Thermodynamic and surface properties of Sb-Sn and In-Sn liquid alloys

The thermodynamic properties of Sb-Sn and In-Sn liquid alloys have been studied using the quasi-chemical model for compound forming binary alloys and that for simple regular alloys. The concentration fluctuation S _cc(0) and the Warren-Cowley short-range order parameter (α ₁) were determined for the whole concentration range at a temperature of 770 K. The surface tensions of these liquid alloys were determined for the whole concentration range by using energetics determined from thermodynamic calculations. In all calculations, In-Sn manifested properties very close to alloys of ideal mixing, while Sb-Sn showed properties that are asymmetric about equiatomic composition. Our results suggest that a weak complex of the form SbSn₂ could be present in the Sb-Sn alloy at a temperature of about 770 K.     

Thermodynamics and surface properties of liquid Cu–B alloys

The study of the thermodynamic and the surface properties of liquid Cu–B alloys can help better understanding of a complex interfacial chemistry related to liquid Cu–brazes in contact with boride substrates. Despite a simplicity of the Cu–B phase diagram, only a few thermodynamic data are available in the literature, while in the case of the surface properties a complete lack of data is evident. The quasi-chemical approximation (QCA) for the regular solution has been applied to describe the mixing behaviour of liquid Cu–B alloys in terms of their thermodynamic and surface properties as well as the microscopic functions. In view of joining processes related to liquid Cu–brazes/solid boride systems a particular attention is paid to the surface properties of the Cu-rich part of the system and the calculated values are substantiated by the new surface tension experimental data of liquid Cu and Cu–10 at.% B alloy. The tests have been performed by the sessile-drop method under the same experimental conditions. Considering the experimental uncertainties, the effect of oxygen on the surface tension of liquid Cu and Cu–10 at.% B alloy has been analysed by simple model that combines the physical property data included in Butler’s equation with the oxygen solubility data and it gives the same results as Belton’s adsorption equation.     

Thermodynamic properties and ordering in liquid NaK alloys

The thermodynamic activities of sodium and potassium were determined by vapour-phase absorption spectrophotometry of atomic resonance lines. Both components exhibit significant positive deviations from ideality. Excess Gibbs energies computed from the activity data were combined with available heat-of-mixing data to yield values for excess entropies. The entropy of mixing which was found to be ideal in the sodium-rich liquid alloys provides no support for the earlier speculations about the existence of Na₂K molecules therein. The partial molar excess entropy of sodium in dilute solution in potassium was found to be surprisingly large and negative for a system of this type. A plausible model, involving sodium-sodium pairing, is proposed to account for the loss of configurational entropy.     

Surface properties of liquid In-Zn alloys

The measurements of surface tension and density of zinc, indium and liquid In-Zn alloys containing 0.9, 0.85, 0.75, 0.70, 0.60, 0.40, 0.25 and 0.10 mole fraction of In were carried out using the method of maximum pressure in gaseous bubbles (MBP) as well as dilatometric technique. The technique of sessile drop was additionally applied in the measurements of surface tension for pure indium and zinc. The measurements were performed at temperature range 474-1151 K. The isotherms of surface tension calculated based on Butler's equation at 700 and 1100 K corresponded well with the experimental values for zinc content lower than 0.6 mole fraction. The surface tension calculated for alloys of higher zinc concentrations (0.6 < X_Zn < 0.95) had a positive value of the surface tension temperature coefficient (dσ/dT), which did not coincide with the experimental results. The density as well as molar volume of liquid In-Zn alloys showed almost identical behaviour like the ideal solutions. The observed little deviations were contained within assessed experimental errors.     

Bulk and surface properties of liquid Al-Mg, Au-Sn, and Mg-Tl compound forming alloys

We have used phenomenological models based on statistical mechanics to study the bulk and surface properties of Au-Sn, Al-Mg, and Mg-Tl binary liquid alloys. Our study reveals that the three alloys are weakly ordered systems with the most stable intermetallic complexes at temperatures of 823 K, 1073 K and 923 K been AuSn, Al₃Mg₂ and Mg₄Tl, respectively. An analysis of Warren-Cowley short-range order parameter indicates that the weakest intermetallic compound is Al-Mg while Au-Sn is observed to be more chemically ordered than Mg-Tl. Furthermore, our surface properties calculations shows that Mg-atom and Sn-atom segregate to the surface over the whole concentration range of Al-Mg and Au-Sn alloys, respectively. In Mg-Tl, there is a competing effect between Tl-atom being drawn into the bulk and at the same time Tl-atom wanting to segregate to the surface over the whole concentration range.     

