Microscopic observation of the segmental orientation autocorrelation function for entangled and constrained polymer chains

Previous work on probing the dynamics of reptating polymer chains in terms of the segmental orientation autocorrelation function (OACF) by multiple-quantum (MQ) NMR relied on the time-temperature superposition (TTS) principle as applied to normalized double-quantum (DQ) build-up curves. Alternatively, an initial-rise analysis of the latter is also possible. These approaches are subject to uncertainties related to the relevant segmental shift factor or parasitic signals and inhomogeneities distorting the build-up at short times, respectively. Here, we present a simple analytical fitting approach based upon a power-law model of the OACF, by the way of which an effective power-law time scaling exponent and the amplitude of the OACF can be estimated from MQ NMR data at any given temperature. This obviates the use of TTS and provides a robust and independent probe of the shape of the OACF. The approach is validated by application to polymer melts of variable molecular weight as well as elastomers. We anticipate a wide range of applications, including the study of physical networks with labile junctions.