The relaxation behavior of polymers with long linear flexible chains of uniform length has been investigated by means of dynamic mechanical analysis. The relaxation time spectrum (H(λ)) follows a scaling relationship with two self-similar regions, one for the entanglement and terminal zone, and a second one for the transition to the glass. This can be described in its most general form (termed “BSW spectrum”) as H(λ) = Heλne + Hgλ−ng for λ < λmax and H(λ) = 0 for λmax < λ, where He, Hg, ne, ng are material constants and λmax is the molecular weight dependent cut-off of the self-similar behavior. In this study, the dynamic mechanical response has been measured and analyzed for four highly entangled, nearly monodisperse polybutadienes with molecular weights from 20000 to 200000. The data are well represented by the BSW spectrum with scaling exponents of ne = 0.23 and ng = 0.67. The values of the exponents obtained in this work are about the same as those found for polystyrene samples in a previous study. This suggests that the two types of polymers have a similar relaxation pattern. However, at this point further refinement of the experiments is needed before being able to draw definite conclusions about the universality of the exponents.
Relaxation time spectrummonodisperse polymerself-similaritypolybutadiene melt