Regulating porous microstructure of polyimide aerogels toward efficient shape memory performance

The development of lightweight shape memory materials with exceptional thermal insulation properties is highly important in aerospace applications. Herein, shape memory polyimide (PI) aerogels was fabricated by molecularly designed PI molecular chains through freeze gelation and subsequent thermal imidization. The freezing conditions were controlled to regulate the porous microstructures of the aerogels. The interactions between PI chains formed physically crosslinked netpoints, which could overcome the expansive force and capillary force, thereby creating a stable porous structure. Because shape memory was thermally activated, the shape memory mechanisms associated with the thermal conductivity of the aerogels were comprehensively explored. Upon decreasing the pore size, dense frameworks were formed, contributing to the improved thermo-mechanical and compressive properties. Moreover, the heat transfer efficiency in the aerogel skeleton was enhanced, resulting in a rapid shape recovery response. Benefiting from the physically crosslinked structures, including entangled chains and π-π interactions, the fabricated PI aerogels demonstrated exceptional shape fixation and recovery capabilities. These findings may provide guidelines for designing smart aerogels for aerospace applications.