Step-strain

Rheometric Scientific markets several devices designed for characterizing viscoelastic fluids. These instmments measure the response of a Hquid to sinusoidal oscillatory motion to determine dynamic viscosity as well as storage and loss moduH. The Rheometric Scientific line includes a fluids spectrometer (RFS-II), a dynamic spectrometer (RDS-7700 series II), and a mechanical spectrometer (RMS-800). The fluids spectrometer is designed for fairly low viscosity materials. The dynamic spectrometer can be used to test soHds, melts, and Hquids at frequencies from 10 to 500 rad/s and as a function of strain ampHtude and temperature. It is a stripped down version of the extremely versatile mechanical spectrometer, which is both a dynamic viscometer and a dynamic mechanical testing device. The RMS-800 can carry out measurements under rotational shear, oscillatory shear, torsional motion, and tension compression, as well as normal stress measurements. Step strain, creep, and creep recovery modes are also available. It is used on a wide range of materials, including adhesives, pastes, mbber, and plastics. 

The relaxation of the stress resulting from a step strain can be observed experimentally and we can see that it is the result of diffusive motion of the microstructural elements. Although we can have a mechanistic picture, what does this mean in terms of our measurements We have the very striking result that our material classification must depend on the time t, i.e. the experimental or observation time. Hence, we can usefully classify material behaviour into three categories ... 

In an experiment when we apply a step strain the rate of application of the strain influences the relaxation of the stress at short times. There are other factors which can influence the response that is observed. For example it is common for elastic samples to resonate with the applied actuator and transmit transient waves through the sample. This can lead to fluctuations in the stress at short times. A typical example is shown in Figure 4.14. 

These two experiments are fundamentally different in the nature of the applied deformation. In the case of the relaxation experiment a step strain is applied whereas the modulus is measured by an applied oscillating strain. Thus we are transforming between the time and frequency domains. In fact during the derivation of the storage and loss moduli these transforms have already been defined by Equation (4.53). In complex number form this becomes... 

Each submolecule will experience a frictional drag with the solvent represented by the frictional coefficient /0. This drag is related to the frictional coefficient of the monomer unit (0- If there are x monomer units per link then the frictional coefficient of a link is x(0- If we aPply a step strain to the polymer chain it will deform and its entropy will fall. In order to attain its equilibrium conformation and maximum entropy the chain will rearrange itself by diffusion. The instantaneous elastic response can be thought of as being due to an entropic spring . The drag on each submolecule can be treated in terms of the motion of the N+ 1 ends of the submolecules. We can think of these as beads linked... 

We have expressed the relaxation behaviour in terms of the number of chains per unit volume. At this stage we are considering the polymer in an undiluted state. Suppose we now apply a step strain to the melt in the linear regime. Two different zones of behaviour can be seen relative to the time re. This is the time at which the tube constraints begin to affect the relaxation of the chain ... 

It became clear in the early development of the tube model that it provided a means of calculating the response of entangled polymers to large deformations as well as small ones [2]. Some predictions, especially in steady shear flow, lead to strange anomaUes as we shall see, but others met with surprising success. In particular the same step-strain experiment used to determine G(t) directly in shear is straightforward to extend to large shear strains y. In many cases of such experiments on polymer melts both Hnear and branched, monodisperse and polydisperse,the experimental strain-dependent relaxation function G(t,Y) may be written... 

Reasons have been advanced for both an increase and a decrease of the tube diameter with strain. A justification of the former view might be the retraction process itself [38]. If it acts in a similar way to the dynamic dilution and the effective concentration of entanglement network follows the retraction then Cgjy < E.u > so that a < E.u On the other hand one might guess that at large strains the tube deforms at constant tube volume La. The tube length must increase as < E.u >,so from this effect a < E.u > . Indeed, Marrucci has recently proposed that both these effects exist and remain unnoticed in step strain because they cancel [69] Of course this is far from idle speculation because there is another situation in which such effects would have important consequences. This is in conditions of continuous deformation, to which we now turn. 

