Thermodynamics and phase relationships of transition metal-sulfur systems: IV. thermodynamic properties of the Ni-S liquid phase and the calculation of the Ni-S phase diagram

An associated solution model is applied to describe the thermodyanmic properties of the liquid Ni-S phase. This model assumes the existence of ‘NiS’ (l) species in the liquid in addition to Ni(l) and S(l). With two solution parameters for the binaries Ni-‘NiS’ and ‘NiS’-S, this model is able to describe the thermodynamic behavior of the liquid phase over a wide range of temperature and composition. Using this model for the liquid phase, a statistical thermodynamic model for the monosulfide phase and empirical thermodynamic equations for β₁-Ni₃S₂ and β₂-Ni₄S₃, the Ni-S phase diagram is calculated. The calculated diagram is in excellent agreement with the available experimental data with the exception that the eutectic composition for the equilibrium L₁ + δ + η and those of the two liquids for the equilibriumL ₁ + L ₂ + η differ from the experimental data by more than 2 at. pct S. Formerly Post-Doctorl Research Associate, University of Wisconsin-Milwaukee is now Lecturer, Department of Metallurgical Engineering, Indian Institute of Technology, Kanpur, India     

Determination of the Phase Equilibria in the Mn-Sn-Zn System at 500 °C

The isothermal section of the Mn-Sn-Zn system at 500 °C was determined with 20 alloys. The alloys were prepared by melting the pure elements in evacuated quartz capsules. The alloy samples were examined by means of X-ray diffraction (XRD) and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy. A new ternary phase Mn₄Zn₈Sn (λ) was found to have a bcc structure with a lattice parameter a = 0.92508 (5) nm. Its composition range spans 25 to 35 at. pct Mn, 4 to 8 at. pct Sn, and 55 to 70 at. pct Zn. The Zn is substituted for Mn in Mn₃Sn, Mn₂Sn, and Mn₃Sn₂. The solubility of Zn in Mn₃Sn, Mn₂Sn, and Mn₃Sn₂ was measured to be about 17, 12, and 4 at. pct, respectively. The phase boundaries of the liquid and β-Mn phases were well established. The following 3 three-phase equilibria were well determined: (1) β-Mn + ε-MnZn₃ + Mn₃Sn, (2) λ + Mn₃Sn + Mn₂Sn, and (3) L + λ + Mn₂Sn. The additional 5 three-phase equilibria, which are ε-MnZn₃ + λ + Mn₃Sn, ε ₁-MnZn₃ + ε-MnZn₃ + λ, ε ₁-MnZn₃ + λ + L, Mn₂Sn + L + MnSn₂, and Mn₃Sn₂ + MnSn₂ + Mn₂Sn, were deduced and shown with dashed lines in the present isothermal section.     

Thermal properties and interfacial reaction between the Sn-9Zn-<Emphasis Type="Italic">x</Emphasis>Ag lead-free solders and Cu substrate

The thermal properties and interfacial reaction between the Sn-9Zn-xAg lead-free solders and Cu substrate, such as solidus and liquidus temperatures, heat of fusion, intermetallic compounds, and adhesion strength, have been investigated. Two endothermic peaks appear in the DSC curve when the Ag content in the Sn-9Zn-xAg solder alloy is above 1.5 wt pct. The solidus temperatures of the Sn-9Zn-xAg solder alloys are around 197 °C, but the liquidus temperatures decrease from 225.3 °C to 221.7 °C and 223.6 °C with increasing the Ag content in the solder alloy from 1.5 to 2.5 and 3.5 wt pct, respectively. Three intermetallic compounds, namely, Cu₆Sn₅, Cu₅Zn₈, and Ag₃Sn are observed at the Sn-9Zn-xAg/Cu interface. The Cu₅Zn₈ is formed close to the Cu substrate, Ag₃Sn is adjacent to it, and Cu₆Sn₅ is nearest the Sn-9Zn-1.5Ag solder alloys. A bi-structural Cu₆Sn₅ layer with hexagonal η-Cu₆Sn₅ and monoclinic η′-Cu₆Sn₅ is found at the Sn-9Zn-1.5Ag/Cu interface due to Ag dissolution. A maximum adhesion strength of 10.7±0.8 MPa is obtained at the Sn-9Zn-2.5Ag/Cu interface as soldered at 250 °C for 30 seconds.     

