Thermal properties and phase transitions in blends of Nylon-6 with silk fibroin

The thermal and structural properties of binary blends of Nylon-6 (N6) and a chemically related biopolymer, Bombyx mori silk fibroin (SF), are reported in this work. Homopolymers and blends, in composition ratios of N6/SF ranging from 95/05 to 70/30, were investigated by thermogravimetric (TG) analysis, differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy and wide angle X-ray scattering (WAXS). Silk fibroin typically degrades at temperatures just above 210C, which occurs within the melting endotherm of N6. In TG studies, the measured mass remaining was slightly greater than expected, indicating the blends had improved thermal stability. No beta sheet crystals of SF were detected by FTIR analysis of the Amide I region. Strong interaction between N6 and SF chains was observed, possibly as a result of formation of hydrogen bonds between N6 and SF chains. DSC analysis showed that the addition of SF to N6 caused a decrease in the crystallization temperature, the melting temperature of the lowest melting crystals and the crystallinity of N6. Furthermore, the alpha-crystallographic phase dominates and the gamma-crystallographic phase was not observed in N6/SF blends, in contrast to the homopolymer N6, which contains both phases. We suggest that the addition of SF might result in changes of the chain extension of N6, which lead to the appearance of alpha-rather than gamma-phase crystals.