Effect of pH of Sulfate Solution on Electrochemical Behavior of Pb-Free Solder Candidates of SnZn and SnZnCu Systems

The corrosion resistance of the next generation solders is one of the key factors responsible for reliability of solder joints. The paper focuses on the comparative studies of corrosion behavior of Pb-free solder candidates of binary Sn-Zn and ternary Sn-Zn-Cu systems. The accelerated corrosion tests were made by means of voltammetric measurements carried out in the sulfate solution. The effect of its pH on the electrochemical behavior of selected alloys was identified.     

Advances in Pb-free Solder Microstructure Control and Interconnect Design

New electronics applications demanding enhanced performance and higher operating temperatures have led to continued research in the field of Pb-free solder designs and interconnect solutions. In this paper, recent advances in the microstructural design of Pb-free solders and interconnect systems were discussed by highlighting two topics: increasing β-Sn nucleation in Sn-based solders, and isothermally solidified interconnects using transient liquid phases. Issues in β-Sn nucleation in Sn-based solders were summarized in the context of Swenson’s 2007 review of the topic. Recent advancements in the areas of alloy composition manipulation, nucleating heterogeneities, and rapid solidification were discussed, and a proposal based on a multi-faceted solidification approach involving the promotion of constitutional undercooling and nucleating heterogeneities was outlined for future research. The second half of the paper analyzed two different approaches to liquid phase diffusion bonding as a replacement for high-Pb solders, one based on the application of the pseudo-binary Cu-Ni-Sn ternary system, and the other on a proposed thermodynamic framework for identifying potential ternary alloys for liquid phase diffusion bonding. All of the concepts reviewed relied upon the fundamentals of thermodynamics, kinetics, and solidification, to which Jack Smith substantially contributed during his scientific career.     

Evaluation of corrosion behaviour of a new class of Pb‐free solder materials (Sn‐In‐Zn)

In view of the need for a lead‐free drop in replacement for the widely used 40Pb‐60Sn near eutectic solder, new Sn‐In‐Zn based alloys with substantially the same melting point have been developed. The corrosion resistance and the influence of zinc content on electrochemical behaviour of some special alloys Sn‐In‐Zn in 3% NaCl solution has been investigated using electrochemical techniques. The good resistance of this ternary system is confirmed. In decreasing dissolution rate, they are ranked as follows: 40Pb‐60Sn, Sn‐10.6In‐27Zn, Sn‐11In‐23Zn and Sn‐13In‐12Zn. The increase of zinc content induces a decrease of corrosion resistance of ternary Sn‐In‐Zn alloys. So, the Sn‐In‐Zn system with low indium and zinc concentrations might be a good candidate for solder materials and present a good corrosion resistance.     

Evaluation of Bulk Mechanical Properties of Selected Lead-Free Solders in Tension and in Shear

Lead-free solders are fast emerging as better alternatives to Sn-Pb solders. The reliability of a soldered joint to withstand imposed stresses in an assembly is decided by its mechanical properties. The present work is about the investigation of tensile and shear properties of four binary eutectic alloys Sn-3.5Ag, Sn-58Bi, Sn-0.7Cu, Sn-9Zn and a ternary alloy Sn-57Bi-1.3Zn in comparison with conventional Sn-38Pb alloy. It is observed that the lead-free solders have better mechanical properties than the latter. SEM studies of tensile and shear fracture show ductile dimples circular in tension and parabolic in shear modes supporting the mechanical behavior of the alloys investigated. Eutectic alloys Sn-Ag, Sn-Zn, and Sn-Cu form potential substitutes for Sn-Pb for electronic interconnects exposed to high temperatures, while Sn-Bi and Sn-Bi-Zn are attractive alternatives in addressing the need of lower processing temperatures in printed circuit boards and other applications.     

A Comparative Biocompatibility Analysis of Ternary Nitinol Alloys

Nitinol alloys are rapidly being utilized as the material of choice in a variety of applications in the medical industry. It has been used for self-expanding stents, graft support systems, and various other devices for minimally invasive interventional and endoscopic procedures. However, the biocompatibility of this alloy remains a concern to many practitioners in the industry due to nickel sensitivity experienced by many patients. In recent times, several new Nitinol alloys have been introduced with the addition of a ternary element. Nevertheless, there is still a dearth of information concerning the biocompatibility and corrosion resistance of these alloys. This study compared the biocompatibility of two ternary Nitinol alloys prepared by powder metallurgy (PM) and arc melting (AM) and critically assessed the influence of the ternary element. ASTM F 2129-08 cyclic polarization in vitro corrosion tests were conducted to evaluate the corrosion resistance in phosphate buffered saline (PBS). The growth of endothelial cells on NiTi was examined using optical microscopy.     

