Hydrophobic, Electrostatic, and Dynamic Polymer Forces at Silicone Surfaces Modified with Long-Chain Bolaform Surfactants

Michael V. Rapp, Stephen H. Donaldson, Matthew A. Gebbie, Saurabh Das, Yair Kaufman, Yonas Gizaw, Peter Koenig, Yuri Roiter, Jacob N. Israelachvili

Research output: Contribution to journalArticlepeer-review

4 Scopus citations


Surfactant self-assembly on surfaces is an effective way to tailor the complex forces at and between hydrophobic-water interfaces. Here, the range of structures and forces that are possible at surfactant-adsorbed hydrophobic surfaces are demonstrated: certain long-chain bolaform surfactants - containing a polydimethylsiloxane (PDMS) mid-block domain and two cationic α, ω-quarternary ammonium end-groups - readily adsorb onto thin PDMS films and form dynamically fluctuating nanostructures. Through measurements with the surface forces apparatus (SFA), it is found that these soft protruding nanostructures display polymer-like exploration behavior at the PDMS surface and give rise to a long-ranged, temperature- and rate-dependent attractive bridging force (not due to viscous forces) on approach to a hydrophilic bare mica surface. Coulombic interactions between the cationic surfactant end-groups and negatively-charged mica result in a rate-dependent polymer bridging force during separation as the hydrophobic surfactant mid-blocks are pulled out from the PDMS interface, yielding strong adhesion energies. Thus, (i) the versatile array of surfactant structures that may form at hydrophobic surfaces is highlighted, (ii) the need to consider the interaction dynamics of such self-assembled polymer layers is emphasized, and (iii) it is shown that long-chain surfactants can promote robust adhesion in aqueous solutions. Direct force measurements reveal that long-chain (polydimethylsiloxane) bolaform surfactants self-assemble on silicone surfaces to form dynamically fluctuating nanostructures that protrude into solution. Sparingly low concentrations of these surfactants mediate remarkably strong adhesion between a polymer and a mineral surface in aqueous solution, via both specific Coulombic bonds and non-specific hydrophobic interactions.

Original languageEnglish
Pages (from-to)2058-2068
Number of pages11
Issue number17
StatePublished - 6 May 2015
Externally publishedYes


  • adhesion
  • nanostructures
  • polymers
  • self-assembly
  • surface forces apparatus

ASJC Scopus subject areas

  • Engineering (miscellaneous)
  • Chemistry (all)
  • Materials Science (all)
  • Biotechnology
  • Biomaterials


Dive into the research topics of 'Hydrophobic, Electrostatic, and Dynamic Polymer Forces at Silicone Surfaces Modified with Long-Chain Bolaform Surfactants'. Together they form a unique fingerprint.

Cite this