At present, silicone rubber-based ablative composites are usually enhanced by carbon fibers (CFs) to protect the case of solid rocket motors (SRMs). However, the effect of the CFs’ length on the microstructure and ablation properties of the silicone rubber-based ablative composites has been ignored. In this work, different lengths of CFs were introduced into silicone rubber-based ablative composites to explore the effect of fiber length, and ceramic layers of various morphologies were constructed after ablation. It was found that a complete and continuous skeleton in ceramic layers was formed by CFs over 3 mm in length. In addition, the oxyacetylene ablation results showed that the linear ablation rate declined from 0.233 to 0.089 mm/s, and the maximum back-face temperature decreased from 117.7 to 107.9 °C as the length of the CFs increased from 0.5 to 3 mm. This can be attributed to the fact that successive skeletons concatenated and consolidated the ceramic fillers as well as residues to form an integrated, robust, and dense ceramic layer.

Ethylene–propylene–diene monomer (EPDM) composites were usually enhanced with ablative additives to protect solid rocket motor (SRMs) casings. However, the poor thermal insulation caused by the high thermal conductive ablative fillers can lead to rocket motor failure. Herein, the novel EPDM composites containing alternating layers of ablative EPDM (AM) and heat-insulated EPDM (HM) were prepared through layer-multiplying extrusion. Compared with conventional EPDM ablative material, the multilayer composites showed enhanced thermal insulation and mechanical properties that could be further improved by tuning the number of layers. The ablation and thermal insulation properties possessing in AM and HM layers could be combined by forced assembly during co-extrusion, and the alternating multilayer composite was capable of showing the effect of each component. In particular, compared with AM, the maximum back-face temperature with 40 alternating layers of AM/HM decreased from 96.2 °C to 75.6 °C during oxyacetylene test, while the good ablation properties were preserved in the AM component. This significant improvement was attributed to the planar orientation and densification of ablative additives, and the interruption of conductive pathways in the through-plane direction of AM/HM alternating laminate. The anisotropic EPDM composites featuring mechanical robustness, good ablative resistance and thermal insulation suggest considerable potential application in the aerospace industry.