Phase equilibria of the Sn–Ag–Ni ternary system and interfacial reactions at the Sn–Ag/Ni joints

There are no previous phase equilibria studies of the Sn–Ag–Ni ternary system, even though the phase equilibria information is important for the electronic industry. The isothermal section of the Sn–Ag–Ni ternary system at 240 °C has been determined in this study both by experimental examination and thermodynamic calculation. Experimental results show no existence of ternary compounds in the Sn–Ag–Ni system, and all the constituent binary compounds have very limited solubilities of the ternary elements. The binary Ni₃Sn₂ phase is very stable and is in equilibrium with most of the phases, Ag₃Sn, ζ-Ag₄Sn, Ag, Ni₃Sn₄ and Ni₃Sn phases. A preliminary thermodynamic model of the ternary system is developed based on the models of the three binary constituent systems without introducing any ternary interaction parameters. This ternary thermodynamic model is used with a commercial software Pandat to calculate the Sn–Ag–Ni 240 °C isothermal section. The phase relationships determined by calculation are consistent with those determined experimentally. Besides phase equilibria determination, the interfacial reactions between the Sn–Ag alloys with Ni substrate are investigated at 240, 300 and 400 °C, respectively. It is found that the phase formations in the Sn–3.5wt%Ag/Ni couples are very similar to those in the Sn/Ni couples.     

Liquid-state interfacial reactions in Sn–Zn/Pd couples and phase equilibria of the Sn–Zn–Pd system at 260 °C

This study investigated the effects of Zn contents on the reaction products and microstructural evolution in the liquid/solid Sn–Zn/Pd interfacial reactions at 260 °C. A uniform Pd₂Zn₉ layer was formed at the Sn–9 wt.%Zn/Pd interface. The reaction phase transited from Pd₂Zn₉ to PdSn₄ when the Zn content decreased from 2 wt.% to 1 wt.%. The most striking feature is that the PdSn₄ growth was greatly suppressed with only 0.5 wt.% Zn addition in solders. Additionally, a drastic microstructural evolution was observed in the Sn–1.5 wt.%Zn/Pd reaction. The Pd₂Zn₉ layer was initially formed and then it was detached from the interface due to the decrease in the Zn content. Subsequently, the dominant phase changed to the PdSn₄ phase. Furthermore, a partial isothermal section in the Sn–Zn–Pd ternary system (less than 20 at.%Pd) at 260 °C was experimentally determined. The liquid apex of the liquid + PdSn₄ + Pd₂Zn₉ tie-triangle was located at Sn–2.7 at.%Zn–1.0 at.%Pd. The phase transition from Pd₂Zn₉ to PdSn₄ in the interfacial reactions was in good agreement with the phase equilibria relationship.     

Phase equilibria of Al–Fe–Sn ternary system

The isothermal sections of Al–Fe–Sn ternary system at 973 and 593 K were determined experimentally by the equilibriated alloy method using scanning electron microscopy coupled with energy-dispersive spectrometry and X-ray diffractometry. Experimental results show that no ternary compound is found on these two sections. The maximum solubility of Fe in the liquid phase is 1.6% (mole fraction) at 973 K and those of Fe and Al in the liquid phase are 0.6% and 5.1% (mole fraction) at 593 K, respectively. The maximum solubility of Sn in the Fe–Al compounds is 4.2% (mole fraction) at 973 K and 2.3% (mole fraction) at 593 K. All the Fe–Al compounds can be in equilibrium with the liquid phase.     

