Experimental study of Ti–Sn–Y system phase equilibria at 473 K

The phase equilibria of the Ti–Sn–Y ternary system at 473 K have been investigated mainly by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and differential thermal analysis (DTA). The existences of 10 binary compounds, Ti₃Sn, Ti₂Sn, Ti₅Sn₃, Ti₆Sn₅, Ti₂Sn₃, Sn₃Y, Sn₂Y, Sn₁₀Y₁₁, Sn₄Y₅ and Sn₃Y₅ were confirmed. The 473 K isothermal section was found to consist of 13 single-phase regions, 23 two-phase regions and 11 three-phase regions. There is no new ternary compound found in the work. None of the phases in this system reveals a remarkable homogeneity range at 473 K.     

Microstructure identification of devitrified Cu–Ti–Zr–Ni bulk amorphous alloy

The microstructures of devitrified Cu–Ti–Zr–Ni bulk amorphous alloy were identified by X-ray diffractometry (XRD) and transmission electron microscope (TEM). XRD and TEM examinations show that the deep eutectic structures of the tested alloy consist of CuTi₂–Cu₁₀Zr₇, Cu₃Ti–CuZr, Cu₃Ti–Cu₁₀Zr₇–CuZr low-order eutectics. Moreover, short-range ordering clusters in the melt with configuration similar to that of Cu₁₀Zr₇ compound may contribute to the glass forming ability of bulk amorphous Cu–Ti–Zr–Ni alloy.     

Experimental phase diagram of the Ti-Si-Sn ternary system at 473 K

The phase diagram of the ternary system Ti-Si-Sn system at 473 K was investigated by means of powder X-ray diffraction (XRD), differential thermal analysis (DTA) and scanning electron microscope (SEM) with energy dispersive analysis (EDX). The isothermal section consists of 14 single phase regions, 26 binary phase regions and 13 ternary phase regions. The 10 binary compounds, namely Ti₃Si, Ti₅Si₃, Ti₅Si₄, TiSi, TiSi₂, Ti₃Sn, Ti₂Sn, Ti₅Sn₃, Ti₆Sn₅, Ti₂Sn₃, have been confirmed at 473 K. Moreover, a ternary phase with the crystal structure of tetragonal W₅Si₃ structure type and I4/mcm space group is confirmed in the Ti-Si-Sn system. The combined results of both EDX and XRD show that the composition of this ternary phase is 60.25-61.03 at.% Ti, 15.01-21.77 at.% Si and balance Sn.     

Influence of thermal cycling on shear strength of Cu–Sn3.5AgIn–Cu joints with various content of indium

This work presents an investigation on the influence of thermal cycling of Cu–Sn3.5AgIn–Cu joints for various content of indium. Solders Sn–3.5Ag containing 0, 6.5 and 9 mass% In were prepared by rapid quenching of appropriate alloys. Joints Cu–solder–Cu were prepared in furnace at 280 °C and 1800 s. Thermal cycling was in the interval room temperature (RT)–150 °C up to 1000 cycles and in the interval RT–180 °C for 500 cycles. The shear strength of the joints with indium-free solder decreases with increasing number of cycles. On the contrary shear strength of joints with indium containing solders increases with increasing number of cycles. It is related with the thickness of Cu₆Sn₅ phase which makes the interface between Cu substrate and solder. In the first case the thickness of this phase is growing with increasing number of cycles, in the second case the amount of this phase is reducing with increasing the number of cycles due to the support of dissolution of copper from Cu₆Sn₅ phase into the Sn–Ag–In solder by indium. X-ray diffraction analysis of original solders as well as of uncycled and 1000 times cycled joints made with all three kinds of solders is given.     

Strong bonding of infrared brazed α2-Ti3Al and Ti–6Al–4V using Ti–Cu–Ni fillers

Infrared dissimilar brazing of α₂-Ti₃Al and Ti–6Al–4V using Ti–15Cu–25Ni and Ti–15Cu–15Ni filler metals has been performed in this study. The brazed joint consists primarily of Ti-rich and Ti₂Ni phases, and there is no interfacial phase among the braze alloy, α₂-Ti₃Al and Ti–6Al–4V substrates. The existence of the Ti₂Ni intermetallic compound is detrimental to the bonding strength of the joint. The amount of Ti₂Ni decreases with increasing brazing temperature and/or time due to the depletion of Ni content from the braze alloy into the Ti–6Al–4V substrate during brazing. The shear strength of the brazed joint free of the blocky Ti₂Ni phase is comparable with that of the α₂-Ti₃Al substrate, and strong bonding can thus be obtained.     

