Comments and reconciliation of the Ni–Bi‐system thermodynamic reassessments

The binary Ni‐Bi alloys as well as multicomponent materials comprising systems like Ni‐Bi‐Sn, Ni‐Bi‐Sb etc. are recently considered as prospective for design of lead‐free solders. For that reason various authors focused their attention to the Ni‐Bi system thermodynamics. The studies identified five phases in the above system. Two of them (i.e., (Ni) and liquid), were treated as disordered substitutional solutions. The phase NiBi₃ is stoichiometric and a standard two‐sublattice model was repeatedly applied to describe its Gibbs free energy, while for the nonstoichiometric NiBi phase, a three‐sublattice model was retained. The pure bismuth phase ((Bi)) is stoichiometric as well. The results are discussed and compared to literature thermochemical and topological data. In liquid state, strong repulsions between nickel and bismuth atoms are anticipated in the nickel rich‐side, but no data about a liquid phase miscibility gap is available yet. Therefore, the stability of the liquid phase has to be reassured, in spite of positive deviations from ideal behaviour. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Application of diffusion couple technique for the determination of the Ti‐Bi‐Sn phase diagram

The system Ti‐Bi‐Sn has been investigated by solid/liquid diffusion couples at 500, 600, 700 and 800°C. A non‐negligible solubility of Sn into solid Bi is found. Diffusion layers of the recently revealed ternary compound Ti₃BiSn have been observed, thus its existence has been confirmed. Data about the homogeneity ranges of the binary end‐system compounds have been obtained. The assessed growth constants of the diffusion layers are comprised in the interval 10^‐12 –10^‐14 m².s^‐1. The phases participating in the hypothetical ternary eutectic reaction, probably are: (Bi), (Sn), Liquid and Ti₂Sn₃. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural Studies on Ni75(SnSi)25 and Ni75(SnBi)25 Alloys

Ternary alloys on the quasi-binary system Ni₃Sn(r) in equilibrium condition. It has been observed that these phases undergo transformations at high temperatures but upto 500 °C room temperature modifications are stable. The two phases do not have any appreciable solid solubility in either of them. The phase Ni₃Si(r) crystallizes in to Cu₃Au (Li₂) structure where as Ni₃Sn(r) is based on c.p.h. structure with a = 5.305 A°, c = 4.254 A°. No new ternary phase has been detected in Ni₃Sn Ni₃Si section. The investigated alloys of the Ni Sn Bi system contain 75 at.% Ni. All the ternary alloys show simultaneous occurrence of three phases, namely Ni₃Sn(r), NiBi and Ni(Sn) in equilibrium state. The phase NiBi has NiAs(B8) type of structure. Due to non-existence of isostructural phases in the two binary systems (Ni Sn and Ni Bi), single solid solution phases are not formed. Widely differing atomic sizes of nickel and bismuth atoms restrict the formation of solid solution of bismuth in nickel in contrast to Ni(Sn) where atomic size factor is favourable.     

Effect of Bi‐content on hardness and micro‐creep behavior of Sn‐3.5Ag rapidly solidified alloy

In the present paper, the influence of 1, 3, 5 and 10 % Bi (weight %) as ternary additions on structure, melting and mechanical properties of rapidly solidified Sn‐3.5Ag alloy has been investigated. The effect of Bi was discussed based on the experimental results. The experimental results showed that the alloys of Sn‐3.5Ag, Sn‐3.5Ag‐1Bi and Sn‐3.5Ag‐3Bi are composed of two phases; Ag₃Sn IMC embedded in Sn matrix phase, which indicated that the solubility of Bi phase in Sn‐matrix was extended to 3 % as a result of rapid solidification. Bi precipitation in Sn matrix was only observed in Sn‐3.5Ag‐5Bi and Sn‐3.5Ag‐10Bi alloys. Also, addition of Bi decreased continuously the melting point of the eutectic Sn‐3.5Ag alloy to 202.6 °C at 10 % Bi. Vickers hardness of Sn‐3.5Ag rapidly solidified alloy increased with increasing Bi content up to 3 % due to supersaturated solid solution strengthening hardening mechanism of Bi phase in Sn matrix, while the alloys contain 5 and 10 % Bi exhibited lower values of Vickers hardness. The lower values can be attributed to the precipitation of Bi as a secondary phase which may form strained regions due to the embrittlement of Bi atom. In addition, the effect of Bi addition on the micro‐creep behavior of Sn‐3.5Ag alloy as well as the creep rate have been described and has been calculated at room temperature. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Diffusion couple studies of the Ti‐Bi‐Zn system

