The influence of low‐temperature crystallization on the tensile elastic modulus of natural rubber

When natural rubber crystallizes at low temperatures, there is an increase in elastic modulus of up to two orders of magnitude. This phenomenon has been studied at various temperatures in the range 0 to −55°C for samples held at tensile strains of up to 500%. There is an induction period associated with the nucleation of crystallites, before any increase in modulus is observed. The induction period increases with decreasing strain and passes through a minimum with increasing temperature at −25°C. The growth rate subsequent to nucleation is successfully described in terms of Avrami‐type rate relationships. The Avrami rate coefficient is independent of temperature and follows a simple exponential function of strain. The equilibrium extent of the modulus increase has also been studied by means of experiments of up to three months' duration. The equilibrium modulus increases with decreasing temperature—as predicted by Flory's thermodynamic theory.