Rheology extensional flow

Oscillatory shear experiments are the preferred method to study the rheological behavior due to particle interactions because they directly probe these interactions without the influence of the external flow field as encountered in steady shear experiments. However, phenomena that arise due to the external flow, such as shear thickening, can only be investigated in steady shear experiments. Additionally, the analysis is complicated by the different response of the material to shear and extensional flow. For example, very strong deviations from Trouton s ratio (extensional viscosity is three times the shear viscosity) were found for suspensions [113]. 

Demonstrations are given of the importance of extensional or elongational viscosity in the foam process. New polypropylenes are compared in extensional flow and it is shown how rheological differences allow the prodnction of low density foam on tandem extrnsion equipment. 6 refs. 

Three uniform, steady extensional flows, which are related to post-die flows and useful to study rheological behavior, and the ability of constitutive equations to predict such behavior, are listed below, and are shown on Fig. 3.2. 

Rheological Response of Polymer Melts in Steady, Uniform, Extensional Flows... 

Wagner et al. (63-66) have recently developed another family of reptation-based molecular theory constitutive equations, named molecular stress function (MSF) models, which are quite successful in closely accounting for all the start-up rheological functions in both shear and extensional flows (see Fig. 3.7). It is noteworthy that the latest MSF model (66) is capable of very good predictions for monodispersed, polydispersed and branched polymers. In their model, the reptation tube diameter is allowed not only to stretch, but also to reduce from its original value. The molecular stress function/(f), which is the ratio of the reduction to the original diameter and the MSF constitutive equation, is related to the Doi-Edwards reptation model integral-form equation as follows ... 

Also noteworthy is the appreciable coalescence caused by the shear flows in the single screws, of the rheology section of the TSMEE following the mixing element section. Flow of dispersed immiscible blends involves continuous breakdown and coalescence of the dispersed domains (122). Shear flows, where droplet-to-droplet collisions are frequent—in contrast to extensional flows—favor coalescence over dispersion. The presence of compatibilizers shifts the balance toward reduced coalescence rate. Macosko et al. (123) attribute this to the entropic repulsion of the compatibilizer molecules located at the interface as they balance the van der Waals forces and reduce coalescence, as shown on Fig. 11.36. 

The maximum strain rate (e < Is1) for either extensional rheometer is often very slow compared with those of fabrication. Fortunately, time-temperature superposition approaches work well for SAN copolymers, and permit the elevation of the reduced strain rates kaj to those comparable to fabrication. Typical extensional rheology data for a SAN copolymer (h>an = 0.264, Mw = 7 kg/mol,Mw/Mn = 2.8) are illustrated in Figure 13.5 after time-temperature superposition to a reference temperature of 170°C [63]. The tensile stress growth coefficient rj (k, t) was measured at discrete times t during the startup of uniaxial extensional flow. Data points are marked with individual symbols (o) and terminate at the tensile break point at longest time t. Isothermal data points are connected by solid curves. Data were collected at selected k between 0.0167 and 0.0840 s-1 and at temperatures between 130 and 180 °C. Also illustrated in Figure 13.5 (dashed line) is a shear flow curve from a dynamic experiment displayed in a special format (3 versus or1) as suggested by Trouton [64]. The superposition of the low-strain rate data from two types (shear and extensional flow) of rheometers is an important validation of the reliability of both data sets. 

A few rheometers are available for measurement of equi-biaxial and planar extensional properties polymer melts [62,65,66]. The additional experimental challenges associated with these more complicated flows often preclude their use. In practice, these melt rheological properties are often first estimated from decomposing a shear flow curve into a relaxation spectrum and predicting the properties with a constitutive model appropriate for the extensional flow [54-57]. Predictions may be improved at higher strains with damping factors estimated from either a simple shear or uniaxial extensional flow. The limiting tensile strain or stress at the melt break point are not well predicted by this simple approach. 

However, rheological measurements are also performed with other types of flow or stress fields. If a uniaxial extensional flow field is applied to a material, the stress distribution can be described by... 

We have illustrated the many ways in which elongational flow behavior can provide novel information about the behavior of macromolecules. Special emphasis has been given to rheological changes associated with extensional flow fields. 

In order to maximize blend properties, three factors must be controlled LCP domain orientation, LCP domain morphology (geometry), and interfacial adhesion. The first two factors depend on the rheology of the matrix and reinforcement phase and on the deformation fields to which they are exposed. As with neat LCPs, extensional flow fields have a greater influence on orientation than do shear fields. The LCP should ideally have an equal or lower viscosity than the matrix to ensure deformation. 

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