Article(id=1251457066431361053, tenantId=1146029695717560320, journalId=1251194703438200922, issueId=1251457062706820082, articleNumber=null, orderNo=null, doi=10.14106/j.cnki.1001-2028.2025.0118, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1742140800000, receivedDateStr=2025-03-17, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1776300215585, onlineDateStr=2026-04-16, pubDate=1759593600000, pubDateStr=2025-10-05, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1776300215585, onlineIssueDateStr=2026-04-16, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1776300215585, creator=13041195026, updateTime=1776300215585, updator=13041195026, issue=Issue{id=1251457062706820082, tenantId=1146029695717560320, journalId=1251194703438200922, year='2025', volume='44', issue='10', pageStart='1119', pageEnd='1244', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=null, createTime=1776300214696, creator=13041195026, updateTime=1776300327814, updator=13041195026, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1251457537212629591, tenantId=1146029695717560320, journalId=1251194703438200922, issueId=1251457062706820082, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1251457537212629592, tenantId=1146029695717560320, journalId=1251194703438200922, issueId=1251457062706820082, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=1229, endPage=1236, ext={EN=ArticleExt(id=1251457066641076262, articleId=1251457066431361053, tenantId=1146029695717560320, journalId=1251194703438200922, language=EN, title=Influence of Ni particles on the melting characteristics and mechanical properties of SAC305solder, columnId=1251457065399563262, journalTitle=Electronic Components and Materials, columnName=Research & Development, runingTitle=null, highlight=null, articleAbstract=

To address the temperature gradient requirements for low-temperature soldering and high-temperature service,variable-temperature solders were developed,and the regulatory effects of Ni particle content on their properties and those of brazed joints were clarified. Using 4#SAC305solder powder as the base material,2-5 μm Ni particles and HP01high-activity flux were compounded to prepare Ni-based variable temperature solder paste. The effects of Ni content on the melting characteristics and wettability of the solder paste,as well as the growth of intermetallic compounds(IMCs)at the brazed joint interface and changes in shear strength during aging,were investigated. The results show that when the Ni content is 10%,the solder's melting point can rise to 227 ℃,with only a marginal increase observed after high-temperature storage. Wettability initially enhanced and subsequently decreased as the Ni content increased,resulting in a 60% reduction in the spread area observed at 20% Ni. The growth of the interfacial IMC layer corresponds well with the square root of the aging duration,achieving a thickness of 37.611 μm after 360hours of aging at 20% Ni. Under the same Ni content,shear strength decreases with prolonged aging,and under the same aging condition,it decreases with increasing Ni content. The solder paste with 10% Ni exhibitsminimal impact on shear strength due to aging,and its fracture surface displays a mixed ductile-brittle characteristic. The variable-temperature solder with 10% Ni content demonstrates the best overall performance,effectively raises the solder's melting point while exhibiting excellent stability during high-temperature service,thereby meeting the requirements for temperature gradient applications.

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针对低温焊接与高温服役场景下的温度梯度需求,开发了变温焊料,并明确了Ni颗粒含量对焊料及钎焊接头性能的调控规律。以4#SAC305钎料粉为基体,复配2~5 μm Ni颗粒与HP01高活性助焊剂,制备了Ni颗粒可变温锡膏;研究Ni含量(质量分数)对锡膏熔化特性、润湿性的影响,及时效过程中钎焊接头界面金属间化合物(IMC)生长与剪切强度变化。结果表明:当Ni含量为10%时,焊料的熔点上升至227 ℃,在高温储存后熔点仅微幅上升。随着Ni含量的增加,润湿性先升高后降低,在Ni含量达到20%时,铺展面积减少了60%。界面IMC层的厚度与时效时间的平方根呈现良好的拟合关系,在20%Ni含量下时效360h后,IMC层的厚度达到37.611 μm。相同Ni含量下,随着时效时间的延长,剪切强度会降低;而在相同时效时间下,随着Ni含量的增加,剪切强度也会减小。10%Ni含量的焊料剪切强度受时效影响较小,且断口表现出韧脆混合的特征。10%Ni含量的变温焊料综合性能最优,既提高焊料熔点,又在高温服役中表现出良好稳定性,可满足温度梯度使用需求。

