Effect of Ag and Ni on the melting point and solderability of SnSbCu solder alloys

To improve the properties of Sn10Sb8Cu solder alloy, two new solders(SnSbCuAg and SnSbCuNi)were formed by adding small amounts of Ag or Ni into the solder alloy. The results show that the melting point of the SnSbCuAg solder alloy decreases by 14.1℃ and the spreading area increases by 16.5% compared to the matrix solder.The melting point of the SnSbCuNi solder alloy decreases by 5.4℃ and the spreading area is slightly less than that of the matrix solder. Microstructure analysis shows that adding trace Ag makes the melting point decline due to the dispersed distribution of SnAg phase with low melting point. Adding trace Ni,Cu_6Sn_5 and (Cu,Ni)_6Sn_5 with polyhedron shape on the copper substrate can be easily seen in the SnSbCuNi solder alloy,which makes the viscosity of the melting solder increase and the spreading property of the solder decline.     

电子封装中的无铅Sn-3.8Ag-0.5Cu/Cu界面研究

针对钎料与焊盘间形成IMC层的厚度是影响可靠性的一个关键因素．对无铅钎料Sn-3．8Ag-0．5Cu与Cu盘进行了重熔,采用Olympus（光学金相显微镜）,SEM（扫描电镜）和EDX（能谱X射线）界面分析手段,研究了合金Sn-3．8Ag-0．5Cu与Cu焊盘接头的钎焊性和在焊接过程中IMC的形成与长大机理,探讨了IMC厚度与保温时间的变化规律．研究结果表明,无铅钎料合金Sn-3．8Ag-0．5Cu在钎焊务件下与Cu焊盘能够实现良好的连接,其连接层为Cu6Sn5金属间化合物,重熔时的IMC层生长基本上符合抛物线规律．     

Sn-Ag-xCu-Bi-Ni/Cu焊点界面IMC演变

为了研究低银无铅焊点界面金属间化合物(IMC)的形成与演变,以低银无铅焊点Sn-Ag-xCu-Bi-Ni/Cu为研究对象,研究了钎料中Cu质量分数对界面IMC厚度、形貌和成分的影响.实验结果表明,随着钎料中Cu质量分数的增加,回流焊后焊点IMC层厚度变薄,IMC晶粒尺寸增大,IMC晶粒形貌由颗粒状转变为棱柱状以及鹅卵石状,同时界面IMC成分发生由(Cu,Ni)6Sn5向Cu6Sn5的转变.高温时效后,界面IMC层厚度增长.当钎料中Cu质量分数超过1%时,时效后生成较厚的Cu3Sn化合物层,对焊点可靠性不利.钎料中Cu质量分数应控制在1%以下.     

Effects of nano-sized Ag reinforcing particulates on the microstructure of Sn-0.7Cu solder joints

Composite solders were prepared by mechanically dispersing different volumes of nano-sized Ag particles into the Sn-0.7Cu eutectic solder.The effects of Ag particle addition on the microstrueture of Sn-0.7Cu solder joints were investigated. Besides, the effects of isothermal aging on the microstructural evolution in the interfacial intermetallic compound (IMC) layer of the Sn-0.7Cu solder and the composite solder reinforced with l vol% Ag particles were analyzed, respectively. Experimental results indicate that the growth rate of the interfacial IMC layer in the Ag particles reinforced composite solder joint is much lower than that in the Sn-0.7Cu solder joint during isothermal aging. The Ag particles reinforced composite solder joint exhibits much lower layer-growth coefficient for the growth of the IMC layer than the corresponding solder joint.     

Effect of adding Ce on interfacial reactions between Sn-3.0Ag-0.5Cu solder and Cu substrate

The formation and the growth of Cu-Sn intermetallic compound （IMC） layer at the interface between Sn-3.0Ag-0.5Cu-xCe solder and Cu substrate during soldering and aging were studied. The results show that Cu6Sn5 IMC is observed at the interface between solder and Cu substrate in all conditions. After aging for 120 h,the Cu3Sn IMC is then obtained. With increasing aging time,the scalloped Cu6Sn5 structure changes to a plate structure. The Cu3Sn film always forms with a relatively planar interface. By adding a small amount of the rare earth element Ce （only 0.1%,mass fraction） into the Sn-3.0Ag-0.5Cu solder alloy,the growth rate of the Cu-Sn IMC at the interface of solder alloy system is decreased. When the time exponent is approximately 0.5,the growth of the IMC layer is mainly controlled by a diffusion over the studied time range.     

