Superposition time-stress

The second important consequence of the relaxation times of all modes having the same temperature dependence is the expectation that it should -bp possible to superimpose linear viscoelastic data taken at different temperatures. This is commonly known as the time-temperature superposition principle. Stress relaxation modulus data at any given temperature Tcan be superimposed on data at a reference temperature Tq using a time scale multiplicative shift factor uj- and a much smaller modulus scale multiplicative shift factor hf. 

Undervacuum Stress Relaxation Studies. The stress relaxation behavior of the Nafion system presents some unusual characteristics. The relaxation master curves of the precursor, as well as of Nafion in its acid and salt forms, are very broad and are characterized by a wide distribution of relaxation times. The individual stress relaxation curves and the master curves for the precursor (45), Nafion acid and Nafion-K (46), are shown in Figures 14, 15 and 16 with the reference temperatures Indicated in the captions. Time-temperature superposition of stress relaxation data appears to be valid in the precursor and in the dry Nafion acid, at least over the time scale of the experiments. In the case of Nafion-K, time-temperature superposition is not valid, because it leads to a breakdown at low temperatures, which is reestablished at high temperatures (above ISO C). Similar behavior was also observed for a low molecular weight (5x10 ) styrene ionomer. The addition of small amounts of water to the Nafion acid can lead to a breakdown in the time-temperature superposition. The Influence of crystallinity and of strong ionic interaction will be discussed in the section on underwater stress relaxation studies. 

FIGURE 7. Illustration of time-temperature superposition (a) stress relaxation modulus at various temperatures T [Pg.44]

The effects of a number of environmental factors on viscoelastic material properties can be represented by a time shift and thus a shift factor. In Chapter 10, a time shift associated with stress nonlinearities, or a time-stress-superposition-principle (TSSP), is discussed in detail both from an analytical and an experimental point of view. A time scale shift associated with moisture (or a time-moisture-superposition-principle) is also discussed briefly in Chapter 10. Further, a time scale shift associated with several environmental variables simultaneously leading to a time scale shift surface is briefly mentioned. Other examples of possible time scale shifts associated with physical and chemical aging are discussed in a later section in this chapter. These cases where the shift factor relationships are known enables the constitutive law to be written similar to Eq. 7.53 with effective times defined as in Eq. 7.54 but with new shift factor functions. This approach is quite powerful and enables long-term predictions of viscoelastic response in changing environments. 

The Schapery method given by Eqs. 10.25 and 10.26 is a mathematical definition of a time-stress-superposition-principle or TSSP that is analogous to the TTSP. Later it will be shown how to obtain stress dependent compliance and modulus master curves from experimental data using TSSP much in the same manner as temperature dependent master curves were determined from experimental data using the TTSP. 

Empirical Approach To Time-Stress-Superposition (TSSP)... 

Again, as for the section on time dependent yielding it is necessary to consider how to obtain data that can be useful in preventing failure over the lifetime of a structure that may be intended to last for 20 to 100 years. The only rational means for this is some type of accelerated testing such as that offered by the time-temperature or time-stress-superposition procedure. Also, it is reiterated that failure is a stochastic event and of necessity a reliable statistical analysis should be performed. 

Starkova O, Yang J and Zhang Z (2007) Application of time-stress superposition to nonlinear creep of polyamide 66 filled with nanoparticles of various azes. Compos Sci Tec/moi 67 2691-2698. 

Joshi, Y. M. and Reddy, G. R. K. 2008. Aging in a colloidal glass in creep flow Time-stress superposition. Phys. Rev. E 77 021501. 

The mobility of a material is influenced not only by temperature but also by stress, as was already discussed above when we dealt with plastic flow phenomena. Figure 10 (bottom) shows that, similar to high temperatures, stress also increases the yield stress. Instead of TTS, now time-stress superposition (TSS), employing Eyring stress aaivation, is applied to shift the data onto a master curve that coincides with the master curve obtained by temperature annealing. ... 

The isothermal curves of mechanical properties in Chap. 3 are actually master curves constructed on the basis of the principles described here. Note that the manipulations are formally similar to the superpositioning of isotherms for crystallization in Fig. 4.8b, except that the objective here is to connect rather than superimpose the segments. Figure 4.17 shows a set of stress relaxation moduli measured on polystyrene of molecular weight 1.83 X 10 . These moduli were measured over a relatively narrow range of readily accessible times and over the range of temperatures shown in Fig. 4.17. We shall leave as an assignment the construction of a master curve from these data (Problem 10). 

Fig. 49. Illustration of the time—temperature superposition principle as based on stress—relaxation data for polyisobutylene (299,300). To convert Pa to...

Now consider the situation in which the stress, ai, was applied at time, ti, and an additional stress, Boltzmanns Superposition Principle states that the total strain at time, t, is the algebraic sum of the two independent responses. 

The predicted strain variation is shown in Fig. 2.43(b). The constant strain rates predicted in this diagram are a result of the Maxwell model used in this example to illustrate the use of the superposition principle. Of course superposition is not restricted to this simple model. It can be applied to any type of model or directly to the creep curves. The method also lends itself to a graphical solution as follows. If a stress is applied at zero time, then the creep curve will be the time dependent strain response predicted by equation (2.54). When a second stress, 0 2 is added then the new creep curve will be obtained by adding the creep due to 02 to the anticipated creep if stress a had remained... 

This is simpler than the first solution but this approach is only convenient for the simple loading sequence of stress on-stress off. If this sequence is repeated many times then this superposition approach becomes rather complex. In these cases the analytical solution shown below is recommended but it should be remembered that the equations used were derived on the basis of the superposition approach illustrated above. 

