We discuss the manner in which the dynamics of tracer polystyrene chains varies with the concentration of matrix polystyrene chains dissolved in toluene. Using fluorescence correlation spectroscopy and theory, it is shown that the cooperative diffusi
on coefficient of the matrix polystyrene chains can be measured by fluorescence correlation spectroscopy in the semidilute entangled concentration regime. In addition the self-diffusion coefficient of the tracer polystyrene chains can be detected for arbitrary concentrations. The measured cooperative diffusion coefficient is independent of the molecular weight of the tracer polystyrene chains because it is a characteristic feature of the transient entanglement network.
We present a comprehensive investigation of polymer diffusion in the semidilute regime by fluorescence correlation spectroscopy (FCS) and dynamic light scattering (DLS). Using single-labeled polystyrene chains, FCS leads to the self-diffusion coeffic
ient while DLS gives the cooperative diffusion coefficient for exactly the same molecular weights and concentrations. Using FCS we observe a new fast mode in the semidilute entangled concentration regime beyond the slower mode which is due to self-diffusion. Comparison of FCS data with data obtained by DLS on the same polymers shows that the second mode observed in FCS is identical to the cooperative diffusion coefficient measured with DLS. An in-depth analysis and a comparison with current theoretical models demonstrates that the new cooperative mode observed in FCS is due to the effective long-range interaction of the chains through the transient entanglement network.