The isothermal section of the Ti–Co–Zr ternary system at 773 K

The phase equilibria of the Ti–Co–Zr ternary system at 773 K have been investigated mainly by powder X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive analysis (EDX). The isothermal section consists of 16 single-phase regions, 31 two-phase regions and 16 three-phase regions. There are 11 binary compounds, i.e. CoZr₃, CoZr₂, CoZr, Co₂Zr, Co₂₃Zr₆, Co₁₁Zr₂, TiCo₃, h-TiCo₂, c-TiCo₂, TiCo, Ti₂Co in the system. The existence of two ternary compounds Co₁₀Ti₇Zr₃ and Co₆₆Ti₁₇Zr₁₇ has been confirmed at 773 K. Co₂Zr, CoZr₃ and TiCo have a range of homogeneity. The solubilities of Ti in CoZr was determined to be up to 8.1 at.% Ti.     

The 260 °C phase equilibria of the Sn–Sb–Cu ternary system and interfacial reactions at the Sn–Sb/Cu joints

The isothermal section of the Sn–Sb–Cu ternary system at 260 °C has been determined in this study by experimental examination. Experimental results show no existence of ternary compounds in the Sn–Sb–Cu system. An extensive region of mutual solubility existing between the two binary isomorphous phases, Cu₃Sn and Cu₄Sb, was determined and labeled as δ. Intermetallic compounds (IMCs) Cu₂Sb, SbSn, and Cu₆Sn₅ are in equilibrium with the δ solid solution. Up to about 6.5 at.%Sb can dissolve in the Cu₆Sn₅ phase, and the solubility of Sn in the Cu₂Sb is approximately 6.2 at.%. Each of the Sb and SbSn phases has a limited solubility of Cu. Only one stoichiometric compound, Sb₂Sn₃, exists. Besides phase equilibria determination, the interfacial reactions between the Sn–Sb alloys and Cu substrates were investigated at 260 °C. Sb was observed to be present in the Cu₆Sn₅ and δ phases, and Sb did not form Sn–Sb IMCs in the interfacial reactions. Moreover, the addition of up to 7 wt% of Sb into Sn does not significantly affect the total thickness of IMC layers. It was found that the phase formations in the Sn–Sb/Cu couples are very similar to those in the Sn/Cu couples.     

Sn effect on microstructure and mechanical properties of ultrafine eutectic Ti–Fe–Sn alloys

Microstructural investigations on ultrafine eutectic (Ti₆₅Fe₃₅)_100−xSn_x alloys with x = 0, 1 and 3 at.% reveal that additional Sn is effective to control formation of the micron-scale dendrites and to decrease the length-scale of lamellar spacing with enhancing macroscopic plasticity at room temperature compression. Hence, it is possible to understand the influence of the microstructural change on the plasticity of the ultrafine eutectic Ti–Fe–Sn alloys.     

Formation and properties of Ti-based Ti–Zr–Cu–Fe–Sn–Si bulk metallic glasses with different (Ti + Zr)/Cu ratios for biomedical application

Ti-based Ti–Zr–Cu–Fe–Sn–Si bulk metallic glasses (BMGs) free from highly toxic elements Ni and Be were developed as promising biomaterials. The influence of (Ti + Zr)/Cu ratio on glass-formation, thermal stability, mechanical properties, bio-corrosion resistance, surface wettability and biocompatibility were investigated. In the present Ti-based BMG system, the Ti₄₇Zr_7.5Cu₄₀Fe_2.5Sn₂Si₁ glassy alloy exhibited the highest glass forming ability (GFA) corresponding to the largest supercooled liquid region, and a glassy rod with a critical diameter of 3 mm was prepared by copper-mold casting. The Ti-based BMGs possess high compressive strength of 2014–2185 MPa and microhardness of 606–613 Hv. Young's modulus of the Ti₄₇Zr_7.5Cu₄₀Fe_2.5Sn₂Si₁ glassy alloy was about 100 GPa, which is slightly lower than that of Ti–6Al–4V alloy. The Ti₄₇Zr_7.5Cu₄₀Fe_2.5Sn₂Si₁ glassy alloy with high GFA exhibited high bio-corrosion resistance, and good surface hydrophilia and cytocompatibility. The mechanisms for glass formation as well as the effect of (Ti + Zr)/Cu ratio on bio-corrosion behavior and biocompatibility are discussed.     

