We report on a novel polymer‐derived synthesis approach that yields boron carbide monoliths and metal‐reinforced B4C cermets. This single‐step approach relies on a preceramic powder blend of boron and an acetylenic resin with a high char yield. At low temperatures below 1500°C and without applied pressures, preceramic precursor reaction bond together and form nanocrystalline refractory B4C matrices. Resulting near net shape boron, carbide monoliths exhibit small crystal grain sizes, maintain chemical purity, and exhibit morphological homogeneity. We reinforce the refractory carbide with five different metals and demonstrate the influence of each on the density, hardness, oxidation stability, and electronic conductivity of resulting cermet composites. We assess the optimal synthesis and reinforcement strategies that tailor these nanostructured materials for inexpensive and high‐performing engineering applications.
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