SnAgCu-Bi-Ni无铅微焊点的电迁移行为

以直径为400μm的SnAgCu-Bi-Ni(Ag<1%)微焊点为对象,研究了微焊点在电流时效过程中的电迁移行为.对球栅阵列(ball grid array,BGA)焊点组装电路在不同温度下进行不同时长的电流时效试验.从焊点微观组织和硬度梯度的变化两个方面分析了电迁移现象的行为规律.研究结果表明,电迁移试验后焊点阴极区域金属间化合物(intermetallic compound,IMC)分解,附近形成大量微空洞,Cu焊盘大量消耗,焊点中部和阳极形成了大量(Cu,Ni,)6Sn5化合物,附近形成大量小丘,电迁移作用导致焊点内部微硬度形成由阳极向阴极递减的梯度分布,较高的试验温度显著加快电迁移进程.     

元素Cu对BNi-7钎料组织和润湿性能的影响

在钎焊温度为980℃,保温时间为30 min的条件下,向BNi-7钎料中添加质量分数为9%的合金元素Cu,利用扫描电镜、同步热分析仪以及对比实验,分析元素Cu对BNi-7钎料微观组织、熔化特性以及润湿性能的影响.结果表明,添加合金元素Cu,钎料润湿铺展过程中相的种类不变,但Ni基固溶体厚度增加,共晶组织里的韧性Ni(Fe,Cr,Cu)固溶体数量增加;随着合金元素Cu的添加,钎料的固液相线温度逐渐降低,但熔化温度范围增大;对于添加9%Cu的BNi-7钎料,由于前驱膜的变宽,促进了钎料的润湿,润湿性能良好.     

时效处理对CuCrSnZn/SnAgCu钎料接头界面及剪切性能影响

为了探讨引线框架铜合金与无铅钎料钎焊接头界面性能,采用扫描电镜及万能材料实验机,分析了引线框架用CuCrSnZn合金与SnAgCu系无铅钎料钎焊接头,在160℃时效不同时间的过程中界面形貌及接头剪切性能的演变过程.结果表明,时效前,钎焊接头界面处形成了一层长针状的Cu6Sn5;不同时间时效处理后,接头界面IMC层厚度有不同程度的增加,Cu6Sn5变长变粗,逐渐离开界面进入钎料内部,靠近铜合金片材基体的一侧会出现极薄的一层Cu3Sn层.无铅钎料钎焊接头时效25h剪切强度可到27.3 MPa,其后逐渐降低.未时效、时效25 h和50 h断裂发生在钎料基体内部,时效至300 h,断裂位置向界面金属间化合物处转移,剪切断口断裂形式逐渐由韧性断裂向脆性断裂转变.     

金属间化合物对Sn-Ag-Cu无铅钎料钎焊接头性能的影响

采用扫描电镜、能谱分析、透射电镜、X射线衍射和电子衍射等分析手段,研究了Cu含量对Sn-Ag-Cu/Cu钎焊接头界面处生成的金属间化合物Cu6Sn5的生长形态对接头剪切强度的影响。结果表明:在Sn-Ag-Cu钎焊接头的界面处有扇贝状的Cu6Sn5金属间化合物的生成,调整Cu含量,可改变Cu6Sn5的形状和避免大柱状的Cu6Sn5生成,提高接头剪切强度,钎焊接头的断裂主要是韧性断裂。时效试验结果表明:当时效温度为室温、时间为1000 h时,Cu含量高的Sn-Ag-Cu钎料所生成Cu6Sn5的形态变化为长的空心截面六边形柱体,由于Cu6Sn5所形成的空心孔洞导致Sn-Ag-Cu/Cu界面成为强度弱区,从而使接头的剪切强度有所下降。     

Sn-Ag共晶钎料与Cu基板界面反应的热力学计算

为探讨热力学计算在无铅焊料的设计与研究领域中的应用,依据局部平衡理论,通过热力学相图计算,采用商业计算软件Thermo—Calc进行了计算与模拟工作．预测出250℃焊接温度下Sn—Ag共晶焊料与Cu基板界面处金属间化合物的形成序列;根据Scheil-Gulliver模型模拟了剩余液态钎料非平衡凝固过程,对相演变信息进行了预测．综合计算模拟结果,确定焊接接头的组织是由Cu6Sn5、Cu3Sn、、Ag3Sn和富Sn相（BCT—Sn）组成,有效地预测了界面反应行为,与实验结果吻合较好．     

Effects of particle size on the mechanical properties of particle-reinforced Sn-Ag composite solder joint

Particulate size has significant influenced on the mechanical properties of particle-reinforced composite solder joints. In this current research, Cu or Ni reinforcement particles were mechanically added to the Sn-3.5Ag eutectic solder, and the effects of the particle size on the mechanical properties of particle-reinforced composite solder joint were systematically studied. This investigation touched on how mechanical properties of the solder joints are affected by particles size. A quantitative formula was set up to correlate the mechanical property of the solder joint with particle size in different processing conditions. Besides, the fracture mechanism of the composite solder joint was analyzed.     