Constitution of the high-Al region of Al–Cu–Rh

Phase equilibria between 540 and 1010 °C were studied in Al–Cu–Rh alloys containing more than 50 at.% Al. Congruent equiatomic AlRh dissolves more than 40 at.% Cu and extends up to 58 at.% Al at the high-Cu part of its compositional range. High-temperature cubic C-Al₅Rh₂ (C-phase) dissolves up to 13 at.% Cu, “Al₃Rh” (₆-phase) up to 15 at.% Cu and Al₉Rh₂ up to 1.5 at.% Cu. The solubility of the third element in other binary Al–Rh and Al–Cu phases is below 0.5 at.%. Close to the high-Cu limit of the C-phase region the fcc C₂-phase structurally related to the C-phase is formed. Stable decagonal phase (D₁-phase) is formed below 1005 °C in a compositional range extending from Al₆₅Cu₁₆Rh₁₉ to Al₆₂Cu₂₃Rh₁₅, which shifts to higher Cu concentrations with decreasing temperature. An additional ternary phase forming around the Al₇₀Cu₂₀Rh₁₀ composition below 660 °C was revealed. Partial 1010, 990, 900, 800, 700, 600 and 540 °C isothermal sections were determined.     

Effect of composition and milling parameters on the critical ball milling of Ti–Si–B powders

The absence of brittle phases and elevated temperature during ball milling of a powder mixture containing a large amount of ductile component can contribute to reach an excessive agglomeration denoting a critical ball milling (CBM) behavior. This work reports in the effect of composition and milling parameters on the CBM behavior of Ti–Si–B powders. High-purity elemental Ti–Si–B powder mixtures were processed in a planetary ball mill in order to prepare the Ti₆Si₂B compound and two-phase Ti + Ti₆Si₂B alloys. TiH₂ chips instead of titanium powder were used as a starting material. To avoid elevated temperature in the vials during ball milling of Ti–Si–B powders the process was interrupted after each 10 min followed by air-cooling. Following, the milled powders were hot-pressed at 900 °C for 1 h. Samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive spectrometry (EDS). Short milling times followed by air-cooling contributed to obtain a large amount of powders higher than 75% in the vials. Only Ti and TiH₂ peaks were observed in XRD patterns of Ti–Si–B and TiH₂–Si–B, respectively, suggesting that extended solid solutions were achieved. The large amount of Ti₆Si₂B and Ti + Ti₆Si₂B structures were formed during hot pressing from the mechanically alloyed Ti–Si–B and TiH₂–Si–B powders.     

Intrinsic and Interdiffusion in Cu-Sn System

Solid-solid diffusion couples assembled with disks of copper, tin and intermetallics (Cu₃Sn and Cu₆Sn₅) were employed to investigate the Kirkendall effect in the copper-tin system at the temperature of 200 °C. In the Cu(99.9%)/Sn diffusion couple, inert alumina particles used as markers were identified in the Cu₆Sn₅ phase, while microvoids were observed at the Cu/Cu₃Sn interface. The Cu(99.9%)/Sn and Cu(99.9%)/Cu₆Sn₅ diffusion couples annealed at 200 °C for 10 days were analyzed for intrinsic diffusion coefficients of Cu and Sn in the Cu₆Sn₅ and Cu₃Sn phases, respectively with due consideration of changes in molar volume. Interdiffusion, integrated and effective interdiffusion coefficients were also calculated for the intermetallic phases. Diffusion couples annealed at 125-400 °C for various times were analyzed for the kinetic parameters such as growth rate constants and activation energies for the formation of Cu₃Sn and Cu₆Sn₅ phases. Uncertainties in the calculated intrinsic diffusivities of Cu and Sn arise mainly from the non-planar morphologies of the interfaces and the non-planar distribution of the markers. Intrinsic diffusion coefficients based on average locations of the marker plane indicate that Cu is the faster diffusing component than Sn in both the Cu₃Sn and Cu₆Sn₅ phases.     

Formation, properties and microstructure of amorphous/crystalline composite Ag20Cu30Ti50 alloy using miscibility gap

The aim of the work was to produce the amorphous/crystalline composite with uniform distribution of fine crystalline soft phase. Silver–copper–titanium Ag₂₀Cu₃₀Ti₅₀ alloy was prepared using 99.95 wt% Ag, 99.95 wt% Cu, 99.95 wt% Ti that were arc-melted in argon atmosphere. Then the alloy was melt spun on a copper wheel with linear velocity of 33 m/s. Investigation of the microstructure for both arc-melt massive sample and melt-spun ribbons was performed with use of scanning electron microscope (SEM) with EDS, light microscope (LM) and X-ray diffraction. The thermal stability was evaluated by differential scanning calorimetry (DSC). The properties such as Young modulus and Vickers hardness number before and after crystallization of the amorphous matrix were measured with use of nanoindenter. The microstructure was investigated by transmission electron microscope (TEM). It was found, that the alloy has a tendency for separation within the liquid state due to the miscibility gap which resulted in segregation into Ti–Cu–Ag matrix and Ag-base spherical particles after arc-melting. During rapid cooling through the melt spinning the Ag₂₀Cu₃₀Ti₅₀ alloy formed an amorphous/crystalline composite of fcc silver-rich spherical particles within the amorphous Ti–Cu–Ag matrix.     

