Flexible Biocomposites with Enhanced Interfacial Compatibility Based on Keratin Fibers and Sulfur-Containing Poly(urea-urethane)s

Abstract

Feathers are made of keratin, a fibrous protein with high content of disulfide-crosslinks and hydrogen-bonds. Feathers have been mainly used as reinforcing fiber in the preparation of biocomposites with a wide variety of polymers, also poly(urea-urethane)s. Surface compatibility between the keratin fiber and the matrix is crucial for having homogenous, high quality composites with superior mechanical properties. Poly(urea-urethane) type polymers are convenient for this purpose due to the presence of polar functionalities capable of forming hydrogen-bonds with keratin. Here, we demonstrate that the interfacial compatibility can be further enhanced by incorporating sulfur moieties in the polymer backbone that lead to new fiber-matrix interactions. We comparatively studied two analogous thermoplastic poly(urea-urethane) elastomers prepared starting from the same isocyanate-functionalized polyurethane prepolymer and two aromatic diamine chain extenders, bis(4-aminophenyl) disulfide (TPUU-SS) and the sulfur-free counterpart bis(4-aminophenyl) methane (TPUU). Then, biocomposites with high feather loadings (40, 50, 60 and 75 wt %) were prepared in a torque rheometer and hot-compressed into flexible sheets. Mechanical characterization showed that TPUU-SS based materials underwent higher improvement in mechanical properties than biocomposites made of the reference TPUU (up to 7.5-fold higher tensile strength compared to neat polymer versus 2.3-fold). Field Emission Scanning Electron Microscope (FESEM) images also provided evidence that fibers were completely embedded in the TPUU-SS matrix. Additionally, density, thermal stability, and water absorption of the biocomposites were thoroughly characterized.