Properties of SnAgCu/SnAgCuCe soldered joints for electronic packaging

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.     

Subcritical crack growth and power law exponent of Y–Si–Al–O(–N) glasses in aqueous environment

The subcritical crack growth resistance in water of a Y–Si–Al–O and Y–Si–Al–O–N glasses has been investigated with three point bending experiments. It has been shown that the SCG behaviour of the Y–Si–Al–O–N glass is superior to that of the Y–Si–Al–O glass. This is reflected by the power law exponent n which is 21 for the Y–Si–Al–O glass and 63 for the Y–Si–Al–O–N glass. Mechanistic implications of these observations are discussed.     

Phase Diagrams of Pb-Free Solders and their Related Materials Systems

Replacing Pb–Sn with Pb-free solders is one of the most important issues in the electronic industry. Melting, dissolution, solidification and interfacial reactions are encountered in the soldering processes. Phase diagrams contain equilibrium phase information and are important for the understanding and prediction of phase transformation and reactive phase formation at the solder joints. This study reviews the available phase diagrams of the promising Pb-free solders, and their related materials systems. The solders are Sn–Ag, Sn–Cu, Sn–Ag–Cu, Sn–Zn, Sn–Bi, Sn–In and Sn–Sb. The materials systems are the solders with the Ag, Au, Cu, Ni substrates, such as Sn–Ag–Au, Sn–Ag–Ni, Sn–Cu–Au, and Sn–Cu–Ni ternary systems. For the Pb-free solders and their related ternary and quaternary systems, preliminary phase equilibria information is available; however, complete and reliable phase diagrams over the entire compositional and temperature ranges of soldering interests are lacking.     

Mechanical properties of rapidly solidified ribbons of some AI–Si based alloys

Continuous uniform ribbons of Al–16 Si, Al–12.5 Si–1 Ni and Al–12.5 Si–1 Mg were prepared by melt spinning. Microhardness was measured. The as-melt spun values were 1280, 1370 and 1500 MN m-2 which relax on thermal ageing to 700, 700 and 800 MN m-2 for Al–16 Si, Al–Si–Ni and Al–Si–Mg, respectively. The hardness values of the melt spun ribbons are higher than the as-cast rods from which the ribbons were produced by a factor ranging from 1.8–2.2 times. Tensile testing at room temperature shows that the load–elongation curves are linear with a change of slope occurring in some of the specimens. These curves also show serrations in the case of as-melt spun and the intermediately annealed Al–Si specimens, while no serration was observed in the fully annealed samples. No serration was observed in the Al–Si–Ni and Al–Si–Mg alloys. UTS values were 420, 270 and 100 MN m-2 for Al–16 Si, Al–Si–Ni and Al–Si–Mg, respectively. These values show that the rapid solidification process improved the tensile properties significantly in Al–16 Si and Al–Si–Ni alloys while no significant improvement can be detected for Al–Si–Mg alloy. A discussion is given on hardness relaxation and tensile testing results in terms of silicon precipitation. This revised version was published online in November 2006 with corrections to the Cover Date.     

Suppressing the growth of interfacial Cu–Sn intermetallic compounds in the Sn–3.0Ag–0.5Cu–0.1Ni/Cu–15Zn solder joint during thermal aging

Evolution of interfacial phase formation in Sn–3.0Ag–0.5Cu/Cu (wt%), Sn–3.0Ag–0.5Cu–0.1Ni/Cu, Sn–3.0Ag–0.5Cu/Cu–15Zn, and Sn–3.0Ag–0.5Cu–0.1Ni/Cu–15Zn solder joints are investigated. Doping Ni in the solder joint can suppress the growth of Cu₃Sn and alter the morphology of the interfacial intermetallic compounds (IMCs), however it shows rapid growth of (Cu,Ni)₆Sn₅ at the Sn–3.0Ag–0.5Cu–0.1Ni/Cu interface. In comparison with the Cu substrates, the Cu–Zn substrates effectively suppress the formation of Cu–Sn IMCs. Among these four solder joints, the Sn–3.0Ag–0.5Cu–0.1Ni/Cu–15Zn solder joint exhibits the thinnest IMC, and only (Cu,Ni)₆(Sn,Zn)₅ formed at the interface after aging. It is revealed that the presence of Ni acts to enhance the effect of Zn on the suppression of Cu–Sn IMCs in the SAC305–0.1Ni/Cu–15Zn solder joint. The limited formation of IMCs is related to the elemental redistribution at the joint interfaces during aging. The Sn–3.0Ag–0.5Cu–0.1Ni/Cu–15Zn joint can act as a stabilized interconnection due to the effective suppression of interfacial reaction.     

