Creating surfactant nanoparticles for block copolymer composites through surface chemistry

Bumjoon J. Kim, Joona Bang, Craig J. Hawker, Julia J. Chiu, David J. Pine, Se Gyu Jang, Seung Man Yang, Edward J. Kramer

Research output: Contribution to journalArticle

140 Citations (Scopus)

Abstract

A simple strategy to tailor the surface of nanoparticles for their specific adsorption to and localization at block copolymer interfaces was explored. Gold nanoparticles coated by a mixture of low molecular weight thiol end-functional polystyrene (PS-SH) (M n = 1.5 and 3.4 kg/mol) and poly(2-vinylpyridine) homopolymers (P2VP-SH) (M n = 1.5 and 3.0 kg/mol) were incorporated into a lamellar poly(styrene-b-2-vinylpyridine) diblock copolymer (PS-b-P2VP) (M n = 196 kg/mol). A library of nanoparticles with varying PS and P2VP surface compositions (F PS) and high polymer ligand areal chain densities was synthesized. The location of the nanoparticles in the PS-b-P2VP block copolymer was determined by transmission electron microscopy. Sharp transitions in particle location from the PS domain to the PS/P2VP interface, and subsequently to the P2VP domain, were observed at F PS = 0.9 and 0.1, respectively. This extremely wide window of F PS values where the polymer-coated gold nanoparticles adsorb to the interface suggests a redistribution of PS and P2VP polymers on the Au surface, inducing the formation of amphiphilic nanoparticles at the PS/P2VP interface. In a second and synthetically more challenging approach, gold nanoparticles were covered with a thiol terminated random copolymer of styrene and 2-vinylpyridine synthesized by RAFT polymerization. Two different random copolymers were considered, where the molecular weight was fixed at 3.5 kg/mol and the relative incorporation of styrene and 2-vinylpyridine repeat units varied (F PS = 0.52 and 0.40). The areal chain density of these random copolymers on Au is unfortunately not high enough to preclude any contact between the P2VP block of the block copolymer and the Au surface. Interestingly, gold nanoparticles coated by the random copolymer with F PS = 0.4 were dispersed in the P2VP domain, while those with F PS = 0.52 were located at the interface. A simple calculation for the adsorption energy to the interface of the nanoparticles with different surface arrangements of PS and P2VP ligands supports evidence for the rearrangement of thiol terminated homopolymers. An upper limit estimate of the adsorption energy of nanoparticles uniformly coated with a random arrangement of PS and P2VP ligands where a 10% surface area was occupied by P2VP -mers or chains was ∼1 k BT, which indicates that such nanoparticles are unlikely to be segregated along the interface, in contrast to the experimental results for nanoparticles with mixed ligand-coated surfaces.

Original languageEnglish
Pages (from-to)12693-12703
Number of pages11
JournalLangmuir
Volume23
Issue number25
DOIs
Publication statusPublished - 2007 Dec 4

Fingerprint

Surface chemistry
block copolymers
Surface-Active Agents
Nanoparticles
Block copolymers
Surface active agents
surfactants
chemistry
nanoparticles
composite materials
Composite materials
copolymers
Gold
Copolymers
Ligands
Sulfhydryl Compounds
thiols
gold
Adsorption
Styrene

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Colloid and Surface Chemistry

Cite this

Kim, B. J., Bang, J., Hawker, C. J., Chiu, J. J., Pine, D. J., Jang, S. G., ... Kramer, E. J. (2007). Creating surfactant nanoparticles for block copolymer composites through surface chemistry. Langmuir, 23(25), 12693-12703. https://doi.org/10.1021/la701906n

Creating surfactant nanoparticles for block copolymer composites through surface chemistry. / Kim, Bumjoon J.; Bang, Joona; Hawker, Craig J.; Chiu, Julia J.; Pine, David J.; Jang, Se Gyu; Yang, Seung Man; Kramer, Edward J.

In: Langmuir, Vol. 23, No. 25, 04.12.2007, p. 12693-12703.

Research output: Contribution to journalArticle

Kim, BJ, Bang, J, Hawker, CJ, Chiu, JJ, Pine, DJ, Jang, SG, Yang, SM & Kramer, EJ 2007, 'Creating surfactant nanoparticles for block copolymer composites through surface chemistry', Langmuir, vol. 23, no. 25, pp. 12693-12703. https://doi.org/10.1021/la701906n
Kim, Bumjoon J. ; Bang, Joona ; Hawker, Craig J. ; Chiu, Julia J. ; Pine, David J. ; Jang, Se Gyu ; Yang, Seung Man ; Kramer, Edward J. / Creating surfactant nanoparticles for block copolymer composites through surface chemistry. In: Langmuir. 2007 ; Vol. 23, No. 25. pp. 12693-12703.
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