Electrospun Polymer Nanofibers: Mechanical and Thermodynamic Perspectives

This article reviews and discusses some open problems concerning polymer materials of reduced sizes and dimensions. Such objects exhibit exceptional physical properties when compared with their macroscopic counterparts. More specifically, abrupt increases in polymer nanofiber elastic modulus have been observed when diameters drop below a certain value. In addition, temperature dependence of elastic modulus is highly influenced by fiber diameter. Mechanical ( macroscopic) analyses have failed to provide satisfactory explanations for the mechanisms ruling such features, calling for detailed microscopic examination of the systems in question. A hypothesis bridging the current knowledge gaps is presented. The key element of this hypothesis is based on confinement of the supermolecular microstructure of polymer nanofibers and its dominant role in the deformation process. This suggestion challenges the commonly held view suggesting that surface effects are the most significant parameters impacting mechanical and thermodynamic nanofiber behaviors. The review will focus on the mechanical and thermodynamic properties of electrospun polymer nanofibers, selected as representatives of nanoscale polymer objects. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 691-707, 2011