Influence of granulated blast furnace slag on the reaction,structure and properties of fly ash based geopolymer

Ground granulated blast furnace slag (GBFS) has been used to alter the geopolymerisation behaviour of fly ash. The influence of varying amount of GBFS (5–50%) on the reaction kinetics has been studied using isothermal conduction calorimetry. It was observed that the reaction at 27 °C is dominated by the GBFS activation, whereas the reaction at 60 °C is due to combined interaction of fly ash and GBFS. The reaction product of geopolymerisation has been characterised using X-ray diffraction and scanning electron microscopy–X-ray microanalysis. Alumino–silicate–hydrate (A–S–H) and calcium–silicate–hydrate (C–S–H) gels with varying Si/Al and Ca/Si ratio are found to be the main reaction products. Coexistence of A–S–H and C–S–H gel further indicates the interaction of fly ash and GBFS during geopolymerisation. Attempt has been made to relate the microstructure with the properties of the geopolymers.     

Microstructure and corrosion properties of as sub-rapid solidification Mg–Zn–Y–Nd alloy in dynamic simulated body fluid for vascular stent application

Magnesium alloy stent has been employed in animal and clinical experiment in recent years. It has been verified to be biocompatible and degradable due to corrosion after being implanted into blood vessel. Mg–Y–Gd–Nd alloy is usually used to construct an absorbable magnesium alloy stent. However, the corrosion resistant of as cast Mg–Y–Gd–Nd alloy is poor relatively and the control of corrosion rate is difficult. Aiming at the requirement of endovascular stent in clinic, a new biomedical Mg–Zn–Y–Nd alloy with low Zn and Y content (Zn/Y atom ratio 6) was designed, which exists quasicrystals to improve its corrosion resistance. Additionally, sub-rapid solidification processing was applied for preparation of corrosion-resisting Mg–Zn–Y–Nd and Mg–Y–Gd–Nd alloys. Compared with the as cast sample, the corrosion behavior of alloys in dynamic simulated body fluid (SBF) (the speed of body fluid: 16 ml/800 ml min⁻¹) was investigated. The results show that as sub-rapid solidification Mg–Zn–Y–Nd alloy has the better corrosion resistance in dynamic SBF due to grain refinement and fine dispersion distribution of the quasicrystals and intermetallic compounds in α-Mg matrix. In the as cast sample, both Mg–Zn–Y–Nd and Mg–Y–Gd–Nd alloys exhibit poor corrosion resistance. Mg–Zn–Y–Nd alloy by sub-rapid solidification processing provides excellent corrosion resistance in dynamic SBF, which open a new window for biomedical materials design, especially for vascular stent application.     

Influence of arsenic, antimony and phosphorous on the microstructure and corrosion behavior of brasses

The effect of minor additions of As, Sb and P on phase distribution and corrosion behavior has been studied in brasses. The alloys investigated were 60Cu–39Zn–1Pb, 48.95Cu–45Zn–5Pb–1Sn–0.05As, 48.90Cu–45Zn–5Pb–1Sn–0.05As–0.05Sb and 48.85Cu–45Zn–5Pb–1Sn–0.05As–0.05Sb–0.05P. Immersion tests in 1% CuCl₂ solution indicated that the addition of As improved corrosion resistance while the combined addition of As + Sb and As + Sb + P was not beneficial. The hardness increased significantly with the addition of As, Sb and P. Microstructural observations indicated an increase in β phase fraction in the As, Sb and P containing alloys. X-ray diffraction studies confirmed the formation of intermetallic compounds in As, Sb and P containing alloys. Based on the microstructural observations, the intermetallic compounds appear to be primarily precipitated in the β phase with As + Sb and As + Sb + P additions. The lower corrosion resistance of the alloys 48.90Cu–45Zn–5Pb–1Sn–0.05As–0.05Sb and 48.85Cu–45Zn–5Pb–1Sn–0.05As–0.05Sb–0.05P has been related to increase in β phase volume fraction and precipitation of intermetallic compounds in the β phase.     

