Toughening mystery of natural rubber deciphered by double network incorporating hierarchical structures

As an indispensible material for modern society, natural rubber possesses peerless mechanical properties such as strength and toughness over its artificial analogues, which remains a mystery. Intensive experimental and theoretical investigations have revealed the self-enhancement of natural rubber due to strain-induced crystallization. However a rigorous model on the self-enhancement, elucidating natural rubber's extraordinary mechanical properties, is obscured by deficient understanding of the local hierarchical structure under strain. With spatially resolved synchrotron radiation micro-beam scanning X-ray diffraction we discover weak oscillation in distributions of strain-induced crystallinity around crack tip for stretched natural rubber film, demonstrating a soft-hard double network structure. The fracture energy enhancement factor obtained by utilizing the double network model indicates an enhancement of toughness by 3 orders. It's proposed that upon stretching spontaneously developed double network structures integrating hierarchy at multi length-scale in natural rubber play an essential role in its remarkable mechanical performance.