Flow-induced enhancement of concentration fluctuations in polymer mixtures

Many mixtures of high-molecular-weight polymers are partially miscible, separating into two co-existing phases in some ranges of temperature and concentration. Generally these binary blends exhibit lower critical solution temperature (LCST) behaviour, becoming phase separated as the temperature is raised. We have been undertaking a systematic study of the effect of simple shear flow on the miscibility limits of a number of high-molecular-weight binary polymer blends exhibiting lower critical-solution temperatures. Using a parallel-plate shear cell and light-scattering detection, we have observed large shifts in the cloud-point curves as blends are heated while shear is applied, and we have been able to show, using ancillary measurements of glass-transition temperatures on quenched samples, that these effects are the results of changes in the miscibility of the blends and not artefacts of the scattering techniques. Both shear-induced 'mixing' and 'demixing' have been observed-the latter in temperature ranges well below the quiescent cloud points. We have investigated the kinetics of the appearance of the two-phase structures, and this is very reminiscent of the spinodal decomposition processes observed in zero shear from these blends. Small-angle neutron scattering is very sensitive to the rather short wavelength concentration fluctuations (a few nanometres) in binary systems, both in the stable one-phase region and in the early stages of instability in the two-phase region. Small-angle neutron-scattering results on blends sheared and quenched at temperatures far below the spinodal temperature show the effects of the shear in modifying the blend's structure factors.