Linear viscoelastic range functions

The viscoelastic response of polymer melts, that is, Eq. 3.1-19 or 3.1-20, become nonlinear beyond a level of strain y0, specific to their macromolecular structure and the temperature used. Beyond this strain limit of linear viscoelastic response, if, if, and rj become functions of the applied strain. In other words, although the applied deformations are cyclic, large amplitudes take the macromolecular, coiled, and entangled structure far away from equilibrium. In the linear viscoelastic range, on the other hand, the frequency (and temperature) dependence of if, rf, and rj is indicative of the specific macromolecular structure, responding to only small perturbations away from equilibrium. Thus, these dynamic rheological properties, as well as the commonly used dynamic moduli... 

The function F(t — t ) is related, as with the temporary network model of Green and Tobolsky (48) discussed earlier, to the survival probability of a tube segment for a time interval (f — t ) of the strain history (58,59). Finally, this Doi-Edwards model (Eq. 3.4-5) is for monodispersed polymers, and is capable of moderate predictive success in the non linear viscoelastic range. However, it is not capable of predicting strain hardening in elongational flows (Figs. 3.6 and 3.7). 

Time-temperature superposition was first suggested by H. Leaderman who discovered that creep data can be shifted on the horizontal time scale in order to extrapolate beyond the experimentally measured time frame (9-10). The procedure was shown to be valid for any of the viscoelastic functions measured within the linear viscoelastic range of the polymer. The time-temperature superposition procedure was first explicitly applied to experimental data by... 

In the linear viscoelastic range, various other material functions relate to one another (Ferry, 1980)... 

DMA experiments are performed under conditions of very small strain so that the material response is in the linear viscoelastic range. This means that the magnitude of stress and strain are linearly related and the deformation behavior is completely described by the complex modulus function, which is a function of time only. The theory applies both for the case of a tensile deformation or simple extension and for shear. In the latter case the comparable modulus is with components G ico) and G" co). As a first-order approximation, E = 3G. The theory is developed assuming deformation under isothermal conditions, and temperature does not appear (nor is implicit) as a variable. 

In principle, the shear viscosity function in the linear viscoelastic range reduces to... 

PP bead foams of a range of densities were compressed using impact and creep loading in an Instron test machine. The stress-strain curves were analysed to determine the effective cell gas pressure as a function of time under load. Creep was controlled by the polymer linear viscoelastic response if the applied stress was low but, at stresses above the foam yield stress, the creep was more rapid until compressed cell gas took the majority of the load. Air was lost from the cells by diffusion through the cell faces, this creep mechanism being more rapid than in extruded foams, because of the small bead size and the open channels at the bead bonndaries. The foam permeability to air conld be related to the PP permeability and the foam density. 15 refs. 

The linear viscoelastic properties are often expressed in terms of an auxiliary function, the relaxation time distribution, H(x) H(x)dlnx is the portion of the initial modulus contributed by processes with relaxation times in the range lnt, InT + dlnt ... 

For strain rates lower than 8x10 s, it was found that the rheological behaviour is nearly linear viscoelastic Fig. 5 shows the tensile stress-growth function CT (0,t) = EXT]E (E,t) at 123°C for three different strain rates in the linear range after about 1000s, the stress reaches a... 

Frequency sweep studies in which G and G" are determined as a function of frequency (o)) at a fixed temperature. When properly conducted, frequency sweep tests provide data over a wide range of frequencies. However, if fundamental parameters are required, each test must be restricted to linear viscoelastic behavior. Figure 3-31... 

Since the linear viscoelasticity of a material is described with a material function G(t), any experiment which gives full information on G(t) is sufficient it is not necessary to give the stresses corresponding to various strain histories. We will restrict the discussion to incompressible isotropic materials. In this case, different types of deformation such as elongation and shear give equivalent information in the range of linear viscoelasticity. Several types of experiments measure relaxation modulus, creep compliance, complex modulus etc which are equivalent to the relaxation modulus (1). 

Linear viscoelasticity is the simplest viscoelastic behavior in which the ratio of stress to strain is a function of time alone and not of the strain or stress magnitude. Under a sufficiently small strain, the molecular structure will be practically unaffected, and linear viscoelastic behavior will be observed. At this sufficiently small strain (within the linear range), a general equation that describes all types of linear viscoelastic behavior can be developed by using the Boltzmann superposition principle (Dealy and Wiss-brun, 1990). For a sufficiently small strain (yo) in the experiment, the relaxation modulus is given by... 

Generally PSAs are well known for their very viscoelastic behavior, which is necessary for them to function properly. It was therefore important to characterize first the effect of the presence of diblocks on the linear viscoelastic behavior. Since a comprehensive study on the effect of the triblock/diblock ratio on the linear viscoelastic properties of block copolymer blends has recently been reported [46], we characterized the linear viscoelastic properties of our PSA only at room temperature and down to frequencies of about 0.01 Hz. Within this frequency range all adhesives have a very similar behavior in terms of elasticity, as can be seen in Fig. 22.10. The differences appear at low frequency, a regime where the free iso-prene end of the diblock chain is able to relax. This relaxation process is analogous to the relaxation of an arm of a star-like polymer [47], and causes G to drop to a lower plateau modulus, the level of which is only controlled by the density of triblock chains actually bridging two styrene domains [46]. 

These linear viscoelastic dynamic moduli are functions of frequency. For a suspension or an emulsitm material at low frequency, elastic stresses relax and viscous stresses dominate with the result that the loss modulus, G", is higher than the storage modulus, G. For a dilute solution, G" is larger than G over the entire frequency range, but they approach each other at higher frequencies as shown in Fig. 3. 

Generalization of Hooke s law shows that in the range of linear viscoelasticity, material parameters become a function of time ... 

Figure 38 Master curves of elastic storage (S, ) and viscous loss (S", o) linear viscoelastic moduli of the 12-arm 12 828 (a) and 64-am 6430 (b) star-PBd polymers in the temperature range from 150 up to -103°C, with reference temperature-83 °C. Solid arrows represent the various transitions and corresponding crossover frequencies (cos. glass to Rouse-like transition cof.. transition to rubber plateau

A decisive step towards the description of the micellar dynamics was taken with the first quantitative measurements of the linear viscoelastic response of these solutions. The pioneering works were those of Rehage, Hoffmann, Shikata, and Candau and their coworkers [14,19-33], The most fascinating result was that the viscoelasticity of entangled wormlike micelles was characterized by a single exponential in the response function. The stress relaxation function G t) was found of the form G t) = Goexp(-f/Ti ) over a broad temporal range, where Go denotes the elastic modulus and Xr is the relaxation time. Since then, this property was found repeatedly... 

The linear viscoelastic phenomena described in the preceding chapter are all interrelated. From a single quite simple constitutive equation, equation 7 of Chapter 1, it is possible to derive exact relations for calculating any one of the viscoelastic functions in shear from any other provided the latter is known over a sufficiently wide range of time or frequency. The relations for other types of linear deformation (bulk, simple extension, etc.) are analogous. Procedures for such calculations are summarized in this chapter, together with a few remarks about relations among nonlinear phenomena. 

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