•Ag Nanopaste offer a great potential for brazing Ni200.•The brazing pressure has a significant influence on the shear strength.•High shear strength of joint is achieved at higher brazing temperature.•Elements diffusing was detected during brazing process.Ag nanopastes and Cu-Ag core-shell nanowire nanopastes were used for brazing Ni 200. The influences of the brazing temperature and brazing pressure on the mechanical properties and microstructure of joints were investigated. The results show that the shear strength of joint was significantly improved from 12 MPa to 46 MPa with increasing the brazing temperature from 300 °C to 850 °C and brazing pressure from 7 MPa to 26 MPa. It is indicated that both a high brazing pressure and brazing temperature are beneficial for the diffusions between adjacent nanoparticles and nanowires, the seam and based materials and thereby improve the shear bonding strength. Successful joints of 40.6 MPa bonding strength were achieved with 700 °C brazing temperature, which indicated that silver nanopaste can be used for brazing Ni at a lower brazing temperature than that of commercial BAg-8 brazing filler metals.Download high-res image (325KB)Download full-size image

•Comparative studies on Sn whisker growth in Sn-0.3Ag-0.7Cu-1Pr solder under different environments were conducted.•Ambient temperature and oxygen level are two important factors that can affect Sn whisker growth.•Growth mechanisms of whiskers under different environments were clarified.In this study, comparative studies on Sn whisker growth in Sn-0.3Ag-0.7Cu-1Pr solder under different environments were conducted to investigate factors like ambient temperature, oxygen level, and 3.5 wt% NaCl solution on whisker growth. The experimental results revealed that ambient temperature and oxygen level are two important factors that could determine the oxidation rate of PrSn3 phase, thus indirectly affecting the growth rate of Sn whiskers. In addition, mechanisms of whisker growth under these three environments were established from the perspective of atom diffusion based on the “compressive stress-induced” theory. Although whiskers under different environments were all squeezed out from Pr oxides (hydroxides), the forms of their driving forces were different. For whiskers squeezed out in air whether at room temperature or 150 °C, the driving force is the compressive stress produced by lattice expansion due to the oxidation of PrSn3 phase. The representative example was whiskers' growth at 150 °C, which could be simplified as three stages: (1) squeezing out, (2) cracking and (3) bursting out. For whisker growth in 3.5 wt% NaCl solution, the driving force for much fewer whiskers' growth was proposed to come from lateral stress provided by interfacial IMC layer growth. Moreover, Sn nanoparticles and their agglomerations were also found to form under the driving force of the potential difference between Sn atoms and Sn crystals. Their morphologies could also be affected by factors of ambient temperature, oxygen level and Cl− ions in corrosive liquid.Download high-res image (100KB)Download full-size image

To improve the mechanical properties of AA6082 weld welded by tungsten inert gas welding using AA4043 welding wire, the effect of addition of Ti and/or Sr on continuous cast and rolled AA4043 welding wire was investigated. Experimental results indicated that Ti and Sr are excellent modifiers, which improve the microstructure of the AA4043 welding wire and enhance the mechanical properties of the AA6082 weld. It was found that the combinative addition of Ti and Sr can effectively modify both the α(Al) dendrites and eutectic Si phases compared with individual addition of Ti or Sr. In addition, Ti and/or Sr also changed the microstructure of the AA6082 weld. The tensile strength of the AA6082 weld reached the maximum value when 0.08% Ti and 0.025% Sr were added simultaneously. These results indicate that the combinative addition of Ti and Sr can be an effective composite modifier.

Effect of Pr element on the wettability, microstructure, interface morphology and mechanical property of Sn–0.3Ag–0.7Cu–0.5Ga–xPr solder has been studied. The result exhibits that the wettability of solders could significantly be improved by adding an approximate amount of Pr, for the forming of well-distributed PrSn3 IMCs could serve as the sites of heterogeneous nucleation, subsequently leading to the refinement of β-Sn matrix and reducing the growth of IMCs. Therefore, the thickness of the IMC layers at the interface (Cu plate/solder) is reduced, implying that the morphology is optimized. The promotion of mechanical properties is also correlated to the refining of IMC layer.

