NSE Results from Dilute Solutions of Linear Polymers

2 NSE Results from Dilute Solutions of Linear Polymers 0-Conditions 

Neutron Spin Echo Investigations on the Segmental Dynamics 

Obviously, in the case of PS these discrepancies are more and more reduced if the probed dimensions, characterized by 2ti/Q, are enlarged from microscopic to macroscopic scales. Using extremely high molecular masses the internal modes can also be studied by photon correlation spectroscopy [111,112], Corresponding measurements show that - at two orders of magnitude smaller Q-values than those tested with NSE - the line shape of the spectra is also well described by the dynamic structure factor of the Zimm model (see Table 1). The characteristic frequencies QZ(Q) also vary with Q3. Flowever, their absolute values are only 10-15% below the prediction. 

In the case of dynamic mechanical relaxation the Zimm model leads to a specific frequency ( ) dependence of the storage [G ( )] and loss [G (cd)] part of the intrinsic shear modulus [G ( )] [1]. The smallest relaxation rate l/xz [see Eq. (80)], which determines the position of the log G (oi) and log G (o ) curves on the logarithmic -scale relates to 2Z(Q), if R3/xz is compared with Q(Q)/Q3. The experimental results from dilute PDMS and PS solutions under -conditions [113,114] fit perfectly to the theoretically predicted line shape of the components of the modulus. In addition l/xz is in complete agreement with the theoretical prediction based on the pre-averaged Oseen tensor. 

In contrast to -conditions a large number of NSE results have been published for polymers in dilute good solvents [16,110,115-120]. For this case the theoretical coherent dynamic structure factor of the Zimm model is not available. However, the experimental spectra are quite well described by that derived for -conditions. For example, see Fig. 42a and 42b, where the spectra S(Q, t)/S(Q,0) for the system PS/d-toluene at 373 K are shown as a function of time t and of the scaling variable (Oz(Q)t)2/3. As in Fig. 40a, the solid lines in Fig. 42a result from a common fit with a single adjustable parameter. No contribution of Rouse dynamics, leading to a dynamic structure factor of combined Rouse-Zimm relaxation (see Table 1), can be detected in the spectra. Obviously, the line shape of the spectra is not influenced by the quality of the solvent. As before, the characteristic frequencies 2(Q) follow the Q3-power law, which is 

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