Environmentally friendly solders 3-4 beyond Pb-based systems

Based on environmental considerations, global economic pressures, enacted by legislations in several countries, have warranted the elimination of lead from solders used in electronic applications.Sn3.5Ag, SnAgCu, and Sn0.7Cu have emerged among various lead-free candidates as the most promising solder alloys to be utilized in microelectronic industries.However, with the vast development and miniaturization of modern electronic packaging, new requirements such as superior service capabilities have been posed on lead-free solders.In order to improve the comprehensive property of the solder alloys, two possible approaches were adopted in the current research and new materials developed were patented.One approach was involved with the addition of alloying elements to make new ternary or quaternary solder alloys.Proper addition of rare earth element such as La and Ce have rendered solder alloys with improved mechanical properties, especially creep rupture lives of their joints.Another approach, the composite approach, was developed mainly to improve the service temperature capability of the solder alloys.Composite solders fabricated by mechanically incorporating various reinforcement particles to the solder paste have again exhibited enhanced properties without altering the existing processing characteristics.The recent progress and research efforts carried out on lead-free solder materials in Beijing University of Technology were reported.The effects of rare earth addition on the microstructure, processing properties, and mechanical properties were presented.The behaviors of various Sn-3.5Ag based composite solders were also explicated in terms of the roles of reinforcement particles on intermetallic growth, steady-state creep rate, the onset of tertiary creep, as well as the overall creep deformation in the solder joints.Thermomechanical fatigue (TMF) behavior of the solder alloys and composite solders were investigated with different parameters such as ramp rate, dwell time, etc.The damage accumulation features and residual mechanical properties of the thermomechanically-fatigued composite solder joints were compared with non-composite solder joints.To match the lead-free alloys, various types of water soluble no-clean soldering flux have also been developed and their properties were presented.     

Corrosion characterization of tin-lead and lead free solders in 3.5 wt.% NaCl solution

The corrosion resistance of Sn-Pb and several candidate lead free solders were investigated in 3.5 wt.% NaCl solution through potentiodynamic polarisation. Results showed that in NaCl solution lead free solders had better corrosion resistance than Sn-Pb solder and the corrosion resistance of lead free solders was similar, but the corrosion resistance of Sn-Ag solder was better than that of Sn-Ag-Cu and Sn-Cu solders. The corrosion products for Sn-Pb solder had a two-layered structure with Sn-rich phases at the outer layer and looser Pb-rich phases at the inner layer. The loose Pb-rich layer was detrimental to the corrosion property. The corrosion product on the surface of all these solders was tin oxide chloride hydroxide.     

Structural and elastic properties of eutectic Sn-Cu lead-free solder alloy containing small amount of Ag and In

Sn-Cu alloys have been considered as a candidate for high temperature lead-free microelectronic solders. In the present study, the change in microstructure, attenuation and elastic behavior associated with alloying of Ag and/or In into the eutectic Sn-Cu solder alloy system have been evaluated. The study involved measurements of longitudinal and shear wave velocities, attenuation, hardness, bulk and shear moduli, Young's and Poisson's ratio. The results of attenuation show that a clear attenuating effect in the ternary Sn-Cu-Ag and Sn-Cu-In alloys is realized, whereas the quaternary Sn-Cu-Ag-In solder displays an obscure attenuating effect. The obscure effect is mainly attributed to the competition for In between Sn and Ag, which results in weak interface formed between intermetallic compounds (IMCs) and β-Sn matrix. Likewise, Poisson's ratio results indicate that its value decreases with increasing the elastic moduli and ultrasonic velocities of Ag and In-containing alloys. The analyzed enhanced ductility of Sn-0.7Cu and Sn-0.7Cu-2In alloys and brittleness of Sn-0.7Cu-2Ag and Sn-0.7Cu-2Ag-2In alloys were rationalized on the basis of Poisson's ratio and the quotient of shear modulus to bulk modulus (Pugh's ratio). Microstructural analysis revealed that the origin of change in the elastic properties of the ternary and quaternary alloys is ascribed to smaller β-Sn dendrite grain dimensions and formation of new IMCs in the ternary and quaternary alloys.     

