Entangled system shear viscosity

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 ... 

P 14. — — Shear viscosities of polyisobutene systems. — A study of polymer entanglement. Polymer 3, 11—16 (1962). 

Despite the fact that here one has the typical composition of a microemulsion, i.e., surfactant-water-oil, one does not find a low viscosity microemulsion but instead a highly viscous system. The addition of water results in the formation of flexible cylindrical reverse micelles that form a transient network of entangled micelles and has been characterized by means of dynamic shear viscosity measurements [73,74]. Light scattering experiments on systems with cyclohexane as the oil have demonstrated that a water-induced micellar growth occurs and that these systems may be described analogously to semidilute polymer solutions [75-77]. 

While Eq. (2.33) is valid for monodispersedathermal polymers, in reality polymers are polydispersed and do interact with each other. Consequently, application of the model to a real system requires that the influence of individual molecular weight fractions on the rheological functions is taken into account. For example, in the simplest case of the zero-shear viscosity-composition dependence for entangled systems [194, 195] the prediction is ... 

Once the chains are long enough to reach the asymptotic characteristic ratio discussed in Chapter 2, it is found that the measured shear viscosity increases linearly with molecular weight for many polymer liquids. This phenomenon can be explained in terms of the dynamics of individual polymer chains as long as the system is below the entanglement limit. The basic theory is due to Rouse and is described in detail by Ferry.i ... 

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