The step-strain experiments discussed above furnish the simplest example of a strong flow. Many other flows are of experimental importance transient and steady shear, transient extensional flow and reversing step strains, to give a few examples. Indeed the development of phenomenological constitutive equations to systematise the wealth of behaviour of polymeric liquids in general flows has been something of an industry over the past 40 years [9]. It is important to note that it is not possible to derive a constitutive equation from the tube model in... 

Figure 3. Contour length relaxation after a large step strain.

The application of stress relaxation is shown in Figure 3. The relaxation modulus (G) is determined after a step strain as a function of time. A step strain is applied to the sample causing a stress. The modulus is measured as the stress relaxes. The stress relaxation modulus shows how molecular weight affects the relaxation process as a function of time as depicted in Figure 4. 

Transient birefringence measurements were used by Larson et al. [112] to test the validity of the Lodge-Meissner relationship for entangled polymer solutions. This relationship states that the ratio of the first normal stress difference to the shear stress following a step strain is simply Nx/%xy - y, where y is the strain. Those authors found the relationship was valid, except for ultrahigh molecular weight materials. 

Immediately following a step strain deformation, all of the segments of a fully entangled melt can be assumed to have the same degree of orientation. In other words, both the short and the long chains will be characterized by identical functions (uu)f Q+, where... 

Figure 10.7 The relaxation of birefringence and dichroism following a step strain. The...

When reptation is used to develop a description of the linear viscoelasticity of polymer melts [5, 6], the same underlying hypothesis ismade, and the same phenomenological parameter Ng appears. Basically, to describe the relaxation after a step strain, for example, each chain is assumed to first reorganise inside its deformed tube, with a Rouse-like dynamics, and then to slowly return to isotropy, relaxing the deformed tube by reptation (see the paper by Montfort et al in this book). Along these lines, the plateau relaxation modulus, the steady state compliance and the zero shear viscosity should be respectively ... 

The relaxation modulus G(t) is the value of the transient stress per unit strain in a step-strain experiment. This type of experiment may be achieved with modem rotary rheometers with a limited resolution in time (roughly 10 2 s). If one wishes to evaluate G(t) at shorter times, it is necessary to derive G(t) from the high frequency G (co) data by an inverse Carson-Laplace transform. 

Figure 8 Relaxation of a polymeric chain after a step-strain deformation[6] process A (8c) reequilibration of chain segments process B (8d) reequilibration across slip links process C (8e) reptation.

Measurements of the nonlinear relaxation modulus G(t,y) have also been carried out using the plate-plate geometry. Various step strains were applied on the sample and the stress relaxations were recorded. Since the shear strain is known to be inhomogeneous in such a geometry, a correction of the apparent relaxation Ga(t,y) modulus has to be taken into accoimt to get the real relaxation modulus for the maximum strain in the disk sample. This procedure is very similar to that proposed by Rabinowitch in Poiseuille flow, wherein the shear rate is also non-homogeneous, and has already been described by Soskey and Winter [36]. The correction factor is ... 

Firstly, it has been shown that there may be many experimental problems in a direct determination of the experimental fimction. In shear, damping functions obtained from step strain and from step strain rate experiments do not match each other. This poses an important question on the validity of the separability assumption in the short time rai e. Significant departures from this factorization have already been observed in the case of narrow polystyrene fractions by Takahashi et al. [54]. These authors found that time-strain superposition of the linear and nonlinear relaxation moduli was only possible above a cert2un characteristic time. It is interesting to note that this is predicted by the Doi-Edwards theory [10] and according to this theory, this phenomena is attributed to an additional decrease of the modulus connected to a tube contraction process and time-strain separability may hold after this equilibration process has been completed. Other examples of non-separability were also reported by Einaga et al. [55] and more recently by Venerus et al. [56] for solutions. 

D.C.Venerus, C.M.Vrentas, J.S.Vrentas, Step strain deformations for viscoelastic fluids experiment, J. Rheol. 34 (1990), 657-682. 

Doi and Edwards (1978a, 1979) explained this strain softening using an extension of the tube model of de Gennes. Suppose that the melt is subjected to a step strain and... 

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