W_xNbMoTa refractory high-entropy alloys with four different tungsten concentrations (x = 0, 0.16, 0.33, 0.53) were fabricated by laser cladding deposition. The crystal structures of W_xNbMoTa alloys are all a single-phase solid solution of the body-centered cubic (BCC) structure. The size of the grains and dendrites are 20 μm and 4 μm on average, due to the rapid solidification characteristics of the laser cladding deposition. These are much smaller sizes than refractory high-entropy alloys fabricated by vacuum arc melting. In terms of integrated mechanical properties, the increase of the tungsten concentration of W_xNbMoTa has led to four results of the Vickers microhardness, i.e., H_v = 459.2 ± 9.7, 476.0 ± 12.9, 485.3 ± 8.7, and 497.6 ± 5.6. As a result, NbMoTa alloy shows a yield strength (σ_b) and compressive strain (ε_p) of 530 Mpa and 8.5% at 1000 °C, leading to better results than traditional refractory alloys such as T-111, C103, and Nb-1Zr, which are commonly used in the aerospace industry.

The conventional method of preparing metal–ceramic composite structures causes delamination and cracking defects due to differences in the composite structures’ properties, such as the coefficient of thermal expansion between metal and ceramic materials. Laser-directed energy deposition (LDED) technology has a unique advantage in that the composition of the materials can be changed during the forming process. This technique can overcome existing problems by forming composite structures. In this study, a multilayer composite structure was prepared using LDED technology, and different materials were deposited with their own appropriate process parameters. A layer of Al₂O₃ ceramic was deposited first, and then three layers of a NbMoTa multi-principal element alloy (MPEA) were deposited as a single composite structural unit. A specimen of the NbMoTa–Al₂O₃ multilayer composite structure, composed of multiple composite structural units, was formed on the upper surface of a φ20 mm × 60 mm cylinder. The wear resistance was improved by 55% compared to the NbMoTa. The resistivity was 1.55 × 10⁻⁵ Ω × m in the parallel forming direction and 1.29 × 10⁻⁷ Ω × m in the vertical forming direction. A new, electrically anisotropic material was successfully obtained, and this study provides experimental methods and data for the preparation of smart materials and new sensors.