Preparation of Cellulose Nanofibril/Regenerated Silk Fibroin Composite Fibers

Wet-spun silk fibers have attracted the attention of many researchers because of 1) the unique properties of silk as a biomaterial, including good biocompatibility and cyto-compatability and 2) the various methods available to control the structure and properties of the fiber. Cellulose nanofibrils (CNFs) have typically been used as a reinforcing material for natural and synthetic polymers. In this study, CNF-embedded silk fibroin (SF) nanocomposite fibers were prepared for the first time. The effects of CNF content on the rheology of the dope solution and the characteristics of wet-spun CNF/SF composite fibers were also examined. A 5% SF formic acid solution that contained no CNFs showed nearly Newtonian fluid behavior, with slight shear thinning. However, after the addition of 1% CNFs, the viscosity of the dope solution increased significantly, and apparent shear thinning was observed. The maximum draw ratio of the CNF/SF composite fibers decreased as the CNF content increased. Interestingly, the crystallinity index for the silk in the CNF/SF fibers was sequentially reduced as the CNF content was increased. This phenomenon may be due to the fact that the CNFs prevent ${\beta}$-sheet crystallization of the SF by elimination of formic acid from the dope solution during the coagulation process. The CNF/SF composite fibers displayed a relatively smooth surface with stripes, at low magnification (${\times}500$). However, a rugged nanoscale surface was observed at high magnification (${\times}10,000$), and the surface roughness increased with the CNF content.