Investigation of the linear flow regime of commercial polymers by numerical conversion of MVM creep measurements

A new experimental and numerical method has been developed to characterize the terminal flow behavior of polydisperse, commercial grade polymer melts over a wide dynamic range of time/frequency scales. Experimentally, an MVM rheometer specifically designed for long time scale (t 10⁴ s) creep measurements is used to measure the creep compliance of three commercial polymers: two high density polyethylenes and one polystyrene. The long time scale MVM creep data are complemented in the short time scale regime by creep data from an industrial plate-plate rheometer. The time-dependent creep data is combined and converted to a discrete retardation spectra using a nonlinear regularization algorithm to address the ill-posed nature of the interconversion. The retardation spectrum is analytically converted to dynamic moduli and compared with independently measured dynamic moduli. In the overlapping frequency region, calculations and measurements show excellent agreement and the combined data span a much larger dynamic range than either independent data set. The calculated and measured dynamic moduli data are combined and a retardation spectrum with a vastly expanded dynamic range is generated. Combining long time scale MVM creep compliance data and dynamic moduli data exploits the intrinsic sensitivities of controlled strain and controlled stress rheological experiments and is a powerful means to greatly expand the experimentally accessible dynamic range of time/frequency. This approach is particularly useful for commercial polymers with broad molecular weight distributions and commensurately large distributions of relaxation times.