In this study, trace amount of rare earth Pr was added into Sn–0.3Ag–0.7Cu low-Ag solder to enhance properties of solders. Experimental results indicated that optimal amount of Pr addition (~0.06 wt%) can improve properties of wettability, shear force and ductility of Sn–0.3Ag–0.7Cu low-Ag solder. This is because that solder with optimal Pr addition not only had a refined microstructure but also owned a regular and thin interfacial IMC layer after soldering on Cu substrate. Meanwhile, we have explained the change of morphology and thickness of interfacial IMC layer after Pr addition based on Kim and Tu’s kinetic model of interfacial IMC growth. However, it was found excessive Pr addition led to the formation of PrSn3 phase, which was easy to be oxidized and became a great deterioration on the properties referred above. Besides, the fracture mode of solder joint also gradually changed from ductile fracture to cleavage fracture. Moreover, this oxidized PrSn3 became the birthplace of Sn whisker since it provided abundant supply of Sn sources and compressive stress for Sn whisker growth. By the in-situ observation of Sn whisker growth in 0.5 wt% Pr-doped solder joint, we obtained that the incubation period of Sn whisker is very short and its growth rate may have a great decrease with time extending. Besides, it was found after 1 day at room temperature, spindly and rod-like Sn whiskers also grew in 0.5 wt% Pr-doped solder joint besides dot-shaped Sn whisker that grew in 0.5 wt% Pr-doped solder matrix. We suggest this may be related with the extra compressive stress provided by interfacial IMC layer growth in 0.5 wt% Pr-doped solder joint.

This work offers an analysis of the microstructure and the growth rate of an intermetallic compound within the aged AA 6061 aluminum alloy-304 stainless steel joint brazed with Zn-15Al and Zn-15Al-0.2Zr filler metals. The effect of zirconium addition on mechanical integrity of the brazed joint was studied. The experimental results confirm that the thickness of the Fe-Al intermetallic layer formed at the brazed seam/stainless steel interface increases with the increase of the aging time. Furthermore, it is established that the growth rate of the intermetallic layer for the Zn-15Al-0.2Zr brazed joint was lower than that for Zn-15Al. The results also indicate that the shear strength of both Zn-15Al and Zn-15Al-0.2Zr brazed joints decreases monotonously during aging. The value of the strength after aging lasting for 800 h for Zn-15Al and Zn-15Al-0.2Zr has decreased by 20 and 17%, respectively. The fracture of joints occurred at the interface between the brazed seam and the Fe4Al13 intermetallic layer. The morphology of the surfaces exhibits a cleavage fracture.

The effect of Si on the brazability and the microstructures of Al-40Zn-xSi filler metals were studied, and the microstructures and the mechanical properties of the joints brazed with Al-40Zn-xSi filler metals were investigated. The results indicate that the Al-40Zn-xSi filler metal presents the best wettability on 6061 aluminum alloy when Si content is and 4.0 wt%. The microstructure of the filler metal indicates that the primary silicon particles could be found when the silicon content exceeds 4.0 wt%. Al-Si eutectic mixed with Zn-Al eutectoid is located at α-Al interdendritic regions in the brazed seam after cooling with water. Moreover, the Al-40Zn-4Si joint possesses the optimum shear strength of 142.28 MPa. However, the excess of Si would increase the amount of brittle eutectic structure and primary silicon particles in the brazed joints, and thereby the mechanical properties will be deteriorated.

Brazing of a 6061 aluminum alloy to 304 stainless steel has been conducted using a Zn–15Al–xZr filler metal and the effects of Zirconium (Zr) addition on the properties and microstructures of Zn–15Al filler metals were investigated. The experimental results indicated that the liquidus temperature of Zn–15Al–xZr was approximately 445 °C and Zr addition had little influence on the melting point of the Zn–15Al–xZr filler metal. Moreover, adding an appropriate amount of Zr appeared to refine the η-Zn dendrites and improve the microstructure of the filler metal. However, an excessive amount of Zr led to the formation of Zr-bearing compounds in the Zn–15Al–xZr alloy. The results also indicated that the thickness of the intermetallic compound layer of Fe4Al13 along the brazed seam/stainless steel interface was significantly reduced and a layer as thin as 0.93 μm was observed at the interface of Zn–15Al–0.2Zr brazed joint. This imparted a 10% increase to the average shear strength of the joints brazed with Zn–15Al–0.2Zr in comparison to the Zn–15Al filler metal.

