Comparative Study of Strain-Dependent Structural Changes of Silkworm Silks: Insight into the Structural Origin of Strain-Stiffening

Structure–property relationships of silk is an intriguing topic for silk-based biomaterials research since these features are related to biomimicking the processing in natural silk fiber formation which results in excellent mechanical properties. Strain-stiffening is common for spider silks and nonmulberry silkworm silks. However, the structural origin of strain-stiffening remains unclear. In this paper, the strain-dependent structural change of Antheraea pernyi silkworm silk is studied by X-ray fiber diffraction and Fourier transform infrared spectroscopy under stretching. Based on a combination of mechanical and structural analysis, the molecular origins of strain-stiffening in A. pernyi silk were determined. The relatively high content of the β-sheets within the amorphous domains in A. pernyi silk is responsible for strain-stiffening, where “molecular spindles” enhance the extensibility and toughness of the fiber.