Viscoelastic stress Terms Links

For cross-linked polymers at equilibrium (Chapter 14, Section Cl), an equation of this form provides a good empirical fit to stress-strain relations up to moderate extensions," although it is not a proper constitutive equation and is inconsistent with behavior in other types of deformation. " "" The data of Fig. 13-19 and many other examples "" " " " are quite well described by equation 31 with time-dependent Cl and C2 as illustrated in Fig. 13-20. The sum, 6(C + C2), corresponds to the relaxation modulus E(t) of linear viscoelasticity. The term with Ci (which corresponds to neo-Hookean strain dependence) relaxes first and the term with C2 relaxes about two decades later. 

The study of elastic and viscoelastic materials under conditions of cyclic stress or strain is called dynamic mechanical analysis, DMA. The periodic changes in either stress or strain permits the analysis of the dynamic response of the sample in the other variable. The analysis has certain parallels to the temperature-modulated differential thermal analysis described in Sect 4.4, where the dynamic response of the heat-flow rate is caused by the cyclic temperature change. In fact, much of the description of TMDSC was initially modeled on the more fully developed DMA. The instruments which measure stress versus strain as a function of frequency and temperature are called dynamic mechanical analyzers. The DMA is easily recognized as a further development of TMA. Its importance lies in the direct link of the experiment to the mechanical behavior of the samples. The difficulty of the technique lies in understanding the macroscopic measurement in terms of the microscopic origin. The... 

Two principal approaches have been used to model the yield behaviour of polymers. The first approach addresses the temperature and strain-rate dependence of the yield stress in terms of the Eyring equation for thermally activated processes [39]. This approach has been applied to many amorphous and crystalline polymers (see Section 12.5.1) and links have been established with molecular relaxation processes determined by dynamic mechanical and dielectric measurements and with non-linear viscoelastic behaviour determined by creep and stress relaxation. The Eyring approach assumes that the yield process is velocity controlled, i.e. the yield process relates to existing thermally activated processes that are accelerated by the application of the yield stress to the point where the rate of plastic deformation reaches the applied macroscopic strain rate. This approach has... 

Hooke s law, the direct proportionality between stress and strain in tension or shear, is often assumed such that the constitutive equations for a purely elastic solid are o = fjs for unidirectional extension and x = qy in simple shear flow. The latter expression is recognized from Chapter 7 as the constitutive relationship for a Newtonian fluid and, in analogy to Hooke s law for elastic solids, is sometimes termed Newton s law of viscosity. For cross-linked, amorphous polymers above 7, a nonlinear relationship can be derived theoretically. For such materials v = 0.5. When v is not 0.5, it is an indication that voids are forming in the sample or that crystallization is taking place. In either case, neither the theoretical equation nor Hooke s law generally applies. Before turning to one of the simplest mathematical models of viscoelasticity, it is important to recall that the constitutive equations of a purely viscous fluid are a = fj for elongational flow and x = qy for shear flow. 

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