Isothermal section of the ternary Sn-Cu-Ni system and interfacial reactions in the Sn-Cu/Ni couples at 800 °C

The isothermal section of the Sn-Cu-Ni system at 800 °C has been experimentally determined. There is no ternary compound. A solid solution with a very wide compositional range, the γ phase is formed between the Ni₃Sn(H) phase and Cu₄Sn(H) phase; however, both of these two binary phases are not stable at 800 °C. The binary Ni₃Sn₂ phase also has extensive ternary solubility. The homogeneity ranges of both the γ and Ni₃Sn₂ phases are very large in parallel to the Cu-Ni side, but relatively narrow along the Sn direction. This phenomenon indicates that Cu and Ni are exchangeable in both phases. Three kinds of reaction couples, Sn-55 at. pct Cu/Ni, Sn-65 at. pct Cu/Ni, and Sn-75 at. pct Cu/Ni, were prepared and reacted at 800 °C for 5 to 20 minutes. The reaction paths are liquid/Ni₃Sn₂/γ/Ni₃Sn(L)/Ni for the Sn-55 at. pct Cu/Ni and Sn-65 at. pct Cu/Ni couples, and the reaction path is liquid/γ/Ni₃Sn(L)/Ni for the Sn-75 at. pct Ni couples.     

The growth of Cu-Sn intermetallics at a pretinned copper-solder interface

This article reports a comparative study of the formation and growth of intermetallic phases at the interface of Cu wetted with a thick solder joint or a thin, pretinned solder layer. The η phase (Cu₆Sn₅) forms when Cu is wet with eutectic solder at temperatures below 400 °C. The intermetallic layer is essentially unaffected by aging at 70 °C for as long as 13 weeks. On aging a eutectic joint at 170 °C, the η-phase intermetallic layer thickens and ε phase (Cu₃Sn) nucleates at the Cu/intermetallic interface and grows to a thickness comparable to that of the η phase, while a Pb-rich boundary layer forms in the solder. The aging behavior of a thin, pretinned eutectic layer is qualitatively different. At 170 °C, the Sn in the eutectic is rapidly consumed to form η-phase intermetallic, which converts to ε phase. The residual Pb withdraws into isolated islands, and the solderability of the surface deteriorates. When the pretinned layer is Pb-rich (95Pb-5Sn), the Sn in the layer is also rapidly converted into η phase, in the form of dendrites penetrating from the intermetallic at the Cu interface and discrete precipitates in the bulk. How ever, the development of the intermetallic largely ceases when the Sn is consumed; ε phase does not form, and the residual Pb remains as an essentially continuous layer, preserving the solderability of the sample. These observations are interpreted in light of the Cu-Sn and Pb-Sn phase diagrams, the temperature of initial wetting, and the relative diffusivities of Cu and Sn in the solder and intermetallic phases. A.J. SUNWOO, Formerly with the Lawrence Berkeley Laboratory, Berkeley, CA,     

Analysis of low-temperature intermetallic growth in copper-tin diffusion couples

A multiphase diffusion model was constructed and used to analyze the growth of the ε- and η-phase intermetallic layers at a plane Cu-Sn interface in a semi-infinite diffusion couple. Experimental measurements of intermetallic layer growth were used to compute the interdiffusivities in theε andη phases and the positions of the interfaces as a function of time. The results suggest that interdiffusion in the ε phase(≈D _ε) is well fit by an Arrhenius expression with D₀ = 5.48 × 10⁻⁹ m²/s andQ = 61.9 kJ/mole, while that in the η phase (≈D_η) has D₀ = 1.84 × 10⁻⁹ m²/s andQ = 53.9 kJ/mole. These values are in reasonable numerical agreement with previous results. The higher interdiffusivity in theη phase has the consequence that theη phase predominates in the intermetallic bilayer. However, the lower activation energy for interdiffusion in theη phase has the result that theε phase fills an increasing fraction of the intermetallic layer at higher temperature: at 20 °C, the predicted ε-phase thickness is ≈10 pct of that ofη, while at 200 °C, its thickness is 66 pct of that ofη. In the absence of a strong Kirkendall effect, the original Cu-Sn interface is located within theη-phase layer after diffusion. It lies near the midpoint of theη-phase layer at higher temperature (220 °C) and, hence, appears to shift toward the Sn side of the couple. The results are compared to experimental observations on intermetallic growth at solder-Cu interfaces.     

Determination of the isothermal sections of the Al-Ni-Si ternary system at 750 °C and 850 °C

The phase equilibria of the Al-Ni-Si ternary system at 850 °C and 750 °C have been investigated using scanning electron microscopy (SEM) and electron-probe microanalysis (EPMA). Isothermal sections at 850 °C and 750 °C were constructed based on experimental data from 53 alloys heat treated at 850 °C for 1200 hours and at 750 °C for 1440 hours, respectively. The phase equilibria among the following intermetallics and solid-solution phases are described: Ll₂-Ni₃(Al,Si), B2-NiAl, Ni₅Si₂, δ-Ni₂Si, ϑ-Ni₂Si(τ ₄), Ni₃Si₂, NiSi, NiSi₂, Ni₂Al₃, NiAl₃, Ni₂AlSi(τ ₂), Ni₃Al₆Si(τ ₃), Ni₁₆AlSi₉(τ ₅), the fcc solid solution, and the diamond (Si) phase. In addition, a phase, temporarily designated as Ni₅(Al,Si)₃(τ ₆), was observed for the first time at both 750 °C and 850 °C. This phase is probably the stabilization of Ni₅Al₃ by Si to higher temperatures than the binary Ni₅Al₃, which is only stable at <∼700 °C.     