Phase equilibria and structural investigations of the general NiAs-type in the ternary system Ni–Sn–Te

The ternary system Ni–Sn–Te was investigated by means of light optical microscopy (LOM), powder X-ray diffraction (XRD), differential thermal analysis (DTA) and scanning electron microscopy (SEM) in combination with energy dispersive X-ray spectroscopy (EDX). Two isothermal sections at 600 and 800 °C were investigated experimentally. The two ternary compounds, Ni_5.78SnTe₂ (space group I4/mmm, Pearson symbol tI18) and Ni_3−xSnTe₂ (space group P6₃/mmc, Pearson symbol hP12), already known from literature, were confirmed, although Ni_3−xSnTe₂ was found only at 600 °C. At higher temperatures a continuous phase field of the general NiAs-type structure was discovered between NiTe_2−x and Ni₃Sn₂ HT. It ranges continuously from 34 to 63 at.% Ni, covering CdI₂-types, as well as Ni₂In-type domains; thus a continuous transition from the CdI₂ to Ni₂In type is confirmed, to the best of our knowledge, for the first time. Lattice parameter variations and the transition CdI₂–NiAs–Ni₂In in the ternary phase field were analysed.Furthermore, vertical sections at 10, 40, 55, 60 and 70 at.% Ni were determined. A liquidus surface projection and a reaction scheme of the system were constructed as well. Altogether, 17 invariant phase reactions, including 3 eutectic reactions, 2 peritectic reactions, 11 transition reactions and one maximum were discovered.     

Phase equilibria of Co−Mo−Zn ternary system

To experimentally determine the isothermal sections of Co−Mo−Zn ternary system at 600 and 450 °C, the equilibrated alloy and diffusion couple methods were adopted by using scanning electron microscopy coupled with energy-dispersive spectrometry, X-ray diffractometry and electron probe microanalysis. Experimental results show that there are six three-phase regions on the Co−Mo−Zn isothermal section at 600 °C and nine three-phase regions on the Co−Mo−Zn isothermal section at 450 °C. No ternary compound is found in these two isothermal sections. Both the maximum solubilities of Mo in the Co−Zn compounds (γ-Co₅Zn₂₁, γ₁-CoZn₇, γ₂-CoZn₁₃ and β₁-CoZn) and that of Zn in ε-Co₃Mo are no more than 1.5 at.%. The maximum solubilities of Zn in μ-Co₇Mo₆ are determined to be 2.1 at.% and 2.7 at.% at 600 and 450 °C, respectively. In addition, the maximum solubilities of Co in MoZn₇ and MoZn₂₂ are 0.5 at.% and 4.7 at.% at 450 °C, respectively.     

Phase equilibria in Ti–Ni–Pt ternary system

Phase equilibria in Ti–Ni–Pt ternary system have been experimentally determined through diffusion triple technique combined with alloy samples approach. Assisted with electron probe microanalysis (EPMA) and X-ray diffraction (XRD) techniques, isothermal sections at 1073 and 1173 K of this system were constructed and existence of ternary phase Ti₂(Ni,Pt)₃ was confirmed. In addition, binary compounds Ti₃Pt₅ and TiPt_3– were found to be stable at 1073 and 1173 K, and remarkable ternary solubility in some binary compounds was detected, e.g., solubility of Pt in TiNi can be up to about 36% (molar fraction) at 1073 K and 40% (molar fraction) at 1173 K. Furthermore, a ternary invariant transition reaction TiNi₃+Ti₃Pt₅→Ti₂(Ni,Pt)₃+TiPt₃₊ at a temperature between 1073 and 1173 K was deduced.     

Phase diagram calculation and predication of Au–Pd–Zr ternary system

Au-Pd-Zr ternary alloy phase diagram at 25℃ was calculated by Panda phase calculation software,and the thermodynamic data were based on three binary alloy phase diagrams:Pd-Au,Au-Zr,and Pd-Zr.Five composition points in the ternary phase diagram were selected to predict the precipitation order.One(32Au-32Pd-36Zr) of the five composition points in ternary phase diagram was chosen to verify the correctness of the phase diagram calculation and the precipitation order by scanning electron microscopy(SEM),energy dispersive spectroscopy(EDS),and X-ray diffraction(XRD).The unknown phase in XRD patterns was predicated by EDS and materials studio(MS) software.The experimental results show that there are seven key ternary reactions points and 17 phase regions in all isothermal sections at 25℃.The thermodynamic process and microstructure for the alloy phase can be described in order according to the vertical section in phase diagram.The phase compositions of the chosen one point are consistent with calculation prediction.The unknown phase in XRD patterns should be Zr_2AuPd by the first principle X-ray simulation.     

