix composite:Effect of Mg on secondary phase separation[J]. Journal of Materials Research and Technology,2020,9(6):15989-15995. YUAN D W,ZENG H,XIAO X P,et al. Effect of Mg addition on Fe phase morphology,distribution and aging kinetics of Cu-6.5Fe alloy[J]. Materials Science and Engineering:A,2021,812:141064. YU X Y,SONG Y F,WANG C C,et al. Effect of Mg content on the microstructure and properties of high strength,high conductivity Cu-Fe-Cr-Si-Mg alloy[J]. Materials Science and Engineering:A,2023,883:145510. 19-21]。在析出相强化和晶界强化的共同作用下,含Mg合金的硬度更高,且随着析出相的增多,电导率有所下降,这与表1所述相对应。Mg元素的加入对析出相的形成起到了促进作用[ SUN Y Q,PENG L J,HUANG G J,et al. Effects of Mg addition on the microstructure and softening resistance of Cu-Cr alloys[J]. Materials Science and Engineering:A,2020,776:139009. 17],但析出相尺寸由于Mg元素的添加被抑制[ LI L J,KANG H J,ZHANG S R,et al. Microstructure and properties of Cu-Cr-Zr (Mg) alloys subjected to cryorolling and aging treatment[J]. Journal of Alloys and Compounds,2023,938:168656. 22]。
Fig. 2 Properties of C19400 alloy after aging under different deformation amount:(a) Tensile strength and elongation; (b) Electrical conductivity
图2显示:随着轧制变形量的增加,合金的延伸率和电导率逐渐下降,抗拉强度逐渐上升。在60%变形及时效后,无Mg的C19400合金强度提升了约45%,电导率下降了4.7%; 而含Mg的C19400合金的强度提升了约34%,电导率下降了4.6%。合金强度大幅提升、延伸率降低,是由于变形处理导致位错塞积产生的位错强化,以及热处理中位错作为形核点促进析出相形成的时效强化,两者协同作用的结果。合金电导率下降,是由于在Mg元素导致的晶格畸变及变形位错的共同作用下,电子散射增加。在相同时效处理工艺下,增大变形量导致位错密度上升。位错强化效应使合金抗拉强度持续提高,而延伸率则与变形量成反比关系,随变形量的增加逐步降低[ CUI J G,ZHOU R,YANG W D,et al. Effect of Mg on microstructure and properties of Cu-Ni-Fe-P alloy with high strength and high conductivity[J]. Materials Today Communications,2024,41:110513. 12, YUAN D W,XIAO X P,LUO X,et al. Effect of multi-stage thermomechanical treatment on Fe phase evolution and properties of Cu-6.5Fe-0.3Mg alloy[J]. Materials Characterization,2022,185:111707. 24]。值得注意的是,当变形量超过30%,延伸率下降趋势显著减缓。与此同时,合金电导率随变形量增大而降低。
Fig. 3 Properties of rolled C19400 alloy with different Mg contents:(a) Tensile strength; (b) Electrical conductivity and hardness
为了进一步明确Mg元素对合金的影响,依据图3所示性能,选取上述Mg质量分数分别为0,0.46%和0.65%的C19400合金,在进行480 ℃×6 h时效处理后再次检测其性能,结果见表3。由表3可知:Mg含量为0.65%的合金经时效后,其抗拉强度能达到530 MPa,延伸率为4%,电导率为68.74%IACS; 而Mg含量为0.46%的合金经时效处理后,抗拉强度达到524 MPa,电导率达到70.16%IACS。由此可见,合金内Mg元素含量越高,经轧制变形及时效后,抗拉强度和硬度越高。这是由于析出的第二相增多,阻碍了位错的移动,进而使得合金强度和硬度迅速增加[ YU X Y,SONG Y F,WANG C C,et al. Effect of Mg content on the microstructure and properties of high strength,high conductivity Cu-Fe-Cr-Si-Mg alloy[J]. Materials Science and Engineering:A,2023,883:145510. 21]。然而,位错的存在会增大电子散射,进而导致电导率下降。
表3 时效态不同Mg含量下C19400合金的性能
Table 3 Properties of C19400 alloy in the aged state with varying Mg content
Mg质量分数/%
抗拉强度/MPa
屈服强度/MPa
延伸率/%
硬度(HV)
电导率/%IACS
0
495
478
4.3
146±2.02
71.53±0.54
0.46
524
502
4.2
151±1.86
70.16±0.56
0.65
530
513
4
155±2.17
68.74±0.37
2.3 抗高温软化性
图4显示了有Mg和无Mg C19400合金的抗高温软化曲线。由图4可知,两种合金的显微硬度均随退火温度上升呈现下降趋势。对比发现:在相同处理时间与温度下,含Mg合金的硬度明显高于无Mg合金; 无Mg的C19400合金的软化温度为460 ℃左右,而含Mg的C19400合金的软化温度显著提高,达到490 ℃左右; 无Mg合金在约520 ℃之后硬度曲线趋于平缓,含Mg合金在约540 ℃之后趋于平缓。这是由于C19400合金中α-Fe相的生长速度较快,较粗的α-Fe相加速了合金的再结晶,导致快速软化,而Mg元素的加入能够有效地抑制该相的生长,从而抑制由再结晶引起的软化[ CUI J G,ZHOU R,YANG W D,et al. Effect of Mg on microstructure and properties of Cu-Ni-Fe-P alloy with high strength and high conductivity[J]. Materials Today Communications,2024,41:110513. 12, SUN Y Q,PENG L J,HUANG G J,et al. Effects of Mg addition on the microstructure and softening resistance of Cu-Cr alloys[J]. Materials Science and Engineering:A,2020,776:139009. ZENG H,SUI H,WU S J,et al. Evolution of the microstructure and properties of a Cu-Cr-(Mg) Alloy upon thermomechanical treatment[J]. Journal of Alloys and Compounds,2021,857:157582. 17-18]。因此,在C19400合金中添加Mg元素,可以提高合金的硬度和软化温度。
图4 合金在不同温度相同时间下的抗软化性能曲线
Fig. 4 Softening resistance curves of C19400 alloy at different temperatures for the same duration
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[4]
GENGY F,BANY J,WANGB J,et al. A review of microstructure and texture evolution with nanoscale precipitates for copper alloys[J]. Journal of Materials Research and Technology,2020,9(5):11918-11934.
