This work focuses on the development of electrically conducting porous nanocomposite structures by the incorporation of multiwalled carbon nanotubes (MWNT) into electrospun poly(ethylene oxide) (PEO) nanofibers. Electron microscopy confirmed the presence of individual aligned MWNT encapsulated within the fibers and showed fiber morphologies with diameters of 100-200 nm. Electrical conductance measurements of the random nanofiber mats showed that by increasing the concentration of MWNT we were able to produce porous nanocomposite structures with dramatically improved electrical conductivity. Above a percolation threshold of 0.365 ( 0.09 MWNT weight percent (wt %) in PEO the conductance increased by a factor of 10 12 and then became approximately constant as the concentration of MWNT was further increased. Because of this percolation threshold, for a 1 wt % loading of MWNT, the conductivity is essentially maximized. Mechanical testing confirmed that the tensile strength did not change, and there was a 3-fold increase in the Young's modulus when comparing a 1 wt % MWNT loading to the pure electrospun PEO. Thus, the optimal MWNT concentration for PEO nanofiber mats with enhanced mechanical and electrical properties is ∼1 wt %.

Chitosan is an abundantly common, naturally occurring, polysaccharide biopolymer. Its biocompatible, biodegradable, and antimicrobial properties have led to significant research toward biological applications such as drug delivery, artificial tissue scaffolds for functional tissue engineering, and wound-healing dressings. For applications such as tissue scaffolding, formation of highly porous mats of nanometer-sized fibers, such as those fabricated via electrospinning, may be quite important. Previously, strong acidic solvents and blending with synthetic polymers have been used to achieve electrospun nanofibers containing chitosan. As an alternative approach, in this work, polyethylene oxide (PEO) has been used as a template to fabricate chitosan nanofibers by electrospinning in a core-sheath geometry, with the PEO sheath serving as a template for the chitosan core. Solutions of 3 wt % chitosan (in acetic acid) and 4 wt % PEO (in water) were found to have matching rheological properties that enabled efficient core-sheath fiber formation. After removing the PEO sheath by washing with deionized water, chitosan nanofibers were obtained. Electron microscopy confirmed nanofibers of approximately 250 nm diameter with a clear core-sheath geometry before sheath removal, and chitosan nanofibers of approximately 100 nm diameter after washing. The resultant fibers were characterized with IR spectroscopy and X-ray diffraction, and the mechanical and electrical properties were evaluated.

The governing parameters controlling the miscibility of particle additives within polymeric host media are analyzed for the particular case of silica particle fillers embedded within a poly(methyl methacrylate) (PMMA) matrix. For athermal polymer-graft modification of particles (corresponding to equal chemical composition of graft and matrix polymer), compatibility is found to be a sensitive function of the degree of polymerization of graft and host polymer chains as well as the particle radius. In agreement with theoretical predictions, uniform particle dispersion is observed if the degree of polymerization of grafted chains is comparable to (or exceeds) the corresponding value of the polymer matrix. The resulting restriction to high degree of polymerization limits the accessible inorganic fraction that is attainable in athermal particle/polymer blends. In contrast, favorable interaction between grafted polymer chains and the polymeric host (as realized in the case of poly(styrene-r-acrylonitrile)-grafted particles embedded within PMMA matrix) is shown to facilitate thermodynamically stable and uniform particle dispersion across the entire compositional range even in the limit of large particle size, short grafted chains, and high molecular matrix chains. The synthesis of thermoplastic composite materials with inorganic fraction exceeding 50 vol % combining quantitative optical limiting within the UV frequency range and polymer-like mechanical properties is demonstrated.

The role of polymeric ligands on the optical transparency of polymer-matrix composites is analyzed by evaluating the effect of surface modification on the scattering cross-section of particle fillers in uniform particle dispersions. For the particular case of poly(styrene-r-acrylonitrile)-grafted silica particles embedded in poly(methyl methacrylate), it is shown that the tethering of polymeric chains with appropriate optical properties (such as to match the effective refractive index of the brush particle to the embedding matrix) facilitates the reduction of the particle scattering cross-section by several orders of magnitude as compared to pristine particle analogues. The conditions for minimizing the scattering cross-section of particle fillers by polymer-graft modification are established on the basis of effective medium as well as core-shell Mie theory and validated against experimental data on uniform liquid and solid particle dispersions. Effective medium theory is demonstrated to provide robust estimates of the "optimum polymer-graft composition" to minimize the scattering cross-section of particle fillers even in the limit of large particle dimensions (comparable to the wavelength of light). The application of polymer-graft modification to the design of large (500 nm diameter) silica particle composites with reduced scattering cross-section is demonstrated.