Phase equilibria in the Al–Mo–Si system

The ternary Al–Mo–Si phase diagram was investigated by a combination of optical microscopy, powder X-ray diffraction (XRD), differential thermal analysis (DTA), electron probe microanalysis (EPMA) and scanning electron microscopy (SEM). Ternary phase equilibria were investigated within two isothermal sections at 600 °C for the Mo-poor part and 1400 °C for the Mo-rich part of the phase diagram. The solubility ranges of several phases including MoSi₂ (C11_b) as well as Mo(Si,Al)₂ with C40 and C54 structure were determined. The binary high temperature phase Al₄Mo was found to be stabilized at 600 °C by addition of Si. DTA was used to identify 9 invariant reactions and thus constructing a ternary reaction scheme (Scheil diagram) in the whole composition range. A liquidus surface projection was constructed on basis of the reaction scheme in combination with data for primary crystallization from as-cast samples determined by SEM measurements.     

Phase equilibria in the system Al–Co–Si

The Al–Co–Si system was studied for three isothermal sections at 600 °C (equilibria with Si), 800 °C (alloys up to 50 at.% Co) and 900 °C (alloys with more than 50 at.% Co). A total number of seven ternary compounds were characterized in the ternary system and the homogeneity ranges of the various ternary solid solutions of binary Co–Al and Co–Si compounds were studied. X-ray powder diffraction and optical microscopy was used for initial sample characterization and electron probe microanalysis of the annealed samples was used to determine the phase compositions within the ternary system. Lattice parameters have been determined for all ternary compounds and the change of lattice parameters with the composition is given for the solid solution phases.     

Phase equilibria in the system Au–Cu–Si and structural characterization of the new compound Au5±xCu2±xSi

The ternary Au–Cu–Si system was investigated by means of powder X-ray diffraction (XRD) for phase identification, scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX) for microstructures and chemical compositions, light optical microscopy (LOM), and differential thermal analysis (DTA) for the determination of thermal effects. Three isothermal sections were constructed at 250 °C, 400 °C and 650 °C. A new ternary compound τ, Au_5±xCu_2±xSi, was identified and its crystal structure was determined by means of single crystal X-ray diffraction. It adopts a new crystal structure type in space group Pnma, Pearson symbol oP32 and shows a composition range between Au_5.6Cu_1.4Si and Au_4.4Cu_2.6Si at 250 °C. Lattice parameters were found to vary between a = 9.64–9.50 Å, b = 7.61–7.64 Å and c = 6.90–6.89 Å from the Au-rich to the Au-poor composition limit. Three vertical sections, at 10 and 30 at.% Si and at 10 at.% Cu, were constructed based on DTA data and four invariant ternary phase reactions were identified. A partial ternary reaction scheme (Scheil diagram) and a partial liquidus projection are given.     

Phase equilibria in the Ti–Al binary system

New experimental results on the phase equilibria between the β-Ti (A2), α-Ti (A3), α₂-Ti₃Al (D0₁₉) and the γ-TiAl (L1₀) phases in the Ti–Al system using specimens with low levels of oxygen are presented. The results obtained on the α/γ and the α₂/γ equilibria are in good agreement with the previous experimental and calculated phase boundaries, while the ones obtained on the α/β equilibrium deviate significantly from the previously proposed phase diagram. It is confirmed that the β phase field extends to higher aluminum contents and that the width of the α+β two-phase region is very narrow, less than 1 at.% Al. The presence of the A2/B2 order–disorder transition in the β phase is also confirmed by a combination of differential scanning calorimetric (DSC) analysis and extrapolation of ordering phase boundaries from the Ti–Al–X (X=Cr, Fe) ternary systems. A thermodynamic analysis has been carried out taking into account the ordering configurations in the β-Ti (A2)/β₂-TiAl (B2), f.c.c.-Al (A1)/γ-TiAl (L1₀) and α-Ti (A3)/α₂-Ti₃Al (D0₁₉) equilibria. It is proposed that the anomalous α/β equilibrium is due to the A2/B2 ordering reaction.     

