alpha- and beta-relaxations in neat and antiplasticized polybutadiene

Dielectric spectroscopy was carried out to measure the alpha-relaxation (lo cal segmental motion) and the higher frequency, secondary relaxation (beta- mode) in 1,4-polybutadiene, both neat and containing a nonpolar diluent, mi neral oil. The a-relaxation shifted to lower frequencies (antiplasticizatio n) in the presence of the diluent, suggesting the glass temperature of the latter is higher than the T-g of the polymer (i.e., >187K). The T-g of neat mineral oil cannot be determined directly, due to crystallization. While t he diluent increased the magnitude of the alpha-relaxation times, it had no effect on the beta-relaxation. Moreover, neither the shape of the alpha-re laxation function nor its temperature dependence was influenced by the dilu ent. From this we conclude that the main effect of the mineral oil was to i ncrease the local friction, without changing the degree of intermolecular c ooperativity of the molecular motions. We also find that near the glass tem perature, there is rough agreement between the time scale of the secondary relaxation process and the value of a noncooperative relaxation time estima ted from theory. This approximate correspondence between the two relaxation times also holds for 1,2 polybutadiene. However, the beta-process cannot b e identified with the noncooperative alpha-relaxation, and the relationship between them is not quantitative. (C) 2000 John Wiley & Sons, Inc.