Thermal Properties and Wetting Behavior of High Temperature Zn-Al-In Solders

Solders for ultrahigh-temperature applications were defined by Vianco as those able to sustain working conditions with temperatures as high as 573 K, with momentary temperature rise up to 623 K. Zn-Al eutectic alloy (12 at.% Al) fits such defined criteria with respect to its melting temperature. It was found that small additions of indium to Zn-Al eutectic lower its melting temperature. The aim of this work is to assess if and to what extent thermal properties and wetting behavior are affected. It was found that addition of In increases electrical resistivity and coefficient of thermal expansion value. Wetting angles on Cu and Al substrates of liquid Zn-Al eutectic-based alloys containing up to 1.5 at.% of In were studied with the sessile drop method, after wetting at 773 K in the presence of flux. A decrease of apparent wetting angle was observed with increasing concentration of In. After wetting tests solidified alloy-substrate couples were cross-sectioned and examined with scanning electron microscopy coupled with electron dispersive X-ray analysis.     

Measurements of electrical and thermal properties with growth rate,alloying elements and temperature in the Al–Si–X alloys

In this work, effect of alloying elements (X = Cu, Co, Ni, Sb and Bi) and growth rates on the microstructure, physical properties (electrical resistivity, enthalpy and specific heat) of the directionally solidified Al–Si eutectic alloy have been investigated. Al–12.6Si–2X (wt. %) samples were prepared using metals of 99.99% high purity in the vacuum atmosphere. These alloys were directionally solidified under constant temperature gradient, G (7.80 K/mm) and different growth rates, V (8.3–166.0 μm/s). Flake spacing (λ) and electrical resistivity (ρ) were measured from the solidified samples. The variation of electrical resistivity with temperature in the range of 300–500 K for alloying elements in the Al–Si eutectic cast alloy was also measured. The enthalpy of fusion (ΔH) and specific heat (C_p) for the same alloy were determined by a differential scanning calorimeter from the heating curve during the transformation from solid to liquid.     

Temperature-dependence of electrical resistivity of Cd-Sn, Bi-Sn, and Al-Si eutectic and Al-3wt.%Si hypoeutectic alloys

Cd-Sn, Bi-Cd, and Al-Si eutectic and Al-3wt.%Si hypoeutectic alloys of high-purity (99.99%) metals were produced in a vacuum atmosphere. Current-voltage (I-V) characteristics of these specimens were measured at various temperatures between 100 and 475 K. The electrical resistivity (ρ) and temperature coefficient (α) for each specimen, depending on the temperature, were calculated using results obtained from the I-V measurements. The electrical resistivities and the residual resistivity of the specimens increase with increasing temperature for each alloy system. These results are compared with literature results.     

Wetting of Sn-Zn-<Emphasis Type="Italic">x</Emphasis>In (<Emphasis Type="Italic">x</Emphasis> = 0.5, 1.0, 1.5 wt%) Alloys on Cu and Ni Substrates

Wetting angles of Sn-8.8Zn and Sn-8.8Zn-xIn alloys (x = 0.5, 1.0, 1.5 wt%) were studied with the sessile drop method. Wetting tests were carried out for 900 s in the presence of ORM0 flux at 493, 523, and 573 K on copper and at 523 K on nickel substrates, respectively. It was found that the addition of In to Sn-8.8Zn alloy improves its wetting on both substrates by reducing the value of apparent wetting angle. Also, with increasing temperature a decrease of wetting angle on copper is observed in the case of 0 and 1.5 wt% of In alloys. Solidified solder-substrate couples were cross-sectioned and examined with scanning electron microscopy coupled with electron dispersive X-ray analysis. Interlayers were found at the interface of solders with copper and nickel, and their compositions are close to Cu₅Zn₈ and Ni₅Zn₂₁ intermetallics, respectively. However, in the case of Sn-8.8Zn-1.5/Ni couple small scallops are observed instead of continuous interlayer.     

