Synthesis and characterization of (Al,Si)3(Zr,Ti)-D022/D023 intermetallics: Understanding the stability of silicon substitution

(Al,Si)3(Zr,Ti)-D022/D023 are phases that may form in aerospace and automotive aluminium alloys. The substitution of Zr/Ti in these solid solutions is widely reported in the literature; however, it remains relatively unexplored for Si. In this work, in situ precipitation of (Al,Si)3(Zr,Ti)-D022/D023 intermetallics was performed using Al-Si-Zr-Ti alloys. The precipitation, sedimentation and concentration of numerous intermetallic particles were accomplished by filtrating the residual molten aluminum using a temperature/pressure-controlled vessel adapted with a PoDFA filter. A combination of SEM, TEM, XRD and EMP analysis allowed the identification of (Al,Si)3(Zr,Ti)-D022/D023 intermetallics concentrated within α-FCC matrices of non-Si-doped (sample S2) and Si-doped (samples S4 and S6) alloys. EDS analysis confirmed that Zr and Ti substitute each other in the D022 and D023 phases, whereas Si substitutes in Al sites. Acceptance of Si inside the D023 phase was not expected according to FTlite (FactSage) and TCAL7 (Thermo-Calc) databases. Additionally, Si was found to enhance the formation of (Al,Si)3(Zr,Ti)-D022 intermetallics with high Zr-content, contrary to FactSage 7.3 predictions. TEM results showed intermetallic/FCC crystal coherency for samples S2 and S6, implying that these intermetallics acted as nucleation sites for the Al-phase due to their small lattice mismatch. Furthermore, Si site occupancy was calculated for both (Al,Si)3Ti-D022 and (Al,Si)3Zr-D023 phases via DFT, showing that sites 2b and 4e are the most favorable for Si occupation, respectively. Finally, a thermodynamic model is derived to describe Si substitution upon solidification. Experimental and numerical examinations indicate that Si substitution preferentially occurs in the D022 intermetallics compared to the D023 phase.