Sn-9Zn-xP无铅焊料合金性能研究

以Sn-9Zn合金为研究对象,考察了P的添加对其性能的影响,并对其机制作了初步探讨。通过二次离子质谱(SIMS)分析发现,P的添加显著降低Sn-9Zn合金中的含氧量,从而提高了合金在Cu上的润湿性。P的改善润湿性的效果不仅有利于其工艺性能,也提高了Sn-9Zn/Cu焊点界面的结合强度,只使其塑性略有下降。同时,微量P的添加不改变Sn-9Zn合金与Cu形成的焊点的界面结构。另外,蠕变强度测试结果表明,P的添加能显著提高合金的抗蠕变性能。     

Mechanical properties of Sn–Zn lead-free solder alloys based on the microstructure array

The aim of this study is to develop a comparative experimental study interrelating mechanical properties, solidification thermal parameters and microstructure characteristics of a hypoeutectic Sn–4 wt.% Zn, a hypereutectic Sn–12 wt.% Zn and a eutectic Sn–9 wt.% Zn solder alloys. A water-cooled vertical upward unidirectional solidification system was used to obtain the samples. It was found that a more homogeneous distribution of the eutectic mixture, which occurs for smaller dendritic spacings in hypoeutectic and hypereutectic alloys, increases the ultimate tensile strength. The resulting microstructure of the eutectic Sn-9 wt.% Zn alloy has induced higher mechanical strength than those of the Sn–4 wt.% Zn and Sn–12 wt.% Zn alloys. It was found that the eutectic alloy experiences a microstructural transition from globular-to-needle-like Zn-rich morphologies which depend on the solidification growth rate. It is also shown that a globular-like Zn-rich morphology provides higher ultimate tensile strength than a needle-like Zn-rich eutectic morphology.     

Thermal cycling test in Sn-Bi and Sn-Bi-Cu solder joints

The eutectic SnBi solder alloy is a candidate for Pb-free replacement of the conventional eutectic SnPb solders. This study presents series of results on the binary eutectic SnBi and ternary SnBi-1 wt % Cu a solder joints. Compositional analysis and wettability of the as-fabricated solder alloys are reported. In addition, microstructure, adhesion strength, fracture surface and contact resistance of the solder joints are also evaluated. The results of the wetting balance show that the addition of 1 wt % Cu has little effect on the contact angle of the eutectic SnBi solder alloy with various metallization layers. The adhesion strength of solder joints degrades abruptly after 2000 thermal cycles. In addition, thermal cycling would result in cracking in the solder joints, which is due to the mismatch in thermal expansion coefficients. Portions of the thermal fatigue cracks nucleate at the edge of the solder fillet, and then propagate along the solder/conductor interface. Some cracks are, however, through the Al₂O₃ substrate. The contact resistance of the solder/Cu joint does not increase after thermal cycling since the resistivity of Cu₆Sn₅ is lower than that of the solder. The solder joints of 42Sn-58Bi/Cu, SnBi-1Cu/Cu, 42Sn-58Bi/PtAg, and SnBi-1Cu/PtAg assemblies maintain their integrity after 2000 thermal cycles since the increase in contact resistance is rather small (ΔR<0.5 mΩ).     

Liquid-metal embrittlement of aluminium by several eutectic alloys containing zinc

The liquid-metal embrittlement of aluminium plate wetted with Cd-17% Zn, Sn-10% Zn and In-3% Zn eutectic alloy was investigated by tensile tests in the temperature range 423 to 673 K by means of scanning electron microscopy and X-ray energy dispersion. The fracture strain of specimens wetted with Cd-Zn, Sn-Zn, and In-Zn alloys decreased in the temperature ranges 553 to 623, 473 to 553 and 433 to 503 K, respectively, and the specimens were then intergranularly fractured. The minimum fracture strain was largest for the specimen wetted with In-Zn alloy. Intergranular fracture stress decreased with increasing zinc content in eutectic alloys. Zinc was only detected along the grain boundary adjacent to the crack tips. It is, therefore, thought that zinc diffuses into the grain boundary before cracks are initiated by a liquid metal.     

