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    creep on Polymers - chap13

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
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    8 views73 pages

    Creep On Polymers - Chap13

    Uploaded by

    Nacho
    creep on Polymers - chap13

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
    Flag for inappropriate content
    of 73
    13 Flow Behavior of Polymer Melts and Solutions 13.1 Introduction 13.2 Constitutive Equations 13.3. Second-Order Fluids in Simple Shearing Flow 13.4 Normal Stresses 13.5. Rheometry 13.6 Intrinsic Viscosity of Polymers 13.7 Flow Through a Slit 13.8 Sources of Error in Capillary and Slit Flows 13.9 Coaxial Cylinder: Couette Flow 13.10 Cone-Plate Viscometers 13.11 Plate-Plate Viscometers 13.12 Experimental Determination of Normal Stresses. Coaxial Cylinders 13.13 Factors Governing the Non-Newtonian Behavior of Polymers 13.14. Non-Newtonian Viscosity Models 13.15 Cox-Merz Rule 13.16 Influence of Diluents and Plasticizers, Blends, and Fillers on Flow 13.17 Parameters Influencing the First Normal Stress Difference 13.18 Die Swelling 13.19 Melt Index 13.20 Thixotropy and Rheopexy 13.21 Stretching Flow Problem Sets References 510 510 SiS 517 S18 524 529 531 536 539 S41 542 546 550 552 553 557 558 560 562 563 568 579 509 510 Chapter 13 13.1 INTRODUCTION The flow of polymer melts and concentrated solutions is a complex process in which degradation of energy and memory effects embodied in the visc- osity and the equilibrium recovery compliance function, respectively, play a determinant role. While the viscosity of monomers is perfectly defined at a given temperature, the answer to the question “What is the value of the viscosity of a polymer?” is not a simple one, because the value may vary within several orders of magnitude. Actually, the viscosity of polymers depends on molecular weight, molecular weight distribution, topology of the chains (linear, comb-like, and star structures; irregular branching; etc.), and temperature. In addition, the viscosity of molecular chains, unlike that of monomers or low molecular weight compounds, shows a strong depen- dence on the shear rate. In most cases the viscosity decreases with increasing shear rate. Normal stress effects are also detected in these fluids. For exam- ple, in steady Couette flow, high molecular weight polymers exert a greater normal thrust on the rotating inner cylinder than on the steady outer cylin- der, in opposition to what one would expect on the basis of considering only inertial forces. In cone-plate flow, a greater normal thrust is exerted on the plate near the center than at the edge. In general, normal stress effects increase with shear rate. A mathematical expression relating forces and deformation motions in a material is known as a constitutive equation. However, the establishment of constitutive equations can be a rather difficult task in most cases. For example, the dependence of both the viscosity and the memory effects of polymer melts and concentrated solutions on the shear rate renders it diffi- cult to establish constitute equations, even in the cases of simple geometries. A rigorous treatment of the flow of these materials requires the use of fluid mechanics theories related to the nonlinear behavior of complex materials. However, in this chapter we aim only to emphasize important qualitative aspects of the flow of polymer melts and solutions that, conventionally interpreted, may explain the nonlinear behavior of polymers for some types of flows. Numerous books are available in which the reader will find rigorous approaches, and the corresponding references, to the subject matter discussed here (1-16). 13.2 CONSTITUTIVE EQUATIONS The laws of mechanics alone are not sufficient to determine the relationships between forces and motions in a body. It is necessary to know the evolution with time of functions that depend on the nature of the material, that are in Flow Behavior of Polymer Melts and Solutions si turn specified by means of constitutive equations that must satisfy certain basic physical principles in order to be valid models of the physical behavior of materials. These principles are the causality indifference principle, the local action principle, the frame indifference principle, and the material indifference principle (2,4,6,17—22). The causality indifference principle states that the physical behavior of a material at a time ¢ is independent of all future events. Thus, the stress of material at a point P at time t depends only on motions at times 0 < ¢. The local action principle establishes that the behavior of a particular element of a material is determined by the motion properties of that element and is independent of the behavior of any other element. The causality indifference principle together with the local action principle lead to the principle of determinism, which states that the stress of a given element of a material at time t depends only on the deformation of that element at times 0

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