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

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

Wetting of Cu and Al by Sn-Zn and Zn-Al Eutectic Alloys

Wetting properties of Sn-Zn and Zn-Al alloys on Cu and Al substrates were studied. Spreading tests were carried out for 3 min, in air and under protective atmosphere of nitrogen, with the use of fluxes. In the case of Zn-Al eutectic, spreading tests were carried out at 460, 480, 500, and 520 °C, and in the case of Sn-Zn eutectic at 250, 300, 350, 400, 450, and 500 °C, respectively. Solidified solder/substrate couples were cross-sectioned and subjected to microstructure examination. The spreading tests indicated that the wetting properties of eutectic Sn-Zn alloys, on copper pads do not depend on temperature (up to 400 °C), but in the lack of protective atmosphere, the solder does not wet the pads. Wettability studies of Zn-Al eutectic on aluminum and copper substrates have shown a negative effect of the protective nitrogen atmosphere on the wetting properties, especially for the copper pads. Furthermore, it was noted that with increasing temperature the solder wettability is improved. In addition, densities of liquid solders were studied by means of dilatometric technique.     

Thermal vacancy formation in Co-based Heusler-type alloys Co2MnZ (Z = Si, Ge, Sn)

Thermal vacancy formation was studied for the Heusler-type ferromagnetic alloys Co₂MnZ (Z = Si, Ge, Sn) as a function of temperature (773–1273 K) by the density, electrical resistivity and positron annihilation measurements. The vacancy concentration increased with increase in quenching temperature and particularly, a high vacancy concentration exceeding 2% was observed in Co₂MnGe and Co₂MnSn. Estimated vacancy formation and migration energies were comparable with those for B2-type FeAl and CoGa alloys with high vacancy concentration. Further, the vacancy type and the vacancy site were examined for alloys quenched from 773 K. As a result, it was suggested that the mono-vacancies are randomly distributed over the lattice sites.     

Effect of Cr on Microstructure and Properties of a Series of AlTiCr x FeCoNiCu High-Entropy Alloys

A series of AlTiCr _x FeCoNiCu (x: molar ratio, x = 0.5, 1.0, 1.5, 2.0, 2.5) high-entropy alloys (HEAs) were prepared by vacuum arc furnace. These alloys consist of α-phase, β-phase, and γ-phase. These phases are solid solutions. The structure of α-phase and γ-phase is face-centered cubic structure and that of β-phase is body-centered cubic (BCC) structure. There are four typical cast organizations in these alloys such as petal organization (α-phase), chrysanthemum organization (α-phase + β-phase), dendrite (β-phase), and inter-dendrite (γ-phase). The solidification mode of these alloys is affected by Chromium. If γ-phase is not considered, AlTiCr_0.5FeCoNiCu and AlTiCrFeCoNiCu belong to hypoeutectic alloys; AlTiCr_1.5FeCoNiCu, AlTiCr_2.0FeCoNiCu, and AlTiCr_2.5FeCoNiCu belong to hypereutectic alloys. The cast organizations of these alloys consist of pro-eutectic phase and eutectic structure (α + β). Compact eutectic structure and a certain amount of fine β-phase with uniform distribution are useful to improve the microhardness of the HEAs. More γ-phase and the microstructure with similar volume ratio values of α-phase and β-phase improve the compressive strength and toughness of these alloys. The compressive fracture of the series of AlTiCr _x FeCoNiCu HEAs shows brittle characteristics, suggesting that these HEAs are brittle materials.     

