Extensional flow induced miscibility in a polymer blend

Summary Extensional flows can induce miscibility in a polymer blend of polystyrene with poly(vinyl methyl ether). Miscibility is observed as a change from turbidity to optical clarity when a phase separated blend flows isothermally in planar extension. In a start-up experiment at temperatures above the LCST, optical clarity does not appear instantaneously but after a time which depends on the rate of extension and the temperature, and it appears first near the region of highest extension. This effect is opposite to the observation for polymer solutions which exhibit shear-induced demixing. We attribute this to the fact that enthalpic effects largely determine blend miscibility, while the phase behavior of solutions is essentially controlled by entropic contributions. Since a deformation field decreases the configurational degrees of freedom of a polymer molecule, demixing is favored in solutions. However, the alteration of specific interactions rather than this entropic effect appears to be much more important in blends.