Time–temperature superposition

The time–temperature superposition principle is a concept in polymer physics and in the physics of glass-forming liquids. This superposition principle is used to determine temperature-dependent mechanical properties of linear viscoelastic materials from known properties at a reference temperature. The elastic moduli of typical amorphous polymers increase with loading rate but decrease when the temperature is increased. Curves of the instantaneous modulus as a function of time do not change shape as the temperature is changed but appear only to shift left or right. This implies that a master curve at a given temperature can be used as the reference to predict curves at various temperatures by applying a shift operation. The time-temperature superposition principle of linear viscoelasticity is based on the above observation.

The application of the principle typically involves the following steps:

experimental determination of frequency-dependent curves of isothermal viscoelastic mechanical properties at several temperatures and for a small range of frequencies computation of a translation factor to correlate these properties for the temperature and frequency range experimental determination of a master curve showing the effect of frequency for a wide range of frequencies application of the translation factor to determine temperature-dependent moduli over the whole range of frequencies in the master curve. The translation factor is often computed using an empirical relation first established by Malcolm L. Williams, Robert F. Landel and John D. Ferry (also called the Williams-Landel-Ferry or WLF model). An alternative model suggested by Arrhenius is also used. The WLF model is related to macroscopic motion of the bulk material, while the Arrhenius model considers local motion of polymer chains. Some materials, polymers in particular, show a strong dependence of viscoelastic properties on the temperature at which they are measured. If you plot the elastic modulus of a noncrystallizing crosslinked polymer against the temperature at which you measured it, you will get a curve which can be divided up into distinct regions of physical behavior. At very low temperatures, the polymer will behave like a glass and exhibit a high modulus. As you increase the temperature, the polymer will undergo a transition from a hard “glassy” state to a soft “rubbery” state in which the modulus can be several orders of magnitude lower than it was in the glassy state. The transition from glassy to rubbery behavior is continuous and the transition zone is often referred to as the leathery zone. The onset temperature of the transition zone, moving from glassy to rubbery, is known as the glass transition temperature, or Tg. In the 1940s Andrews and Tobolsky showed that there was a simple relationship between temperature and time for the mechanical response of a polymer. Modulus measurements are made by stretching or compressing a sample at a prescribed rate of deformation. For polymers, changing the rate of deformation will cause the curve described above to be shifted along the temperature axis. Increasing the rate of deformation will shift the curve to higher temperatures so that the transition from a glassy to a rubbery state will happen at higher temperatures. It has been shown experimentally that the elastic modulus (E) of a polymer is influenced by the load and the response time. Time–temperature superposition implies that the response time function of the elastic modulus at a certain temperature resembles the shape of the same functions of adjacent temperatures. Curves of E vs. log(response time) at one temperature can be shifted to overlap with adjacent curves, as long as the data sets did not suffer from ageing effects during the test time (see Williams-Landel-Ferry equation). The Deborah number is closely related to the concept of time-temperature superposition.

Physical principle Consider a viscoelastic body that is subjected to dynamic loading. If the excitation frequency is low enough the viscous behavior is paramount and all polymer chains have the time to respond to the applied load within a time period. In contrast, at higher frequencies, the chains do not have the time to fully respond and the resulting artificial viscosity results in an increase in the macroscopic modulus. Moreover, at constant frequency, an increase in temperature results in a reduction of the modulus due to an increase in free volume and chain movement. Time–temperature superposition is a procedure that has become important in the field of polymers to observe the dependence upon temperature on the change of viscosity of a polymeric fluid. Rheology or viscosity can often be a strong indicator of the molecular structure and molecular mobility. Time–temperature superposition avoids the inefficiency of measuring a polymer's behavior over long periods of time at a specified temperature by utilizing the fact that at higher temperatures and shorter time the polymer will behave the same, provided there are no phase transitions.

Time-temperature superposition

Consider the relaxation modulus E at two temperatures T and T0 such that T > T0. At constant strain, the stress relaxes faster at the higher temperature. The principle of time-temperature superposition states that the change in temperature from T to T0 is equivalent to multiplying the time scale by a constant factor aT which is only a function of the two temperatures T and T0. In other words,

E ( t , T ) = E ( t a T , T 0 ) . {\displaystyle E(t,T)=E({\frac {t}{a_{\rm {T}}}},T_{0})\,.}

The quantity aT is called the horizontal translation factor or the shift factor and has the properties:

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