To study surface and sub-surface nanomechanical properties of electrospun polyacrylonitrile (PAN) nanofibers/polydimethylsiloxane (PDMS) composites.

We investigate surface and sub-surface nanomechanical properties of nanocomposites based on a crosslinked polydimethylsiloxane (PDMS) elastomer and electrospun polyacrylonitrile (PAN) nanofibers. Fabrication of PDMS substrates with anisotropy with respect to surface elasticity and their characterization in terms of local nanomechanical properties are important for many areas of adhesion applications. PDMS nanocomposite substrates with variations in surface elasticity over large areas are prepared by controllably embedding electrospun PAN nanofibers (∼600 nm) in a PDMS matrix using the solution casting technique. Variations of local surface stiffness properties of prepared composites are measured using force spectroscopy and force mapping modes of atomic force microscopy and compared with their macroscopic (bulk) mechanical properties. Since the surface of the prepared nanocomposite is elastically non-homogeneous, our studies are mainly focused on the investigation of the hysteresis (plasticity index) between loading and unloading curves which is a measure of energy dissipation in AFM indentation experiments. The distribution of the local plasticity index in the PAN/PDMS composites is related to the specific organization of electrospun nanofibers at the surface and sub-surface layers of the PDMS matrix. We observed that embedding 0.1-1% PAN nanofibers induces anti-plasticization effects for lower (0.1%) and higher (1%) concentrations of PAN nanofibers which represent the formation of interpenetrating networks and mat-like blended structures of PAN nanofibers within the PDMS matrix.