Tough protein-carbon nanotube hybrid fibers comparable to natural spider silks

Animal silks, especially spider dragline silks, have an excellent portfolio of mechanical properties, but it is still a challenge to obtain artificial silk fibers with similar properties to the natural ones. In this paper, we show how to extrude tough regenerated silk fibers by adding a small amount of commercially available functionalized multiwalled carbon nanotubes (less than 1%) through an environmentally friendly wet-spinning process reported by this laboratory previously. Most of the resulting regenerated silk fibers exhibited a breaking energy beyond 130 MJ m^-3, which is comparable to spider dragline silks (∼160 MJ m^-3). The best of these fibers in terms of performance show a breaking stress of 0.42 GPa, breaking strain of 59%, and breaking energy of 186 MJ m^-3. In addition, we used several advanced characterization techniques, such as synchrotron radiation FTIR microspectroscopy and synchrotron radiation X-ray diffraction, to reveal the toughening mechanism in such a protein-inorganic hybrid system. We believe our attempt to produce such tough protein-based hybrid fibers by using cheap, abundant and sustainable regenerated silkworm protein and commercially available functionalized carbon nanotubes, with simplified industrial wet-spinning apparatus, may open up a practical way for the industrial production of super-tough fiber materials.