Relaxation, modulus

We have used the generalized phenomenological Maxwell model or Boltzmann s superposition principle to obtain the basic equation (Eq. (4.22) or (4.23)) for describing linear viscoelastic behavior. For the kind of polymeric liquid studied in this book, this basic equation has been well tested by experimental measurements of viscoelastic responses to different rate-of-strain histories in the linear region. There are several types of rate-of-strain functions A(t) which have often been used to evaluate the viscoelastic properties of the polymer. These different viscoelastic quantities, obtained from different kinds of measurements, are related through the relaxation modulus G t). In the following sections, we shall show how these different viscoelastic quantities are expressed in terms of G(t) by using Eq. (4.22). 

The simplest viscoelastic response is the direct measurement of G t) itself. This measurement is done by monitoring the relaxation of the stress induced by the application of a step strain at some initial time, t = 0. As shown in Fig. 4.5, we let the applied strain reach a constant value Aq in a very short period of time e. A perfect step strain is made when e — 0. We further assume that the strain being applied within the period e changes with time linearly. That is, the rate-of-strain is the constant, A = Ao/e, from t = —t to t = 0, and is zero before t = —e and after t = 0. Then Eq. (4.22) can be written as 

By applying the L hospital rule or the property of the Dirac delta function (see Appendix l.A) to Eq. (4.27) 

G t) = —a t)/Xo. This result is expected from the definition of G t) as used in Boltzmann s superposition principle. The way in which G t) is obtained from Eq. (4.27) also illustrates an experimental problem encountered in the measurement of G t). Experimentally the application of a strain involves the movement of a mechanical device, often a motor, which has a rate limit. Thus, e cannot be infinitely small experimentally. At Ao 0.1, the order of 0.05 s for e is basically the state of the art. How an experiment is affected by a finite e is a relative matter. If the relaxation times of G t), which are the interest of study, are sufficiently larger than e, errors caused by the finite e are negligible. 

Shown in Fig. 4.6 are the curves of relaxation modulus, G t), of a series of nearly monodisperse polystyrene samples of different molecular weights. The higher the molecular weight, the slower the relaxation rate. In these measurements, the step deformation rise time is 0.04 s, which is much shorter than the relaxation times of interest in these curves. The most noteworthy is the appearance of a modulus plateau when the molecular weight is sufficiently large. As will be discussed in the later chapters, the entanglement molecular weight Mg can be calculated from the plateau modulus Gn- The analyses of these relaxation modulus curves in terms of the extended reptation theory developed in Chapter 9 will be detailed 

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Several functions are used to characterize tire response of a material to an applied strain or stress [4T]. The tensile relaxation modulus E(t) describes tire response to tire application of a constant tensile strain l/e -. 

Here is tire tensile stress and = lL-/L-, where is tire initial lengtli of tire sample and AL is tire sample elongation. In shear experiments, tire shear relaxation modulus G(t) is defined as where... 

Returning to the Maxwell element, suppose we rapidly deform the system to some state of strain and secure it in such a way that it retains the initial deformation. Because the material possesses the capability to flow, some internal relaxation will occur such that less force will be required with the passage of time to sustain the deformation. Our goal with the Maxwell model is to calculate how the stress varies with time, or, expressing the stress relative to the constant strain, to describe the time-dependent modulus. Such an experiment can readily be performed on a polymer sample, the results yielding a time-dependent stress relaxation modulus. In principle, the experiment could be conducted in either a tensile or shear mode measuring E(t) or G(t), respectively. We shall discuss the Maxwell model in terms of shear. 

The shear relaxation modulus of the bead-spring system is given by an... 

For an experiment carried out in shear it is possible to define a shear relaxation modulus at some time t as... 

The creep modulus will vary with time, i.e. decrease as time increases, in a manner similar to that shown for the relaxation modulus. The classical variation of these moduli is illustrated in Fig. 2.9. On log-log scales it is observed that there is a high value of creep or relaxation modulus at short times. This is referred to as the Unrelaxed Modulus and is independent of time. Similarly at long times there is a low value Relaxed Modulus which is also independent of time. 

As indicated above, the stress-strain presentation of the data in isochronous curves is a format which is very familiar to engineers. Hence in design situations it is quite common to use these curves and obtain a secant modulus (see Section 1.4.1, Fig. 1.6) at an appropriate strain. Strictly speaking this will be different to the creep modulus or the relaxation modulus referred to above since the secant modulus relates to a situation where both stress and strain are changing. In practice the values are quite similar and as will be shown in the following sections, the values will coincide at equivalent values of strain and time. That is, a 2% secant modulus taken from a 1 year isochronous curve will be the same as a 1 year relaxation modulus taken from a 2% isometric curve. 

Example 2.18 A particular grade of polypropylene can have its relaxation modulus described by the equation... 