Properties and microstructure of Sn-9Zn lead-free solder alloy bearing Pr

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.     

A new filler metal with low contents of Cu for high strength aluminum alloy brazed joints

The effect of Cu with low contents of 10, 12, 15 wt.% on the microstructure and melting point of Al–Si–Cu–Ni alloy has been investigated. Results showed that low-melting-point properties of Al–Si–Cu–Ni alloys with low contents of Cu were attributed to disappearance of Al–Si binary eutectic reaction and introduction of Al–Si–Cu–Ni quaternary reaction. With raising Cu content from 10 to 15 wt.%, the amount of complex eutectic phases formed during low temperature reactions (Al–Cu, Al–Si–Cu and Al–Si–Cu–Ni alloy reactions) increased and the melting temperature of Al–Si–Cu–Ni filler metals declined. Brazing of 6061 aluminum alloy with Al–10Si–15Cu–4Ni (all in wt.%) filler metal of a melting temperature range from 519.3 to 540.2 °C has been carried out successfully at 570 °C. Sound joints can be obtained with Al–10Si–15Cu–4Ni filler metal when brazed at 570 °C for holding time of 60 min or more, and achieved high shear strength up to 144.4 MPa.     

A wettability study of Cu/Sn/Ti active braze alloys on alumina

Active brazing is one of the ideal ways to make metal/ceramic joints. The active braze alloy contains active element(s), such as: Ti, Zr, Cr... etc., reacting and wetting the ceramic surfaces during brazing. Therefore, a strong chemical bonding can be formed after brazing. Cu base active braze alloys are alternatives among active braze alloys. With the aid of additional melting point depressant, Sn, in Cu-Ti alloys, the intermetallic phase in the active braze can be changed. However, its ability to braze structural ceramics, e.g. alumina, needs further study. The purpose of this research is concentrated on the wettability study of the Cu/Sn/Ti alloy on polycrystalline alumina. Based on the experimental results, the minimum Ti content is 6 wt pct in order to effectively wet alumina. Volume fraction of the intermetallic phase in the braze will be greatly increased if the Ti content in the alloy is increased to 12 wt pct. According to sessile drop test results, 70Cu-21Sn-9Ti demonstrates the best wetting ability on alumina. Meanwhile, the Sn content in Cu/Sn/Ti alloy should be less than 21 wt pct in order to maintain proper wettability of the braze. In addition, Cu/Sn/Ti alloys have both lower wetting angle on alumina and lower thermal expansion coefficients than commercial Ticusil® braze.     

Wetting Behavior and Interfacial Reactions in (Sn-9Zn)-2Cu/Ni Joints during Soldering and Isothermal Aging

The wetting property of (Sn-9Zn)-2Cu (wt pct) on Ni substrate and the evolution of interfacial microstructure in (Sn-9Zn)-2Cu/Ni joints during soldering as well as isothermal aging were studied.The wetting ability of eutectic Sn-9Zn solder on Ni substrate was markedly improved by adding 2 wt pct Cu into this solder alloy.Plate-like Cu5Zn8 intermetallic compounds (IMCs) were detected in (Sn-9Zn)-2Cu solder matrix.A continuous Ni5Zn21 IMC layer was formed at (Sn-9Zn)-2Cu/Ni interface after soldering.This IMC layer kept its type and integrality even after aging at 170℃ for up to 1000 h.At the early aging stage (before 500 h), the IMC layer grew fast and its thickness followed a linear relationship with the square root of aging time.Thereafter,however, the thickness increased very slowly with longer aging time.When the joints were aged for 1000 h,a new IMC phase, (Cu,Ni)5Zn8, was found in the matrix near the interface.The formation of (Cu,Ni)5Zn8phase can be attributed to the diffusion of Ni atoms into the solder matrix from the substrate.     