The difference in the types of intermetallic compound formed between the cathode and anode of an Sn–Ag–Cu solder joint under current stressing

An investigation of microstructural evolution with various current densities in a lead-free Cu/SnAgCu/Au/Cu solder system was conducted in this study. Current stressing induced migration of Cu toward the anode and resulted in the formation of Cu₆Sn₅ at the interface. The consumption rates of Cu were calculated to be 2.24 × 10⁻⁷ μm/s and 5.17 × 10⁻⁷ μm/s at 1.0 × 10³ A/cm² and 2.0 × 10³ A/cm², respectively, while the growth rates of Cu₆Sn₅ were 6.33 × 10⁻⁷ μm/s and 7.72 × 10⁻⁷ μm/s. The atomic fluxes of Cu were found to be 2.50 × 10¹² atom/cm² s and 5.88 × 10¹² atom/cm² s at the above-mentioned current densities. The diffusivities of Cu in Cu₆Sn₅ were 2.02 × 10⁻¹¹ cm²/s and 2.38 × 10⁻¹¹ cm²/s under 1.0 × 10³ A/cm² and 2.0 × 10³ A/cm² of current stressing. Current stressing effectively enhances the migration of Cu in Cu₆Sn₅ and results in a 1000-fold increase of magnitude in diffusivity compared to thermal aging. (Cu_1−x,Au_x)₆Sn₅ compound was formed near the anode after a long period of current stressing.     

BGA焊点界面化合物纳米压痕力学行为

利用纳米压痕法对BGA焊点(Cu,Ni)₆Sn₅,Cu₆Sn₅,Cu₃Sn界面化合物(IMC)进行了压痕试验.基于Oliver-Pharr法确定了(Cu,Ni)₆Sn₅,Cu₆Sn₅,Cu₃Sn的弹性模量和压痕硬度,研究了加载速率对IMC纳米压痕力学行为的影响及其变化规律.结果表明,锯齿流变效应与加载速率的大小是相关的.在加载速率较小的情况下(Cu,Ni)₆Sn₅,Cu₆Sn₅,Cu₃Sn都具有锯齿流变效应,但程度不同;在加载速率较大的情况下(Cu,Ni)₆Sn₅,Cu₃Sn锯齿流变效应不明显,而Cu₆Sn₅的锯齿流变效应相对明显.(Cu,Ni)₆Sn₅,Cu₆Sn₅,Cu₃Sn界面IMC的弹性模量分别为126,118,135 GPa;压痕硬度分别为6.5,6.3,5.8 GPa;含镍的(Cu,Ni)₆Sn₅化合物弹性模量和压痕硬度均比Cu₆Sn₅的值要高.     

Microstructural evolution of intermetallic compounds in Sn–3.5Ag–X (X = 0, 0.75Ni, 1.0Zn and 1.5In)/Cu solder joints during liquid aging

In this paper, the microstructural evolution of IMCs in Sn–3.5Ag–X (X = 0, 0.75Ni, 1.0Zn, 1.5In)/Cu solder joints and their growth mechanisms during liquid aging were investigated by microstructural observations and phase analysis. The results show that two-phase (Ni₃Sn₄ and Cu₆Sn) IMC layers formed in Sn–3.5Ag–0.75Ni/Cu solder joints during their initial liquid aging stage (in the first 8 min). While after a long period of liquid aging, due to the phase transformation of the IMC layer (from Ni₃Sn₄ and Cu₆Sn phases to a (Cu, Ni)₆Sn₅ phase), the rate of growth of the IMC layer in Sn–3.5Ag–0.75Ni/Cu solder joints decreased. The two Cu₆Sn₅ and Cu₅Zn₈ phases formed in Sn–3.5Ag–1.0Zn/Cu solder joints during the initial liquid aging stage and the rate of growth of the IMC layers is close to that of the IMC layer in Sn–3.5Ag/Cu solder joints. However, the phase transformation of the two phases into a Cu–Zn–Sn phase speeded up the growth of the IMC layer. The addition of In to Sn–3.5Ag solder alloy resulted in Cu₆(Sn_x,In_1?x)₅ phase which speeded up the growth of the IMC layer in Sn–3.5Ag–1.5In/Cu solder joint.     