Ag is used as a beneficial alloy element in no matter solders or brazing filler metals. Obviously, the addition of Ag has a positive function on melting temperature, wettability, mechanical property and conductivity of filler metals. Therefore, Ag is still widely used in many researches and production in spite of that Ag is very expensive. Respectively, three kind of typical solders (Sn–Ag–Cu, Sn–Zn and Sn–Bi) and brazing filler metals (Ag–Cu–Zn, Cu–P, and Zn–Al) have been chosen for illustration. This article summarizes research status on the studying of Ag-contained solders and brazing filler metals, also analyses influence rules of Ag addition on the change of filler metals’ physical property, microstructure as well as mechanical property. Moreover, the problems and difficulties in the process of study Ag-contained solders and brazing filler metals have been presented. Synchronously, some suggestions have been put forward which may solve the problems and difficulties mentioned above, which provides theory guide for the follow-up study of Ag-contained solders and brazing filler metals, and their prospects are also looked ahead.

Cerium and titanium were added to an Al-42Zn-6.5Si brazing alloy, and the subsequent microstructures of the brazing alloy and the 6061 Al alloy brazing seam were investigated. The microstructures of filler metals and brazed joints were characterized by scanning electron microscopy and X-ray energy dispersion spectrometry. A new Ce-Ti phase formed around the silicon phase in the modified filler metal and this saturation phenomenon was analyzed. Interestingly, following brazing of the 6061 alloy, there is no evidence of the Ce-Ti phase in the brazing seam. Because of the mutual solubility of the brazing alloy and base metal, the quantity of the solvent increases, and the solute Ce and Ti atoms assume an undersaturated state.

The novel Al-Si-Zn filler metals containing Ti and Sr were used for brazing of 6061 aluminum alloy. The results indicate that the addition of Zn into the Al-Si filler metal lowers the solidus temperature from 583 °C to around 520 °C. The minor addition of modification element Sr and refine element Ti into Al-Si-Zn alloy WILL cause the remarkable modification of Al-Si eutectic and the α-Al phase is also refined. The main phases in the filler metals as well as the brazed seams are α-Al, η-Zn, and Si phases. The large clusters of Al-Si eutectic in the Al-Si-Zn-Sr-0.04Ti brazed seam are refined by further adding 0.08 wt% Ti, the refined Al-Si eutectic is homogeneously distributed among α-Al phase. Diffusion layers can be found in the brazed interface, the Mn-Fe phase is also found in the brazed seam due to the diffusion of 6061 base metal into the brazing alloy which is helpful for reduce the formation of acicular β-Fe.

Al-6.5Si-42Zn and Al-6.5Si-42Zn-0.09Sr filler metals were used for brazing 6061 aluminum alloy. Air cooling and water cooling were applied after brazing. Si phase morphologies in the brazing alloy and the brazed joints were investigated. It was found that zinc in the Al-Si filler metals could reduce the formation of eutectic Al-Si phase and lower the brazing temperature at about 520°C. Adding 0.09wt% Sr element into the Al-6.5Si-42Zn alloy caused α-Al phase refinement and transformed acicular Si phase into the finely fiber-like. After water cooling, Zn element dissolved into the Al-Si eutectic area, and η-Zn phase disappeared in the brazed joints. Tensile strength testing results showed that the Sr-modified filler metal could enhance the strength of the brazed joints by 13% than Al-12Si, while water-cooling further improved the strength at 144 MPa.