尺寸效应下的无铅微焊点研究进展

为了研究无铅微焊点在尺寸效应下的可靠性,综述了微焊点的界面反应机制,常用添加元素对微连接金属间化合物(IMC)的作用及微焊点在尺寸效应下的主要问题.分析表明,IMC层主要由两种铜锡化合物Cu6 Sn5和Cu3 Sn组成.微焊点的连接形式有焊盘小尺寸微焊点和微通孔焊盘无铅微焊点两种,柯肯达尔(Kirkendall)孔洞、电迁移及焊料尺寸都会对接头的力学性能、拉伸强度和剪切强度造成较大的影响.同时,压力钎焊等新工艺可以促进焊料中元素的扩散,从而对抑制接头组织中脆性相和提高钎焊接头强度有显著效果.     

Effects of rapid solidification process and 0.1%Pr/Nd addition on characteristics of Sn-9Zn solder alloy and interfacial properties of Cu/solder/Cu joints

Rapidly solidified Sn-9Zn-0.1Pr(/Nd) alloy foils were prepared by melt-spinning method. Through comparison, the effects of rapid solidification process and 0.1%Pr/Nd(mass fraction) addition on the microstructure, thermodynamic characteristic of Sn-9Zn solder alloy were analyzed. The tensile-shear tests were used to evaluate the mechanical properties of solder/Cu joints. The results show that the rapid solidification process can greatly refine the microstructure of Sn-9Zn-0.1Pr(/Nd) alloys. After rapid solidification, the effects of Pr/Nd addition on microstructure are depressed. The pasty range of the rapidly solidified Sn-Zn-RE solders is also reduced significantly. The mechanical properties of solder/Cu joints are obviously improved using the rapidly solidified Sn-9Zn-0.1Pr(/Nd) solder alloy, which results in the formation of uniform interface. The promotion effect of Nd addition in Sn-9Zn alloy on the interfacial reaction of solder/Cu joint is more remarkable than that of Pr.     

Electromigration in eutectic SnAg solder reaction couples with various ambient temperatures and current densities

The electromigration behavior of eutectic SnAg solder reaction couples was studied at various temperature (25 and 120℃)when the current density was held constant at 10~4 A/cm~2 or 5×10~3 A/cm~2. Under the current density of 10~4 A/cm~2, scallop type Cu_6Sn_5 spalls and migrates towards the direction of electron flow at room ambient temperature (25℃), but transforms to layer type Cu_3Sn and leaves Kirkendall voids in it at high ambient temperature (120℃). Under the current density of 5×10~3 A/cm~2 plus room ambient temperature,no obvious directional migration of metal atoms/ions is found. Instead, the thermal stress induced by mismatch of dissimilar materials causes the formation of superficial valley at both interfaces. However, when the ambient temperature increases to 120℃, the mobility of metal atoms/ions is enhanced, and then the grains rotate due to the anisotropic property of metal atoms/ions is enhanced, and then the grains due to the anisotropic property of β-Sn.     

低煤级煤中部分元素有机亲合性的定量研究

运用逐级化学提取方法研究了低煤级煤中Co,Ni,Cr,V,Sb等11种元素有机亲合性，结果表明：1）低煤级煤中存在有机态的微量元素，不同元素的有机亲合性差异较大，不同样品中同一元素的有机亲合性也存在一定差异，这可能与煤中该元素的丰度和性质，成煤地质条件有关；2）低煤级煤中与煤大分子结合的w(Co),w(Ni),w(V),w(Sb)的平均值为13％，80％，69％，36％，33％，与胡敏酸结合的平均值为30％，6％，17％，13％，与富里酸结合的平均值为69％，3％，3％，21％，18％，3）低煤级煤中Zn,Cd,Cu,Pb等亲硫元素也表现出一定的有机亲合性，其中，与煤大分子结合的w(Zn),w(Cd),w(Cu),w(Pb)平均值为22％，21％，40％，23％，与胡敏酸结合的平均值为9％，7％，14％，与富时酸结合的平均值为20％，13％，22％，13％。     