Microstructure and properties of Ti–Co–Si ternary intermetallic alloys

Ti–Co–Si ternary intermetallic alloys with Ti₅Si₃ as the main reinforcing phase and intermetallic TiCo as the toughening matrix were fabricated by the laser-melting deposition (LMD) process. Microstructure of the intermetallic alloys was characterized by OM, SEM, XRD and EDS. High-temperature oxidation resistance of the alloys was evaluated by isothermal oxidation at 1173 K and metallic dry-sliding wear property was evaluated at room temperature. The effect of reinforcing phase Ti₅Si₃ content on hardness, oxidation and wear resistance of the alloys was investigated. Results indicate that microstructure of the alloys transforms from hypoeutectic to hypereutectic, while hardness and oxidation resistance increases with the increasing Ti₅Si₃ content. The alloys have good oxidation resistance at 1173 K and the oxidation kinetic curves are approximately parabolic. Wear resistance of the alloys is insensitive to the microstructure and is up to 15–19 times higher than the hardened tool steel 1.0%C–1.5%Cr under dry-sliding wear test conditions. The excellent wear resistance of alloys is attributed to the effective reinforcement of Ti₅Si₃ and the excellent toughness of the intermetallic TiCo.     

Effect of intermetallic compound thickness on shear strength of 25 μm diameter Cu-pillars

The chip-to-chip bonding technique using Cu-pillars bump is widely applied in 3D chip stacking technology. The excessive growth of intermetallic compounds (IMC) is expected to increase the propensity to brittle failure. Typically, the thickness of the IMC layer is used to indicate the risk of failure of solder joints. This study investigates the effects of Cu₆Sn₅ and Cu₃Sn compounds on the single-joint shear strength of Cu-pillar bumps 25 μm in diameter joined with Sn–3.5 wt%Ag–0.7 wt%Cu (SAC 357) alloy. The influence of heat treatment on the shear strength of the Cu-pillar structures is studied by applying two types of heat treatment: (i) a standard conveyor furnace process and (ii) isothermal holding at 240 °C for holding times up to 30 min. The change in mechanical strength was then established as a function of total IMC thickness through shear test experiments. Shear strength was measured with different displacement rates of 70, 130 and 500 μm s⁻¹. The shear height, from the tip of the shear tool to Cu pad substrate, varied from 11 μm to 16 μm in 1 μm steps. The variation in shear force values through the interfacial system, from pure Cu-pillar to solder ball, are discussed in relation to the failure shape observations. For low shearing heights (11–12 μm), mainly Cu material is probed and high shear force values are measured. For high shearing heights (15–16 μm), the probed materials are Cu₆Sn₅ and Sn and low shear force values are measured. For intermediate shearing heights (13–14 μm) the probed materials are Cu₃Sn and Cu₆Sn₅ and the Cu/Cu₃Sn interface seems to be as strong as the Cu₃Sn/Cu₆Sn₅ interface, despite the fact that almost all the Kirkendall voids are located in Cu/Cu₃Sn interface.     

Microstructural and mechanical analysis on Cu–Sn intermetallic micro-joints under isothermal condition

This study focuses on the mechanism of phase transformation from Cu₆Sn₅ into Cu₃Sn and the homogenization process in full intermetallics (IMCs) micro-joints, which were prepared by soldering the initial Cu/Sn/Cu structure through high temperature storage in vacuum environment as the Transient Liquid Phase (TLP) process. From the microstructural observation by electron backscatter diffraction (EBSD), a mixture of IMCs phases (Cu₆Sn₅ and Cu₃Sn) has been found to constitute the sandwich-structured Cu/IMCs/Cu joints. With the dwell time increasing at 533 K, there were two layers of Cu₃Sn emerging from both sides of copper substrates with the depletion of Cu₆Sn₅ layer, toward merging each other in the IMCs interlayer. Then the Cu₃Sn grains with various sizes became more homogenous columnar crystallites. Meanwhile, some equiaxial ultra-fine grains accompanied with the Kirkendall voids, were found only in adjacent to the electroplated copper. In addition, a specific type of micropillar with the size ∼5 μm × 5 μm × 12 μm fabricated by focus ion beam (FIB) was used to carry out the mechanical testing by Nano-indentation, which confirmed that this type of joint is mechanically robust, regardless of its porous Cu₃Sn IMC interconnection.