Interfacial microstructure and properties of Sn–0.7Cu–0.05Ni/Cu solder joints with trace amounts Nd additions have been investigated in this paper. The evolution of interfacial morphology of SCN solder joints with and without the presence of Nd under long-term room ambience was also studied. The greatest improvement to the solderability and tensile strength of SCN-xNd are obtained at 0.05 wt.% Nd. Meanwhile, the morphology and growth of interfacial intermetallic (IMC) layer are greatly improved by adding Nd, and the propensity for IMC spalling from the interface of solder joint is definitely reduced with the presence of rare earth Nd, since the sponge-like structure was completely inhibited in the solder joint containing Nd. In addition, a significant amount of Sn whiskers were present on the surface of NdSn3 phases in the SCN0.15Nd/Cu solder joints, and the reason for this phenomenon has been briefly discussed.Highlights► The combined effects of rare earth Nd and Ni elements on Cu–Sn interfacial IMC layer of solder joint are discussed for the first time. The research investigates the effects of trace amounts of Nd on properties and microstructure of Sn–0.7Cu–0.05Ni solder. Afterwards, the evolution of interfacial microstructures and properties of SCN solder joints with and without the presence of Nd under long-term room ambience condition was studied, which is essential for the property stability and reliability of solder joint.

Effects of trace amount addition of rare earth Nd on the properties of eutectic Sn–Zn solder were studied in this paper. Results indicate that adding trace rare earth element Nd could remarkably improve the solderability and mechanical properties of Sn–9Zn solder joints. Especially when the content of Nd was 0.06 wt%, the wettability of the solder was improved significantly, and the shear force of Sn–9Zn–0.06Nd solder joint was enhanced by 19.6% as well as pull force increased by 26.6% compared to that of Sn–9Zn solder joint,respectively. It is also found that addition of rare earth Nd could refine the microstructure of the solder and some NdSn3 phase appeared in the solder matrix. Moreover, the IMCs thickness at the solder/Cu interface was reduced. NdSn3 phase appeared at the interface with excessive addition of Nd, which is the key reason that deteriorates the mechanical properties of soldered joint.

In the present work, effects of trace amount of Pr on the microstructure, wettability and mechanical properties of Sn-9Zn solder were studied. The range of Pr content in Sn-9Zn solder alloys varied from 0.01 to 0.25 wt%. Test results indicate that adding appropriate amount of Pr can evidently improve the wettability and mechanical properties of the Sn-9Zn solder alloy. The Sn-9Zn-0.08Pr solder shows the best comprehensive properties compared to other solders with different Pr content. At the same time, notable changes in microstructure were found compared with the Pr-free alloy. The needle-like Zn-rich phase in the Sn-9Zn solder was refined and became more uniform. Moreover, the thickness of the IMC layer at Sn-9Zn/Cu substrate was remarkably depressed with Pr addition.

Nowadays, a major concern of Sn–Cu based solder alloy today is focused on continuously improving the comprehensive properties of the solder joints formed between the solders and substrates. The key issues and improvements about Sn–Cu–X (X = Ni, rare earths, Zn, Co, Ga, In, Bi, secondary particles etc.) solder are outlined and evaluated in this paper which compared to Sn–Cu solder. It can be summarized that by adding appropriate amounts of certain alloying elements X to Sn–Cu solder, and it is possible to tailor the properties of the solder, such as the melting and solidification behaviors, wettability, microstructure, interfacial reactions and mechanical properties of the solder. The reliability issues related to the implementation of Sn–Cu–X solder in advanced electronics system are also introduced, which indicates that further development on the Sn–Cu–X solders are to be underway.

The wetting properties and interfacial microstructures of Sn–9Zn–xGa lead-free solders with Cu substrate were investigated. The wetting property is improved remarkably with the increase of Ga content in the Sn–9Zn lead-free solder. The lower surface tension, which results from the decrease of the oxidation of the Zn atoms owing to the formation of the Ga-rich protective film covered on the liquid solder, is the key reason for the better wettability. During soldering, the Cu5Zn8 compounds layer form at the interface of Sn–9Zn/Cu and the IMCs formed at the solder/Cu surface become much thicker when the Ga content is from 0.1 wt.% to 3 wt.%. However, neither Cu–Sn compounds nor Ga-rich phases are observed at the solder/Cu surface.