Wettability of NiAl by a liquid Ni–Si–B alloy

An investigation of the wettability of the intermetallic compound NiAl by a liquid Ni–4.5 wt% Si–3.2 wt% B filler metal is presented in this paper. Dynamic observations of spreading of Ni–Si–B droplets, conducted using hot-stage light microscopy, are correlated with post-cooling microscopy and analysis. The paper examines the influence of the oxide layer on the NiAl substrates, on the progression of spreading of the Ni–Si–B liquid. Termination of spreading of the Ni–Si–B droplets by the onset of isothermal solidification at the spreading front is considered. Spreading of the Ni–Si–B droplets was found to be rapid until the onset of isothermal solidification at the spreading front. However, once isothermal solidification commenced, negligible further spreading was observed. The Ni–Si–B filler metal was observed to spread by undermining of the substrate oxide. However, a marked reaction occurred between the substrate oxide and the Ni–Si–B filler metal. This reaction served to remove the substrate oxide layer. The paper contrasts the mechanisms of substrate oxide undermining and isothermal solidification of liquid Ni–Si–B droplets on NiAl with those occurring during the spreading of the same liquid on pure nickel and Ni–Cr alloys. This revised version was published online in November 2006 with corrections to the Cover Date.     

TLP bonding of SiCp/2618Al composites using mixed Al–Ag–Cu system powders as interlayers

Mixed Al–Ag–Cu and Al–Ag–Cu–Ti powders were used as interlayers for transient liquid phase diffusion bonding (TLP bonding) of SiC particulate reinforced 2618 aluminum alloy matrix composite (SiCp/2618Al MMC). The results show that by using mixed Al–Ag–Cu powder with the eutectic composition as an interlayer, SiCp/2618Al MMC can be TLP bonded at 540 °C, however, the joining layer is porous. Adding a certain amount of titanium into the Al–Ag–Cu interlayer, the TLP bonding quality can be improved. The titanium added into the Al–Ag–Cu interlayer has an effect of shortening the solidification time of the joining layer, thus decreasing SiC particles from the parent materials entering into the joining layer. The joints bonded using Al–Ag–Cu–Ti interlayers have a maximum shear strength of 101 MPa when 2.1% titanium is added.     

Correlation between interfacial microstructure and shear behavior of Sn–Ag–Cu solder ball joined with Sn–Zn–Bi paste

Sn–8Zn–3Bi solder paste was applied as a medium to joint Sn–3.2Ag–0.5Cu solder balls and Cu/Ni/Au metallized ball grid array substrates at 210 °C. Sn–Ag–Cu joints without Sn–Zn–Bi addition were also conducted for comparison. The shear behavior of the specimens was investigated after multiple reflow and thermal aging. For each strength test, more than 40 solder balls were sheared. The shear strength of Sn–Ag–Cu specimens kept constant ranging from 15.5 ± 1.3 N (single reflow) to 16.2 ± 1.0 N (ten reflows) and the fractures occurred in the solder. Shear strength of Sn–Ag–Cu/Sn–Zn–Bi specimens fell from 15.9 ± 1.7 N (single reflow) to 13.4 ± 1.6 N (ten reflows). After single reflow, Sn–Ag–Cu/Sn–Zn–Bi specimens fractured in the solder along Ag–Au–Cu–Zn intermetallic compounds and at Ni metallization. After ten reflows, fractures occurred in the solder and at solder/Ni–Sn–Cu–Zn intermetallic compound interface. The shear strengths of the Sn–Ag–Cu and Sn–Ag–Cu/Sn–Zn–Bi packages changed little after aging at 150 °C. Sn–Ag–Cu/Sn–Zn–Bi joints kept higher strength than Sn–Ag–Cu joints. Sn–Ag–Cu joints fractured in the solder after aging. But the fractures of Sn–Ag–Cu/Sn–Zn–Bi specimens shifted to the solder with aging time.     

