Macromolecules, Vol.53, No.8, 3097-3109, 2020
Strain-Induced Crystallization in Natural Rubber: Flory's Theory Revisited
In this paper, some aspects of the physical mechanisms involved in strain-induced crystallization (SIC) in cross-linked natural rubber networks are discussed. The theory of SIC as developed by Flory is considered within a somehow innovative perspective, in analogy to the liquid-gas phase transformation. A simple lever rule is proposed to relate the crystallinity index to the local and global draw ratios. Equilibrium properties are considered first. Some simple experiments are discussed within this framework to enlighten some fundamental aspects of SIC. As the order parameter for SIC is the draw ratio of the amorphous phase, the importance of directly measuring this parameter is emphasized. Special emphasis is put on the relaxation of the remaining amorphous fraction that accompanies SIC. The question of crystallization kinetics underlies most aspects of SIC. We show that the actual time dependence of the crystalline content may be related to the mechanism of strain relaxation in a quite simple manner using the lever rule mentioned above. Crystallization kinetics is also fundamental to explain the hysteretic behavior observed in dynamical conditions. Similarities and differences with static SIC are discussed. We transpose the classical theory of nucleation to the case of SIC, and we discuss the kinetics within this framework.