Joining of Cu,Ni, and Ti Using Au-Ge-Based High-Temperature Solder Alloys

Au-Ge-based solder alloys are promising alternatives to lead containing solders due to the fact that they offer a combination of interesting properties such as good thermal and electrical conductivity and high corrosion resistance in addition to a relatively low melting temperature (361 °C for eutectic Au-28Ge at.%). By adding a third element to the eutectic Au-28Ge alloy not only the Au content could be reduced but also the melting temperatures could be further decreased. In this study, in addition to the eutectic Au-28Ge (at.%) two ternary alloys were chosen from the Au-Ge-Sb and Au-Ge-Sn system, respectively. The soldering behavior of these alloys in combination with the frequently used metals Cu, Ni, and Ti was investigated. The interface reactions and microstructures of the joints were characterized in detail by SEM and EDX analysis. For the determination of the mechanical properties, shear tests were conducted. Mean shear strength values up to 104 MPa could be achieved.     

Beschichtungssysteme für Verbindungselemente in Kontakt mit Leichtmetallen

Coating systems for joining elements in contact with light metals Galvanic corrosion of light metal alloys can only be avoided, if the steel fasteners are given an electrochemically compatible protection or if the corrosion circuit is interrupted by electric insulating layers. Current density vs. potential curves of chromated zinc alloy coatings show, that by means of zinc nickel coatings a largely electrochemical adaption to the equilibrium potential of quenchaged aluminium alloys of the type AlMgSi is possible. On the other hand, the equilibrium potentials of chromated systems based on ZnFe, ZnCo respectively, are too low to avoid galvanic corrosion on aluminium. In practicerelated corrosion tests on joining elements, this result was confirmed. Besides this, zinc- and aluminium-bearing sintersystems, galvanic tin depositions as well as ternary mechanical coatings based on ZnSnAl have been proved to be compatible with AlMgSi-type alloys. For coating systems in contact with magnesium a satisfactory protection against galvanic corrosion can be achieved effectively with insulating top coats. The results with suitable duplex systems are presented and recommendations for practical applications are derived.     

Al对低中子吸收截面Ti-Zr-Nb高熵合金的微观结构和腐蚀行为的影响

针对Al对低中子吸收截面Ti-Zr-Nb系高熵合金的微观结构和腐蚀行为进行了研究。比较了不含Al和含15at%Al的Ti-Zr-Nb合金的相图、微观结构、氧化行为和腐蚀行为。相图计算结果表明,在熔点下Ti-Zr-Nb三元合金为bcc相,添加的Al会倾向于在合金中形成不同的金属间化合物,而缩小相图中bcc单相区的温度区。XRD和TEM结果表明,熔炼获得的Ti-Zr-Nb三元合金为简单的bcc结构,而Al会导致晶体结构转变为有序的B2结构。通过热重分析和高压釜试验对Ti-Zr-Nb系高熵合金的腐蚀行为进行了研究。结果表明,在腐蚀过程中,Ti-Zr-Nb三元合金的氧化膜容易发生剥落,而添加Al会提高氧化层的稳定性,但不会改变腐蚀氧化层的主要氧化物种类。通过计算反应速率常数和激活能对氧化动力学进行了研究,发现添加Al的Ti-Zr-Nb系合金的高温氧化性能与Zr合金接近。     

Electrochemical and mechanical behaviour of Sn‐2.5Ag‐0.5Cu and Sn‐48Bi‐2Zn solders

In this paper, two tin‐based alloys (Sn‐2.5Ag‐0.5Cu and Sn‐48Bi‐2Zn) are proposed as new lead‐free solders. Alloys have been developed by melting pure elements. Samples have been evaluated in terms of microstructure, corrosion resistance and mechanical features. Corrosion tests have been performed in 3% NaCl solution by polarization curves and electrochemical impedance spectroscopy (EIS). SEM observations and EDS analysis were carried out on samples before and after corrosion tests. Static monotonic tensile tests have been performed on three specimens for each alloy. SEM and EDS analysis revealed the presence of Sn‐Ag and Sn‐Cu intermetallic compounds within the Sn‐Ag‐Cu alloy. As a result of corrosion test, the Sn‐Ag‐Cu alloy showed a better corrosion resistance with respect to Sn‐Bi‐Zn. Both alloys evidenced good mechanical properties higher than the traditional Sn‐Pb system. Sn‐Ag‐Cu seems to be a suitable soldering material.     

