稀土铈在Sn-Zn无铅钎料表面的高温氧化行为

通过俄歇电子能谱法和X射线光电子能谱法研究了Sn-9Zn-0.15Ce和Sn-9Zn-0.002Al-0.2Ga-0.25Ag-0.15Ce两种钎料表面Ce元素的分布和存在形式.结果表明,铈在Sn-9Zn-0.15Ce钎料表面0~40 nm范围内的富集区浓度达到30%(原子分数)左右,是基体内部的250倍,主要以CeO2和Ce2O3形态存在.在Sn-9Zn-0.15Ce钎料中复合添加镓和铝后,Ga元素在钎料表面0~6 nm范围内富集,Al元素在表面2~20 nm范围内富集并主要以氧化态形式存在.Ce元素富集在距离钎料表面2~60 nm的范围内,处于Ga,Al元素富集层的下方;由Ga,Al元素富集层构成的致密保护膜可显著降低表面铈被氧化的概率.     

超低银SnAgCu钎料微焊点力学性能

研究了复合添加Ga/Nd元素对超低银Sn-0.3Ag-0.7Cu钎料微焊点力学性能的影响. 结果表明,复合添加适量Ga/Nd元素可以显著改善微焊点界面组织,抑制微焊点界面附近金属间化合物的生成,从而提高微焊点的力学性能,相比母合金微焊点剪切力提高幅度达到约16%;微焊点的力学性能随着时效时间的增加而降低,降低幅度优于未添加Ga/Nd的微焊点. Sn-0.3Ag-0.7Cu-0.5Ga-0.1Nd钎料微焊点的力学性能在时效处理后仍保持较好的水平,已接近Sn-3.8Ag-0.7Cu钎料微焊点的90%,具有良好的工业应用前景.     

Sn-9Zn-xAg无铅钎料润湿性能及焊点力学性能

研究了合金元素Ag的添加量对Sn-9Zn无铅钎料润湿性能及其焊点力学性能的影响.结果表明,当Ag元素的添加量(质量分数)为0.3%时,钎料具有最好的润湿性能,焊点的力学性能最佳,焊接接头的断口形貌显示钎料与铜基板接头断口处有明显的韧窝,是典型的韧性断裂;当Ag元素的添加量(质量分数)为0.5%～1.0%时,钎料的润湿性能下降,当Ag元素的添加量(质量分数)增加到1.0%时,焊点的力学性能有所下降,在断口的韧窝底部有大颗的Cu-Zn,Ag-Zn金属间化合物.因此,Sn-9Zn无铅钎料中合金元素Ag的最佳添加量(质量分数)为0.3%.     

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%.     

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.     

Ga、Al对Sn-Zn钎料耐蚀及高温抗氧化性能的影响

采用侵蚀失重法研究Ga、Al对Sn-9Zn钎料在3.5%NaCl水溶液中耐腐蚀性的影响.结果表明,添加Ga元素后,腐蚀产物的粘附性提高,均匀覆盖在钎料表面上,提高了钎料的耐蚀性能;添加Al以后,Zn和Al被选择性腐蚀,腐蚀随着Al含量的增加而加剧.采用热重分析(TGA)和俄歇电子能谱(AES)研究Ga、Al对Sn-9Zn钎料高温抗氧化性的影响.结果表明,Ga可在钎料表面形成一层集肤层;Al可在钎料表面形成一层致密的氧化膜,两者均可阻挡空气中的氧向钎料内部扩散,从而大大改善钎料的高温抗氧化性.     

ZL102合金用低温软钎料的研究

Sn-9Zn共晶钎料可以用于钎焊钎焊性极差的铸造铝合金ZL102，在Sn-9Zn钎料的基础上添加In元素，以提高钎料对ZL102合金的润湿。本文对Sn-9Zn和Sn-9Zn-5In两种软钎料对ZL102合金润型，界面结合等方面进行研究，分析实验结果可知，Sn-9Zn-5In钎料的性能优于Sn-9Zn共晶钎料。     

微量Nd对Sn-6.5Zn合金及钎料/Cu界面结构的影响

研究了微量稀土元素Nd的添加对Sn-6.5Zn合金组织及钎料/Cu焊点界面金属间化合物(IMC)特征的影响.结果表明:微量Nd元素在Sn-6.5Zn钎料中的添加能够显著细化合金组织和形成均匀细密界面IMC层;添加0.1 wt％Nd元素即能促进钎料/Cu焊点界面反应及界面区域成分的均匀性.     

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.     

锆元素对Zn-15Al钎料组织和性能的影响

通过扫描电镜、X射线衍射和纳米压痕等方法研究了微量Zr元素对铝合金/不锈钢异种金属钎焊用Zn-15Al钎料显微组织和性能的影响.结果表明,微量Zr元素的添加对钎料的熔点没有明显影响.Zr元素对Zn-15Al钎料基体中η-Zn相有明显细化作用,当Zr元素的质量分数为0.2%时,细化效果最佳;Zr元素的添加量过多时,钎料中形成块状的Al₂ZnZr化合物.当Zr元素的质量分数为0.2%时,Zn-15Al-0.2Zr钎料在不锈钢和铝合金母材上的铺展面积较Zn-15Al钎料分别提高了15.9%和10.2%,钎焊接头抗剪强度达到最大值143 MPa.Zn-15Al,Zn-15Al-0.2Zr,Zn-15Al-0.3Zr 3种钎料的蠕变应力指数分别为6.64,7.35,8.07.     

