Isothermal viscoelastic properties of PMMA and LDPE over 11 decades of frequency and time: a test of time-temperature superposition

Many instruments used to measure viscoelastic properties are only capable of subjecting a sample to a limited range of loading frequencies. For thermorheologically simple materials, it is assumed that a change in temperature is equivalent to a shift of the viscoelastic behavior on the log frequency or time axis. For many materials, time-temperature superposition appears to work well for modulus or compliance curves over three decades of time or frequency, but some deviations are known if the window is expanded to five or six decades. To apply a more stringent test of the validity of time-temperature superposition, broadband viscoelastic spectroscopy is used to isothermally study polymethylmethacrylate and low-density polyethylene at several temperatures in the glassy region. Shear modulus and damping (tan delta) are measured isothermally over a wide range (up to 11 decades) of time and frequency. Results indicate that, while modulus curves can be approximately superimposed, the damping (tan delta) curves change in height and shape with temperature.