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通信作者:闫焉服,教授,博士,主要研究方向为先进材料连接。E-mail:
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Ni, Sn含量变化对Cu-Ni-Sn合金时效过程的影响[D].赣州:江西理工大学, 2021., articleTitle=null, refAbstract=null)], funds=null, companyList=[AuthorCompany(id=1251457071053484235, tenantId=1146029695717560320, journalId=1251194703438200922, articleId=1251457066431361053, xref=null, ext=[AuthorCompanyExt(id=1251457071057678540, tenantId=1146029695717560320, journalId=1251194703438200922, articleId=1251457066431361053, companyId=1251457071053484235, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=School of Materials Science and Engineering, Henan University of Science and Technology, Luoyang 471023, Henan Province, China), AuthorCompanyExt(id=1251457071061872845, tenantId=1146029695717560320, journalId=1251194703438200922, articleId=1251457066431361053, companyId=1251457071053484235, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=河南科技大学 材料科学与工程学院,河南 洛阳 471023)])], 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journalId=1251194703438200922, articleId=1251457066431361053, language=CN, label=图11, caption=不同Ni颗粒含量对复合焊料拉剪强度的影响, figureFileSmall=fzFSCmKI1GPcVaoq4y8ipg==, figureFileBig=AqSYC+qclokTqlkh+/ur9Q==, tableContent=null), ArticleFig(id=1251457078099915251, tenantId=1146029695717560320, journalId=1251194703438200922, articleId=1251457066431361053, language=EN, label=Tab. 1, caption=

Effect of Ni content after reflow on the melting characteristics of temperature-variable solder

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成分固相线(℃)峰值(℃)液相线(℃)熔程(℃)
SAC305217.6222.5228.410.8
SAC305+1%Ni219.7234.6243.323.6
SAC305+3%Ni221236244.223.2
SAC305+5%Ni223.1236.4245.622.5
SAC305+10%Ni227240.6248.921.9
SAC305+15%Ni226.1238.324720.9
SAC305+20%Ni224.3238.1246.622.3
), ArticleFig(id=1251457078187995641, tenantId=1146029695717560320, journalId=1251194703438200922, articleId=1251457066431361053, language=CN, label=表1, caption=

回流后Ni含量对变温焊料熔化特性的影响

, figureFileSmall=null, figureFileBig=null, tableContent=
成分固相线(℃)峰值(℃)液相线(℃)熔程(℃)
SAC305217.6222.5228.410.8
SAC305+1%Ni219.7234.6243.323.6
SAC305+3%Ni221236244.223.2
SAC305+5%Ni223.1236.4245.622.5
SAC305+10%Ni227240.6248.921.9
SAC305+15%Ni226.1238.324720.9
SAC305+20%Ni224.3238.1246.622.3
), ArticleFig(id=1251457078271881727, tenantId=1146029695717560320, journalId=1251194703438200922, articleId=1251457066431361053, language=EN, label=Tab. 2, caption=

Influence of Ni content on the melting characteristics of temperature-variable solders after high-temperature storage

, figureFileSmall=null, figureFileBig=null, tableContent=
成分固相线(℃)峰值(℃)液相线(℃)熔程(℃)
SAC305218.6223.5228.910.3
SAC305+1%Ni219.7233.6240.320.6
SAC305+3%Ni221.2236.8240.519.3
SAC305+5%Ni224.3236.8242.718.4
SAC305+10%Ni226.8239.6245.118.3
SAC305+15%Ni226.1238.7246.220.1
SAC305+20%Ni224.2238.1245.721.5
), ArticleFig(id=1251457078343184898, tenantId=1146029695717560320, journalId=1251194703438200922, articleId=1251457066431361053, language=CN, label=表2, caption=

