Polymer rheology shear stress

The dependence of Vs on rheological parameters-shear stress on the wall and /notion coefficient — as far as the author knows, for filled polymers was not investigated somewhat completely, though its determination is necessary for a specific solution of hydrodynamic problems related to the flow of filled polymers. 

Hydraulic fracturing fluids are solutions of high-molecular-weight polymers whose rheological behavior is non-Newtonian. To describe the flow behavior of these fluids, it is customary to characterize the fluid by the Power Law parameters of Consistency Index (K) and Behavior Index (n). These parameters are obtained experimentally by subjecting the fluid to a series of different shear rates (y) and measuring the resultant shear stresses (t). The slope and Intercept of a log shear rate vs log shear stress plot yield the Behavior Index (n) and Consistency Index (Kv), respectively. Consistency Indices are corrected for the coaxial cylinder viscometers by ... 

Polymer rheology can respond nonllnearly to shear rates, as shown in Fig. 3.4. As discussed above, a Newtonian material has a linear relationship between shear stress and shear rate, and the slope of the response Is the shear viscosity. Many polymers at very low shear rates approach a Newtonian response. As the shear rate is increased most commercial polymers have a decrease in the rate of stress increase. That is, the extension of the shear stress function tends to have a lower local slope as the shear rate is increased. This Is an example of a pseudoplastic material, also known as a shear-thinning material. Pseudoplastic materials show a decrease in shear viscosity as the shear rate increases. Dilatant materials Increase in shear viscosity as the shear rate increases. Finally, a Bingham plastic requires an initial shear stress, to, before it will flow, and then it reacts to shear rate in the same manner as a Newtonian polymer. It thus appears as an elastic material until it begins to flow and then responds like a viscous fluid. All of these viscous responses may be observed when dealing with commercial and experimental polymers. 

There are a number of techniques that are used to measure polymer viscosity. For extrusion processes, capillary rheometers and cone and plate rheometers are the most commonly used devices. Both devices allow the rheologist to simultaneously measure the shear rate and the shear stress so that the viscosity may he calculated. These instruments and the analysis of the data are presented in the next sections. Only the minimum necessary mathematical development will he presented. The mathematical derivations are provided in Appendix A3. A more complete development of all pertinent rheological measurement functions for these rheometers are found elsewhere [9]. 

Rheological properties of filled polymers can be characterised by the same parameters as any fluid medium, including shear viscosity and its interdependence with applied shear stress and shear rate elongational viscosity under conditions of uniaxial extension and real and imaginary components of a complex dynamic modulus which depend on applied frequency [1]. The presence of fillers in viscoelastic polymers is generally considered to reduce melt elasticity and hence influence dependent phenomena such as die swell [2]. 

Melt flow rheology measurements were obtained on the MBAS polymer using an Instron capillary rheometer. The data reported were obtained using an 0.056-inch capillary, 90° included angle, with an L/D of 36. In Figure 5 the maximum shear stress (lb/in2) is plotted vs. the apparent shear rate (sec 1). The apparent viscosity (lb-sec/in2) vs. tem-... 

Cooke BJ, Matheson AJ (1976) Dynamic viscosity of dilute polymer solutions at high frequencies of alternating shear stress. J Chem Soc Faraday Trans II 72(3) 679-685 Curtiss CF, Bird RB (1981a) A kinetic theory for polymer melts. I The equation for the single-link orientational distribution function. J Chem Phys 74 2016—2025 Curtiss CF, Bird RB (1981b) A kinetic theory for polymer melts. II The stress tensor and the rheological equation of state. J Chem Phys 74(3) 2026—2033 Daoud M, de Gennes PG (1979) Some remarks on the dynamics of polymer melts. J Polym Sci Polym Phys Ed 17 1971-1981... 

Another peculiar property of LCPs is shown in Fig. 15.47, where the transient behaviour of the shear stress after start up of steady shear flow is shown for Vectra A900 at 290 °C at two shear rates. We will come back to this behaviour in Chap. 16 for lyotropic systems where this behaviour is quite common and in contradistinction to the transient behaviour of conventional polymers, as presented in Fig. 15.9. This damped oscillatory behaviour is also found for simple rheological models as the Jeffreys model (Te Nijenhuis 2005) and according to Burghardt and Fuller, it is explicable by the classic Leslie-Ericksen theory for the flow of liquid crystals, which tumble, rather than align, in shear flow. Moreover, it is extra complicated due to the interaction between the tumbling of the molecules and the evolving defect density (polynomial structure) of the LCP, which become finer, at start up, or coarser, after cessation of flow. 

It is well known in polymer rheology that a torsional parallel-plate flow cell develops certain secondary flow and meniscus distortion beyond some stress level [ 14]. For viscoelastic melts, this can happen at an embarrassingly low stress. The critical condition for these instabilities has not been clearly identified in terms of the shear stress, normal stress, and surface tension. It is very plausible that the boundary discontinuity and stress intensification discussed in Sect. 4 is the primary source for the meniscus instability. On the other hand, it is well documented that the first indication of an unstable flow in parallel plates is not a visually observable meniscus distortion or edge fracture, but a measurable decay of stress at a given shear rate [40]. The decay of the average stress can occur in both steady shear and frequency-dependent dynamic shear. 

Influence of addition of free polymer on the rheology of the suspensions Fig. 3 shows the effect of addition of PEO (Mjj=20,000, 35,000 and 90,000 respectively) on the extrapolated yield value obtained from the shear stress-shear rate curves using the Haake Rotovisko. On the other hand. Figure 4 shows the results obtained using the Deer rheometer in which Tg was directly obtained. Although the trend obtained is the same, the yield values obtained using the Deer rheometer are significantly... 

A more serious deficiency resides in reliance on MFI to characterize different polymers. No single rheological property can be expected to provide a complete prediction of the properties of a complex material like a thermoplastic polymer. Figure 11-27 shows log — log flow curves for polymers having the same melt index, at the intersection of the curves, but very differeni viscosities at higher shear stress where the materials are extruded or molded. This is the main reason why MFI is repeatedly condemned by purer practitioners of our profession. The parameter is locked into industrial practice, however, and is unlikely to be displaced. 

Figure 7.9 Shear-stress dependence of the relative viscosity for dispersions in white spirit of acrylic copolymer particles of radius a = 157 nm at a volume fraction of p =0.40 for differing concentrations of nonadsorbing polyisobutylene polymer of molecular weight 411,000. The particles had been stabilized by addition of a comb-graft copolymer of PMMA backbone (which adsorbed to the particles) with non-adsorbing poly(12-hydroxystearic acid) teeth. The con-centrations (in weight per unit volume) of polyisobutylene are 1.0% ( ), 0.85%(B), 0.6%(D), 0.5%(V), 0.4%( ), and 0.1 %(0)- (From Bus-call et al. 1993, with permission from the Journal of Rheology.)...

Figure 7.12 Shear-stress dependence of the relative viscosity for dispersions in water of charged polystyrene particles of radius a = 115 nm with nonadsorbing Dextran T-500 polymer (synthesized from glucose) added as a depletion flocculant. The polymer molecular weight is 298,(HX), and its radius of gyration Rg is 15.8 nm. Volume fractions and polymer concentrations are

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