An investigation on the molecular mobility through the glass transition of chlorinated butyl rubber

In this paper, dynamic mechanical analysis (DMA), dielectric spectroscopy (DS) and positron annihilation lifetime spectroscopy (PALS) were used to study chlorinated butyl rubber (CIIR), in order to shed light on its unique relaxation behaviors. The dynamic mechanical loss tangent of CIIR reveals an asymmetrical broad structure with a maximum peak on the high-temperature side and a shoulder peak on the low-temperature side. DS clarifies that the shoulder peak, which exactly corresponds to the ɛ″ peak, is the α process originating from the local segmental motion. While the maximum peak is assigned to the slow process arising from the motion of longer chain segments. The slow process exhibits stronger frequency dependence than the α process. The PALS analysis also shows the two processes; moreover, it suggests that CIIR exhibits very effective chain packing. It is due to the effective chain packing that the motion of longer chain segments is retarded and separates from the local segmental motion in time scale. This effect is another reason for the two-peak structure of CIIR, besides the low intermolecular co-operativity.