The surface tension of liquid Cu-Fe-Sb alloys

The results of study on the influence of temperature and iron and antimony on the surface tension of liquid ternary Cu-Fe-Sb systems are presented. The measurements were carried out with the sessile drop method, in a broad range of the alloy additions concentration (Fe and Sb). It was demonstrated that the surface tension varies as a linear function of temperature and concentration of iron. It was also demonstrated that antimony, in examined alloys, shows the properties characteristic of a surface-active substance, significantly reducing the surface tension value. The changes of the surface tensions as a function of concentration of antimony were described with the Szyszkowski's equation. Composition of surface layer, enriched with an antimony, was determined basing on the model, which used data regarding properties of binary systems. The surface tension values of Cu-Fe-Sb systems was also computed from model and compared with experimental data. A good agreement was obtained.     

Structure and properties of some glass-forming liquid alloys

Some physical properties (kinematic viscosity, surface tension and magnetic susceptibility) of some Fe-based metallic melts of easily glass-forming alloys have been measured during heating and subsequent cooling. The results indicate that molten liquid metallic alloys undergo a number of structural transformations ranging from the initial microheterogeneous state formed after melting up to the true solution state. Studies by small angle neutron scattering on a eutectic SnPb melt confirm this conclusion in that two families of different sizes have been seen, one in the range 1 to 2 nm and one of size larger than 100 nm. Both kind of particles have relatively sharp interfaces and the size of the smaller particles is found to depend on temperature. Received 25 February 1999 and Received in final form 28 October 1999     

Electrical and thermoelectrical properties of selenium-tellurium liquid alloys

A study has been made of the electrical conductivity and thermoelectric power of liquid alloys Te_1-x Se _x with 0≤-x≤-0.5. The temperature range extends from undercooling to about 900°C for electrical conductivity and 750°C for thermoelectric power. A partial conservation after melting of covalent bonds between the atoms of the chains leads to a liquid model in which Gubanov's theory predicts an energy band gap. The experimental results in the intrinsic semiconductor range give the band gap and the mobility ratio values. The thermal gap changes from 1.2 to 3 ev between pure tellurium and the alloy with 70 at. % selenium. There is a large increase in hole mobility with atomic % selenium. For x≥0.2 the low temperature results of the electrical conductivity can be explained by the existence of localized states in the band gap. The high temperature measurements show a trend to the metallic state, but this state cannot be reached at one atmosphere pressure even for tellurium.     

Surface and transport properties of Au-In liquid alloys

Thermodynamic quantities on Au-In liquid alloys have been used as the input data for the interaction parameter calculations in the framework of the complex formation model (CFM). Once the interaction energies are computed the surface (surface tension and surface composition) and transport properties (chemical diffusion and viscosity) as well as the microscopic functions (concentration fluctuations in the long-wavelength limit and chemical short-range order parameter) have been calculated. The concentration and temperature dependent surface tension values have been compared with our new set of experimental data, obtained by the large drop method in the temperature range of T = 1273-1493 K. The anomalous change of surface tension for some alloy compositions may be attributed to a retention of order in the Au-In melts which is similar to the atomic arrangement in solid Au-In.     

Theoretical and computer simulation study of density fluctuations in liquid binary alloys

The dynamical properties of liquid alloys are investigated by means of memory function equations and molecular-dynamics simulation. A simple model for the second-order memory function in a binary liquid, based on Mori's memory function formalism, is proposed and applied in numerical calculations of the time correlation functions and dynamic structure factor of liquid K_0.7Cs_0.3 and K_0.3Cs_0.7 alloys. Obtained results are discussed in comparison with the results of computer simulations. Received: 27 February 1998 / Revised: 24 July 1998 / Accepted: 27 July 1998     

Thermophysical properties of undercooled liquid Co-Mo alloys

Using electromagnetic levitation in combination with the oscillating drop technique and drop calorimeter method, the surface tensions and specific heats of undercooled liquid Co-10 wt% Mo, Co-26.3 wt% Mo, and Co-37.6 wt% Mo alloys were measured. The containerless state during levitation produces substantial undercoolings up to 223 K (0.13 T _L), 213 K (0.13 T _L) and 110 K (0.07 T _L) respectively for these three alloys. In their respective undercooling ranges, the surface tensions were determined to be 1895 m0.31(T m1744), 1932 m0.33(T m1682), and 1989 m0.34(T m1607) mN m^?1. According to the Butler equation, the surface tensions of these three Co-Mo alloys were also calculated, and the results agree well with the experimental data. The specific heats of these three alloys are determined to be 41.85, 43.75 and 44.92 J mol^?1 K^?1. Based on the determined surface tensions and specific heats, the changes in thermodynamics functions such as enthalpy, entropy and Gibbs free energy are predicted. Furthermore, the crystal nucleation, dendrite growth and Marangoni convection of undercooled Co-Mo alloys are investigated in the light of these measured thermophysical properties.     

Thermal properties of liquid alloys of magnesium-lead system

The temperature variations of the density of liquid magnesium-lead alloys were measured by the gamma-method in the temperature range from the liquidus temperature to 950–1000 K for compositions of 19.11, 33.45, 52.46, and 83.06 at. % Pb. It is shown that within the estimated errors (0.25–0.30 %), the alloy density depends linearly on the temperature. Approximation dependences ρ(T) were obtained for every studied composition together with generalizing density-temperature and density-concentration dependences for the range of 0–100 at. % Pb. The work was financially supported by the Russian Foundation for Basic Research (Grant No. 06-08-00040).     

