Polymer melts viscoelasticity

In the last twenty years, major advances in the characterisation of polymer melt viscoelasticity has taken place and in addition applied mathematicians have produced numerical codes that enable viscoelastic fluids to be modelled for processing conditions. Within the last few years it has become possible to reasonably accurately predict the way in which a viscoelastic polymer will flow into, within and out of an extrusion die. The accurate prediction of die swell is nearly possible and advances are being made to predict the onset of extrusion instabilities. 

Baig, C. and Mavrantzas, V.G. (2009) Multiscale simulation of polymer melt viscoelasticity guided from nonequilibrium statistical thermodynamics atomistic nonequilibrium molecular dynamics coupled with Monte Carlo in an expanded statistical ensemble. Phys. Rev. B, 79, 144302. 

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]. 

Graessley W W 1993 Viscoelasticity and flow in polymer melts and concentrated solutions Physical Properties of Polymers ed J E Mark et al (Washington, DC ACS) pp 97- 143... 

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 ... 

The significance of G G tan 5, Tj, and Tj is that they can be determined experimentally and used to characterize real materials. These parameters depend on frequency and temperature, and this dependence can be used to define behavior. For example, viscoelastic fluids are often characterized by log—log plots of one or more of these quantities vs the angular frequency CO, as shown in Figure 21, which illustrates the behavior of a polymer melt (149). 

Piston Cylinder (Extrusion). Pressure-driven piston cylinder capillary viscometers, ie, extmsion rheometers (Fig. 25), are used primarily to measure the melt viscosity of polymers and other viscous materials (21,47,49,50). A reservoir is connected to a capillary tube, and molten polymer or another material is extmded through the capillary by means of a piston to which a constant force is appHed. Viscosity can be determined from the volumetric flow rate and the pressure drop along the capillary. The basic method and test conditions for a number of thermoplastics are described in ASTM D1238. Melt viscoelasticity can influence the results (160). 

Viscoelastic Measurement. A number of methods measure the various quantities that describe viscoelastic behavior. Some requite expensive commercial rheometers, others depend on custom-made research instmments, and a few requite only simple devices. Even quaHtative observations can be useful in the case of polymer melts, paints, and resins, where elasticity may indicate an inferior batch or unusable formulation. Eor example, the extmsion sweU of a material from a syringe can be observed with a microscope. The Weissenberg effect is seen in the separation of a cone and plate during viscosity measurements or the climbing of a resin up the stirrer shaft during polymerization or mixing. 

In Section 4.2.2 the central role of atomic diffusion in many aspects of materials science was underlined. This is equally true for polymers, but the nature of diffusion is quite different in these materials, because polymer chains get mutually entangled and one chain cannot cross another. An important aspect of viscoelastic behavior of polymer melts is memory such a material can be deformed by hundreds of per cent and still recover its original shape almost completely if the stress is removed after a short time (Ferry 1980). This underlies the use of shrink-fit cling-film in supermarkets. On the other hand, because of diffusion, if the original stress is maintained for a long time, the memory of the original shape fades. 

The EMT analysis indicated that the stress relaxes in proportion to the number of bonds removed. The initial linear decrease of E/Eq with is intuitively appealing and is the basis for many linear constitutive theories of polymers. An example is the Doi-Edwards theory of viscoelasticity of linear polymer melts [49] in which... 

Though experimental data on suspensions of fibers in Newtonian dispersion media give more or less regular picture, a transition to non-Newtonian viscoelastic liquids, as Metzner noted [21], makes the whole picture far or less clear. Probably, the possibility to make somewhat general conclusions on a longitudinal flow of suspensions in polymer melts requires first of all establishing clear rules of behavior of pure melts at uniaxial extension this problem by itself has no solution as yet. 

Bubbles are formed instantaneously. This conclusion made in [33] is based on estimates taken from earlier works [37]. As seen from the above cited works by S. E. Sosin et al., this is not always true viscoelastic liquids under triaxial stretching stress are not destroyed instantly. The existence of an induction period may produce a considerable effect on foam growth kinetics upon free foaming, when pressure is lowered instantaneously from P > Pcr to P < Pcr in a melt with dissolved gas. However, it would appear that microfaults in polymer melts, which are caused by factors... 

The above considerations illustrate the difficulties of trying to formulate equations descriptive of rheological behavior of polymer melts with gas bubbles. An optimistic approach to the solution of this task is contained in [60, 61]. The content of these works is revealed by their titles On the Use of the Theory of Viscoelasticity for Describing of the Behaviour of Porous Material and for the Calculation of construction... 

C. Friedrich, K. Mattes, and D. Schulze, Non-linear Viscoelastic Properties of Polymer Melts as Analyzed by LAOS-FT Experiments, lUPAC Macro 2004, Paris, France, July 4—9, 2004, Paper 6.1.3. 

Here we describe the strain history with the Finger strain tensor C 1(t t ) as proposed by Lodge [55] in his rubber-like liquid theory. This equation was found to describe the stress in deforming polymer melts as long as the strains are small (second strain invariant below about 3 [56] ). The permanent contribution GcC 1 (r t0) has to be added for a linear viscoelastic solid only. C 1(t t0) is the strain between the stress free state t0 and the instantaneous state t. Other strain measures or a combination of strain tensors, as discussed in detail by Larson [57], might also be appropriate and will be considered in future studies. A combination of Finger C 1(t t ) and Cauchy C(t /. ) strain tensors is known to express the finite second normal stress difference in shear, for instance. 

Molecular Constitutive Equations for Polymer Melts in Viscoelastic Flow Solvers... 

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