Hierarchical Self‐Assembly of Poly(Urethane)/Poly(Vinylidene Fluoride‐co‐Hexafluoropropylene) Blends into Highly Hydrophobic Electrospun Fibers with Reduced Protein Adsorption Profiles

Electrospinning of blend systems, combining two or more polymers, has gained increasing interest for the fabrication of fibers that combine properties of the individual polymers. Here, a versatile method to produce hydrophobic fibers composed of poly(vinylidene fluoride‐ co ‐hexafluoropropylene) (PVDFhfp) and polyurethane (PUR) is presented. PVDFhfp containing fibers are expected to reduce protein adsorption. In a one‐step process, blend solutions are electrospun into homogeneous nonwoven membranes with fiber diameters in the range of 0.6 ± 0.2 to 1.4 ± 0.7 µm. Surface fluorine concentrations measured by X‐ray photospectroscopy show an asymptotic dependency in function of the PVDFhfp to PUR ratio, reaching values close to pure PVDFhfp at a weight per weight ratio of 10% PVDFhfp to 90% PUR. This fluorine enrichment on the surface suggests a gradient structure along the fiber cross‐section. At increased surface fluorine concentration, the contact angle changes from 121 ± 3° (PUR) to 141 ± 4° (PUR/PVDFhfp). Furthermore, these highly hydrophobic fibers present significantly reduced fibrinogen or albumin adsorption compared to PUR membranes.