Compressible, Thermally Insulating, and Fire Retardant Aerogels through Self-Assembling Silk Fibroin Biopolymers Inside a Silica Structure-An Approach towards 3D Printing of Aerogels.

Thanks to the exceptional materials properties of silica aerogels, this fascinating highly porous material has found high-performance and real-life applications in various modern industries. However, a requirement for a broadening of these applications is based on the further improvement of the aerogel properties, especially with regard to mechanical strength and postsynthesis processability with minimum compromise to the other physical properties. Here, we report an entirely novel, simple, and aqueous-based synthesis approach to prepare mechanically robust aerogel hybrids by cogelation of silk fibroin (SF) biopolymer extracted from silkworm cocoons. The synthesis is based on sequential processes of acid catalyzed (physical) cross-linking of the SF biopolymer and simultaneous polycondensation of tetramethylorthosilicate (TMOS) in the presence of 5-(trimethoxysilyl)pentanoic acid (TMSPA) as a coupling agent and subsequent solvent exchange and supercritical drying. Extensive characterization by solid-state 1H NMR, 29Si NMR, and 2D 1H-29Si heteronuclear correlation (HETCOR) MAS NMR spectroscopy as well as various microscopic techniques (SEM, TEM) and mechanical assessment confirmed the molecular-level homogeneity of the hybrid nanostructure. The developed silica-SF aerogel hybrids contained an improved set of material properties, such as low density (ρb,average = 0.11-0.2 g cm-3), high porosity (∼90%), high specific surface area (∼400-800 m2 g-1), and excellent flexibility in compression (up to 80% of strain) with three orders of magnitude improvement in the Young's modulus over that of pristine silica aerogels. In addition, the silica-SF hybrid aerogels are fire retardant and demonstrated excellent thermal insulation performance with thermal conductivities (λ) of 0.033-0.039 W m-1 K-1. As a further advantage, the formulated hybrid silica-SF aerogel showed an excellent printability in the wet state using a microextrusion-based 3D printing approach. The printed structures had comparable properties to their monolith counterparts, improving postsynthesis processing or shaping of the silica aerogels significantly. Finally, the hybrid silica-SF aerogels reported here represent significant progress for a mechanically customized and robust aerogel for multipurpose applications, namely, as a customized thermal insulation material or as a dual porous open-cell biomaterial used in regenerative medicine.