Spinning conditions affect structure and properties of Nephila spider silk

Raman spectroscopy is used to elucidate the effect of spinning conditions upon the structure and mechanical properties of silk spun by Nephila spiders from the major ampullate gland. Silk fibers produced under natural spinning conditions with spinning rates between 2 and 20 mm s−1 differed in microstructure and mechanical properties from fibers produced either more slowly or more rapidly. The data support the “uniform strain” hypothesis that the reinforcing units in spider silk fibers are subjected to the same strain as the fiber, to optimize the toughness. In contrast, in the case of synthetic high-performance polymer fibers, the both units and the fiber experience uniform stress, which maximizes stiffness. The comparison of Nephila major and minor ampullate silks opens an intriguing window into dragline silk evolution and the first evidence of significant differences between the two silks providing possibilities for further testing of hypotheses concerning the uniform strain versus uniform stress models. Impact statement It is well established that the microstructure and mechanical properties of engineering materials are controlled by the conditions employed to both synthesize and process them. Herein, we demonstrate that the situation is similar for a natural material, namely spider silk. We show that for a spider that normally produces silk at a reeling speed of between 2 and 20 mm s−1, silk produced at speeds outside this natural processing window has a different microstructure that leads to inferior tensile properties. Moreover, we also show that the silk has a generic microstructure that is optimized to respond mechanically to deformation such that the crystals in the fibers are deformed under conditions of uniform strain. This is different from high-performance synthetic polymer fibers where the microstructure is optimized such that crystals within the fibers are subjected to uniform stress. Graphic abstract