The Effect of Wetting Gravity Regime on Shear Strength of SAC and Sn-Pb Solder Lap Joints

The failure of solder joints due to imposed stresses in an electronic assembly is governed by shear bond strength. In the present study, the effect of wetting gravity regime on single-lap shear strength of Sn-0.3Ag-0.7Cu and Sn-2.5Ag-0.5Cu solder alloys reflowed between bare copper substrates as well as Ni-coated Cu substrates was investigated. Samples were reflowed for 10 s, T _gz (time corresponding to the end of gravity regime) and 100 s individually and tested for single-lap shear strength. The single-lap shear test was also carried out on eutectic Sn-Pb/Cu- and Sn-Pb/Ni-coated Cu specimens to compare the shear strength values obtained with those of lead-free alloys. The eutectic Sn-Pb showed significantly higher ultimate shear strength on bare Cu substrates when compared to Sn-Ag-Cu alloys. However, SAC alloys reflowed on nickel-coated copper substrate exhibited higher shear strength when compared to eutectic Sn-Pb/Ni-coated Cu specimens. All the substrate/solder/substrate lap joint specimens that were reflowed for the time corresponding to the end of gravity regime exhibited maximum ultimate shear strength.     

High temperature lead-free solder for microelectronics

This paper reports results of a four-year industrial consortium effort to develop lead-free solders for high-temperature applications (up to 160°C). Work included preliminary evaluations of 32 tin-based alloys, a screening of the thermomechanical fatigue performance of 13 promising alloys, and a full manufacturability and fatigue testing of the seven most promising of those alloys, namely Sn-3.5Ag, Sn-4Ag-1Cu, Sn-4Ag-0.5Cu, Sn-2.5Ag-0.8Cu-0.5Sb, Sn-4.6Ag-1.6Cu-1Sb-1Bi, Sn-3.3Ag-1Cu-3.3Bi, and Sn-3.5Ag-1.5In (compositions in weight percent). Eight different components were used on the reliability test vehicle, and the alloys were compared through Weibull analysis. In addition, the same seven experimental alloys were tested with ball grid array packages cycled up to 100°C or 125°C. All the lead-free alloys performed well, but those containing bismuth showed especially outstanding performance. In general, the ternary and higher alloys performed as well or better than the industry standard tin-silver eutectic, suggesting that solders other than the tin-silver eutectic should be considered for high-reliability, high-temperature applications. Frank W. Gayle is with NIST, Stop 8555, 100 Bureau Drive, Gaithersburg, MD 20899, frank.gayle@nist.gov.     

Pb-Free solders: Part 1. Wettability testing of Sn−Ag−Cu alloys with Bi additions

Maximum bubble pressure, dilatometric, and meniscographic methods were used in the investigations of the surface tension, density, wetting time, wetting force, contact angle, and interfacial tension of liquid alloys of Sn−Ag−Cu eutectic composition with various additions of Bi. Density and surface tension measurements were conducted in the temperature range 250–900 °C. Surface tensions at 250 °C measured under a protective atmosphere of Ar−H₂ were combined with data from meniscographic studies done under air or with a protective flux. The meniscographic data with a nonwetted teflon substrate provided data on interfacial tension (solder-flux), surface tension in air, and meniscographic data with a Cu substrate allowed determinations of wetting time, wetting force, and calculation of contact angle. The calculated wetting angles from meniscographic studies for binary Sn−Ag eutectic and two ternary Sn−Ag−Cu alloys were verified by separate measurements by the sessile drop method under a protective atmosphere with a Cu substrate. Additions of Bi to both ternary alloys improve the wettability and move the parameters somewhat closer to those of traditional Sn−Pb solders.     

Surface tension and wetting behaviour of molten Bi–Pb alloys

The present work represents an experimentally based investigation on the surface properties of molten Bi, Pb and Bi–Pb alloys. The surface tensions of the two pure elements and of seven alloys were measured by the sessile-drop method over the temperature range 623–773 K. In addition the wetting behaviour of the eutectic Bi–Pb alloy on AISI 316L substrate was also investigated in the same temperature range. The results obtained show general agreement with other reported measurements on pure elements and their alloys as well as with calculated surface tension values obtained by the application of the compound formation model (CFM).     

