Thermophysical Properties of Ag and Ag–Cu Liquid Alloys at 1098K to 1573K

The surface tension and density of liquid Ag and Ag–Cu alloys were measured with the sessile drop method. The sessile drop tests were carried out at temperatures from 1098K to 1573 K, on cooling (temperature decreasing stepwise) under a protective atmosphere of high purity Ar (6N). The density of liquid Ag and Ag–Cu alloys decreases linearly with increasing temperature, and an increase in concentration of copper results in a lower density. The surface tension dependence on temperature can be described by linear equations, and the surface tension increases with increasing Cu content. The results of the measurements show good agreement with existing literature data and with thermodynamic calculations made using the Butler equation.     

Liquid–solid interfacial reactions of Sn–Ag and Sn–Ag–In solders with Cu under bump metallization

Intermetallic compounds formed during the liquid–solid interfacial reaction of Sn–Ag and Sn–Ag–In solder bumps on Cu under bump metallization at temperatures ranging from 240 to 300 °C were investigated. Two types of intermetallic compounds layer, η Cu₆Sn₅ type and ε Cu₃Sn type, were formed between solder and Cu. It was found that indium addition was effective in suppressing the formation of large Ag₃Sn plate in Sn–Ag solder. During interfacial reaction, Cu consumption rate was mainly influenced by superheat of solder, contact area between solder and Cu and morphology of intermetallic compounds. The growth of η intermetallic compounds was governed by a kinetic relation: ΔX = tⁿ, where the exponent n values for Sn–Ag/Cu and Sn–Ag–In/Cu samples at 240 °C were 0.35 ± 0.01 and 0.34 ± 0.02, respectively. The n values increased with reaction temperature, and it was higher for Sn–Ag/Cu than that for Sn–Ag–In/Cu sample at the same temperature. After Cu was exhausted, ε intermetallic compound was converted to η intermetallic compound. The mechanisms for such growth of interfacial intermetallic compounds during the liquid–solid reaction were investigated.     

Effects of reflow atmosphere and flux on Sn whisker growth of Sn–Ag–Cu solders

We evaluated the Sn whisker growth behavior of Sn–Ag–Cu solder fillets on lead frames of quad flat packages (QFPs) upon OSP printed circuit boards that were exposed to 85 °C/85% relative humidity (RH) exposure. Three different concentrations of halogen flux for activated Sn-3.0wt%Ag–0.5wt%Cu were used to solder in air and in an inert N₂ reflow atmosphere. The lead frames of the QFPs consisted of Sn plated Cu and Fe-42wt%Ni (alloy 42). Sn whiskers were observed on the surface of the QFP solder fillet joints that were reflowed with halogen containing flux in an air atmosphere. A substantial amount of Sn oxides were formed in those solder fillets while whisker growth and the amount of Sn oxides increased with the halogen content. Sn oxide formation apparently enhanced whisker formation. The combination of air reflow atmosphere and high halogen flux was the worst combination for solder fillet oxidation resulting in Sn whisker formation regardless of the electrode’s lead frame composition of Cu or alloy 42. In contrast, an inert N₂ reflow atmosphere obviously prevented Sn whisker formation on Sn–Ag–Cu solder fillets under all conditions used in this work.     

Effect of microstructure and Ag3Sn intermetallic compounds on corrosion behavior of Sn–3.0Ag–0.5Cu lead-free solder

In this paper, the effects of microstructure on the corrosion behavior of Sn–3.0Ag–0.5Cu (SAC305) lead-free solder were investigated by potentiodynamic polarization and atmospheric corrosion test. Scanning electron microscopy and X-ray diffraction were used to characterize the samples after the electrochemical and atmospheric corrosion tests. Results showed that commercial SAC305 solder exhibits better corrosion resistance than air-cooled and furnace-cooled SAC305 solders both in 3.5 wt% NaCl solution and at 60 °C/100 % relative humidity condition.     

Thermophysical Properties of Five Binary Copper–Nickel Alloys

Thermophysical properties (e.g., specific enthalpy, heat of fusion, electrical resistivity, thermal volume expansion) are measured in the liquid phase up to very high temperatures by an extreme fast pulse-heating method. Heating rates of about 10⁸ K · s^?1 are applied by self-heating of wire-shaped metallic specimens with a current of approximately 10,000 A. Pure elements seem to be still close to thermal equilibrium as the obtained results are in good agreement with those obtained by static methods. However, this situation might be different for alloys. The rapid volume heating can shift diffusion-controlled phase transitions at heating to higher temperatures or even make them not noticeable anymore. The simple binary Cu–Ni system was chosen to test the heating rate dependence; this system is well known and shows complete miscibility in the liquid and solid ranges of interest. This study is a further step to test the performance of the fast pulse-heating method being applied to simple and more complex alloys. Measured results of enthalpy, heat of fusion, heat capacity, and electrical resistivity in the vicinity of the melting range are presented. The results of enthalpy and heat capacity agree with simple mixing rules. The measured electrical resistivity of different compositions is compared to results obtained by electromagnetic levitation measurements.     

