Nickel content-dependent microstructure and mechanical properties of TiZrNbHfNi high entropy alloy thin films

Alloying is known as an effective strategy to improve the mechanical properties of metallic materials. Here we show that the microstructure and mechanical behavior of a TiZrNbHf1.6 high entropy alloy film can be highly tuned by Ni addition. The newly designed TiZrNbHf1.6Nix (x = 0, 0.4, 1.2, 1.8, 2.5, 3.0, 4.6) alloy films are synthesized by co-sputtering Ti, Zr, Nb, Hf and Ni elemental targets. The microstructure and mechanical behavior of the alloy films are investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), and nano/micro-indentations. The microstructural analysis indicates that the TiZrNbHf1.6 film has a single bodycentered cubic with columnar-nanograined structure. As Ni content increases to 0.4 or above, the films show a complete amorphous structure. Our theoretical analysis shows that the transition from the crystalline to the amorphous structure can be attributed to the large atomic radius difference and the change of the thermodynamic parameters (e.g., mixing entropy and mixing enthalpy) due to the Ni addition. Compared to the TiZrNbHf1.6 film with a hardness of 4.8 GPa, a hardness increase of 8-35% is achieved in the Ni-doped alloy films (5.2-6.5 GPa) as measured by nanoindentation. The elevated hardness may be attributed to the severe lattice distortion and the amorphous structure induced by the Ni addition. Furthermore, microindentation reveals a diversity of deformation behavior in those films with different Ni content. A homogeneous deformation (slight plastic pileup) occurred in the films with Ni content of 1.2 and 4.6, which is close to the deformation behavior of the crystal TiZrNbHf1.6 film. While the film with a Ni content of 1.8 exhibits a catastrophic cracking deformation. Finally, multiple shear banding dominates the deformation of these films with Ni content of 0.4, 2.5 and 3.0. Our findings demonstrate that ultrastrong and highly deformable amorphous high entropy alloy thin films can be developed by appropriate element addition, making them promising materials for corrosion and wear-resistant coatings.