Dense SiOC-Si
3N
4 composites have been obtained employing mixtures with 10 % of Si
3N
4 (SN10) or 5 % Si
3N
4- and an extra amount of carbon-5 % carbon nanofibers- (SN5N5) using spark plasma sintering (SPS). SPS produces densification at 1300/1400 °C and delays the carbothermal reaction of SiO
2/Si
3N
4 up to 1600 °C. It is observed the formation of a percolating network of SiC nanodots/nanowires widespread all over the matrix decorated with graphene-like carbon generated by Joule heating during SPS. The evolution of the C
free is studied by conventional/non-conventional Raman parameters. In this sense, SN5N5–16 and SN10–17 show a C
free phase composed by large highly tortuous and ordered graphene layers with the highest degree of interconnection and crystallinity determinant for understanding the highest thermal and electrical conductivities (1.91 WmK
−1 and 33.6 Sm
−1). Finally, this material displays a low coefficient of thermal expansion (1.26×10
−6 K
−1), remarkable resistance against oxidation to 1400 °C and high absorptance (95.8 %).
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