Enthalpies of mixing of liquid systems for lead-free soldering: Cu–Sb–Sn system

Using two different types of high temperature drop calorimeters, partial and integral enthalpies of mixing of liquid alloys were determined in the ternary Cu–Sb–Sn system. The system was investigated along four sections at 1100 K. Experimental data were used to find ternary interaction parameters by applying the Redlich–Kister–Muggianu model for substitutional solutions, and a full set of parameters describing the concentration dependence of the enthalpy of mixing was derived. From these, the isoenthalpy curves were constructed for 1100 K. The entire system shows exothermic enthalpy of mixing at the given temperature.     

Viscosity of liquid Cu–Sn alloys

We investigated of the kinematic viscosity of liquid Cu–Sn alloys upon heating and subsequent cooling by the method of the oscillating cylinder. For the liquids alloys Cu75Sn25, Cu50Sn50, Cu48Sn52, Cu32Sn68, and Cu17Sn83, the temperature dependencies of the viscosity upon heating deviate from the Arrhenius relation. The temperature dependencies of viscosity show the Arrhenius-like behaviour upon cooling for all investigated alloys. A discrepancy between the temperature dependencies of viscosity obtained upon heating and cooling arised. We built the concentration dependences of the kinematic viscosity of liquid Cu–Sn alloys upon cooling. The increase of the values of viscosity and activation energy of viscous flow in the concentration range corresponding to the existence of intermetallic compounds Cu₃Sn in the solid state was observed. These results were qualitatively interpreted using the concept of microheterogeneities of liquid alloys.     

Viscosity of liquid Co–Sn alloys: thermodynamic evaluation and experiment

Shear viscosity measurements were performed for liquid Co–Sn alloys over a wide temperature range above the respective liquidus temperatures. A high temperature oscillating-cup viscometer was used. It was found experimentally that viscosity as a function of temperature obeys an Arrhenius law. The data were compared with calculated values, obtained from different thermodynamic approaches. A good agreement was found between experimental results and calculated ones by the Budai–Benkö–Kaptay model.     

Thermodynamic evaluation of viscosity in In–Zn and Sn–Zn liquid alloys

A theoretical formalism that links thermodynamic properties to transport properties has been used to study the viscosity of Sn–Zn and In–Zn liquid alloys at various temperatures. The formalism was successful at describing the thermodynamic properties of these alloys and showed a better estimation of the viscosity of the Sn–Zn alloy than that of the In–Zn alloy.     

Surface tension of liquid high-entropy equiatomic alloys of a Cu–Sn–Bi–In–Pb system

An experimental study of the temperature dependences of the surface tension of liquid high-entropy equiatomic alloys of a Cu–Sn–Bi–In–Pb system is conducted. Measurements are made within the temperature range of t _L to 1300°C in the mode of heating and subsequent cooling of a sample. Overcooling of a melt prior to crystallization is detected. The depth of overcooling grows along with the number of components in the melt, while the temperature coefficient of surface tension falls. The experimental results qualitatively interpreted within the concepts of the specific surface entropy of a liquid.     

Liquid–liquid phase equilibrium in ternary immiscible Al–Bi–Sn melts

In this paper, the liquid-phase separation of ternary immiscible Al–Bi–Sn melts was studied with resistivity and thermal analysis methods at different temperatures. The resistivity–temperature curves appear anomalous and abrupt change as rising temperature, corresponding to the distinctive and low peak of melting process in the differential scanning calorimetry (DSC) curves, indicative of the occurrence of the liquid-phase separation. The anomalous behaviour of the resistivity temperature dependence is attributable to concentration–concentration fluctuations. The microheterogeneity–microhomogeneity transformation causes large fluctuations in concentration, which make the randomness and chaos of the atoms larger, leading to the greater impediment to electron movement and the sharp rise of resistivity. The addition of tin to the Al–Bi immiscible alloys decreases the monotectic reaction. It is concluded that concentration–concentration fluctuations are responsible for the anomalous behaviour of resistivity and DSC methods.     

Thermodynamics and vacuum distillation studies of liquid Al–Ga and In–Sn alloys

Activities of components in liquid Al–Ga and In–Sn alloys, the separation coefficients and vapour–liquid phase equilibrium in vacuum distillation were predicted using the molecular interaction volume model as a function of the activity coefficients. The results indicated that both Al and In are preferentially volatilised into vapour phase while Ga and Sn remain in residue. Similarly, we found that both the mass fraction and the content of Al and In in vapour phase increase as distillation temperature increases such that when the content of Al is 0.005985 wt% and In is 0.004141 wt% in vapour phase, respectively, in liquid phase, it was 70 wt% at T = 1073 K for both. The calculated values of activity and activity coefficients at various temperatures are presented. Comparison of the predicted values with experimental data indicates good agreement, thus verifying from statistical thermodynamics viewpoint that the model is stable and reliable.     