Effect of a Trace of Bi and Ni on the Microstructure and Wetting Properties of Sn-Zn-Cu Lead-Free Solder

The microstructure and melting behavior of Sn-9Zn-2Cu （SZC） lead-free solder with 3 wt pct Bi and various amount of Ni additions were studied. The wetting properties and the interracial reaction of Sn-Zn-Cu with Cu substrate were also examined. The results indicated that the addition of 3 wt pct Bi could decrease the melting point of the solder and Ni would refine the microstructure and the rod-shape Cu5Zn8 phase changed into square-shape （Cu, Ni）5Zn8 phase. The addition of Bi, Ni greatly improved the wettability of SZC solder. In addition, the interracial phase of the solders/Cu joint was typical planar Cu5Zn8 in SZC-3Bi-INi alloy.     

A novel method of reducing melting temperatures in SnAg and SnCu solder alloys

With the increasing use of lead-free solder alloys in modern electronics, low melting materials are often required to protect the heat-sensitive parts during soldering operation. Alloy systems based on Sn/Cu/Ag offer more reliable solutions and address the current problems involved with soldering process. Nanoparticles melt relatively at low temperatures compared to their bulk counter parts and we introduce a robust method of synthesizing nanoscale solder pastes for wave soldering applications. Nanoparticles of Sn-3.5Ag and Sn-0.7Cu alloys were prepared with stir casting followed by mechanical attrition. The size dependent melting properties of the eutectic alloys were studied by differential scanning calorimetry technique and the results showed a reduction of 4.7 and 5.0 °C melting temperatures in the alloys when reduced from bulk to 92 nm and 96 nm sizes respectively. The nanosize effects were also theoretically calculated and compared with experimental data.     

Design of lead-free candidate alloys for low-temperature soldering applications based on the hypoeutectic Sn–6.5Zn alloy

The coupling effect of both minor alloying addition and reducing the amount of Zn phase have been proposed as an important strategy to improve the integrity and reliability of eutectic Sn–9Zn solder joints. In this work, the changes in microstructures, thermal behaviors and mechanical properties associated with the alloying of Ni and Sb to eutectic Sn–Zn after reducing the amount of Zn phase were explored. Thermal analysis confirmed that Ni and Sb additions being effective in reducing the amount of undercooling, while the melting temperature and pasty range remained at the hypoeutectic Sn–6.5Zn level. The resulting ultimate (UTS), yield tensile strength (YS) and elongation (El) of Sn–6.5Zn–0.5Ni and Sn–6.5Zn–0.5Sb alloys were experimentally determined and compared with the corresponding results of plain Sn–6.5Zn solder alloy. It was found that the Sn–6.5Zn–0.5Ni and Sn–6.5Zn–0.5Sb alloys examined comply with the compromise between high mechanical strength and ductility. Microstructural analysis revealed that the origin of change in mechanical properties was attributed to the enhanced solid solution effect of Sb and the flower shaped (Ni, Zn)₃Sn₄ intermetallics (IMC) phase produced by Ni addition. The Sn–6.5Zn–0.5Sb alloy has the highest UTS and appropriate ductility of all alloys examined. This finding indicates the capability of newly developed ternary solder alloys to serve a much wider array of value-added applications.     

Effects of indium addition on properties and wettability of Sn–0.7Cu–0.2Ni lead-free solders

This paper reports the investigation on indium addition into Sn–0.7Cu–0.2Ni lead-free solder to improve its various performances. The effects of indium addition on melting temperature, coefficient of thermal expansion (CTE), wettability, corrosion resistance and hardness of the solder alloys were studied. The results showed that when the addition of indium was ⩽0.3 wt.%, the change in melting temperature of Sn–0.7Cu–0.2Ni–xIn solders was negligible, but the melting range of the solder alloy increased. The CTE and spreading area of Sn–0.7Cu–0.2Ni–xIn solders on copper both increased with the addition of indium. An optimal CTE was 17.5 × 10⁻⁶/°C by adding 0.3 wt.% indium. At this concentration, the spreading area of solder on copper was about 15.6% larger than that of Sn–0.7Cu–0.2Ni indium-free solder. The corrosion resistance also increased with the addition of indium increasing, and the corrosion rate of Sn–0.7Cu–0.2Ni–0.3In solder was reduced by 32.8% compared with Sn–0.7Cu–0.2Ni alloy after 14 days in 5% hydrochloric acid solution at room temperature. However, a decrease of 11.7% in hardness of the solder was found when 0.3 wt.% indium was added.     

