Low shear rate

The modification of the surface force apparatus (see Fig. VI-4) to measure viscosities between crossed mica cylinders has alleviated concerns about surface roughness. In dynamic mode, a slow, small-amplitude periodic oscillation was imposed on one of the cylinders such that the separation x varied by approximately 10% or less. In the limit of low shear rates, a simple equation defines the viscosity as a function of separation... 

Minimization of the elastic behavior of the fluid at high deformation rates that are present when high molecular weight water-soluble polymers are used to obtain cost-efficient viscosities at low shear rates. 

Many industrially important fluids cannot be described in simple terms. Viscoelastic fluids are prominent offenders. These fluids exhibit memory, flowing when subjected to a stress, but recovering part of their deformation when the stress is removed. Polymer melts and flour dough are typical examples. Both the shear stresses and the normal stresses depend on the history of the fluid. Even the simplest constitutive equations are complex, as exemplified by the Oldroyd expression for shear stress at low shear rates ... 

Welan has similar properties to xanthan gum except that it has increased viscosity at low shear rates and improved thermal stabiUty and compatibihty with calcium at alkaline pH (90). The increased thermal stabiUty has led to its use as a drilling mud viscosifter especially for high temperature weUs. The excellent compatibihty with calcium at high pH has resulted in its use in a variety of specialized cement and concrete appHcations. 

Solutions of rhamsan have high viscosity at low shear rates and low gum concentrations (90). The rheological properties and suspension capabiUty combined with excellent salt compatibihty, make it useful for several industrial apphcations including agricultural fertilizer suspensions, pigment suspensions, cleaners, and paints and coatings. 

Melt Viscosity. As shown in Tables 2 and 3, the melt viscosity of an acid copolymer increases dramatically as the fraction of neutralization is increased. The relationship for sodium ionomers is shown in Figure 4 (6). Melt viscosities for a series of sodium ionomers derived from an ethylene—3.5 mol % methacrylic acid polymer show that the increase is most pronounced at low shear rates and that the ionomers become increasingly non-Newtonian with increasing neutralization (9). The activation energy for viscous flow has been reported to be somewhat higher in ionomers than in related acidic... 

Apparent viscosity of a grease at low shear rates, eg, below about 10, is approximately equal to the yield stress divided by the shear rate. This... 

The other models can be appHed to non-Newtonian materials where time-dependent effects are absent. This situation encompasses many technically important materials from polymer solutions to latices, pigment slurries, and polymer melts. At high shear rates most of these materials tend to a Newtonian viscosity limit. At low shear rates they tend either to a yield point or to a low shear Newtonian limiting viscosity. At intermediate shear rates, the power law or the Casson model is a useful approximation. 

Depending on the concentration, the solvent, and the shear rate of measurement, concentrated polymer solutions may give wide ranges of viscosity and appear to be Newtonian or non-Newtonian. This is illustrated in Eigure 10, where solutions of a styrene—butadiene—styrene block copolymer are Newtonian and viscous at low shear rates, but become shear thinning at high shear rates, dropping to relatively low viscosities beyond 10 (42). The... 

Brabender Plasti-Corder C 1-102 low shear rate fair to good C. W. Brabender OHG, Duisburg,... 

Controlled stress viscometers are useful for determining the presence and the value of a yield stress. The stmcture can be estabUshed from creep measurements, and the elasticity from the amount of recovery after creep. The viscosity can be determined at very low shear rates, often ia a Newtonian region. This 2ero-shear viscosity, T q, is related directly to the molecular weight of polymer melts and concentrated polymer solutions. 

Curves for the viscosity data, when displayed as a function of shear rate with temperature, show the same general shape with limiting viscosities at low shear rates and limiting slopes at high shear rates. These curves can be combined in a single master curve (for each asphalt) employing vertical and horizontal shift factors (77—79). Such data relate reduced viscosity (from the vertical shift) and reduced shear rate (from the horizontal shift). 

