Tailoring Core-Shell Polymer-Coated Nanoparticles as Block Copolymer Surfactants

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The effect of core-shell polymer-coated nanoparticles on block copolymer morphology is investigated systematically by controlling particle positioning within a block copolymer template. Our approach of varying the areal chain density (Sigma) of short thiol terminated polystyrene (PS-SH) brushes on the particles where the molecular weight (M(n)) of the PS ligands (2.5 kg/mol) is used to control the fraction of the particles adsorbed to the interface of PS-b-P2VP diblock copolymer domains (M(n) = 196 kg/mol). The change in Sigma from 2.38 to 0.49 chains/nm(2) brings systematic control over the fraction of Au particles bound to the PS/ P2VP interface (f(i)), this fraction ranging from 0 to 95%. Particles with Sigma of 2.38 chains/nm(2) (f(i) similar to 0) were observed to localize within the PS domains and further produce a macroscopic particle aggregated phase separate from the PS-b-P2VP mesophase. In contrast, decreasing the 2: of PS chains provides for strong binding of Au nanoparticles to the PS/P2VP interfaces as a consequence of preferential wetting of one block of the copolymer (P2VP) to the Au substrate. Interestingly, the addition of low volume fractions (phi(P)) of such nanoparticle surfactants (Sigma < 1.1 chains/nm(2)) to lamellar diblock copolymers initially leads to a decrease in lamellar thickness, a consequence of decreasing interfacial tension, up to a critical value of phi(P) beyond which the block copolymer adopts a bicontinuous morphology. The relationship between domain spacing and morphology of block copolymer with the level of nanoparticle surfactants will be discussed based on a strong-segregation model. In addition, the rational design of nanoparticle surfactants based on the nature and density of the grafted chains will be described.
Publisher
AMER CHEMICAL SOC
Issue Date
2009
Language
English
Article Type
Article
Keywords

GOLD NANOPARTICLES; DIBLOCK-COPOLYMER; MOLECULAR-WEIGHT; BICONTINUOUS MICROEMULSIONS; SOLAR-CELLS; BLENDS; LOCATION; MIXTURES; HOMOPOLYMER; COMPOSITES

Citation

MACROMOLECULES, v.42, no.16, pp.6193 - 6201

ISSN
0024-9297
DOI
10.1021/ma9009406
URI
http://hdl.handle.net/10203/97178
Appears in Collection
CBE-Journal Papers(저널논문)
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