This paper presents the results of microstructural analysis of novel preceramic paper-derived SiCf/SiC composites fabricated by spark plasma sintering. The sintering temperature and pressure were 2100/2200 °C and 60/100 MPa, respectively. The content of fibers in the composites was approx. 10 wt %. The SiCf/SiC composites were analyzed by positron annihilation methods, X-ray diffraction technology, scanning electron microscopy, and Raman spectroscopy. Longer sintering time causes the proportion of the 6H-SiC composition to increase to ~80%. The increase in sintering temperature from 2100 °C to 2200 °C leads to partial transition of 4H-SiC to 6H-SiC during the sintering process, and the long-life component of positrons indicates the formation of Si vacancies. The Raman characteristic peaks of turbostratic graphite appear in the Raman spectrum of SiC fibers, this is caused by the diffusion of carbon from the surface of the SiC fiber and the preceramic paper during the high-temperature sintering process.