A plastic with a time dependent creep modulus as in the previous example is stressed at a linear rate to 40 MN/m in 100 seconds. At this time the stress in reduced to 30 MN/m and kept constant at this level. If the elastic and viscous components of the modulus are 3.5 GN/m and 50 x 10 Ns/m, use Boltzmann s Superposition Principle to calculate the strain after (a) 60 seconds and (b) 130 seconds. 

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. 

With crystalline plastics, the main effect of the crystallinity is to broaden the distribution of the relaxation times and extend the relaxation stress too much longer periods. This pattern holds true at both the higher and low extremes of crystallinity (Chapter 6). With some plastics, their degree of crystallinity can change during the course of a stress-relaxation test. This behavior tends to make the Boltzmann superposition principle difficult to apply. 

A creep test can be carried out with an imposed stress, then after a time have its stress suddenly changed to a new value and have the test continued. This type of change in loading allows the creep curve to be predicted. The simple law referred to earlier as the Boltzmann superposition principle, hold for most materials, so that their creep curves can thus be predicted. 

Rubbery materials beyond the gel point have been studied extensively. A long time ago, Thirion and Chasset [9] recognized that the relaxation pattern of a stress r under static conditions can be approximated by the superposition of a power law region and a constant limiting stress rq at infinite time ... 

To get accurate distributions of relaxation or retardation times, the expetimcntal data should cover about 10 or 15 decades of time. It is impossible to get experimental data covering such a great range of times at one temperature from a single type of experiment, such as creep or stress relaxation-t Therefore, master curves (discussed later) have been developed that cover the required time scales by combining data at different temperatures through the use of time-temperature superposition principles. 

The Boltzmann superposition principle states that the response of a material to a given load is independent of the response of the material to ary load that is already on the material. Another consequence of this principle is that the deformation of a specimen is directly proportional to the applied stress when all deformations are compared at equivalent, times... 

Thus (he time scale / at /, divided by an is equivalent to the scale at On a log scale, log a, is thus the horizontal shift factor required for superposition. An important consequence of equation (22) is that a, or log (ii is the same for a given polymer (or solution) no matter what experiment is being employed. Thai is. creep and stress-relaxation curves are shifted by the same amount. 

The temperature-time superposition principle is illustrated in Figure 8 by a hypothetical polymer with a TK value of 0°C for the case of stress relaxation. First, experimental stress relaxation curves are obtained at a series of temperatures over as great a time period as is convenient, say from 1 min to 10 min (1 week) in (he example in Figure 8. In making the master curve from the experimental data, the stress relaxation modulus ,(0 must first be multiplied by a small temperature correction factor/(r). Above Tg this correction factor is where Ttrt is the chosen reference... 

Figure 8 WLF time-temperature superposition applied to stress-relaxation data obtained at several temperatures to obtain a master curve. The master curve, made by shifting the data along the horizontal axis by amounts shown in the insert for r> is shown with circles on a line.

If the Boltzmann superposition principle holds, the creep strain is directly proportional to the stress at any given time, f Similarly, the stress at any given lime is directly proportional to the strain in stress relaxation. That is. the creep compliance and the stress relaxation modulus arc independent of the stress and slrai . respectively. This is generally true for small stresses or strains, but the principle is not exact. If large loads are applied in creep experiments or large strains in stress relaxation, as can occur in practical structural applications, nonlinear effects come into play. One result is that the response (0 l,r relaxation times can also change, and so can ar... 

For glassy and crystalline polymers there are few data on the variation of stress relaxation with amplitude of deformation. However, the data do verily what one would expect on the basis of the response of elastomers. Although the stress-relaxation modulus at a given time may be independent of strain at small strains, at higher initial fixed strains the stress or the stress-relaxation modulus decreases faster than expected, and the lloltz-nuinn superposition principle no longer holds. 

Time is the major (actor in determining the mechanical properties of a polymer. This is seen directly in creep and stress-relaxation experiments. These tests cover long periods of time, so that they are sensitive to the types of molecular motions that require long times. Tfrey give little direct information on the types of molecular motion that take place at short times. However, by using the time-temperature superposition principle and the WLF equations, access to these short times can be achieved even though they may not easily be attainable by direct experimentation. 

There are many types of deformation and forces that can be applied to material. One of the foundations of viscoelastic theory is the Boltzmann Superposition Principle. This principle is based on the assumption that the effects of a series of applied stresses acting on a sample results in a strain which is related to the sum of the stresses. The same argument applies to the application of a strain. For example we could apply an instantaneous stress to a body and maintain that stress constant. For a viscoelastic material the strain will increase with time. The ratio of the strain to the stress defines the compliance of the body ... 

The application of a linearly ramped strain can provide information on both the sample elasticity and viscosity. The stress will grow in proportion to the applied strain. The ratio of the strain over the applied time gives the shear rate. Applying the Boltzmann Superposition Principle we obtain the following expression ... 

An important and sometimes overlooked feature of all linear viscoelastic liquids that follow a Maxwell response is that they exhibit anti-thixo-tropic behaviour. That is if a constant shear rate is applied to a material that behaves as a Maxwell model the viscosity increases with time up to a constant value. We have seen in the previous examples that as the shear rate is applied the stress progressively increases to a maximum value. The approach we should adopt is to use the Boltzmann Superposition Principle. Initially we apply a continuous shear rate until a steady state... 

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