Critical scattering in polymer melts

Abstract

Critical phenomena in two classes of polymer melts have been examined by small-angle neutron scattering (SANS); single component block polymers which undergo an order-disorder phase transition, and binary polymer mixtures which exhibit liquid-liquid phase separation behavior. A model set of 1,4-polybutadiene-l,2-polybutadiene diblock copolymers containing perdeuterated 1,4-polybutadiene blocks were investigated by SANS in the disordered state. The SANS spectra exhibit a peak in the scattering intensity which diverges at the ordering transition, in close agreement with mean-field theory. Binary blends of perdeuterated and protonated 1,4-polybutadiene homopolymers have been found to form regular solutions characterized by an upper critical solution temperature (UCST). Near the critical point, these mixtures exhibit classical critical scattering as measured by SANS. The second set of results raises serious questions regarding the widely held assumption that deuterated and protonated polymers form ideal mixture.