Olafson, Katy N. | Search NASA

DOE OSTI2017

Confined dynamics of grafted polymer chains in solutions of linear polymer

Here, we measure the dynamics of high molecular weight polystyrene grafted to silica nanoparticles dispersed in semidilute solutions of linear polymer. Structurally, the linear free chains do not penetrate the grafted corona but increase the osmotic pressure of the solution, collapsing the grafted polymer and leading to eventual aggregation of the grafted particles at high matrix concentrations. Dynamically, the relaxations of the grafted polymer are controlled by the solvent viscosity according to the Zimm model on short time scales. On longer time scales, the grafted chains are confined by neighboring grafted chains, preventing full relaxation over the experimental time scale. Adding free linear polymer to the solution does not affect the initial Zimm relaxations of the grafted polymer but does increase the confinement of the grafted chains. Finally, our results elucidate the physics underlying the slow relaxations of grafted polymer.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Engineering Crystal Modifiers: Bridging Classical and Nonclassical Crystallization

The use of growth modifiers in natural, biological, and synthetic crystallization is a ubiquitous strategy for controlling growth and achieving desired physicochemical properties. For crystals that grow classically (i.e., monomer-by-monomer addition), theories of crystallization are well established and the field of growth modification is rather mature, although many questions remain regarding the molecular driving forces of modifier–crystal interactions. A new frontier in crystallization is the application of classical methods to tailor materials that grow nonclassically (i.e., growth by the addition of species more complex than monomers). A recent surge of interest and activity in this field has been driven by mounting evidence of both inorganic and organic materials that grow via nonclassical pathways. In these systems, the challenge of elucidating the mechanism(s) of crystallization is underscored by a diversity of growth units that far outnumber those available for classical routes. In this Perspective, we consider growth modification in nonclassical crystallization, including examples in the literature, the challenges associated with elucidating the modes of modifier action, and to what degree classical theories can be applied to these complex problems as a means of establishing versatile blueprints for crystal engineering.

36 MATERIALS SCIENCE↗