Influence of zirconium on grain refining efficiency of Al–Ti–C master alloys

The influence of Zirconium on the grain refinement performance of Al–Ti–C master alloys and the effect mechanism has been studied in this paper. The experimental results show that Zr not only results in poisoning the Al–Ti–B master alloy, but also poisons the Al–Ti–C master alloys. The poisoning effect is more obvious at higher melting temperature. When 0.12%Zr is added into the melt, the grain refinement performance of Al–5Ti–0.4C refiner with 0.2% addition level absolutely disappears at 800 °C. The experimental results also show that it is difficult to refine the commercial purity Al containing 0.15%Zr by Al–5Ti–0.4C master alloy. Further experiments show that the Zr element can interact with both TiAl₃ and TiC phases. If both of them are present, Zr preferentially reacts with TiAl₃ phase.     

The variation of beta phase morphology after creep and negative creep for duplex titanium alloys

The creep resistance of SP700 (Ti–4.5Al–3V–2Mo–2Fe) is superior to Ti–6–4 (Ti–6Al–4V) at 500 °C under a constant load corresponding to an initial stress of 100 MPa. The β phase grains in the SP700 alloy prefer to orient along the loading axis in contrast to the Ti–6–4 alloy. The grain growth occurs during the stress drop incubation period. The observation of different amounts of negative creep/anelasticity upon loading is closely associated with the difference in the amount of grain/subgrain coarsening.     

Study of thermodynamic properties of liquid binary alloys by a pseudopotential method

On the basis of the Percus–Yevick hard-sphere model as a reference system and the Gibbs–Bogoliubov inequality, a thermodynamic perturbation method is applied with the use of the well-known model potential. By applying a variational method, the hard-core diameters are found which correspond to a minimum free energy. With this procedure, the thermodynamic properties such as the internal energy, entropy, Helmholtz free energy, entropy of mixing, and heat of mixing are computed for liquid NaK binary systems. The influence of the local-field correction functions of Hartree, Taylor, Ichimaru–Utsumi, Farid–Heine–Engel–Robertson, and Sarkar–Sen–Haldar–Roy is also investigated. The computed excess entropy is in agreement with available experimental data in the case of liquid alloys, whereas the agreement for the heat of mixing is poor. This may be due to the sensitivity of the latter to the potential parameters and dielectric function.     

Effect of polymers on the nanostructure and on the carbonation of calcium silicate hydrates: a scanning transmission X-ray microscopy study

This study investigated the effects of organic polymers (polyethylene glycol and hexadecyltrimethylammonium) on structures of calcium silicate hydrates (C–S–H) which is the major product of Portland cement hydration. Increased surface areas and expansion of layers were observed for all organic polymer modified C–S–H. The results from attenuated total reflectance–Fourier transform infrared (ATR–FTIR) spectroscopic measurements also suggest lowered water contents in the layered structures for the C–S–H samples that are modified by organic polymers. Scanning transmission X-ray microscopy (STXM) results further supports this observation. We also observed difference in the extent of C–S–H carbonation due to the presence of organic polymers. No calcite formed in the presence of HDTMA whereas formation of calcite was observed with C–S–H sample modified with PEG. We suggest that the difference in the carbonation reaction is possibly due to the ease of penetration and diffusion of the CO₂. This observation suggests that CO₂ reaction strongly depends on the presence of organic polymers and the types of organic polymers incorporated within the C–S–H structure. This is the first comprehensive study using STXM to quantitatively characterize the level of heterogeneity in cementitious materials at high spatial and spectral resolutions. The results from BET, XRD, ATR–FTIR, and STXM measurements are consistent and suggest that C–S–H layer structures are significantly modified due to the presence of organic polymers, and that the chemical composition and structural differences among the organic polymers determine the extent of the changes in the C–S–H nanostructures as well as the extent of carbonation reaction.     

Corrosion behaviour of aluminium alloys in ethanol fuels

In this study, the corrosion behaviour of several aluminium alloys in ethanol fuels was investigated by immersion and polarization tests. The corrosion properties of cast aluminium alloys (Al–17wt%Si–4wt%Cu–Mg, Al–8wt%Si–3wt%Cu, Al–7wt%Si–Mg and Al–17wt%Si–4wt%Cu–Mg with a chemically deposited nickel layer) in ethanol blended gasoline fuels were examined at various ethanol and water contents and various temperatures. Electrochemical and gravimetric measurements revealed a pronounced acceleration of the corrosion process above the boiling point. Additions of water restrain the corrosion. Increasing the ethanol content and the temperature leads to a higher corrosion sensitivity of the aluminium alloys. Furthermore, the nickel layer is very protective in all tested fuels. For aluminium alloys, a theory of the corrosion process in ethanol blended gasoline fuels is proposed.     