高温储存后Ni含量对变温焊料熔化特性的影响

, figureFileSmall=null, figureFileBig=null, tableContent=
成分固相线(℃)峰值(℃)液相线(℃)熔程(℃)
SAC305218.6223.5228.910.3
SAC305+1%Ni219.7233.6240.320.6
SAC305+3%Ni221.2236.8240.519.3
SAC305+5%Ni224.3236.8242.718.4
SAC305+10%Ni226.8239.6245.118.3
SAC305+15%Ni226.1238.7246.220.1
SAC305+20%Ni224.2238.1245.721.5
), ArticleFig(id=1251457078531928585, tenantId=1146029695717560320, journalId=1251194703438200922, articleId=1251457066431361053, language=EN, label=Tab. 3, caption=

Relationship between total IMC thickness in the interface layer of thermally cycled solder and aging time

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成分总IMC厚度(μm)
0h120h240h360h
SAC3053.5593.5163.0363.469
SAC305+1%Ni10.71612.94416.52421.738
SAC305+3%Ni12.63118.54021.03223.127
SAC305+5%Ni17.66322.99226.66729.452
SAC305+10%Ni22.27429.92131.19029.706
SAC305+15%Ni24.63230.07131.29432.960
SAC305+20%Ni25.60033.36536.75337.611
), ArticleFig(id=1251457078628397579, tenantId=1146029695717560320, journalId=1251194703438200922, articleId=1251457066431361053, language=CN, label=表3, caption=

变温焊料界面层总IMC厚度与时效时间的关系

, figureFileSmall=null, figureFileBig=null, tableContent=
成分总IMC厚度(μm)
0h120h240h360h
SAC3053.5593.5163.0363.469
SAC305+1%Ni10.71612.94416.52421.738
SAC305+3%Ni12.63118.54021.03223.127
SAC305+5%Ni17.66322.99226.66729.452
SAC305+10%Ni22.27429.92131.19029.706
SAC305+15%Ni24.63230.07131.29432.960
SAC305+20%Ni25.60033.36536.75337.611
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Ni颗粒对SAC305钎料熔化特性及力学性能的影响
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周慧 , 闫焉服 , 程江洋
电子元件与材料 | 研究与试制 2025,44(10): 1229-1236
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电子元件与材料 | 研究与试制 2025, 44(10): 1229-1236
Ni颗粒对SAC305钎料熔化特性及力学性能的影响
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周慧, 闫焉服 , 程江洋
作者信息
  • 河南科技大学 材料科学与工程学院,河南 洛阳 471023

通讯作者:

通信作者:闫焉服,教授,博士,主要研究方向为先进材料连接。E-mail:
Influence of Ni particles on the melting characteristics and mechanical properties of SAC305solder
Hui ZHOU, Yanfu YAN , Jiangyang CHENG
Affiliations
  • School of Materials Science and Engineering, Henan University of Science and Technology, Luoyang 471023, Henan Province, China
出版时间: 2025-10-05 doi: 10.14106/j.cnki.1001-2028.2025.0118
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针对低温焊接与高温服役场景下的温度梯度需求,开发了变温焊料,并明确了Ni颗粒含量对焊料及钎焊接头性能的调控规律。以4#SAC305钎料粉为基体,复配2~5 μm Ni颗粒与HP01高活性助焊剂,制备了Ni颗粒可变温锡膏;研究Ni含量(质量分数)对锡膏熔化特性、润湿性的影响,及时效过程中钎焊接头界面金属间化合物(IMC)生长与剪切强度变化。结果表明:当Ni含量为10%时,焊料的熔点上升至227 ℃,在高温储存后熔点仅微幅上升。随着Ni含量的增加,润湿性先升高后降低,在Ni含量达到20%时,铺展面积减少了60%。界面IMC层的厚度与时效时间的平方根呈现良好的拟合关系,在20%Ni含量下时效360h后,IMC层的厚度达到37.611 μm。相同Ni含量下,随着时效时间的延长,剪切强度会降低;而在相同时效时间下,随着Ni含量的增加,剪切强度也会减小。10%Ni含量的焊料剪切强度受时效影响较小,且断口表现出韧脆混合的特征。10%Ni含量的变温焊料综合性能最优,既提高焊料熔点,又在高温服役中表现出良好稳定性,可满足温度梯度使用需求。