Solutions of methylceUuloses are pseudoplastic below the gel point and approach Newtonian flow behavior at low shear rates. Above the gel point, solutions are very thixotropic because of the formation of three-dimensional gel stmcture. Solutions are stable between pH 3 and 11 pH extremes wiU cause irreversible degradation. The high substitution levels of most methylceUuloses result in relatively good resistance to enzymatic degradation (16). 

If there is particle—particle interaction, as is the case for flocculated systems, the viscosity is higher than in the absence of flocculation. Furthermore, a flocculated dispersion is shear thinning and possibly thixotropic because the floccules break down to the individual particles when shear stress is appHed. Considered in terms of the Mooney equation, at low shear rates in a flocculated system some continuous phase is trapped between the particles in the floccules. This effectively increases the internal phase volume and hence the viscosity of the system. Under sufficiently high stress, the floccules break up, reducing the effective internal phase volume and the viscosity. If, as is commonly the case, the extent of floccule separation increases with shearing time, the system is thixotropic as well as shear thinning. 

Processing PC resins by extmsion or injection-molding methods requires melt temperatures of 290—320°C. High melt viscosity at low shear rates prevents mold flash and drool. At injection shear rates, apparent viscosities decrease, and easy melt flow allows manufacture of large, complex parts. 

It has already been mentioned that polymer melts are non-Newtonian and are in fact under normal circumstances pseudoplastic. This appears to arise from the elastic nature of the melt which will be touched on only briefly here. In essence, under shear, polymers tend to be oriented. At low shear rates Brownian motion of the segments occurs so polymers can coil up at a faster rate than they are oriented and to some extent disentangled. At high shear rates such re-entangling rates are slower than the orientation rates and the polymer is hence apparently less viscous. 

This rubber has a very high melt viscosity and this was reduced by using a polar flow promoter such as zinc stearate at levels of 9.5 and 19%. This not only reduced the viscosity at low shear rates but also increased the level of pseudoplasticity so that at the high shear rates used in injection moulding flow was even more enhanced. 

Injection moulding and extrusion may be carried out at temperatures in the range of 300-380°C. The polymer has a high melt viscosity and melt fracture occurs at a lower shear rate (about 10 s ) than with low-density polyethylene (about 10 s ) or nylon 66 (about 10 s ). Extruders should thus be designed to operate at low shear rates whilst large runners and gates are employed in injection moulds. 

Nazem [31] has reported that mesophase pitch exhibits shear-thinning behavior at low shear rates and, essentially, Newtonian behavior at higher shear rates. Since isotropic pitch is Newtonian over a wide range of shear rates, one might postulate that the observed pseudoplasticity of mesophase is due to the alignment of liquid crystalline domains with increasing shear rate. Also, it has been reported that mesophase pitch can exhibit thixotropic behavior [32,33]. It is not clear, however, if this could be attributed to chemical changes within the pitch or, perhaps, to experimental factors. 

It may be seen that when y 1, this equation reduces to the Power Law (5.23) but as shown in Fig. 5.7, it also predicts the low shear rate situation very well. 

At low shear rates, aqueous solutions of polyacrylamide are pseudoplastic. With increasing shear rates and temperature the viscosity of the solutions decrease. At high shear rates during violent mixing and pumping operations the molecular weight of polyacrylamide decreases by destruction of macromolecules. 

PEs, as other polymers, exhibit nonlinear behavior in their viscous and elastic properties under practical processing conditions, i.e., at high-shear stresses. The MFI value is, therefore, of little importance in polymer processing as it is determined at a fixed low-shear rate and does not provide information on melt elasticity [38,39]. In order to understand the processing behavior of polymers, studies on melt viscosity are done in the high-shear rate range viz. 100-1000 s . Additionally, it is important to measure the elastic property of a polymer under similar conditions to achieve consistent product quality in terms of residual stress and/or dimensional accuracy of the processed product. 

Nobile et al. [3] reported that viscosity of a polycar-bonate-TLCP blend can increase or decrease in the same system at the same temperature, depending on the shear condition. At very low shear rates the viscosity was found to increase with TLCP loading, whereas at high shear rates a significant drop was observed. But in all of these cases, the way in which the TLCPs alter the bulk polymer flow is not yet well understood. 

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