Phase equilibria and structural investigations in the system Al–Fe–Si

The Al–Fe–Si system was studied for an isothermal section at 800 °C in the Al-rich part and at 900 °C in the Fe-rich part, and for half a dozen vertical sections at 27, 35, 40, 50 and 60 at.% Fe and 5 at.% Al. Optical microscopy and powder X-ray diffraction (XRD) was used for initial sample characterization, and Electron Probe Microanalysis (EPMA) and Scanning Electron Microscopy (SEM) of the annealed samples was used to determine the exact phase compositions. Thermal reactions were studied by Differential Thermal Analysis (DTA). Our experimental results are generally in good agreement with the most recent phase diagram versions of the system Al–Fe–Si. A new ternary high-temperature phase τ₁₂ (cF96, NiTi₂-type) with the composition Al₄₈Fe₃₆Si₁₆ was discovered and was structurally characterized by means of single-crystal and powder XRD. The variation of the lattice parameters of the triclinic phase τ₁ with the composition Al_2+xFe₃Si_3?x (?0.3 < x < 1.3) was studied in detail. For the binary phase FeSi₂ only small solubility of Al was found in the low-temperature modification LT-FeSi₂ (ζ_β) but significant solubility in the high-temperature modification HT-FeSi₂ (ζ_α) (8.5 at.% Al). It was found that the high-temperature modification of FeSi₂ is stabilized down to much lower temperature in the ternary, confirming earlier literature suggestions on this issue. DTA results in four selected vertical sections were compared with calculated sections based on a recent CALPHAD assessment. The deviations of liquidus values are significant suggesting the need for improvement of the thermodynamic models.     

Experimental investigation of phase equilibria and microstructure in the Co–Ti–V ternary system

The phase equilibria in the Co–Ti–V ternary system have been investigated by means of optical microscopy (OM), electron probe microanalyzer (EPMA), differential scanning calorimetry (DSC), field emission scanning electron microscope (SEM) and X-ray diffraction (XRD). The mechanical properties were measured by compressive tests. Four isothermal sections of the Co–Ti–V ternary system at 800 °C, 1000 °C, 1100 °C and 1200 °C were experimentally established. The results show that: (1) there is no ternary compound in this system; (2) the CoTi₂ phase and Co₃Ti phase stabilized by the V addition; (3) a large solubility of Ti in the σ-Co₂V₃ phase was observed at all isothermal sections of 800 °C, 1000 °C, 1100 °C and 1200 °C; (4) The alloy with the distribution of fine cuboidal Co₃Ti (L1₂) in (αCo) phase was observed. (5) The compressive strength of Co_77.29Ti_5.83V_16.88 (at.%) alloy at room temperature was measured to be about 1985 MPa. The newly determined phase equilibria in this system will provide useful information for the development of Co-based and Ti-based materials.     

Phase equilibria and mechanical properties of the Ir–W–Al system

Phase equilibria in the Ir–W, Ir–Al and Ir–W–Al systems at temperatures between 1100 °C and 1600 °C were experimentally investigated using diffusion couples and two- or three-phase alloys, and the mechanical properties of γ′ (L1₂) strengthened Ir–W–Al alloys were examined by hardness and compression tests at room and elevated temperatures. The phase boundaries between the γ(A1)/ε′(D0₁₉), ε′/ε(A3) and ε/ε″(B19) in the Ir–W system at 1400 °C–1600 °C and those between the γ/β(B2) and β/Al_2.7Ir in the Ir–Al system at 1100 °C–1400 °C were determined. The phase diagrams in the Ir-rich corner of the Ir–W–Al ternary system at 1300 °C and 1400 °C were also determined. The existence of the γ′ phase of the Ir₃(W,Al) ternary compound was confirmed, and this system was found to consist of the γ, γ′, ε, ε′ and β phases in the Ir-rich portion. It was also found from hardness and compression tests up to 1200 °C that Ir–Al–W alloys having the γ + γ′ structure with a small lattice misfit show high hardness and strength at room and high temperatures.     

