Viscous flow polymer melts

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... 

Melt Viscosity. The study of the viscosity of polymer melts (43—55) is important for the manufacturer who must supply suitable materials and for the fabrication engineer who must select polymers and fabrication methods. Thus melt viscosity as a function of temperature, pressure, rate of flow, and polymer molecular weight and stmcture is of considerable practical importance. Polymer melts exhibit elastic as well as viscous properties. This is evident in the swell of the polymer melt upon emergence from an extmsion die, a behavior that results from the recovery of stored elastic energy plus normal stress effects. 

Creep of polymers is a major design problem. The glass temperature Tq, for a polymer, is a criterion of creep-resistance, in much the way that is for a metal or a ceramic. For most polymers, is close to room temperature. Well below Tq, the polymer is a glass (often containing crystalline regions - Chapter 5) and is a brittle, elastic solid -rubber, cooled in liquid nitrogen, is an example. Above Tq the Van der Waals bonds within the polymer melt, and it becomes a rubber (if the polymer chains are cross-linked) or a viscous liquid (if they are not). Thermoplastics, which can be moulded when hot, are a simple example well below Tq they are elastic well above, they are viscous liquids, and flow like treacle. 

The less simple polymers (like the epoxies, the polyesters and the formaldehyde-based resins) are networks each chain is cross-linked in many places to other chains, so that, if stretched out, the array would look like a piece of Belgian lace, somehow woven in three dimensions. These are the thermosets if heated, the structure softens but it does not melt the cross-links prevent viscous flow. Thermosets are usually a bit stiffer than amorphous thermoplastics because of the cross-links, but they cannot easily be crystallised or oriented, so there is less scope for changing their properties by processing. 

These two moduli are not material constants and typical variations are shown in Fig. 5.3. As with the viscous components, the tensile modulus tends to be about three times the shear modulus at low stresses. Fig. 5.3 has been included here as an introduction to the type of behaviour which can be expected from a polymer melt as it flows. The methods used to obtain this data will be described later, when the effects of temperature and pressure will also be discussed. 

The flow behavior of the polymer blends is quite complex, influenced by the equilibrium thermodynamic, dynamics of phase separation, morphology, and flow geometry [2]. The flow properties of a two phase blend of incompatible polymers are determined by the properties of the component, that is the continuous phase while adding a low-viscosity component to a high-viscosity component melt. As long as the latter forms a continuous phase, the viscosity of the blend remains high. As soon as the phase inversion [2] occurs, the viscosity of the blend falls sharply, even with a relatively low content of low-viscosity component. Therefore, the S-shaped concentration dependence of the viscosity of blend of incompatible polymers is an indication of phase inversion. The temperature dependence of the viscosity of blends is determined by the viscous flow of the dispersion medium, which is affected by the presence of a second component. 

Though the accuracy of description of flow curves of real polymer melts, attained by means of Eq. (10), is not always sufficient, but doubtless the equation of such a structure based on the idea of relaxation mechanism of non-Newtonian polymer flow, correctly reflects the main peculiarities of viscous properties. Therefore while discussing the effect a filler has on the viscosity properties of polymer melts, besides the dependences Y(filler modifies the characteristic time of relaxation. According to [19], a possible form of the X versus

[Pg.86]

A similar thing takes place when we consider flow curves obtained at different temperatures. As seen from Fig. 7, if we take a region of low shear rates, then due to the absence of the temperature dependence Y, the apparent activation energy vanishes. At sufficiently high shear rates, when a polymer dispersion medium flows, the activation energy becomes equal to the activation energy of the viscous flow of a polymer melt and the presence of the filler in this ratio is of little importance. 

When a stress is applied to the bulk polymer melt, the mass flows in the direction that relieves the stress. At the molecular level, the probability of a molecular jump becomes higher in the direction of the stress than in any other direction and hence these stress-relieving motions predominate, leading to the observed pattern of flow. There is evidence that the molecular unit of flow is not the complete macromolecule but rather a segment of the molecule containing up to 50 carbon atoms. Viscous flow takes place by successive jumps of such segments until the entire macromolecule has shifted. 

Rheology deals with the deformation and flow of any material under the influence of an applied stress. In practical apphcations, it is related with flow, transport, and handling any simple and complex fluids [1], It deals with a variety of materials from elastic Hookean solids to viscous Newtonian liquid. In general, rheology is concerned with the deformation of solid materials including metals, plastics, and mbbers, and hquids such as polymer melts, slurries, and polymer solutions. 

Pressure-sensitive adhesives Pressure-sensitive adhesions are actually viscous polymer melts at room temperature. The polymers must be applied at temperatures above their Tg to permit rapid flow. The adhesive is made to flow by application of pressure. When the pressure is removed, the viscosity of the polymer is sufficient to hold and adhere to the surface. Many tapes are of this type where the back is smooth and coated with a nonpolar coating so as not to bond with the sticky surface. The two adhering surfaces can be separated, but only with some difficulty. 

Fig. 6. The effect of spherical and rod-shaped filler particles on the viscous flow of a polymer melt as a function of shear rate (the concentration of spheres is higher than that of the rods) [4]...

After this paper was completed, a number of studies were carried out which analyzed the structure of the family of steady solutions and the conditions of ignition in spherical and cylindrical vessels. Regarding these studies, see the monograph by Ya.B. et al.2 In this same monograph one may find literature on various applications of the concept of thermal explosion in other problems of physics, in particular, in the physics of polymers where, as was first shown by A. G. Merzhanov and his colleagues, as a result of viscous heating, steady flow of the polymer becomes impossible in the motion of polymer melts. 

Heating and cooling often take place while the polymer melt flows, making viscous dissipation an influencing factor during the process. However, since most plastic parts are thin, the conduction often occurs only across the thickness and the viscous heating is a result of shear within the narrow gap of a die or mold cavity. For such cases, the equations reduce to,... 

To simplify the problem, we can assume that the polymer bar moves at a constant speed Usy, and that a film of constant thickness, 5, exists between the bar and the heated plate. In addition, we assume that the polymer melt is Newtonian and that the viscosity is independent of temperature. The Newtonian assumption is justified by low rates of deformation that develop in this relatively slow flow problem. Furthermore, due to these low rates of deformation we can assume that the convective and viscous dissipation effects are negligible. 

Viscoelastic materials are those which exhibit both viscous and elastic characterists. Viscoelasticity is also known as anelasticity, which is present in systems when undergoing deformation. Viscous materials, like honey, polymer melt etc, resist shear flow (shear flow is in a solid body, the gradient of a shear stress force through the body) and strain, i.e. the deformation of materials caused by stress, is linearly with time when a stress is applied [1-4]. Shear stress is a stress state where the stress is parallel or tangencial to a face of the material, as opposed to normal stress when the stress is perpendicular to the face. The variable used to denote shear stress is r which is defined as ... 

---