The ultrafine structure of multiphase ceramics TiB2-Ti0.9W0.1-SiC formed by the in-situ reactive hot-pressing process has been characterized using high-resolution electron microscopy (HREM) and analytical electron microscopy. The results reveal that TIB2 crystallized into plate-like shapes, containing TiC plate precipitates. Three different orientation relationships between TIC precipitates and the TiB2 matrix were determined and the formation mechanism was proposed. Crystalline intergranular phase containing Fe, Si and Ti elements were formed at grain edge intersections. Along the TiB2 plates, the intergrowth of 6H-SiC bands were often found. An orientation relationship between the 6H-SiC and TiB2, in which [<11(2)over bar 0>](TIB2)//[<11(2)over bar 0>](SiC) and (0001)(TiB2)//(0001)(SiC), was found and the atomic structures at the TiB2/6H-SiC interface have been investigated by HREM combined with image simulations of several proposed models. Comparison of simulated images and the experimentally observed image resulted into an optimal structure model with Ti-B-C-Si stacking sequence at the interface.
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