Lightweight materials that combine high mechanical strength, insulation, and fire resistance are of great interest to many industries. This work explores the properties of environmentally friendly alginate aerogel composites as potential sustainable alternatives to petroleum-based materials. This study analyzes the effects of two additives (tannic acid and montmorillonite clay), the orientation that results during casting, and the crosslinking of the biopolymer with glutaraldehyde on the properties of the aerogel composites. The prepared aerogels exhibited high porosities between 90% and 97% and densities in the range of 0.059–0.191 g/cm
3. Crosslinking increased the density and resulted in excellent performance under loading conditions. In combination with axial orientation, Young’s modulus and yield strength reached values as high as 305 MPa·cm
3/g and 7 MPa·cm
3/g, respectively. Moreover, the alginate-based aerogels exhibited very low thermal conductivities, ranging from 0.038 W/m·K to 0.053 W/m·K. Compared to pristine alginate, the aerogel composites’ thermal degradation rate decreased substantially, enhancing thermal stability. Although glutaraldehyde promoted combustion, the non-crosslinked aerogel composites demonstrated high fire resistance. No flame was observed in these samples under cone calorimeter radiation, and a minuscule peak of heat release of 21 kW/m
2 was emitted as a result of their highly efficient graphitization and fire suppression. The combination of properties of these bio-based aerogels demonstrates their potential as substituents for their fossil-based counterparts.
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