The system Ti‐Bi‐Zn has been investigated using diffusion couples consisting of solid Ti and liquid (Bi+Zn) phase. The diffusion paths at 400, 500, 700 and 800 °C have been traced by means of electron microprobe analyses. The growth constants of the diffusion layers are roughly assessed. The phase diagram data obtained in this investigation are compared with previous studies of equilibrated alloys. The existence of the ternary compound TiBiZn has been confirmed. The formation of another phase with approximate formulae Ti₄Bi₃Zn to Ti₉Bi₇Zn₄ has been observed at high temperatures. The latter compound as well as the ternary extension of the Ti_XBi_Y (X ≈ 5, Y ≈ 6) phase react easily with air. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Glass formation of Ti–Ni–Sn ternary alloys correlated with TiNi–Ti3Sn pseudo binary eutectics

Glass-forming ability (GFA) of Ti–Ni–Sn ternary alloys was investigated. Applying recent models based on atomic size ratio and efficient packing, the composition favoring the glass formation is predicted. Our experiments indicate that the optimized glass-forming composition is located at Ti₅₆Ni₃₈Sn₆, with the critical thickness of complete glass formation approaching 100 μm for the melt-spun ribbons. The Ti₅₆Ni₃₈Sn₆ metallic glass exhibits a sizable supercooled liquid region (ΔT_x) of about 35 K and a reduced glass transition temperature (T_rg) of 0.52. We demonstrate that the glass formation of the Ti₅₆Ni₃₈Sn₆ alloy correlates with the (L → TiNi + Ti₃Sn) pseudo binary eutectic reaction in Ti–Ni–Sn ternary system, which has an invariant temperature and composition at ～1370 K and ～Ti₅₈Ni₃₄Sn₈, respectively. With respect to Sn-free Ti–Ni binary alloys, the GFA is enhanced for the Ti–Ni–Sn ternary alloys, but the improvement is limited possibly due to changes in the crystalline phases competing with glass formation.     

Effect of indium content and rapid solidification on microhardness and micro‐creep of Sn‐Zn eutectic lead free solder alloy

The Sn‐Zn alloys have been considered as lead‐free solders. In this paper, the effect of 0.0, 0.5, 1.0, 1.5 and 2.0 wt.% Indium as ternary additions on melting temperature, structure, microhardness and micro‐creep of the Sn‐9Zn lead‐free solders were investigated. It is shown that the alloying additions of Indium to the Sn‐Zn binary system result in a suppression of the melting point to 187.9 °C. From x‐ray diffraction analysis, a new intermetallic compound phase, designated β‐In₃Sn is detected. The formation of an intermetallic compound phase causes a pronounced increase in the electrical resistivity and mechanical strength. Also, an interesting connection between dynamic Young's modulus and the axial ratio (c/a) of the unit cell of the β‐Sn was found in which Young's modulus increases with increasing the axial ratio (c/a). The ternary Sn‐9Zn‐xIn exhibits creep resistance superior to Sn‐9Zn binary alloy. The better creep resistance of the ternary alloy is attributed to solid solution effect and precipitation of In₃Sn in the Sn matrix. The addition of small amounts of In is found to refine the effective grain size and consequently, improves hardness. The 89%Sn‐9%Zn‐2%In alloy is a lead‐free solder designed for possible drop‐in replacement of Pb‐Sn solders. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Enhancement of solder properties of Sn‐9Zn lead‐free solder alloy

