"Self-concentration" effects on the dynamics of a polychlorinated biphenyl diluted in 1,4-polybutadiene.

The mobility of isolated polychlorinated biphenyl (PCB54) in 1,4-polybutadiene (PB) has been investigated by means of broadband dielectric spectroscopy. The aim was to provide new insights about the effect of the environment on the dynamics of PCB54. The authors' results indicate that PCB54 structural dynamics is neither independent of the PB matrix nor slaved to the matrix itself. The authors interpret these results as a consequence of the limited size of cooperatively rearranging regions (CRRs) involved in PCB54 structural relaxation possessing an effective concentration different from the macroscopic one. This implies a non-negligible influence of "self-concentration," already proven for the component segmental dynamics in polymer blends, also in the relaxation of binary mixtures involving low molecular weight glass formers. This allowed the evaluation of the size of CRR, which was about 1 nm for PCB54 in PB. This means that the cooperativity extends over the first shell around PCB54 molecules.