INCOLOY 908, a low coefficient of expansion alloy for high-Strength cryogenic applications: Part I. Physical metallurgy

INCOLOY 908 is a low coefficient of thermal expansion (COE) iron-nickel base superalloy that was developed jointly by The Massachusetts Institute of Technology and the International Nickel Company for cryogenic service. The alloy is stable against phase transformation during prolonged thermal treatments and has a COE compatible with that of Nb₃Sn. These properties make the material ideal for use as a structural component in superconducting magnets using Nb₃Sn. The evolution of microstructure has been studied as a function of time at temperature over the temperature range of 650 °C to 900 °C for times between 50 and 200 hours. A detailed analysis of precipitated phases has been conducted using X-ray diffraction (XRD), transmission electron microscopy (TEM), and analytical scanning and scanning transmission electron microscopy (STEM) techniques. The primary strengthening phase has been found to be γ’, Ni₃(Al, Ti). INCOLOY 908 is stable against overaging, which is defined as the transformation of γ’ to η, Ni₃Ti, for times to 100 hours at temperatures up to 750 °C. Upon overaging, the strengthening phase transforms to η. A new phase,H _x, has been identified and characterized.     

Thermodynamics and Phase Relationships of Transition Metal-Sulfur Systems: II. The Nickel-Sulfur System

The thermodynamic activity of sulfur in the β₁-Ni₃S₂, β₂-Ni₄S₃, γ-Ni₆S₅ and δ-NiS phases was determined as a function of composition over the temperature interval, 823 to 1023 K, using a gas equilibration technique. The data obtained in the present study as well as those reported in the literature are evaluated to yield thermodynamic equations of state for all the intermediate phases. Several forms of the Ni-S phase diagram are presented. The previously reported “Ni₃S₂” phase was found to consist of two phases designated as β₁-Ni₃S₂ and β₂-Ni₄S₃ in the present study.     

Effect of retrogression and reaging treatments on the microstructure of Ai-7075-T651

The effect of the retrogression and reaging treatments (RRA) on the microstructure of Al-7075 in the T651 temper, both in the matrix and on grain boundaries, was studied using transmission electron microscopy. The processes occurring in the matrix during the retrogression treatment are principally the dissolution of small particles of the η’ transition phase, transformation to η of the larger particles of η’, coarsening of the three commonly observed variants of the η phase precipitates (η₁, η₂, and η₄), and precipitation of new η phase particles, particularly the η₁ variant. The main process occurring during the reaging treatment is either growth of partially dissolved η’ particles or precipitation of the η’ phase. These lead to a microstructure containing many fine η’ precipitates and some larger η₁ and η₂ particles with a smaller amount of coarse η₄ particles, resulting in a broad particle size distribution. The high strength of the 7075 alloy in the RRA temper is believed to arise from the relatively high overall concentration of particles in this dispersion. The retrogression treatment produces rapid initial coarsening of the grain boundary particles, which are primarily η phase precipitates, resulting in an increase in their volume per unit grain boundary area,V _A . The beneficial effect of the RRA treatment on the susceptibility of 7075-T651 to SCC is believed to be due, at least partially, to the increased value ofV _A produced by the RRA treatment. Formerly Visiting Assistant Research Engineer in the Department of Materials Science and Engineering, University of California, Los Angeles, CA     

Constitution of the Lead-Tin-Strontium System up to 36 Atomic Percent Sr

The constitution of the Pb-Sn-Sr system from the Pb-Sn binary up to 36 at. pct Sr was determined by differential thermal analysis, metallography, microprobe analysis, and X-ray diffraction. Pb₃Sr forms a continuous series of solid solutions with Sn₃Sr, and is referred to here as the8 phase. Sn₄Sr was the only other intermetallic phase found and is designated here as γ. A eutectic-like trough is formed between (Pb) and δ. It originates at 1.0 at. pct Sr and 324.5 °C (the (Pb)/Pb₃Sr eutectic) and falls monotonically to ~75 at. pct Pb, 24.5 at. pct Sn, and 0.45 at. pct Sr at 283 °C. At 283 °C, a Class II, four-phase reaction occurs: L + δ→ (Pb) + γ. A eutectic-like trough between (Pb) and γ falls from the four-phase plane at 283 °C to the ternary eutectic at ~26 at. pct Pb, ~74 at. pct Sn and <0.3 at. pct Sr at 182 °C. The ternary eutectic reaction is L → (Pb) + (Sn) + γ.     

