Abstract
Chain dynamics in a series of styrene-butadiene rubbers (SBR) was studied with the aid of the dipolar correlation effect (DCE) and field-cycling NMR relaxometry (FCR). The typical time scales of the two techniques are t>10−4 s and t<10−3 s, respectively, and therefore complementary. The crosslink density of the polymer networks was varied in a wide range. In order to prevent sinusoidal undulations of the stimulated-echo attenuation curves due to spin exchange between groups with different chemical-shift offsets, the DCE of the samples was examined using a modified radio frequency pulse sequence with additional π pulses inserted in the free-evolution intervals. Residual dipolar couplings can thus be probed in samples where chemical-shift and dipolar interactions are of the same order. The dipolar correlations probed with the DCE in SBR networks turned out to exist on a time scale exceeding 300 ms. The short-time fluctuations (probed by FCR) and the long-time dynamics (probed by DCE) can be approached by power-law dipolar correlation functions with exponents −0.78±0.02 and −1.5±0.1, respectively. The crossover time is in the order of 1 ms. In contrast to FCR, the DCE data strongly depend on the crosslink density but not on the temperature in a range from 30 to 80 °C. On this basis determinations of the crosslink density may be possible as an alternative to the usual mechanical torsion modulus measurements.
Published Version
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