Linear viscoelastic flow relaxation time

The Eyring analysis does not explicity take chain structures into account, so its molecular picture is not obviously applicable to polymer systems. It also does not appear to predict normal stress differences in shear flow. Consequently, the mechanism of shear-rate dependence and the physical interpretation of the characteristic time t0 are unclear, as are their relationships to molecular structure and to cooperative configurational relaxation as reflected by the linear viscoelastic behavior. At the present time it is uncertain whether the agreement with experiment is simply fortuitous, or whether it signifies some kind of underlying unity in the shear rate dependence of concentrated systems of identical particles, regardless of their structure and the mechanism of interaction. 

For a quenched lamellar phase it has been observed that G = G"scales as a>m for tv < tvQ. where tvc is defined operationally as being approximately equal to 0.1t and r is a single-chain relaxation time defined as the frequency where G and G" cross (Bates et al. 1990 Rosedale and Bates 1990). This behaviour has been accounted for theoretically by Kawasaki and Onuki (1990). For a PEP-PEE diblock that was presheared to create two distinct orientations (see Fig. 2.7(c)), Koppi et al. (1992) observed a substantial difference in G for quenched samples and parallel and perpendicular lamellae. In particular, G[ and the viscosity rjj for a perpendicular lamellar phase sheared in the plane of the lamellae were observed to exhibit near-terminal behaviour (G tv2, tj a/), which is consistent with the behaviour of an oriented lamellar phase which flows in two dimensions. These results highlight the fact that the linear viscoelastic behaviour of the lamellar phase is sensitive to the state of sample orientation. 

A review by Bird and Wiest [6] gives a more complete list of existing viscoelastic models. The upper convective model and the White-Metzner model are very similar with the exception that the White-Metzner model incorporates the strain rate effects of the relaxation time and the viscosity. Both models provide a first order approximation to flows, in which shear rate dependence and memory effects are important. However, both models predict zero second normal stress coefficients. The Giesekus model is molecular-based, non-linear in nature and describes thepower law region for viscosity andboth normal stress coefficients. The Phan-Thien Tanner models are based on network theory and give non-linear stresses. Both the Giesekus and Phan-Thien Tanner models have been successfully used to model complex flows. 

In most non-crystalline linear polymers described to date, the relaxation mechanism (in the absence of such extraneous factors as degradation) is the simple molecular flow, or the a mechanism. Exceptions have been found, for instance in the case of the polysulfides (4,54,56,57) or pol5mrethanes (57) in which far above the gla transition temperature a ixmd interchange mechanism was observed. For a number of reasons (which will be described below), it is of interest to study viscoelasticity of polymers which are subject to both mechanisms, i. e., a and (as bond-interchange will be called due to the intrinsically chemical nature of the reaction), particularly if both mechanisms occur with comparable relaxation times. Among the benefits of such a study, particularly in the case of the ionic inorganic polymers would be ... 

As discussed in Sect. 4, in the fluid, MCT-ITT flnds a linear or Newtonian regime in the limit y 0, where it recovers the standard MCT approximation for Newtonian viscosity rio of a viscoelastic fluid [2, 38]. Hence a yrio holds for Pe 1, as shown in Fig. 13, where Pe calculated with the structural relaxation time T is included. As discussed, the growth of T (asymptotically) dominates all transport coefficients of the colloidal suspension and causes a proportional increase in the viscosity j]. For Pe > 1, the non-linear viscosity shear thins, and a increases sublin-early with y. The stress vs strain rate plot in Fig. 13 clearly exhibits a broad crossover between the linear Newtonian and a much weaker (asymptotically) y-independent variation of the stress. In the fluid, the flow curve takes a S-shape in double logarithmic representation, while in the glass it is bent upward only. 

Equation (10) cannot be applied until A, the equivalent relaxation time for the fluid, is known. However, A is defined by the linear Maxwell model, and actual polymer solutions exhibit marked nonlinear viscoelastic properties [5,6,7]. For both fresh and shear degraded solutions of Separan AP 30 polyacrylamide, which exhibit pronounced drag reduction in turbulent flow, Chang and Darby [8] have measured the nonlinear viscosity and first normal stress functions, and Tsai and Darby [6] have reported transient elastic properties of similar solutions, A nonlinear hereditary integral function containing six parameters has been proposed to represent the measured properties [8], The apparent viscosity function predicted by this model is ... 

It appears, then, that the mechanical degradation process is intimately connected with the molecular structure of the macromolecule and the resulting fluid rheology that arises from this structure. For a flexible coil macromolecule, such as HPAM or polyethylene oxide, the polymer solutions are known to display viscoelastic behaviour (see Chapter 3) and thus a liquid relaxation time, may be defined as the time for the fluid to respond to the changing flow field in the porous medium. It may be computed from several possible models (Rouse, 1953 Warner, 1972 Durst et al, 1982 Haas and Durst, 1982 Bird et al. 1987). The finite extendible non-linear elastic (FENE) (Warner, 1972 Bird et al, 1987a Haas and Durst, 1982 Durst et al, 1982) dumbbell model of the polymer molecule may be used to find the relaxation time, tg, as it is known that this model provides a good description of HPAM flow in porous media (Durst et al, 1982 Haas and Durst, 1982) the expression for fe is ... 

Nonlinear rheology vastly extends all the phenomena (elastic, viscous, and linear time dependent) discussed in Chapters 1-3. Elastic, viscous, and linear viscoelastic behaviors are but coastal zones on a continent of nonlinear rheology see Figure 4.1.2. The abscissa on Figure 4.1.2 is the Deborah number, which is generally defined as the ratio of the material s characteristic relaxation time k to the characteristic flow time t. 

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