Composites Part B 324 (2026) 113908

Keywords:Ceramization, Composites, Phenolic, Shape memory polymers, Thermal deformation

TRapid advancement of deep-space exploration vehicles places increasing demands on smart thermal deformation  materials for high efficiency, adaptability, and stability. To solve the shape instability in smart deformable  materials at elevated temperatures, a shape memory ceramizable phenolic composite (SMCPC) is proposed by  synergistically incorporating the inorganic fillers into a phenolic–boric acid copolymer network. Linear phenolic  segments and boric acid serve as the reversible and fixed phases respectively, providing excellent shape memory  behavior with a shape recovery rate of 93%. While inorganic functional fillers are employed to trigger high-temperature ceramization, enabling rapid transition from a polymeric system to a mechanically robust  ceramic structure. The oxide-filled phenolic composite exhibits a high char yield of 71.7% at 1000^◦C, leading to  a relative 37.9% increase of the phenolic matrix. At elevated temperatures, the carbonized phenolic matrix  promotes thermochemical reduction of oxides, forming a multiphase ceramic framework composed of metal  carbides, residual oxides, and graphitized carbon that endows the composite with excellent ablation resistance.  Finally, the composite containing 24 wt% HfO₂  exhibits the lowest mass ablation rate of 0.038 g/s, representing a  69.8% reduction compared with the phenolic matrix. Although the material systems show a relative brittleness,  the established new strategy of “deformation–recovery–ceramization” enables the potential application of shape  memory polymers in extreme environments.

Likai Hu, Fenghua Zhang, Binghuan Gao, Lan Luo, Yanju Liu, Jinsong Leng

Synergistic design of ceramizable and ablation-resistant shape memory oxide-filled phenolic composites for self-adaptive thermal deformation.pdf