Pseudoplastic thinning

A common choice of functional relationship between shear viscosity and shear rate, that u.sually gives a good prediction for the shear thinning region in pseudoplastic fluids, is the power law model proposed by de Waele (1923) and Ostwald (1925). This model is written as the following equation... 

Figure l.l Shear thinning behaviour of pseudoplastic fluids... 

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. 

Many microbial polysaccharides show pseudoplastic flow, also known as shear thinning. When solutions of these polysaccharides are sheared, the molecules align in the shear field and the effective viscosity is reduced. This reduction of viscosity is not a consequence of degradation (unless the shear rate exceeds 105 s 1) since the viscosity recovers immediately when die shear rate is decreased. This combination of viscous and elastic behaviour, known as viscoelasticity, distinguishes microbial viscosifiers from solutions of other thickeners. Examples of microbial viscosifiers are ... 

This equation is based on the assumption that pseudoplastic (shear-thinning) behaviour is associated with the formation and rupture of structural linkages. It is based on an experimental study of a wide range of fluids-including aqueous suspensions of flocculated inorganic particles, aqueous polymer solutions and non-aqueous suspensions and solutions-over a wide range of shear rates (y) ( 10 to 104 s 1). 

In general, for shear-thinning pseudoplastic fluids the apparent viscosity will gradually decrease with time if there is a step increase in its rate of shear. This phenomenon is known as thixotropy. Similarly, with a shear-thickening fluid the apparent viscosity increases under these circumstances and the fluid exhibits rheopexy or negative-thixotropy. 

In pseudoplastic substances shear thinning depends mainly on the particle or molecular orientation or alignement in the direction of flow, this orientation is lost or regained at the same speed. Additionally many dispersions show this potential for particle or molecule interactions, this leads to bonds creating a three-dimensional network structure. They are often build-up from relatively weak hydrogen or ionic bonds. When the network is disturbed. 

Many fluids show a decrease in viscosity with increasing shear rate. This behavior is referred to as shear thinning, which means that the resistance of the material to flow decreases and the energy required to sustain flow at high shear rates is reduced. These materials are called pseudoplastic (Fig. 3a and b, curves B). At rest the material forms a network structure, which may be an agglomerate of many molecules attracted to each other or an entangled network of polymer chains. Under shear this structure is broken down, resulting in a shear... 

The typical viscous behavior for many non-Newtonian fluids (e.g., polymeric fluids, flocculated suspensions, colloids, foams, gels) is illustrated by the curves labeled structural in Figs. 3-5 and 3-6. These fluids exhibit Newtonian behavior at very low and very high shear rates, with shear thinning or pseudoplastic behavior at intermediate shear rates. In some materials this can be attributed to a reversible structure or network that forms in the rest or equilibrium state. When the material is sheared, the structure breaks down, resulting in a shear-dependent (shear thinning) behavior. Some real examples of this type of behavior are shown in Fig. 3-7. These show that structural viscosity behavior is exhibited by fluids as diverse as polymer solutions, blood, latex emulsions, and mud (sediment). Equations (i.e., models) that represent this type of behavior are described below. 

Under conditions of steady fully developed flow, molten polymers are shear thinning over many orders of magnitude of the shear rate. Like many other materials, they exhibit Newtonian behaviour at very low shear rates however, they also have Newtonian behaviour at very high shear rates as shown in Figure 1.20. The term pseudoplastic is used to describe this type of behaviour. Unfortunately, the same term is frequently used for shear thinning behaviour, that is the falling viscosity part of the full curve for a pseudoplastic material. The whole flow curve can be represented by the Cross model [Cross (1965)] ... 

The flow behaviour of aqueous coating dispersions, because of their high pigment and binder content, is often complex. They have viscosities which are not independent of the shear rate and are therefore non-Newtonian. Shear thickening (when the viscosity of the dispersion increases with shear rate) and shear thinning or pseudoplastic behaviour (when the viscosity decreases with shear rate), may... 

Use anionic polymers such as polyacrylic acids cross-linked with allyl ethers of pentaerythritol or sucrose as thickeners, if a gel structure and pseudoplastic (shear-thinning) properties are desirable. Consider adding colloidal alumina to further increase the viscosity at pH 13 [ 15]. 

The non-linear response of plastic materials is more challenging in many respects than pseudoplastic materials. While some yield phenomena, such as that seen in clay dispersions of montmorillonite, can be catastrophic in nature and recover very rapidly, others such as polymer particle blends can yield slowly. Not all clay structures catastrophically thin. Clay platelets forming an elastic structure can be deformed by a finite strain such that they align with the deforming field. When the strain... 

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. 

Before the viscosity can be calculated from capillary data, as mentioned above, the apparent shear rate, 7 , must be corrected for the effect of the pseudoplastic nature of the polymer on the velocity profile. The calculation can be made only after a model has been adopted that relates shear stress and shear rate for this concept of a pseudoplastic shear-thinning material. The model choice is a philosophical question [11] after rheologlsts tried numerous models, there are in general two simple models that have withstood substantial testing when the predictions are compared with experimental data [1]. The first Is ... 

Fluids with shear stresses that at any point depend on the shear rates only and are independent of time. These include (a) what are known as Bingham plastics, materials that require a minimum amount of stress known as yield stress before deformation, (b) pseudoplastic (or shear-thinning) fluids, namely, those in which the shear stress decreases with the shear rate (these are usually described by power-law expressions for the shear stress i.e., the rate of strain on the right-hand-side of Equation (1) is raised to a suitable power), and (c) dilatant (or shear-thickening) fluids, in which the stress increases with the shear rate (see Fig. 4.2). 

Non-Newtonian Viscosity In the cone-and-plate and parallel-disk torsional flow rheometer shown in Fig. 3.1, parts la and 2a, the experimentally obtained torque, and thus the % 2 component of the shear stress, are related to the shear rate y = y12 as follows for Newtonian fluids T12 oc y, implying a constant viscosity, and in fact we know from Newton s law that T12 = —/ . For polymer melts, however, T12 oc yn, where n < 1, which implies a decreasing shear viscosity with increasing shear rate. Such materials are called pseudoplastic, or more descriptively, shear thinning Defining a non-Newtonian viscosity,2 t],... 

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