Nanoparticle-directed self-assembly of amphiphilic block copolymers

Amanda C. Kamps, Brenda L. Sanchez-Gaytan, Robert J Hickey, Nigel Clarke, Michael Fryd, So Jung Park

Research output: Contribution to journalArticle

38 Scopus citations

Abstract

Nanoparticles can form unique cavity-like structures in core-shell type assemblies of block copolymers through the cooperative self-assembly of nanoparticles and block copolymers.Weshow that the self-assembly behavior is general for common as-synthesized alkyl-terminated nanoparticles for a range of nanoparticle sizes. We examined various selfassembly conditions such as solvent compositions, nanoparticle coordinating ligands, volume fraction of nanoparticles, and nanoparticle sizes in order to elucidate the mechanism of the radial assembly formation. These experiments along with strong segregation theory calculations indicated that both the enthalpic interaction and the polymer stretching energy are important factors in the coassembly formation. The slightly unfavorable interaction between the hydrophobic segment of polymers and alkyl-terminated nanoparticles causes the accumulation of nanoparticles at the interface between the polymer core and the shell, forming the unique cavity-like structure. The coassemblies were stabilized for a limited range of nanoparticle volume fractions within which the inclusion of nanoparticle layers reduces the polymer stretching. The volume fraction range yielding the well-defined radial coassembly structure was mapped out with varying nanoparticle sizes. The experimental and theoretical phase map provides the guideline for the coassembly formation of as-synthesized alkyl-terminated nanoparticles and amphiphilic block copolymers.

Original languageEnglish (US)
Pages (from-to)14345-14350
Number of pages6
JournalLangmuir
Volume26
Issue number17
DOIs
StatePublished - Sep 7 2010

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