Viscoelastic polymeric liquids

Note 5 Homogeneous deformations are commonly used or assumed in the methods employed for characterizing the mechanical properties of viscoelastic polymeric liquids and solids. 

Abstract This chapter deals with capillary instability of straight free liquid jets moving in air. It begins with linear stability theory for small perturbations of Newtonian liquid jets and discusses the unstable modes, characteristic growth rates, temporal and spatial instabilities and their underlying physical mechanisms. The linear theory also provides an estimate of the main droplet size emerging from capillary breakup. Formation of satellite modes is treated in the framework of either asymptotic methods or direct numerical simulations. Then, such additional effects like thermocapiUarity, or swirl are taken into account. In addition, quasi-one-dimensional approach for description of capillary breakup is introduced and illustrated in detail for Newtonian and rheologically complex liquid jets (pseudoplastic, dilatant, and viscoelastic polymeric liquids). 

Keywords Capillary instability of liquid jets Curvature Elongational rheology Free liquid jets Linear stability theory Nonlinear theory Quasi-one-dimensional equations Reynolds number Rheologically complex liquids (pseudoplastic, dilatant, and viscoelastic polymeric liquids) Satellite drops Small perturbations Spatial instability Surface tension Swirl Temporal instability Thermocapillarity Viscosity... 

Keywords Bending instability of liquid jets Buckling of liquid jets Electrified liquid jets Electrospinning Elongational rheology Newtonian and rheologically complex liquids Quasi-one-dimensional equations of the dynamics of liquid jets Small and finite perturbations Viscoelastic polymeric liquids... 

Different molecular theories have been established [27-32] to describe the viscoelasticity of polymeric liquids. Due to their importance, a brief survey of the different theories will be given below. 

Non-linear viscoelastic flow phenomena are one of the most characteristic features of polymeric liquids. A matter of very emphasised interest is the first normal stress difference. It is a well-accepted fact that the first normal stress difference Nj is similar to G, a measure of the amount of energy which can be stored reversibly in a viscoelastic fluid, whereas t12 is considered as the portion that is dissipated as viscous flow [49-51]. For concentrated solutions Lodge s theory [52] of an elastic network also predicts normal stresses, which should be associated with the entanglement density. 

Materials/machine interactions, three-dimensional viscoelastic behavior and stability of polymeric liquids ... 

For common liquids, the viscosity is a material constant which is only dependent on temperature and pressure but not on rate of deformation and time. For polymeric liquids, the situation is much more complicated viscosities and normal stress coefficients differ with deformation conditions. Because polymer melts are viscoelastic their flow is accompanied by elastic effects, due to which part of the energy exerted on the system is stored in the form of recoverable energy. For this reason the viscosities are time and rate dependent polymer melts are viscoelastic. 

Finally, there are complex fluids that are intermediate between solid and liquid in more than one of the ways listed above. Liquid crystalline polymers (LCPs) are both viscoelastic and liquid crystalline. Ordered block copolymers are viscoelastic and anisotropic. Glassy polymers possess long viscoelastic time scales both because they are glassy and because they are polymeric. Filled polymer melts possess the properties of both polymer melts and suspensions. 

Figure 3.10 Predictions of the temporary network model [Eq. (3-24)] (lines) compared to experimental data (symbols) for start-up of uniaxial extension of Melt 1, a long-chain branched polyethylene, using a relaxation spectrum fit to linear viscoelastic data for this melt. (From Bird et al. Dynamics of Polymeric Liquids. Vol. 1 Fluid Mechanics, Copyright 1987. Reprinted by permission of John Wiley Sons, Inc.)...

The Rouse model is the earliest and simplest molecular model that predicts a nontrivial distribution of polymer relaxation times. As described below, real polymeric liquids do in fact show many relaxation modes. However, in most polymer liquids, the relaxation modes observed do not correspond very well to the mode distribution predicted by the Rouse theory. For polymer solutions that are dilute, there are hydrodynamic interactions that affect the viscoelastic properties of the solution and that are unaccounted for in the Rouse theory. These are discussed below in Section 3.6.1.2. In most concentrated solutions or melts, entanglements between long polymer molecules greatly slow polymer relaxation, and, again, this is not accounted for in the Rouse theory. Reptation theories for entangled... 

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. 

Linear viscoelasticity is the simplest type of viscoelastic behavior observed in polymeric liquids and solids. This behavior is observed when the deformation is very small or at the initial stage of a large deformation. The relationship between stress and strain may be defined in terms of the relaxation modulus, a scalar quantity. This is defined in Equation 22.7 for a sudden shear deformation ... 

To illustrate what happens in the case of polymeric liquids with respect to linear viscoelasticity, let us consider the following equation, which is a general relationship between stress and strain rate ... 

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