Glassy and Polymer Dynamics of Elastomers by 1H-Field-Cycling NMR Relaxometry: Effects of Fillers.

1H spin-lattice relaxation rate (R1) dispersions were acquired by field-cycling (FC) NMR relaxometry between 0.01 and 35 MHz over a wide temperature range on polyisoprene rubber (IR), either unfilled or filled with different amounts of carbon black, silica, or a combination of both, and sulfur cured. By exploiting the frequency-temperature superposition principle and constructing master curves for the total FC NMR susceptibility, χ″(ω) = ωR1(ω), the correlation times for glassy dynamics, τs, were determined. Moreover, the contribution of polymer dynamics, χpol″(ω), to χ″(ω) was singled out by subtracting the contribution of glassy dynamics, χglass″(ω), well represented by the Cole-Davidson spectral density. Glassy dynamics resulted moderately modified by the presence of fillers, τs values determined for the filled rubbers being slightly different from those of the unfilled one. Polymer dynamics was affected by the presence of fillers in the Rouse regime. A change in the frequency dependence of χpol″(ω) at low frequencies was observed for all filled rubbers, more pronounced for those reinforced with silica, which suggests that the presence of the filler particles can affect chain conformations, resulting in a different Rouse mode distribution, and/or interchain interactions modulated by translational motions.