The effect of alloying element gallium on the polarization characteristics of Pb-free Sn-Zn-Ag-Al-XGa solders in NaCl solution

The polarization characteristics of Sn-8.5Zn-0.5Ag-0.1Al-XGa lead-free solders were investigated in 3.5% NaCl solution where X ranges from 0.05-1.5 wt%. The results show that Ga affects the anodic polarization behaviour of the solders. Passivation behaviour is observed for all the investigated Sn-8.5Zn-0.5Ag-0.1Al-XGa solders. Increase in the Ga content from 0.05 to 0.25 wt% increases the ability for passivation but the oxide film formed due to passivity is not so protective. However Ga content > 0.25 wt% enhances corrosion and decreases the protective power of the passive film. The magnitude of the passivation current densities depend on the composition of the solders and the potentials applied. Layers of oxides of tin and zinc are responsible for the passivation behaviour. XRD and SEM results revealed the formation of corrosion products like SnO, ZnO, SnO₂ at different potentials during the polarization study.     

The polarization characteristics of Pb-free Sn-8.5Zn-XAg-0.1Al-0.05Ga alloy in 3.5% NaCl solution

The polarization characteristics of Pb-free Sn-8.5Zn-XAg-0.1Al-0.05Ga alloy with varying Ag content were investigated in 3.5% NaCl solution. The value of Ag content i.e X varied from 0.1 wt% to 2 wt%. An increase in the Ag content up to 2 wt% resulted in a progressive increase in the corrosion current density and shifted the corrosion potential (E_corr) towards more active values. These changes were also reflected in the corrosion rate of the solder alloy. However the linear polarization resistance values decreased with increase in the weight content of silver. Increasing the Ag content from 0.1 to 2 wt% did not show a significant improvement in the passivation behaviour of the solder alloy as reflected in the passivation current density (i_p) and critical current density (i_cc) values. XPS and SIMS depth profile results revealed that the oxides of Zn and Sn were present in high concentrations on the outer surface of the solder alloy along with very low concentration of Al₂O₃.     

The Inhibition of Tin Whiskers on the Surface of Sn-8Zn-3Bi-0.5Ce Solders

Through the refinement of the (Ce, Zn)Sn₃ intermetallic phase, the formation of tin whiskers, previously observed on the surface of a Sn-3Ag-0.5Cu-0.5Ce solder, was prevented in a Sn-9Zn-0.5Ce alloy. However, whisker growth can still occur on the surface of Sn-8Zn-3Bi-0.5Ce solder after air storage at room temperature and at 150 °C due to the formation of large (Ce, Zn)Sn₃ intermetallic clusters. Further experiments showed that decreasing the Bi-content in this Sn-8Zn-0.5Ce alloy to 1 and 2 wt.% can recover the beneficial effects of Zn additions on the refinement of the (Ce, Zn)Sn₃ phase and obviously reduce the appearance of tin whiskers. In addition, alloying the Sn-8Zn-3Bi-0.5Ce solder with 0.5 wt.% Ge, which increases the oxidation resistance of the (Ce, Zn)Sn₃ intermetallic clusters, can also effectively inhibit tin whisker growth.     

工业纯Sn和Sn-3Ag-0.5Cu合金在沈阳大气环境下自然暴露的初期腐蚀行为

通过沈阳大气环境下的自然暴露实验研究工业纯Sn和Sn-3Ag-0.5Cu合金的早期大气腐蚀行为。采用扫描电子显微镜(SEM)和X射线光电子能谱仪(XPS)分析了表面腐蚀产物的形貌与成分。结果表明:工业纯Sn与Sn-3Ag-0.5Cu合金在沈阳工业大气环境下自然暴露后都很快发生了表面腐蚀并失泽,早期腐蚀产物疏松、龟裂并易于剥落。XPS深度分析表明:自然条件下暴露18 d后,表面腐蚀产物层厚度约为400 nm。工业大气中的悬浮物颗粒对腐蚀的形核和扩展起重要作用,Sn-3Ag-0.5Cu合金中的第二相Ag3Sn和Cu6Sn5作为阴极存在,但对大气腐蚀的加速影响不大。     

In对Sn-8Zn-3Bi无铅钎料润湿性的影响

首先采用铺展法测试了Sn-8Zn-3Bi-(0～5)In钎料合金的铺展性.结果表明,少量In的加入提高了钎料的润湿性.当In含量达到0.5%时(质量分数,下同),钎料在铜基底上的铺展面积最大.采用气泡最大压力法对Sn-8Zn-3Bi-(0～1.5)In钎料熔体进行了表面张力测试.加入0.5%的In大大降低了Sn-8Zn-3Bi钎料熔体的表面张力,但进一步增加In的含量导致熔体表面张力增大.最后采用润湿平衡法对上述钎料进行了润湿力测试.结果表明0.5%In的加入使合金的润湿力达到最大,其原因是钎料/铜界面的界面张力减小.     

