• A novel non-solvent induced phase separation method using CaCl2 and fluorinated polyurethane enables scalable fabrication of highly permeable protective textiles (HPPT) with micro/nano-network structures.
• The optimized HPPT achieves a balance between protection and comfort: high hydrostatic pressure (12.86 kPa) and small pore size (1.03 μm) ensure liquid repellency, while high porosity (69%) and interconnected pores provide excellent air (14.24 mm/s) and moisture (7.92 kg/m²/d) permeability.
• Molecular dynamics simulations and dynamic phase transition observations reveal the diffusion–dissolution–phase separation mechanism, offering theoretical guidance for pore structure regulation in protective textiles.
• The HPPT outperforms commercial protective materials in comfort, presenting a promising solution to enhance healthcare worker performance and well-being during prolonged wear.
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