The ladder phenyl/vinyl polysilsesquioxane (PhVPOSS) was used to improve the flame-retardancy performances of ethylene-vinyl acetate copolymer (EVA)/aluminum hydroxide (ATH) composites due to the reactivity of its vinyl groups. FTIR, XPS, ¹H NMR, and SEM-EDS data demonstrated the PhVPOSS grafting onto EVA molecular chains. The PhVPOSS improved the thermal stability of EVA/ATH composites, as shown by the thermogravimetric analysis (TGA). Furthermore, with the cone calorimeter (CONE) experiments, EVA/ATH/PhVPOSS showed better fire safety than the EVA/ATH composites, with the PHRR, PSPR, and PCOP reduced by 7.89%, 57.4%, and 90.9%, respectively. The mechanism investigations of flame retardancy revealed that the charring behaviors of the EVA/ATH/PhVPOSS composites were improved by the formation of Si-C bonds and Si-O bonds, and a more compact and denser char layer can contribute more to the barrier effect.

Polymer-based sandwich structures have garnered significant interest as energy-absorbing protective materials. However, common damage modes in composite sandwich panels include matrix cracking, delamination, core crushing or core fracture, and debonding between the face sheets and the core. Among these, face–core debonding is one of the most prevalent failure mechanisms. This paper investigates a sandwich configuration designed to enhance blast resistance by incorporating a self-adhesive, stiffened polyimide foam (ASPI) into a steel–foam–steel architecture. The thermogravimetric analysis exhibits that ASPI foam obtained excellent thermal stability, and the residual mass retention at 800 °C was more than 36.2%. Experimental results show that at scaled distances of 1.077 m/kg^1/3 and 1.292 m/kg^1/3, the ASPI foam-based sandwich panels exhibited mid-span displacements as low as 8.5 mm and 6.7 mm, respectively. Under a scaled distance of 1.077 m/kg^1/3, the mid-span displacement of the ASPI foam-based sandwich structure decreased from 15.0 mm to 8.5 mm, representing a 43.3% reduction compared with that of the neat polyimide foam-based sandwich structure. Moreover, compared with neat PI foam, the ASPI foam exhibited superior adhesion to steel face sheets, and no interfacial debonding was observed after blast loading. To further elucidate the underlying damage mechanisms under blast loading, a well-validated finite element model was developed and employed. Complementary scanning electron microscopy (SEM) analyses were conducted to examine the microstructural morphology of the ASPI foam core’s cross-section and surface after blast exposure. This study presents an investigation of a lightweight, self-adhesive, high-thermal stability, blast-resistant polymer-based composite foam.