Zero shear

In amoriDhous poiymers, tiiis reiation is vaiid for processes tiiat extend over very different iengtii scaies. Modes which invoived a few monomer units as weii as tenninai reiaxation processes, in which tire chains move as a whoie, obey tire superjDosition reiaxation. On tire basis of tiiis finding an empiricai expression for tire temperature dependence of viscosity at a zero shear rate and tiiat of tire mean reiaxation time of a. modes were derived ... 

Which range should be considered The answer is the region near the origin of a plot like Fig. 2.2 for pseudoplastic materials. The slope of the tangent to a pseudoplastic curve at the origin is called the viscosity at zero rate of shear. Note that this is an extrapolation to a limit rather than an observation at zero shear (which corresponds to no flow). We shall use the symbol to indicate the viscosity of a polymer in the limit of zero shear, since the behavior is Newtonian (subscript N)in this region. 

The dynamic viscosity is related to the loss component of the shear modulus through the result 77= G"/co As co 0, the dynamic viscosity approaches the zero shear viscosity of an ordinary Uquid, 77 -... 

Polymer solutions are often characterized by their high viscosities compared to solutions of nonpolymeric solutes at similar mass concentrations. This is due to the mechanical entanglements formed between polymer chains. In fact, where entanglements dominate flow, the (zero-shear) viscosity of polymer melts and solutions varies with the 3.4 power of weight-average molecular weight. 

Figure 8.5. Apparent viscosity-shear rate curves for dilatant fluid, a Newtonian fluid and pseudoplastic fluid which have the same apparent viscosity at zero shear rate...

Figure 8.6. Relationship between molecular weight and zero shear rate viscosity for melts of linear...

Typical of thermoplastics (see Chapter 8) the melts are pseudoplastic and also in common with most thermoplastics the zero shear rate apparent viscosity of linear polyethylene is related to the weight average molecular weight by the relationship... 

Since pc 1/2, we observe that Me 2Mg, as commonly observed. Mg is determined from the onset of the rubbery plateau by dynamic mechanical spectroscopy and Me is determined at the onset of the highly entangled zero-shear viscosity law, T) M. This provides a new interpretation of the critical entanglement molecular weight Mg, as the molecular weight at which entanglement percolation occurs while the dynamics changes from Rouse to reptation. It also represents the... 

While comparing the shear thinning behavior of HP LDPE and LLDPE having identical MFI (2.0 g/10 min), the value of zero shear viscosity (170) of the former has been found higher than the latter despite the lower Mn... 

The viscosities of most real shear-thinning fluids approach constant values both at very low shear rates and at very high shear rates that is, they tend to show Newtonian properties at the extremes of shear rates. The limiting viscosity at low shear rates mq is referred to as the lower-Newtonian (or zero-shear /x0) viscosity (see lines AB in Figures 3.28 and 3.29), and that at high shear rates Mo0 is the upper-Newtonian (or infinite-shear) viscosity (see lines EF in Figures 3.28 and 3.29). 

For a shear-thickening fluid the same arguments can be applied, with the apparent viscosity rising from zero at zero shear rate to infinity at infinite shear rate, on application of the power law model. However, shear-thickening is generally observed over very much narrower ranges of shear rate and it is difficult to generalise on the type of curve which will be obtained in practice. 

Thus, the apparent viscosity falls from infinity at zero shear rate ( / r T Ry) to pp at infinite shear rate, i.e. the fluid shows shear-thinning characteristics. 

Because it is very difficult to measure the flow characteristics of a material at very low shear rates, behaviour at zero shear rate can often only be assessed by extrapolation of experimental data obtained over a limited range of shear rates. This extrapolation can be difficult, if not impossible. From Example 3.10 in Section 3.4.7, it can be seen that it is sometimes possible to approximate the behaviour of a fluid over the range of shear rates for which experimental results are available, either by a power-law or by a Bingham-plastic equation. 

When the fluid behaviour can be described by a power-law, the apparent viscosity for a shear-thinning fluid will be a minimum at the wall where the shear stress is a maximum, and will rise to a theoretical value of infinity at the pipe axis where the shear stress is zero. On the other hand, for a shear-thickening fluid the apparent viscosity will fall to zero at the pipe axis. It is apparent, therefore, that there will be some error in applying the power-law near the pipe axis since all real fluids have a limiting viscosity po at zero shear stress. The procedure is exactly analogous to that used for the Newtonian fluid, except that the power-law relation is used to relate shear stress to shear rate, as opposed to the simple Newtonian equation. 