Wetting and Microstructure Evolution of the Sn-Zn-Ag/Cu Interface

Wetting of Cu substrates by Sn-Zn eutectic-based alloys with 0.5, 1, and 1.5 wt.% of Ag was studied. Wetting tests were performed at 523 K, in the presence of ALU33^® flux, for 15, 30 and 60 s, respectively. The results indicated that the content of Ag in the alloys does not have significant effect on the contact angle. Selected, solidified Sn-8.8Zn-xAg/Cu couples were cross-sectioned and subjected to SEM-EDS study of the interfacial microstructure. The results revealed that the microstructure of the Sn-Zn-Ag/Cu interface evolves with time and is different from Sn-Zn/Cu interface. The continuous interlayers are observed at the interface. Composition of the interlayers was analyzed with EDS and their thickness measured.     

Thermal and electrical properties of Ni-V alloys at high temperatures

We present the results of a complex investigation of the thermal diffusivity, electrical resistivity, thermal conductivity, and additional electrical resistivity of ten Ni-V alloys containing from 1.5 to 15.6 wt % vanadium in a temperature range of 300–1650 K. Conclusions have been made concerning the effect of different mechanisms of conduction-electron scattering on the kinetic and thermal properties of the Ni-V alloys studied.     

Interfacial Phenomena in Al/Al,Al/Cu,and Cu/Cu Joints Soldered Using an Al-Zn Alloy with Ag or Cu Additions

The studies of soldered joints were carried out in systems: Al/solder/Al, Al/solder/Cu, Cu/solder/Cu, where the solder was (Al-Zn)_EUT, (Al-Zn)_EUT with 0.5, 1.0, and 1.5 at.% of Ag and (Al-Zn)_EUT with 0.5, 1.0, and 1.5 at.% of Cu addition. Brazing was performed at 500 °C for 3 min. The EDS analysis indicated that the composition of the layers starting from the Cu pad was CuZn, Cu5Zn8, and CuZn4, respectively. Wetting tests were performed at 500 °C for 3, 8, 15, and 30 min, respectively. Thickness of the layers and their kinetics of growth were measured based on the SEM micrographs. The formation of interlayers was not observed from the side of Al pads. On the contrary, dissolution of the Al substrate and migration of Al-rich particles into the bulk of the solder were observed.     

Wetting and Interfacial Chemistry of SnZnCu Alloys with Cu and Al Substrates

Wetting of Cu and Al pads by Sn-Zn eutectic-based alloys with 0.5, 1, and 1.5 wt.% of Cu was studied at 250 °C, in the presence of ALU33® flux, with wetting times of 15, 30, 60, and 180 s, respectively. With increasing wetting time the wetting angle decreases only slightly and the angles on Cu pads are higher than those on Al pads. Selected, solidified solder-pad couples were cross-sectioned and subjected to SEM-EDS study of the interfacial microstructure. The results revealed that the microstructure of the SnZnCu/Cu interface is much different from SnZnCu/Al interface. In the first case continuous interlayers are observed while in the latter case there is no interlayer but the alloy dissolves the substrate along grain boundaries.     

Deformation Behavior Immediately After Indentation Load Change in Ultrafine-Grained Al-Mg Solid Solution Alloys

Instrumented indentation tests were performed to study how grain boundaries and solute atoms affect creep and instantaneous plastic deformation in ultrafine-grained (UFG) Al-Mg solid solution alloys with average grain size d = 0.3 ? 1.0 μm at T = 373 K. In the results for Al-1.0 mol% Mg, the degree of instantaneous plastic displacement generated with a rapid increase in the load was smaller when the grain diameter was smaller. On the other hand, creep occurs more readily in materials with a smaller grain diameter. When the load was rapidly decreased during creep, the indenter displacement gradually decreased over time. The degree of reverse creep that occurs is greater when the grain diameter is smaller. In light of these test results and reports in the related literature, reverse creep is thought to occur because of inverted movement of piled-up dislocations near the grain boundaries. For the case of Al-xMg (x = 0.5, 1.0, 2.0 mol%), the results show that as the solute concentration increases, the occurrence of instantaneous plastic deformation, creep, and reverse creep becomes less likely. Overall, the results indicate that the plastic deformation behavior obtained by the testing conditions of present study for UFG Al-Mg alloys could be explained based on understanding of the behavior of course-grained materials.     

