In-situ formation of surface “self-protective” graphitic layer on phenolic resin-based thermal protection composites

Phenolic resin (PR) composites are widely utilized as thermal protection materials for high-speed aircraft, where their protection mechanisms have been investigated in earlier studies. However, it remained indistinct about the evolution behavior of the outermost surface and its subsequent effects on the ablation performance. Herein, this work re-investigated the morphological transformation and chemical conversion on the outermost surface of a silica fiber-reinforced PR board after ablation by means of combined experimental characterizations at micro- and nanoscale (SEM, TEM, Raman spectroscopy, XRD, XPS) and computational study (ReaxFF-based molecular dynamic simulation). For the first time, our study revealed that its outermost ablated surface demonstrated a distinct evolution behavior in terms of both the in-situ formation of “self-protective” graphitic layer and the radial redistribution of surface carbonaceous substances with different degrees of graphitization, leading to varied ablation resistance along the radial direction of the PR board. In addition, the computational study investigates the ablation-induced graphitization and its influence on the ablative resistance of PR surface. It indicated that, at equivalent energy flux density, PR with graphitized structures exhibited improved thermal protection performance, which can be attributed to decreased thermal conductivity and increased density, leading to a reduced ablation recession rate. Such revelation provides an alternative route in the design of PR-based ablative materials with enhanced ablation resistance.