微量稀土元素铈对Sn-Ag-Cu无铅钎料物理性能和焊点抗拉强度的影响

研究了微量稀土元素铈对Sn-3．5Ag-0．5Cu无铅钎料的物理性能、润湿性能、焊点抗拉强度和显微组织的影响。结果表明，添加微量的铈后，钎料的导电性能提高，密度下降；铈含量（质量分数）在0．03％和0．05％时可以改善钎料的润湿性；特别是0．03％质量分数时晶粒组织最为细小均匀，焊点抗拉强度也最高；当铈含量（质量分数）大于0．1％时对钎料的性能产生不利影响，润湿时间升高，焊点抗拉强度大幅降低，因此稀土元素铈的最佳含量（质量分数）应为0．03％。     

微米Sn-Ag-Cu-RE粉体材料的制备与表征

首次制备出了微米Sn-Ag-Cu-RE合金粉体，微米Sn-Ag-Cu-RE合金粉体呈圆滑的球形，粒度呈梯度分布，其铺展性能、扩展率都得到了显的改善。微米Sn-Ag-Cu-RE合金粉体固相线温度为190．643-193．645℃，较块体SnAg-Cu合金的熔点221℃降低了28℃；液相线温度为216．963-218．368℃，较块体Sn-Ag-Cu合金的熔点降低了3℃。试验结果表明，微米Sn-Ag-Cu-RE合金粉体的“表面效应”显。该为无铅钎料的研发和应用提供了一个新的思路。     

温度与镀层对Sn-Ag-Cu无铅钎料润湿性的影响

采用润湿平衡法测试了Sn-Ag-cu无铅钎料在两种试验温度下和三种基体上的润湿时间和润湿力,研究了钎焊温度对Sn-Ag-Cu无铅钎料在不同基体上润湿性能的影响。研究结果表明,温度升高显著提高无铅钎料对基体的润湿能力,在260℃时,Sn-Ag-Cu无铅钎料的润湿时间已接近Sn-Pb的润湿时间,润湿力大于Sn-Pb钎料的润湿力;Sn-Ag-Cu钎料在Ni／Au、SnBi镀层上的润湿时间明显小于在无镀层基体上的润湿时间,且Sn-Ag-Cu钎料在三种基体上的润湿时间分别较在235℃时下降了34％～67％。     

Pr,Nd对Sn0.3Ag0.7Cu0.5Ga无铅钎料显微组织的影响

分析了添加两种稀土元素Pr,Nd对Sn-0.3Ag-0.7Cu-0.5Ga无铅钎料基体组织、焊点界面组织的影响并测定了焊点抗剪强度.结果表明,在该钎料中分别添加Pr,Nd元素可以改善钎料的显微组织,且加入Pr元素的效果优于Nd.添加Pr元素的钎料基体组织中金属间化合物分布均匀,而后者易在晶界处产生“区域”状金属间化合物,成为裂纹的发源地.稀土元素的吸附作用可以降低钎料与铜基板界面反应的剧烈程度,从而改善界面的形貌.添加Pr元素的钎料可以更好地与铜基板结合,从而提高了焊点的抗剪强度.     

稀土元素Nd对Sn-9Zn无铅钎料性能的影响

研究了添加稀土元素Nd对Sn-9Zn无铅钎料的润湿性能、显微组织和焊点力学性能的影响.结果表明,Nd元素的加入改善了钎料的润湿性能,质量分数为0.06%时,钎料的润湿力最大,润湿时间最短,润湿性能达到最佳.随着Nd元素的加入,钎料的基体组织得到细化,富锌相逐渐减少,当元素Nd的添加量大于0.06%时,钎料的显微组织中出现小块状稀土元素Nd和Sn的金属间化合物.无铅钎料Sn-9Zn中稀土元素Nd的添加量为0.06%时,剪切力和拉伸力达到最大,分别提高了19.6%和26.6%,力学性能最佳.     

