The supreme mechanical performance of natural rubber (NR) is commonly attributed to strain-induced crystallization (SIC). The SIC of NR during uniaxial stretch has been extensively investigated, whereas that under multiaxial deformation has been rarely reported, which is close to real service conditions (i.e., tire). In this work, the crystallization behavior of NR under biaxial stretch was studied with in situ synchrotron radiation wide-angle X-ray diffraction in combination with a custom-built biaxial stretch machine. It is observed that biaxial stretch frustrates the SIC of NR: within λx/λy < 1.6, where λx and λy are stretch ratios of two mutually perpendicular axes, no crystallization emerges even under large drawing ratio until sample fracture at ambient temperature. This finding challenges the common wisdom of the self-reinforcement mechanism of SIC in NR under multiaxial deformation in real service conditions. A theoretical SIC model is proposed, which can decouple the contributions of conformational entropy reduction ΔSf and amorphous chain orientation f to final Gibbs free energy change (ΔG) during multiaxial deformation. This model quantitatively renders a reproduction of the crystallinity during the biaxial stretch, which is well consistent with experimental results and can be further generalized for flow-induced crystallization of semicrystalline polymers.
Keywords: X-ray diffraction; entropy; flow-induced crystallization; natural rubber; phase transition.