变温焊料  /  熔化特性  /  润湿性  /  热效应  /  剪切强度

To address the temperature gradient requirements for low-temperature soldering and high-temperature service,variable-temperature solders were developed,and the regulatory effects of Ni particle content on their properties and those of brazed joints were clarified. Using 4#SAC305solder powder as the base material,2-5 μm Ni particles and HP01high-activity flux were compounded to prepare Ni-based variable temperature solder paste. The effects of Ni content on the melting characteristics and wettability of the solder paste,as well as the growth of intermetallic compounds(IMCs)at the brazed joint interface and changes in shear strength during aging,were investigated. The results show that when the Ni content is 10%,the solder's melting point can rise to 227 ℃,with only a marginal increase observed after high-temperature storage. Wettability initially enhanced and subsequently decreased as the Ni content increased,resulting in a 60% reduction in the spread area observed at 20% Ni. The growth of the interfacial IMC layer corresponds well with the square root of the aging duration,achieving a thickness of 37.611 μm after 360hours of aging at 20% Ni. Under the same Ni content,shear strength decreases with prolonged aging,and under the same aging condition,it decreases with increasing Ni content. The solder paste with 10% Ni exhibitsminimal impact on shear strength due to aging,and its fracture surface displays a mixed ductile-brittle characteristic. The variable-temperature solder with 10% Ni content demonstrates the best overall performance,effectively raises the solder's melting point while exhibiting excellent stability during high-temperature service,thereby meeting the requirements for temperature gradient applications.

