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Abstract

Studies of the local segmental relaxation in rubbery networks reveal a variety of behaviors. In experiments on networks with labeled junctions, whereby the motion of the crosslink site is specifically monitored, the segmental relaxation function broadens, accompanied by a larger activation energy, in a manner well-described by the coupling model of relaxation. The more usual experiment simply measures bulk relaxation, without discriminating among different relaxing entities. For networks, crosslinking introduces a distribution of relaxation behaviors, related to the proximity of a moiety to the junctions. The resulting inhomogeneously broadened relaxation function is difficult to analyze; nevertheless, a heightened sensitivity to temperature (larger activation energy) is exhibited, from which inferences can be made regarding the shape of the relaxation function. Finally, the segmental relaxation of highly crosslinked microgels is ostensibly homogeneous. Interestingly, however, the inverse correlation between the stretch exponent, β, and the activation energy, observed quantitatively in conventional networks, is violated by the microgels.