Rouse Viscosity, related

The viscosity relates to the longest relaxation time in a system. If we consider Rouse diffusion along the tube with a Rouse diffusion coefficient DJ l/ NQ) then an initial tube configuration is completely forgotten when the mean-square displacement along the tube fulfils (r (t))tube=(contour length ly. Thus, for the longest relaxation time, we obtain ... 

A more quantitative interpretation of the scattering data involves molecular models. As an example, we turned to the Rouse model [20] developed for solutions and extended to melts [21]. As this model is unable to account for the molecular weight dependence of zero-shear viscosity (t o M ) above the critical molecular weight (Mc 35 000 for PS), the analysis wall be extended as a next step to other models which are more realistic for entangled systems. A basic result of the Rouse model relates the monomeric friction coefiBcient Co and the zero-shear viscosity t o ... 

Within the Rouse model for polymer dynamics the viscosity of a melt can be calculated from the diffusion constant of the chains using the relation [22,29,30] ... 

In summary, the chain dynamics for short times, where entanglement effects do not yet play a role, are excellently described by the picture of Langevin dynamics with entropic restoring forces. The Rouse model quantitatively describes (1) the Q-dependence of the characteristic relaxation rate, (2) the spectral form of both the self- and the pair correlation, and (3) it establishes the correct relation to the macroscopic viscosity. 

The theoretical prediction of these properties for branched molecules has to take into account the peculiar aspects of these chains. It is possible to obtain these properties as the low gradient Hmits of non-equilibrium averages, calculated from dynamic models. The basic approach to the dynamics of flexible chains is given by the Rouse or the Rouse-Zimm theories [12,13,15,21]. How-ever,both the friction coefficient and the intrinsic viscosity can also be evaluated from equilibrium averages that involve the forces acting on each one of the units. This description is known as the Kirkwood-Riseman (KR) theory [15,71 ]. Thus, the translational friction coefficient, fl, relates the force applied to the center of masses of the molecule and its velocity... 

The incorporation of non-Gaussian effects in the Rouse theory can only be accomplished in an approximate way. For instance, the optimized Rouse-Zimm local dynamics approach has been applied by Guenza et al. [55] for linear and star chains. They were able to obtain correlation times and results related to dynamic light scattering experiments as the dynamic structure factor and its first cumulant [88]. A similar approach has also been applied by Ganazzoli et al. [87] for viscosity calculations. They obtained the generalized ZK results for ratio g already discussed. 

Spring-bead models relate frictional force to the relative velocity of the medium at the point of interaction. The entanglement friction coefficient above is defined in terms of the relative velocity of the passing chain. Since the coupling point lies, on the average, midway between the centers of the two molecules involved, the macroscopic shear rate must be doubled when applying the result to a spring-bead model. Substitution of 2 CE for Con in the Rouse expression for viscosity yields... 

A generalisation of the theory for the case of arbitrary values of internal viscosity was done by Pokrovskii and Tonkikh (1988). We may note that the case when ( i=0 and zv = 2, corresponds to an ideally flexible freely-draining macromolecule, and reproduces the relations indicated by Rouse (1953). 

Figure 3.66 shows the steady-shear viscosity for a polymer system at three molar masses. Note the plateau in viscosity at low shear rates (or the zero-shear viscosity). Also note how the zero-shear viscosity scales with to the power 3.4. (This is predicted by Rouse theory (Rouse, 1953).) Figure 3.67 shows the viscosity and first normal-stress difference for a high-density polyethylene at 200 C. Note the decrease in steady-shear viscosity with increasing shear rate. This is termed shear-thinning behaviour and is typical of polymer-melt flow, in which it is believed to be due to the polymer chain orientation and non-affine motion of polymer chains. Note also that the normal-stress difference increases with shear rate. This is also common for polymer melts, and is related to an increase in elasticity as the polymer chain motion becomes more restricted normal to flow at higher shearing rates. 

According to the modified Rouse theory of Section A1 of Chapter 10, for uncross-linked polymers of sufficiently low molecular weight to avoid entanglements, the monomeric friction coefficient is related to the steady-flow viscosity by the following equation, which can be obtained from equations 4 and 10 of Chapter 10 and was originally derived by Bueche. ... 

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