Light driven PVDF fibers based on photochromic nanosilica@naphthopyran fabricated by wet spinning

Photoresponsive polyvinylidene fluoride (PVDF) fibers doped with naphthopyran-functionalized silica nanoparticles (SiO2@NPT) were successfully prepared by dry-jet we spinning. The incorporated photochromic nanomaterials, SiO2@S1 and SiO2@S2, were previously prepared by covalent post-grafting of the silylated NPTs-2H-naphtho[1,2-b]pyran derivatives, S1 and S2 - onto nano-sized SiO2 (15 +/- 3 nm). The morphological and chemical characterization of the resulting doped fibers PVDF@SiO2@S1 and PVDF@SiO2@S2 was evaluated by scanning electron microscopy with energy dispersive spectroscopy and Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR). Both PVDF@SiO2@S1 and PVDF@SiO2@S2 fibers presented average diameters of 133 +/- 8 mu m and 98 +/- 7 mu m, respectively, and a porous outer surface. The presence of the SiO2@NPT within the fibers was confirmed through the observation of dense clusters embedded within the polymeric matrix. Furthermore, the FTIR-ATR spectra of the fibers revealed that the PVDF matrix was composed of alpha and beta crystalline and amorphous phases. The PVDF@SiO2@S1 and PVDF@SiO2@S2 fibers showed photoresponsive properties under UV and sunlight irradiation, exhibiting fast coloration kinetics and good optical contrast (Delta E-ab* = 7.2 and 15.1, respectively), and changing from a pale orange and an off-white color to a more intense yellow-orange and purple coloration, respectively, in less than 1 min. Moreover, they showed an initial fast bleaching, losing half of their color in less than 30 min (t(1/2) = 28 and 20 min for PVDF@SiO2@S1 and PVDF@SiO2@S2 fibers, respectively), but displaying a residual coloration that took 1 and 2 h to return to the initial uncolored state (t(3/4) = 95 and 49 min, respectively). The PVDF@SiO2@S2 fibers presented the best photochromic performance.