225d Connecting the Depletion Flocculation and Interfacial Wetting Behaviors of Polymer-Grafted Nanoparticles in Polymer Solutions and Melts

David L. Green, Department of Chemical Engineering, University of Virginia, 102 Engineers Way, Charlottesville, VA 22904 and Nupur Dutta, Chemical Engineering, University of Virginia, 102 Engineers Way, Charlottesville, VA 22904.

Engineered composites are often formulated by grafting polymer brushes to the surfaces of nanoparticles to disperse them into polymer solutions and melts. In these suspensions it is well established that nanoparticles can exhibit a wide variety of phase behaviors through depletion flocculation at low-to-moderate free polymer concentrations. However, few studies fundamentally elucidate the fate of polymer-grafted particles in concentrated polymer solutions and melts. Researchers who have studied these systems predict that ungrafted and grafted nanoparticles, once destabilized by depletion flocculation, should restabilize in concentrated polymer solutions. In contradiction, we will show the results of recent light scattering experiments on polydimethylsiloxane (PDMS)-grafted silica nanospheres in PDMS/cyclohexane mixtures which indicate that at high free polymer volume fractions (0.5 – 1.0 v/v) the interfacial wetting of the grafted brush is needed to stabilize the nanoparticles against aggregation. We correlate this behavior to wetting phase diagrams that predict the regions of stability and instability for the PDMS-g-silica nanoparticles. Overall, these studies represent new ways of quantifying the factors that control the dispersion of polymer-grafted nanoparticles in concentrated polymer solutions and melts – systems that are ubiquitous in formulating engineered composites.