Small Viscoelasticity

In this chapter we examine the elastic behavior of polymers. We shall see that this behavior is quite different from the elasticity displayed by metals and substances composed of small molecules. This is a direct consequence of the chain structure of the polymer molecules. In many polymers elasticity does not occur alone, but coupled with viscous phenomena. The combination of these effects is called viscoelasticity. We shall examine this behavior as well. 

The various elastic and viscoelastic phenomena we discuss in this chapter will be developed in stages. We begin with the simplest the case of a sample that displays a purely elastic response when deformed by simple elongation. On the basis of Hooke s law, we expect that the force of deformation—the stress—and the distortion that results-the strain-will be directly proportional, at least for small deformations. In addition, the energy spent to produce the deformation is recoverable The material snaps back when the force is released. We are interested in the molecular origin of this property for polymeric materials but, before we can get to that, we need to define the variables more quantitatively. 

A parameter indicating whether viscoelastic effects are important is the Deborah number, which is the ratio of the characteristic relaxation time of the fluid to the characteristic time scale of the flow. For small Deborah numbers, the relaxation is fast compared to the characteristic time of the flow, and the fluid behavior is purely viscous. For veiy large Deborah numbers, the behavior closely resembles that of an elastic solid. 

It has been also shown that when a thin polymer film is directly coated onto a substrate with a low modulus ( < 10 MPa), if the contact radius to layer thickness ratio is large (afh> 20), the surface layer will make a negligible contribution to the stiffness of the system and the layered solid system acts as a homogeneous half-space of substrate material while the surface and interfacial properties are governed by those of the layer [32,33]. The extension of the JKR theory to such layered bodies has two important implications. Firstly, hard and opaque materials can be coated on soft and clear substrates which deform more readily by small surface forces. Secondly, viscoelastic materials can be coated on soft elastic substrates, thereby reducing their time-dependent effects. 

For those not familiar with this type information recognize that the viscoelastic behavior of plastics shows that their deformations are dependent on such factors as the time under load and temperature conditions. Therefore, when structural (load bearing) plastic products are to be designed, it must be remembered that the standard equations that have been historically available for designing steel springs, beams, plates, cylinders, etc. have all been derived under the assumptions that (1) the strains are small, (2) the modulus is constant, (3) the strains are independent of the loading rate or history and are immediately reversible, (4) the material is isotropic, and (5) the material behaves in the same way in tension and compression. 

Mechanical properties of plastics are invariably time-dependent. Rheology of plastics involves plastics in all possible states from the molten state to the glassy or crystalline state (Chapter 6). The rheology of solid plastics within a range of small strains, within the range of linear viscoelasticity, has shown that mechanical behavior has often been successfully related to molecular structure. Studies in this area can have two objectives (1) mechanical characterization of... 

Viscoelastic and rate theory To aid the designer the viscoelastic and rate theories can be used to predict long-term mechanical behavior from short-term creep and relaxation data. Plastic properties are generally affected by relatively small temperature changes or changes in the rate of loading application. 

Linear viscoelasticity Linear viscoelastic theory and its application to static stress analysis is now developed. According to this theory, material is linearly viscoelastic if, when it is stressed below some limiting stress (about half the short-time yield stress), small strains are at any time almost linearly proportional to the imposed stresses. Portions of the creep data typify such behavior and furnish the basis for fairly accurate predictions concerning the deformation of plastics when subjected to loads over long periods of time. It should be noted that linear behavior, as defined, does not always persist throughout the time span over which the data are acquired i.e., the theory is not valid in nonlinear regions and other prediction methods must be used in such cases. 

Since these double-base proplnts consist essentially of a single phase which bears the total load in any application of force, their mechanical property behavior is significantly different from composite proplnts. In the latter formulations, the hydrocarbon binder comprises only about 14% of the composite structure, the remainder being solid particles. Under stress, the binder of these proplnts bears a proportionately higher load than that in the single phase double-base proplnts. At small strain levels, these proplnts behave in a linear viscoelastic manner where the solids reinforce the binder. As strain increases, the bond between the oxidizer and binder breaks down... 

Because of the assumption that linear relations exist between shear stress and shear rate (equation 3.4) and between distortion and stress (equation 3.128), both of these models, namely the Maxwell and Voigt models, and all other such models involving combinations of springs and dashpots, are restricted to small strains and small strain rates. Accordingly, the equations describing these models are known as line viscoelastic equations. Several theoretical and semi-theoretical approaches are available to account for non-linear viscoelastic effects, and reference should be made to specialist works 14-16 for further details. 

Polymers which creep readily have large values of / polymers which hardly creep at all have small values. For viscoelastic polymers below their glass transition temperature, there is a characteristic creep curve, as illustrated in Figure 7.6. 

It was pointed out in Section 26.2.1 that the friction coefficient is considerably larger on a rough track than on a smooth one when the log ajv values of the master curve are small, i.e., when the temperature is high, and the speed is low, i.e., when the viscoelastic losses are low. Moreover, the adhesion friction, which enables tangential stresses to be built up, is low. 

The first term on the right-hand side of Eq. (21), due to viscous dissipation, involves liqnid viscosity, t, and a logarithmic ratio of drop contact radius and a molecnlar cntoff, . This viscons term [5] is, however, small compared to the viscoelastic dissipa-... 

---