화학공학소재연구정보센터
Macromolecules, Vol.46, No.6, 2323-2330, 2013
Indentation of Highly Charged PSPM Brushes Measured by Force Spectroscopy: Application of a Compressible Fluid Model
Highly charged dense poly(sulfopropyl methacrylate) polyelectrolyte brushes were indented with an atomic force microscopy (AFM) tip as well as with an 8 mu m silica colloidal probe at different ionic strengths ranging from Millipore water to 1 M NaCl. The force response during indentation was fitted to a phenomenological equation analogous to the equation of state of a compressible fluid. In this way, internal energy and brush thickness were obtained as a function of ionic strength. Long-range forces decayed exponentially with distance. The characteristic decay lengths were much larger than the Debye screening lengths at the respective ionic strengths. It was therefore concluded that long-range repulsion was due to compression of a loose corona of polymers in front of the dense part of the brush. The size of the indentor determines which region of the brush can be explored by AFM. The tip probes the denser parts of the brush, while with the colloidal probe the corona of the brush can be investigated. The obtained fits of the experimentally measured force distance curves were used as regularization tools for obtaining the brush swelling pressure or "force per unit area" as a function of brush compression. The swelling pressure as a function of brush thickness, h, followed over a wide range a power law close to similar to h(-2). This approach allowed deriving fundamental brush parameters on a thermodynamical basis like the compressibility as a function of thickness.