Characterization of Microstructure and Molecular Dynamics with High Frequency Oscillatory Techniques

To characterize the rheological behaviour of complex viscoelastic fluids, polymer melts and other soft materials, motor-drive controlled rheometers are mainly used, either at constant stress or strain rate, or in the oscillatory mode. The latter has proved advantageous to discover the viscoelastic functions G*, η*, J* as fingerprints of the material under investigation, it's composition, molecular modelling and applicability. A conclusive analysis of such a viscoelastic spectrum can only be achieved if the amplitudes chosen guarantee linearity and if the frequency range covers more than 6 decades to reach the low kHz-domain. Investigations of many materials with motor-drive controlled rheometers are limited at higher frequencies and reach the above mentioned goal by applying the time-temperature superposition principle, i.e. the mastercurve technique. Since this method is restricted to rheologically simple materials (e.g. some polymer melts), but exclude those of small activation energies and others with temperature-sensitive chemical/physical structures including phase transitions, oscillating rheometry should be extended into higher real-frequency ranges, to establish useful linear viscoelastic spectroscopy. Since complex fluids can have structural arrangement over a wide range of lengthscales and their relaxation mechanisms can impact the dynamics over a wide range of timescales, multiple techniques need to be employed in order to accurately and fully establish the links between rheology, microstructure & dynamics. This is also critical information, required for fully validating developed theory and models. In this talk, advantages and limits of classical oscillatory rheometry will be covered, handling and principle of operation of two high frequency options are introduced and typical examples for real frequency spectra on soft matter, such as polymer melts, polymer solutions and weak gels will be shown. A xanthum gum based system has been investigated not only by traditional rheology and high frequency mechanical rheology but also through DWS based optical microrheology. The talk will focus on how unique insights from each of these techniques leads to a better understanding of the overall microstructure-rheology linkages in this system.