Melting Newtonian

FIG. 8 Melt Newtonian viscosity t]q of PE at 180°C vs weight average molecular weight My, of samples examined. (From Ref. 4.)... 

Polymers owe much of their attractiveness to their ease of processing. In many important teclmiques, such as injection moulding, fibre spinning and film fonnation, polymers are processed in the melt, so that their flow behaviour is of paramount importance. Because of the viscoelastic properties of polymers, their flow behaviour is much more complex than that of Newtonian liquids for which the viscosity is the only essential parameter. In polymer melts, the recoverable shear compliance, which relates to the elastic forces, is used in addition to the viscosity in the description of flow [48]. 

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. 

Non-Newtonian Fluids Die Swell and Melt Fracture. Eor many fluids the Newtonian constitutive relation involving only a single, constant viscosity is inappHcable. Either stress depends in a more complex way on strain, or variables other than the instantaneous rate of strain must be taken into account. Such fluids are known coUectively as non-Newtonian and are usually subdivided further on the basis of behavior in simple shear flow. 

Pseudoplastic fluids are the most commonly encountered non-Newtonian fluids. Examples are polymeric solutions, some polymer melts, and suspensions of paper pulps. In simple shear flow, the constitutive relation for such fluids is... 

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... 

Rheology. Both PB and PMP melts exhibit strong non-Newtonian behavior thek apparent melt viscosity decreases with an increase in shear stress (27,28). Melt viscosities of both resins depend on temperature (24,27). The activation energy for PB viscous flow is 46 kj /mol (11 kcal/mol) (39), and for PMP, 77 kJ/mol (18.4 kcal/mol) (28). Equipment used for PP processing is usually suitable for PB and PMP processing as well however, adjustments in the processing conditions must be made to account for the differences in melt temperatures and rheology. 

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. 

Unlike shear viscosity, extensional viscosity has no meaning unless the type of deformation is specified. The three types of extensional viscosity identified and measured are uniaxial or simple, biaxial, and pure shear. Uniaxial viscosity is the only one used to characterize fluids. It has been employed mainly in the study of polymer melts, but also for other fluids. For a Newtonian fluid, the uniaxial extensional viscosity is three times the shear viscosity ... 

Capillary viscometers are useful for measuring precise viscosities of a large number of fluids, ranging from dilute polymer solutions to polymer melts. Shear rates vary widely and depend on the instmments and the Hquid being studied. The shear rate at the capillary wall for a Newtonian fluid may be calculated from equation 18, where Q is the volumetric flow rate and r the radius of the capillary the shear stress at the wall is = r Ap/2L. 

Polymer melts are frequendy non-Newtonian. In this case the earlier expression given for the shear rate at the capillary wall does not hold. A correction factor (3n + 1)/4n, called the Rabinowitsch correction, must be appHed in such a way that equation 21 appHes, where 7 is the tme shear rate at the wall and nis 2l power law factor (eq. 22) determined from the slope of a log—log plot of the tme shear stress at the wad, T, vs 7. For a Newtonian hquid, n = 1. A tme apparent viscosity, Tj, can be calculated from equation 23. 

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. 

At the same time it is not surprising that polymer melts are non-Newtonian and do not obey such simple rules. Fortunately, if we make certain assumptions, it is possible to analyse flow in certain viscometer geometries to provide measurements of both shear stress (t) and shear rate (7) so that curves relating the two (flow curves) may be drawn. 

In the specific case of polymer melts these almost invariably are of the pseudoplastic type. In such cases the flow behaviour index n is less than 1 the greater the divergence from Newtonian behaviour the lower its value. 

As a complication some sources define a flow index as the reciprocal of that defined above so that some care has to be taken in interpretation. In such cases the values are greater than unity for polymer melts and the greater the value the greater the divergence from Newtonian behaviour.)... 

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. 

The melt viscosity is highly non-Newtonian in that the apparent viscosity drops considerably with increasing shear rate. Melt viscosities are about the average encountered with plastics materials but there is a considerable variation between grades. 

Only a limited amount of information is available concerning the effects of molecular weight distribution. There is, however, evidence that the narrower the distribution the more Newtonian are the melt flow properties. It has been noted... 

Studies of melt flow properties of polypropylene indicate that it is more non-Newtonian than polyethylene in that the apparent viscosity declines more rapidly with increase in shear rate. The melt viscosity is also more sensitive to temperature. Van der Wegt has shown that if the log (apparent viscosity) is plotted against log (shear stress) for a number of polypropylene grades differing in molecular weight, molecular weight distribution and measured at different temperatures the curves obtained have practically the same shape and differ only in position. 

The narrow molecular weight distribution means that the melts are more Newtonian (see Section 8.2.5) and therefore have a higher melt viscosity at high shear rates than a more pseudoplastic material of similar molecular dimensions. In turn this may require more powerful extruders. They are also more subject to melt irregularities such as sharkskin and melt fracture. This is one of the factors that has led to current interest in metallocene-polymerised polypropylenes with a bimodal molecular weight distribution. 

In common with other thermoplastic melts polystyrene exhibits pseudoplastic behaviour. At shearing stresses below 60/M,J, MPa (where = average molecular weight), the ratio of shear stress to shear rate is almost constant and the melt is substantially Newtonian. Above this shear stress non-Newtonian... 

Hot melt viscometer. Simple bob in cup viscometers are available which measure viscosity at various temperatures. Fortunately, hot melts are — almost without exception — Newtonian at their application temperatures, so shear rate is not critical. 

In practice there are a number of other factors to be taken into account. For example, the above analysis assumes that this plastic is Newtonian, ie that it has a constant viscosity, r). In reality the plastic melt is non-Newtonian so that the viscosity will change with the different shear rates in each of the three runner sections analysed. In addition, the melt flow into the mould will not be isothermal - the plastic melt immediately in contact with the mould will solidify. This will continuously reduce the effective runner cross-section for the melt coming along behind. The effects of non-Newtonian and non-isothermal behaviour are dealt with in Chapter 5. 

Equations (5.21), (5.22) and (5.23) are useful for the high strain rates experienced in injection moulding or extrusion but unfortunately they do not predict the low strain rate situation very well where plastic melts tend towards Newtonian behaviour (ie n -) 1). This is illustrated in Fig. 5.7. 

A slit die is designed on the assumption that the material is Newtonian, using apparent viscous properties derived from capillary rheometer measurements, at a particular wall shear stress, to calculate the volumetric flow rate through the slit for the same wall shear stress. Using the correction factors already derived, obtain an expression for the error involved in this procedure due to the melt being non-Newtonian. Also obtain an expression for the error in pressure drop calculated on the same basis. What is the magnitude of the error in each case for a typical power law index n = 0.377... 

A polymer melt is injected into a circular section channel under constant pressure. What is the ratio of the maximum non-isothermal flow length to the isothermal flow length in the same time for (a) a Newtonian melt and (b) a power law melt with index, n = 0.3. 

Chapter 5 deals with the aspects of the flow behaviour of polymer melts which are relevant to the processing methods. The models are developed for both Newtonian and Non-Newtonian (Power Law) fluids so that the results can be directly compared. 

Chapter 4 describes in general terms the processing methods which can be used for plastics and wherever possible the quantitative aspects are stressed. In most cases a simple Newtonian model of each of the processes is developed so that the approach taken to the analysis of plastics processing is not concealed by mathematical complexity. Chapter 5 deals with the aspects of the flow behaviour of polymer melts which are relevant to the processing methods. The models are developed for both Newtonian and Non-Newtonian (Power Law) fluids so that the results can be directly compared. 

---