Tuning polymer crystallinity via the appropriate selection of inorganic nanoadditives

Abstract Controlling the crystallization behavior of semicrystalline polymers is of paramount importance since it largely determines their final properties. A way to affect crystallinity is via the addition of (nanosized) additives to the polymer matrix, commonly utilized to improve polymer properties. In the present article, we demonstrate that one can control the degree of polymer crystallinity in poly(ethylene oxide)/silica, PEO/SiO2, nanohybrids by utilizing nanoparticles of different sizes, thus, by introducing a varying degree of chain confinement and of chain adsorption capability. More importantly, tuning of the degree of crystallinity is achieved when mixtures of silica nanoparticles of different sizes are introduced in order to take advantage of both the enhanced chain confinement and the different adsorption capacity of the nanoparticles. Polymer crystallinity can, indeed, be controlled by modifying the ratio of large to small nanoparticles for constant polymer concentration. Moreover, for specific ternary systems, even systems with zero crystallinity can be obtained.