稀土元素Ce对锡银铜无铅钎料显微组织的影响

研究了不同含量的稀土Ce对Sn-3．8Ag-0．7Cu无铅钎料的显微组织的影响，结果表明，微量稀土Ce的加入可以细化组织，抑制金属间化合物的生长。稀土Ce含量为0．03％（质量分数）时，组织均匀、细小，钎料润湿性能好，钎缝力学性能佳。当Ce含量为0．03％（质量分数）时，无铅钎料组织中开始出现黑色的富Ce相，并随Ce量的增加而增多。对显微组织的分析和理论计算表明，含稀土Ce锡银铜无铅钎料组织中的黑色的富Ce相为Ce与Sn的化合物。     

Effects of Ga,Al, Ag,and Ce multi-additions on the wetting characteristics of Sn-9Zn lead-free solder

An orthogonal method was used to evaluate the effects of Ga, Al, Ag, and Ce multi-additions on the wetting characteristics of Sn-9Zn lead-free solders by wetting balance method. The results show that the optimal loading of Ga, Al, Ag, and Ce was 0.2 wt.%, 0.002 wt.%, 0.25 wt.%, and 0.15 wt.%, respectively. Intermetallic compounds (IMCs) formed at the interface between Sn-9Zn-0.2Ga-0.002Al-0.25Ag-0.15Ce solder and Cu substrate were investigated by scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS) analysis. The SEM images illustrate that the IMCs can be divided into two portions from the substrate side to the solder side: a planar Cu₅Zn₈ layer and an additional continuous scallop-like AgZn₃ layer. The EDS analysis also shows that Ga segregates in the solder abutting upon the interface. X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) of the surface components of Sn-9Zn-0.2Ga-0.002Al-0.25Ag-0.15Ce solder indicate that Al aggregates at the surface in the form of Al₂O₃ protective film, which prevents the further oxidation of the solder surface. On the other hand, Ce aggregates at the subsurface, which may reduce the surface tension of the solder and improve the wettability in consequence.     

Effect of cerium on microstructure and mechanical properties of Sn-Ag-Cu system lead-free solder alloys

The melting point, spreading property, mechanical properties and microstructures of Sn-3.0Ag-2.8Cu solder alloys added with micro-variable-Ce were studied by means of optical microscopy, scanning electron microscopy（SEM） and energy dispersive X-ray（EDX）. The results indicate that the melting point of Sn-3.0Ag-2.8Cu solder is enhanced by Ce addition; a small amount of Ce will remarkably prolong the creep-rupture life of Sn-3.0Ag-2.8Cu solder joint at room temperature, especially when the content of Ce is 0.1%, the creep-rupture life will be 9 times or more than that of the solder joint without Ce addition; the elongation of Sn-3.0Ag-2.SCu solder is also obviously improved even up to 15.7%. In sum, the optimum content of Ce is within 0.05%-0.1%.     

Effects of bismuth on growth of intermetallic compounds in Sn-Ag-Cu Pb-free solder joints

The effects of Bi addition on the growth of intermetallic compound （IMC） formation in Sn-3.8Ag-0.7Cu solder joints were investigated. The test samples were prepared by conventional surface mounting technology. To investigate the element diffusion and the growth kinetics of intermetallics formation in solder joint, isothermal aging test was performed at temperatures of 100, 150, and 190 ℃, respectively. The optical microscope （OM） and scanning electron microscope （SEM） were used to observe microstructure evolution of solder joint and to estimate the thickness and the grain size of the intermetallic layers. The IMC phases were identified by energy dispersive X-ray （EDX） and X-ray diffractometer （XRD）. The results clearly show that adding about 1.0% Bi in Sn-Ag-Cu solder alloy system can refine the grain size of the IMC and inhibit the excessive IMC growth in solder joints, and therefore improve the reliability of the Pb-free solder joints. Through observation of the microstructural evolution of the solder joints, the mechanism of inhibition of IMC growth due to Bi addition was proposed.     