Lipophilic ternary complexes in liquid–liquid extraction of trivalent lanthanides

The formation of ternary complexes between lanthanide ions [Nd(III) or Eu(III)], octyl(phenyl)-N,N-diisobutyl-carbamoylmethylphosphine oxide (CMPO), and bis-(2-ethylhexyl)phosphoric acid (HDEHP) was probed by liquid–liquid extraction and spectroscopic techniques. Equilibrium modeling of data for the extraction of Nd(III) or Eu(III) from lactic acid media into n-dodecane solutions of CMPO and HDEHP indicates the predominant extracted species are of the type [Ln(AHA)₂(A)] and [Ln(CMPO)(AHA)₂(A)], where Ln?=?Nd or Eu and A represents the DEHP^? anion. FTIR (for both Eu and Nd) and visible spectrophotometry (in the case of Nd) indicate the formation of the [Ln(CMPO)(A)₃] complexes when CMPO is added to n-dodecane solutions of the LnA₃ compounds. Both techniques indicate a stronger propensity of CMPO to complex Nd(III) versus Eu(III).     

Thermodynamic properties of liquid copper–lanthanum alloys

Mixing enthalpies of alloys in the Cu–La system are measured using isoperibolic calorimetry method over the ranges 0 < x _La < 0.185 at 1400–1430 K and 0.659 < x _La < 1 at 1370 K. They have moderate exothermic values over the whole concentration range and agree with literature data. Activities of the components, enthalpies and entropies of formation of intermetallics in this system, and its phase diagram are optimized using an ideal associated solution (IAS) model, and agree with most literature data. The updated thermodynamic properties can be used in further investigation of multicomponent systems based on the binary Cu–La.     

Enthalpies of formation of SmCo alloys in the composition range 10–22 at. % Sm

Several intermetallic compounds exist in the composition range 10–22 at.% Sm(Sm₂Co₁₇, SmCo₅, Sm₂Co₇) but their preparation as single-phase specimens is very difficult. In order to determine the enthalpies of formation of these compounds, measurements were carried out on four alloys containing respectively 12.9 at.% Sm, 16.4 at.% Sm, 17 at.% Sm and 19.8 at.% Sm, annealed in the temperature range 950–1100 °C. The compositions of the phases present in each specimen were deduced from the characterization of the measured alloys by scanning electron microscopy, electron microanalysis and X-ray diffraction.The heats of formation were deduced from solution calorimetry in molten tin. The variation of the experimental results as a function of the samarium content enabled the enthalpy of formation of SmCo₅ ( − 40.8 kJ mol⁻¹) to be determined. The same ΔH_f value as determined for the phase quenched from 950 °C was measured for SmCo₅ kept at room temperature after very slow cooling. This result did not confirm the eutectoid decomposition previously reported for SmCo₅.The extrapolation of the measured values for the higher and lower samarium contents leads to the evaluation of the enthalpies of formation of Sm₂Co₁₇ (−152 kJ mol⁻¹) and Sm₂Co₇ (−99kJ mol⁻¹).     

Cyclic voltammetric behavior of Pd–Pt–Rh ternary alloys

The electrochemical behavior of Pd–Pt–Rh alloys has been investigated using cyclic voltammetry (CV). The alloys were prepared by electrochemical codeposition as limited volume electrodes (less than 1 m in thickness). The morphology of the alloy surface and bulk compositions were examined by the SEM/EDAX method. Surface oxides generation (oxygen adsorption) and oxides reduction (oxygen desorption) currents together with hydrogen adsorption and hydrogen absorption signals can be distinguished on CV curves. During potential cycling through the full hydrogen–oxygen potential range Rh and Pd are preferentially dissolved, which is reflected in a dramatic transformation in the voltammogram shape. The composition changes involve not only the surface but also some atomic layers beneath the surface.     

Thermodynamic properties of lead–sodium–antimony liquid alloys

The thermodynamic properties of lead–sodium–antimony liquid alloys were determined by the emf method. The thermodynamic properties of the edge binary systems, sodium–lead, sodium–antimony, and lead–antimony, were analyzed. The possibility of approximately estimating the thermodynamic properties of the ternary system on the basis of data on the edge binary systems using the simplest geometric models was demonstrated. The sodium-containing alloys show significant negative deviations from the ideal behavior. All the data are given for 900 K.     

Liquid phase separation of ternary Al–In–Sn/Ge monotectic type alloys investigated with calorimetric method

The phase equilibrium, thermodynamic properties and liquid demixing patterns for binary Al_100−xIn_x, ternary (Al_100−xIn_x)₉₀Sn₁₀ and (Al_100−xIn_x)₉₀Ge₁₀ (x = wt.%) alloys are investigated by differential scanning calorimetry (DSC) method. The corresponding phase diagrams are experimentally established, and it is found that both monotectic temperature and critical temperature for immiscibility gap decrease when either Sn or Ge is added to binary Al_100−xIn_x alloys. The enthalpy of fusion for binary Al–In alloys, ternary Al–In–Sn and Al–In–Ge alloys shows linear functions with In content, and the introduction of Sn and Ge elements decreases the enthalpy of fusion. The liquid phase separation mechanism is discussed in relation to the DSC curves and solidified microstructures. It is demonstrated that the core and shell phases can be altered by the addition of Ge element in (Al_100−xIn_x)₉₀Ge₁₀ alloys as compared with those in binary Al_100−xIn_x and ternary (Al_100−xIn_x)₉₀Sn₁₀ alloys. This provides an effective way to switch the inner and outer phases for core–shell structure.