Constitutive equations reptation model

Wagner et al. (63-66) have recently developed another family of reptation-based molecular theory constitutive equations, named molecular stress function (MSF) models, which are quite successful in closely accounting for all the start-up rheological functions in both shear and extensional flows (see Fig. 3.7). It is noteworthy that the latest MSF model (66) is capable of very good predictions for monodispersed, polydispersed and branched polymers. In their model, the reptation tube diameter is allowed not only to stretch, but also to reduce from its original value. The molecular stress function/(f), which is the ratio of the reduction to the original diameter and the MSF constitutive equation, is related to the Doi-Edwards reptation model integral-form equation as follows ... 

The prediction of the above equation is the closest of any molecular theory to experimentally observed 3.4 power. A constitutive equation based on the reptation model can be written as ... 

While these functions have been adjusted to describe shear and uniaxial extensional flows, they seem to work poorly for planar extension of LDPE (Samurkas et al. 1989). Planar extensional flow represents a particularly difficult test for K-BKZ-type constitutive equations, since fits to shear data fix all the model parameters required for planar extension, and there is therefore no wiggle room left to obtain a fit to the latter. (This is because I = I2 in both shear and planar extension.) A recent non-K-BKZ molecular constitutive equation derived from reptation-related ideas shows improved qualitative agreement with planar extensional data (McLeish and Larson 1998). 

Curtiss and Bird introduce reptation in a maimer which does not involve the tube concept, at least not in an explicit way. Their model leads to a constitutive equation in which the stress is the sum of two contributions. On contribution is exactly 1/3 the expression obtained by Doi and Edwards when those workers invoke the independent alignment approximation, i.e., that contribution is a special case of the BKZ relative strain equation. The othCT contribution depends on strain rate and is proportional to a link tension coefficent c (0 < e < 1) which diaracterizes the forces along the chain arising from the continued displacements of chain relative to surroundings. 

CONSTITUTIVE EQUATION FOR REPTATION MODEL 277 From eqns (7.239)-(7.241), one has... 

In 1978, Doi and Edwards adopted this view and developed the tube theory for polymer melts. The main objective of this work was to derive the constitutive equations for polymer melts from a molecular level model. It was in this work that the tube concept and reptational motion were combined for a concise mathematical description of polymer melt dynamics. 

The simplest nonlinear tube model is the classical Doi-Edwards (DE) constitutive equation for linear polymers, which accounts for reptation and affine rotation of tube segments. The Doi-Edwards equation predicts thinning in both shear and extension, because it accounts for orientation of tube segments, but it is unable to predict extension thickening because it neglects the stretching of tube segments. Inclusion of tube stretch leads to the Doi-Edwards-Marrucci-... 

The DE Constitutive Equations. The DE model (52-56) made a major breakthrough in polymer viscoelasticity in that it provided an important new molecular physics based constitutive relation (between the stress and the applied deformation history). This section outlines the DE approach that built on the reptation-tube model developed above and gave a nonlinear constitutive equation, which in one simplified form gives the K-BKZ equation (70,71). The model also inspired a significant amount of experimental work. One should begin by... 

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