N2对Sn-Ag-Cu钎料与元器件引线无铅镀层润湿性的影响

以Sn-3．5Ag-0．5Cu钎料主要研究对象，配合免清洗助焊剂，基于润湿平衡原理测量了钎料对Sn、Sn—Cu、Sn—Bi三种镀层的润湿特性，研究了五种温度、三种镀层、两种气氛条件对润湿行为的影响。结果表明，空气气氛下，温度较低时Sn-Bi镀层的润湿性能相对较好，温度较高时三种镀层的润湿性相当；采用氮气保护后可明显改善钎料润湿性，润湿时间缩短22％-40％，同一温度下的三种镀层的润湿性能相当。     

稀土元素Ce对Sn-Cu-Ni无铅钎料铺展性能及焊点力学性能的影响

研究了不同含量稀土元素Ce对Sn-Cu-Ni钎料铺展性能及其焊点力学性能及钎料显微组织的影响规律.结果表明,随着稀土元素Ce含量的增加,钎料在铜基板上的铺展面积逐渐增大,当Ce元素含量达到0.05%时,钎料的铺展面积达到最大.Sn-Cu-Ni钎料中添加适量的稀土元素Ce,能够细化钎料组织,从而提高焊点的力学性能.当Ce元素的含量为0.05%左右时,焊点的力学性能达到最佳值.Ce元素含量超过0.05%后,继续增大稀土元素Ce的添加量,Sn-Cu-Ni钎料的显微组织又变得粗大,铺展性能有所降低,焊点力学性能也随之有所下降.     

合金元素Ga对Sn-9Zn无铅钎料性能的影响

研究了合金元素Ga的添加量对Sn-9Zn无铅钎料熔化特性、润湿性能及其焊点力学性能的影响.结果表明,添加合金元素Ga以后,合金的熔点显著降低,熔化温度区间有所增大,润湿性能得到明显改善;合金元素Ga的添加量(质量分数)在0.5%时,钎料的晶粒组织最为细小均匀,钎料焊点的力学性能最佳;当合金元素Ga的添加量大于1%时,钎料的润湿性能趋于稳定,钎料组织中晶界处出现黑色富Ga相,钎料焊点的力学性能大幅度降低.因此,Sn-9Zn无铅钎料中合金元素Ga的最佳添加量为0.5%.     

稀土元素对Sn-9Zn合金润湿性的影响

Zn的活泼性使Sn-9Zn无铅钎料的润湿性和抗氧化性很差，在Sn-9Zn合金中加入适量混合稀土元素(Ce，La)可以改善其润湿性能。分别在245，260和290℃通过润湿平衡实验对钎料的润湿性进行了研究，并对RA，RMA，R和WWR4种不同钎剂进行了比较。结果表明：在运用活性松香钎剂时，微量混合稀土元素可以显著提高Sn-9Zn合金润湿性；而提高钎焊温度也可以改善润湿性能。     

稀土元素Ce对锡银铜无铅钎料润湿性及钎缝力学性能的影响

采用STA-5100型可焊性测试仪和STR-1000微焊点强度测试仪，对添加了稀土元素Ce的Sn-3．8Ag-0．7Cu无铅钎料的润湿性及钎缝的力学性能进行了研究。试验结果表明，Ce的加入，可以改善钎料的润湿性，质量百分含量为0．03％～0．05％时效果最好，温度升高以及通人氮气均可以明显地提高Sn-3．8Ag-0．7Cu—Ce无铅钎料的润湿性；当Sn-3．8Ag-0．7Cu钎料中稀土元素Ce的质量百分含量为0．03％时，钎缝的力学性能最佳。     