[5]
KIMH G,HANS Z,EUHK,et al. Effects of C addition and thermo-mechanical treatments on microstructures and properties of Cu-Fe-P alloys[J]. Materials Science and Engineering:A,2011,530:652-658.
[6]
LUD P,WANGJ,ZENGW J,et al. Study on high-strength and high-conductivity Cu-Fe-P alloys[J]. Materials Science and Engineering:A,2006,421(1/2):254-259.
[7]
WENC Y,QIUY,ZHANGZ G,et al. Deformation behavior of heterogeneous lamellar Cu-Fe-P immiscible alloys with enhanced strength and ductility produced by laser powder bed fusion[J]. Journal of Alloys and Compounds,2024,971:172675.
[8]
XIEM,LIF,ZHOUS F,et al. Effect of laser energy density on microstructure and properties Cu-Fe-P immiscible alloys fabricated by laser selective melting:heterogeneous and high strength and magnetic[J]. Journal of Materials Research and Technology,2023,26:2759-2769.
LIUK M,LUD P,ZHOUH T,et al. Effect of Ag micro-alloying on the microstructure and properties of Cu-14Fe in situ composite[J]. Materials Science and Engineering:A,2010,527(18/19):4953-4958.
[11]
PANGY J,CHAOG H,LUANT Y,et al. Microstructure and properties of high strength,high conductivity and magnetic Cu-10Fe-0.4Si alloy[J]. Materials Science and Engineering:A,2021,826:142012.
[12]
CUIJ G,ZHOUR,YANGW D,et al. Effect of Mg on microstructure and properties of Cu-Ni-Fe-P alloy with high strength and high conductivity[J]. Materials Today Communications,2024,41:110513.
MONZENR,WATANABEC. Microstructure and mechanical properties of Cu-Ni-Si alloys[J]. Materials Science and Engineering:A,2008,483:117-119.
[17]
SUNY Q,PENGL J,HUANGG J,et al. Effects of Mg addition on the microstructure and softening resistance of Cu-Cr alloys[J]. Materials Science and Engineering:A,2020,776:139009.
[18]
ZENGH,SUIH,WUS J,et al. Evolution of the microstructure and properties of a Cu-Cr-(Mg) Alloy upon thermomechanical treatment[J]. Journal of Alloys and Compounds,2021,857:157582.
[19]
JEONGY B,JOH R,PARKH J,et al. Mechanical properties and microstructural change in (Cu-Fe) immiscible metal matrix composite:Effect of Mg on secondary phase separation[J]. Journal of Materials Research and Technology,2020,9(6):15989-15995.
[20]
YUAND W,ZENGH,XIAOX P,et al. Effect of Mg addition on Fe phase morphology,distribution and aging kinetics of Cu-6.5Fe alloy[J]. Materials Science and Engineering:A,2021,812:141064.
[21]
YUX Y,SONGY F,WANGC C,et al. Effect of Mg content on the microstructure and properties of high strength,high conductivity Cu-Fe-Cr-Si-Mg alloy[J]. Materials Science and Engineering:A,2023,883:145510.
[22]
LIL J,KANGH J,ZHANGS R,et al. Microstructure and properties of Cu-Cr-Zr (Mg) alloys subjected to cryorolling and aging treatment[J]. Journal of Alloys and Compounds,2023,938:168656.
YUAND W,XIAOX P,LUOX,et al. Effect of multi-stage thermomechanical treatment on Fe phase evolution and properties of Cu-6.5Fe-0.3Mg alloy[J]. Materials Characterization,2022,185:111707.