Relaxation Time-temperature superposition

The time-temperature superpositioning principle was applied f to the maximum in dielectric loss factors measured on poly(vinyl acetate). Data collected at different temperatures were shifted to match at Tg = 28 C. The shift factors for the frequency (in hertz) at the maximum were found to obey the WLF equation in the following form log co + 6.9 = [ 19.6(T -28)]/[42 (T - 28)]. Estimate the fractional free volume at Tg and a. for the free volume from these data. Recalling from Chap. 3 that the loss factor for the mechanical properties occurs at cor = 1, estimate the relaxation time for poly(vinyl acetate) at 40 and 28.5 C. 

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

The WLF equation can be widely applied, and demonstrates the equivalence of time and temperature, the so-called time-temperature superposition principle, on the mechanical relaxations of an amorphous polymer. The equation holds up to about 100° above the glass transition temperature, but after that begins to break down. 

Since we are interested in this chapter in analyzing the T- and P-dependences of polymer viscoelasticity, our emphasis is on dielectric relaxation results. We focus on the means to extrapolate data measured at low strain rates and ambient pressures to higher rates and pressures. The usual practice is to invoke the time-temperature superposition principle with a similar approach for extrapolation to elevated pressures [22]. The limitations of conventional t-T superpositioning will be discussed. A newly developed thermodynamic scaling procedure, based on consideration of the intermolecular repulsive potential, is presented. Applications and limitations of this scaling procedure are described. 

Time-temperature superposition [10] increases the accessible frequency window of the linear viscoelastic experiments. It applies to stable material states where the extent of reaction is fixed ( stopped samples ). Winter and Chambon [6] and Izuka et al. [121] showed that the relaxation exponent n is independent of temperature and that the front factor (gel stiffness) shifts with temperature... 

Time-temperature superposition. Because of the relatively strong relaxations in the frequency range at room temperature (300 K), oscillation measurements were also performed at 345, 390 and 435 K in addition the D networks were measured at 265 K. 

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. 

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.

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. 

In the interval between 198 K and 253 K, the form of the structural relaxation does not change114 as is evidenced by the success of the time-temperature superposition shown in Figure 21. One can also see from this figure that an additional regime intervenes between the short-time dynamics (first 10% of the decay at the lowest temperatures) and the structural relaxation (last 80% of the decay). We will identify this regime as the MCT (3-regime... 

Time-temperature superposition is frequently applied to the creep of thermoplastics. As mentioned above, a simple power law equation has proved to be useful in the modelling of the creep of thermoplastics. However, for many polymers the early stages of creep are associated with a physical relaxation process in which the compliance (D t)) changes progressively from a lower limit (Du) to an upper limit (DR). The rate of change in compliance is related to a characteristic relaxation time (x) by the equation ... 

Because of equipment limitations in measuring stress and strain in polymers, the time-temperature superposition principle is used to develop the viscoelastic response curve for real polymers. For example, the time-dependent stress relaxation modulus as a function of time and temperature for a PMMA resin is shown in... 

Moreover, we note that recently in reconstructing relaxation times via the time-temperature superposition principle using double quantum nuclear magnetic resonance (DQ-NMR) the and power laws were invoked without giving the spatial information of NSE [75]. 

The time-temperature superposition principle has practical applications. Stress relaxation experiments are practical on a time scale of 10 to 10 seconds (10 to 10 hours), but stress relaxation data over much larger time periods, including fractions of a second for impacts and decades for creep, are necessary. Temperature is easily varied in stress relaxation experiments and, when used to shift experimental data over shorter time intervals, can provide a master curve over relatively large time intervals, as shown in Figure 5.65. The master curves for several crystalline and amorphous polymers are shown in Figure 5.66. 

Figure 3.5 Stress relaxation plot for obtained using time-temperature superposition. (After J. Fried, Plastics Engineering, July 1982, with permission.)...

In Eq. (4.13) NT is the total number of internal degrees of freedom per unit volume which relax by simple diffusion (NT — 3vN for dilute solutions), and t, is the relaxation time of the ith normal mode (/ = 1,2,3NT) for small disturbances. Equation (4.13), together with a stipulation that all relaxation times have the same temperature coefficient, provides, in fact, the molecular basis of time-temperature superposition in linear viscoelasticity. It also reduces to the expression for the equilibrium shear modulus in the kinetic theory of rubber elasticity when tj = oo for some of the modes. 

In addition to the primary glass-rubber relaxation which follows the empirical shifts determined by Eq. (26), part of the recoverable compliance does not obey time-temperature superposition. The shortest time data at the lowest temperatures has a component which shifts according to the Arrhenius temperature dependence... 

Many amorphous homopolymers and random copolymers show thermorheologically simple behavior within the usual experimental accuracy. Plazek (23,24), however, found that the steady-state viscosity and steady-state compliance of polystyrene cannot be described by the same WLF equation. The effect of temperature on entanglement couplings can also result in thermorheologically complex behavior. This has been shown on certain polymethacrylate polymers and their solutions (22, 23, 26, 31). The time-temperature superposition of thermorheologically simple materials is clearly not applicable to polymers with multiple transitions. The classical study in this area is that by Ferry and co-workers (5, 8) on polymethacrylates with relatively long side chains. In these the complex compliance is the sum of two contributions with different sets of relaxation mechanisms the compliance of the chain backbone and that of the side chains, respectively. 

Since the relaxation mechanisms characteristic of the constituent blocks will be associated with separate distributions of relaxation times, the simple time-temperature (or frequency-temperature) superposition applicable to most amorphous homopolymers and random copolymers cannot apply to block copolymers, even if each block separately shows thermorheologically simple behavior. Block copolymers, in contrast to the polymethacrylates studied by Ferry and co-workers, are not singlephase systems. They form, however, felicitous models for studying materials with multiple transitions because their molecular architecture can be shaped with considerable freedom. We report here on a study of time—temperature superposition in a commercially available triblock copolymer rubber determined in tensile relaxation and creep. 

In an investigation of the birefringence and stress relaxation of Kraton 101 cast from solution in toluene and in methyl ethyl ketone, Wilkes and Stein (33) considered the relaxation modulus to be a weighted average of the moduli of the pure polybutadiene and polystyrene phases. Ferry and co-workers, in their investigations of time-temperature superposition in polymethacrylates with relatively long side chains, found the com-... 

Because of the uncertainties involved in the decomposition, this procedure would not appear to be a practical way to determine the AHa value needed for Equation 8. It does, however, demonstrate three important points (1) it is the compliances of the mechanisms that are additive (2) T0 and AHa can be obtained from plots such as those shown in Figures 7 and 8 of shift data determined in either relaxation or creep experiments without decomposition of compliance master curves (3) Equation 8 describes time-temperature superposition in Kraton 102 adequately within the experimental accuracy. 

---