硫氰酸铵-氯化钠-溴化十六烷基吡啶金翁-水体系浮选分离锌(Ⅱ)

由实验得知,在水溶液中Zn(Ⅱ)与硫氰酸铵、溴化十六烷基吡啶生成不溶于水的三元缔合物,在少量氯化钠存在下,此三元缔合物沉淀于水相上层并与水分成界面清晰的两相,分相过程中Zn(Ⅱ)被定量浮选.实现了Zn(Ⅱ)与Fe(Ⅱ)、Al(Ⅲ)、Co(Ⅱ)、Ni(Ⅱ)、Mn(Ⅲ)等离子的分离,是一种无毒且更为简便、经济、快速的分离方法.     

价电子结构与合金元素对NiAl力学性能的影响

运用固体与分子经验电子理论,计算了添加几种常用合金元素M(M=Cr,Mn,Fe,Co,Cu)的合金(NiM)Al相空间价电子结构,并采用相结构因子nA、ρLV表征和评判了合金元素M对NiAl金属间化合物塑性和硬度的影响。研究结果表明,采用宏合金化的方法虽然可以提高合金的硬度,却降低了合金的塑性。合金化后NiAl硬度增加的次序为(Ni0.875Mn0.125)Al>(Ni0.875Co0.125)Al>(Ni0.875Fe0.125)Al>(Ni0.875Cr0.125)Al>(Ni0.875Cu0.125)Al>NiAl,塑性降低次序则与硬度增加次序相反。     

快凝合金La(NiMn)5.6的贮氢性能

借助X-ray及吸放氢性能测试装置研究了非化学计量比快凝合金La(NiMn)5.6的结构和贮氢性能以及A端、B端元素替代对合金的影响,测试了不同温度下合金的PCT曲线.结果表明,快速凝固(35 m/s)条件下合金La(NiMn)5.6均可获得过饱和CaCu5型单相组织.A端以Ce取代La,使平台压力增大,最大吸氢量减小,但滞后降低;B端以Sn取代Ni,改善了合金的活化特性,并使平台降低,吸放氢滞后减小.     

煤矿区城市PM_(10)元素组成特征及来源研究

采集河南省煤矿区代表城市平顶山市夏季和冬季的PM10样品,利用电感耦合等离子质谱测定PM10中Li,V,Cr,Co,Ni,Cu,Zn,Ga,As,Rb,Sr,Mo,Cd,Sn,Sb,Cs,Ce,Ba,Tl,Pb,Bi,Ti,Mn等23种元素的全样和水溶部分的浓度.研究结果表明,平顶山市PM10中全样和水溶性元素的总浓度均为冬季大于夏季,除部分地壳元素之外,来源于人为污染特别是燃煤的Ni,Cu,Zn,As,Cd,Sn,Sb,Tl,Pb,Bi等元素的浓度也为冬季大于夏季.Rb,Cs,Mo,Cd,Sb,Tl,Mn,Co,Ni等元素以水溶状态存在,Ga,Sn,Ce,Pb,Bi,Ti等元素多以不溶状态存在.富集因子分析结果表明,PM10中Ni,Cu,Zn,As,Mo,Cd,Sn,Sb,Tl,Pb,Bi等元素主要来自人为污染,Li,V,Cr,Co,Ga,Ti,Mn等元素主要来源于地壳.因子分析结果表明,平顶山市夏季和冬季PM10主要来源于燃煤和地壳,分别占49.98%和36.97%.Ni,Cu是以生产煤炭为主的平顶山市PM10中的代表性元素.     

图们江中游表层沉积物的重金属污染特征与生态风险评价

采用电感耦合等离子体质谱法(ICP-MS)测定了图们江中游表层沉积物中As、Cd、Cr、Co、Cu、Ni、Pb、Zn的含量,并对其生态风险进行了评价.研究表明:表层沉积物中8种重金属的浓度在0.48～241.81 mg/kg之间,平均浓度的高低顺序为As、Pb、Zn、Cu、Ni、Cr、Co、Cd; 8个采样点中,白龙(T5)、日光(T6)、图们公园(T7)3处采样点的污染较为严重; 地积累指数(I_geo)评价结果显示,污染程度的高低顺序为Pb、Cd、Cu、As、Ni、Co、Zn、Cr