Polymeric solutions constitutive equations

Often times concentrated polymeric solutions cannot be treated as Newtonian fluids, however, and this tends to offset the simplifications which result from the creeping flow approximation and the fact that the boundaries are well defined. The complex rheological behavior of polymeric solutions and melts requires that nonlinear constitutive equations, such as Eqs. (l)-(5), be used (White and Metzner, 1963) ... 

In the first place, the averaged model equations are highly nonlinear and require sophisticated numerical analysis for solution. For example, the attempt to obtain numerical solutions for motions of polymeric liquids, based upon simple continuum, constitutive equations, is still not entirely successful after more than 10 years of intensive effort by a number of research groups worldwide [27]. It is possible, and one may certainly hope, that model equations derived from a sound description of the underlying microscale physics will behave better mathematically and be easier to solve, but one should not underestimate the difficulty of obtaining numerical solutions in the absence of a clear qualitative understanding of the behavior of the materials. 

We can see that Eqs. (2 101) (2-104) are sufficient to calculate the continuum-level stress a given the strain-rate and vorticity tensors E and SI. As such, this is a complete constitutive model for the dilute solution/suspension. The rheological properties predicted for steady and time-dependent linear flows of the type (2-99), with T = I t), have been studied quite thoroughly (see, e g., Larson34). Of course, we should note that the contribution of the particles/macromolecules to the stress is actually quite small. Because the solution/suspension is assumed to be dilute, the volume fraction is very small, (p 1. Nevertheless, the qualitative nature of the particle contribution to the stress is found to be quite similar to that measured (at larger concentrations) for many polymeric liquids and other complex fluids. For example, the apparent viscosity in a simple shear flow is found to shear thin (i.e., to decrease with increase of shear rate). These qualitative similarities are indicative of the generic nature of viscoelasticity in a variety of complex fluids. So far as we are aware, however, the full model has not been used for flow predictions in a fluid mechanics context. This is because the model is too complex, even for this simplest of viscoelastic fluids. The primary problem is that calculation of the stress requires solution of the full two-dimensional (2D) convection-diffusion equation, (2-102), at each point in the flow domain where we want to know the stress. 

The thermodynamic data for fluoride complexes of aluminum, from published literature (12), were recalculated to zero ionic strength by means of the Debye-Hiickel equation. These, with stability data from our experiments with aluminum hydroxide species, provide a basis for deciding which complexes will be predominant when pH and dissolved fluoride concentrations are known. Conclusions drawn concerning the hydroxide species show that the polymeric aggregates of Al(OH)3 should be considered colloidal and they are not included in this calculation as equilibrium solute species. Hydroxide complexes of significance are the monomer A10H- and the anion Al(OH)4". Fluoride complex species constitute the series AlFn " where n ranges from one to six. 

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