SnAgCuRE系无铅钎料与表面贴装元器件的润湿适配性

采用润湿平衡法选用商用水洗钎剂,研究SnAgCuRE系无铅钎料与表面贴装元器件的润湿适配性。研究结果表明,当Sn2.5Ag0.7CuxRE系钎料合金中RE添加量为0.1%时,在钎焊温度为250℃、预热时间为15s、浸渍时间为5s的情况下,其与表面贴装元器件具有较好的润湿适配性,即具有较大的润湿力、较小的润湿角,其润湿力达到现行商用Sn3.8Ag0.7Cu钎料的水平,完全能够满足表面组装行业对无铅钎料润湿性能的要求。     

Ag,Al,Ga对Sn-9Zn无铅钎料润湿性能的影响

采用润湿平衡法测试了Sn-9Zn-X(X为Ag,Al,Ga)无铅钎料分别配合ZnCl2-NH4Cl钎剂和免清洗助焊剂,在空气和氮气保护的两种条件下的润湿性能,分析研究了合金元素Ag,Al,Ga的添加量对Sn-9Zn-X无铅钎料润湿性的影响规律.结果表明,合金元素Ag,Al,Ga在Sn-9Zn中的最佳添加量(质量分数)分别为0.3%,0.005%～0.02%,0.5%.采用氮气保护可以显著改善Sn-9Zn-X无铅钎料的润湿性,而Sn-9Zn-X无铅钎料配合ZnCl2-NH4Cl钎剂时具有较好的润湿性,甚至优于Sn-3.5Ag-0.5Cu在相同条件下的润湿性.这一研究结果表明,通过研发适合于Sn-Zn系无铅钎料的高性能助焊剂,从而改善Sn-Zn系钎料的润湿性能是完全可行的.     

温度与镀层对Sn-Cu-Ni无铅钎料润湿性能的影响

采用润湿平衡法测定了在不同试验温度下Sn-Cu-Ni无铅钎料在Cu,Au/Ni/Cu,SnBi/Cu三种基板上的润湿时间和润湿力,研究了钎焊温度对Sn-Cu-Ni无铅钎料在不同基板上润湿性能的影响.结果表明,温度升高使Sn-Cu-Ni无铅钎料的表面张力减小,能显著缩短钎料在铜片上的润湿时间,提高润湿力;Ni/Au或SnBi等镀层能显著降低钎料/基板界面张力,因此Sn-Cu-Ni无铅钎料在Au/Ni/Cu或SnBi/Cu基板上的润湿性能优于在Cu基板上的润湿性能.     

Effects of Bi and rare earth metal on the microstructure and properties of Zn-based high-temperature solder

A novel Zn-based high-temperature solder was developed to join copper/steel at moderate temperature. The effects of Bi and rare earth metal on the microstructures, wettability of solders as well as the mechanical properties of solder joints were investigated. The results indicated that with the addition of Bi into Zn-Cu-Sn (ZCS) alloy, significant improvement in wettability is realized. When the content of Bi element is 1.5 wt. % in the solder, the spreading area researched over 200 mm². Further more, with the addition of RE, refined primary ε-CuZn₅ phases were formed and the shear strength of the solder joint was largely improved.     

氮气保护对Sn-Cu-Ni-Ce无铅钎料润湿性的影响

基于润湿平衡原理测定了不同温度与不同气氛下Sn-Cu-Ni-Ce钎料在Cu基板上的润湿行为,研究了气氛、温度以及微量稀土元素Ce对其润湿性能的影响.结果表明,采用氮气保护时,Cu基板表面张力提高,钎料表面张力降低,润湿时间缩短了20%～50%,润湿力也显著提高;温度升高使Sn-Cu-Ni-Ce钎料的表面张力减小,显著缩短了钎料在Cu基板上的润湿时间;稀土元素Ce可显著降低熔融钎料的表面张力和钎料/基板间的界面张力,从而使Sn-Cu-Ni-Ce钎料的润湿性能较Sn-Cu-Ni钎料有了显著的改善.