| Summary: | Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 2011. === Cataloged from student submitted PDF version of thesis. === Includes bibliographical references. === Electrospinning is a straight forward method to produce fibers with diameter on the order of a few tens of nanometers to the size approaching commercial fibers (on the order of 10 prm or larger). Recently, the length scale effect on physical properties has attracted great attention because of the potential to produce new materials with unique behavior. In general, the behavior of commercial fibers can be investigated by traditional experiments, and that of nanofibers can be studied by molecular dynamics simulation or Monte Carlo technique. However, the transition of their properties from the bulk to the nanoscale materials is not well understood. Electrospinning provides us a bridge to understand the properties of fibers transiting from the behavior of the bulk material to that of the nanofibers. Among these areas, I am interested in the possible remarkable changes in mechanical properties that may occur in electrospun fibers due to the size effect, where the comprehensive understanding is still lacking. My research objectives are to understand mechanical properties of electrospun polymeric fibers as a function of their size, structure and morphology. The first part of my research is to study internal structures and external topographies of electrospun fibers, and to understand their effect on mechanical properties. Amorphous polystyrene (PS) and semicrystalline polyacrylonitrile (PAN) were dissolved in a high boiling point solvent, dimethylformamide (DMF), for electrospinning. When electrospun in a high-humidity environment, the interior of these fibers was found to be highly porous rather than consolidated, despite the smooth and nonporous appearance of the fiber surfaces. The formation of interior porosity is attributed to the miscibility of water, a nonsolvent for the polymers in solution, with DMF. The resulting morphology is a consequence of the relatively rapid diffusion of water into the jet, leading to a liquid-liquid phase separation that precedes solidification due to evaporation of DMF from the jet. When electrospun in a low humidity environment, the fibers exhibit a wrinkled morphology that can be explained by a buckling instability. Understanding which structures and morphology form under a given set of conditions is achieved through the comparison of three characteristic times: the drying time, the buckling time and the phase separation time. The structures and morphology have important consequences for the properties of the fibers such as their mechanical strength and stiffness. === (cont.) Secondly, we studied the size effects of single electrospun fibers on their stiffness and strength. The Young's modulus and yield strength of individual electrospun fibers of amorphous poly(trimethyl hexamethylene terephthalamide) (PA 6(3)T) have been obtained in uniaxial extension. The Young's modulus is found to exhibit values in excess of the isotropic bulk value, and to increase with decreasing fiber diameter for fibers with diameter less than roughly 500 nm. The yield stress is also found to increase with decreasing fiber diameter. These trends are shown to correlate with increasing molecular level orientation within the fibers with decreasing fiber diameter. Using Ward's aggregate model, the correlation between molecular orientation and fiber modulus can be explained, and reasonable determinations of the elastic constants of the molecular unit are obtained. Finally, we identified a relation of stiffness between single electrospun fibers and their nonwoven fabrics. This is of interest because adequate mechanical integrity of nonwoven fabrics is generally a prerequisite for their practical usage. The Young's modulus of electrospun PA 6(3)T nonwoven fabrics were investigated as a function of the diameter of fibers that constitute the fabric. Two quantitative microstructure-based models that relate the Young's modulus of these fabrics to that of the fibers are considered, one assuming straight fibers and the other allowing for sinuous fibers. This study is particularly important for meshes comprising fibers because of our recent discovery of an enhanced size effect on their Young's modulus as well as the tendency towards a curved fiber topology between fiber junctions. The governing factors that affect the mechanical properties of nonwoven mats are the fiber network, fiber curvature, intrinsic fiber properties, and fiber-fiber junctions. Especially for small fibers, both the intrinsic fiber properties and fiber curvature dominate the mechanical behavior of their nonwoven fabrics. This thesis helps us to understand the mechanism behind the enhanced mechanical behavior of small fibers, and to identify determining parameters that can be used to tailor their mechanical performance. === by Chia-Ling Pai. === Ph.D.
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