The eutectic alloy Sn‐9Zn was considered as a potential alternative to lead‐tin solder alloys when compared with other solders. In this paper, ternary, quaternary and penternary additions of the elements Bi, Cu and In were added to the eutectic alloy as a trial to improve its properties. The results showed that, the penternary alloy has properties superior to those of the binary, ternary and quaternary alloys. The alloy of composition Sn‐9Zn‐1Bi‐2Cu‐2In has the most suitable properties as a candidate alloy for lead‐free solder. It has a lower melting point, 186°C, which is very close to that of Sn‐37Pb solder, a lower value of electrical resistivity, 16.5 μΩ.cm, compared with that of Sn‐37Pb (17 μΩ.cm), higher value of the Young's modulus, 47 GPa, compared with 45 GPa of Sn‐37Pb and a higher value of the Vickers hardness, 191 MPa, compared with 129 MPa of Sn‐37Pb eutectic alloy. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Contribution to the Ti‐Bi phase diagram

The system Ti‐Bi has been investigated by solid/liquid diffusion couples at 400, 500, 600 and 700 °C. Indication that the growth rate of the diffusion layers at 500 °C is linear has been found, with a growth constant of around 5 × 10^–11 m.s^–1. The existence of the Ti₂Bi phase has been confirmed. Some formerly unknown binary phases (TiBi, Ti₂Bi₃, TiBi₂) have been observed. The phase TiBi is, probably, identical with Ti₈Bi₉ reported previously. All intermediate phases suffer air corrosion, but in various degrees. A tentative variant of the Ti‐Bi phase diagram, including the newly found compounds, has been constructed. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Theoretical prediction of bulk glass forming ability (BGFA) of Ti-Cu based multicomponent alloys

The bulk glass forming ability (BGFA) of Ti-Cu based multicomponent alloys has been evaluated via theoretical modeling and computer simulation studies based on a combination of electronic theory of alloys in the pseudopotential approximation and the statistical thermodynamical theory of liquid alloys. The magnitude of atomic ordering energies, calculated by means of the electronic theory of alloys in the pseudopotential approximation, was subsequently used for calculation of the key thermodynamic parameters such as enthalpy, entropy and Gibbs free energy of mixing, viscosity, and critical cooling rate of the binary Ti-Cu and ternary Ti-Cu-X alloys. The potential alloying elements (X) can be divided in two groups defined by their effect on the variation of the negative heat of mixing and their influence on the critical cooling rate. Most of the predicted candidate alloying elements from either X_I (Al, Si, Ag) or X_II (Co, Ni, Fe, Sn, Be) and/or both groups have already been used successfully for the fabrication of new Ti-Cu based bulk metallic glasses. It was also shown that the critical cooling rate appears to be a more important parameter rather than the change in the negative heat of mixing for the prediction of candidate alloying elements improving BGFA.     

T(x) phase diagram of the CuSbS2–CuInS2 system and solubility limit of Sb in CuInS2

The starting ternary compounds CuInS₂ and CuSbS₂ and alloys of the CuSbS₂–CuInS₂ system with the molar fractions of CuInS₂ (x) equal to 0.05, 0.15, 0.25, 0.375, 0.50, 0.625, 0.75, 0.85, and 0.95 were prepared and the phase relations in this system were investigated by X‐ray powder diffraction, optical microscopy, scanning electron microscopy, and differential thermal analysis. It was shown that the T–x phase diagram of the CuInS₂–CuSbS₂ system has a eutectic character with the eutectic temperature of 807 K. The alloys of the CuSbS₂–CuInS₂ system with the molar fraction of CuInS₂ in the range from 0.038 to 0.941 at room temperature are two‐phased, and the limits of solubility are 0.059 molar fractions for CuSbS₂ in CuInS₂ and 0.038 molar fractions for CuInS₂ in CuSbS₂.     

