Highly Porous, Rigid-Rod Polyamide Aerogels with Superior Mechanical Properties and Unusually High Thermal Conductivity

We report here the fabrication of polyamide aerogels composed of poly-p-phenylene-terephthalamide, the same backbone chemistry as DuPont's Kevlar. The all-para-substituted polymers gel without the use of cross-linker and maintain their shape during processing-an improvement over the meta-substituted cross-linked polyamide aerogels reported previously. Solutions containing calcium chloride (CaCl₂) and para-phenylenediamine (pPDA) in N-methylpyrrolidinone (NMP) at low temperature are reacted with terephthaloyl chloride (TPC). Polymerization proceeds over the course of 5 min resulting in gelation. Removal of the reaction solvent via solvent exchange followed by extraction with supercritical carbon dioxide provides aerogels with densities ranging from 0.1 to 0.3 g/cm³, depending on the concentration of calcium chloride, the formulated number of repeat units, n, and the concentration of polymer in the reaction mixture. These variables were assessed in a statistical experimental study to understand their effects on the properties of the aerogels. Aerogels made using at least 30 wt % CaCl₂ had the best strength when compared to aerogels of similar density. Furthermore, aerogels made using 30 wt % CaCl₂ exhibited the lowest shrinkage when aged at elevated temperatures. Notably, whereas most aerogel materials are highly insulating (thermal conductivities of 10-30 mW/m K), the polyamide aerogels produced here exhibit remarkably high thermal conductivities (50-80 mW/(m K)) at the same densities as other inorganic and polymer aerogels. These high thermal conductivities are attributed to efficient phonon transport by the rigid-rod polymer backbone. In conjunction with their low cost, ease of fabrication with respect to other polymer aerogels, low densities, and high mass-normalized strength and stiffness properties, these aerogels are uniquely valuable for applications such as lightweighting in consumer electronics, automobiles, and aerospace where weight reduction is desirable but trapping of heat may be undesirable-applications where other polymer aerogels have to date otherwise been unsuitable-creating new opportunities for commercialization of aerogels.