variable-temperature solder  /  melting characteristics  /  wettability  /  thermal effect  /  shear strength
周慧, 闫焉服, 程江洋. Ni颗粒对SAC305钎料熔化特性及力学性能的影响. 电子元件与材料, 2025 , 44 (10) : 1229 -1236 . DOI: 10.14106/j.cnki.1001-2028.2025.0118
Hui ZHOU, Yanfu YAN, Jiangyang CHENG. Influence of Ni particles on the melting characteristics and mechanical properties of SAC305solder[J]. Electronic Components and Materials, 2025 , 44 (10) : 1229 -1236 . DOI: 10.14106/j.cnki.1001-2028.2025.0118
随着电子贴装技术的快速发展,晶圆级芯片尺寸封装(WL-CSP)通常需要经历多次回流[1-3],然而现有的温度梯度焊料已经无法满足高端封装技术的发展需求,温度梯度钎料制备已经成为先进电子封装的研究热点[4-5]
闫焉服课题组[6-7]对Cu/Ag/Ni颗粒增强的锡基复合钎料展开了深入研究,研究结果显示这些颗粒显著地提升了锡基复合钎料的抗蠕变性能和力学性能;其中质量分数为1%Cu颗粒增强SnPb基复合钎料的蠕变寿命较基体钎料提高了17倍;质量分数为5%Ag颗粒增强SnCu基复合钎料的蠕变寿命较基体钎料提高了23倍;质量分数为5%和10%的Ni颗粒增强锡铅基复合钎料的蠕变寿命分别较基体钎料提高了85倍和168倍。Ni颗粒增强型SnBi无铅钎料的制备和性能研究显示,Ni颗粒可能对熔化特性有重要影响。高源[8]通过向Sn-0.3Ag-0.7Cu钎料合金中添加微量纳米Ni颗粒,研究结果表明微量的Ni对钎料熔点的影响并不显著。顾鑫[9]通过混合搅拌的方式制备了SAC305/(0.01%~0.5%)Ag复合锡膏,采用DSC测试分析纳米Ag颗粒对焊料合金热特性的影响。发现随着纳米Ag颗粒添加量的增加,焊料合金的熔点呈现出先升高后降低的趋势,其中最大升温幅度达到了2.2 ℃。石成杰[10]在SAC305中加入质量分数为10%的Cu颗粒,使焊料熔点提升了13 ℃。Mokhtari等[11]通过机械混合法,在Sn-Bi焊料中添加了质量分数为30%的Cu颗粒,使得焊缝熔点从139 ℃提升至201 ℃。综上所述,颗粒增强复合钎料不仅能够提升抗蠕变性能和力学性能,同时还会对复合钎料的熔化特性产生一定影响。然而,从现有文献来看目前针对高含量Ni颗粒对SAC305钎料熔化特性影响的研究相对较少。
本文以SAC305无铅钎料作为研究对象,深入研究了Ni对SAC305无铅复合钎料熔化特性的影响、焊接接头在时效过程中的组织演变规律,以及在时效条件下不同Ni含量对复合焊料剪切强度的影响,通过开展相关分析探究其影响机理,为丰富多温度梯度软钎料体系及多级封装技术的发展提供参考。
基体钎料选用北京康普锡威科技生产的4#SAC305粉末,增强颗粒为2~5μmNi颗粒,由广州金属冶金(集团)提供。将4#SAC305粉末与Ni颗粒按多种比例精确混合,制备复合焊粉基底。随后,将此复合焊粉与HP01高活性助焊剂按严格的质量配比88∶12均匀混合,最终生成颗粒强化的复合焊膏。Ni颗粒在复合焊粉中的质量分数分别为1%,3%,5%,10%,15%,20%,机械混合时间不少于30min。然后将混合物装入锡膏专用密封罐,再放入锡膏搅拌机中搅拌3min,以保证金属颗粒在复合焊膏中均匀分布。取出后冷藏保存备用,制备流程如图1所示。
选取一块尺寸为40mm×40mm×1mm(长×宽×高)的铝基板,在其表面精确涂布0.3g复合焊膏,随后使用962D八段回流焊机进行回流实验,得到无铅复合焊点。实验峰值温度设定为250 ℃,钎焊时长为120s。使用DSC300型差示扫描量热仪开展熔点测试,准确称取10mg样品,设置测量温度范围为0~300℃,并选择10 ℃/min的升温速率。测试过程中,样品在纯氩气的保护氛围中进行,以防止氧化影响。