Tensile creep behavior of Sn–Ag–Cu–Ni multicomponent lead-free solder alloy

In the process of electronic packaging, the dissolution of under bump metallizations, such as Cu and Ni, into liquid solder occurs during soldering, which can change the original solder to a multicomponent one. Under the trend of miniaturization, it is quite necessary to evaluate the properties of multicomponent solder with excessive Cu and Ni compositions. In this study, the tensile creep behavior of Sn–3.5Ag–2.0Cu–0.5Ni multicomponent lead-free solder alloy is investigated at three temperatures, i.e., 303, 348 and 393 K. The steady-rate creep rates are obtained in the range of 10^?4–10^?8 s^?1, when the normalized stress, σ/E, is in the range of 10^?4–10^?3. Based on the Dorn equation, the apparent stress exponent (n _a), threshold stress (σ _th), and activation energy of creep (Q _C) are calculated at the three temperatures. It is found that the Sn–3.5Ag–2.0Cu–0.5Ni solder alloy shows a better creep performance than pure tin and eutectic Sn–3.5Ag solder due to the strengthening effect of Ag₃Sn and (Cu,Ni)₆Sn₅ IMC precipitations. The true stress exponent for creep is identified to be 7, indicating that the creep behave is controlled by the dislocation-pipe diffusion in the tin matrix.     

Development of a Sn–Ag–Cu solder reinforced with Ni-coated carbon nanotubes

In this study, Ni-coated carbon nanotubes (Ni-CNTs) were incorporated into the 95.8Sn-3.5Ag-0.7Cu solder alloy using the powder metallurgy route. Up to 0.3 wt% of Ni-CNTs were successfully incorporated. The effects of Ni-CNTs on the physical, thermal and mechanical properties of Sn–Ag–Cu solder alloy were investigated. With the addition of increasing weight percentages of Ni-CNTs, the composite solders showed a corresponding decrease in density values and improved wetting properties. The thermomechanical property results showed an improvement in thermal stability for the composite solders. Mechanical characterization revealed an improvement in ultimate tensile strength (up to 12%) and 0.2% yield strength (up to 8%) with the addition of 0.05 wt% Ni-CNTs in the solder.     

Annealing effect to constitutive behavior of Sn–3.0Ag–0.5Cu solder

Sn–Ag–Cu based solder alloys are replacing Sn–Pb solders in electronic packaging structures of commercial electric devices. In order to evaluate the structural reliability, the mechanical property of solder material is critical to the numerical simulations. Annealing process has been found to stabilize material properties of Sn–37Pb solder material. In the current study, the annealing effect on tensile behaviour of Sn–3.0Ag–0.5Cu (SAC305) solder material is investigated and compared with Sn–37Pb solder. It is found that the tensile strength for both materials are more stabilized and consistent after the annealing process, nevertheless, the annealing process will improve the plasticity of SAC305 solder dominated by dislocation motion, and impede the occurrence of hardening deformation in Sn–37Pb solder dominated by grain-boundary sliding mechanism. Furthermore, the annealing effect is quantified in the proposed constitutive model based on unified creep–plasticity theory. The parameters are calibrated against the measured stress–strain relationships at the tensile strain rates ranging from 1?×?10^?4 to 1?×?10^?3 s^?1. The numerical regressions for dominant parameters in the proposed model reveal the intrinsic differences between SAC305 and Sn–37Pb solders under annealing treatment.     

Interface behavior and performance of Sn–Ag–Cu lead-free solder bearing Tb

Journal of Materials Science: Materials in Electronics - To further improve the performance of the Sn–3.5Ag–0.5Cu solder, trace amount of rare earth Tb was added. The wettability, shear...     

Combined effects of Ag content and cooling rate on microstructure and mechanical behavior of Sn–Ag–Cu solders

Sn–0.7 wt%Cu–1.0 wt%Ag and Sn–0.7 wt%Cu–2.0 wt%Ag alloys were directionally solidified under transient conditions undergoing cooling rates varying from 0.1 to 25 K/s. The microstructure was characterized along the castings lengths and the present experimental results include the secondary dendrite arm spacing (λ₂) and its correlation with: the tip cooling rate ($\dot{T}$) during solidification and microhardness (HV), yield tensile strength (σ_y), ultimate tensile strength (σ_u) and elongation to fracture (δ). The aim is to examine the effects of Ag content and tip cooling rate on both the microstructure and mechanical properties. The initiation of tertiary branches within the dendritic arrangement, as well as the distinct morphologies of the intermetallic compounds (IMC) related to the solidification cooling rate was also assessed for both examined alloys. While the Cu₆Sn₅ phase appeared as large faceted crystals along the entire casting length, very fine Ag₃Sn spheroids prevailed at higher cooling rates (>7.5 K/s and > 4.0 K/s for 1.0 wt%Ag and 2.0 wt%Ag alloying, respectively) with a mixture of Ag₃Sn coarser spheroids and fibers predominating at lower cooling rates. The Sn–0.7 wt%Cu–2.0 wt%Ag alloy exhibited smaller dendritic spacings and HV of about two times higher than the corresponding values of the Sn–0.7 wt%Cu–1.0 wt%Ag alloy. A single Hall–Petch equation is proposed relating δ to λ₂ for both alloys, which means that the increase in Ag content from 1.0 to 2.0 wt% does not affect the elongation. It is shown that δ decreases with the increase in λ₂.     

