Layer-by-Layer Integration of Electrospun Nanofibers in FDM 3D Printing for Hierarchical Composite Fabrication

This study presents a novel integrated manufacturing approach that combines fused deposition modeling (FDM) 3D printing with in situ electrospinning to fabricate hierarchical composite structures composed of polylactic acid (PLA) reinforced with polyacrylonitrile (PAN) nanofibers. A mounting fixture was employed to enable layer-by-layer nanofiber deposition directly onto printed PLA layers in a continuous automated process, eliminating the need for prefabricated electrospun nanofiber mats. The influences of nozzle temperature (210-230 °C) and electrospinning time (5-15 min per layer) on mechanical, thermal, and morphological properties were systematically investigated. Optimal performance was achieved at an FDM nozzle temperature of 220 °C with 5 min of electrospinning time (sample E1), showing a 36.5% increase in tensile strength (71 MPa), a 33.3% increase in Young's modulus (2.8 GPa), and a 62.0% increase in flexural strength (128 MPa) compared with the neat PLA. This enhancement resulted from the complete infiltration of molten PLA into the thin nanofiber mats, creating true fiber-matrix integration. Excessive nanofiber content (15 min ES) caused a 36.5% reduction in strength due to delamination and incomplete infiltration. Thermal analysis revealed a decrease in glass transition temperature (1.2 °C) and onset of thermal degradation (5.3-15.2 °C) with nanofiber integration. Fracture morphology confirmed that to achieve optimal properties, it was critical to balance the nanofiber reinforcement content with the depth of infiltration, as excessive content created poorly bonded interleaved layers. This integrated fabrication platform enables the production of lightweight hierarchical composites with multiscale, custom-made reinforcement for applications in biomedical scaffolds, protective equipment, and structural components.