In Situ Synthesis of RMB₆-TMB₂ Composite Nanopowders via One-Step Solid-State Reduction

RMB₆-TMB₂ (RM = rare earth elements, TM = transition metal elements) composites retain superior field emission properties of RMB₆ while addressing its inherent mechanical limitations by constructing a eutectic structure with TMB₂. Herein, an in situ route for synthesizing RMB₆-TMB₂ composite nanopowders with homogeneous phase distribution using reduction reactions was proposed. The LaB₆-ZrB₂ composite nanopowders were synthesized in situ for the first time using sodium borohydride (NaBH₄) as both a reducing agent and boron source, with lanthanum oxide (La₂O₃) and zirconium dioxide (ZrO₂) serving as metal sources. The effects of the synthesis temperature on phase compositions and microstructure of the composites were systematically investigated. The LaB₆-ZrB₂ system with a eutectic weight ratio exhibited an accelerated reaction rate, achieving a complete reaction at 1000 °C, 300 °C lower than that of single-phase ZrB₂ synthesis. The composite phases were uniformly distributed even at nanoscale. The composite powder displayed an average particle size of ~170 nm when synthesized at 1300 °C. With the benefit of the in situ synthesis method, LaB₆-TiB₂, CeB₆-ZrB₂, and CeB₆-TiB₂ composite powders were successfully synthesized. This process effectively addresses phase separation and contamination issues typically associated with traditional mixing methods, providing a scalable precursor for high-performance RMB₆-TMB₂ composites.