Shear induced mixing/demixing: Blends of homopolymers, of homopolymers plus copolymers, and blends in solution

Shear may shift the phase boundary towards the homogeneous state (shear induced mixing, SIM), or in the opposite direction (shear induced demixing, SID). SIM is the typical behavior of mixtures of components of low molar mass and polymer solutions, SID can be observed with solutions of high molar mass polymers and polymer blends at higher shear rates. The typical sequence with increasing shear rate is SIM, then occurrence of an isolated additional immiscible area (SLD), melting of this island into the main miscibility gap, and finally SIM again. A three phase line originates and ends in two critical end points. Raising pressure increases the shear effects. For copolymer containing systems SID is sometimes observed at very low shear rates, preceding the just mentioned sequence of shear influences.

Theoretical representation of shear and pressure influence on the phase separation behavior of PVME/PS mixture

In the framework of lattice fluid model, the Gibbs energy and equation of state are derived by introducing the energy (E-s) stored during flow for polymer blends under shear. From the calculation of the spinodal of poly(vinyl methyl ether) (PVME) and polystyrene (PS) mixtures, we have found the influence of E., an equation of state in pure component is inappreciable, but it is appreciable in the mixture. However, the effect of E, on phase separation behavior is extremely striking. In the calculation of spinodal for the PVME/PS system, a thin, long and banana miscibility gap generated by shear is seen beside the miscibility gap with lower critical solution temperature. Meanwhile, a binodal coalescence of upper and lower miscibility gaps is occurred. The three points of the three-phase equilibrium are forecasted. The shear rate dependence of cloud point temperature at a certain composition is discussed. The calculated results are acceptable compared with the experiment values obtained by Higgins et at. However, the maximum positive shift and the minimum negative shift of cloud point temperature guessed by Higgins are not obtained, Furthermore, the combining effects of pressure and shear on spinodal shift are predicted.

Periodic vortex breakdown in wide spherical gaps

The flow field with vortex breakdown in wide spherical gaps was studied numerically by a finite difference method under the axisymmetric condition. The result shows that the flow bifurcates to periodic motion as the Reynolds number or the eccentricity of the spheres increases. (C) 1997 American Institute of Physics.