Detection of fast and slow crystallization processes in instantaneously-strained samples of cis-1,4-polyisoprene

Cross-linked samples of natural rubber (NR) and synthetic cis-1,4-polyisoprene (IR) were instantaneously expanded to a predetermined strain ratio, αs, using a newly-designed high-speed tensile tester. Crystallization behavior after the cessation of deformation was investigated. The high-cycle wide-angle X-ray diffraction (WAXD) measurements could successfully reveal the drastic progress of crystallization within the first a few hundred milliseconds. Quantitative analysis of diffraction intensity clarified coexistence of fast and slow crystallization processes; time constants τf and τs, and amplitude If and Is, respectively, were estimated for these processes. The values of τf were in the range of 50-200 ms, while τs ranged between 2.5 and 4.5 s. Almost linear dependence of If and Is on αs was clarified. The crystallite size in the directions both parallel and perpendicular to the stretching direction decreased with the increase in time-averaged nominal stress. The crystal lattice deformed almost linearly with the average nominal stress. For the fast process, correlation between crystallization and stress relaxation was not recognized, while linear relationship between them was found for the slow process. In every case, strain-induced crystallization was found to be the major origin of stress relaxation. Based on the results, effects of strain on crystallization of polymer melt were discussed.