Facile Entropy-Driven Segregation of Imprinted Polymer-Grafted Nanoparticle Brush Blends by Solvent Vapor Annealing...

Polymer-grafted nanoparticles (PGNPs) have attracted extensive research interest due to their potential for enhancing mechanical and electrical properties of both bulk polymer composite materials, as well as thin polymer films incorporating these nanoparticles (NPs). In previous studies, we have shown that an entropic driving force serves to organize low-molecular-mass PGNPs in imprinted blend films of PGNPs with low-molecular-mass homopolymers. In this work, we developed a novel solvent vapor annealing soft lithography (SVA-SL) method to overcome the technical difficulties in processing the high-molecular-mass PGNP blends due to the intrinsically sluggish melt annealing kinetics found in the phase separation of these blend PGNP materials. In particular, we utilized SVA-SL to create nanopatterns in blends of PGNPs having relatively high-molecular-mass-grafted layers but with cores of NPs having greatly different sizes. The minimization of the entropic free energy in the present system corresponded to larger PGNPs partitioning almost exclusively into the "mesa" regions of the imprinted PGNP blend films, as quantified by the estimation of the partition coefficient, K_p. The use of the SVA-SL processing method is important because it allows facile imprint patterning of PGNP materials and large-scale organization of the PGNPs even when the grafted chain lengths are long enough for the chains to be highly entangled, allowing enhanced thermo-mechanical property enhancements of the resulting films and a corresponding extended range of potential nanotech applications.