Chain dynamics length scales

The bond fluctuation model not only provides a good description of the diffusion of polymer chains as a whole, but also the internal dynamics of chains on length scales in between the coil size and the length of effective bonds. This is seen from an analysis of the normalized intermediate coherent scattering function S(q,t)/S(q,0) of single chains ... 

Phillies, et a/. (69) present results confirming Streletzky and Phillies s(64) prior interpretation that HPC solutions have a dominant, concentration-independent characteristic dynamic length scale, namely the radius of a polymer chain, which for this species is i 50 nm. In particular (i) There are distinct small-probe and large-probe phenomenologies, with the division between small and large probes being about 50 nm, the same at all polymer concentrations, (ii) For small probes, the relative amplitude of the sharp and broad modes depends markedly on scattering vector q with a crossover near q 70 nm. (iii) The mean relaxation rate of the small-probe broad mode increases markedly near 50 nm. (iv) The probe intermedi-... 

Viscoelastic and transport properties of polymers in the liquid (solution, melt) or liquid-like (rubber) state determine their processing and application to a large extent and are of basic physical interest [1-3]. An understanding of these dynamic properties at a molecular level, therefore, is of great importance. However, this understanding is complicated by the facts that different motional processes may occur on different length scales and that the dynamics are governed by universal chain properties as well as by the special chemical structure of the monomer units [4, 5],... 

Since the transition from dilute to semi-dilute solutions exhibits the features of a second-order phase transition, the characteristic properties of the single- chain statics and dynamics observed in dilute solutions on all intramolecular length scales, are expected to be valid in semi-dilute solutions on length scales r < (c), whereas for r > E,(c) the collective properties should prevail [90]. 

Under -conditions the situation is more complex. On one side the excluded volume interactions are canceled and E,(c) is only related to the screening length of the hydrodynamic interactions. In addition, there is a finite probability for the occurrence of self-entanglements which are separated by the average distance E,i(c) = ( (c)/)1/2. As a consequence the single chain dynamics as typical for dilute -conditions will be restricted to length scales r < (c) [155,156],... 

Fig. 1.2 Richness of dynamic modulus in a bulk polymer and its molecular origin. The associated length scales vary from the typical bond length ( A) at low temperatures to interchain distances ( 10 A) around the glass transition. In the plateau regime of the modulus typical scales involve distances between entanglements of the order of 50-100 A. In the flow regime the relevant length scale is determined by the proper chain dimensions...

The above expressions provide a universal description of the dynamics of a Gaussian chain and are valid for real linear polymer chains on intermediate length scales. The specific (chemical) properties of a polymer enter only in terms of two parameters N =Rl and The friction parameter is gov-... 

We now address the dynamic structure factor which incorporates all time-dependent correlations of segments along the chain. While the early MD-sim-ulations of Kremer and Grest did very well with the msd, the dynamic structure factor was only poorly described. Figure 3.25b displays a comparison with NSE results on PEP and PE, where the simulation results were mapped to the experiment in terms of time units measured by (F= f/r ) and length scales measured by the tube diameter d(Q = Qld) [50]. 

Recently a very detailed study on the single chain dynamic structure factor of short chain PIB (M =3870) melts was undertaken with the aim to identify the leading effects limiting the applicability of the Rouse model toward short length scales [217]. This study was later followed by experiments on PDMS (M =6460), a polymer that has very low rotational barriers [219]. Finally, in order to access directly the intrachain relaxation mechanism experiments comparing PDMS and PIB in solution were also carried out [186]. The structural parameters for both chains were virtually identical, Rg=19.2 (21.3 A). Also their characteristic ratios C =6.73 (6.19) are very similar, i.e. the polymers have nearly equal contour length L and identical persistence lengths, thus their conformation are the same. The rotational barriers on the other hand are 3-3.5 kcal/mol for PIB and about 0.1 kcal/mol for PDMS. We first describe in some detail the study on the PIB melt compared with the PDMS melt and then discuss the results. 

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