Elastic dumbbell model constitutive equation

It can be shown using Eq. (1-20) that the upper-convected Maxwell equation is equivalent to the Lodge integral equation, Eq. (3-24), with a single relaxation time. This is shown for the case of start-up of uniaxial extension in Worked Example 3.2. Thus, the simplest temporary network model with one relaxation time leads to the same constitutive equation for the polymer contribution to the stress as does the elastic dumbbell model. 

Equations (3-32)-(3-34) are equivalent to the so-called Oldroyd-B equation. The Oldroyd-B equation is a simple, but qualitatively useful, constitutive equation for dilute solutions of macromolecules (see Section 3.6.2). Refinements to the simple elastic dumbbell model, such as the effects of the nonlinearity of the force-extension relationship at high extensions, are discussed in Section 3.6.2.2.I. 

There are two forms of phenomenological equations for describing Brownian motion the Smoluchowski equation and the Langevin equation. These two equations, essentially the same, look very different in form. The Smoluchowski equation is derived from the generalization of the diffusion equation and has a clear relation to the thermodynamics of irreversible processes. In Chapters 6 and 7, its application to the elastic dumbbell model and the Rouse model to obtain the rheological constitutive equations will be discussed. In contrast, the Langevin equation, while having no direct relation to thermodynamics, can be applied to wider classes of stochastic processes. In this chapter, it will be used to obtain the time-correlation function of the end-to-end vector of a Rouse chain. 

We will discuss Eq. (3.20) further in Chapters 6 and 7, where it will be used to obtain the rheological constitutive equations of the elastic dumbbell model and the Rouse chain model. 

Rheological Constitutive Equation of the Elastic Dumbbell Model... 

An important concept in continuum mechanics is the objectivity, or admissibility, of the constitutive equation. There are the covariant and contravariant ways of achieving objectivity. The molecular theories the elastic dumbbell model of this chapter, the Rouse model to be studied in the next chapter, and the Zimm model which includes the preaveraged hydrodynamic interaction, all give the result equivalent to the contravariant way. In this appendix, we limit our discussion of continuum mechanics to what is needed for the molecular theories studied in Chapters 6 and 7. More detailed discussions of the subject, particularly about the convected coordinates, can be found in Refs. 5 and 6. 

The elastic dumbbell model studied iu Chapter 6 is both structurally and djmamicaUy too simple for a poljmier. However, the derivation of its constitutive equation illustrates the main theoretical steps involved. In this chapter we shall apply these theoretical results to a Gaussian chain (or Rouse chain) containing many bead-spring segments (Rouse segments). First we obtain the Smoluchowski equation for the bond vectors. After transforming to the normal coordinates, the Smoluchowski equation for each normal mode is equivalent in form to the equation for the elastic dumbbell. 

The starting point of a molecular constitutive theory is a simple mechanical model for the molecule that captures its most salient traits. Thus, flexible polymer molecules have been represented by elastic dumbbells and bead-spring chains, and rigid polymers by rigid dumbbells and rigid rods. For its simplicity, the evolution of the model molecule is easily described by a convection-diffusion equation. Then a Fokker-Planck equation is written for the probability distribution function of an ensemble of these molecules. Finally, the macroscopic stress tensor is derived in terms of the distribution function. This kinetic theory framework was pioneered by Kirkwood (see, for example, Ref. ). 

This process has been examined theoretically by a number of authors (29-31), who derived constitutive equations based upon finitely extendable nonlinear elastic (FENE) dumbbell models (29), bead-rod models (30), and bead-spring models (31). There is general agreement that a large increase in elongational viscosity should be expected. 

Similar to the elastic dumbbell case, we can obtain the various viscoelastic properties from the constitutive equation of the Rouse model. The main difference between the two models is that the elastic dumbbell... 

This is the constitutive equation or rheological equation of state for the elastic dumbbell suspensions. It is identical to the upper-convected Maxwell model, eq. 4.3.7. The molecular dynamics have led to a proper (frame-indifferent) time derivative and to a definition... 

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