Neutron and X-ray Scattering Characterization of Silica Nanoparticle-Stabilized Polymer Hybrid Latex Particles

A robust route to produce poly(methyl methacrylate) (pMMA) hybrid latex particles (radius ∼250 nm) that are selectively "armored" with silica nanoparticles (radius 12.5 nm) through addition of vinyltriethoxysilane was previously shown ( J. Colloid Interface Sci. 2018, 528, 289-300).Depending on synthesis conditions, the extent of nanoparticle attachment could be varied; however, the mechanism behind this attachment during latex growth remained unclear. The dual population of particles present (silica + polymer) means that particle sizing by dynamic light scattering is ambiguous. Furthermore, the low glass transition temperature (T_g) of polymers such as poly(butyl acrylate) (pBA) typically used in film-forming applications for decorative coatings (i.e., paints) means that the hybrid latex particles are too "soft" for robust analysis through atomic force microscopy (AFM) and scanning electron microscopy (SEM). Here, we show that small- and ultrasmall-angle neutron scattering (SANS and USANS), along with complementary data from small-angle X-ray scattering (SAXS), reveals that these armored hybrid latex particles adopt a raspberry-type configuration, supporting their core-shell structure. The number of nanoparticles present on the surface of the hybrid latex can be adjusted by addition of one of a diverse range of alkyl- or perfluoroalkyl-silanes to alter silica nanoparticle hydrophobicity, and quantified through analysis of scattering data. The approach therefore provides a novel, nonperturbative, and in situ method of quantifying nanoparticle attachment to polymer latex particles.