CoNiFeCr high entropy alloy (HEA) was used as a binder in cemented carbides for developing a new high-performance binder. The microstructure of WC-HEA cemented carbides with different binder components and carbon contents was subsequently studied. It was observed that the (Cr,W)C phase precipitated at the WC/HEA interface, and a coherent interface with a low degree of misfit was formed between WC and (Cr,W)C, thereby resulting in a significant reduction in the interfacial energy and stress concentration. The (Cr,W)C phase exerted a pinning force (Zener-drag) on the moving grain boundaries, which effectively inhibited the growth of WC grains. As a result, compared with WC-Co, WC-CoNiFeCr had smaller WC grain size, smoother grain shape and larger mean free path (MFP) of the binder, which resulted in slightly lower hardness and higher transverse rupture strength (TRS) and fracture toughness. The lower limit of carbon content in WC-CoNiFeCr was higher than that of WC-Co. With the addition of Ni, the width of the two-phase region became wider, whereas the width of the two-phase region became narrower with the addition of Fe and Cr.

As a crucial component of cemented carbide, the binder phase exerts a profound influence on its microstructure and mechanical properties. In this study, ultrafine-grained WC-10CoNiFe and WC-10Co cemented carbides, with grain sizes ranging from 0.25 to 0.4 μm, were fabricated via powder mixing, forming, and sintering processes utilizing 0.4 μm WC powder as the starting material. The effects of carbon content (5.44–5.50 wt%) and sintering temperatures (1410–1500 °C) on the grain organization and mechanical properties of these cemented carbides were systematically investigated. The results revealed that WC-10CoNiFe achieved its optimal mechanical properties at a carbon content of 5.46 wt% and a sintering temperature of 1450 °C, exhibiting a flexural strength of 2999 MPa and a hardness of 1765 HV. Likewise, WC-10Co attained its peak performance at a carbon content of 5.48 wt% and a sintering temperature of 1410 °C, with a flexural strength of 3598 MPa and a hardness of 1853 HV. Remarkably, the finer grain size of the WC-10CoNiFe alloy (0.261 µm), compared to that of WC-10Co (0.294 µm), can be ascribed to the suppression of the dissolution–reprecipitation process by the multi-principal-element alloy binder. This study demonstrated the synergistic regulation of microstructure and mechanical properties in ultrafine-grained cemented carbides through the incorporation of a multi-principal-element alloy binder. This innovative strategy not only effectively refines the grain size but also endows the alloy with exceptional mechanical properties, offering a valuable new perspective for the research and development of high-performance cemented carbides.

To enhance the oxidation resistance of Mo-based TZM alloy (Mo-0.5Ti-0.1Zr-0.02C, wt%), a novel MoSi₂-ZrB₂ composite coating was applied on the TZM substrate by a two-step process comprising the in situ reaction of Mo, Zr, and B₄C to form a ZrB₂-MoB pre-layer followed by pack siliconizing. The as-packed coating was composed of a multi-layer structure, consisting of a MoB diffusion layer, an MoSi₂-ZrB₂ inner layer, and an outer layer of mixture of MoSi₂ and Al₂O₃. The composite coating could provide excellent oxidation-resistant protection for the TZM alloy at 1600 °C. The oxidation kinetic curve of the composite coating followed the parabolic rule, and the weight gain of the coated sample after 20 h of oxidation at 1600 °C was only 5.24 mg/cm². During oxidation, a dense and continuous SiO₂-baed oxide scale embedded with ZrO₂ and ZrSiO₄ particles showing high thermal stability and low oxygen permeability could be formed on the surface of the coating by oxidation of MoSi₂ and ZrB₂, which could hinder the inward diffusion of oxygen at high temperatures. Concurrently, the MoB inner diffusion layer played an important role in hindering the diffusion of Si inward with regard to the TZM alloy and could retard the degradation of MoSi₂, which could also improve the long life of the coating.

To improve the oxidation resistance of Mo-based alloys, a novel (Mo,Hf)Si₂-Al₂O₃ composite coating was fabricated on a Mo-based alloy by the method of slurry sintering. The isothermal oxidation behavior of the coating was evaluated at 1400 °C. The microstructure evolution and phase composition of the coating before and after oxidation exposure were characterized. The anti-oxidant mechanism for the good performance of the composite coating during high-temperature oxidation was discussed. The coating had a double-layer structure consisting of a MoSi₂ inner layer and a (Mo,Hf)Si₂-Al₂O₃ outer composite layer. The composite coating could offer more than 40 h of oxidation-resistant protection at 1400 °C for the Mo-based alloy, and the final weight gain rate was only 6.03 mg/cm² after oxidation. A SiO₂-based oxide scale embedded with Al₂O₃, HfO₂, mullite, and HfSiO₄ was formed on the surface of the composite coating during oxidation. The composite oxide scale exhibited high thermal stability, low oxygen permeability, and enhanced thermal mismatch between oxide and coating layers, thus improving the oxidation resistance of the coating.