Effects of Si on the Microstructures and Mechanical Properties of High-Chromium Cast Iron

Effect of Si on the microstructures and mechanical properties of high-chromium cast iron was investigated. The eutectic carbides are refined greatly and a transformation of matrix from austenitic matrix to pearlite is observed with increase in Si content from 0.5 to 1.5 wt.%. The refinement of eutectic microstructure is attributed to the decrease in the eutectic temperature, while the transformation from austenite matrix to pearlite is associated with the increase in solubility of carbon in the matrix. In the pearlite matrix, two types of pearlite are observed: one with lamellar pearlite, distributing at the periphery, and the second one with granular pearlite at the center. The density of secondary carbides precipitated from the matrix increases greatly with addition of Si from 0.5 to 1.5 wt.%, which is associated with more carbon and chromium elements confined in the matrix in the alloy containing 1.5 wt.%. More rod-like particles are observed in the alloy containing 0.5 wt.% Si, while the morphology of secondary carbides of alloy containing 1.5 wt.% is granular. The mechanical properties are improved with a 7% increase in tensile strength from 586 to 626 MPa and impact toughness from 5.8 to 7.3 J cm^?2.     

Workability Studies on High Al Ferritic Fe–Al–C Alloys

Iron-based alloys with high-carbide (Fe₃AlC_0.5) volume fractions (up to 40%) may be obtained by careful aluminum and carbon additions. These need to be hot worked to obtain a uniform distribution of the carbide. The workability of two alloy compositions (Fe–11 wt.% Al with 0.5 wt.% C and 1.1 wt.% C) was investigated using a strain-induced crack opening (SICO) test in a Gleeble 3800 thermomechanical simulator. SICO tests were conducted in the temperature range of 1,073–1,373 K at strain rates of 0.05–0.1 s^?1. Both alloys exhibited good workability with no tendency for cracking despite their high aluminum and carbon contents. However, refinement of microstructure due to thermomechanical processing could only be observed at 1,373 K for both alloys. At lower temperatures, a slightly aligned and elongated structure was observed. It is proposed that the higher solubility of carbon with an increase in temperature as well as the transformation of matrix from ferrite to austenite may play an important role in determining the optimum working temperature for these alloys.     

Microstructure and thermophysical properties of Mg−2Zn−xCu alloys

The microstructure and thermophysical properties of Mg−2Zn−xCu alloys (x=0.5, 1.0 and 1.5, at.%) were investigated through microstructural and thermophysical characterization, heat treatment, and first-principles calculations. It was found that the addition of Cu had influence on the microstructure and thermophysical properties of the alloy. As the Cu content increased, the content of the MgCuZn phase increased in the as-cast alloys along with the electrical and thermal conductivities. After solution treatment, the eutectic structure partially decomposed and Zn atoms dissolved into the matrix, leading to the decrease in both the electrical and thermal conductivities of the alloy. During the early stages of the aging treatment, solute atoms precipitated from the matrix, thus increasing the electrical conductivity of the alloy. After aging for 24 h, the thermal conductivity of Mg−2Zn−1.5Cu alloy reached the maximum of 147.1 W/(m·K). The thermostable MgCuZn phases were responsible for increasing the electrical and thermal conductivities. Smaller amounts of Zn atoms dissolved in the matrix resulted in smaller lattice distortion and higher conductivities. The first-principles calculations findings also proved that the MgCuZn phases had very high conductance.