Thermophysical Properties of 75Ni–15Mo–10Re Alloy

The true heat capacity, thermal expansion, thermal conductivity, electrical resistance, and density of NMR-75 alloy (75 wt % Ni, 15 wt % Mo, and 10 wt % Re) are investigated in a temperature range of 300–1300 K. The enthalpy, mean coefficient of thermal expansion, thermal diffusivity, and Lorentz number are calculated from the obtained experimental data. The measurement results show that a reversible structural transformation occurs in the alloy in a temperature range of 750–960 K. In accordance with the phase diagram, the ternary system of the alloy consists of an a-solid molybdenum–nickel solution, which is in equilibrium with a -solid rhenium–nickel solution and a Ni₄Mo intermetallic compound. On heating the alloy in a temperature range of 750–960 K, the intermetallic compound transforms into the -solid molybdenum–nickel solution with the absorption of heat, while the ordered structure transforms into a disordered one. The thermal effect Q = 6 kJ/kg and the activation energy of alloy disordering E = 2.2 eV are estimated. The transformation proper is regarded as a second-order transition.     

Influence of Sn and Bi Additions on the Structures and Wear Properties of Cu–Sn–P–Ce cBN Tools

In this work Sn and Bi were added to Cu–Sn–P–Ce for improving its microstructures and properties. Structures of the three matrices were investigated by XRD, SEM and EDS. The Cu₄₁Sn₁₁ became the main microstructure with some pores, the grinding ratio increased, and the grinding efficiency improved slightly with the addition of Sn to Cu–Sn–P–Ce. Bi was distributed in the form of simple substance, the grinding ratio increased, and the grinding efficiency greatly reduced with the addition of Bi to Cu–Sn–P–Ce.     

Investigation on Sn grain number and crystal orientation in the Sn–Ag–Cu/Cu solder joints of different sizes

Polarized light microscopy and electron backscatter diffraction have been used to quantify the number of β-Sn grains and to examine the Sn crystallographic orientation in Sn–Ag–Cu/Cu solder joints, respectively. The effect of solder joint size on the Sn grain features was investigated due to the miniaturization of solder joints. The Sn–Ag–Cu solder joints of different sizes were found to contain only several β-Sn crystal grains and most solder joints were comprised of no more than three Sn grains. The solder joints showed a preferred crystal orientation. The c crystal axis of β-Sn grains tended to be at a small angle with solder pads. Specific orientation relationships were observed to be prevalent between neighboring β-Sn grains. The grain number, crystal orientation and misorientation were independent of solder joint size.     

Reliability studies of Sn–9Zn/Cu and Sn–9Zn–0.3Ag/Cu soldered joints with aging treatment

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.     

Effect of tin on melting temperature and microstructure of Ag–Cu–Zn–Sn filler metals

Abstract

To develop low melting point filler metals for brazing TiNi shape memory alloy (SMA) and stainless steel (SS), a series of Ag–22Cu–Zn–Sn (wt-%) filler metals have been studied. Using differential thermal analysis (DTA) analysis, the melting temperatures of Ag–22Cu–Zn–Sn filler metals were determined. The results show that the increase of zinc and tin contents drastically decreases the solidus and liquidus temperatures of the Ag–22Cu–Zn–Sn filler metals and the melting temperatures of the Ag–22Cu–18Zn–Sn filler metals with 5–8 wt-%tin are < 650°C. Metallographic observations indicate that the increase of zinc and tin in the Ag–22Cu–Zn–Sn filler metals helps the formation of eutectic structure and inhibits the formation of α-Ag and α-Cu solid solutions, but the increase of tin also causes the formation of Ag₃Sn and Cu₄₁Sn₁₁ brittle compounds. The results of mechanical property tests of the laser brazed joints of TiNi SMA and SS show that the proper increase of zinc and tin in Ag–22Cu–Zn–Sn filler metals is favourable for improving the strength of the laser brazed joints of TiNi SMA and SS.     

Effect of Bi content on spalling behavior of Sn–Bi–Zn–Ag/Cu interface

The effect of the Bi content on the formation of intermetallic compounds (IMCs) layers between the Sn-xBi-0.9Zn-0.3Ag lead-free solder (with x = 1, 2, 3 and 4, in weight percent, hereafter) and Cu substrate was investigated. The structure of the IMC layer in the soldered interface varies apparently with increasing the Bi content. When the Bi content is 1 wt%, the interface soldered is consisted of CuZn and Cu₆Sn₅ IMC layers, which are separated by an intermediate solder layer. As the Bi content increases, the spalling phenomenon tends to disappear. Moreover, the layer between the Sn-2Bi-0.9Zn-0.3Ag solder and Cu substrate is thicker than others. The evolution of the soldered interfacial structure could be attributed to the existence of Bi.