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New open-access paper out in ACS Polymerson the control of the crystalline and electroactive phase of PVDF aerogels of interest for multiple applications from energy harvesting to thermal/acoustic insulation.

Poly(vinylidene fluoride) Aerogels with α, β, and γ Crystalline Forms: Correlating Physicochemical Properties with Polymorphic Structures

Sruthi Suresh, Turkan Nabiyeva, Laure Biniek,* and E. Bhoje Gowd*

ACS Polym. Au, 2024 

Strategic customization of crystalline forms of poly(vinylidene fluoride) (PVDF) aerogels is of great importance for a variety of applications, from energy harvesters to thermal and acoustic insulation. Here, we report sustainable strategies to prepare crystalline pure α, β, and γ forms of PVDF aerogels from their respective gels using a solvent exchange strategy with green solvents, followed by a freeze-drying technique. The crucial aspect of this process was the meticulous choice of appropriate solvents to enable the formation of thermoreversible gels of PVDF by crystallization-induced gelation. Depending on the polymer−solvent interactions, the chain conformation of PVDF can be modulated to obtain gels and aerogels with specific crystalline structures. The crystalline pure α-form and piezoelectric β-form aerogels were readily obtained by using cyclohexanone and γ-butyrolactone as gelation solvents. On the other hand, the γ-form aerogel was obtained using a binary solvent system consisting of dimethylacetamide and water. These aerogels with distinct crystalline structures exhibit different morphologies, mechanical properties, hydrophobicities, acoustic properties, and electrical properties. Measurement of thermal conductivity for these aerogels showed exceptionally low thermal conductivity values of ∼0.040 ± 0.003 W m−1 K−1 irrespective of their crystal structures. Our results showcase the fabrication approaches that enable PVDF aerogels with varied physicochemical properties for multifunctional applications.