Enthalpies of mixing in ternary Al–Gd–Mn liquid alloys

The enthalpies of mixing in liquid alloys of the ternary Al–Gd–Mn system were determined over a wide range of compositions by means of isoperibolic calorimetry at 1650 K. The measurements of the partial enthalpies of components were performed along five sections: for the ΔH̅ Al (sections with x Gd/x Mn = 0.30/0.70 and 0.65/0.35 for x Al changed from 0 up to 0.30); for the ΔH̅ Gd (x Al/x Mn = 0.80/ 0.20 and 0.50/0.50 for x Gd changed from 0 up to 0.30); for the ΔH̅ Mn (x Al/x Gd = 0.29/0.71 for x Mn changed from 0 up to 0.26). The enthalpies of mixing in the ternary system were found to be exothermic and steadily increasing in absolute values from the Mn corner towards the Al–Gd constituent binary system, reaching the minimum value of approximately – 37 kJ · mol–1 in the vicinity of the Al0.6Gd0.4 composition, evidently related to the formation of stable Al2Gd phase.

The enthalpies of mixing of ternary liquid Ag-Ca-Ge alloys

Partial and integral enthalpies of mixing of the ternary Ag–Ca–Ge melts were determined for the first time by the high-temperature isoperibolic calorimetry at 1300–1550 K. The experiments were performed for six sections with a constant ratio of two components up to the molar fraction of the third component equal to 0.3. The enthalpies of mixing in this ternary system are exothermic values which increase in absolute value from the Ag corner of the concentration triangle towards the constituent binary Ca–Ge system. The minimum value of the integral enthalpy of mixing was obtained for Ca0.6Ge0.4 composition of the Ca–Ge binary system (about –58.00 kJ mol–1). The enthalpies of mixing of the ternary Ag–Ca–Ge melts are calculated for the whole concentration triangle by the Redlich-Kister-Muggianu method, taking into account the term of specific ternary interaction defined from our experimental data. The topology of the isoenthalpies of mixing is determined.

Enthalpies of mixing in binary Cu–Eu and ternary Al–Cu–Eu liquid alloys

The enthalpies of mixing in liquid alloys of the binary Cu-Eu and ternary Al-Cu-Eu systems were determined over a wide range of compositions by means of isoperibolic calorimetry in the temperature range 1 300 - 1450 K. The enthalpies of mixing in the Cu-Eu system demonstrate small exothermic effects (ΔHmin = -4.1 ± 0.5 kJ · mol-1at xCu = 0.70). The measurements for the liquid ternary Al- Cu-Eu alloys were performed along five sections (xCu/ xEu = 0.70/0.30; 0.50/0.50 and 0.27/0.73 for xAl changed from 0 up to 0.30 and xAl/xEu = 0.20/0.80 and 0.47/0.53 for xCu changed from 0 up to 0.30). The enthalpies of mixing in the ternary system were found to be exothermic and increasing in absolute values from the Al corner towards the Al0.40Cu0.60-Al0.60Eu0.40section and from the constituent binary Cu-Eu system towards the same section. The minimum value of the integral enthalpy of mixing is expected in the vicinity of the Al0.6Eu0.4composition of the binary constituent Al-Eu system (about -23.00 kJ · mol-1).

FEATURES OF COMPONENT INTERACTION IN LIQUID ALLOYS OF TERNARY Al-Ge-3d-Me (Me = Mn, Fe, Ni, Cu) SYSTEMS

The features of the component interaction in liquid alloys of ternary Al-Ge-3d-Me systems (Me = Mn, Fe, Ni, Cu) are described. A joint analysis of the concentration dependences of the enthalpies of mixing of liquid alloys previously obtained by the authors via high-temperature calorimetry, and also of the phase diagrams of the constituent binary systems was carried out. The relationship between the enthalpy values and the type of short-range ordering in liquid alloys of the studied systems was established. The visual similarity of the topology of the projections of ΔmH isolines of the Al-Ge-Fe (Ni, Cu) liquid alloys and a completely different course of the isolines of the enthalpies of mixing for the liquid Al-Ge-Mn alloys are established. The changes in the absolute values of the ΔmHmin from system to system are observed. The enthalpies are approximately the same for the Al-Ge-Mn and Al-Ge-Fe systems (about -20 kJ⋅mol-1), they increase significantly from Al-Ge-Fe to Al-Ge-Ni (-50 kJ⋅mol-1), and then decrease substantially towards the Al-Ge-Cu system (-15 kJ⋅mol-1). For the Al-Ge-Mn (Fe, Ni, Cu) liquid alloys the lines of extreme interaction are located near the 3d-corner of the concentration triangle. These lines connect the compositions of the most stable intermetallic compounds in binary Al(Ge)-Mn(Fe, Ni, Cu) systems. It has been shown that the thermodynamic properties of Al-Ge-Fe (Ni, Cu) liquid alloys are mainly determined by the pair interaction of the components of the constituent binary Al-Fe(Ni, Cu) and Ge-Fe(Ni, Cu) systems, the influence of Al-Fe(Ni, Cu) systems being prevailed. For the Al-Ge-Mn system, the interaction of components in the Ge-Mn binary system gives the main contribution to the thermodynamic properties of the ternary system. The Al-Ge-Mn (Fe, Cu) systems are characterized by significantly lower absolute values of the heats of alloy formation compared to the Al-Ge-Ni one. The specified characteristics of component interaction in the ternary systems under consideration and different values of the enthalpies of mixing are determined by the peculiarities and regular changes of the electronic structure of 3d metals across the 3d series from Mn to Cu.

MODELING OF THERMODYNAMIC PROPERTIES OF THE MELTS OF TERNARY Ge-Mn-Gd SYSTEM

In the present work, the Gibbs energies of mixing of liquid alloys of the Ge-Mn-Gd ternary system were determined, which was made on the basis of an analysis of published data on the thermodynamic properties of liquid alloys of boundary binary systems that form the ternary Ge-Mn-Gd, as well as on the basis of the model calculations in these binary systems. To determine the activities of the components, the Gibbs energies of mixing, and the enthalpies of mixing of liquid alloys of the Ge-Mn(Gd) systems, for which alloying process is accompanied by significant heat release, an ideal associated solution model was applied. For the melts of the Mn-Gd system, which are characterized by rather insignificant exothermic effects, a model of regular solutions was used. The surface of the Gibbs energy of mixing for the alloys of the Ge-Mn-Gd ternary system has been determined on the basis of the concentration dependences of the Gibbs energies of mixing obtained for constituent binary systems under the assumption of additivity of pair interactions using the Redlich-Kister-Muggianu method. The obtained topology of the Gibbs energy isolines projections is compared with the thermochemical properties of liquid alloys of this system that we have determined earlier. A comparative analysis of the topology of these surfaces in the Ge-Mn-Gd system led to the conclusion that the surfaces of ΔG and ΔmH monotonically decrease from the manganese-rich angle of the diagram towards the Ge-Gd side of the concentration triangle. The minimum value of the thermodynamic characteristics of mixing of the ternary liquid alloys corresponds to the composition, which coincides with the composition of the most stable intermetallic compound in the Ge-Gd system. From the course of isolines of free energies and integral enthalpies of mixing, one can also conclude about the influence of a short-range order, existed in the Ge-Mn system near the composition with a mole fraction of mangan greater than 0.7, on the properties of ternary alloys in the vicinity of this composition. Thus, the topology of isolines and the large exothermic values of the obtained thermodynamic properties allow us to make a reasonable conclusion that the strong interaction between unlike components inherent in the Ge-Gd system in the solid state is also maintained for liquid alloys of the Ge-Mn-Gd system.