A Standard Model for the viscoelastic behaviour of plastics consists of a spring element in scries with a Voigt model as shown in Fig. 2.86. Derive the governing equation for this model and from this obtain the expression for creep strain. Show that the Unrelaxed Modulus for this model is and the Relaxed Modulus is fi 2/(fi + 2>. 

Object in this section is to review how rheological knowledge combined with laboratory data can be used to predict stresses developed in plastics undergoing strains at different rates and at different temperatures. The procedure of using laboratory experimental data for the prediction of mechanical behavior under a prescribed use condition involves two principles that are familiar to rheologists one is Boltzmann s superposition principle which enables one to utilize basic experimental data such as a stress relaxation modulus in predicting stresses under any strain history the other is the principle of reduced variables which by a temperature-log time shift allows the time scale of such a prediction to be extended substantially beyond the limits of the time scale of the original experiment. 

The relaxation modulus (or any other viscoelastic function) thus obtained is a mean s of characterizing a material. In fact relaxation spectra have been found very useful in understanding molecular motions of plastics. Much of the relation between the molecular structure and the overall behavior of amorphous plastics is now known. 

The resulting data can then be presented as a series of curves much like the isometric stress curves in Fig. 2-27. A relaxation modulus similar to the creep modulus can also be derived from the relaxation data. It has been shown that using the creep modulus calculated from creep curves can approximate the decrease in load from stress relaxation. 

Stress Relaxation Modulus vs Age for Times of 0.01, 0.1 andiO Seconds. P 429... 

The transition strongly affects the molecular mobility, which leads to large changes in rheology. For a direct observation of the relaxation pattern, one may, for instance, impose a small step shear strain y0 on samples near LST while measuring the shear stress response T12(t) as a function of time. The result is the shear stress relaxation function G(t) = T12(t)/ < >, also called relaxation modulus. Since the concept of a relaxation modulus applies to liquids as well as to solids, it is well suited for describing the LST. 

Fig. 2. Relaxation modulus G(t) of a set of polydimethylsiloxane samples with increasing extent of crosslinking plotted against time of crosslinking. The linear PDMS chains (Mn 10 000, polydis-persity index 2) were endlinked with a four-functional silane crosslinker catalyzed by a platinum compound. Samples with different extent of reaction were prepared by poisoning the reaction at different times. The actual extent of reaction was not determined. Two of the samples are clearly before the gel point (LST) and two beyond. The third sample is very close to the gel point. Data of Chambon and Winter [5] evaluated by Baumgartel and Winter [8]...

Beyond the LST, p > pc, the material is a solid. The solid state manifests itself in a finite value of the relaxation modulus at long times, the so-called equilibrium modulus... 

The linear viscoelastic behavior of liquid and solid materials in general is often defined by the relaxation time spectrum 11(1) [10], which will be abbreviated as spectrum in the following. The transient part of the relaxation modulus as used above is the Laplace transform of the relaxation time spectrum H(l)... 

The scaling of the relaxation modulus G(t) with time (Eq. 1-1) at the LST was first detected experimentally [5-7]. Subsequently, dynamic scaling based on percolation theory used the relation between diffusion coefficient and longest relaxation time of a single cluster to calculate a relaxation time spectrum for the sum of all clusters [39], This resulted in the same scaling relation for G(t) with an exponent n following Eq. 1-14. 

It is interesting to note here that the cluster mass distribution and the relaxation modulus G(t) at the LST scale with cluster mass and with time, respectively, while all other variables (dynamic and static) scale with the distance from pc in the vicinity of the gel point. 

The time-dependent rheological behavior of liquids and solids in general is described by the classical framework of linear viscoelasticity [10,54], The stress tensor t may be expressed in terms of the relaxation modulus G(t) and the strain history ... 

The relaxation modulus is often expressed with the relaxation time spectrum, Eq. 1-4 ... 

The limiting storage modulus (at low frequencies) and relaxation modulus (at long times) become finite at high concentration, while they are zero at low concentration [97-102],... 

Adolf and Martin [15] postulated, since the near critical gels are self-similar, that a change in the extent of cure results in a mere change in scale, but the functional form of the relaxation modulus remains the same. They accounted for this change in scale by redefinition of time and by a suitable redefinition of the equilibrium modulus. The data were rescaled as G /Ge(p) and G"/Ge(p) over (oimax(p). The result is a set of master curves, one for the sol (Fig. 23a) and one for the gel (Fig. 23 b). 

The relaxation modulus evolves gradually during gelation. A set of data along the lines of Fig. 2 gives a good estimate of where the gel point occurs. The problem with it is that one cannot decide very well when exactly G(t) has straightened out into a power law. 

If the self-similar spectrum extends over a sufficiently wide time window, approximate solutions for the relaxation modulus G(t) and the dynamic moduli G (co), G"(co) might be explored by neglecting the end effects... 

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