Doctor of Philosophy (PhD)


Mechanical and Industrial Engineering

Document Type



The design approach and validation of single phase senary refractory high entropy alloys (HEAs) MoNbTaTiVW and HfNbTaTiVZr were presented in first part of this dissertation. The design approach was to combine phase diagram inspection of available binary and ternary systems and Calculation of Phase Diagrams (CALPHAD) prediction. Experiments using X-ray diffraction and scanning electron microscopy techniques verified single phase microstructure in body centered cubic lattice for both alloys. The observed elemental segregation agrees well with the solidification prediction using Scheil model. The lattice constant, density and microhardness were measured to be 0.3216 nm, 4.954 GPa and 11.70 g/cm3 for MoNbTaTiVW and 0.334 nm, 5.5 GPa and 9.36 g/cm3 for HfNbTaTiVZr.

To elaborate the single-phase stability of HEAs, CrxMoNbTaVW was examined over a certain range of Cr content in the second part of this dissertation. The change in composition led to different BCC structures with different microstructures and physical properties. Microstructure characterizations were performed using X-ray diffraction and scanning electron microscopy. Chemical micro-segregation during solidification predicted using the Scheil model generally agrees with the experimental results. The lattice constant, density, and Vickers' micro-hardness of the high-entropy alloy samples in the as-cast state are measured and discussed. For CrxMoNbTaVW, x=2.0 case appears exceeding the upper limit of maintaining a single BCC phase HEA, determined by the XRD patterns. The elemental dependence of the mixing thermodynamic properties (entropy, enthalpy and Gibbs energy) in BCC phase in the senary system is analyzed. The calculated entropy of mixing and enthalpy of mixing for CrMoNbTaVW are 14.7 J/K/mol and −662.5 J/mol respectively.

Phase predictions and characterizations on as-solidified septenary refractory high-entropy alloy, CrMoNbReTaVW, are presented in the third part of the dissertation. The simulated solidification process predicts a single body-centered-cubic (BCC) crystal structure with the tendency of compositional segregation. X-ray diffraction results confirm the “single-phase-like” BCC structure, while further experimental characterizations reveal the existence of multiple grains with significantly different compositions yet the same crystal structure and similar lattice.

For better understanding of corrosion properties of high entropy alloys, the CALPHAD method was further used to simulate the Pourbaix diagram and the corrosion layer evolutions under equilibrium conditions for CoCrFeNi based HEAs in the last part of the dissertation. The oxidation layer pitting and forming potential were calculated and compared favorably with published experimental results on CoCrFeNi, CoCrFeNiCu and CoCrFeNiAl0.5 HEAs.



Committee Chair

Guo, Shengmin