Hybrid Silica–PVA Nanofibers via Sol–Gel Electrospinning

We report on the synthesis of poly­(vinyl alcohol) (PVA)–silica hybrid nanofibers via sol–gel electrospinning. Silica is synthesized through acid catalysis of a silica precursor (tetraethyl orthosilicate (TEOS) in ethanol–water), and fibers are obtained by electrospinning a mixture of the silica precursor solution and aqueous PVA. A systematic investigation on how the amount of TEOS, the silica–PVA ratio, the aging time of the silica precursor mixture, and the solution rheology influence the fiber morphology is undertaken and reveals a composition window in which defect-free hybrid nanofibers with diameters as small as 150 nm are obtained. When soaked overnight in water, the hybrid fibers remain intact, essentially maintaining their morphology, even though PVA is soluble in water. We believe that mixing of the silica precursor and PVA in solution initiates the participation of the silica precursor in cross-linking of PVA so that its −OH group becomes unavailable for hydrogen bonding with water. FTIR analysis of the hybrids confirms the disappearance of the −OH peak typically shown by PVA, while formation of a bond between PVA and silica is indicated by the Si–O–C peak in the spectra of all the hybrids. The ability to form cross-linked nanofibers of PVA using thermally stable and relatively inert silica could broaden the scope of use of these materials in various technologies

Hybrid Carbon Silica Nanofibers through Sol–Gel Electrospinning

A controlled sol–gel synthesis incorporated with electrospinning is employed to produce polyacrylonitrile–silica (PAN–silica) fibers. Hybrid fibers are obtained with varying amounts of silica precursor (TEOS in DMF catalyzed by HCl) and PAN. Solution viscosity, conductivity, and surface tension are found to relate strongly to the electrospinnability of PAN–silica solutions. TGA and DSC analyses of the hybrids indicate strong intermolecular interactions, possibly between the −OH group of silica and −CN of PAN. Thermal stabilization of the hybrids at 280 °C followed by carbonization at 800 °C transforms fibers to carbon–silica hybrid nanofibers with smooth morphology and diameter ranging from 400 to 700 nm. FTIR analysis of the fibers confirms the presence of silica in the as-spun as well as the carbonized material, where the extent of carbonization is also estimated by confirming the presence of −CC and −CO peaks in the carbonized hybrids. The graphitic character of the carbon–silica fibers is confirmed through Raman studies, and the role of silica in the disorder of the carbon structure is discussed

Fibrillar Structure of Methylcellulose Hydrogels

It is well established that aqueous solutions of methylcellulose (MC) can form hydrogels on heating, with the rheological gel point closely correlated to the appearance of optical turbidity. However, the detailed gelation mechanism and the resulting gel structure remain poorly understood. Herein the fibrillar structure of aqueous MC gels was precisely quantified with a powerful combination of (real space) cryogenic transmission electron microscopy (cryo-TEM) and (reciprocal space) small-angle neutron scattering (SANS) techniques. The cryo-TEM images reveal that MC chains with a molecular weight of 300 000 g/mol associate into fibrils upon heating, with a remarkably uniform diameter of 15 ± 2 nm over a range of concentrations. Vitrified gels also exhibit heterogeneity in the fibril density on the length scale of hundreds of nanometers, consistent with the observed optical turbidity of MC hydrogels. The SANS curves of gels exhibit no characteristic peaks or plateaus over a broad range of wavevector, <i>q</i>, from 0.001–0.2 Å^–1. The major feature is a change in slope from <i>I</i> ∼ <i>q</i>^–1.7 in the intermediate <i>q</i> range (0.001 – 0.01 Å^–1) to <i>I</i> ∼ <i>q</i>^–4 above <i>q</i> ≈ 0.015 Å^–1. The fibrillar nature of the gel structure was confirmed by fitting the SANS data consistently with a model based on the form factor for flexible cylinders with a polydisperse radius. This model was found to capture the scattering features quantitatively for MC gels varying in concentration from 0.09–1.3 wt %. In agreement with the microscopy results, the flexible cylinder model indicated fibril diameters of 14 ± 1 nm for samples at elevated temperatures. This combination of complementary experimental techniques provides a comprehensive nanoscale depiction of fibrillar morphology for MC gels, which correlates very well with macro-scale rheological behavior and optical turbidity previously observed for such systems