Debye Force‐Mediated Topological Evolution of Electrospun Fibrous Networks Into Self‐Healing Dense Membranes and Tubes

ABSTRACT To circumvent the processing bottlenecks of high‐viscosity self‐healing materials, this work introduces a secondary cooperative manufacturing route based on “solvation dissociation–electric field‐induced spinning molding–spontaneous topological fusion,” enabling the fabrication of seamless tubular and membrane‐like architectures. Initially, the target self‐healing matrix, P(BMA‐EA), was synthesized via ultraviolet (UV) curing using benzyl methacrylate (BMA) and ethyl acrylate (EA). To dissolve the highly entangled networks, hexafluoro isopropanol (HFIP) was deployed as a decoupling solvent. In the electrospinning phase, the application of a high‐voltage electric field effectively counteracted the macroscopic rheological constraints, yielding smooth, stretched fibers with an average diameter of 7.120 ± 0.962 μm. The fiber nets collected by sedimentation or on a drum can, at room temperature, be driven by Debye force and spontaneously achieve microscopic topological fusion within the shortest time of 0.5 h, transforming from a porous network to a dense continuum. The monomer ratios of BMA and EA (1:3, 1:5, 1:7) are the main factors influencing the macroscopic mechanical self‐healing efficiency of the secondary formed membranes (after 12 h of room temperature healing, the percentages were 49.291% ± 5.242%, 74.342% ± 2.984%, and 86.589% ± 7.931%, respectively). Furthermore, needle‐puncture evaluations on three‐layer tubular structures revealed that manual compression substantially catalyzed pinhole closure. Following a 10 min compression, the tubular structure (BMA: EA = 1:5) withstood a hydrostatic pressure of up to 26.6 kPa without any leakage. Overall, this methodology circumvents the limitations of conventional molding techniques for highly viscous dynamic polymers, offering fresh insights into their three‐dimensional structural processing.