Phase equilibria of Zn-Al-Ti ternary system at 450 and 600 °C

The phase relationships in the Zn-Al-Ti system at 450 and 600 °C were experimentally determined using equilibrated alloys method. The specimens were investigated by means of scanning electron microscopy coupled with energy dispersive spectroscopy and X-ray diffractometry. Eleven and eight three-phase regions are confirmed in the 450 and 600 °C isothermal sections, respectively. The Ti₂Al₅ which only exists at high temperature (990-1199.4 °C) in Ti-Al binary system is confirmed in two isothermal sections due to the dissolution of zinc. The T phase is confirmed as a ternary compound rather than an extension phase of TiZn₃ at 450 °C. The T₂ phase is a new ternary phase stable at 450 and 600 °C in Zn-Al-Ti ternary system.     

Phase equilibria and thermodynamic calculation of the Co–Ta binary system

Experimental investigation and thermodynamic evaluation of the Co–Ta binary phase diagram was carried out. Equilibrium compositions obtained in two-phase alloys and diffusion couples were measured by electron probe microanalyzer (EPMA). A very narrow λ₃(C36) + λ₂(C15) two-phase region is confirmed to be present around 26.5 at.% Ta at temperatures between 950 °C and 1448 °C. Equilibrium relationships above 1500 °C among the liquid, Laves (λ₁(C14), λ₂ and λ₃, whose stoichiometry is described by Co₂Ta), μ(D8_b) and CoTa₂(C16) phases were investigated by microstructural examination in as-cast Co-(24–60 at.%)Ta alloys. The solvus temperature of the γ′ Co₃Ta (L1₂) phase precipitated in the 5.8 at.%Ta γ(Co) and the peritectoid temperature of the Co₇Ta₂ phase in an 8.5 at.%Ta alloy were determined to be 1013 °C and 1033 °C, respectively, by differential scanning calorimeter (DSC). Fine precipitates of the γ′ phase precipitated in the γ (A1) matrix were observed by transmission electron microscope (TEM). Analyzing the present experimental results synthetically, the γ′ Co₃Ta phase was identified to be a metastable phase, of which the γ/γ′ transition temperature of the stoichiometric Co₃Ta alloy was estimated to be 2000 °C. Thermodynamic assessment of the Co–Ta binary system was carried out based on the present results as well as on experimental data in the literature. Calculated results of not only stable but also metastable equilibria were found to be in good agreement with the revised phase diagram. The evaluated stability of the metastable γ′ Co₃Ta coincides with the enthalpy of formation (ΔH(γ'Co₃Ta) = −23.44 kJ/mol) calculated by the ab initio method.     

Phase equilibria in the Fe-Mo-Ti ternary system at 1000 °C

An isothermal section of the Fe-Mo-Ti ternary system at 1000 °C has been constructed using data acquired from a series of seven alloys. The limit of solubility of Fe in the continuous A2 phase field between Ti and Mo has been determined, as have the extents to which Mo may be accommodated in the B2 TiFe phase, and Ti in the D8₅ Fe₇Mo₆ phase. The B2, D8₅ and C14 Fe₂ (Ti, Mo) intermetallics were found to have limited tolerance for non-stoichiometric compositions. The positions of the A2 + B2 + C14 and A2 + C14 + D8₅ three-phase fields were determined, along with the extents of the A2 + B2, A2 + D8₅, A2 + C14, C14 + B2 and C14 + D8₅ two-phase fields. No ternary phases were observed in any of the alloys studied.