• Multiphase ceramic nanofibers (MPC-NFs) are fabricated using sol-gel method, electrospinning, and calcination. • Fibers consist of crystalline α-alumina and mullite phases surrounded by an amorphous phase. • MPC-NFs possess improved structural flexibility and thermal properties at extreme conditions. • Aerogels based on ceramic nanofibers could be useful for high-temperature insulation or shielding.

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