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.     

In对Al-Mg-Ga-Sn-(In)铝合金阳极组织及电化学性能的影响

在Al基体中添加Mg、Ga、Sn、In合金元素,通过正交试验设计了9组铝-空气电池阳极材料。采用动电位极化试验、析氢试验和恒电流放电试验对铝合金阳极的电化学性能进行优化,通过扫描电镜和能谱测试仪观察了合金的显微组织及成分。结果表明,没有添加In元素的1号合金(Al-0.5Mg-0.05Sn-0.05Ga)、5号合金(Al-Mg-0.1Sn-0.2Ga)和9号合金(Al-2Mg-0.2Sn-0.1Ga)铝阳极具有较差的放电性能和较高的自腐蚀速率,而添加0.05wt% In元素的7号铝阳极(Al-2Mg-0.05Sn-0.2Ga-0.05In)具有最好的放电电压(平均电位-1.968 V)和抗腐蚀性能 (自腐蚀速率0.193 mL·cm^-2·min^-1)。对比去腐蚀产物后的合金表面形貌,发现5号合金的腐蚀表面布满较深的腐蚀坑,这增加了铝合金的自腐蚀,而7号合金的表面具有较浅的腐蚀坑,这减缓了电解液中离子传递和自腐蚀速率。 因此,7号铝合金适合用作铝-空气电池阳极材料。     

Effects of Al, Ga, and Ag on the anti-oxidation and wetting reactions of Sn-9Zn-X solders

The effects of Ca, Al, and Ag on the anti-oxidation of Sn-9Zn-X solders and the interface reactions between the solders and Cu substrate were investigated by Auger electron spectroscopy (AES) and scanning electron microscope (SEM) analysis, respectively. The mechanism of improving the wettability of Sn-g Zn lead-flee solder by adding Ca, Al, and Ag was also revealed. The AES analysis indicated that Al and Ca might enrich on the molten solder surface which resulted in improving the anti-oxidation of Sn-gZn-O. O05Al and Sn-gZn-O. 3C, a alloys. The addition of Ca reduced the apparent activation energy and promoted the interface reaction. With the addition of 0.3 wt. % Ag, some scallop-like intermetallic compounds (IMCs) formed at the interface, according to the energy dispersive spectroscopy (EDS) analysis, these scallop-like IMCs might be the mixture of Ag-Zn and Cu-Sn compounds.     

Solderability and intermetallic compounds formation of Sn-9Zn-xAg lead-free solders wetted on Cu substrate

The eutectic Sn-9Zn alloy was doped with Ag (0 wt.%-1 wt.%) to form Sn-9Zn-xAg lead-free solder alloys. The effect of the addition of Ag on the microstructure and solderability of this alloy was investigated and intermetallic compounds (IMCs) formed at the solder/Cu interface were also examined in this study. The results show that, due to the addition of Ag, the microstructure of the solder changes. When the quantity of Ag is lower than 0.3 wt.%, the needle-like Zn-rich phase decreases gradually. However, when the quantity of Ag is 0.5 wt.%-1 wt.%, Ag-Zn intermetallic compounds appear in the solder. In particular, adding 0.3 wt.% Ag improves the wetting behavior due to the better oxidation resistance of the Sn-9Zn solder. The addition of an excessive amount of Ag will deteriorate the wetting property because the glutinosity and fluidity of Sn-9Zn-(0.5, 1)Ag solder decrease. The results also indicate that the addition of Ag to the Sn-Zn solder leads to the precipitation of ε-AgZn₃ from the liquid solder on preformed interfacial intermetallics (Cu₅Zn₈). The peripheral AgZn₃, nodular on the Cu₅Zn₈ IMCs layer, is likely to be generated by a peritectic reaction L + γ-Ag₅Zn₈ → ɛ-AgZn₃ and the following crystallization of AgZn₃.     

用循环极化曲线研究Al和铝合金的点蚀行为

通过循环极化确定纯Al和Al-7Zn-0.1Sn-0.015Ga (质量分数,%) 合金在3.5%NaCl溶液中的自腐蚀电位E_corr、点蚀电位E_pit、点蚀转变电位E_ptp和保护电位E_rp,并通过Al和铝合金在这些特征电位的点蚀形貌研究了它们的点蚀行为及点蚀扩展机理。结果表明：在点蚀电位时开始出现点蚀坑,随着电位升高点蚀坑迅速向横向和纵向扩展直至保护电位;纯Al的点蚀坑为窄而深的方形点蚀形貌,蚀坑内部为粗糙的结晶状结构,且表面出现明显的丝状腐蚀。Al-7Zn-0.1Sn-0.015Ga合金的点蚀形貌为宽而浅的圆形腐蚀坑,蚀坑内部比较光滑,且丝状腐蚀消失。合金元素能明显活化合金,降低点蚀坑深度,改善其腐蚀形貌。