- Poly(methyl methacrylate) (PMMA)/silica/cetyltrimethylammonium bromide (CTAB) composites were prepared through surfactant catalyzed free radical polymerizations at 40 °C. Fumed silica particles controlled the morphology of the polymeric composites producing porous structures. The internal structures of the porous composite were determined using temperature-modulated differential scanning calorimetry (TMDSC). The fumed silica particles were encapsulated by an incompletely covered CTAB monolayer, with a crystallization temperature, T C,CTAB = 76 °C, and a mixed PMMA/CTAB shell, with T C,CTAB = 63 °C. The fumed silica surfaces acted as inhibitors for PMMA free radical polymerizations. Much of the PMMA formed in the composites was adsorbed on the silica, as evidenced by its elevated glass transition temperature compared to bulk. The enhanced decomposition of the initiator was catalyzed by CTAB and resulted in free radical polymerization of PMMA at 40 °C, which is considerably lower than the temperatures normally used for PMMA synthesis by free radical means with thermal initiation. These lowered polymerization temperatures allow energy efficient production of composites, which can incorporate temperature sensitive materials.