Polymer grafting from 10-nm individual particles: proving control by neutron scattering

Abstract

The core–shell structure of nanoparticles (5 nm radius) of silica grafted with polymer growing from the particle (“grafting from”) is characterized by small angle neutron scattering (SANS), to our knowledge for the first time. This is made possible by a good control of the colloidal dispersion at each step of the synthesis. With this aim, we have improved our chemical procedure based on atom transfer radical polymerization (ATRP), which allows a good control of kinetics and polydispersity: the reaction takes place in a polar solvent, and the reaction medium remains always crystal clear. For such small particles, in contrary to direct space imaging, SANS is appropriate for in situ characterization of the polymer corona as well as of the silica core using contrast matching provided by mixing normal and deuterated solvent. This allows checking of the level of aggregation at the nanoscale, which is found to be limited to a few percent of the particles in the reaction batch. After an initial slight increase, it is reduced by further polymerization, while the polymer layer grows progressively. After purification, grafted silica can be characterized accurately: its scattering can be fitted by a model of a silica core containing three to five particles surrounded by a polymer shell of thickness 7 nm. This is in good agreement with chain length and grafting density (214 sites per particle) evaluated by chemical analysis; hence SANS provides quantitative insight on chemical synthesis.