Time-temperature master curve

The time-temperature master curve of Figure 1, determined using the smni manual method outlined above, is rqilotted in Figure 2 and ounpared to a KWW fit to these data [solid line]. It is immediately clear that the KWW equation does not adequately describe the relaxation behavior over the whole range of data. 

Fipre 1. Stress relaxation rqwnse at a strain of 2% as a function of temperature and the time - temperature master curve. 

Fig. 3.30. The time-temperature master curve for a nearly monodisperse polystyrene [35].

Figure 7.26 (a) Time-temperature master curve of modulus for PMMA at 120°C by shifting data in Figure 7.25(a). (b)Time-temperature master curve for PMMA tan 5, using same shift factors as... 

Figure 35.3 Rubbery modulus ( ) MPa) versus PEGDA cross-linker content for PEGDA/ PEGMEA, PEGDA/PEGA, and PEGDA/water networks, where is evaluated from time-temperature master curves at — 40°C. [Reprinted with permission fiom Kalakkuimath et al. (2005).

Figure 35.4 Time temperature master curves for PEGDA/PEGA copolymer networks T f = —40°C. Solid curves are KWW best fits. [Reprinted with permission from Kalakkunnath et al. (2005). Copyright 2005 American Chemical Society.]...

Figure S. Comparision of the time - temperature and time - strain master curves.

The storage and loss shear moduli, G and G", vs. oscillation frequency ta, and the creep compliance J vs. time t, measured at each concentration and tanperature, were temperature shifted with respect to frequency or time. These temperature master curves at each concentration were then shifted to overlap one another along the frequency or time axis. The dynamic shear moduli master curves as a function of reduced frequency (oa ac are shown in fig. 4.4, and the shear creep compliance master curves as a function of reduced time tlajUc are shown in fig. 4.5. Master curves... 

One way to obtain long-term information is through the use of the time-temperature-superposition principle detailed in Chapter 7. Indeed, J. Lohr, (1965) (the California wine maker) while at the NASA Ames Research Center conducted constant strain rate tests from 0.003 to 300 min and from 15° C above the glass transition temperature to 100° C below the glass transition temperature to produce yield stress master curves for poly(methyl methacrylate), polystyrene, polyvinyl chloride, and polyethylene terephthalate. It should not be surprising that time or rate dependent yield (rupture) stress master curves can be developed as yield (rupture) is a single point on a correctly determined isochronous stress-strain curve. Whether linear or nonlinear, the stress is related to the strain through a modulus function at the yield point (mpture) location. As a result, a time dependent master curve for yield, rupture, or other failure parameters should be possible in the same way that a master curve of modulus is possible as demonstrated in Chapter 7 and 10. 

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). 

Note that subtracting an amount log a from the coordinate values along the abscissa is equivalent to dividing each of the t s by the appropriate a-p value. This means that times are represented by the reduced variable t/a in which t is expressed as a multiple or fraction of a-p which is called the shift factor. The temperature at which the master curve is constructed is an arbitrary choice, although the glass transition temperature is widely used. When some value other than Tg is used as a reference temperature, we shall designate it by the symbol To. 

This allows the production of master curves, which can be used to estimate changes ia modulus or other properties over a long period of time by shorter tests over different temperatures. 

Master curves can be used to predict creep resistance, embrittlement, and other property changes over time at a given temperature, or the time it takes for the modulus or some other parameter to reach a critical value. For example, a mbber hose may burst or crack if its modulus exceeds a certain level, or an elastomeric mount may fail if creep is excessive. The time it takes to reach the critical value at a given temperature can be deduced from the master curve. Frequency-based master curves can be used to predict impact behavior or the damping abiUty of materials being considered for sound or vibration deadening. The theory, constmction, and use of master curves have been discussed (145,242,271,277,278,299,300). 

Thus all the different temperature related data in Fig. 2.58 could be shifted to a single master curve at the reference temperature (7 ). Alternatively if the properties are known at Tref then it is possible to determine the property at any desired temperature. It is important to note that the shift factor cannot be applied to a single value of modulus. This is because the shift factor is on the horizontal time-scale, not the vertical, modulus scale. If a single value of modulus 7, is known as well as the shift factor ar it is not possible to... 

In order to produce the master curve illustrated, each section would have been completed in the time range 10 -10" s, but at different temperatures. Combining the sections then produces the overall master curve. 

Figure 1. Time-temperature superimposed master curves of storage and loss moduli as functions of reduced frequency. The four networks belong to the D family. Numbers indicate wt. % dicumyl peroxide.

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 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.

Master curves are important since they give directly the response to be expected at other times at that temperature. In addition, such curves are required to calculate the distribution of relaxation times as discussed earlier. Master curves can be made from stress relaxation data, dynamic mechanical data, or creep data (and, though less straightforwardly, from constant-strain-rate data and from dielectric response data). Figure 9 shows master curves for the compliance of poly(n. v-isoprene) of different molecular weights. The master curves were constructed from creep curves such as those shown in Figure 10 (32). The reference temperature 7, for the... 

The WLF equation can be used to convert data from a master curve created at one temperature to that at another temperature or to find the temperature dependence of the response at a selected time scale. In the... 

This form is also known as the Williams-Watts functiont (145). It is a powerful yet simple form to use in fitting data, since it can accommodate any slope in the transition region. However, equation (40) cannot describe a complete master curve from glassy to rubbery state with a single value ofp. Instead, P (or m) is taken to be time (or temperature) dependent. 

Several attempts have been made to superimpose creep and stress-relaxation data obtained at different temperatures on styrcne-butadiene-styrene block polymers. Shen and Kaelble (258) found that Williams-Landel-Ferry (WLF) (27) shift factors held around each of the glass transition temperatures of the polystyrene and the poly butadiene, but at intermediate temperatures a different type of shift factor had to be used to make a master curve. However, on very similar block polymers, Lim et ai. (25 )) found that a WLF shift factor held only below 15°C in the region between the glass transitions, and at higher temperatures an Arrhenius type of shift factor held. The reason for this difference in the shift factors is not known. Master curves have been made from creep and stress-relaxation data on partially miscible graft polymers of poly(ethyl acrylate) and poly(mcthyl methacrylate) (260). WLF shift factors held approximately, but the master curves covered 20 to 25 decades of time rather than the 10 to 15 decades for normal one-phase polymers. 

Figure 14 Master curve generated from mean-square displacements at different temperatures, plotting them against the diffusion coefficient at that temperature times time. Shown are only the envelopes of this procedure for the monomer displacement in the bead-spring model and for the atom displacement in a binary Lennard-Jones mixture. Also indicated are the long-time Fickian diffusion limit, the Rouse-like subdiffusive regime for the bead-spring model ( ° 63), the MCT von Schweidler description of the plateau regime, and typical length scales R2 and R2e of the bead-spring model.

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