Oxidation of multicomponent two-phase alloys

The high-temperature corrosion behavior of two-phase alloys presents a number of differences compared to that of single-phase alloys. These differences are mainly a consequence of the limitations that the presence of two phases impose on the diffusion of the alloy components. In this review, it is shown that the exclusive scale formation of the more stable, slow-growing oxide is more difficult on a two-phase alloy, requiring a higher concentration of the more reactive alloy component than for a corresponding single-phase alloy. The main types of corrosion behavior for binary two-phase alloys are also considered, showing that if diffusion in the alloy is slow the scale structure will closely reflect that of the starting material. When diffusion in the alloy is not negligible, the scale structure becomes similar to what forms on single-phase alloys. The oxidation of two-phase ternary alloys is shown to be even more complex than the two-phase binary alloys. The principal added complexity compared to the binary alloys is that diffusion in the ternary alloys may also occur in the presence of two metal phases, as a result of an extra degree of freedom in the ternary system. The oxidation behavior of two-phase ternary alloys is discussed in the context of a number of recent experimental results.     

Converting to lead-free solders: An automotive industry perspective

The solder tests currently used in defining solder alloy properties are not sufficient for selecting interconnect materials for improved reliability and reduced cost in automotive electronic applications. A “preventive” design approach based upon more accurate models of failure mechanisms and life prediction than are currently available will be required in order to assess solder alloys and to determine whether lead-free solders will provide improved reliability and lower-cost manufacturing options when compared to the lead-based solders currently used.     

In vitro biodegradability of Mg-2Gd-xZn alloys with different Zn contents and solution treatments

This study aims to investigate the addition of Zn on the corrosion property and cytocompatibility of Mg-2Gd-xZn(x= 0,3,4 and 5;wt%)alloys,which were prepared by gravity permanent mold casting and solution treatment,respectively.The results show that the intermetallic phases of these ternary alloys are mainly composed of Mg_(12)GdZn and Mg_3GdZn_3.The content of secondary phases as well as the grain size is greatly dependent on the Zn addition.Compared to the binary Mg-2 Gd alloy,the corrosion resistance of the most ternary alloys is significantly improved.Furthermore,the in vitro cell culture study demonstrates the potential cytocompatibility of the developed ternary alloys.It indicates that a series of Mg-2Gd-xZn(x= 0,3,4 and 5;wt%)with medically acceptable corrosion rate are developed and show great potential use as a new type of biodegradable implants.     

Ti对Zr-Nb二元合金β结构稳定性和力学性能的影响

利用团簇成分式方法设计了[Zr-Zr₁₄](Zr,Nb)3系列二元合金,进而采用Ti替代部分Zr形成三元合金;采用真空铜模吸铸快冷技术制备合金棒材,利用XRD、OM、TEM等对其进行微观组织表征和力学性能测试。结果表明,随着Nb含量增加,Zr-Nb二元合金基体结构从hcp-α向bcc-β转变,β结构稳定的同时伴随有ω相析出。适量Ti添加可显著抑制ω相的析出,进一步改善了合金的β结构稳定性。其中,单相bcc-β合金[Ti-Zr₁₄]Nb3(Zr-17.37Nb-2.98Ti,质量分数,%)表现出低弹性模量(E=57 GPa)的同时具有最佳的力学性能(屈服强度σYS=557 MPa、延伸率δ=15.5%)。     

Assessment of Corrosion Resistance and Metal Ion Leaching of Nitinol Alloys

Nitinol usage for biomedical implant devices has received significant attention due to its high corrosion resistance and biocompatibility. However, surface treatments are known to affect surface charge, surface chemistry, morphology, wettability, and corrosion resistance. In this investigation, the corrosion resistance of a binary and various ternary Nitinol alloys was determined after being subjected to electropolishing, magnetoelectropolishing, and water boiling and passivation. Cyclic polarization in vitro corrosion tests were conducted in Phosphate Buffer Saline (PBS) in compliance with ASTM F 2129-08 before and after surface treatments. The concentrations of dissolved metal ions in the electrolyte were also determined by ICPMS.     

Assessment of Corrosion Resistance and Metal Ion Leaching of Nitinol Alloys

Nitinol usage for biomedical implant devices has received significant attention due to its high corrosion resistance and biocompatibility. However, surface treatments are known to affect surface charge, surface chemistry, morphology, wettability, and corrosion resistance. In this investigation, the corrosion resistance of a binary and various ternary Nitinol alloys was determined after being subjected to electropolishing, magnetoelectropolishing, and water boiling and passivation. Cyclic polarization in vitro corrosion tests were conducted in Phosphate Buffer Saline (PBS) in compliance with ASTM F 2129-08 before and after surface treatments. The concentrations of dissolved metal ions in the electrolyte were also determined by ICPMS.