Wet‐chemical synthesis and characterization of NiBi nano‐ and micro‐particles

Preparation and characterization of NiBi nano‐ and micro‐particles are presented. Firstly, predetermined compositions were obtained by simultaneous precipitation from solutions of Bi(NO₃)₃ and Ni(NO₃)₂. The precipitates were heated under oxygen flow and in air, and thereafter reduced to metals under hydrogen flow at 673 K. Correlation between the predetermined and the actual compositions of the products was found. Characterization of the precipitates was carried out employing X‐ray diffraction, scanning and transmission electron microscopy. Nickel‐bismuth intermetallic phase (NiBi) particles with nano‐ and micro‐dimensions were observed in the samples after reduction. The other possible Ni–Bi intermediate phase (NiBi₃) did not form at these conditions although its presence was expected according to the phase diagram. This finding might be useful for the implementation of Bi‐based solders where the growth of the compound NiBi₃ in the solder joints must be prevented. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Melting Diagrams of the Quaternary Systems Ga–In–As–Ge and Ga–In–As–Sn

Equilibria between quaternary liquid phases Ga–In–As–Ge(–Sn) and the ternary solid phase Ga–In–As have been calculated by application of the KRUPKOWSKI formalism on the excess free enthalpy. Experimental liquidus data were obtained from solubility experiments in a LPE equipment. Results of calculation and experimental liquidus data are compared.     

Temperature‐concentration oscillations of crystal‐solution phase equilibria in the presence of trace impurities of surface‐active agents

Using the examples of aqueous salt solutions NaNO₃, KNO₃, RbNO₃, K₂SO₄, NaBr·2H₂O, KBr, and NH₄NO₃, it was experimentally proven that the new phenomena, i.e. temperature‐concentration oscillations of crystal‐solution phase equilibria detected previously in the range of 15–45 °C remain in the presence of trace impurities (10^‐4–10^‐3 wt. %) of ion‐active organic matters. The signs of breaks transformation into pair oscillations of “maximum‐minimum” type are established for the K₂SO₄, NaBr, KBr solutions. The efficiency of influence of trace impurities on phase equilibria sharply rises in the areas of the temperature‐concentration oscillations (the saturation temperature ranges up to 10 K). The impurity efficiency is promoted by the presence of the amides in its content (as compared with the sulphates) and an increase in length of the hydrocarbon radical. The phenomenon is absent in case of an addition of ion‐inactive compounds. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Thermodynamic assessment of the Cu‐Mg‐Si system in its copper‐rich region

A thermodynamic assessment of the ternary Cu‐Mg‐Si system was made in its copper‐rich region in relation with the development of a thermodynamic database for Cu‐Mg alloys. The adjustable parameters of the binary end‐systems (Cu‐Mg, Cu‐Si and Mg‐Si) were taken from the literature and those of the Cu‐Mg‐Si system were optimized using experimental thermodynamic and topological data. For the sake of simplicity, the solution phases were described with the substitutional solution model and the intermetallic compounds were treated as plain semi‐stoichiometric phases ((A,B)_pC_q‐type). The assessment developed is applicable for magnesium contents up to 20 wt% (i.e. magnesium mole fractions ≈0.4) and silicon contents up to 16 wt% (i.e. silicon mole fractions ≈0.3). (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Die Löslichkeiten von GaP und GaAs in Sn und Bi

The pseudo-binary GaAs Bi, GaPs Bi and GaP Sn phase diagrams were investigated by Differential Thermal Analysis (DTA), and a theoretical analysis on the basis of the regular solution model for Ga GaAs Bi, Ga GaPs Bi and Ga GaP Sn has been presented. The solubilities of GaAs and GaP in Sn and Bi in the temperature range of 600–1200°C were determined. The solubility of the compounds decreases in the order Sn Ga Bi.     

Development of performance‐improved global positioning system (GPS) patch antenna based on sol‐gel‐synthesized dual‐phase (Bi4Ti3O12)X – (CaCu3Ti4O12)1–X composites

