Hard-sphere particles in nonpolar solvents are an essential tool for colloid scientists. Sterically stabilized poly(methyl methacrylate) (PMMA) particles have long been used as the exemplary hard-sphere system. However, neither the particles themselves nor the poly(12-hydroxystearic acid) (PHSA) stabilizer necessary to prevent aggregation in nonpolar solvents are commercially available. To counter this, several alternatives have been proposed. In recent years, there has been an increased interest in poly(dimethylsiloxane) (PDMS) stabilizers as a commercially available alternative to PHSA, yet the structure of particles made in this way is not as well understood as those produced using PHSA. In this work, we employ small-angle neutron scattering to determine the internal structure of PDMS-stabilized PMMA particles, synthesized with and without an additional crosslinking agent. We report data consistent with a homogeneous PMMA core with a linearly decaying PDMS shell. The thickness of the shell was in excess of 50 nm, thicker than the PHSA layer typically used to stabilize PMMA but consistent with reports of the layer thickness for similar molecular weight PDMS at planar surfaces. We also show that the amount of the hydrogenous material in the particle core of the crosslinked particles notably exceeds the amount of added ethylene glycol dimethacrylate crosslinker, suggesting some entrapment of the PDMS stabilizer in the PMMA matrix.
Read full abstract