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.     

Development of novel brasses to resist dezincification

The effect of alloying Sn, Pb, As, Sb and P on the dezincification of commercial brass 60Cu-39Zn-1Pb has been investigated in 1% CuCl₂ solution by immersion studies and electrochemical measurements. Specimens with a smooth surface finish exhibited more resistance to dezincification. Appreciable inhibitive effect on dezincification was observed for the 55Cu-40Zn-3Pb-2Sn brass composition. The galvanic coupling of lead phase with the matrix accelerated corrosion. To improve the dezincification resistance of the Sn containing brass, As, Sb and P were added at two different levels (0.05% and 0.1%). Brass of composition 48.95Cu-45Zn-5Pb-1Sn-0.05As was more resistant indicating the synergistic effect of Sn and As. The effect of 0.05 and 0.1% of arsenic addition with various concentrations of zinc was also studied. The alloy of composition 57.90Cu-40Zn-2Pb-0.1As showed better corrosion resistance than the alloy containing 1% Sn and 0.05% As (48.95Cu-45Zn-5Pb-1Sn-0.05As). To understand the influence of Sn and As on the dezincification of commercial brass, linear polarization and cyclic voltammetry experiments were conducted for the alloys 60Cu-39Zn-1Pb, 55Cu-40Zn-3Pb-2Sn and 57.90Cu-40Zn-2Pb-0.1As. Linear polarization measurements indicated that the alloys 55Cu-40Zn-3Pb-2Sn and 57.90Cu-40Zn-2Pb-0.1As possessed higher resistance to corrosion than commercial brass. Inspection of cyclic voltammograms revealed that the peak current densities as well as the passive current density were lower for the alloys 55Cu-40Zn-3Pb-2Sn and 57.90Cu-40Zn-2Pb-0.1As than the alloy 60Cu-39Zn-1Pb. The surface layer on the alloys 60Cu-39Zn-1Pb, 55Cu-40Zn-3Pb-2Sn and 57.90Cu-40Zn-2Pb-0.1As after immersion of 72 h in 1% CuCl₂ solution were analyzed by X-ray diffraction and scanning electron microscopy. Higher enrichment of Sn and As at the interface of surface layer and metal was indicated for the alloys 55Cu-40Zn-3Pb-2Sn and 57.90Cu-40Zn-2Pb-0.1As, respectively.     

人工模拟海洋大气环境下Sn-0.7Cu无铅焊料的点蚀行为及微量Ga的影响

通过人工海水的盐雾干-湿实验模拟海洋大气环境,研究了Sn-0.7Cu和Sn-0.7Cu-0.01Ga合金的腐蚀行为.采用SEM和XPS分析了合金表面腐蚀形貌及腐蚀产物成分,采用XRD分析了腐蚀产物的结构.结果表明:Sn-0.7Cu合金腐蚀初期发生明显的点蚀,点蚀易于在富Cu区萌生,且以触须状向外扩展;腐蚀后期腐蚀产物分层,龟裂且易于剥落,此时腐蚀产物不具有保护性.XRD分析表明.腐蚀产物主要为非晶态Sn的氧化物,同时有少量的SnCl_2·2H_2O;微量元素Ga能显著提高Sn-0.7Cu合金的抗盐雾腐蚀性能.XPS分析表明,微量元素Ga在表面存在明显的富集行为,并形成一种致密的保护性氧化膜,它是提高Sn-0.7Cu合金抗盐雾腐蚀性能的主要原因.     