利用精密电子天平精确地称取0.3g颗粒增强复合焊膏,再放置于尺寸为30mm×30mm×0.3mm的紫铜板上。随后,采用962D回流焊机进行实验,实验设定钎焊温度为250℃,钎焊时长设定为2min。采用已知面积的标准参照物(一元硬币)作为参照,并将铺展试样和参照物拍摄对照,然后用Photoshop软件测定铺展试样面积S,计算公式如式(1)所示:
式中:S为焊点实际铺展面积(mm2);S2为焊点铺展面积的测量值(mm2);S0为标准参照物面积的测量值(mm2);S1为标准参照物的实际面积(mm2)。
沿润湿试样中心进行裁剪,使用Photoshop软件测量横截面(图2)中的润湿角θlθr。由公式(2)可求出润湿角θ:
在尺寸为60mm×25mm×2mm的紫铜板上开展搭接实验,确保每组的钎料添加量及常温下在铜板上的涂抹面积保持一致,搭接区域尺寸统一设定为25mm×10mm。采用回流焊接炉进行实验,设定焊接温度为250 ℃。焊接实验结束后,将试样置于真空干燥箱中进行时效处理,设定温度为150℃,按照0,120,240,360h的时间节点依次取出时效样件。力学性能测试在WDW-100型微机控制电子万能试验机上进行,剪切速度设定为1mm/min,实验温度为25 ℃,为确保数值准确性,接头拉剪强度测试值取3个试样的平均值。再利用线切割机器将复合焊料/Cu基板试样切割出横截面,并对横截面进行打磨、抛光处理。随后,采用JSM—5610LV型扫描电子显微镜(SEM)及能谱仪(EDS)对横截面的组织形貌与成分展开观察分析。
图3为试样DSC曲线示意图。根据ICTA标准化委员会相关规定,DSC曲线的前基线延长线与峰的前沿最大斜率处切线的交点代表熔点,前基线是指在熔化过程之前接近水平的基线。图3中A点对应的点TA是外推起始点温度(固相线温度),也即熔点,该点由峰前沿最大斜率处的切线与前基线延长线的交点确定,B点对应的点TB是液相线温度,C点对应的温度是峰值。熔程即为液相线温度与固相线温度之差。
表1图4为回流后Ni颗粒含量对变温焊料熔化特性的影响。可以看出:在Ni质量分数从0%增加至10%的过程中,变温焊料的熔点、峰值、液相线均随Ni质量分数增加而呈现出升高的趋势;当Ni元素的质量分数达到10%时,焊料的熔点达到最高值227℃,相较于基体钎料熔点提高了10 ℃。在Ni质量分数为15%和20%时,变温焊料的熔点相较于10%时略有下降,但熔点仍保持在较高水平且高于基体钎料。随着Ni含量的增加,熔程虽表现出一定波动,但总体保持相对稳定,且高于基体钎料。这是由于在基体钎料中加入Ni颗粒在回流后组成成分除了β-Sn和Ag3 Sn以外,还有(Ni,Cu)3 Sn4、(Ni,Cu)6 Sn5相,多种合金在熔化时,由于熔化温度不同,从而使熔程变大,对焊接性能会产生不利影响。
图5为Ni颗粒变温焊料回流后的扫描电镜(SEM)图。从图中可以看出,Ni颗粒与基体焊料已发生冶金反应,并两者紧密结合在一起,其中黑色部分表示难溶且未与基体焊料反应的Ni颗粒。除紧邻Ni颗粒的灰色金属间化合物(IMC)外,变温焊料内部还散布着不含Ni颗粒内核的IMC。通过EDS检测,此灰色部分IMC为Sn-Ni-Cu的三元合金或者固溶体,银白色相为Ag3 Sn。对于1%Ni颗粒添加的变温焊料而言(如图5(a)),灰色IMC呈散点状,SAC305作为近共晶焊料,成分均匀,熔点与基体焊料相近。但是对于10%Ni颗粒添加的变温焊料而言(如图5(b)),此时部分Ni颗粒团聚,其周围的灰色IMC交织并逐渐连成一片,随着Ni含量增加,团聚现象加剧,IMC生成量也随之增多。由于微米Ni颗粒具有较大的比表面积,因此会消耗更多的Sn,进而导致SAC305合金中β-Sn相的含量显著降低。相组成发生变化,也偏离了共晶成分。由于SAC305焊料本身属于近共晶类型,因此复合锡膏的熔点会相应升高。对于添加了20% Ni颗粒的变温焊料,其熔点稍有下降。其原因在于无铅复合焊料的熔点不仅与相组成的变化有关,还受到相组成热特性的影响。Ni颗粒与β-Sn相的吸热效应对焊料熔点的降低作用明显超过了Ni颗粒周围IMC增多所导致的熔点升高影响,因此熔点降低。
表2为高温储存后Ni颗粒含量对变温焊料熔化特性的影响。高温储存对变温焊料的熔点影响并不显著,总体上熔点随Ni含量的增加呈现先升后降的趋势。当Ni质量分数为10%时,熔点达到最高值226.8 ℃,相较于基体焊料高出8.2 ℃。此时液相线略有降低,熔程也略有减小。随着Ni含量的增加,熔程呈现先下降后略微上升的趋势,且变化幅度较小。由于熔化范围的缩小有助于变温焊料的实际应用,可有效减轻焊接过程中对基板的侵蚀和偏析现象。固相和液相线温度的变化可归因于加入金属元素后,合金成分更接近或远离共晶成分的特性[14]