Effects of rare earth Nd on solderability of the Sn3.8Ag0.7Cu alloy were studied by wetting balance method, and the mechanical properties (such as pull-force and shear-force) of the joints soldered with SnAgCu–XNd solders were determined using STR-1000 joint strength tester. Moreover, the microstructures of SnAgCu–XNd solders bearing different amount of Nd as well as the intermetallic compounds (IMCs) formed at solder/Cu interface during soldering have been investigated using optical microscopy, scanning electron microscopy and energy dispersive X-ray analysis, respectively. The results indicate that trace amount of Nd addition can remarkably improve the solderability and mechanical properties of SnAgCu solder. At the same time, it is found that rare earth Nd in SnAgCu solder could refine and improve microstructure of the solder, some bigger IMC plates in SnAgCu solder were replaced by fine granular IMCs. Moreover, the thickness of the intermetallic layer at the Cu/solder interface was reduced significantly. In summary, we suggest that the most suitable content of rare earth Nd is about 0.05 wt% and it will be inadvisable when the Nd exceeds 0.25 wt%.

The influences of different Ce content on the properties of Sn–9Zn lead-free solder were investigated. The results indicate that Ce plays an important role not only in the structure and the solderability, but also in the interfacial structure of Sn–9Zn–xCe/Cu and mechanical property of soldered joint. Sn–9Zn–0.08Ce shows finer and more uniform microstructure than Sn–9Zn, and when the quantity of Ce is 0.5–1 wt%, some dark Sn–Ce compounds appear in the solder. With the addition of 0.08 wt% Ce, the solderability of solder is significantly improved because the surface tension of molten solder is decreased. Adding Ce makes the Cu5Zn8 IMCs formed at the interface of solder/Cu become much thicker than that of Sn–9Zn/Cu because much more content of Zn diffuse to the interface of solder/Cu to react with Cu. Results also indicate that adding 0.08 wt% Ce to the solder enhances mechanical property of soldered joint. When the Ce content is 0.1–0.5 wt%, some hard and brittle Cu–Zn IMCs appear in the bottom of dimples and the pull force of soldered joint decreases.

The objective of this review is to study the interfacial intermatallic compounds (IMCs) between Sn–Ag–Cu based solders and common substrates, which play a crucial role in solder joints typically present in Pb-free electronics manufacturing. The microstructural evolution of IMCs at the solder/substrate interfaces is analyzed, while the models and theories describing the formation/growth mechanism of interfacial IMCs are also introduced. We focus on the influence of a variety of factors that have been reported recently, including substrates, minor alloying, mechanical stress, electromigration and thermomigration etc., as full understanding of the mechanisms that determine the formation and growth of interfacial IMCs is important to reach for developing high reliability solder joints. In the end of this review, the characteristics of the IMCs are compared and illustrated, which have marked effect on the mechanical properties and fracture behavior as well as reliability of solder joints.

The microstructures, wettabilities and mechanical properties of Sn–9Zn–xAg (x = 0, 0.1, 0.3, 0.5, 1 wt%) lead-free solders were investigated, respectively in this paper. Results show that, when the quantity of Ag added to the solder is 0.3 wt%, the microstructure of the solder becomes finer and more uniform than Sn–9Zn, and when the quantity of Ag is exceeded 0.3 wt% (upto 0.5–1 wt%), the AgZn3 intermetallic compounds appear in the solder. In particular, adding 0.3 wt% Ag improves the wettability due to the better oxidation resistance of the Sn–9Zn–0.3Ag solder. Results also indicate that adding 0.3 wt% Ag to the solder enhances mechanical property of soldered joint, at which the fracture micrographs show that plenty of small and uniform dimples could be observed on the Sn–9Zn–0.3Ag soldered joints fractures. When the content of Ag is upto 1 wt%, some Cu–Zn and Ag–Zn intermetallic compounds appear on the bottom of dimples, and the mechanical property of the soldered joint decreases.

