Rheological measurements extensional viscosity

Additional complications can occur if the mode of deformation of the material in the process differs from that of the measurement method. Most fluid rheology measurements are made under shear. If the material is extended, broken into droplets, or drawn into filaments, the extensional viscosity may be a more appropriate quantity for correlation with performance. This is the case in the parting nip of a roUer in which filamenting paint can cause roUer spatter if the extensional viscosity exceeds certain limits (109). In a number of cases shear stress is the key factor rather than shear rate, and controlled stress measurements are necessary. 

Extensional viscosity that results purely from shear deformation seems to be of less interest, but has been measured (108). The rheology of several different polymer melts in terms of shear viscosity and uniaxial and biaxial extensional viscosity has been compared (231). Additional information on the measurement of extensional viscosity are also available (105,238—240). 

While dynamic mechanical and steady shear measurements are frequently used in rheology studies of surfactant systems, extensional viscosity measurements are lacking. This can be attributed to the difficulties associated with such measurements and the lack of commercial laboratory instrumentation since the discontinuance of the Rheometric Scientific RFX rheometer. For many detergent compositions, the relatively low viscosity further complicates such measurements. There appear to be very few data on extensional or elongation viscosity for detergent consumer products and actives in the technical literature at this time. 

In this section, only measurements of shear viscosity have been addressed. However, some other devices are available that can assist in the characterization of the rheology of polymer melts under different types of deformation, other than shear. For instance, extensional viscosities can... 

Various instruments are available to measure the viscosity of polymer melts and solutions, and more generally their rheological behavior, which include capillary and rotational viscometers. The former can be used to measure parameters such as shear viscosity, melt fracture, and extensional viscosity, which are important for many polymer processes. The latter type of device can be used in either steady or oscillatory mode, thus providing a measure of the viscosity as well as viscoelasticity (G", G, and tan 5) as a function of frequency and temperature. 

The morphology may affect the rheological properties under shear and extension in different manners. If the dispersed phase is rigid but deformable, it more effectively contributes to the rheological properhes of the blend. In Section 8.3.2, the transient extensional viscosity was measured at a lower temperature than the melting temperature of the dispersed phase. Rigid fibrils enhance extensional viscosity even with a small amount of the dispersed phase (1 wt%). Nevertheless, the morphological effect under shear flow is not... 

In marked contrast to measurements of shear rheological properties, such as apparent viscosity in steady shear, or of complex viscosity in small amplitude oscillatory shear, extensional viscosity measurements are far from straightforward. This is particularly so in the case of mobile elastic liquids whose rheology can mitigate against the generation of well-defined extensional flow fields. 

The uniaxial extensiometers described so far are suitable for use with viscous materials only. They cannot, for example, be used to measure the steady extensional viscosity of such commercially important polymers as nylons and polyesters used in the textile industry, and which may have shear viscosities as low as 100 Pa sec at processing temperatures. As a consequence, other techniques are needed but these invariably involve nonuniform stretching. Here one cannot require that the stress or the stretch rate be constant. Also, the material is usually not in a virgin (stress-free) state to begin with. One can therefore not obtain the extensional viscosity directly from these measurements. Nonetheless, data from properly designed non-uniform stretching experiments can be profitably analyzed with the help of rheological constitutive equations. In addition, such data provide a simple measure of resistance that polymeric fluids offer to extensional deformation. 

The rheological responses measured at low values of strain better reflect the effects of the blend structure. For multiphase systems, there are serious disagreements between the predictions of continuum-based theories and experiments, that is, between the small and large deformation behavior. For example, the identity of zero-deformation rate dynamic and steady state viscosity is seldom found, and so is the Trouton rule. Similarly, the derived by Cogswell, relationship between the extensional viscosity and the capillary entrance pressure drop, and derived by Tanner equation for calculating the first normal stress difference from the extrudate swell, are rarely valid. 

Usually, elasticity of the solid specimen is measured by elongation and the force / is expressed with the tensile elasticity E and the elongation ratio a. Viscosity of liquid or solution is measured by shear y and expressed with shear viscosity tj and shear rate y. However, unvulcanized rubber and plastics are in semisolid states in the course of processing of rubber compounds and, therefore, tensile or extensional viscosity is also employed. Measurements of various rheological properties were reviewed in the literature [1]. 

Rheological measurements are performed so as to obtain a test fluid s material functions. Under viscometric flows we have seen that the shear viscosity and the primary and secondary normal stress differences suffice to rheologically characterize the fluid. If the flow field is extensional and the material is able to attain a state of dynamic equilibrium, then one measures the extensional viscosity otherwise, we measure the extensional viscosity growth or decay functions. In this section, we will examine steady and dynamic shear plus uniaxial extensional tests, since these make up the majority of routine rheological characterization. 

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