Effect of heat treatment on structure and properties of dispersed-type dental amalgam

Effect of heat treatment of Ag–Cu–Pd dispersant particles on the structure, mechanical properties and mercury vapor release rate of an Ag–Cu–Sn/Ag–Cu–Pd-based dental amalgam has been investigated. Experimental results indicate that crystallinity of dispersant Ag-Cu–Pd alloy increases with increasing HTT, with most notable increase occurring between 100 and 200 °C. Increasing HTT of Ag–Cu–Pd alloy does not change much of the mercury/alloy ratio for amalgamation, but largely reduces working/setting time of the amalgam. The Ag–Cu–Pd particles in 7 d-aged amalgam are comprised primarily of an outer Sn/Cu/Pd-rich zone and an inner Ag/Cu/Pd-rich zone with eutectic-type morphology and chemical distribution. The annealing-enhanced Pd segregation effect is most significantly observed in the amalgam derived from 300 °C-annealed Ag–Cu–Pd dispersant. This amalgam also has the highest compressive strength, highest DTS, and lowest creep rate. Higher annealing temperature causes mechanical property of the amalgam to deteriorate. The initial mercury vapor release rates of amalgams derived from 100, 200 and 300 °C-annealed Ag–Cu–Pd dispersant are significantly lower than that derived from 400 °C-annealed dispersant.     

Using direct hot-rolling approach to obtain dual-phase weathering steel Cu–P–Cr–Ni–Mo

A weathering steel Cu–P–Cr–Ni–Mo has been developed which exhibits special continuous cooling transformation characteristics which permit the desired dual-phase (DP) microstructure to be obtained by direct hot-rolling. Hot-rolling procedures to obtain DP microstructures have been designed based on the continuous cooling transformation diagram of weathering steel Cu–P–Cr–Ni–Mo. The results show that the microstructures of DP weathering steels Cu–P–Cr–Ni–Mo are characterized by an irregular distribution of island-shaped martensite–austenite in the matrix of polygonal ferrite grains. DP weathering steel Cu–P–Cr–Ni–Mo with favorable corrosion resistant property, weldability and mechanical properties, such as, high strain hardening exponent values, a lower ratio of yield to tensile strength, and higher strengths; and is obtained successfully by direct hot-rolling.     

Tuning the stress induced martensitic formation in titanium alloys by alloy design

Two novel titanium alloys, Ti–10V–2Cr–3Al and Ti–10V–1Fe–3Al (wt%), have been designed, fabricated, and tested for their intended stress-induced martensitic (SIM) transformation behavior. The results show that for Ti–10V–1Fe–3Al the triggering stress for SIM transformation is independently affected by the β domain size and β phase stability, when the value of the molybdenum equivalent is higher than ~9. The triggering stress was well predicted using the equations derived separately for the commercial Ti–10V–2Fe–3Al alloy. For samples containing β with a lower molybdenum equivalence value, pre-existing thermal martensite is also present and this was found to have an obstructive effect on SIM transformation. In Ti–10V–2Cr–3Al, the low diffusion speed of Cr caused local gradients in the Cr level for many heat treatments leading even to martensite free zones near former β regions.     

Formation of dendritic precipitates in the beta phase of Cu-based alloys

The isothermal treatment of the β phase in some Cu-based alloys produces its decomposition by an earlier precipitation of γ phase. During their growth, by means of a diffusion-controlled process, the precipitates show evidences of morphological changes. In the first stages and for a Cu–Zn–Al alloy, the morphology is spherical and cuboidal, but develops more complex shapes such as dendrites, owing to composition fields, interphase overlapping, crystallography characteristics, and relative orientation. In this work, a dendritic γ precipitate characterization is done and morphological theoretical predictions are applied, for Cu–Zn–Al and Cu–Al–Be alloys.