Sn–Zn solder alloys have been considered as one of the more attractive lead-free solders since it can easily replace Sn–Pb eutectic alloy without increasing the soldering temperature. However, there are still some problems to be resolved, such as the argument about the poor oxidation resistance and embrittlement behavior. In order to overcome these drawbacks, and further enhance the properties of Sn–Zn lead-free solder alloys, a small amount of alloying elements (rare earths, Bi, Ag, Al, Ga, In, Cr, Cu, Sb, Ni, Ge) added into Sn–Zn alloys were selected by many researchers. For example, a small amount of Al, P, Bi, Ga can improve the high-temperature oxidation resistance of Sn–Zn solders remarkably as well as Cr. This paper summarizes the effects of alloying elements on the wettability, oxidation resistance, melting behavior, mechanical properties, creep properties, microstructures and intermetallic compounds layer of Sn–Zn lead-free solders.

Wetting balance method is used to evaluate the effects of Ga, Al, Ag, and Ce multi-additions on the solderability of Sn–9Zn lead-free solders, results show that the optimal addition amounts of Ga, Al, Ag, and Ce is 0.2, 0.002, 0.25, and 0.15 wt% respectively. The surface property of Sn–9Zn–0.2Ga–0.002Al–0.25Ag–0.15Ce solder is studied by X-ray photoelectron spectroscopy and auger electron spectroscopy analysis; results indicate that Al aggregates on the surface as a compact aluminum oxide film which prevents the further oxidation. The aggregation of Ce on the subsurface can reduce the surface tension of solder, and improve the solderability accordingly. Meanwhile, SEM and XRD analysis indicate that Cu5Zn8 and AgZn3 intermetallic compounds form at the interface between Sn–9Zn–0.2Ga–0.002Al–0.25Ag–0.15Ce solder and Cu substrate, while AuZn3 and AuAgZn2 form at the interface between solder and Cu/Ni/Au substrate. Moreover, results also indicate that the mechanical property of soldered joints is improved duo to the dispersion strengthening effects of AgZn3 in Sn–9Zn–0.2Ga–0.002Al–0.25Ag–0.15Ce solder.

The influences of different Ga content on the properties of Sn–9Zn lead-free solder were investigated. The results indicate that Ga plays an important role not only in the structure and melting behavior, but also in the solderability and mechanical property. Sn–9Zn–0.5Ga shows finer and more uniform microstructure than Sn–9Zn. With the addition of low-melting-point Ga, TL (liquidus temperature) and TS (solidus temperature) of the alloys decreases with increasing of Ga content while △T (liquidus temperature minus solidus temperature) increases. Ga can improve the oxidation resistance and reduce the surface tension of solder, so the solderability of Sn–9Zn–xGa lead-free solder is significantly improved. When the content of Ga is 0.5 wt.%, the pull force of soldered joint is 16.1 N, enhanced by 11% compared to that of Sn–9Zn, and the fracture micrographs show that the joint failed in a ductile manner. The addition of 3 wt.%Ga resulted in a brittle failure. The introduction of 0.5 wt.% Ga into Sn–9Zn alloy improves creep resistance of the solder.

For quad flat packages (QFP256), lead-free soldered joints reliability in service is a critical issue. In this paper, soldering experiments of quad flat package (QFP256) devices were carried out by means of infrared reflow soldering system with Sn–3.8Ag–0.7Cu and Sn–3.8Ag–0.7Cu–0.03Ce lead-free solders, respectively, and the mechanical properties of micro-joints of the QFP devices were tested and studied by STR micro-joints tester. The results indicate that the tensile strength of Sn–Ag–Cu–Ce soldered joints is better than that of Sn–Ag–Cu soldered joints. In particular, the addition of trace Ce to the Sn–Ag–Cu solder can refine the microstructures and decrease the thickness of the intermetallic compound layer of Sn–Ag–Cu solder alloys. In addition, the stress–strain response of Sn–Ag–Cu/Sn–Ag–Cu–Ce soldered joints in quad flat packaging was investigated using finite element method based on Garofalo–Arrhenius model. The simulated results indicate creep distribution of soldered joints is not uniform, the heel and toe of soldered joints, the area between soldered joints and leads are the creep concentrated sites. The creep strain of Sn–Ag–Cu–Ce soldered joints is lower than that of Sn–Ag–Cu soldered joints.

