Polarized Catalytic Polymer Nanofibers.

Molecular scale modifications were achieved by spontaneous polarization which is favored in enhancements of ß-crystallization phase inside polyvinylidene fluoride (PVDF) nanofibers (NFs). These improvements were much more effective in nano and submicron fibers compared to fibers with relatively larger diameters. Metallic nanoparticles (NPs) supported by nanofibrous membranes opened new vistas in filtration, catalysis, and serving as most reliable resources in numerous other industrial applications. In this research, hydrogenation of phenol was studied as a model to test the effectiveness of polarized PVDF nanofiber support embedded with agglomerated palladium (Pd) metallic nanoparticle diameters ranging from 5-50 nm supported on polymeric PVDF NFs with ~200 nm in cross-sectional diameters. Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Atomic Force Microscopy (AFM), Energy Dispersive X-Ray Spectroscopy (EDX), Fourier Transform Infrared Spectroscopy (FTIR) and other analytical analysis revealed both molecular and surface morphological changes associated with polarization treatment. The results showed that the fibers mats heated to their curie temperature (150 °C) increased the catalytic activity and decreased the selectivity by yielding substantial amounts of undesired product (cyclohexanol) alongside with the desired product (cyclohexanone). Over 95% phenol conversion with excellent cyclohexanone selectivity was obtained less than nine hours of reaction using the polarized PVDF nanofibers as catalytic support structures.

Polyvinylidene fluoride molecules in nanofibers, imaged at atomic scale by aberration corrected electron microscopy.

Atomic scale features of polyvinylidene fluoride molecules (PVDF) were observed with aberration corrected transmission electron microscopy. Thin, self-supporting PVDF nanofibers were used to create images that show conformations and relative locations of atoms in segments of polymer molecules, particularly segments near the surface of the nanofiber. Rows of CF2 atomic groups, at 0.25 nm intervals, which marked the paths of segments of the PVDF molecules, were seen. The fact that an electron microscope image of a segment of a PVDF molecule depended upon the particular azimuthal direction, along which the segment was viewed, enabled observation of twist around the molecular axis. The 0.2 nm side-by-side distance between the two fluorine atoms attached to the same carbon atom was clearly resolved. Morphological and chemical changes produced by energetic electrons, ranging from no change to fiber scission, over many orders of magnitude of electrons per unit area, promise quantitative new insights into radiation chemistry. Relative movements of segments of molecules were observed. Promising synergism between high resolution electron microscopy and molecular dynamic modeling was demonstrated. This paper is at the threshold of growing usefulness of electron microscopy to the science and engineering of polymer and other molecules.

Fabrication, Polarization of Electrospun Polyvinylidene Fluoride Electret Fibers and Effect on Capturing Nanoscale Solid Aerosols.

Electrospun polyvinylidene fluoride (PVDF) fiber mats with average fiber diameters (≈200 nm, ≈2000 nm) were fabricated by controlled electrospinning conditions. These fiber mats were polarized using a custom-made device to enhance the formation of the electret ß-phase ferroelectric property of the fibers by simultaneous uniaxial stretching of the fiber mat and heating the mat to the Curie temperature of the PVDF polymer in a strong electric field of 2.5 kV/cm. Scanning electron microscopy, Fourier transform infrared spectroscopy, thermal gravimetric analysis, differential scanning calorimetry and Brunauer-Emmett-Teller (BET) surface area analyses were performed to characterize both the internal and external morphologies of the fiber mat samples to study polarization-associated changes. MATLAB simulations revealed the changes in the paths of the electric fields and the magnetic flux inside the polarization field with inclusion of the ferroelectric fiber mats. Both polarized and unpolarized fiber mats were challenged as filters against NaCl particles with average particle diameters of about 150 nm using a TSI 8130 to study capture efficiencies and relative pressure drops. Twelve filter experiments were conducted on each sample at one month time intervals between experiments to evaluate the reduction of the polarization enhancement over time. The results showed negligible polarization loss for the 200-nm fiber sample. The polarized mats had the highest filter efficiencies and lowest pressure drops.