Relaxation time Maxwell model

Figure 12.10 Storage and loss moduli G and G" as functions of frequency 0) for a solution of 15 mM CPyCl and 12.5 mM NaSal at T = 20°C. The data are similar to the predictions of the single-relaxation-time Maxwell model. (Reprinted with permission from Rehage and Hoffmann, Journal of Physical Chemistry 92 4712 Copyright 1988, American Chemical Society.)...

Relaxation Time - Maxwell proposed a model in the 19 century to describe the time-dependent behavior of viscous materials such as pitch or tar. This model has also been applied to plastics and polymers. A parameter has been defined in this model called relaxation time that is a characteristic of the plastic material. Relaxation time is the ratio of viscosity to the Young s modulus of elasticity. 

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 velocity gradient leads to an altered distribution of configuration. This distortion is in opposition to the thermal motions of the segments, which cause the configuration of the coil to drift towards the most probable distribution, i.e. the equilibrium s configurational distribution. Rouse derivations confirm that the motions of the macromolecule can be divided into (N-l) different modes, each associated with a characteristic relaxation time, iR p. In this case, a generalised Maxwell model is obtained with a discrete relaxation time distribution. 

This equation, based on the generalized Maxwell model (e.g. jL, p. 68), indicates that G (o) can be determined from the difference between the measured modulus and its relaxational part. A prerequisite, however, is that the relaxation spectrum H(t) should be known over the entire relaxation time range from zero to infinity, which is impossible in practice. Nevertheless, the equation can still be used, because this time interval can generally be taken less wide, as will be demonstrated below. 

Figure 2 Stress relaxation of a Maxwell model on a logarithmic time scale. Model is the same as Figure 1.

The spring is elastically storing energy. With time this energy is dissipated by flow within the dashpot. An experiment performed using the application of rapid stress in which the stress is monitored with time is called a stress relaxation experiment. For a single Maxwell model we require only two of the three model parameters to describe the decay of stress with time. These three parameters are the elastic modulus G, the viscosity r and the relaxation time rm. The exponential decay described in Equation (4.16) represents a linear response. As the strain is increased past a critical value this simple decay is lost. 

A stress relaxation experiment can be performed on a wide range of materials. If we perform such a test on a real material a number of deviations are normally observed from the behaviour of a single Maxwell model. Some of these deviations are associated with the application of the strain itself. For example it is very difficult to apply an instantaneous strain to a sample. This influences the measured response at short experimental times. It is often difficult to apply a strain small enough to provide a linear response. A Maxwell model is only applicable to linear responses. Even if you were to imagine an experiment where a strain is... 

Suppose the multiple Maxwell model which describes the material we are interested in is composed of m processes each with an elasticity Gj, a viscous process with a viscosity rjj and a corresponding relaxation time ty. We can form the relaxation function by adding all these models together ... 

One feature of the Maxwell model is that it allows the complete relaxation of any applied strain, i.e. we do not observe any energy stored in the sample, and all the energy stored in the springs is dissipated in flow. Such a material is termed a viscoelastic fluid or viscoelastic liquid. However, it is feasible for a material to show an apparent yield stress at low shear rates or stresses (Section 6.2). We can think of this as an elastic response at low stresses or strains regardless of the application time (over all practical timescales). We can only obtain such a response by removing one of the dashpots from the viscoelastic model in Figure 4.8. When a... 

The relaxation spectrum greatly influences the behaviour observed in experiments. As an example of this we can consider how the relaxation spectrum affects the storage and loss moduli. To evaluate this we need to change the kernel to that for a Maxwell model in oscillation and replace the experimental time by oscillation frequency ... 

The range of frequencies used to calculate the moduli are typically available on many instruments. The important feature that these calculations illustrate is that as the breadth of the distributions is increased the original sigmoidal and bell shaped curves of the Maxwell model are progressively lost. A distribution of Maxwell models can produce a wide range of experimental behaviour depending upon the relaxation times and the elastic responses present in the material. The relaxation spectrum can be composed of more than one peak or could contain a simple Maxwell process represented by a spike in the distribution. This results in complex forms for all the elastic moduli. 

Figure 4.15 The stress growth function for a Maxwell model with a relaxation time tr...

The mathematics underlying transformation of the data from different experiments can be applied to simple models. In the case of the relationship between G (a>) and G(t) it is straightforward. To give an example, consider a Maxwell model. It has an exponentially decaying modulus with time. We have indicated that the relationship between the complex modulus and the relaxation function is given by Equation (4.117). So if we substitute the relaxation function into this expression we get... 

The sum over weighted relaxation times is heavily dominated by the longest time (the reptation time) r gp=L /7T Dp. Because of this the frequency-dependent dissipative modulus, G"(cd) is expected to show a sharp maximum The higher modes do modify the prediction from that of a single-mode Maxwell model, but only to the extent of reducing the form of G"(a>) to the right of the maximum from ccr to In fact, experiments on monodisperse linear polymers... 

Since polymers are viscoelastic solids, combinations of these models are used to demonstrate the deformation resulting from the application of stress to an isotropic solid polymer. Maxwell joined the two models in series to explain the mechanical properties of pitch and tar (Figure 14.2a). He assumed that the contributions of both the spring and dashpot to strain were additive and that the application of stress would cause an instantaneous elongation of the spring, followed by a slow response of the piston in the dashpot. Thus, the relaxation time (t), when the stress and elongation have reached equilibrium, is equal to rj/G. 

Thus, according to Equation 14.8 for the Maxwell model or element, under conditions of constant strain, the stress will decrease exponentially with time and at the relaxation time t = T, s will equal 1/e, or 0.37 of its original value, So-... 

A further development is possible by noting that the high frequency shear modulus Goo is related to the mean square particle displacement (m ) of caged fluid particles (monomers) that are transiently localized on time scales ranging between an average molecular collision time and the structural relaxation time r. Specifically, if the viscoelasticity of a supercooled liquid is approximated below Ti by a simple Maxwell model in conjunction with a Langevin model for Brownian motion, then (m ) is given by [188]... 

Note that the model given in Ref. 47) takes into account the distortion of potential barriers in activation flow under the action of stress. Relaxation time is 0k = 0k exp (—mWk) (here mk = yk/RT where yk is constant, R is gas constant, T is temperature). Normally, two Maxwell s elements (N = 2) and one viscous element with vis-... 

Here we have three parameters r/o the zero-shear-rate viscosity, Ai the relaxation time and A2 the retardation time. In the case of A2 = 0 the model reduces to the convected Maxwell model, for Ai = 0 the model simplifies to a second-order fluid with a vanishing second normal stress coefficient [6], and for Ai = A2 the model reduces to a Newtonian fluid with viscosity r/o. If we impose a shear flow,... 

The model represents a liquid (able to have irreversible deformations) with some additional reversible (elastic) deformations. If put under a constant strain, the stresses gradually relax. When a material is put under a constant stress, the strain has two components as per the Maxwell Model. First, an elastic component occurs instantaneously, corresponding to the spring, and relaxes immediately upon release of the stress. The second is a viscous component that grows with time as long as the stress is applied. The Maxwell model predicts that stress decays exponentially with time, which is accurate for most polymers. It is important to note limitations of such a model, as it is unable to predict creep in materials based on a simple dashpot and spring connected in series. The Maxwell model for creep or constant-stress conditions postulates that strain will increase linearly with time. However, polymers for the most part show the strain rate to be decreasing with time [23-26],... 

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