Effects of Pr addition on wettability, microstructure of Sn3.8Ag0.7Cu solder were studied, the mechanical properties of solder joints were investigated and the fracture morphologies were also analyzed in this paper. The results indicate that adding appropriate amount of Pr can evidently improve the wettability of solder, and it is also found that Pr can refine the β-Sn dendrites and reduce the intermetallic compounds growth inside the solder due to the fine PrSn3 particles formed in the solder which can act as heterogeneous nucleation sites. Moreover, the joints soldered with the SnAgCuPr solders possess sound mechanical properties which may result from the finer microstructure improved by the Pr.

In this study, the interfacial reactions and joint reliabilities of Sn–9Zn/Cu and Sn–9Zn–0.3Ag/Cu were investigated during isothermal aging at 150 °C for aging times of up to 1,000 h. Cu5Zn8 IMCs layer is formed at the as-soldered Sn–9Zn/Cu interface. Adding 0.3wt.% Ag results in the adsorption of AgZn3 on the Cu5Zn8 IMCs layer. The as-soldered Sn–9Zn/Cu and Sn–9Zn–0.3Ag/Cu joints have sufficient pull strength. The thickness of the IMCs layer formed at the interface of Sn–9Zn/Cu and Sn–9Zn–0.3Ag/Cu both increase with increasing aging time. Correspondingly, both the pull forces of the Sn–9Zn and Sn–9Zn–0.3Ag soldered joints gradually decrease as the aging time prolonged. However, the thickness of the IMCs layer of Sn–9Zn–0.3Ag/Cu increases much slower than that of Sn–9Zn/Cu and the pull force of Sn–9Zn–0.3Ag soldered joint decreases much slower than that of Sn–9Zn soldered joint. After aging for 1,000 h, some Cu–Sn IMCs form between the Cu5Zn8 IMC and the Cu substrate, many voids form at the interface between the Cu5Zn8 layer and solder alloy, and some cracks form in the Cu5Zn8 IMCs layer of Sn–9Zn/Cu. The pull force Sn–9Zn soldered joint decreases by 53.1% compared to the pull force measured after as-soldered. Fracture of Sn–9Zn/Cu occurred on the IMCs layer on the whole and the fracture micrograph implies a brittle fracture. While the pull force of Sn–9Zn–0.3Ag soldered joint decreases by 51.7% after aging at 150 °C for 1,000 h. The fracture mode of Sn–9Zn–0.3Ag soldered joint is partially brittle at the IMCs layer, and partially ductile at the outer ring of the solder.

In order to improve the properties of Sn–3.8Ag–0.7Cu and Sn–0.5Cu–0.05Ni solders, 0–0.1 wt.% of rare earth Ce was added to the base alloys, and the microstructures were studied. Meanwhile, the solderability of solders on Cu substrate was determined by the wetting balance method, the mechanical properties of soldered joints were investigated by the pull-force test and the fracture morphologies were analyzed. It is found that the new solder alloys possess better solderability than the base solder alloys, and the greatest improvement to the solderability of Sn–3.8Ag–0.7Cu–xCe is obtained with around 0.03–0.05 wt.% Ce, while the optimal Ce content is in the range of 0.05–0.07 wt.% for Sn–0.5Cu–0.05Ni–xCe solders. The results also indicate that the mechanical properties of soldered joints are improved with increasing Ce addition, with peak mechanical properties at Sn–3.8Ag–0.7Cu–0.03Ce and Sn–0.5Cu–0.05Ni–0.05Ce. The grain sizes of solder alloys are refined due to the addition of Ce, thus the mechanical properties of soldered joints are improved simultaneously.