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。     

Wetting and interfacial reaction characteristics of Sn-1.2Ag-0.5Cu-xIn quaternary solder alloys

Through the use of a wetting balance technique, the wetting characteristics of Sn-1.2Ag-0.5Cu-xIn quaternary solder alloys with respect to the In content and soldering temperature were investigated to validate the applicability of compositions with a low Ag content as solder material. It was found that a small addition (0.4–0.6 wt.%) of In significantly improved the wetting properties of the Sn-1.2Ag-0.5Cu-xIn composition at soldering temperatures ranging from 230 °C to 240 °C due to the excellent wetting property of In. In an observation of the interfacial reaction, it was found that the added In element did not participate in the interfacial reaction with a Cu or Ni pad, unlike in the Sn-Ag-Cu-In case, which has a high In content. The package or boardside IMC layers in Sn-1.2Ag-0.5Cu-0.4In joints were thinner than those of Sn-3.0Ag-0.5Cu, especially after aging.     

Correlations between IMC thickness and three factors in Sn-3Ag-0.5Cu alloy system

The effects of Ni content, soldering temperature and time on the IMC thickness in Sn-3Ag-0.5Cu and Sn-3Ag-0.5Cu-0.2Co alloys were researched using uniform design method and computer programs. For each alloy, the factors were divided into three levels in the experiment. Two correlative equations are given by regression. They indicate that the effects of three factors on the function are in the mutual and quadratic forms. And the analysis of variance shows the equations are sound and meaningful. Using the equations, it is easy to search, predict and control the IMC thickness. The existence of element Co accelerates the crystallization and growing up oflMC.     

Sn-6Bi-2Ag(Cu, Sb)无铅钎料合金微观组织分析

利用差示扫描量热计 (DSC)测定了Sn 6Bi 2Ag ,Sn 6Bi 2Ag 0 .5Cu ,Sn 6Bi 2Ag 2 .5Sb三种新无铅钎料合金的熔化温度。结果表明 ,少量Cu的加入能降低Sn Bi Ag系无铅钎料合金的熔化温度 ,而Sb的加入使合金的熔化温度升高。利用光学显微镜 (OM )、扫描电子显微镜 (SEM )、能谱分析 (EDX)对合金的微观组织进行了分析与比较 ,钎料合金的微观组织与冷却条件和合金元素的含量有关 ,Sb的加入使析出相的尺寸细化。硬度测定表明Sn Bi Ag(Cu ,Sb)无铅钎料合金的硬度远大于纯Sn的硬度 ,加入少量的Cu(0 .5 % ) ,Sb(2 .5 % )对Sn Bi Ag系钎料合金的硬度影响较小     

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.     

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。     

Microstructure and Electro-Physical Properties of Sn-3.0Ag-0.5Cu Nanocomposite Solder Reinforced with Ni Nanoparticles in the Melting-Solidification Temperature Range

The electrical conductivity of nanocomposite Sn-3.0Ag-0.5Cu alloys with two different weight percentages of Ni nanoparticles (1.0 and 2.0 wt.%) was measured over a wide temperature range. The samples were produced using a cold pressing method: Sn-3.0Ag-0.5Cu powder and Ni nanopowder were mechanically mixed and pressed into 8 mm diameter rods. Ni nanoparticles were synthesized via a chemical reduction method and characterized by a core/shell structure. Temperature dependencies of the electrical conductivity revealed a hysteresis between the heating and cooling curves in a wide temperature range above the melting temperature. This fact is connected with structure transformations accompanied by a dissolution of Ni nanoparticles, which should be retarded due to an oxide/hydroxide shell on the surface of the nanoparticles. A microstructure analysis of the samples in the solid state showed a fine distribution of intermetallic compounds in the Sn-based matrix. The Ni atoms substituted for Cu atoms in the Cu₆Sn₅ compound forming a (Cu,Ni)₆Sn₅ phase.     