As a first attempt, a series of composite materials of general formula (Bi₄Ti₃O₁₂)_X – (CaCu₃Ti₄O₁₂)_1–X (BTO_X – CCTO_1–X) (X = 0–1.0) is synthesized by a sol‐gel combustion method. The phase changes, including their formation and evolution during the gradual substitution of BTO into CCTO are analyzed from the X‐ray diffraction pattern. The Jana2006 refinement plotting method proves that formation of an ideal dual‐phase composite system with separate orthorhombic and cubic phases occurs. A surface morphological study revealed that the BTO_X – CCTO_1–X composites are composed of small CCTO grains embedded in large BTO grains and both coexisted with a bimodal distribution. The possible vibrational modes of interactions between the constituent phases are determined from Raman spectra. Our inexpensive, combustion method for BTO_0.2 – CCTO_0.8 gives a high dielectric constant (ε′ = 3232) at 100 Hz at room temperature. The nature behind these data is revealed that the BTO‐CCTO composite can be applicable for the fabrication of miniaturized global positioning system (GPS) patch antennas. The fabricated GPS patch antenna shows optimum results of small size (2.37 mm × 1.18 mm), return loss (‐14.419) and wide bandwidth (350 MHz) to be operated at 1.57 GHz.     

Structure formation in liquid and amorphous metallic alloys

Bulk metallic glasses developed in last 15 years represent a new class of amorphous metallic alloys. These multi-component metallic alloys can be obtained at relatively low cooling rates, which allow the production of large-scale materials by conventional casting processes. Furthermore, bulk metallic glasses show a glass transition well below the crystallization temperature enabling hot deformation, but also to investigate the glass transition phenomenon in a metallic system. The thermal behavior of Zr- and Pd-based bulk metallic glasses was studied by in situ X-ray diffraction at elevated temperatures. The temperature dependence of the X-ray structure factor of the glassy state can be well described by the Debye theory. At the caloric glass transition the temperature dependence of the structure alters, pointing to a continuous development of structural changes in the liquid state. The short-range order of the glass, of the super-cooled liquid, and of the equilibrium melt is found to be very similar. The existence of complex chemically ordered clusters in the melt is supposed to be related to the high glass-forming ability of the alloys. The microstructure of metallic glasses consisting of elements with negative enthalpy of mixing is homogeneous at dimensions above 1 nm. Phase separation in the liquid state appears in metallic systems with large positive enthalpy of mixing of the elements like Nb–Y. Thermodynamic calculations of the Ni–Nb–Y phase diagram show that the miscibility gap of the monotectic binary Nb–Y system extends into the ternary up to large Ni content. Experimental evidence of the phase separation in ternary Ni–Nb–Y melts is obtained by in situ X-ray diffraction at elevated temperatures and differential scanning calorimetry. The phase separated melt can be frozen into a two-phase amorphous metallic alloy by rapid quenching from the liquid. The microstructure depends on the chemical composition and consists of two amorphous regions, one Nb-enriched and the other Y-enriched, with a size distribution from several nanometers up to micrometer dimension. The experimental results confirm the close relationship between the structure of metallic glasses and the corresponding under-cooled liquids.     

Growth of Heterostructures Based on InAs–AlxGa1–xSb

It is reported on the liquid phase epitaxial (LPE) growth of heterostructures on the base of InAs–Al_xGa_1–xSb. The paper includes the investigation of epitaxial layers of Al_xGa_1–xSb alloys on InAs substrates and results of experiments for the determination of optimum growth regimes.     

High‐strength bimodal ultrafine Ti‐based alloys with enhanced ductility

Bulk Ti₆₅Fe₃₅ and (Ti₆₅Fe₃₅)_96.15‐xSn_3.85Nb_x (x = 0, 3, 5 and 7 at.%) alloys were prepared by cold crucible levitation melting, and tested in compression at room temperature. The Sn and Nb modified hypereutectic Ti‐Fe alloys exhibited improved mechanical properties under compression. (Ti₆₅Fe₃₅)_93.15Sn_3.85Nb₃ alloy displayed an ultimate compressive strength of 2.7 GPa and a compressive plastic strain of 15%. Electron microscope observations revealed Ti‐Fe(Sn,Nb) alloys having a bimodal microstructure with micrometer‐scale primary TiFe dendrites distributed in an ultrafine eutectic (β‐Ti+TiFe) matrix. The orientation relationship of β‐Ti with TiFe phases is TiFe (011)[100] ∥ β‐Ti (011)[100]. The improved mechanical properties are attributed to the morphology of the phase constituents and the larger lattice mismatches between β‐Ti and TiFe phases due to the additions of Sn and Nb.