Effect of zinc additions on structure and properties of Sn–Ag eutectic lead-free solder alloy

The effects of a third element, i.e., Zn in the range of 0.5–2.5 wt.%, on structure and properties of the binary Sn–Ag eutectic lead-free solder alloy were investigated. To identify the structure of the resulting alloys, X-ray diffraction analysis has been carried out. Resistivity, contact angles, Vickers microhardness and Young’s modulus have been measured. The results showed that all Zn contents were restricted in formation of Ag-Zn compound indicated by X-ray diffraction peaks, which increased continuously in the number and intensity as Zn content increased. Adding Zn up to 1.5 wt.% improved the wetting and mechanical properties. Above that, wetting angle increased due to the increase in AgZn compound, which may accumulated at the interface between solders and copper- substrate resulting a decrease in the adhesive strength. The alloy of composition Sn-3.5Ag-1.5Zn has the most improved properties between the others.     

Effect of thermal ageing on (Sn-Ag, Sn-Ag- Zn)/PtAg, Cu/Al2O3 solder joints

As-fabricated solders of eutectic Sn-Ag and ternary Sn-3.5 wt% Ag-1 wt% Zn alloys are coupled with metallized substrates including PtAg/Al2O3 and Cu/Al2O3 to simulate the solder joint in microelectronics. The growth mechanism of intermetallics and the mechanical properties of solder joints after thermal ageing (150 °C and 200 °C) are evaluated. In this study, a 1206 passive device/solder/metallization/Al2O3 surface mount technology (SMT) assembly is employed, and a Cu stud is attached on the ceramic substrate assembly to evaluate mechanical properties and the fracture morphology by the pull-off test. In addition, microstructure evolution of the interfacial morphology, elemental and phase distribution are probed with the aid of scanning electron microscopy (SEM), electron probe micro-analysis (EPMA) and X-ray diffraction (XRD) techniques. There are two intermetallics (Cu3Sn and Cu6Sn5) formed at the eutectic Sn-Ag solder/Cu metallized layer interface, while only Cu6Sn5 is observed in the Sn-3.5 Ag-1Zn/Cu system. However, in the PtAg metallized substrate, only Ag3Sn is present, regardless of which solders are employed. Cu6Sn5 and Ag3Sn in the Sn-3.5 Ag-1Zn system contain 2–5 at% Zn due to the higher solubility of Zn in both Cu and Ag. The adhesion strength decreases as the time increases for all solder joint systems in the thermal ageing test. The solder joint with eutectic Sn-Ag alloy exhibits higher fracture load than that with Sn-3.5 Ag-1Zn alloy. From the fracture surface analysis, as the ageing time increases, the fracture takes place from the solderconductor interface toward the inside of the IMC (intermetallic compound). © 1998 Kluwer Academic Publishers     

Effect of Rapid Solidification on Structure and Properties of Some Lead-Free Solder Alloys

Four of the binary lead-free solder alloys of compositions Sn-0.5Cu, Sn-3.5Ag, Sn-5Sb and Sn-9Zn, were rapidly solidified by melt-spinning technique as a technique for producing new alloy compositions. The results show that rapid solidification causes formation of some intermetallic compounds such as Ag₃Sn and Cu₆Sn₅ in the two alloys Sn-3.5Ag and Sn-0.5Cu, which cannot be formed at the equilibrium phase diagram at these compositions; contraction in the volume of the unit cell of the tetragonal Sn; reduction of the melting points due to the decrease in the crystalline size of Sn matrix; and formation of some vacancies in the resulting alloys, which cause reduction of the measured density than that calculated by mixture rule and increase the electrical resistivity.     

