Phase equilibria and microstructure development in Mg-rich Mg-Gd-Sr alloys: Experiments and CALPHAD assessment

Mg-Sr alloys are promising to fabricate orthopedic implants. The alloying of rare earth elements such as Gd may improve the comprehensive mechanical properties of Mg-Sr alloys. The information on the phase diagram and the microstructure development are required to design chemical composition and microstructure of Gd alloyed Mg-Sr alloys. The phase equilibria and the microstructure development in Mg-rich Mg-Gd-Sr alloys (Gd, Sr < 30 at. %) are experimentally investigated via phase identification, chemical analysis, and microstructure observation with respect to the annealed ternary alloys. The onset temperatures of liquid formation are measured by differential scanning calorimetry. A thermodynamic database of the Mg-rich Mg–Gd–Sr ternary system is developed for the first time via CALPHAD (CALculation of PHAse Diagram) approach assisted by First-Principles calculations. The thermodynamic calculations with the developed database enable a well reproduction of the experimental findings and the physical-metallurgical understanding of the microstructure formation in solidification and annealing.     

Thermodynamic assessment of the La-Mg system

A thermodynamic modeling and optimization of the La-Mg system is carried out by means of the CALPHAD method taking into account the latest experimental results. The liquid, bcc-La, fcc-La, dhcp-La and hcp-Mg solutions are modeled as substitutional solutions (La, Mg) using the Redlich-Kister formalism. The LaMg, LaMg₂, La₅Mg₄₁, La₂Mg₁₇ and LaMg₁₂ phases are treated as stoichiometric compounds, and the non-stoichiometry of LaMg₃ is described as (La,Mg)_0.25Mg_0.75. The results are in good agreement with the set of experimental data which were carefully discussed and selected.     

Thermodynamic description of the Al-Li-Zn system

The Al-Li-Zn system was critically assessed using the CALPHAD technique. The solution phases (liquid, bcc, fcc and hcp) were described by the substitutional solution model. The compounds Al₂Li₃ and Al₄Li₉ in the Al-Li system had homogeneity ranges of Zn and were treated as (Al,Zn)₂Li₃ and (Al,Zn)₄Li₉ in the Al-Li-Zn system, respectively. The compounds αLi₂Zn₃, βLi₂Zn₃, αLi₂Zn₅, βLi₂Zn₅ and αLiZn₄ in the Li-Zn system had no solubility of the third component Al in the Al-Li-Zn system. A two-sublattice model (Al,Li,Zn)_0.2(Al,Li,Zn)_0.8 was applied to describe the compound βLiZn₄ in the Al-Li-Zn system in order to cope with the order-disorder transition between hexagonal close-packed solution (hcp-A3) and βLiZn₄ with the Mg-type structure. The ternary compound τ₂ with a NaTl-type structure (B32) had the same structure with the compounds AlLi in the binary Al-Li system and LiZn in the binary Li-Zn system. In the present work, the three compounds AlLi, LiZn and τ₂ were treated as one phase by a two-sublattice model (Al,Li,Zn)_0.5(Al,Li,Zn)_0.5 in order to cope with the order-disorder transition between B32(AlLi, LiZn and τ₂) and body-centered cubic solid solution (bcc-A2). The ternary intermetallic compounds τ₁ and τ₃ in the Al-Li-Zn system were treated as the formula Li(Al,Zn)₂ and (AlLi,Zn)Zn₃, respectively. A set of self-consistent thermodynamic parameters describing the Gibbs energy of each individual phase as a function of composition and temperature in the Al-Li-Zn system was obtained.     

Experimental investigation and thermodynamic assessment of the Cu-Sn-Ti ternary system

The Cu-Sn-Ti ternary system has been studied via experiments and thermodynamic modelling. In the experimental section, the composition of the alloys was selected based on the preliminary calculations and available literature data. Metallography, scanning electron microscopy and electron probe microanalysis were employed to analyse alloy samples prepared by arc-melting after annealing at 800 °C for 760 h. Solid phase relations at 800 °C were established. In contrast to earlier reports, the CuSn₃Ti₅ phase was interpreted as a binary intermetallic compound (Sn₃Ti₅) with extended Cu solubility. In the modelling section, three binary sub-systems were critically evaluated and updated according to the new experimental data and theoretical calculations reported in literature. According to their crystal structures and homogeneity ranges, appropriate sublattice models were proposed for SnTi₃,SnTi₂,Sn₃Ti₅ and Sn₅Ti₆. A set of self-consistent thermodynamic parameters for the Cu-Sn-Ti ternary system was obtained by considering the present experimental results and reported experimental information. The calculated results compare with the available experimental data to validate the present thermodynamic assessment.