图6中,添加10%Ni的变温焊料经高温储存后,Ni颗粒周围的IMC厚度并未明显增厚,仅观察到Ni颗粒更为明显地团聚现象。变温焊料的熔化特性变化规律以及焊料内部的微观组织在回流和高温储存后均未发生显著改变,这表明变温机理保持一致。
图7为Ni颗粒添加变温焊料及SAC305基体焊料回流后铺展面积和润湿角的变化情况。可以看出,当Ni质量分数小于5%时,变温焊料均表现出较好的润湿性。当Ni质量分数小于1%时,变温焊料润湿面积增加,润湿角减小;Ni质量分数在1%~3%之间,润湿面积略有降低,但仍高于基体焊料;在Ni质量分数超过3%后,随着Ni含量的继续增加,变温焊料的润湿面积先增后减;当Ni质量分数达到5%以上时,润湿面积显著下降。由此可见少量Ni颗粒的添加能降低液态变温焊料的界面张力,从而略微增加润湿面积。然而,Ni金属颗粒在焊接过程中活性较高,易生成氧化物,进而阻碍焊料的润湿。且Ni添加量越多,生成的氧化物也越多,进而阻碍作用愈发明显。当Ni质量分数超过3%时,这种阻碍作用对变温焊料的影响将逐渐超越Ni颗粒添加所减少的界面张力对变温焊料产生的影响。Ni含量越高,变温焊料的黏度越大,从而对润湿面积产生影响。且由图4可知,添加Ni的变温焊料熔点均高于基体钎料,这意味着在相同的钎焊工艺条件下,添加Ni的变温焊料的过热度相较于基体钎料会有所降低,从而导致添加Ni颗粒的变温焊料的润湿性均差于基体钎料。当Ni质量分数为20%时,焊料的铺展面积相较于未添加Ni时下降了60%。
综上所述,变温焊料的润湿性能受多种因素影响,包括其黏度、母材间的界面张力以及过热度。随着锡膏黏度的增大,焊点的铺展将受到阻碍;而降低界面张力则有助于扩大润湿面积。此外,通过提高过热度,还可以进一步改善锡膏的润湿性能。在实际生产过程中,需综合考量这些因素所产生的影响。
图8为回流后时效前不同Ni含量添加变温焊料焊接接头微观组织图。Ni质量分数分别为1%,3%,5%,10%,15%,20%。此时,IMC层并未呈扇贝状形态[15],其表面呈微锯齿状,内部则呈孔洞状。随着Ni含量的递增,IMC层逐渐变厚且变得更为疏松。当Ni质量分数为20%时,Ni颗粒在焊料层发生了团聚,如图8(f)所示。
此外,IMC层内还嵌入了大量细小颗粒状的Ag3Sn化合物。这是由于具有孔洞状的(Cu,Ni)6 Sn5化合物为界面附近的各种元素提供了扩散的通道,基板上Cu可以通过这些通道扩散到钎料中生成(Cu,Ni)6 Sn5层,进而使得Ag浓度相对增加与Sn形成Ag3 Sn化合,此时Sn元素通过孔洞状的(Cu,Ni)6 Sn5扩散到Cu基板上形成薄薄一层Cu3 Sn。根据文献[16],Ni-Sn的亲和力大于Cu-Sn的亲和力,因此Ni可以取代Cu6Sn5中Cu的位置形成(Cu,Ni)6Sn5,此类IMC因吉布斯自由能降低而保持稳定。因此添加Ni颗粒的变温焊料在Cu基板上能够形成Cu6Sn5、Cu3Sn及(Cu,Ni)6 Sn5化合物。
图9展示了在150 ℃下,不同时效时间与不同Ni含量添加的变温焊料焊接接头的微观组织图,其中Ni质量分数分别为1%,5%,10%和20%。3%Ni与5% Ni以及15%Ni与10%Ni的变温焊料在微观界面层形貌上分别呈现出相似性。从图9可以看出,焊料层中添加Ni颗粒的变温焊料呈现出不同程度的团聚现象。且同一时效下,随着Ni含量的增加,IMC层逐渐增厚。时效过程中,具有高表面能及强活性的未溶解Ni颗粒倾向于吸附在界面处的IMC晶粒表面,从而降低其表面自由能。另外Cu基板上Cu和变温焊料中的Sn、Ni同时向IMC中扩散,由于Ni在Sn中的扩散系数远大于Cu在Sn的扩散系数,因此在界面Cu6 Sn5的外表面,形成了(Cu,Ni)6 Sn5这一界面化合物层,这在一定程度上也促进了IMC在时效中的增厚。
当在150℃下时效120h后,所有添加了Ni颗粒的变温焊料界面均未观察到裂纹现象。当时效时间延长至240h时,仅1%Ni焊料的IMC层未出现裂纹,而其他添加了不同Ni含量的变温焊料在IMC层均出现了不同程度的裂纹;特别是20%Ni变温焊料,其IMC层甚至发生了断裂。当时效时间达到360h时,含20%Ni的变温焊料在Cu基板与IMC的界面处出现完全断裂。