A study of Sn-Bi-Ag-(In) lead-free solders

Sn-Bi-Ag-(In) solder alloys have been extensively studied in the study. The experimental results reveals that the liquidus temperatures of Sn-(1–5) Bi-(2–3.5)Ag-(0–10)In solders are between 201.7 and 225.3°C, which were higher than that of the most popular eutectic Pb-Sn solder (183°C). Additions of (5–10) wt% In into Sn-Bi-Ag solders can effectively decrease the melting point of the solder alloy. However, the gap between T _s and T _L temperatures increases with the additions of Bi and In into Sn-Bi-Ag-(In) solders. Although there is no flux applied during soldering, most Sn-Bi-Ag-(In) solder alloys can well bond the Au/Ni metallized copper substrate. 94Sn-3Bi-3Ag solder demonstrates the lowest wetting angle of 45° among all test samples. Thermal expansion coefficients of both 94Sn-3Bi-3Ag and 90Sn-2Bi-3Ag-5In solders are slightly less than that of 63Sn-37Pb. Both 90Sn-2Bi-3Ag-5In/substrate and 94Sn-3Bi-3Ag/substrate interfaces demonstrate similar reaction kinetics in the experiment. The stability of the interface is greatly impaired during 90°C aging. Some locations of the electroless Ni layer break down, and new phases are formed nearby the interface during aging treatment. Initially, the growth of Ni-rich (Ni,Cu)₃Sn₄ phase dominates the interfacial reaction. However, the growth of Cu-rich (Cu,Ni)₆Sn₅ phase will dominate the reaction layer for specimens aged at 90°C for long time periods.     

Effect of Y<Subscript>2</Subscript>O<Subscript>3</Subscript> particles on microstructure formation and shear properties of Sn-58Bi solder

In the present study, varying weight percentages of Y₂O₃ particles (3–5 μm) from 0 to 3% were incorporated into eutectic Sn-Bi solder matrix to form composite solders. It is found that the reinforcement particles were well dispersed in the solder matrix. They depressed the growth of intermetallic compound (IMC) layers and reduced the size of IMC grains. Since the Y₂O₃ particles serve as additional nucleation sites for the formation of primary Bi-rich phase, the size of both Bi-rich phase and the IMCs were decreased gradually with the Y₂O₃ content increasing. Shear tests were also conducted on as—soldered joints. The growth of solid-state intermetallic compounds layer was examined by thermal aging of the solder/Cu couple for a temperature range from 60 to 120°C and time periods from 50 to 500 h. Compared with Sn-58Bi solder, finer eutectic microstructures were obtained with Y₂O₃ addition after long time aging. The apparent activation energies calculated for the growth of the intermetallic compound layers were 72 ± 5 kJ/mol of Sn-58Bi, 74 ± 4 kJ/mol of Sn-58Bi-0.5wt%Y₂O₃, 81 ± 5 kJ/mol of Sn-58Bi-1wt% Y₂O₃ and 81 ± 7 kJ/mol of Sn-58Bi-3wt.% Y₂O₃, respectively.     

Effect of addition of Al and Cu on the properties of Sn–20Bi solder alloy

This study investigates the effect of the composite addition of Al and Cu on the microstructure, physical properties, wettability, and corrosion properties of Sn–20Bi solder alloy. Scanning electron microscopy and X-ray diffraction were used to identify the microstructure morphology and composition. The spreading area and contact angle of the Sn–20Bi–x (x?=?0, 0.1 wt% Al, 0.5 wt% Cu, and 0.1 wt% Al–0.5 wt% Cu) alloys on Cu substrates were used to measure the wettability of solder alloys. The results indicate that the alloy with 0.1 wt% Al produces the largest dendrite and the composite addition of 0.1 wt% Al and 0.5 wt% Cu formed Cu₆Sn₅ and CuAl₂ intermetallic compounds in the alloy structure. And the electrical conductivity of Sn–20Bi–0.1Al is the best, which reaches 5.32 MS/m. The spread area of the solder alloy is reduced by the addition of 0.1 wt% Al and 0.5 wt% Cu, which is 80.7 mm². The corrosion products of Sn–20Bi–x solder alloys are mainly lamellar Sn₃O(OH)₂Cl₂ and the corrosion resistance of 0.1 wt% Al solder alloy alone is the best. The overall corrosion resistance of Sn–20Bi–0.1Al–0.5Cu is weakened and the corrosion of solder alloy is not uniform.