The effects of Ga–Al, Ga–Ag and Al–Ag binary additions on the wetting characteristics of Sn–9Zn–X–Y lead-free solders are studied by the wetting balance method. Experimental results show that Sn–9Zn–1.0Ga–0.3Ag, Sn–9Zn–0.005Al–0.3Ag, and Sn–9Zn–0.3Ga–0.002Al possess better wettability than the other alloys tested. The mechanism by which Ga, Al, and Ag additions improve the wettability is also proposed. It appears that dense aluminum oxide film formation and the enrichment of Ga on the surface may protect the bulk liquid solder from further oxidation. Moreover, results also indicate that, AgZn3 IMCs layer formed at the interface, which may release reaction energy during the wetting, results in improving the wettability of the solder.

In order to further enhance the properties of lead-free solder alloys such as SnAgCu, SnAg, SnCu and SnZn, trace amount of rare earths were selected by lots of researchers as alloys addition into these alloys. The enhancement include better wettability, physical properties, creep strength and tensile strength. For Sn3.8Ag0.7Cu bearing rare earths, when the rare earths were La and Ce, the creep-rupture life of solder joints can be remarkably improved, nine times more than that of the original Sn3.8Ag0.7Cu solder joints at room temperature. In addition, creep-rupture lifetime of RE-doped solders increases by over four times for SnAg and seven times for SnCu. This paper summarizes the effects of rare earths on the wettability, mechanical properties, physical behavior and microstructure of a series of lead-free solders.

Ternary lead free solder alloys Sn–Ag–Cu were considered as the promising alternatives to conventional SnPb alloys comparing with other solders. In the present work, effects of trace amounts of rare earth Ce on the wettability, mechanical properties and microstructure of Sn–Ag–Cu solder have been investigated by means of scanning electron microscopy and energy dispersive X-ray analysis systematically. The results indicate that adding trace amount of rare earth Ce can remarkably improve the wettability, mechanical strength of Sn–Ag–Cu solder joint at different temperature, especially when the content of rare earth Ce is at about 0.03%, the tensile strength will be 110% times or more than that of the lead free solder joint without rare earth Ce addition. Moreover, it was observed that the trace amount of rare earth Ce in Sn–Ag–Cu solder may refine the joint matrix microstructure, modify the Cu6Sn5 intermetallic phase at the copper substrate/solder interface, and the intermetallic compound layer thickness was reduced significantly. In addition, since rare earth Ce possesses a higher affinity to Sn in the alloy, adding of rare earth Ce can also lead to the delayed formation and growth of the intermetallic compounds of Ag3Sn and Cu6Sn5 in the alloy.

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.

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.

Effects of mischmetal (RE) and/or Ti modifier on the microstructure including α-Al dendrites, eutectic Si phases and other secondary phases of Al-Si brazing and/or welding alloys were investigated by differential scanning calorimetry (DSC), optical microscopy (OM), scanning electron microscopy (SEM). The DSC results showed that an addition of RE decreased the eutectic temperature and caused supercooling, promoting the nucleation of eutectic Si crystals. In addition, the maximum temperature of the first endothermic peak varied with the different RE contents, which had a good correlation with the microstructural modification of the eutectic Si phase. The α-Al dendrites were well refined by increasing the cooling rate or adding 0.08 wt.% of Ti. When 0.05 wt.% RE was added to the Al-5Si-0.08Ti alloy, the morphology of eutectic Si phase was transformed from coarse platelet to fine fibers and the mechanical properties of the resulting welding rod were well improved. Whereas, when excess RE was added, a large number of β-Fe phases appeared and the aspect ratios of β-Fe phases increased. The morphologies and chemical components of two kinds of RE-containing intermetallic compounds (IMCs) were also discussed.(a) x=0.05, cross-sectional metallographic structure; (b) x=0.05, longitudinal-sectional metallographic structure; (c) x=0, cross-sectional SEM structure; (d) x=0.01, cross-sectional SEM structure; (e) x=0.05, cross-sectional SEM structure; (f) SEM microstructure of hot-extruded AST-0.02Sr welding rod for comparisonDownload high-res image (107KB)Download full-size image