Ionic Polymer Nanocomposites Subjected to Uniaxial Extension: A Nonequilibrium Molecular Dynamics Study

We explore the behavior of coarse-grained ionic polymer nanocomposites (IPNCs) under uniaxial extension up to 800% strain by means of nonequilibrium molecular dynamics simulations. We observe a simultaneous increase of stiffness and toughness of the IPNCs upon increasing the engineering strain rate, in agreement with experimental observations. We reveal that the excellent toughness of the IPNCs originates from the electrostatic interaction between polymers and nanoparticles, and that it is not due to the mobility of the nanoparticles or the presence of polymer-polymer entanglements. During the extension, and depending on the nanoparticle volume fraction, polymer-nanoparticle ionic crosslinks are suppressed with the increase of strain rate and electrostatic strength, while the mean pore radius increases with strain rate and is altered by the nanoparticle volume fraction and electrostatic strength. At relatively low strain rates, IPNCs containing an entangled matrix exhibit self-strengthening behavior. We provide microscopic insight into the structural, conformational properties and crosslinks of IPNCs, also referred to as polymer nanocomposite electrolytes, accompanying their unusual mechanical behavior.