The demand of water-resistant and breathable materials applied to a separation medium and protective garments is steadily increasing. Typical approaches to obtain these functional materials are based on hydrophobic agents and porous substrates with small fiber diameter, tiny pore, and high porosity. However, a fluorinated hydrophobic finishing agent usually employed in providing effective waterproofness is limited with respect to their environmental persistence and toxic potential. Herein, with the aim to keep a balance between the water-resistance and breathability as well as mechanical properties, we fabricate a novel fluoride-free functional membrane by electrospun polyacrylonitrile (PAN) nanofibers modified with polydimethylsiloxane (PDMS). As determined by morphological, DSC, and FT-IR analyses, the curing reaction of PDMS macromolecules formed an abundance of hydrophobic adhesive structures, which improved the waterproof performance dramatically and imparted relative good breathability at the same time. By systematically tuning the curing temperature as well as the concentration of PDMS, the modified PAN membranes with 4 wt % PDMS possessed good water-resistance (80.9 kPa), modest vapor permeability (12.5 kg m d), and air permeability (9.9 mm s). Compared with pristine PAN membranes, the modified membranes were endowed with enhanced tensile stress of 15.7 MPa. The good comprehensive performance of the as-prepared membranes suggested their potential applications in protective clothing, membrane distillation, self-cleaning materials, and other medical products. Furthermore, the proposed relationship between porous structure and waterproof/breathable property as one considerable principle is applicable to designing functional membranes with different levels of protective and comfortable performance.

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Waterproof and breathable membranes that provide a high level of protection and comfort are promising core materials for meeting the pressing demand for future upscale protective clothing. However, creating such materials that exhibit environmental protection, high performance, and ease of fabrication has proven to be a great challenge. Herein, we report a novel strategy for synthesizing fluorinated polyurethane (C6FPU) containing short perfluorohexyl (-CF) chains and introduced it as hydrophobic agent into a polyurethane (PU) solution for one-step electrospinning. A plausible mechanism about the dynamic behavior of fluorinated chains with an increasing C6FPU concentration was proposed. Benefiting from the utilization of magnesium chloride (MgCl), the fibrous membranes had dramatically decreased maximum pore sizes. Consequently, the prepared PU/C6FPU/MgCl fibrous membranes exhibited an excellent hydrostatic pressure of 104 kPa, a modest water vapor transmission rate of 11.5 kg m d, and a desirable tensile strength of 12.4 MPa. The facile fabrication of PU/C6FPU/MgCl waterproof and breathable membranes not only matches well with the tendency to be environmentally protective but also fully meets the requirements for high performance in extremely harsh environments.

Superhydrophobic waterproof-breathable membranes have attracted considerable interest owing to their multifunctional applications in self-cleaning, anti-icing, anticorrosion, outdoor tents, and protective clothing. Despite the researches pertaning to the construction of superhydrophobic functional membranes by nanoparticle finishing have increased drastically, the disconnected particle component is easy to fall off from the membranes under deformation and wear conditions, which has restricted their wide use in practice. Here, robust superhydrophobic microporous membranes were prepared via a facile and environmentally friendly strategy by dip-coating amino-silicone oil (ASO) onto the electrospun polyacrylonitrile (PAN) membranes, followed by SiO nanoparticles (SiO NPs) blade coating. Compared with hydrophilic PAN membranes, the modified membranes exhibited superhydrophobic surface with an advancing water contact angle up to 156°, after introducing ASO as low surface energy substance and SiO NPs as filler to reduce the pore size and construct the multihierarchical rough structure. Varying the concentrations of ASO and SiO NPs systematically, the PAN electrospun membranes modified with 1 wt % ASO and 0.1 wt % SiO NPs were endowed with good water-resistance (74.3 kPa), relative low thermal conductivity (0.0028 W m K), modest vapor permeability (11.4 kg m d), and air permeability (20.5 mm s). Besides, the inorganic-organic hybrid coating of ASO/SiO NPs could maintain its superhydrophobicity even after 40 abrasion cycles. The resulting membranes were found to resist variations on the pH scale from 0 to 12, and retained their water repellent properties when exposed to harsh acidic and alkali conditions. This facile fabrication of durable fluorine-free superhydrophobic membranes simultaneous with good waterproof-breathable performance provides the advantages for potential applications in self-cleaning materials and versatile protective clothing.

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