Kinetics of spreading in initial stages in metallic systems with different types of interaction between components. IV. Effect of chemical reaction on the kinetics of spreading in tin—Iron group metal systems

A droplet flowing over onto a plate introduced from above has been used to study the kinetics of spreading and to describe the observable characteristics of spreading of tin on iron, cobalt, nickel, and the intermetallic compounds Ni₃Sn, Ni₃Sn₂ under a vacuum of (2–4)·10⁻³ Pa at 400–1000°C, droplet mass 0.01–0.06 g. We show by a formal kinetic analysis of experimental data that in the low-temperature range (400–500°C) the kinetic regime dominates, and in the high-temperature range (600–1000°C) the inertial—kinetic regime dominates. In spreading of tin on iron, cobalt, nickel, and the intermetallic compounds Ni₃Sn and Ni₃Sn₂, the nature of the interaction corresponds to the phase equilibrium in the studied systems. The results for the kinetics of spreading of tin on nickel and the intermetallic compound Ni₃Sn showed that spreading of the main bulk is preceded by spreading of a precursor film. Deceased. Institute for Problems of Materials Science, Ukraine National Academy of Sciences, Kiev. Translated from Poroshkovaya Metallurgiya, Nos. 7–8(402), pp. 65–72, July–August, 1998.     

Precipitation of the δ-Ni3Nb phase in two nickel base superalloys

The precipitation of the equilibrium δ-Ni₃Nb phase has been studied in two niobium bearing nickel base superalloys—INCONEL 718 and INCONEL* 625—both of which are hardenable by the precipitation of the metastableγ″-Ni₃Nb phase. The morphology and the distribution of precipitates have been examined and the crystallographic orientation relationship between the austenite and theδ phases has been determined. The nucleation of theδ phase at stacking faults within pre-existing δ" precipitates has been discussed.     

Thermodynamic description of Sn-Y and Mg-Sn-Y systems

The thermodynamic optimization of the Sn-Y and Mg-Sn-Y systems was critically carried out by means of the CALPHAD（CALculation of PHAse Diagram） technique. In the Sn-Y system, the solution phases（liquid, bcc, bct and hcp） were described by the substitutional solution model. The compound Sn3Y5, which has a homogeneity range, was treated as the formula（Sn, Y）3（Sn, Y）2Y3 by a three-sublattice model in accordance with the site occupancies. In the Mg-Sn-Y system, the liquid phase was treated as the formula（Mg, Sn, Y, Mg2Sn） using an associated solution model, and bcc, bct and hcp were treated as the formula（Mg, Sn, Y）. The compound Sn3Y5 was treated as the formula（Sn, Y, Mg）3（Sn, Y, Mg）2Y3. The ternary compound MgSnY was treated as stoichiometric compound. A set of self-consistent thermodynamic parameters of the Mg-Sn-Y system was obtained. The projection of the liquidus surfaces and the reaction scheme of the Mg-Sn-Y system were predicted.     

Reaction of Tungsten with Liquid Co ― Sn Alloys

The solubility of tungsten in Co Sn melts and the growth kinetics of a W₆Co₇ phase layer at the tungsten melt interface were studied at 1200°C. The liquid alloys composition in the three-phase equilibrium W W₆Co₇ melt was established as (at. fraction) 0.51 Co, 0.49 Sn, 2.3·10^–3 W. The solubility of tungsten in the investigated range of melt compositions is well represented by the equation lgx _W = –0.964-3.420x _Sn, where x _W and x _Sn are atomic fractions of the elements in the melt. The calculated thermodynamic properties can be used for the analysis of other systems which include cobalt and tungsten.     

Thermodynamic study and the phase diagram of the Mg-Sn system

By means of concentration cells of the following type, Mg (l)MgCl2 in (LiCl-KCl)_eut (l)Mg-Sn (1), the partial thermodynamic data of Mg in Mg-Sn liquid solutions have been obtained in the composition range of 0.1 ≤X _Mg ≤ 0.75 and at temperatures from 950 to 1100 K. These values are compared with thermodynamic data reported in the literature and used for the evaluation to obtain a complete set of thermodynamic functions for phase diagram calculations and for further interpretation by the associate model. This model, which accepts the existence of ‘Mg₂Sn as-sociates’ in the liquid alloys, enables calculations of viscosity by Kucharski’s method corre-lating properly with experimental data. Mutual correlations between thermodynamic properties, physical properties, structure, and the phase diagram of the Mg-Sn system were shown to in-dicate a maximum chemical short-range order close to the composition Mg2Sn.