     

Mechanical and bio-corrosion properties of quaternary Mg–Ca–Mn–Zn alloys compared with binary Mg–Ca alloys

Binary Mg–xCa alloys and the quaternary Mg–Ca–Mn–xZn were studied to investigate their bio-corrosion and mechanical properties. The surface morphology of specimens was characterized by X-ray diffraction (XRD), Fourier-transformed infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). The results of mechanical properties show that the yield strength (YS), ultimate tensile strength (UTS) and elongation of quaternary alloy increased significantly with the addition of zinc (Zn) up to 4 wt.%. However, further addition of Zn content beyond 4 wt.% did not improve yield strength and ultimate tensile strength. In contrast, increasing calcium (Ca) content has a deleterious effect on binary Mg–Ca alloys. Compression tests of the magnesium (Mg) alloys revealed that the compression strength of quaternary alloy was higher than that of binary alloy. However, binary Mg–Ca alloy showed higher reduction in compression strength after immersion in simulated body fluid. The bio-corrosion behaviour of the binary and quaternary Mg alloys were investigated using immersion tests and electrochemical tests. Electrochemical tests shows that the corrosion potential (E_corr) of binary Mg–2Ca significantly shifted toward nobeler direction from −1996.8 to −1616.6 mV_SCE with the addition of 0.5 wt.% manganese (Mn) and 2 wt.% Zn content. However, further addition of Zn to 7 wt.% into quaternary alloy has the reverse effect. Immersion tests show that the quaternary alloy accompanied by two secondary phases presented higher corrosion resistance compared to binary alloys with single secondary phase. The degradation behaviour demonstrates that Mg–2Ca–0.5Mn–2Zn alloy had the lowest degradation rate among quaternary alloys. In contrast, the binary Mg–2Ca alloy demonstrated higher corrosion rates, with Mg–4Ca alloy having the highest rating. Our analysis showed the Mg–2Ca–0.5Mn–2Zn alloy with suitable mechanical properties and excellent corrosion resistance can be used as biodegradable implants.     

Spreading Dynamics and Interfacial Characteristics of Sn-3.0Ag-0.5Cu-<Emphasis Type="Italic">x</Emphasis>Bi Melting on Cu Substrates

The effects of Bi addition on the properties of Sn-3.0Ag-0.5Cu molten alloy on Cu substrates are discussed using wettability and interface microstructure analysis. The changes of the contact angles between Sn-3.0Ag-0.5Cu-xBi and Cu substrates with the spreading time are described by Dezellus model. It indicates that the spreading process is governed by the interfacial reaction during the dwelling time. The interface microstructure is observed to clarify the effects of reactions on the spreading behavior. It is found that Cu₆Sn₅ is formed adjacent to the solder and Cu₃Sn appears over the substrate with Bi added at 613K, indicating that Bi exists between the intermetallics and the addition of Bi can hinder the diffusion of copper towards the interior of the solder. Therefore the existence of Bi decreases the agglomeration of Cu-Sn grains. The growth of intermetallics is thus limited and the shape of intermetallics transforms from scallop to zigzag consequently. However, the segregation phenomenon appears when the additive amount of Bi is more than 5.5mass %, which could lead to the occurrence of fracture and degrade the performance of Sn-3.0Ag-0.5Cu-xBi alloy. The results of the present study provide basic physical and chemical data for the application of lead-free solder in the future microgravity space environment.