Structure and collapse of a surface-grown strong polyelectrolyte brush on sapphire

Iain E. Dunlop, Robert K. Thomas, Simon Titmus, Victoria Osborne, Steve Edmondson, Wilhelm T. S. Huck, Jacob Klein

Research output: Contribution to journalArticlepeer-review


We have used neutron reflectometry to investigate the behavior of a strong polyelectrolyte brush on a sapphire substrate, grown by atom-transfer radical polymerization (ATRP) from a silane-anchored initiator layer. The initiator layer was deposited from vapor, following treatment of the substrate with an Ar/H 2O plasma to improve surface reactivity. The deposition process was characterized using X-ray reflectometry, indicating the formation of a complete, cross-linked layer. The brush was grown from the monomer [2-(methacryloyloxy)ethyl]trimethylammonium chloride (METAC), which carries a strong positive charge. The neutron reflectivity profile of the swollen brush in pure water (D 2O) showed that it adopted a two-region structure, consisting of a dense surface region ∼100 Å thick, in combination with a diffuse brush region extending to around 1000 Å from the surface. The existence of the diffuse brush region may be attributed to electrostatic repulsion from the positively charged surface region, while the surface region itself most probably forms due to polyelectrolyte adsorption to the hydrophobic initiator layer. The importance of electrostatic interactions in maintaining the brush region is confirmed by measurements at high (1 M) added 1:1 electrolyte, which show a substantial transfer of polymer from the brush to the surface region, together with a strong reduction in brush height. On addition of 10 -4 M oppositely charged surfactant (sodium dodecyl sulfate), the brush undergoes a dramatic collapse, forming a single dense layer about 200 Å in thickness, which may be attributed to the neutralization of the monomers by adsorbed dodecyl sulfate ions in combination with hydrophobic interactions between these dodecyl chains. Subsequent increases in surfactant concentration result in slow increases in brush height, which may be caused by stiffening of the polyelectrolyte chains due to further dodecyl sulfate adsorption.

Original languageEnglish
Pages (from-to)3187-3193
Number of pages7
Issue number6
StatePublished - 14 Feb 2012

All Science Journal Classification (ASJC) codes

  • Condensed Matter Physics
  • Spectroscopy
  • General Materials Science
  • Surfaces and Interfaces
  • Electrochemistry


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