Studies on droplet size distributions during coalescence in immiscible polymer blends filled with silica nanoparticles

Abstract

The effect of silica nanoparticles on the morphology of (10/90 wt%) PDMS/PBD blends during the shear induced coalescence of droplets of the minor phase at low shear rate was investigated systematically in situ by using an optical shear technique. Two blending procedures were used: silica nanoparticles were introduced to the blends by pre-blending silica particles first in PDMS dispersed phase (procedure 1) or in PBD matrix phase (procedure 2). Bimodal or unimodal droplet size distributions were observed for the filled blends during coalescence, which depend not so much on the surface characteristics of silica but mainly on blending procedure. For pure (10/90 wt%) PDMS/PBD blend, the droplet size distribution exhibits bimodality during the early coalescence. When silica nanoparticles (hydrophobic and hydrophilic) were added to the blends with procedure 1, bimodal droplet size distributions disappear and unimodal droplet size distributions can be maintained during coalescence; the shape of the different peaks is invariably Gaussian. Simultaneously, coalescence of the PDMS droplets was suppressed efficiently by the silica nanoparticles. It was proposed that with this blending procedure the nanoparticles should be mainly kinetically trapped at the interface or in the PDMS dispersed phase, which provides an efficient steric barrier against coalescence of the PDMS dispersed phase. However, bimodal droplet size distributions in the early stage of coalescence still occur when incorporating silica nanoparticles into the blends with procedure 2, and then coalescence of the PDMS droplets cannot be suppressed efficiently by the silica nanoparticles. It was proposed that with this blending protocol the nanoparticles should be mainly located in the PBD matrix phase, which leads to an inefficient steric barrier against coalescence of the PDMS dispersed phase; thus the morphology evolution in these filled blends is similar to that in pure blend and bimodal droplet size distributions can be observed during the early coalescence. These results imply that exploiting non-equilibrium processes by varying preparation protocol may provide an elegant route to regulate the temporal morphology of the filled blends during coalescence.