title: Confined Pattern-Directed Assembly of Polymer-Grafted Nanoparticles in a Phase Separating Blend with a Homopolymer Matrix.
abstract: The controlled organization of nanoparticle (NP) constituents into superstructures of well-defined shape, composition and connectivity represents a continuing challenge in the development of novel hybrid materials for many technological applications. We show that the phase separation of polymer-tethered nanoparticles immersed in a chemically different polymer matrix provides an effective and scalable method for fabricating defined submicron-sized amorphous NP domains in melt polymer thin films. We investigate this phenomenon with a view towards understanding and controlling the phase separation process through directed nanoparticle assembly. In particular, we consider isothermally annealed thin films of polystyrene-grafted gold nanoparticles (AuPS) dispersed in a poly(methyl methacrylate) (PMMA) matrix. Classic binary polymer blend phase separation related morphology transitions, from discrete AuPS domains to bicontinuous to inverse domain structure with increasing nanoparticle composition is observed, yet the kinetics of the AuPS/PMMA polymer blends system exhibit unique features compared to the parent PS/PMMA homopolymer blend. We further illustrate how to pattern-align the phase-separated AuPS nanoparticle domain shape, size and location through the imposition of a simple and novel external symmetry-breaking perturbation via soft-lithography. Specifically, submicron-sized topographically patterned elastomer confinement is introduced to direct the nanoparticles into kinetically controlled long-range ordered domains, having a dense yet well-dispersed distribution of non-crystallizing nanoparticles. The simplicity, versatility and roll-to-roll adaptability of this novel method for controlled nanoparticle assembly should make it useful in creating desirable patterned nanoparticle domains for a variety of functional materials and applications.
authors.affiliation: Department of Polymer Engineering, the University of Akron, Akron, OH 44325.
authors.forename: Ren
authors.initials: R
authors.lastname: Zhang
authors.affiliation: Department of Materials Science and Engineering, Carnegie Mellon University, 5000 Forbes Ave, Pittsburgh, PA 15213.
authors.forename: Bongjoon
authors.initials: B
authors.lastname: Lee
authors.affiliation: Department of Materials Science and Engineering, Carnegie Mellon University, 5000 Forbes Ave, Pittsburgh, PA 15213.
authors.forename: Michael R
authors.initials: MR
authors.lastname: Bockstaller
authors.affiliation: Materials Science and Engineering Division, NIST, Gaithersburg, MD 20889.
authors.forename: Jack F
authors.initials: JF
authors.lastname: Douglas
authors.affiliation: Materials Science and Engineering Division, NIST, Gaithersburg, MD 20889.
authors.forename: Christopher M
authors.initials: CM
authors.lastname: Stafford
authors.affiliation: Department of Chemical Engineering, Columbia University, 116th St & Broadway, New York, NY 10027.
authors.forename: Sanat K
authors.initials: SK
authors.lastname: Kumar
authors.affiliation: Department of Chemistry, Howard University, Washington D.C 20059.
authors.forename: Dharmaraj
authors.initials: D
authors.lastname: Raghavan
authors.affiliation: Department of Polymer Engineering, the University of Akron, Akron, OH 44325.
authors.forename: Alamgir
authors.initials: A
authors.lastname: Karim
keywords: confinement; nanoparticles; pattern directed assembly; phase separation; polymer nanocomposites; symmetry breaking; ultrathin blend films