Thinning, shear

Growth of shear viscosity as a function of time after startup of steady shearing at various shear rates y for a 7.53% vol% solution of polybutadiene (M = 350,000) in a hydrocart on oil. The dashed line is the prediction of linear viscoelasticity. Replotted from Menezes and Graessley (1980). 

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C2.1.8.2 SHEAR THINNING AND NORMAL STRESS IN POLYMER MELTS... 

Flow behaviour of polymer melts is still difficult to predict in detail. Here, we only mention two aspects. The viscosity of a polymer melt decreases with increasing shear rate. This phenomenon is called shear thinning [48]. Another particularity of the flow of non-Newtonian liquids is the appearance of stress nonnal to the shear direction [48]. This type of stress is responsible for the expansion of a polymer melt at the exit of a tube that it was forced tlirough. Shear thinning and nonnal stress are both due to the change of the chain confonnation under large shear. On the one hand, the compressed coil cross section leads to a smaller viscosity. On the other hand, when the stress is released, as for example at the exit of a tube, the coils fold back to their isotropic confonnation and, thus, give rise to the lateral expansion of the melt. 

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... 

Shaving products Shaw process Shear breeding Shear energy Shearlings Shearometer Shear plane Shear rate Shear stresses Shear test Shear thinning behavior Shear viscosity Sheath-core fiber... 

In packed beds of particles possessing small pores, dilute aqueous solutions of hydroly2ed polyacrylamide will sometimes exhibit dilatant behavior iastead of the usual shear thinning behavior seen ia simple shear or Couette flow. In elongational flow, such as flow through porous sandstone, flow resistance can iacrease with flow rate due to iacreases ia elongational viscosity and normal stress differences. The iacrease ia normal stress differences with shear rate is typical of isotropic polymer solutions. Normal stress differences of anisotropic polymers, such as xanthan ia water, are shear rate iadependent (25,26). 

The process of flushing typically consists of the foUowing sequence phase transfer separation of aqueous phase vacuum dehydration of water trapped in the dispersed phase dispersion of the pigment in the oil phase by continued appHcation of shear thinning the heavy mass by addition of one or more vehicles to reduce the viscosity of dispersion and standardization of the finished dispersion to adjust the color and rheological properties to match the quaHty to the previously estabHshed standard. 

For a Hquid under shear the rate of deformation or shear rate is a function of the shearing stress. The original exposition of this relationship is Newton s law, which states that the ratio of the stress to the shear rate is a constant, ie, the viscosity. Under Newton s law, viscosity is independent of shear rate. This is tme for ideal or Newtonian Hquids, but the viscosities of many Hquids, particularly a number of those of interest to industry, are not independent of shear rate. These non-Newtonian Hquids may be classified according to their viscosity behavior as a function of shear rate. Many exhibit shear thinning, whereas others give shear thickening. Some Hquids at rest appear to behave like soHds until the shear stress exceeds a certain value, called the yield stress, after which they flow readily. 

The square root of viscosity is plotted against the reciprocal of the square root of shear rate (Fig. 3). The square of the slope is Tq, the yield stress the square of the intercept is, the viscosity at infinite shear rate. No material actually experiences an infinite shear rate, but is a good representation of the condition where all rheological stmcture has been broken down. The Casson yield stress Tq is somewhat different from the yield stress discussed earlier in that there may or may not be an intercept on the shear stress—shear rate curve for the material. If there is an intercept, then the Casson yield stress is quite close to that value. If there is no intercept, but the material is shear thinning, a Casson plot gives a value for Tq that is indicative of the degree of shear thinning. 

The Williamson equation is useful for modeling shear-thinning fluids over a wide range of shear rates (15). It makes provision for limiting low and high shear Newtonian viscosity behavior (eq. 3), where T is the absolute value of the shear stress and is the shear stress at which the viscosity is the mean of the viscosity limits TIq and, ie, at r = -H... 

The Cross equation assumes that a shear-thinning fluid has high and low shear-limiting viscosity (16) (eq. 4), where a and n are constants. 

Experimentally, it is sometimes difficult to detect differences between a shear-thinning Hquid in which the viscosity decreases with increasing shear, and a thixotropic material in which the viscosity decreases with time, because of the combined shear and time effects that occur during a series of measurements. This is especially tme if only a few data points are collected. In addition, most materials that are thixotropic are also shear thinning. In fact. 

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... 

Dispersion of a soHd or Hquid in a Hquid affects the viscosity. In many cases Newtonian flow behavior is transformed into non-Newtonian flow behavior. Shear thinning results from the abiHty of the soHd particles or Hquid droplets to come together to form network stmctures when at rest or under low shear. With increasing shear the interlinked stmcture gradually breaks down, and the resistance to flow decreases. The viscosity of a dispersed system depends on hydrodynamic interactions between particles or droplets and the Hquid, particle—particle interactions (bumping), and interparticle attractions that promote the formation of aggregates, floes, and networks. 

Other Factors Affecting the Viscosity of Dispersions. Factors other than concentration affect the viscosity of dispersions. A dispersion of nonspherical particles tends to be more viscous than predicted if the Brownian motion is great enough to maintain a random orientation of the particles. However, at low temperatures or high solvent viscosities, the Brownian motion is small and the particle alignment in flow (streamlining) results in unexpectedly lower viscosities. This is a form of shear thinning. 

Orifice viscometers should not be used for setting product specifications, for which better precision is required. Because they are designed for Newtonian and near-Newtonian fluids, they should not be used with thixotropic or highly shear-thinning materials such fluids should be characterized by using multispeed rotational viscometers. 

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. 

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