Fe粉对Sn-3Ag-0.5Cu复合钎料组织及性能的影响

通过在钎料中添加Fe粉颗粒,研究其对Sn-3Ag-0.5Cu复合无铅钎料的黏度、熔点、钎焊接头界面微观组织、与Cu基板之间的润湿性及焊点力学性能的影响。结果表明:微米级Fe粉的添加增加了复合钎料焊膏单位体积内焊粉的接触面积,使得焊膏内摩擦力增大,导致复合钎料焊膏的黏度增加;微米级Fe粉的添加对Sn-3Ag-0.5Cu钎料的熔化特性没有显著影响;钎焊时,由于重力偏聚及界面吸附作用,Fe粉颗粒集中沉积于Sn-3Ag-0.5Cu-Fe/Cu钎焊接头界面处靠近钎料一侧,由于增大液态钎料黏度而导致钎料与Cu板间的润湿性降低;与Sn-3Ag-0.5Cu/Cu相比,Sn-3Ag-0.5Cu-Fe/Cu界面处钎料一侧粗大的β-Sn枝晶区消失,取而代之的是细小的等轴晶。Sn-3Ag-0.5Cu-1%Fe/Cu的剪切强度为46 MPa,比Sn-3Ag-0.5Cu/Cu剪切强度提高39%;靠近界面金属间化合物处钎料基体的显微硬度提高约25%。     

稀土Pr对低银Sn-0.3Ag-0.7Cu-0.5Ga钎料蠕变行为影响的研究

为进一步促进电子封装用低银无铅钎料的发展,本文采用纳米压痕法研究了新型含Pr低银Sn-0.3Ag-0.7Cu-0.5Ga (SAC-Ga)钎料显微组织与蠕变性能之间的关系。结果表明,SAC-Ga、SAC-Ga-0.06Pr、SAC-Ga-0.5Pr三种钎料的蠕变位移分别为1717 nm、1144 nm、1472 nm;稀土Pr可通过细化Cu₆Sn₅金属间化合物并促使其均匀分布从而明显提高SAC-Ga钎料的蠕变强度;与SAC-Ga-0.06Pr钎料相比,SAC-Ga-0.5Pr由于过量稀土Pr的表面氧化而导致其蠕变强度有所下降。此外,本文采用Dorn模型研究了含Pr的SAC-Ga钎料的室温蠕变行为并计算了对应的钎料蠕变应力指数n;阐明了Pr对SAC-Ga钎料蠕变强度的强化机理,即当位错遇到细小且均匀分布的Cu₆Sn₅ 金属间化合物时,位错移动只能采用绕过机制,从而提高了含Pr低银钎料的抗蠕变性能。     

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.     

Sn-0.75Cu钎料接头在NaCl溶液中的电化学腐蚀行为(英文)

采用动电位极化及浸出方法研究Sn-0.75Cu钎料及Sn-0.75Cu/Cu接头在3.5%NaCl溶液中的电化学腐蚀行为。极化曲线测试结果表明Sn-0.75Cu钎料的腐蚀速率比Sn-0.75Cu/Cu接头的低。在特殊电位时的形貌观察及相分析表明,在Sn-0.75Cu钎料表面活化溶解区形成腐蚀产物Sn3O(OH)2Cl2。从活化/钝化区开始,Sn-0.75Cu钎料的表面完全被腐蚀产物Sn3O(OH)2Cl2覆盖,并且在极化测试后出现蚀坑。与Sn-0.75Cu钎料合金相比,Sn-0.75Cu/Cu接头的钎料表面在活化区形成较多的Sn3O(OH)2Cl2,在极化测试结束时腐蚀坑的尺寸较大。浸出实验结果证实了Sn-0.75Cu/Cu接头较快的电化学腐蚀速率引起较多的Sn从中接头中释放出来。     

Ca、Mn元素对Mg-Zn系合金在磷酸盐缓冲液中腐蚀行为的影响

本文采用XRD、SEM、EDS、三维轮廓仪和失重法等手段研究了Mg-6Zn、Mg-6Zn-1Ca和Mg-6Zn-Mn合金在磷酸盐缓冲盐溶液(PBS)中的腐蚀行为,并探讨了三种合金的腐蚀机理。结果表明,添加相同含量的Ca和Mn均能使合金的失重率降低,但添加Mn元素后(浸泡10天时W_r=3.91%)比添加Ca元素后(W_r=6.78%)合金的失重率更低,说明Mn元素更有抗PBS腐蚀能力,这与Mn的加入在合金表面形成致密的氧化膜有关;同时,Mg-6Zn-1Mn合金在浸泡过程中表面存在点蚀现象,经分析是由第二相与基体构成原电池导致。在420 ℃不同保温时间(2~20 h)固溶处理后,合金表面的点腐蚀现象随着保温时间的增加而减弱,表明长时间的固溶处理可以减少第二相与镁基体之间的微电偶腐蚀,增加了合金均匀腐蚀的倾向。