A comparison of relaxation time distributions obtained from dynamic light scattering and dynamic mechanical measurements for high-molecular-weight polystyrene in entangled solutions
Abstract:The purpose of this work was to examine possible similarities between the relaxation time distributions for polystyrene in semidilute solutions in the solvent bis(2-ethylhexyl) phthalate (dioctyl phthalate, DOP) obtained from dynamic light scattering (DLS) and dynamic mechanical (DM) measurements. The paper deals mainly with the influence of concentration and molecular weight but also with the role of solvent quality through change in temperature. The DLS and DM relaxation functions have been analyzed by inver… Show more
“…Its characteristic time (hs s i) was found to be independent of the scattering factor q (Fig. 8), which is normally considered to arise from a structural relaxation of a three-dimensional network in the system [27][28][29][30]. Interestingly, the hs s i value (2.2 s) is well agreed with that of the mechanical relaxation time (t R = 2.1 s) obtained by the fit of dynamic rheology data to a Maxwell model.…”
Section: Dynamic Light Scattering Characterizations Of Maxwell Fluidssupporting
“…Its characteristic time (hs s i) was found to be independent of the scattering factor q (Fig. 8), which is normally considered to arise from a structural relaxation of a three-dimensional network in the system [27][28][29][30]. Interestingly, the hs s i value (2.2 s) is well agreed with that of the mechanical relaxation time (t R = 2.1 s) obtained by the fit of dynamic rheology data to a Maxwell model.…”
Section: Dynamic Light Scattering Characterizations Of Maxwell Fluidssupporting
“…[95][96][97][98][99][100][101][102][103] However, the microscopic understanding of the slow relaxation needs to be improved. 104 On the basis of our FCS and DLS measurements shown in Fig- The direct DLS measurement of the slow relaxation confirms our earlier remark that cooperative diffusion becomes highly correlated in the transient entanglement network and can be studied using only a small fraction of labeled polymer chains within FCS.…”
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 coefficient 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.
“…Instead, it may indicate that the distribution of aggregates is very broad. The REPES analysis method can sometimes present artefactual peaks when the distributions are broad and other analysis has been employed (Nicolai, Brown, Hvidt, & Heller, 1990). Therefore, we choose not to further discuss the middle mode, but instead focus on the fast and the slowest mode.…”
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