Madbouly, S. A., Wolf, B. A.

"Shear-Induced Crystallization and Shear-Induced Dissolution of Poly(Ethylene Oxide) in Mixtures with Tetrahydronaphthaline and Oligo(Dimethyl Siloxane-b-Ethylene Oxide) "

Macromolecular Chemistry and Physics 2003, 3,204,417-424.

Abstract: Cloud point temperatures (T-cp) and crystallization temperatures, (T-I/s) were measured at different constant shear rates for the ternary system tetrahydronaphthalene/polyethylene oxide/oligo(dimethyl siloxane-b-ethylene oxide) using a rheo-optical device and in the case of T-1/s additionally a viscometer: This system enables for the first time a joint investigation of both transitions with a given mixture. Shear favors the-homogeneous liquid state and the, formation of crystals. T-cp (liquid/liquid demixing, UCST) shifts to lower and T-1/s (liquid/solid, segregation of PEO) to higher temperatures by several degrees as the shear rate, (gamma) over dot, is increased up to 500 s(-1). The normalized shift in T-cp fits well into previous results for high molecular weight blends, oligomer mixtures; polymer solutions in single solvents and low molecular weight mixtures. A phase separated near critical blend was examined 1 K below its T-cp by means of-a shear cell (Linkam) in the quiescent state and under shear with respect to its morphology. Upon an increase in (gamma) over dot one observes a transition from the co-continuous structures existing in the quiescent state via deformed and oriented particles to string like morphologies. Finally, at sufficiently high shear rates the mixture becomes homogeneous and structures can no longer be seen under the microscope. The morphologies developing after the secession of shear are pointing to pronounced influences of the flow history of the system on the final structure of two phase blends.

preprint number: 233