Macromolecular Design Principles Governing Electrospinning of Polymer Nanofibers

Electrospinning is a versatile technique for producing polymer nanofibers with high ratios of surface area to volume and tunable porosity. Conventional approach to the optimization of processing parameters such as voltage and flow rate frequently encounters limitations in reproducibility and scalability. This review proposes a comprehensive framework that integrates macromolecular design principles with established electrohydrodynamic theories. We analyze how intrinsic molecular traits, specifically, chain entanglement density, molecular weight distribution (MWD), topological architecture, and polymer-solvent thermodynamic interactions define the boundaries of jet stability and solidification. Key findings highlight that while molecular weight establishes a baseline for spinnability, the MWD dictates the dynamic response under extreme deformation. Notably, high-molecular-weight fractions act as elastic load-bearers that suppress capillary breakup. Furthermore, we discuss here how molecular architecture and solvent-mediated segmental mobility determine whether molecular orientation is kinetically trapped or relaxed during the nanosecond timescales of jet flight. By establishing a hierarchical design logic prioritizing molecular and formulation variables over processing parameters, this framework provides a robust strategy to overcome challenges in scalability and reproducibility, positioning electrospinning as a sensitive probe for macromolecular dynamics under extreme elongation.