Flow response Polymer melts

Newtonian shear flow of polymer melts is a stable process. This means that small disturbances in the flow conditions, caused by external effects, are readily suppressed. As the rate of shear increases, however, the elastic response of the melt becomes more pronounced relative to the viscous response. In other words, components of the stress tensor in directions different from the direction of the shear stress become more important. As a result, small disturbances are not so readily compensated and may even be magnified. 

Flow behaviour of polymer melts is still difficult to predict in detail. Here, we only mention two aspects. The viscosity of a polymer melt decreases with increasing shear rate. This phenomenon is called shear thinning [48]. Another particularity of the flow of non-Newtonian liquids is the appearance of stress nonnal to the shear direction [48]. This type of stress is responsible for the expansion of a polymer melt at the exit of a tube that it was forced tlirough. Shear thinning and nonnal stress are both due to the change of the chain confonnation under large shear. On the one hand, the compressed coil cross section leads to a smaller viscosity. On the other hand, when the stress is released, as for example at the exit of a tube, the coils fold back to their isotropic confonnation and, thus, give rise to the lateral expansion of the melt. 

It became clear in the early development of the tube model that it provided a means of calculating the response of entangled polymers to large deformations as well as small ones [2]. Some predictions, especially in steady shear flow, lead to strange anomaUes as we shall see, but others met with surprising success. In particular the same step-strain experiment used to determine G(t) directly in shear is straightforward to extend to large shear strains y. In many cases of such experiments on polymer melts both Hnear and branched, monodisperse and polydisperse,the experimental strain-dependent relaxation function G(t,Y) may be written... 

The steady and dynamic drag-induced simple shear-flow rheometers, which are limited to very small shear rates for the steady flow and to very small strains for the dynamic flow, enable us to evaluate rheological properties that can be related to the macromolecular structure of polymer melts. The reason is that very small sinusoidal strains and very low shear rates do not take macromolecular polymer melt conformations far away from their equilibrium condition. Thus, whatever is measured is the result of the response of not just a portion of the macromolecule, but the contribution of the entire macromolecule. 

Rheological Response of Polymer Melts in Steady Simple Shear-Flow Rheometers... 

Fig. 12.4, the melt is forced into a converging flow pattern and undergoes a large axial acceleration, that is, it stretches. As the flow rate is increased, the axial acceleration also increases, and as a result the polymer melt exhibits stronger elastic response, with the possibility of rupturing, much like silly putty would, when stretched fast. Barring any such instability phenomena, a fully developed velocity profile is reached a few diameters after the geometrical entrance to the capillary. 

Evidence for wall slip was suggested over thirty years ago [9,32,63]. One of the first attempts at a slip mechanism was the performance of a Mooney analysis by Blyler and Hart [32]. Working in the condition of constant pressure, they explicitly pointed out melt slip at or near the wall of the capillary as the cause of flow discontinuity. On the other hand, they continued to insist that bulk elastic properties of the polymer melt are responsible for the flow breakdown on the basis that the critical stress for the flow discontinuity transition was found to be quite insensitive to molecular weight. Lack of an explicit interfacial mechanism for slip prevented Blyler and Hart from generating a satisfactory explanation for the flow oscillation observed under a constant piston speed. 

The aim of the present work has been to establish correlations between bulk macroscopic response of polymer melts under flow and the behaviour at a molecular level as seen by SANS, and to discuss the results in the frame of molecular theories. Two simple and well defined geometries of deformation have been investigated uniaxial elongation and simple shear. The... 

The tendency of polymer molecules to curl-up while they are being stretched in shear flows results in normal stresses in the fluid that greatly affect the flow field in certain cases. Additionally, most polymer melts exhibit an elastic as well as a viscous response to strain. This puts them under the category of viscoelastic materials. There are no precise models accurately representing this behavior in polymers. 

However, various combinations of eiastic and viscous elements have been used to approximate the material behavior of polymer melts. Some models are combinations of springs and dashpots to represent the elastic and viscous responses, respectively. The most common ones being the Maxwell model for a polymer melt and the Kelvin or Voight model for a solid. One model that represents shear thinning behavior, normal stresses in shear flow and elastic behavior of certain polymer melts is the K-BKZ model [28-29]. 

Behavior of Entangled Polymer Melts and Solutions Transient Response. While the steady-state response of polymers in shear and elongational flows is of much interest, there are also many instances in which the transient response is... 

Denson, C.D. and Hylton, D.C. (1980) A rheometer for measuring flie viscoelastic response of pol)mier melts in arbitrary planar and biaxial extensional flow fields, Polym. Engg Sci., 20,535-9. 

This chapter deals with viscoelastic behavior in the liquid state, particular emphasis being placed upon those aspects associated with the flow properties of polymer melts and concentrated solutions. The time-dependent response of polymers in the glassy state and near the glass transition, one variety of viscoelasticity, was discussed in Chapter 2. The concern in this chapter is the response at long times and for temperatures well above the glass transition. The elastic behavior of polymer networks well above the glass transition was discussed in Chapter 1. The conditions here are similar, and elastic effects may be very important in polymeric liquids, but steady-state flow can now also occur because the chains are not linked together to form a network. All the molecules have finite sizes, and, for flexible-chain polymers, the materials of interest in this chapter, the molecules have random-coil conformations at equilibrium (see Chapters 1 and 7). 

Figure 9.2 shows experimental data for a silicone polymer similar to the one used in the squeeze flow experiment shown in Figure 1.9. The material is viscoelastic, since both the storage modulus and the dynamic viscosity are nonzero. At low frequencies the storage modulus goes to zero and the dynamic viscosity goes to a low-frequency asymptotic value. The deformation at low frequencies is sufficiently slow to allow the individual polymer chains to respond to the imposed strain hence, the response is viscous, and it is clear that the low frequency limit of n must be the zero-shear viscosity, t]q. At high frequencies the individual chains are unable to respond and the stress is entirely the consequence of deformation of the entangled network. In this limit the polymer melt is indistinguishable from a cross-linked rubber network, and the deformation is that of an elastic body, with G going to an asymptotic value and rj to zero. The value of G in this rubbery plateau region is known as the shear modulus and is usually denoted G.

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