Calculation of the surface tension of liquid Ga-based alloys

As known, Eyring and his collaborators have applied the structure theory to the properties of binary liquid mixtures. In this work, the Eyring model has been extended to calculate the surface tension of liquid Ga–Bi, Ga–Sn and Ga–In binary alloys. It was found that the addition of Sn, In and Bi into Ga leads to significant decrease in the surface tension of the three Ga-based alloy systems, especially for that of Ga–Bi alloys. The calculated surface tension values of these alloys exhibit negative deviation from the corresponding ideal mixing isotherms. Moreover, a comparison between the calculated results and corresponding literature data indicates a good agreement.     

Bulk and surface properties of liquid X-Zr (X=Ag, Cu) compound forming alloys

The phase diagrams of the Ag-Zr and Cu-Zr systems exhibit the existence of different intermetallic compounds in the solid state, and since the structure of a liquid alloy is in some respects similar to that of a crystal, the compound formation phenomenon in these liquid alloy systems has been analysed through the study of surface properties (surface tension and surface composition), dynamic properties (chemical diffusion and viscosity) and microscopic functions (concentration fluctuations in the long-wavelength limit and chemical short-range order parameter) in the frame of the compound formation model (CFM). Moreover, the associative tendency between unlike constituent elements qualitatively expressed by the microscopic functions indicates the glass-forming ability of both systems at higher Zr-concentrations. These results are in agreement with reported experimental data and confirm the applicability of a statistical mechanical theory in conjunction with the CFM to describe the mixing behaviour of compound forming alloys.     

Theoretical calculations on structural and electronic properties of BGaAsBi alloys

The structural and electronic properties of cubic B _x Ga_1?x As_1?y Bi _y alloys with bismuth (Bi) concentration of 0.0625, 0.125, 0.1875 and 0.25 are studied with various boron (B) compositions by means of density functional theory (DFT) within the Wu-Cohen (WC) exchange correlation potential based on generalized gradient approximation (GGA). For all studied alloy structures, we have implemented geometric optimization before the volume optimization calculations. The obtained equilibrium lattice constants and band gap of studied quaternary alloys are investigated for the first time in literature. While the lattice constant behavior changes linearly with boron concentration, increasing small amount of bismuth concentration alter the lattice constant nonlinearly. The present calculation shows that the band gap decreases with increasing bismuth concentration and direct band gap semiconductor alloy became an indirect band gap with increasing boron concentration. From the band offset calculation we have shown that increasing B and Bi concentration in host GaAs reduced the valance band offset in a heterostructure formed by GaAs and studied alloys.     

Liquid surface and liquid/liquid interface energies of binary subregular alloys and wetting transitions

Energetics and chemistry of liquid surfaces and liquid/liquid interfaces of binary A-B alloys are calculated using a subregular solution model. In this model, two macroscopic energetic parameters are used to produce an asymmetric miscibility gap. They are related to two microscopic parameters which describe the interaction energy between two atoms as a function of the composition of the first coordination shell of each atom. The impact of the asymmetry of the A-B interactions on the surface and interfacial energies and adsorption are analyzed by comparing the results obtained with this subregular model to those calculated for a regular solution. The role of the asymmetry on the prewetting and wetting transitions are also discussed. Calculations performed in the Co-Cu system are in good agreement with experimental data of surface energy.     

Influence of difference in the atomic volumes of the components on the mutual diffusion in liquid binary alloys

Expressions relating the partial diffusion coefficients, macroscopic flow velocity, and mutual diffusion coefficient are obtained. Unlike the known Darken relations, the relations obtained take into account the difference in the atomic volumes of the solution components. The influence of the volume factor is more pronounced when the component concentrations are significantly different.     

Density and related thermophysical properties of metastable liquid Ni-Cu-Fe ternary alloys

The densities of liquid Ni-Cu-Fe ternary alloy system were investigated by molecular dynamics method in combination with a MEAM (Modified Embedded Atom Method) potential model. The temperature range is from 1000 to 2200 K, including both a broad superheating range and a large undercooled regime. The densities of six Ni100−2xCuxFex alloys (x=0,10,20,30,40,50) decrease linearly with the rise of temperature at the superheated and undercooled states, and increase with the enhancement of Ni content. Among the simulated alloys, the densities of only liquid pure Ni and Ni₆₀Cu₂₀Fe₂₀ alloy are available in literatures, which are in good agreement with the calculated values. According to the relationship between the excessive volume and the alloy composition, it can be deduced that Ni100−2xCuxFex alloys deviate from ideal solution. Moreover, a comparison was also performed between the calculated results and the approximated values by Neumann-Kopp's rule. Based on the obtained density data, the thermal expansion coefficients are also derived. It firstly decreases to a minimum value, and then displays a rise with the increase of Ni content.