对所有添加Ni颗粒的变温焊料样品在不同时效时间下的界面总IMC层厚度进行统计,结果如表3所示。表3数据显示,在同一时效时间下,随着Ni颗粒含量增加,变温焊料的IMC厚度呈增厚趋势;同时,对于同一种变温焊料,IMC厚度也随时效时间延长而增厚。最终含20%Ni颗粒的变温焊料在经历360h时效处理后,IMC厚度增至37.611 μm。随后,以时效时间的平方根作为横坐标,界面IMC厚度作为纵坐标,绘制了IMC厚度与时效时间平方根的关系图,二者呈现出良好的线性关系,如图10所示。拟合直线的斜率为IMC生长速率,可以看出Ni添加的变温焊料的斜率均为正,因此说明,同一水平的Ni含量添加变温焊料随着时效时间的延长,IMC厚度是逐渐增加的趋势。同时从斜率上来看,20%Ni颗粒变温焊料的生长速率相对来说是最快的,总的来说不同Ni含量变温焊料界面IMC的生长速率相差并不大。研究显示,在基体焊料SAC305中添加大于1%的Ni颗粒,可能会促进界面金属化合物(IMC)的生长,而非抑制其增长。
图11为Ni颗粒添加变温焊料的剪切强度与时效时间的变化曲线。从图中可以看出,同一Ni含量的变温焊料,随着时效时间的延长,剪切强度呈下降趋势。当时效时间从0h增加到480h时,10%Ni变温焊料的剪切强度仅从42.6MPa下降至36.5MPa,下降幅度为6.1MPa,这显示出剪切强度受时效时间的影响相对较小。且同一时效时间下,变温焊料的剪切强度随着Ni含量的增加而降低。时效480h后,15%Ni变温焊料的剪切强度下降至24.6MPa,而20%Ni变温焊料则降至20MPa,此强度下降是焊料层与IMC层、IMC层与基板之间发生界面断裂所致。
本文制备了Sn-3.0Ag-0.5Cu-xNi焊膏,研究了Ni含量对复合焊膏熔化特性、润湿性及焊点时效下IMC层剪切强度及焊点剪切断口形貌的影响,得到如下主要结论:
(1)Ni颗粒含量对SAC305复合焊膏的熔化特性有一定影响,其变化会进一步影响焊接过热度,进而间接调控铺展性能。添加质量分数为10%的Ni颗粒可使焊料熔点升高至227 ℃,较基体焊料高出10 ℃;高温储存后,熔点变化幅度较小,这为开发温度梯度焊料提供了新的思路。
(2)Ni颗粒含量会显著影响复合焊膏铺展性能。并且适量添加可改善润湿行为。在添加质量分数为10%的Ni颗粒后,变温焊料的润湿性可以满足实际生产要求,能够形成可靠的焊接接头。变温焊料的润湿性能受黏度、界面张力及过热度等多因素共同影响,在实际应用中需综合优化以确保焊接质量。
(3)Ni颗粒含量会显著影响复合焊膏力学性能。界面IMC层的厚度与时效时间的平方根呈良好的线性关系。当Ni质量分数达到10%时,IMC的厚度处于适中水平,此时变温焊料的剪切强度受时效时间的影响较小,这对于优化温度梯度钎料的服役能力以及提升焊接接头的力学性能而言,具有十分重要的意义。
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2025年第44卷第10期
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doi: 10.14106/j.cnki.1001-2028.2025.0118
  • 接收时间:2025-03-17
  • 首发时间:2026-04-16
  • 出版时间:2025-10-05
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  • 收稿日期:2025-03-17
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    河南科技大学 材料科学与工程学院,河南 洛阳 471023

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通信作者:闫焉服,教授,博士,主要研究方向为先进材料连接。E-mail:
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2种不同金属材料的力学参数

Family
属数
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genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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