The rheological behavior of storage XGs was characterized by steady and dynamic shear rheometry [104,266]. Tamarind seed XG [266] showed a marked dependence of zero-shear viscosity on concentration in the semi-dilute region, which was similar to that of other stiff neutral polysaccharides, and ascribed to hyper-entanglements. In a later paper [292], the flow properties of XGs from different plant species, namely, suspension-cultured tobacco cells, apple pomace, and tamarind seed, were compared. The three XGs differed in composition and structural features (as mentioned in the former section) and... 

The mechanism of formation of morphology structures in iPP-E-plastomers blends via shear-dependent mixing and demixing was investigated by optical microscopy and electron microscopy. A single-phase stmcture is formed under high shear condition in injection machine after injection, namely under zero-shear environments, spinodal decomposition proceeds and leads to the formation of a bicontinuous phase stmcture. The velocity of spinodal decomposition and the phase separation depend on the molecular stmcture of iPP and E-plastomer components. 

The above equation is valid for shear rates greater than the zero shear rate. The zero shear rate is itself a function of temperature and is used to calculate the zero shear stress. 

Here r/g is the "zero-shear" viscosity limit, is an activation... 

Obtains a unique curve when log risp (at zero shear rate) is plotted as a function of... 

Rheological determinations are destructive of the structures they measure for this reason they do not portray the actual structure of the dispersion at rest. Accordingly, various methods have been devised for extrapolating to zero the results of measurements at various shear rates. The most useful one has been the conversion of viscosities to fluidities at various shear rates and the extrapolation of the resulting nearly linear relationship to zero shear, as shown in Figure 7. Sometimes a power of the shear rate, D, provides a better distinction between a sol (essentially a liquid) and a gel (essentially a solid), as shown in the figure, but the difference between a finite intercept (sol) and zero fluidity (gel) is largely fictitious because of the dependence of the intercept on the exponent n. 

In most cases polymer solutions are not ideally dilute. In fact they exhibit pronounced intermolecular interactions. First approaches dealing with this phenomenon date back to Bueche [35]. Proceeding from the fundamental work of Debye [36] he was able to show that below a critical molar mass Mw the zero-shear viscosity is directly proportional to Mw whereas above this critical value r 0 is found to be proportional to (Mw3,4) [37,38]. This enhanced drag has been attributed to intermolecular couplings. Ferry and co-workers [39] reported that the dynamic behaviour of polymeric liquids is strongly influenced by coupling points. 

Taking into account the relevance of the range of semi-dilute solutions (in which intermolecular interactions and entanglements are of increasing importance) for industrial applications, a more detailed picture of the interrelationships between the solution structure and the rheological properties of these solutions was needed. The nature of entanglements at concentrations above the critical value c leads to the viscoelastic properties observable in shear flow experiments. The viscous part of the flow behaviour of a polymer in solution is usually represented by the zero-shear viscosity, rj0, which depends on the con-... 

Fig. 5. Double logarithmic plot of zero-shear rate viscosity against concentration and molar mass... 

On the basis of a relationship between T Sp and the dimensionless product c [rj], simple three-term equations can be developed to correlate the zero-shear viscosity with the concentration and molar mass. 

The viscosity level in the range of the Newtonian viscosity r 0 of the flow curve can be determined on the basis of molecular models. For this, just a single point measurement in the zero-shear viscosity range is necessary, when applying the Mark-Houwink relationship. This zero-shear viscosity, q0, depends on the concentration and molar mass of the dissolved polymer for a given solvent, pressure, temperature, molar mass distribution Mw/Mn, i.e. 

A general virial equation can be written for the specific viscosity when the zero-shear value is expressed in its specific form ... 

The experimental zero-shear viscosities obtained for polystyrene (PS) of different molar masses (with a very narrow molar mass distribution Mw/Mn=1.06-1.30) and different concentrations in toluene and fra s-decalin are plotted as log r sp vs. log (c- [r ]) in Fig. 6. 

The zero-shear viscosities measured in toluene solution are listed in Table 1 together with the values of r 0(theor) calculated from Eq. (14). The percentage deviation of the theoretical from the measured viscosities is given in column 8. 

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